Textiles - History, Properties and Performance and Application 2014

CHEMISTRY RESEARCH AND APPLICATIONS
TEXTILES
HISTORY, PROPERTIES AND
PERFORMANCE AND APPLICATIONS
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TEXTILES
HISTORY, PROPERTIES AND
PERFORMANCE AND APPLICATIONS
MD. IBRAHIM H. MONDAL

EDITOR
New York
Copyright 2014 by Nova Science Publishers, Inc.

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CONTENTS
Preface
vii
Contributor Contact Details

Andrej Javorek, Cesar Pulgarin, Eva Bou-Belda,
Gordana S. Uumli, Ignacio Montava, Jaime Gisbert
and Sami Rtimi
ix
Chapter 1
An Exploration of Vintage Fashion Retailing

Julie McColl, Catherine Canning, Louise McBride,
Karina Nobbs and Linda Shearer
Chapter 2
Developing Sustainable Design on Denim Ready-Made Apparels

by Stone and Enzymatic Washing
Md. Ibrahim H. Mondal and Md. Mashiur Rahman Khan
Chapter 3
Digital Textile Printing Using Color Management

Dejana Javorek, Primo Weingerl and Marica Stareini
Chapter 4
Inkjet Printed Photo-Responsive Textiles for Conventional

and High-Tech Applications
Shah M. Reduwan Billah
Chapter 5
Synthesis and Grafting of Cellulose Derivatives from

Cellulosic Wastes of the Textile Industry
Md. Ibrahim H. Mondal and A. B. M. Fakrul Alam
Chapter 6
History, Synthesis and Properties of Azo Pyridone Dyes

Duan . Mijin, Gordana S. Uumli and Nataa V. Valenti
Chapter 7
Smart Textiles and the Effective Uses of Photochromic,

Thermochromic, Ionochromic and Electrochromic
Molecular Switches
19
53
81
123
157
187
Chapter 8
Smart Textiles
Ali Akbar Merati
239
Chapter 9
Overview of Textiles Excavated in Greece

Christina Margariti, Stavroula Moraitou and Maria Retsa
259
vi
Chapter 10
Contents
Innovative Ag-Textiles Prepared by Colloidal, Conventional
Sputtering and HIPIMS Including Fast Bacterial Inactivation:
Critical Issues
Sami Rtimi, Cesar Pulgarin, Rosendo Sanjines and John Kiwi
277
Chapter 11
Fungal Deterioration of Aged Textiles

Katja Kavkler, Nina Gunde-Cimerman, Polona Zalar
and Andrej Demar
315
Chapter 12
Durability of Functionalized Textiles by Microcapsules

Lucia Capablanca, Pablo Monllor, Pablo Daz
and Maria ngeles Bonet
343
Chapter 13
New Approaches and Applications on Cellulosic

Fabric Crosslinking
Eva Bou-Belda, Maria ngeles Bonet, Pablo Monllor,
Pablo Daz, Ignacio Montava and Jaime Gisbert
Chapter 14
Wrinkle Resistant and Comfort Finishing of Cotton Textiles

Vahid Ameri Dehabadi and Hans-Jrgen Buschmann
Chapter 15
Evaluation of Physical and Thermal Comfort Properties of

Copper/Alginate Treated Wool Fabrics by Using Ultrasonic Energy
Muhammet Uzun
355
367
383
Chapter 16
Hemp Fibers: Old Fibers - New Applications

Mirjana Kostic, Marija Vukcevic, Biljana Pejic
and Ana Kalijadis
399
Chapter 17
Textiles Using Electronic Applications

Marica Stareini, Andrej Javorek and Dejana Javorek
447
Chapter 18
Textiles for Cardiac Care

Narayanan Gokarneshan, Palaniappan P. Gopalakrishnan,
Venkatachalam Rajendran and Dharmarajan Anita Rachel
465
Chapter 19
Effect of Clothing Materials on Thermoregulatory Responses

of the Human Body
P. Kandha Vadivu
483
Designing of JuteBased Thermal Insulating Materials

and Their Properties
Sanjoy Debnath
499
Effects of Ring Flange Type, Traveler Weight and Coating on

Cotton Yarn Properties
Muhammet Uzun and Ismail Usta
519
Chapter 20
Chapter 21
Chapter 22
Index
Optical Fiber Examination by Confocal Laser Scanning Microscopy

Andrea Ehrmann
531
547
PREFACE
This book reveals the expanding opportunity of textiles in a wide range of industrial
applications. No longer limited to apparels and home furnishings, textiles are being used in
many sciences and technologies, such as clothing and fashionable materials, smart textiles,
technical textiles, medical textiles, agro-textiles, geo-textiles, electronics, photonics,
intelligent sensors, etc.
This book is intended for all those who are interested and engaged in the latest
developments in the field of textiles, especially chemists, engineers, technologists, application
technicians and colorists of the textile industry, technical colleges and universities.
Textiles are essential and one of the most important classes of materials used by all
people since ancient time. Despite textiles having been around and in use for so long,
advances and improvements continue to be made. This book contains 22 invited contributions
written by leading experts in the field of textiles. Each contribution presents an updated
science and technological advances that have happened during this period and are fully
discussed. The first chapter discusses the present and future prospects of vintage fashion
clothing, i.e., an old fashion clothing and its retailing. Chapter 2 searches for the dynamic best
method for producing specific washing effects and designs on denim ready-made apparels.
The chapters 3 and 4 present a discussion on color management application in the field of
digital printing onto textile substrates, and inject printed photo-responsive textiles used in
fashion and design, self indicating security alert systems, anti-counterfeit and brand
protection. In chapter 5 and 6, an attempt has been made to cover the most up-to-date
information regarding synthesis, and application of cellulose derivatives and azo dyes on
textiles. Smart textiles incorporated with different functionalities have many uses in a variety
of fields, some of them are widely used in the fields of biomedical or healthcare applications.
The smart textiles and its multi-disciplinary applications have been well discussed in chapters
7 and 8. In chapters 9, 10 and 11, preservation of textile objects in different environments like
home, stores, museums etc. have been discussed. These chapters also discussed how to
protect textiles from bacterial and fungal deterioration. An elaborative discussion has been
made in Chapters 12, 13, 14, 15 and 16 on the new applications of textile materials through
modification by physico-chemical methods. The modification has been done to obtain
durable, comfort, sustainable and environment friendly finished products using various
organic and inorganic chemicals for much better performance. Use of micro-capsulation
techniques to modify textiles offers extra-properties, e.g., durable fragrances, skin softeners to
textiles. Electronic applications of textiles have been discussed in chapter 17. Textiles, from
viii
Md. Ibrahim H. Mondal
fibers to fabric, with integrated special electronics are more and more used as special
materials in newly developed smart clothing. The chapter 18 specifically focuses on the
technological advances with regard to development of textiles for cardiology purpose, i.e.,
cardiac care. The thermoregulatory process of human body, the thermal comfort properties of
fabrics and the effect of clothing material on the thermoregulatory process of human body in
different weather conditions has been discussed in Chapter 19. In chapter 20, effort has been
made on diversification of jute specifically, development of jute-based materials for thermal
insulating applications. The main aim of chapter 21 is to utilize the ring flanges and travellers
of ring spinning, which is the most effective staple yarn production process, for the yarn
quality in terms of hairiness, twist, breaking strength and irregularity. The last chapter 22
gives an introduction into the techniques of confocal laser spinning microscopy, and depicts
optical differences between several textile fibers, enabling a non-destructive examination of
natural and chemical fibers.
I am very much grateful to all the specialized contributing authors of this book. My
special appreciation is also extended to Ms. Carra Feagaiga of Nova Science Publishers, Inc.,
for her good collaboration, support and numerous discussions throughout the project for this
book.
I wish thank to my colleagues Professor C. M. Mustafa, Professor F. I. Farouqui, and
Professor M. A. Sayeed for their constant support and encouragement. I also thank my
graduate students, Dr. Md. Mashiur Rahman Khan, Md. Raihan Sharif, Md. Saifur Rahman
and Md. Tariqul Islam for their help during editing this book. Lastly I am thankful to
Khadijatul Qubra and Ishrat Rafia for their constant encouragement, understanding and
support.
Any constructive suggestions and comments are therefore welcome for future revisions
and corrections.
Department of Applied Chemistry & Chemical Engineering,

Rajshahi University, Bangladesh
November 2013
Professor Md. Ibrahim H. Mondal
CONTRIBUTOR CONTACT DETAILS

A. B. M. Fakrul Alam
Polymer and Textiles Research Lab, Department of Applied Chemistry and Chemical
Engineering, University of Rajshahi, Bangladesh
Ali Akbar Merati

Advanced Textile Materials and Technology Research Institute (ATMT), Amirkabir
University of Technology, Tehran, Iran
E-mail: merati@aut.ac.ir
Ana Kalijadis
Laboratory of Physics, Vinca Institute of Nuclear Sciences, University of Belgrade, Mike
Petrovica Alasa 12-14, 11000 Belgrade, Serbia
Andrea Ehrmann
Niederrhein University of Applied Sciences, Faculty of Textile and Clothing Technology,
Webschulstr. 31, 41065 Moenchengladbach, Germany
E-mail: andrea-ehrmann@gmx.de
Andrej Demar
Faculty of Natural Sciences and Engineering, University of Ljubljana, Ljubljana,
Slovenia
Andrej Javorek
University of Ljubljana, Faculty of Natural Sciences and Engineering, Snenika 5,1000
Ljubljana, Slovenia

Biljana Pejic
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000
Belgrade, Serbia
Catherine Canning
Department of Fashion, Marketing and Retailing, Glasgow Caledonian University,
Cowcaddens Road, Glasgow G4OBA, Scotland
Cesar Pulgarin
EPFL-SB-ISIC-GPAO, Ecole Polytechnique Fdrale de Lausanne, Station 6, CH-1015,
Lausanne, Switzerland.
Christina Margariti
Textile conservator, Directorate of Conservation of Ancient and Modern Monuments /
Hellenic Ministry of Culture, 81 Peiraios Avenue, 10553 Athens, Greece
E-mail: chmargariti@culture.gr
Dejana Javorek
University of Ljubljana, Faculty of Natural Sciences and Engineering, Snenika 5, 1000
Ljubljana, Slovenia
E-mail: dejana.javorsek@ntf.uni-lj.si
Dharmarajan Anita Rachel
NIFT TEA College of knitwear fashion, Tiruppur 641 606, India
E-mail: advaitcbe@rediffmail.com
Duan . Mijin
Belgrade, Serbia
E-mail: kavur@tmf.bg.ac.rs
Eva Bou-Belda
Departamento de Ingeniera Textil y Papelera, Universitat Politcnica de Valncia, Plaza
Ferrandiz y Carbonell s/n, 03801 Alcoy, Spain
Gordana S. Uumli
Belgrade, Serbia
xi
Hans-Jrgen Buschmann
Deutsches Textilforschungszentrum Nord-West gGmbH, Universitt Duisburg-Essen,
NETZ / DTNW gGmbH, Carl-Benz-Strae 199, D-47057, Duisburg, Germany
Ignacio Montava
Ismail Usta
Department of Textile Engineering, Faculty of Technology, Marmara University,
Goztepe, Istanbul 34722, Turkey
Jaime Gisbert
John Kiwi
EPFL-SB-ISIC-LPI, Ecole Polytechnique Fdrale de Lausanne, Btiment Chimie,
Station 6, CH-1015, Lausanne, Switzerland
Julie McColl
E-mail: j.mccoll2@gcal.ac.uk
Karina Nobbs
London College of Fashion, 272 Holborn, London WCIV 7CY, UK
Katja Kavkler
Restoration Centre, Institute for the Protection of Cultural Heritage of Slovenia,
Ljubljana, Slovenia
E-mail: katja.kavkler@rescen.si
Linda Shearer
xii

Louise McBride
Lucia Capablanca
Maria Bonet
E-mail: maboar@txp.upv.es
Maria Retsa
Marica Stareini
University of Ljubljana, Faculty of Natural Sciences and Engineering, Snenika 5,
1000 Ljubljana, Slovenia
E-mail: marica.staresinic@ntf.uni-lj.si
Marija Vukcevic
Belgrade, Serbia
E-mail: marijab@tmf.bg.ac.rs
Mashiur Rahman Khan

Polymer and Textile Research Lab., Department of Applied Chemistry and Chemical
Engineering, Rajshahi University, Rajshahi- 6205, Bangladesh and
Department of Apparel Manufacturing Engineering, Bangladesh University of Textiles,
Tejgaon, Dhaka-1208, Bangladesh

E-mail: mihmondal@yahoo.com
xiii
Mirjana Kostic
Belgrade, Serbia
Muhammet Uzun
Institute for Materials Research and Innovation, University of Bolton, Deane Road,
Bolton, BL3 5AB, UK, and
Goztepe, Istanbul 34722, Turkey
E-mail: m.uzun@marmara.edu.tr
Narayanan Gokarneshan
Nataa V. Valenti
Belgrade, Serbia
Nina Gunde-Cimerman
Department of Biology, Biotechnical Faculty, University of Ljubljana, Ljubljana,
Slovenia,
and
Centre of Excellence for Integrated Approaches in Chemistry and Biology of Proteins
(CIPKeBiP), Jamova 39, SI-1000, Ljubljana, Slovenia
P. Kandha Vadivu
Department of Fashion Technology, PSG College of Technology, Coimbatore 641004,
India
E-mail: vadivu67@yahoo.co.in
Pablo Daz
Pablo Monllor
xiv

Palaniappan P. Gopalakrishnan
Polona Zalar
Department of Biology, Biotechnical Faculty, University of Ljubljana, Ljubljana,
Slovenia
Primo Weingerl
University of Ljubljana, Faculty of Natural Sciences and Engineering, Snenika 5,1000
Ljubljana, Slovenia
Rosendo Sanjines
EPFL-SB-IPMC-LNNME Ecole Polytechnique Fdrale de Lausanne, Bat PH, Station 3,
CH-1015, Lausanne, Switzerland
Sami Rtimi
EPFL-SB-ISIC-GPAO, Ecole Polytechnique Fdrale de Lausanne, Station 6, CH-1015,
Lausanne, Switzerland.
E-mail: sami.rtimi@epfl.ch
Sanjoy Debnath
National Institute of Research on Jute & Allied Fibre Technology, Indian Council of
Agricultural Research 12, Regent Park, Kolkata 700 040, West Bengal, India
E-mail: sanjoydebnath@yahoo.com; sanjoydebnath@hotmail.com

Department of Chemistry, Durham University, Durham DH1 3LE, UK and
The School of Textiles and Design, Heriot-Watt University, Galashiels TD1 3HF, UK
E-mail: reduwan.shah@gmail.com or s.m.r.billah@durham.ac.uk
Stavroula Moraitou
Vahid Ameri Dehabadi
NETZ / DTNW gGmbH, Carl-Benz-Strae 199, D-47057, Duisburg, Germany
E-mail: vahid.ameri@dtnw.de

Venkatachalam Rajendran
xv
In: Textiles: History, Properties and Performance

Editor: Md. Ibrahim H. Mondal
ISBN: 978-1-63117-262-5
2014 Nova Science Publishers, Inc.
Chapter 1
AN EXPLORATION OF VINTAGE FASHION RETAILING

Julie McColl1,, Catherine Canning1,
Louise McBride1, Karina Nobbs2 and Linda Shearer1
1
Department of Business Management, Glasgow

Caledonian University, Glasgow, Scotland
2
London College of Fashion, London, UK
ABSTRACT
The purpose of this research is to offer a definition of vintage fashion and consider
the characteristics of the vintage fashion consumer and the positioning of the vintage
fashion store from the perspective of fifteen vintage fashion retailers. The research
indicates that vintage fashion retailers position themselves on the basis of their
uniqueness, based upon their experience, knowledge and skills.
Keywords: Vintage, fashion, definition, customer characteristics, positioning
INTRODUCTION
Over the past decade there has been an increasing trend for vintage fashion clothing [1].
Indeed, McMeekin [2] and Wilson and Thorpe [3] have identified that vintage fashion is a
multimillion pound industry. Previously, second-hand clothing was purchased by low income
groups, economically disadvantaged in terms of mainstream fashion. More recently, however,
vintage clothing has become an alternative or an additional choice to high street fashion [4,
5]. Tolkien [6] has proposed that vintage stores and markets have become a desirable source
for acquiring fashion items. This may be the result of increasing societal acceptance of an
aesthetic shift, with vintage fashion being intended as a means of self-expression and
differentiation [4, 7, 8].
Corresponding author: Julie McColl. Department of Business Management, Glasgow Caledonian University,
Cowcaddens Road, Glasgow G4OBA, Scotland. E-mail: j.mccoll2@gcal.ac.uk.
Julie McColl, Catherine Canning, Louise McBride et al.
The acceptance of second hand clothing as an alternative to high street fashion is partly
due to the resurgence of fashion styles from the 1960s, 1970s and the 1980s [9], and the
influence of celebrity culture [4, 10].
Consumers are increasingly aware of unethical practices in the fashion industry [10-12],
and have become less tolerant towards disposable fashion and more suspicious of the
behavior of global brands [8, 13]. The move of vintage from niche sub-culture to mainstream
may be evidenced by the increased vintage offerings by high street, luxury and online
retailers and by the plethora of guides on selecting and assembling vintage clothing outfits [4,
14, 15, 8, 16]. This apparent increase in vintage offerings has broadened the opportunities for
the consumption of vintage clothing.
The term vintage is widely used yet has never been clearly defined [4, 7], in terms of the
parameters, characteristics and the positioning of the vintage fashion retail store. The
literature on the retailer positioning strategies is clearly established [17-26], however, there is
little published research on vintage fashion retailing, and developments in the market and
their implications for vintage fashion retailers has not been addressed. This exploratory study
defines the concept of vintage fashion and the vintage fashion consumer. It evaluates the
positioning strategies of vintage fashion retailers, explores how they differentiate themselves
in the face of increased competition and considers the implications of the more recent vintage
trend for traditional vintage retailers.
LITERATURE REVIEW
Definition of Vintage
It is difficult to define the concept of vintage, partly due to the lack of agreement
regarding the specific time periods of vintage, antique and retro but also due to
differences in opinion about the constituents of such clothing items.
According to De Long [7, p. 23] in clothing, vintage usually involves the recognition of
a special type or model, and knowing and appreciating such specifics as year or period when
produced or worn. Furthermore, they suggest that vintage clothing is concerned with a
specific time period or setting and is distinguished from antique, historical, consignment, reused or second-hand. Palmer and Clark [4, p. 175], define the term more broadly proposing
that it is used to cover a huge spectrum of clothes that are not newly designed. Tungate [8,
p. 221] offers a more focused definition which highlights the evolution and complexity of the
term, identifying that any one particular item may change through time and usage by the
fashion media, so that second hand becomes known as retro then in turn as vintage. The
increase in availability of vintage and the growth of on-line availability of vintage clothing
has added confusion to the array of vintage definitions [4].
From the customer view point, Tungate [8], proposes that vintage is an intangible concept
which is more about attitude than style of dress.
Similarly Palmer [4], characterises vintage fashion as a symbol of individuality and
originality. A primary aim of this research was to define vintage from the perspective of the
vintage fashion retailer.
Characteristics of the Vintage Consumer

Traditionally the buying of second-hand apparel has been subject to negative meanings as
a mark of poverty [27, 28]. Tselon [29] acknowledged that this type of social judgment has
been discounted by the vintage consumer in their quest for non-conformity to fashion trends.
Silverman [30], recognized increased demand for vintage goods amongst the young consumer
and the middle class consumer. Crewe and Forster [31], agree with this explanation, adding
that these groups acquire vintage fashion for excitement and as a means of displaying
themselves in public. Hansen [32], segments the vintage consumers into young professionals
who want good quality apparel at modest prices, or young people keen on retro subculture
looks like Punk, Rave or Mod styles.
In addition, Woodwards [16] study explored younger consumers affection for vintage
clothing and recognized that the incentive for consumption was to achieve a level of
differentiation from their peers. Additionally, a substantial consumer group has been
acknowledged as taste-makers: stylists, designers and image makers who use it as a means of
inspiration and creativity [33-35]. The ownership, or the wearing of vintage items along with
high street clothes, has become anindication of how fashionable the wearer is, with an
increasing prominence on how the items are sourced, and not just on how the person looks
[16]. The increase in mass market vintage has possibly weakened the authentic charm of
vintage among fashion orientated consumers, i.e., those more concerned with how things
look and being individual in style, than having a deferential concern with the historic and
representative links of these sometimes uncommon items which the vintage connoisseur and
retail experts so value [7, 36, 38].
History and Key Drivers

Vintage as mainstream fashion emerged as a trend in the 1980s [38]. Tolkien [6] has
identified vintage as stemming from the New York social fashion elite, influenced by
sentimental pictures of 1940s couture. In addition, celebrities fueled demand and popularity
of the style by wearing luxury vintage gowns to major award ceremonies and fashion shows.
Others credit Barbra Streisand as the first vintage-couture advocate [39]. In turn, this
encouraged designers such as Marc Jacobs, in the 1990s to create the nouveau vintage look
by reinventing older styles [40].
This trend also occurred in the UK and Europe with designers and celebrities such as
Stella McCartney and Kate Moss inspiring mainstream adoption of vintage fashion [41, 42].
The appreciation of vintage aesthetics which grew in the 1990s helped to decrease the stigma
of wearing second hand clothing, and permitted them to develop in to acceptable sources of
fashion. This resulted in a differentiation both in-store and in the consumers mind, between
vintage and clothing purchased from charity stores [1, 4, 6, 43]. The media has endorsed
vintage fashion as a means of conveying connoisseurship and uniqueness, more recently
extended by the juxtaposition of vintage and contemporary in one ensemble [4, 8].
Jackson and Shaw [44] highlight an important driver in the vintage movement is media
attention on the unethical practices which exist in the fashion industry, resulting in a
consumer backlash against disposable fashion and the beginnings of a slow fashion
movement, who emphasize the importance of quality as opposed to quantity [45].
An additional driver acknowledged by Tungate [8] is customer defiance of expensive,

branded products and trends promoted through marketing communications. In recent years,
the economic downturn has witnessed upcycled fashion items becoming a mainstream
phenomenon; this is the re-working of old clothes into more modern-day, higher value pieces
[46, 47].
The influential retail guru, author and broadcaster Mary Portas, successfully developed
a media campaign in 2009 called Living and Giving which improved the image of charity
shops and further increased demand in vintage clothing [48]. More recently, in a study of
street style Woodward [16], indicated that the trend for vintage has reached maturity and
might now be perceived as commonplace or omnipresent.
In the case of both the retailer and the consumer alike, the uptake of the vintage trend in
the noughties has caused a reduction in the availability of interesting and unusual items,
affecting the market in two ways. Firstly key pieces have increased in value and vintage
fashion has grown to be an investment prospectrivaling the collection of artwork [49-50].
Agins [51] has identified that this is as a result of the widely broadcast view that the couture
industry is declining, with prices accelerating and skilled workmanship growing scarcer.
Secondly it means that traditional vintage consumers are being forced to search extensively
and even globally to source the desired article [52].
In total there are three key drivers of vintage fashion trends. Firstly, the trickle down
feature from celebrities and designers, secondly, the ethical aspect of the fashion industry and
finally the need for individual uniqueness and authenticity. Palmer [4, p. 197) proposes that
vintage has now shifted from subculture to mass culture because of the disappointing fact
that, regardless of price, fashion today is rarely exclusive.
Market Structure and Vintage Retail Formats

Mhango and Niehm [53] suggest that vintage clothing retailers are focused within the
small business sector, and are characteristically independently owned. These include secondhand stores for example thrift or charity shops, estate sales, garage sales, flea markets and
auctions, usually the province of commercially-mediated lateral recycling [31, 54].
Nevertheless, vintage clothing retailers have now developed to comprise multifaceted retail
support functions such as sourcing, supply chain management and visual merchandising [55].
Moreover many charity stores in Great Britain have re-invented themselves as vintage to
increase their apparent brand value and to distinguish themselves from others in the sector
[12]. Mainstream high street retailers such as Top Shop and Urban Outfitters have
successfully sold vintage clothing ranges for a number of years [15]. Tolkien [6] ascertains
that the internet as a significant channel in the distribution of vintage clothing, however this
phenomenon requires an alternative research approach and can be addressed in future studies.
Retail Positioning
Porter's [56, 57] theory of positioning theory has had an lasting impact on the marketing
literature [58-65], and practice [66, 67], as one of the most significant concepts and
fundamental principles of marketing [63, 64], central to strategic marketing success [68].
The positioning strategy implemented by any company is grounded in the needs of the
customer, the behaviour of the competition, and is ultimately how companies can achieve
competitive advantage [69-73].
It is commonly acknowledged that although there are a number of positioning typologies
developed within the marketing planning framework [59, 73-74], there is a lack of empirical
research testing these typologies [61, 64]. Yip [75] has proposed that a number of the
positioning approaches suggested within the literature, are incomplete and may be confusing.
Table 1 offers a summary of positioning typologies. The concepts of these positioning
typologies are considered by the authors as the central means by which the organisation can
attain differentiation, increase competitive advantage and therefore position themselves
within the market [64].
Table 1. Summary of positioning typologies
Author
Aaker and Shansby [59];

Berry [78]; Buskirk [76];
Brown and Sims [77];
Crawford [79]; Hooley, et
al. [63]; Wind [73]
Ries and Trout [66]
Easingwood and Mahajan

[80]
Arnott [61, 58]
Kalafatis, et al. [72]
Positioning constructs i.e., concepts

Features and Benefits
Features, price, advertising, distribution, problem solved, usage
situation, users, competitors, value, time efficiency, high contact,
sensory, benefits, product class dissociation, attributes, price,
quality, use or application, product/service user, product/service
class, competition, direct/indirect, surrogates: nonpareil,
parentage (brand, company, person), manufacture, target, rank,
endorsements, experience, predecessor, innovation-imitation,
superior service-limited service, differentiated benefitsundifferentiated features, tailored offering-standard offering.
Strategic positioning
Market leader, follower, reposition the competition, use the name,
line extension (use of house name).
Reputation/capabilities of organisation: expertise, reliability,
innovativeness, performance, augmentation of product offering:
product augmentation, extra service, people advantage, more
attractive package offering, a superior product through
technology, accessibility, extra attention given to individual
requirements through customisation, satisfaction of more user
needs within the sector through offering a complete product line.
Empathy, solvency, promotions, administrative time, helpfulness,
reliability, attentiveness, staff competence, flexible products,
access to people, reputation, customisation, incentives, social
awareness, security, technology.
Easy to do business, personal contact, product performance,
range of offerings, presence, safety, leadership, distinct identity,
status, country identity, differentiation, attractiveness.
Source: Adapted from Blankson and Kalafatis [64].
Blankson and Kalafatis [64], however, consider existing studies to be descriptive,

difficult to put into practice and based on limited empirical testing, principally in terms of
their representation within consumer marketplaces, their propensity being to represent the
views of management. They propose that the literature lacks an empirically based consumer/
customer derived typology, which can measure the effectiveness of positioning strategies
employed.
Having carried out extensive empirical research, they have proposed a positioning
typology based on customer opinions, which they advise is suitable for both product and
service markets and recommend that managers develop their positioning based on consumer
perceptions of prestige, service, reliability, attractiveness, country of origin and brand name.
These, they propose, are the key differentiating features within the marketplace and can be
successfully deployed in marketing communication.
In the retailing literature, Cook and Walters [19] suggest that a companys market
position is its reaction to its understanding of the needs, desires and behavioural
characteristics of its target customer profile. Retail positioning is defined by Wortzel [81, p.
47] who proposes:
For a retailer, strategic positioning involves providing unique value. Strategic
positioning involves selecting and then bringing to bear an integrated set of tools and
communication techniques that identify and explain the store to the customer.
Walters [18] offers a model of positioning developed as the consequence of wide-ranging

empirical research within the retail sector. The fundamentals of the positioning strategy in
retailing, he suggests, are a visible response to the needs and wants of the identified target
market. The key decision areas for retailers in evolving their marketing strategy are those of
trading format, merchandise strategy, customer service and customer communications
strategy. These decision areas define the retailer positioning strategy, and position them in
terms of what the customer anticipates and customer satisfaction, creating a point of
distinction which separates retailers from their competitors and represents the retail brand [82,
26].
While established as a theoretical model, the strategic elements of Walterss [18] value
added positioning statement are still recognised in the retail marketing literature as the means
by which retailers should position themselves in the market [17-26].
Therefore it forms the basis of a number of empirical studies on retailer brand positioning
[20, 26, 81, 83-88, 89, 90], which stress the possible benefits of developing a clear and
distinctive positioning statement using the elements of the retailing mix. Consequently it was
thought to be the most suitable framework for application within this study. However,
although there are a number of positioning typologies developed in the marketing and
retailing planning context [59, 73-74], there is still a lack of empirical research testing these
typologies [61, 64].
The literature suggests that small retailers, like those addressed within this study, are
different from larger companies in terms of management systems and resources, and that
planning, control and strategy are a result of the personal objectives and personality of the
owner manager [91-93]. However, within the vintage retail sector, this proposition has not
been tested. This research serves to help address this issue.
METHODOLOGY
Small companies are dominant within the vintage retail sector and generally evolve from
the entrepreneurs who are enthusiastic about vintage themselves [12, 14]. The decision to
focus on small scale companies is also supported by evidence provided in the vintage retailing
literature, as existing research focuses on small companies [53, 54]. To be selected for this
study the vintage retailers had to meet some or all of the specifications within the literature.
They had to have high levels of experience in both buying and merchandising and so had to
have been in business for at least two years. The participants of the study therefore had
between two and twenty three years experience of running a vintage retailing company. To
ensure consistency of trading practices, participants were required to trade as bricks and
mortar businesses.
Therefore, participants would provide credible information as to the concept, positioning
and differentiation of small vintage fashion retailers. Thirty nine vintage fashion retailers
from Scottish towns and cities were identified from The Yellow Pages, trade journals and
company websites.
Of these, twenty seven were found to have been in business for over two years, however
one was found to sell only on an online basis. A letter was sent to these twenty six vintage
fashion retailers from the population sample of thirty nine in September of 2009. A follow up
phone call was made a week later. Sixteen retailers responded that they were willing to
participate in the study, however, one potential participant remained unavailable. Therefore
fifteen interviews were carried out with owner/managers of vintage retail stores. All
participants had direct experience in the areas of buying and merchandising within the vintage
retail sector. The owner managers were between twenty three and fifty eight years old.
The interviews took place within the retail premises and were approximately two hours
long. Confidentiality was assured. The interviews were taped, transcribed and retained as
Microsoft Word documents. Analysis was carried out by one member of the research team to
ensure consistency. First of all the transcripts were analysed to identify common
characteristics and emerging themes and issues.
At this stage, a cluster approach was adopted and a framework for theoretical
development began to emerge [94]. These clusters were selected on the basis of significance,
mutual exclusivity and ability to stand by themselves [95]. Yin [95] suggests that data
analysis consists of examining, categorising, tabulating, and testing the content to address the
initial propositions of the research. Interviews were analysed one at a time individually and
then on a cross interview analysis. Patton [96] suggests that the analysis involves the
application of the existing theoretical framework, developed from the literature, and the
subsequent analysis of the interviews to allow for an examination of emerging patterns.
According to the theories and concepts extracted from the literature, the interviewees
were asked open-ended questions about their definition of vintage, the vintage customer,
merchandising and the positioning of the vintage store.
The results and discussion section is therefore divided into three sections. Firstly, the
research seeks to define vintage fashion and investigate the vintage fashion movement,
secondly, the research explores the characteristics of the vintage fashion consumer from the
perspective of the store owner/managers, and finally it explores positioning in relation to the
retail vintage fashion sector.
RESULTS
Defining Vintage Fashion
There was no unified or clear definition of vintage with each vintage retailer offering
differing opinions and suggestions. However, three dimensions emerged. Firstly the age of
the apparel, secondly the style, (a piece of clothing which sums up the era), and finally the
quality of the vintage clothing. The majority stated that fashion which predates the 1990s
would be considered to be vintage. To a number of interviewees vintage could be
categorised as anything up until the 1950s, with anything that pre dates 1980 being classified
as retro, and anything before the 1920s being considered as antique.
Probably not the 1990s but anything before that, especially the 1980s at the
moment. Only the fashion forward are looking for 1990s articles
Some items of clothing were seen to represent the zeitgeist of bygone eras and these were
particularly important to vintage consumers. Examples included a 1950s prom dress or
Diors New Look full skirt. In 1960, Twiggy-style 1960s mini dress, in the 1970s
platform shoes and bell bottom trousers and 1980s pedal pusher short trousers and frilled
shirts from the New Romantic movement.
All participants agreed that, in order to satisfy customers, articles have to be of good
quality. Almost all the participants agreed that vintage fashion was second hand, however, a
few retailers sold old clothing manufactured in the past which was unworn. One retailer was
selling unworn Brutus and Lee denim jeans from the 1970s which had been discovered in
a warehouse. The most desirable items were those which had been bought in a past era but
had rarely or never been worn, for example items which have been kept for special occasions
and were in pristine condition. Examples included evening dresses, a wedding dress or a
formal suit. One participant summed up the general opinion stating:
Vintage fashion isnt something that is just old. If a 50s dress is an ugly hideous
rag- that is what it is, an ugly hideous rag. Vintage is the very, very best of its type.
Characteristics of the Vintage Consumer

Retailers were invited to define the vintage consumer from their own viewpoint.
Participants stated that many of their customers were fashion conscious and young
consumers, with an average age of between eighteen and twenty (many of them students),
however all participants stated that the age range of their consumers was very diverse. It was
found that he 18-25 year old consumers are most likely to be influenced by fashion trends. It
was recognised that this particular segment had adopted the ongoing vintage trend which had
positively increased demand for vintage clothing overall. These younger consumers were seen
to be setting the trend for current trickle up fashion looks such the nerd college look, and
geek chic (spectacles, drainpipe trousers or retro skirts with blouses and tank tops). The
interviewees proposed that these trends had also extended to celebrities and were linked to
sub-culture music trends.
Young consumers were seen to purchase for originality and enjoyment, to display aspects
of their own individual style, and in many cases, price. Participants stressed their ability to
offer uniqueness which people see as a method of individual self expression. There was a
certain status provided by the originality of rare clothing. One proposed:
You always feel quite smug when you say Oh its Vintage theres no way the person
can go out and copy you
The next most important group of consumers identified were older customers (aged 3070) who tended to purchase on price and nostalgia rather than trend. This segment were likely
to invest more time, money and effort in their purchases and were generally more motivated
about the authenticity of the product. For example, a number of participants discussed the
importance to the customer of the story behind the garment; what one termed as vintage
magic. Consumers were buying more than a skirt or shirt, they were buying a piece of
history, and often enjoyed hearing a story behind an item or a treasure. Additionally,
participants highlighted an increase in the number of ethical consumers, conscious of
environmental issues and recycling. This customer group was diverse in age and nature.
Finally, a small proportion of customers were collectors and business customers, for example
television, film and theatre wardrobe designers and stylists for fashion magazines.
Vintage Retailer Positioning

Merchandising Strategy
The main concern by the retailers in sourcing garments was the authenticity of vintage
fashion. Most considered vintage fashion to be authentic by the perceived age and its level of
originality. They particularly sought garments which had been handmade and were therefore
exclusive. Exclusivity is of particular importance as it allows premium pricing and provides
differentiation for the store. Older designer clothing from fashion brands such as Chanel and
Biba are becoming rare and difficult to source. Some of these older garments particularly with
brand names are highly sought after. Products that are mass produced (even older clothing
from the 1980s for example) are less likely to be perceived as authentic and are therefore less
desirable. One retailer stated:
Authentic vintage is an original garment and not a vintage label from a high street
store. They are obviously complete one offs and that in my mind is worth a lot more than
some dress thats been churned out by Marks and Spencer. Back in the 40s, 50s and
60s people were making their own clothes, which are highly desirable now.
Participants explained that they were able to verify the authenticity of garments through
their personal expertise, gained through experience of sourcing and buying. Many retailers
considered themselves to have expert technical knowledge, and could determine garment
authenticity by the stitching, (e.g., of hand sewn products rather than machine produced) the
fabric quality, and the smell of the garments. Because of the increasing difficulty in sourcing
good quality vintage items some retailers had decided to sell more modern items that had
been manufactured more recently but were made to an appropriate vintage design.
10
They understood that the authenticity of these garments was debatable; however they
agreed that consumers wanted to purchase this type of pseudo-vintage product due to the
desire to follow the vintage trend.
Retailers sourced second hand merchandise from a wide variety of second hand stores
and markets both at home and abroad, charity and second hand clothing stores, car boot sales,
recycling plants and many garments are donated by customers or other shoppers who wish to
recycle. Vintage retailers will also recycle clothing back to recycling plants or rag yards if
they are unable to sell the garments.
Merchandise was both bought in bulk by the sack or large load, or handpicked.
Retailers occasionally sourced more exclusive merchandise from private individuals who
perhaps were collectors themselves and chose to trade their personal vintage garments to be
enjoyed by other enthusiasts or vintage collectors.
Some store representatives discussed of more recent emerging markets in Eastern Europe
which offer opportunities for trade and sourcing of vintage clothing, offering alternatives to
what is still available in the UK market. Participants also highlighted France and the US as
fruitful sources. One stated that the US was particularly good for 1920s dresses. One retailer
observed:
I am sure there is a totally untapped market in Russia. I would like to visit there and
raid some wardrobes. Russia is so large and many people dont know the value of vintage
garments yet.
Retailers selected merchandise according to gut feel and intuition and was therefore a
very personal issue. Participants sourced according to their personal expertise of the market,
their customers and their personal knowledge of fashion history. The research found therefore
that this personal expertise was highlighted by all participants as their main point of
differentiation and competitive advantage. In many cases they proposed that a synergy existed
between themselves, their knowledge of style and their customers. In most cases retailers
explained that they understood their regular customers needs and wants and were able to buy
accordingly.
The most popular brands were found to be Biba, Bus Stop, Mary Quant, Burberry, Dior
and Chanel. Unlike high street fast fashion models, stock was not turned around in weeks
however, there is a seasonal approach to vintage merchandise. During the spring and summer,
female consumers were looking for summer dresses, 1950s style dirndl skirts (full skirt
gathered at the waist), miniskirts and more recently in line with changing fashion trends, maxi
dresses. During the winter, the demand was for heavier outerwear and coats, hats, gloves and
scarves. Retailers explained that as a result of catwalk trends, there is still demand for real fur
coats.
Participants explained that consumers believed that the wearing of old, second hand fur
coats was acceptable to many of their customers because these items were manufactured prior
to increased ethical awareness of animal rights issues.
Older fur therefore was perceived as glamorous and stylish despite the recent concerns
surrounding new fur products. Occasion dresses from any vintage era were always in
demand and at Christmas, customers were looking for appropriate glamorous party wear. A
table of the most popular items is outlined in Table 2 below. Selection of these items was
based on more than half of the sample highlighting these product categories:
11
Table 2. Most popular vintage items for men and women

Ladies vintage items
1950s prom dresses
1960s shift dresses,
1970s maxi dresses
Evening wear glamorous gowns, sequined and
embroidered dresses
Real and fake fur coats and jackets
Cashmere jumpers and cardigans
Jewellery and watches
Handbags, scarves and belts
High heels and flat boots for ladies from the
1960s, 1970s and 1980s
Mens vintage items

Formal wear
Evening suits
Suits from the 1950s and 1960s
Traditional dress (Kilts)
Retro Adidas tracksuit tops from the 1970s
Levis jeans and denim jackets
Cowboy boots
Military dress
Leather briefcases
Ties
One of the key challenges that participants highlighted was the procurement of
appropriate, second hand stock which is in good condition. Due to the popularity of the trend,
there is an increasing scarcity of stock as older garments become more worn and therefore
less appealing due to reduced quality. This was seen to be an enduring problem which has
heightened competition in the vintage sector.
There was a level of preparation required for all second hand garments. All the vintage
retailers washed or dry cleaned items before sale. Some items required repairs such as sewing
on buttons or zips, or making alterations such as altering hem lines. However, normally
alterations were minimal so that the authenticity of the garments was not compromised. In
some cases however, participants created new garments by combining two pieces together. If
a part of a garment was too worn out to be sold, sections of garments and fabrics could be
rescued. One participant proposed:
We buy dresses that are full length and we cut them to mini dresses. We actually
have a tailor next door who does all that for us. We have bought blazers and put
accessories on them to make them look more interesting
Customer Service
Personal service was found to be essential to the success of most of the retailers. Most
employees were owner/managers, assisted by partners, friends or family members who had a
vested interest in the success of the store. All retailers explained that they know a high
proportion of their customers very well, considering individual customer tastes, needs and
style when sourcing garments. Some participants would store items for particular customers.
In addition, customers frequently request the sourcing of specific items. Therefore, the basis
of much of the customer service for vintage retailers was the building of relationships.
Additionally, all had a loyal and regular customer base. Many proposed that the development
of these relationships allowed retailers to offer a personalised service. A number of retailers
offered an alteration service for their customers. Therefore differentiation was possible for
these retailers due to the relationships and customer service they developed with their
consumers.
12
Most proposed that they themselves personally were the differentiation through their
passion for the vintage concept, their choice of merchandise, their expert knowledge and
expertise. One participant stated:
Its me. The company is built around my personality, personal style and taste. My
customers like that and they trust my judgement.
Communications
Store image elements were the most important methods of communication for vintage
stores. That is, the window display and the store interior. The window display was seen as
vitally important to generate interest and curiosity from passersby and the unique store
interior and merchandise communicated a distinctive brand image. In terms of traditional
communications, most of the retailers did not use print advertising often due to expense and
due to limited success using this method in the past. A few advertised in local directories and
the Yellow Pages. Many participants explained that local press editorial had proved to be very
effective in increasing awareness and enhancing business profile. The main type of
communication reported that was thought to be essential by all interviewees is word of mouth
(WoM) marketing due to the high levels of personal service outlined above. Positive customer
experiences were thought to be vitally important for promotion and generating custom.
The group was divided in relation to e-marketing. Only half of the participants operated a
website. However, several participants interacted with social media platforms (at varying
levels) in order to connect with the vintage fashion community, to increase brand awareness
and generate enquires and consumer awareness.
Store Trading Format
All the participants in the study were small-scale retailers who were independently
owned. Typically, most stores were single units which were 700-1100sq.ft. in size. Many
were located in secondary geographical locations with a neighbourhood feel. All of the
retailers included in this research described themselves as traditional bricks and mortar
boutique-style shops. Of those that operated websites, most were non transactional, and two
of the stores had their own on-line stores. The majority of sales were traditional, meaning in
store retailer to consumer business. Interestingly, a few retailers had evolved their stores from
market stalls and indicated that a proportion of vintage trade still took place on that basis.
All proprietors explained that the store image was essential to vintage retailing. Many
participants stated that the window styling, store layout and product display was important to
create the atmosphere of a bygone era and many described the stores as quirky and
individual. Each store represented the personality of the owner, with one retailer explaining
that he wanted to create the right kind of vibe with music from a previous era and choosing
items carefully to represent his sense of taste and style. Many displayed interesting pieces that
were collectors items or were appropriate to present the vintage image. Old gramophones,
old bicycles, wallpaper from the 1970s and 1980s, old pictures and pieces of art and various
other pieces of memorabilia were displayed according to the proprietors preference. The
product display varied from store to store. Most displayed clothing in racks similar to new
modern high street retailing and many had containers such as baskets and boxes and shelves
of mixed accessories and jewellery that consumers enjoyed sifting through and hunting for
a treasure or a bargain.
13
CONCLUSION
The vintage movement was mainly something of a fad that was followed by a small
group of innovators such as art school and fashion students. However more recently it would
appear to be an enduring trend, increasing in popularity, growing into a mainstream fashion
phenomenon. This is evidenced by its diverse customer base, adopted by young, fashion
conscious consumers and maintaining a group of diverse traditional vintage customers of a
variety of age groups.
The movement has also gained interest due to more recent concerns over ethical issues
such as recycling and sustainability. This study discovered two main groups of consumers;
young and fashion conscious, interested in current trends and mix and matching from various
styles, high street and vintage and also an older customer with a greater focus on price and
interest in nostalgia. An emerging issue for many customers were their ethical concerns. This
research explores the retailer perspective of the vintage fashion trend. Future research is
necessary, to investigate consumer motivation buying vintage fashion of these different
groups.
This research set out to define the concept of vintage fashion within its current context.
Therefore, vintage fashion can be defined as:
Garments and accessories which are more than twenty years old, which represent a
particular fashion era, and which are valued for their uniqueness and authenticity.
Positioning strategies of vintage fashion retailers was also explored. Table 3 highlights
the key areas of positioning within vintage retailing.
The research therefore revealed that vintage retailers position themselves through their
distinctive retailing mix. Vintage proprietors explained they could source items that were
totally individual and unique. As one store owner stated, You are buying a piece of history
a treasure. This was the main difference between other independent stores.
Table 3. Vintage Retailer Positioning Elements
Customer
communication
Trading format
Individual retail brand

image, quirky and
constantly evolving,
distinctive store
environment, window
and interior displays,
retro props, localised
PR, word of mouth,
growing importance of
social media
Small scale,
independent, single
site, secondary
geographical
location, multichannel
participation,
boutique style,
unique store image
which represents the
personality of the
owner
Source: adapted from Walters [22].
Merchandise
strategy
Sourcing: personal,
diverse, intuitive,
expert and historical
knowledge, global
Product: authentic,
original, exclusive,
rare brands, preowned, handpicked,
limited supply of
merchandise
Customer service
Personal, individual,
relationship based,
long term, synergy
between business
owner and customer,
availability of
adjustments and
alterations,
employee passion
for the vintage
concept
14
Sourcing therefore was an extensive challenging and time consuming process which
reflected the personality and expertise of the proprietors. The quirkiness of the store interior
and environment was also of importance and word of mouth communication was also found
to be very important in terms of promotions. Vintage retailers are often small scale, ownermanaged businesses, and are because of this, closer to their customers and able to form
individual relationships through merchandise supply and customer service. The influence of
the owner/manager, their style and personality is consequently reflected and embedded in the
positioning of the company, offering differentiation of their individual stores in the market.
There remains a gap in the literature in terms of analysis of the vintage customer. The
positioning model above could, in future studies, be used to establish consumer responses to
vintage retailer strategy.
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SAGE Publications.

ISBN: 978-1-63117-262-5
Chapter 2
DEVELOPING SUSTAINABLE DESIGN ON

DENIM READY-MADE APPARELS BY
STONE AND ENZYMATIC WASHING
Md. Ibrahim H. Mondal1, and Md. Mashiur Rahman Khan1,2,
1
Polymer and Textile Research Lab., Department of Applied Chemistry

and Chemical Engineering, Rajshahi University, Rajshahi, Bangladesh
2
Department of Apparel Manufacturing Engineering, Bangladesh
University of Textiles, Tejgaon, Dhaka, Bangladesh
ABSTRACT
Denim is the most preferable apparel of todays youth. Washing is one of the
fundamental chemical processing steps prior to finishing fresh-assembled denim readymade apparels and has the largest effect on outlook appearance and other physicomechanical properties of finished denim apparel. The fresh denim trousers, twill 3/1
weave and composition 100% cotton, have been processed by enzyme washing and
pumice stone-enzyme washing technique using various parameters namely concentrations
of pumice stone (10 to 70%) (owg), concentration of cellulase enzyme (0.5 to 3.5%)
(owg), washing temperatures (40 to 65oC) and treatment times (20 to 60 min) with fixed
pH (4.8) in fiber to liquor ratio of 1:10 in an industrial sample washing machine. In order
to evaluate the influence of these washing parameters on the properties of denim apparel
like tensile strength, fabric weight, color change, stiffness and water absorption has been
determined. Fabric surface was also examined by scanning electron microscope (SEM)
and fluorescence microscope (FM). The washing parameters has a great influences on the
properties of denim. Stone washing increased the softness (by reducing stiffness) and
flexibility (in terms of bending length) of denim apparels and gave a used look
appearance on denim apparel distinctly. The properties of denim apparels are varied
depending on the amount of pumice stone used.
Md. Ibrahim H. Mondal: Polymer and Textile Research Lab., Department of Applied Chemistry and Chemical
Engineering, Rajshahi University, Rajshahi- 6205, Bangladesh. E-mail: mihmondal@yahoo.com.
Md. Mashiur Rahman Khan: Polymer and Textile Research Lab., Department of Applied Chemistry and Chemical
Engineering, Rajshahi University, Rajshahi- 6205, Bangladesh. Department of Apparel Manufacturing
Engineering, Bangladesh University of Textiles, Tejgaon, Dhaka-1208, Bangladesh.
20
Md. Ibrahim H. Mondal and Mashiur Rahman Khan

The results indicate that for producing sustainable denim apparel the optimized
washing condition for the best value is 30% pumice stone with 2.0% cellulase enzyme at
55 oC for 40 min.
Keywords: Denim apparel, cotton, cellulase enzyme, pumice stone, tensile strength, washing,
color fading
1. INTRODUCTION
The increasing demand of denim apparel in the world market has imposed extreme
pressures on the textile industries. The use of chemicals in the textile industry has been
known and applied commercially for many years. In particular, textile washing industries are
using various chemicals in processing denim ready-made apparels for producing specific
washing effects and designs. The research attempts to examine different washing techniques
for the modification of denim apparels and searches for the dynamic best method for
producing sustainable denim apparel designs. Understandably, this concern motivates many
efforts to modify denim apparels with new designs in order to face the challenges of fastchanging fashion trends. Although denim apparel has been popular since the early1980s, the
term sustainable denim is a relatively new concept to the apparel industry. Sustainable
denim has become to be a dominating factor in the apparel industry. Now-a-days, there is
awareness on environmental concern among the customers and buyers. In this respect, present
work has been undertaken to fulfill the current demand of customers using environment
friendly chemicals for denim washing.
Therefore, the study investigated evaluative specifications used by designers and buyers
for producing denim apparel with sustainability. Bangladesh is a textile industry based
developing country. At present, Bangladesh earns about 80% foreign currency from the
textile and RMG sectors. Bangladesh started RMG export in 1977-78 and continues export
under quota to the US till 2004. In January 2005, the RMG sector of Bangladesh faced new
challenges due to the withdrawn of quota by US government. From that time, the US market
is open for all and highly competitive. Currently there are about 5600 ready-made garment
industries in Bangladesh and from these RMG industries Bangladesh earns about 21.51
billion US dollar [1]. To sustain the RMG sector of Bangladesh in the competitive world
market, it is essential to produce new design and fashion apparel with sustainability. Denim
apparel is produced from very strong and stiff denim fabric and its popularity is increasing
day by day in the world market. Without washing/finishing treatment denim apparel is
uncomfortable to wear, hence it can be modified by washing and introduces new look and
fashion. There have been many attempts to use chemicals in various washing techniques like
bleach wash, enzyme wash, stone wash, etc. The washing of denim apparel by enzymatic
process, specially cellulases that would degrade the color of denim and improve the handle
and drape, dimensional stability and surface characteristics reported by Kawamura and
Wakida [2], Tyndall [3], Kumar et al. [4], Duran and Marcela [5], Gubitz and Cavaco-Paulo
[6] and Cortez et al. [7]. Cellulases are introduced to replace aggressive chlorine bleach in
denim washing [8] but the enzymatic attack of cellulase is not only limited to the surfaces, act
synergistically in hydrolysing cellulose to glucose [9], causing unacceptable weight and
strength loss to the fibers.
21
It is believed that if the denim apparels are chemically washed with enzyme and stoneenzyme separately in order to decrease their minimum strength and weight for producing
specific washing effects and designs, their chemical attack would be restricted only to the
surface of the fabric, which is the main purpose of this research work. Thus, the work
proposes the use of bio-degradable cellulase enzyme and stone-enzyme in place of harmful
chemicals and attempts to optimize the process parameters, such as, concentrations of
chemicals, concentrations of pumice stone, temperatures, and times with high wear
performance like durability and longevity (with minimum strength losses) of apparel in
producing sustainable denim apparel.
1.1. Denim Apparel Washing

The washing of apparel generally means cleaning of dirty apparels with soap or
detergent. But industrial apparel washing is a technology which is used to modify the
appearance, outlook, comfort ability and fashion of the apparels. With the changes of time,
human choices, demands, and apparels design and fashion changing very quickly. To meet
the present demand of consumers, apparel manufacturers are adapting new technology and
processes in washing. The washing technology needs various types of chemicals for washing
apparels. Denim washing is the aesthetic finishing process given to the denim apparel to
enhance the fabric properties and provides fashion effects. Various chemicals are used in
various washing processes, e.g., bleaches are used in bleach washing process, enzymes are
used in enzyme washing process, pumice stones are used in stone washing process etc.
1.2. Denim
Denim is a yarn-dyed cotton twill fabric, basically warp yarns are dyed with indigo and
weft yarns are white [10]. Indigo is insoluble dye and diffused on yarn surface [11]. Indigo
dye is popular for denim because it washes down easily and clear bright blue shades are
achieved by washing [12]. Today denim has various washing aspects for designs, it can be
stone washed, bleach washed or enzyme washed. The word denim is derived from the French
word Nimes, the Nimes was the French city where the denim was first produced. The fabric
which was produced in Nimes was called Serge in French. Resultant it was called Serge De
Nimes means fabric of Nimes, later the name was shortened to DENIM.
1.3. Sustainable Design

Sustainability is a vital topic within the design world. Sustainable practices are now
growing in the apparel industry. In the past, apparel designers and merchandisers have
emphasized a products functional, aesthetic, and economic aspects during the design process
[13]. With increased consumer interest in the environmental implications of apparel
production, many companies have introduced sustainable practices [14, 15]. Consumers are
also interested to get fashion products [16] which are a challenge to sustainable practices in
the apparel industry.
22
Figure 1.1. Flow chart of denim manufacturing.
Designers seek to practice environmental responsibility and discover solutions for current
problems [17]. Literature suggests that sustainable practices in the textile and apparel
industries include the use of renewable and non-harmful materials [18-20], applying lowimpact processes [21, 22], the re-cycling of waste materials [23], the eco-friendly, green and
environmental friendly process [24], and fashion product which is one of the biggest barriers
encountered in the apparel industry [25]. Along with increasing global awareness of
environmental problems, consumers awareness of sustainability has risen and consumers are
seeking environmentally friendly clothing, and producers are exploring ways to meet these
demands while processing clothing. Sustainable design includes production processes also. In
producing sustainable design, the designers determine the properties of the products with
sustainability [26]. Sustainability requires a delicate balance of choices. Therefore,
sustainable denim designs represent an apparel product which is fashion oriented,
performance based; and environmental friendly. Therefore, sustainable denim apparel refers
to eco-friendly, fashionable, aesthetic, durable and high wear performance apparel, based on
customers choice.
Sustainable practices are growing in the apparel washing industry. In denim washing
industry, bleaches are commonly used with other chemicals. Most of the cases, textile and
apparel manufacturers are using traditional hydrogen peroxides and hypochlorite bleaches in
processing textile and denim apparels, which has more or less negative-impact in the
environment. Enzymatic washing and stone-enzyme washing processes are now popular and
increasing its use in textile and apparel washing industry, because it is eco-friendly, support
the green chemistry and safe for the environment.
23
In the textile and apparel industries, the concepts of sustainable washing for denim
apparel explore to the enzymatic washing and stone-enzyme washing processes which can be
used to develop sustainable denim designs.
1.4. Literature Review

In the last few years, the popularity of denim apparel washing has been increased and
many researchers have investigated the effect of the washing for denim apparels. Some
important works of various washes on denim apparels are presented below.
Enzymatic Treatment in Denim Apparel Washing

The study of enzymatic washing on denim apparel is important for physical, aesthetical
and environmental point of view. Denim apparel manufactures have washed their apparels for
many years with chemicals to achieve a soft-hand as well as desirable washing effects.
Indigo-dyed denim apparel is the most popular for youth [27]. Therefore, the properties of
denim apparels have been widely studied due to its fundamental importance and its many
applications in current fashion trends. The existing literature in this domain has focused
considerable attention with enzymatic washing for denim apparels. The use of
environmentally friendly, nontoxic, fully biodegradable enzymes have been using in the
modern textile wet process industries for decades. Enzymes are produced by living organism
and one kind of protein that is obtained from fermentations method from naturally existing
bacteria and fungi and attack to a specific molecular group. Structurally, enzyme is a
biological polymer. Cellulases are enzymes and commonly used in textile industry.
According to their amino acid sequences, it consists of either a catalytic domain (CD), or a
cellulose-binding domain (CBD) or both domains [28]. Most of the cellulases used in the
denim washing are fungal (with a CBD of family I, cellulose-binding domain) [29]. CavacoPaulo et al. [30] reported that the cellulases used in the denim washing industry have CBDs
from family I (30-36 amino acids, i.e., fungal cellulases from Trichoderma ressei and
Humicola insolens), whereas CBDs of cellumonas fimi bacteria belong to family II (103-146
amino acids). Commercially, there are mainly two kinds of cellulase being used for denim
washing, namely acid cellulose and neutral cellulase. Acid cellulases are more aggressive on
cotton [31]. Cellulase hydrolyses the cellulose, yielding long chain cellulose polymer to a
short-chain polysaccharides and glucose. The enzymatic action also loosens the indigo dye,
which is more easily removed by the mechanical abrasion of rotating cylinder washing
machine. Cellulases are inducible enzymes synthesized only in the presence of cellulosic
materials or other appropriate inducers [32-36]. Today approximately 80% denim apparels are
treated with cellulase enzymes [37]. Cavaco-Paulo [38] reported that desizing with amylases
was the first applications of enzymes in textile industry [38]. Enzymatic treatment with
amylase enzymes has replaced the harsh processes since the beginning of the last century
[39]. Many commercial -amylases are available now and it is estimated that approximately
15% of all commercial textile enzymes are used in desizing processes [40]. In order to
prevent the yarn breaking during weaving, warp yarns are sized with starch and its
derivatives. The starch is a natural, biodegradable, and a mixture of two polysaccharides,
amylase and amylopectin consisting mainly of -1, 4-linked glucose units [41].
24
Cavaco-Paulo et al. [30, 42] carried out a series of studies to investigate the washing
effects of denim garments by cellulase treatment. From their studies reported that cellulases
are most successful in producing the stone-washed look denim apparels with modified
appearance. Aged/old looked denim with cellulase is the non-homogeneous removal of dye,
giving the fashionable contrast of various blue shades. Cavaco-Paulo [43] reported that
cellulases are always applied in washing processes where strong mechanical action on the
fabric is provided. As a result, the weight and strength loss increased. Nevell [44] reported
that, the primary wall of cotton contains waxes, proteins, lipids, pectins, organic acids and
noncellulosic polysaccharides constituting up to 10% of the total fiber weight and by washing
the fiber loss weight mostly. The secondary wall contains a mature fiber and consists almost
entirely of fibrils of cellulose arranged spirally around the fiber axis [45] and by enzymatic
washing the fibrils of cellulose in secondary wall is slightly disoriented and partly damaged
and strength is lost and softens apparels are produced.
Cavaco-Paulo et al. [30] explained that the slow kinetics of enzymatic degradation of
crystalline cellulose improves fabric and fiber properties (remove fuzz fibers) without
excessive damage. Mori et al. [46] showed that cellulase treatment improves the handle of
cotton fabric. They found that the primary wall of the cotton fiber is eliminated in the initial
step of hydrolysis; as a result a reduction in the fineness of the cotton fibers takes place. They
also suggested that enzymatic hydrolysis occurs in the secondary wall of the cotton fibers,
even during the initial step of hydrolysis so that cotton fabric becomes soft and loses strength.
Also, Walker and Wilson [47], Pedersen et al. [48], Duran and Marcela [5] studied cellulase
on cotton and found that cellulase improves fabric hand and enhance aesthetic properties.
Similar, many studies of cellulase applications on textiles and the properties of cotton fabrics
were reported by Buschle-Diller et al. [49] and Radhakrishnaiah et al. [50]. Heikinheimo et al.
[8] reported that cellulases are introduced to replace aggressive chlorine bleach in textile
industry.
Pumice Stone in Denim Apparel Washing

The fundamental problem of enzyme in denim wash has received considerable attention
from researchers. Such a problem is usually overcome by stone wash. A few but some
important studies of the stone washes are given below.
Pumice stone is generally used on the denim apparel to achieve a soft handle as well as a
desirable bleached-out character. In denim washing, pumice stones are mixed with enzymatic
processes to obtain irregular, nice stone-wash look effects. The surface of pumice stone is
rough, irregular, light weight and perforated and floats on water during washing in machine.
The use of stone makes brushing action on the apparel surface; as a result irregular color
fading effect is produced rapidly. But stone wash causes processing and equipment problems.
The main disadvantages of stone washing are the difficulty of removing residual pumice from
processed clothing items and the damage to the equipment by the overload of tumbling stones
[51]. In spite of these disadvantages, pumice stone is still used in denim washing industries
and researchers using certain researches with pumice stones [52]. Pumice stones combined
with cellulases cause the desired fading and softening of the apparel [53]. They concluded
that mechanical action by pumice stone opens the outermost layers in secondary cell of
cellulosic crystals, thus increasing the part of the cellulose accessible to enzymes and
enhancing enzymatic removal of the dye in presence of pumice stone. Again, pumice stone
with cellulases reduces time in washing process [54].
25
High levels of mechanical friction with pumice stone will produce strong mechanical
abrasion of yarn surfaces, releasing the indigo dye quickly and produced the stone-wash
effect [30, 42]. Feki et al. [55] examined the effect of stone-washing on denim garments and
evaluated compressibility, bending rigidity, shear rigidity and breaking work, but they did not
worked on the other properties like water absorption, elongation at break, tensile strength and
color fading.
1.5. Motivation
From the literature review it is clear that very little investigational study have been
carried out on the effect of chemicals in denim apparel washing. The study of denim apparel
washing with sustainable designs is important for the apparel designers and manufacturers
and is the new challenge in the fast changing current trends. The consumers has interest now
in eco-fashion. To apply a system as an effective wash method for denim with chemicals is
important. Thus to produce specific washing effect, considering sustainability, the analysis of
the effect of parameters in denim washing is necessary. Previously, majority of the studies on
denim apparels were carried out with dry processes. Thus, so far, none have conducted
studies involving the effect of chemical wash for producing sustainable denim apparels,
although denim is very popular apparel. Therefore, from the buyers point of view, consumers
are concern now on sustainable denim designs, which forms the basis of the motivation
behind the present study.
1.6. Present Problems

Previously no work has been reported on denim apparel washing considering
sustainability. The present study is an investigation with the best value for the purpose of
sustainable designs production. In the present investigation, two different types of washes are
considered. One is cellulase washing with various concentrations, temperatures and times in a
fixed amount of washing liquor. Second one is cellulase with pumice stone in denim garment
washing with various concentrations of pumice stones, temperatures and times. The proposed
studies are expected to reveal that the denim performance in such washings are very much
important from those studied in the above literature and it will therefore prove useful from the
manufacturers and designers point of view in choosing the best that suit them.
1.7. Objectives
The aim of this work was to define the optimum conditions for washing of denim readymade apparels in order to achieve the desired finishing effects with minimum negative
impacts in environment and properties. However, the specific aims of the study were:
To investigate the chemical effects and the mechanisms of these effects on denim
apparel washing.
To study the effects of different cellulases on denim apparel properties.
26
To describe how to produce a sustainable denim apparel.

To develop a dynamic washing method for denim apparels.
To carry out the validation of the present wash methods for denim washing includes
enzyme wash, and stone-enzyme wash.
To find out the best washing conditions with specifications for washing denim apparel
with enzyme and /or stone-enzyme that will develop existing method and new dynamic
method will be introduced.
2. EXPERIMENTAL DETAILS
2.1. Materials
The denim apparel and chemicals used in these experiments are listed as:
2.1.1. Denim Apparel

Fabric: All fabric used in this investigation was of 100% cotton twill weave (3/1 LHT.
381 g/m2) denim, manufactured in a Textile mill in Bangladesh.
Apparel: Denim apparels (trouser) were manufactured using the stated denim fabric. The
denim apparel used in these experiments is shown in Figure 2.1 and a summary of the denim
fabric properties is listed in Table 2.1.
Figure 2.1. A portion of denim apparel used.
27
Table 2.1. Properties of the denim fabric used

Property
Material
Warp count, weft count
EPI, PPI
Weight (g/m2)
Weave
Type of dyestuff
Tensile strength-warp (kg-f)
Tensile strength-weft (kg-f)
Elongation-warp (%)
Elongation-weft (%)
Dimensional stability (%)
Denim fabric
100% Cotton
10 Ne, 9 Ne
70, 42
381
3/1 LHT
Indigo
246
137
24
16
2.25
Table 2.2. Properties of the pumice stone used

Property
Material /composition
Size (cm)
Surface
Color
Nature
Weight (g/pc)
Source
Origin
Specifications
SiO2 73.14%, Al2O3 12.36%, Fe2O3 1.38%, Na2O 3.79%, K2O 2.7%,
MgO 0.13%, CaO 0.88%, FeO 0.66%, TiO2 0.1%, others-rest
4-5
Rough
White-slightly
Perforated, water floated
Light (10-12)
Volcanic explosion
Turkey
2.1.2. Cellulase Enzyme

Two different natures of cellulase enzymes, acid cellulase (Genzyme SL, Multichemi
Ltd, Sri Lanka) and neutral cellulase (Bactosol JCP, Clariant Ltd, Swizerland) were used. In
addition, mixtures of acid and neutral cellulases 50/50 were also used. The cellulases are biochemical substance that behaves as a catalyst toward specific reactions. According to
manufacturer, the activity of enzymes; acid enzyme- pH 4.5-5.5, temp 45-650C; neutral
enzyme- pH 6.0-7.0, temp 40-550C. In washing, the enzymes break some of the fibers on the
surface and hence give the fabric a soft, faded and old look effect. The cellulose loosens the
indigo dye and fading effect is produced rapidly during washing.
2.1.3. Pumice Stone
Fresh pumice stones were used for the treatments of stone-enzyme washing. The stones
are available in three sizes i.e., small (2-3 cm), medium (4-5 cm) and large (5-7 cm). Medium
size stone was used for the experiments. These stones are perforated, rough surface, light
weight and floats on water. The pumice stone used in these experiments is shown in Figure
2.2. A summary of the pumice stone properties is listed in Table 2.2.
28
Figure 2.2. Pumice stone used in the experiments.
2.2. Methods
Following processes have been used to perform washing. These are as follows
2.2.1. Desizing
The desizing was conducted in liquor containing Hostapur WCTH 0.6 g/L (a detergent,
BASF, Germany), Luzyme FR-HP 1.2 g/L (a desizing agent, BASF, Germany), AntistainLP30 0.4 g/L (an anti-back staining agent, GDS, India) and material to liquor ratio of 1:10 in
an industrial horizontal sample washing machine (model-NS 2205, Ngai Shing, Hong Kong)
at temperature 60C for 20 min in order to remove the size materials of warp yarns which was
applied in fabric manufacturing to reduce yarn breakage.
After that washed with hot water at 70C, followed by cold water wash at 25C.
2.2.2. Washing
Desized denim trousers were treated with chemicals (depends on wash type) in a sample
washing machine at different concentrations of chemicals, temperatures and times using the
enzyme and stone-enzyme washing methods followed by the standard washing procedure. All
treatments were involved in a rotary cylindrical washing machine at 30 rpm.
2.2.3. Hydro-Extracting Process
Chemically processed denim trousers were squeezed in a laboratory scale hydro-extractor
machine (Roaches, England) to remove excess water from the apparels at 200 rpm for 4 min.
The hydro-extracting machine is shown in Figure 2.4.
29
Figure 2.3. Industrial sample washing machine.
Figure 2.4. The hydro-extracting machine.
2.2.4. Drying Process

The hydro-extracted denim trousers were dried in a steam tumble drier (Opti-Dry,
England) at 75C for 40 min. Treated denim apparels were then evaluated by characterizing
of their physical and mechanical properties. The drying machine is shown in Figure 2.5.
30
Figure 2.5. The tumble drying machine.
2.3. Analysis
Various instruments and machines are used to determine physical and mechanical
properties of denim apparels. The fabric analyses carried out during this study are listed in
Table 2.3.
2.3.1. Measurement of Tensile Strength and Elongation at Break

Tensile strength and elongation at break of denim samples were carried out using a
horizontal (Goodbrand, UK) tensile strength tester according to ASTM D 5034 Grab test
method [56]. Tensile strength and elongation were measured in the warp and weft directions
in treated samples. The Grab test uses two jaws. The specimens are cut to a size of 5 in wide
and 10 in long and then frayed down in the width 4 in (10 cm). The sample is then placed
between the jaws and set the distance 6 in (15 cm) between the jaws, then pulled away from
other. The sample is broken in 20 3sec. At the point of break, tensile force was taken from
the dial and at the same time the value of elongation was taken from the attached scale in the
machine. The force and elongation at this point are noted. Any breaks that occur within 1 cm
of the jaws should be rejected. The mean breaking force and mean extension as a percentage
of initial length are reported.
2.3.2. Measurement of Weight Loss
Fabric weight loss of treated denim samples was measured after conditioning for 24 h at
200C and 65% RH (ASTM D 1776) [57] with a standard cutter and digital balance according
to ASTM D 3776 [58].
31
The weight loss (%) was calculated from the difference in fabric weight (grams/square
meter) before and after the chemical treatments. The apparatus used for weight loss
measurement consists of a circular cutter with a rubber board and a digital balance. First
apparel was placed on a flat table and using scissor fabric is cut 12 x 12 in. Then placed on
rubber board and fabric was cut by circular cutter (dia. 10.1 cm) and then kept the cut sample
on digital balance and taken weight. The weight loss was calculated as percentage using the
weight of untreated and treated samples.
2.3.3. Measurement of Color Change

The effects of the chemical treatments on denim apparel color were evaluated by
estimating the color change value with an AATCC Gray scale to color change according to
AATCC Evaluation Procedure 1 [59]. According to this standard, the changes in the color of
the fabric being tested, that is color fading. A numerical assessment of each effect is made by
comparing the changes with standard Gray scale to color change. The visual difference
between the original and treated denim fabric is compared with the differences represented by
the Gray scale. The difference in the color change is given a numerical value ranging from 5
to 1. Class 5 indicates no change in the original color/shade. Class 1 indicates a noticeable
change in color/shade. Gray scale for color change consists of nine pairs of standard gray
chips, each corresponds a difference in color/shade corresponding to a numerical color
change rating. In order to evaluate color change rating, the specimen was cut from the
untreated denim trouser. Then another specimen was cut from the chemically treated denim
trouser and these two specimens were placed side by side in the same plane and compare with
the Gray scale.
2.3.4. Measurement of Fabric Stiffness
In order to determine the fabric stiffness for this study, a stiffness test were conducted
and measured the bending length of denim samples by Shirley stiffness tester according to BS
3356 [60] at 200C and 65% RH. The higher the bending length, the stiffer is the fabric. To
measure the bending length a horizontal strip of fabric as specimen was cut to a size of 1 in
wide and 6 in long. The fabric sample was then placed under a template. When the tip of the
specimen reaches a plane inclined at 41.50 below the horizontal, the overhanging length was
then observed in centimeters directly from the Shirley apparatus. The bending length is
dependent on the weight of the fabric and its flexibility.
2.3.5. Measurement of Water Absorption
The effects of the chemical treatments on water absorption (rate of uptake) of denim
fabric were measured according to BS 3449 [61]. The water absorption (%) was calculated
from the difference in water absorbed before and after the chemical treatments. The static
immersion test was used for measuring the total amount of water that a fabric will absorb. In
the test weighted samples of the fabric were immersed in water for a given length of time (20
min), taken out and the excess water removed by shaking. They were then weighted again and
the weight of water absorbed was calculated as a percentage of the dry weight of the fabric.
The specimens were cut to a size of 80 x 80 mm at 450 to the warp direction. Then the
samples was conditioned and was taken weight each sample. The samples were then
immersed in distilled water at a temperature of 20 10C to a depth of 10 cm.
32
A sinker was used to hold the specimen at the required depth. In this position the samples
were left for 20 min. After that the samples were taken from the water and the surface water
was removed immediately by shaking them ten times. Then the samples were reweighted and
mean percentage absorption is calculated from the formula:
Absorption = mass of water absorbed / original mass of fabric x 100%
2.3.6. SEM Analysis

Scanning Electronic Microscopy photographs (SEM) were obtained of the chemically
treated denim samples and monitored surface appearance and morphological value. The
scanning electronic microscope (model-S 3400N, Hitachi, Japan) used in this experiment is
shown in Figure 2.6.
2.3.7. FM Analysis
Fluorescence Microscopy photographs (FM) were obtained from the chemically treated
denim samples and analyzed physical changes of yarns in fabrics. The fluorescence
microscope (model- IX71, Olympus, Japan) used in this experiment is shown in Figure 2.7.
3. RESULTS AND DISCUSSION

3.1. Effects of Cellulase Enzyme Concentration
In this experiment, enzymatic treatment of denim apparels with acid, neutral and mixture
of acid and neutral cellulases was performed in the washing machine under the concentrations
of 0.5, 1.0, 2.0, 3.0 and 3.5% (owg).
Figure 2.6. The view of scanning electronic microscope.
33
Figure 2.7. The view of fluorescence microscope.
Table 2.3. Analyses used for denim sample

Analysis
Tensile strength
Stiffness
Color change
Weight
Water absorption
Microscopy
Microscopy
Method used
Grab test
Bending length
Gray scale
Dry weight, conditioning
Static immersion test
SEM
FM
Ref.
ASTM D 5034
BS 3356
AATCC Evaluation 1
ASTM D 3776
BS 3449
The cellulase enzyme hydrolyse cellulose and allowing changes on color and fiber
polymer chain which affects on the fabric properties. The effect of cellulase enzymes with
various concentrations of 0.5-3.5% on the properties of denim apparels in terms of tensile
strength, stiffness, color fading, weight and water absorption was determined and is shown in
Tables 3.1-3.4. From these Tables 3.1-3.4, it can clearly be understood the washing effects
from the each others.
Tensile strength is the measure of the breaking force of the fabric which affects fabric
mechanical property. The tensile strength evolution after enzyme washing with various
concentrations can be seen in Table 3.1.
On washing at various concentrations of cellulase enzymes the tensile strength decreased
due to the cellulose hydrolysis by enzymes. As a result, the warp and weft both yarns in the
fabric are affected by enzyme and the weft yarns are more affected in its strength than warp
due to the undyed weft yarns are more hydrolysed by enzyme.
34
It can be seen from Table 3.1 that, at low concentration (0.5%) of enzyme, 6.5%, 5.6%
and 5.0% strength losses were observed in warp direction when the apparels were treated with
acid, neutral and mixed enzymes; and 22.7%, 19.5% and 18.5% strength losses, respectively
were observed with higher enzyme concentrations (upto 3.5%). Whereas, 11.0%, 8.8% and
8.0% strength loss and 33.0%, 30.8, and 28.6% strength losses were observed in weft
respectively. The decrease in tensile strength at 0.5 to 3.5% was higher with acid cellulase
than neutral cellulose due to the different amino acid compositions of acid and neutral
celluloses. Campos et al. [62] reported that differences in amino acid residues of acid and
neutral cellulases seem to be the main reason for their hydrolysis behavior to cellulose.
Hydrolysis of cellulose would certainly affect fabric tensile strength. Cavaco-Paulo et al. [42]
investigated that during dyeing the insoluble indigo is known to form agglomerates in
aqueous solutions and these indigo molecules bind on warp yarn surface. As a result, in
denim washing, firstly indigo agglomerates are fractioned into smaller particle with
cellulases, and then hydrolyse the cotton yarn/cellulose. On the other hand, cellulases directly
hydrolyse the undyed weft yarns. This seems to be the main reason for high strength loss in
undyed weft than colored warp. Buchert and Heikinheimo [37] and Kleman-Leyer et al. [63]
have previously been obtained similar results for tensile strength with undyed cotton
cellulose.
Table 3.1. Effect of enzyme washing with different concentrations of cellulase on the
tensile strength of denim apparel in warp and weft directions
Cellulase
conc. (%)
0.0
0.5
1.0
2.0
3.0
3.5
Loss in tensile strength in warp

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
6.5
5.6
5.0
10.5
8.9
8.5
16.6
13.4
12.6
22.7
17.0
16.6
22.7
19.5
18.5
Loss in tensile strength in weft

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
11.0
8.8
8.0
13.9
11.7
11.0
22.0
21.3
19.1
28.6
27.2
26.4
33.0
30.8
28.6
fabric weight and color shade of denim apparel in warp and weft directions
Cellulase
conc. (%)
0.0
0.5
1.0
2.0
3.0
3.5
Fabric weight loss, (%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
1.6
1.4
1.1
2.9
2.4
2.5
3.4
3.3
3.2
4.2
3.7
3.4
4.5
4.2
3.7
Color shade loss, (%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
10
10
10
20
10
20
30
20
30
40
30
30
40
30
40
35
stiffness of denim apparel in warp and weft directions
Cellulase
conc. (%)
0.0
0.5
1.0
2.0
3.0
3.5
Stiffness loss in warp direction,(%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
28.9
22.2
22.2
31.1
28.9
28.9
44.0
43.1
43.1
44.7
43.3
43.1
44.9
44.0
43.1
Stiffness loss in weft direction, (%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
6.2
6.2
6.2
9.3
9.3
6.2
15.6
12.5
12.5
18.7
15.6
12.5
18.7
15.6
12.5
water absorption of denim apparel
Cellulase conc. (%)
0.0
0.5
1.0
2.0
3.0
3.5
Acid enzyme
0
15.1
19.1
23.0
23.8
23.8
Water absorption, (%)

Neutral enzyme
0
17.5
20.6
21.4
23.0
23.0
Mixed enzyme
0
16.7
20.6
23.8
25.4
25.4
It is seen from Table 3.2 that, treatment of denim garments under investigation with acid,
neutral and mixed cellulase decreased the weight loss and this decrease is little bit higher at
higher enzyme concentrations up to 3.5%. The main reason of weight losses is the hydrolysis
behavior to cellulose by enzymes. With higher enzyme concentration the rate of hydrolysis
increased and weight loss is increased. During washing, acid and neutral both cellulases are
hydrolysed cotton. First, it attacked on projecting fibers (micro-fibrils) on surface, then
attacked on yarn portion, hydrolyzed them slowly and penetrated inside the fabric.
As a result, fibers are hydrolysed and broken down quicker with the friction of rotating
cylinder of the washing machine. Hydrolysis of cellulose would certainly affect fabric weight
losses in washing process. Table 3.2 shows that acid cellulase caused up to 4.5% weight loss,
neutral cellulase up to 4.2% loss and mixed cellulase up to 3.7% loss at the concentrations of
3.5%.. It is observed that the weight loss decreased more in acid enzyme than neutral enzyme,
and weight loss is less when denim apparel washed with mixed enzymes.
Again, denim hydrolysis was measured by monitoring the color shade change. It can be
seen from the Table 3.2 that the color shade decreased with higher concentrations from 0.5%
to 3.0%. The color shade is not decreased more, with the increasing of concentration from 3.0
to 3.5%. In enzyme washing, the part of the primary wall of indigo-dyed denim apparel is
always in contact with cellulase. At the contact point, the surface dyes are partly detached
from the main fiber chain and indigo dye bonds are broken from the yarn surface. As a result,
the treated denim apparel becomes duller and color is faded. In addition, mechanical friction
inside washing machine accelerate cellulose hydrolyses and destroy color.
36
Grieve et al. (2006) has previously been obtained similar result for color fading of denim
apparels. The results disclose that increasing the cellulase concentration from 0.5 to 3.0% has
effect on color fading and from 3.0 to 3.5% has no effect on color shade change, because
most indigo agglomerates are fractioned into smaller particle at 3.0% cellulase concentration,
and with increased concentration up to 3.5% cellulases, remaining indigo agglomerates are
not fractioned into smaller particle, as a result color will not fade further. It can be seen from
the Table that acid cellulase caused 10 - 40% color loss, neutral cellulase 10 - 30% loss and
mixed cellulase caused 10 - 40% loss. It is observed that the decrease in color shade at 3.5%
was higher with acid cellulase than neutral cellulose. This means that indigo color fading also
depends on the nature of cellulase enzymes with increasing cellulose concentrations.
It can be seen from the Table 3.3 that the stiffness of denim apparels decreased after they
were exposed to acid, neutral, and mixed enzymes at concentrations of 0.5 - 3.5%. After
treatments, the starch of warp yarns are removed first, then it hydrolyzed cellulose similar to
color fading mechanism by cellulases discussed earlier. As a result, bending length was less
and stiffness decreased in comparison to untreated denim for all the three cases. The decrease
in stiffness at concentrations of 0.5 to 3.5% was higher with acid cellulase than neutral
cellulase. Cavaco-Paulo et al. [42] investigated that acid cellulases have a higher affinity for
indigo than neutral cellulases. Thus, more hydrolyses occurred by acid cellulase and stiffness
decreased. It can be seen from the Table that acid cellulase caused 28.9-44.9%, neutral
cellulase 22.2-44.0% and mixed cellulase caused 22.2-43.1% stiffness loss in warp direction
and 6.2-18.7%, 6.2-15.6%, 6.2-12.5% respectively in weft direction. Water absorption is the
measure of the level of water in the denim apparel which affects fabric properties. Table 3.4
shows the changes in water absorption with the increasing of concentration of cellulases from
0.5-3.5% in denim washing, due to the loosening of surface fibers by enzymatic treatment.
The loosening of surface fibers would certainly affect fabric water absorption. From the Table
it can be seen that, the water absorption increased 15.1-23.8% at 0.5-3.0% concentration with
acid cellulase, 17.5-23.0% with neutral enzyme, and 16.7-25.4% with mixed cellulase, and
does not cause any further increase of water absorption when the concentration increased
from 3.0 to 3.5%. With increased water absorption, the denim apparel shows increased water
vapor permeability that means comfortness or softness increased. Therefore, there is a strong
relationship between water absorption and fabric comfortness and softness; which affects the
properties of denim apparels.
3.2. Effect of Temperature in Cellulase Enzyme

Treatment of denim apparels with acid, neutral and mixed cellulase was performed under
the influence of 40, 50, 55, 60 and 65 C. The onset of temperature on loss in tensile strength,
stiffness, color fading and fabric weight, and gain in water absorption is shown in Tables. The
changed /modified value of different physico-mechanical properties of acid, neutral, and
mixrd cellulases treated denim apparels against the effect of various temperatures are listed in
Tables 3.5 - 3.8. Enzyme washing with the effect of temperatures on the strength properties of
denim apparels was measured and is shown in Table 3.5. The effect of temperature at 400C
had practically little effect on the strength properties of denim apparels (6.5-9.3% loss in warp
and 11.0-13.2% loss in weft direction); those at the highest temperature of 650C big effects on
tensile strength (21.5-22.7% in warp and 27.2-30.1% in weft direction) were observed.
37
Table 3.5. Effect of enzyme washing with different temperatures of cellulase on the
tensile strength of denim apparel in warp and weft directions
Temp. (oC)
0.0
40
50
55
60
65

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
9.3
6.5
8.1
13.4
12.1
9.7
16.6
13.4
12.6
21.5
17.8
17.4
22.7
21.5
22.3

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
13.2
11.0
11.7
19.1
16.1
14.7
22.0
21.3
19.1
27.9
22.7
25.0
30.1
27.9
27.2
fabric weight and color shade of denim apparel in warp and weft directions
Temp. (oC)
0.0
40
50
55
60
65

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
2.3
1.8
1.8
2.8
2.3
2.3
3.4
3.3
3.2
4.9
4.4
4.4
5.5
4.5
4.4

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
10
10
10
20
10
20
30
20
30
40
30
30
40
40
40
However, by increasing the temperature upto 650C, 22.7% loss in strength in warp and
30.1% loss in weft direction by acid enzyme was obtained, whereas 21.5% loss in warp and
27.9% loss in weft by neutral enzyme, and 22.35 loss in warp and 27.2% loss in weft by
mixed enzymes was obtained. From the Table 3.5, it is observed that decrease in tensile
strength at 40 to 650C was higher with acid cellulase than neutral cellulase.
This is occurred, due to more fiber degradation with raising temperature in cellulose
washing with acid enzyme than neutral and mixed enzymes.
Table 3.6 shows the decreases in weight of fabric with the increasing of temperature from
40 to 650C. This is due to the removal of projecting fuzz fibers from the fabric surface with
the effect of temperature.
With higher temperature, at 650C, the weight loss was higher for the acid enzyme (5.5%)
than for the neutral (4.5%) and mixed enzyme treated (4.4%) denim apparels. It can be seen
from the Table that acid cellulase caused 2.3-5.5% weight loss, neutral cellulase caused 1.84.5% loss and mixed cellulase caused 1.8-4.4% loss. The effect of temperature on color
fading was monitored and also shown in the same Table.
It can be seen from the Table 3.6 that the denim apparel washing with acid, neutral, and
mixed enzymes decreased the color shade with the increase of temperature from 40 to 650C.
From the Table, it is observed that the decreases in color shade from 40 to 600C was higher
for the acid enzyme (40%) than for the neutral enzyme (30%). In cellulase washing, raising
38
the temperature enhanced the color fading quicker, due to more hydrolysis of cellulose by the
effect of temperature.
The effect of temperature on stiffness was monitored. It can be seen from the Table 3.7
that the decreases in stiffness of denim apparel with the increasing of temperature from 40 to
650C. From the Table 3.7, it is observed that the decreases in stiffness from 40 to 650C were
higher for the mixed enzyme (45.3%) in warp direction than for the acid (44.8%) and the
neutral enzymes (44.4%), whereas, the decreases in stiffness from 40 to 650C were almost
similar in weft direction for the acid enzyme (15.6%), neutral enzyme (15.6%) and the mixed
enzymes (15.6%). In cellulase washing, raising the temperature decreases the stiffness, due to
more hydrolysis of cellulose.
Table 3.8 shows enzyme washing at 400C caused increase in water absorption to 13.4%,
15.1% and 15.8% for acid, neutral and mixed enzymes respectively and the increase was
higher at higher temperature up to 650C.
After enzyme treatment, the water absorption increased to 26.1% at 600C by the mixed
enzyme, 24.6% with neutral enzyme and 23.8% with acid. Therefore, the mixture of acid and
neutral enzymes is the most effective enzyme to increase water absorption when washing was
performed at 600C. The water absorption does not cause further increase when temperature
increased from 60 to 65C in all the three cases.
stiffness of denim apparel in warp and weft directions
Temp. ( C)
0.0
40
50
55
60
65
Stiffness loss in warp direction,(%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
33.3
31.1
28.8
38.2
37.7
36.8
44.0
43.1
43.1
44.7
44.4
44.8
44.8
44.4
45.3

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
6.2
3.1
3.1
12.5
9.3
6.2
15.6
12.5
12.5
15.6
15.6
15.6
15.6
15.6
15.6
water absorption of denim apparel
Temp. (oC)
0.0
40
50
55
60
65
Acid enzyme
0
13.4
15.8
23.0
23.8
23.8

Neutral enzyme
0
15.1
15.8
21.4
24.6
24.6
Mixed enzyme
0
15.8
19.8
23.8
26.1
26.1
39
3.3. Effects of Time in Cellulase Enzyme

Treatment of denim apparels with acid, neutral and mixed cellulase was performed under
the influence of treatment time 20, 30, 40, 50 and 60 min. The onset of time on loss in tensile
strength, stiffness, color fading, fabric weight and gain in water absorption is shown in Tables
3.9 - 3.12.
It can be seen from the Table 3.9 that the decreases in tensile strength of denim apparel
decreases with the increase of washing time from 20 to 60 min. From the Table 3.9, it is
observed that the decrease in tensile strength from 20 to 60 min are higher for the acid
enzyme (22.7% in warp direction) than for the neutral enzyme (21.9%) and for the mixed
enzyme (44.4%), whereas, the decrease in tensile strength in weft direction are 30.1%, 27.2%
and 25.2% respectively.
Table 3.9. Effect of enzyme washing with different times of cellulase on the tensile
strength of denim apparel in warp and weft directions
Time (min)
0.0
20
30
40
50
60

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
9.3
8.9
8.9
13.4
12.1
11.3
16.6
13.4
12.6
20.7
18.6
16.6
22.7
21.9
20.7

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
13.2
11.0
12.5
19.1
14.7
17.6
22.0
21.3
19.1
27.9
26.4
22.7
30.1
27.2
25.2
Table 3.10. Effect of enzyme washing with different times of cellulase on the fabric
weight and color shade of denim apparel in warp and weft directions
Time (min)
0.0
20
30
40
50
60
Acid
enzyme
0
1.8
2.3
3.4
4.4
5.2

Neutral
Mixed
enzyme
enzyme
0
0
1.0
1.5
1.5
2.0
3.3
3.2
3.6
3.9
4.9
4.0
Acid
enzyme
0
10
20
30
30
40

Neutral
Mixed
enzyme
enzyme
0
0
10
10
10
20
20
30
30
30
40
40
In enzyme washing, raising the washing time decreases the tensile strength, due to more
hydrolysis of cellulose with longer time. The decrease in strength mostly occurred with the
time between 40 and 60 min. Increasing the time from 20 to 60 min affects on fabric strength
as well as the durability of apparels. With increasing time, the loss in tensile strength in weft
is higher than warp direction; due to the direct hydrolysis on the undyed weft yarns by
40
enzymes than colored warp yarns. This seems to be the main reason for high strength loss in
weft yarns than warp yarns.
Table 3.11. Effect of enzyme washing with different times of cellulase on the stiffness of
denim apparel in warp and weft directions
Time (min)
0.0
20
30
40
50
60
Stiffness loss in warp direction, (%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
33.3
24.4
33.7
35.7
31.1
36.4
44.0
43.1
43.1
44.5
44.0
44.4
44.8
44.0
44.8

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
3.1
3.1
3.1
12.5
9.3
12.5
15.6
12.5
12.5
16.6
15.6
16.0
18.7
15.6
18.7
Table 3.12. Effect of enzyme washing with different times on the water absorption
Time (min)
0.0
20
30
40
50
60
Acid enzyme
0
15.0
19.0
23.0
23.8
25.3

Neutral enzyme
0
11.1
15.0
21.4
23.0
24.6
Mixed enzyme
0
17.4
22.2
23.8
26.9
28.5
Table 3.10 shows the decrease in weight of fabric after enzyme washing with the
increasing of time from 20 to 60 min. With higher time for 60 min, the weight loss was higher
for the acid enzyme (5.2%) than for the neutral enzyme (4.9%) and mixed enzyme (4.0%). It
can be seen from the Table 3.10 that the color shade of denim apparel decreases with the
increasing washing time from 20 to 60 min. The decrease in color shade from 20 to 40 min
were higher for the acid enzyme (30%) than for the neutral enzyme (20%), whereas, with
increasing time more than 40 min similar results obtained for all the three cases. The changes
in color shade with the increasing of time which affects worn look of denim garments.
Table 3.11 shows the decreases in stiffness with the increase of time from 20 to 60 min
which affects softness of the denim apparels. Table 3.12 shows the changes in water
absorption of denim apparels after washing with acid enzyme, neutral enzyme, and mixed
enzyme from 20 to 60 min. Enzyme washing for 20 min caused increases in water absorption
of 15.0%, 11.1% and 17.4% for acid, neutral and mixed enzymes respectively and this
increase was higher at higher time up to 60 min. The water absorption of denim fabrics
treated with mixed enzymes, acid enzyme and neutral enzyme for 60 min are 28.5%, 25.3%
and 24.6%, respectively.
41
3.4. Effects of Pumice Stone Concentration

In this study, mechanical abrasion was achieved by pumice stone in the washing
machine.
The addition of pumice stone in cellulase treatments accelerates more mechanical
abrasion and allowing enzymatic hydrolysis quicker which affects on the fabric properties.
Cavaco-Paulo et al. [30] have pointed out the importance of mechanical agitation on cellulose
hydrolysis in enzymatic treatments.
Liu et al. [64] reported that mechanical agitation depends on rotation speed, liquor ratio,
load size and processing time. In this study, stone washing effects in presence of enzyme on
fabric properties were determined. A combination of high level of abrasion by pumice stone
and enzyme action may generate fibrillar material on the fabric surface reported by CavacoPaulo et al. [30] Pumice stone gives a used look appearance on denim distinctly.
In this part of study, mechanical abrasion was achieved by pumice stone in the rotating
cylinder of the washing machine at 30 rpm. The effect of pumice stone with various
concentrations (10-70%) (owg) on the properties of denim apparels was determined and is
shown in Tables 3.13-3.16.
Table 3.13. Effect of pumice stone-enzyme washing on the tensile strength of denim
apparel in warp and weft directions
Pumice
stone, (%)
0.0
10
20
30
40
50
60
70

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
14.6
9.7
7.3
18.3
14.6
13.0
22.3
17.8
15.8
27.2
24.3
20.7
29.3
25.2
23.5
33.3
26.4
25.2
34.9
30.0
28.4

direction, (%)
Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
11.0
11.0
9.5
16.1
14.7
12.5
24.2
22.0
19.8
30.1
29.4
28.6
33.8
31.6
30.8
34.5
33.0
32.3
34.5
33.8
33.8
Table 3.14. Effect of pumice stone-enzyme washing on the fabric weight and color shade
of denim apparel
Pumice
stone, (%)
0.0
10
20
30

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
2.3
1.8
1.8
3.4
2.6
2.9
4.2
3.4
3.9

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
30
20
10
30
20
20
40
30
40
42

Table 3.14. (Continued)
Pumice
stone, (%)
40
50
60
70

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
4.5
3.9
4.5
4.9
4.5
4.5
5.2
4.9
4.9
5.5
4.9
5.2

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
50
40
50
60
50
60
60
60
60
60
60
60
Table 3.15. Effect of pumice stone-enzyme washing on the stiffness of denim apparel in
warp and weft directions
0.0
Loss in stiffness in warp direction, (%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
Loss in stiffness in weft direction, (%)

Acid
Neutral
Mixed
enzyme
enzyme
enzyme
0
0
0
10
31.1
28.9
33.3
9.3
6.2
6.2
20
37.7
35.5
40.0
12.5
9.3
12.5
30
44.4
40.0
46.6
15.6
12.5
15.6
40
46.6
44.4
46.6
15.6
12.5
15.6
50
46.6
44.4
46.6
18.7
18.7
18.7
60
48.8
46.6
51.1
18.7
18.7
18.7
70
48.8
48.8
51.1
18.7
18.7
18.7
Pumice
stone, (%)
Table 3.16. Effect of pumice stone-enzyme washing on the water absorption of denim
apparel
Pumice stone, (%)
0.0
10
20
30
40
50
60
70
Acid enzyme
0
15.8
19.8
25.4
26.1
26.9
27.7
27.7

Neutral enzyme
0
17.5
20.6
22.2
23.8
25.4
25.4
25.4
Mixed enzyme
0
16.7
20.6
26.1
26.9
27.7
28.5
28.5
The tensile strength evolution after stone-enzyme washing can be seen in Table 3.13. On
washing at various concentrations of pumice stones the tensile strength decreased due to the
rubbing action provided by the pumice stones. The weave of the fabric used in this study is a
3/1 twill, so the effect of abrasion is more concentrated on warp yarns than weft yarns. When
43
garments are washed with stone, the surface yarns are aggressively affected by the stone rub
action thereby underside yarn surfaces can be retained away from the rub directly. As a result,
warp yarns are more affected by stone in acid enzyme than neutral and mixed enzymes. When
the pumice stone and the mixture enzyme are combined in the washing solution, the fibers
degradation become more important and causes an intensive increase of hydrolysis, which
effects on fabric tensile strength. Klahorst et al. [31] reported that cellulase hydrolyses the
cellulose, yielding long chain cellulose polymer to a short chain polymer. The hydrolysis of
cellulose link breaks the molecule in several pieces, which decompose fiber, consequently the
tensile strength are greatly reduced. It is observed that, at low concentration of pumice stone
(10%), the decreases in tensile strength were 14.6%, 9.7% and 7.3% in warp for acid, neutral
and mixed enzymes. However, at high concentration of pumice stone (70%), high reduction
in strength of denim was obtained for the case of acid enzyme than the neutral and mixed
enzyme.
The cellulase attacks and mechanical agitation may have caused more damage on the
fabric surface by cutting the cellulose chains. Acid enzyme with pumice stone (70%) caused
the highest strength loss (34.9%), whereas the neutral enzyme (30%) and mixed enzyme
(28.4%) had less effect on the strength properties. In practice such high strength loss values
are not acceptable.
Table 3.14 shows the impact of pumice stone on the weight loss of denim apparels. High
weight loss of 5.5% was obtained with 70% pumice stone for acid enzyme, compared to the
weight losses of 4.9% for neutral enzyme and 5.2% for mixed enzyme. Treatments showed
that the mechanical action by pumice stone caused higher weight loss of fabric. It can be seen
from the Table 3.14 that the color shade decreased after they were treated to acid, neutral, and
mixed enzymes at higher pumice stone concentrations particularly from 30 -70%. From the
Table 3.14, it can be observed that the decrease in color shade at 10-70% was higher for acid
enzyme than for neutral enzyme and pumice stone with acid, neutral, and mixed enzyme
caused 10 - 60% color loss.
Table 3.15 shows the losses in stiffness of denim garment. It can be seen from the Table
3.15 that pumice stone with acid cellulase caused 31-49% stiffness loss, neutral cellulase
caused 29-49% loss and mixed cellulases caused 33-51% loss. The stiffness loss is highest in
mixed cellulase than acid and neutral cellulases. From the Table 3.15, it can clearly be
differentiated each value from the others due to the differences in amino acid residues in
cellulases and abrasion by pumice stone.
Table 3.16 shows the effect of pumice stone concentration on water absorption. The
water absorption is increased when washing was performed by pumice stone with acid,
neutral and mixed cellulases due to the loosening of surface fibers by the abrasion of pumice
stones. The water absorption increased approximately 15-26% at 10-30% concentration of
pumice stones. Water absorption does not cause any further increase when the pumice stone
concentration increased from 50 to 70% for all the three cases.
44
3.5. SEM Analysis

The changes in surface appearance of the denim apparels after enzyme washing and
stone-enzyme washing were examined by scanning electron microscope (Model 3400N,
Hitachi, Japan). The surface appearances of the untreated denim samples were also examined
by SEM. The surface appearances as well as denim apparel properties are affected by enzyme
washing and stone-enzyme washing. Figure 3.1 shows the SEM image of untreated cotton
denim apparel. The Figure shows parallel ridges and no fibrils (projecting fibers) and ruptures
visible in the image, because the yarns are coated with size materials and projecting fibers are
not visible on surface.
The Figure 3.2 shows the Scanning Electron Microscopy photograph of enzyme treated
cotton denim apparel. The enzyme treatment was carried out according to the method
described in this chapter with an enzyme concentration of 2.0% (owg) acid cellulase at 550C
for 40 min. After enzyme treatment, a clear increase of cracks, disorients and wrinkle surface
was observed compare to unwashed sample.
Figure 3.3 shows stone-enzyme treated sample and damaged surface in the image are due
to fiber degradation by hydrolysis and abrasion by pumice stone in the washing machine
during processing.
As observed in Figure 3.3 there are more cracks on the surface of fibers. This is caused
by cellulase washing of cotton denim garments and pumice stone enhances more cracks on
surface.
Figure 3.1. Scanning electron microscopy image of untreated denim sample.
Figure 3.2. Scanning electron microscopy image of enzyme treated denim sample.
Figure 3.3. Scanning electron microscopy image of stone-enzyme treated denim sample (hydrolysed
and damaged form).
45
46
3.6. FM Analysis
Figures 3.5-3.6 shows the changes in physical appearance on the yarn surface of denim
apparel after washing with cellulase enzyme and stone-enzyme treatment which were
observed by fluorescence microscope (FM) (model IX71, Olympus, Japan). Figure 3.4 shows
the FM image of untreated warp yarn.
Figure 3.4. Fluorescence microscopy image of untreated warp yarn.
Figure 3.5. Fluorescence microscopy image of enzyme treated warp yarn.
47
Figure 3.6. Fluorescence microscopy image of stone-enzyme treated warp yarn.
As the yarns are dyed and coated with size materials, the surface is smooth and fibrils or
projecting fibers are not visible on surface. Figure 3.5 shows the fluorescence microscopy
photograph of warp yarn treated with the 2.0% concentration of acid cellulase at 550C for 40
min. It is observed that the yarn surface is somewhat damaged by the action of cellulase
enzyme and the extent of damage is increased with the increasing of enzyme concentration.
The Figure 3.6 shows the FM photograph of warp yarn of denim fabric treated with 30%
pumice stone combined with 2.0% (owg) acid cellulase at 550C for 40 min.
It is observed that the yarn surface is highly damaged by the rubbing action of pumice
stone and the extent of damage is increased with the increasing of stone concentration in
washing.
CONCLUSION
An experimental study on the effect of chemicals in denim apparel washing has been
studied by enzyme and stone-enzyme treatments. The works reported in this research are
basically dependent on parameters namely: (i) chemical concentrations (ii) treatment
temperatures (iii) times and (iv) pumice stone concentrations. Cellulase enzymes and pumice
stone-enzyme washing are important chemicals in the apparel washing industry for
processing denim ready-made apparels. Cellulase enzymes provide an ecological way to treat
cotton denim apparels.
Although cellulases have been used for biofinishing cotton in textile industry since the
1980s, many varieties of cellulases are still used in textile processes today and recently used
in denim washing industries. Pumice stones mixed with cellulases have been used for
biostoning denim to get distressed worn look.
48
A problem associated with treatments with cellulases and mixtures with pumice stone is
that the treated garments exhibit high strength and weight losses. Pumice stones mixed with
cellulase enzyme have been used for denim washing to get more worn look appearance.
The study has been confined to the modification of denim apparels with chemicals in
washing processes. In case of enzymatic treatment the effect of cellulase enzyme on the fabric
properties as well as the characteristics of denim apparels in washing process with the
introduction of parameters has been determined.
In case of enzymatic treatment with pumice stone the effect of pumice stone on the fabric
properties as well as the characteristics of denim apparels has also been determined in this
research.
On the basis of the analysis the following conclusions have been drawn:
i)
The results obtained provide new information on the effects of acid, neutral and
mixture of acid and neutral cellulases on denim apparels. The use of 2.0g/L mixed
cellulase was found to be the most effective in preventing strength and weight loss,
determined the most positive results with specific washing effects. In addition, the
results obtained with defined cellulase mixtures provided useful knowledge for
designing new production. It was also shown that neutral cellulase improves water
absorption. Acid cellulase is the most effective at removing color from denim fabrics.
Treatment temperature, time and concentrations of cellulase had a major impact on
enzymatic treatments.
ii) Pumice stone has influence on the properties of denim apparels. The results obtained
in enzymatic washing with pumice stone provide new information on the effects of
pumice stone in acid, neutral and mixture of acid and neutral cellulases on denim
apparels. The use of 30% pumice stone in cellulase washing for all cases was found
to be the most effective in preventing strength and weight loss, determined the most
positive results with washing effects.
For optimal performance in denim apparel washing, the process parameters should be
selected on the basis of fabric type and quality in order to achieve the desired finishing effect
with minimum negative impact. Pumice stone in cellulase treatments gives a used look
appearance on denim apparel distinctly and the properties of denim fabrics are varied
depending on the amount of pumice stone used. It is possible to suggest that any or all of the
parameters in both enzyme washing and stone-enzyme washing methods are responsible to
damage denim apparel through excessive hydrolysis/unwanted abrasion by pumice stone and
changes the values of denim properties. The washing condition should be predetermined for
optimum result.
ACKNOWLEDGMENTS
One of the authors research work was supported by the NSICT Fellowship under the
Ministry of Science, Information and Communication Technology of The Peoples Republic
of Bangladesh.
49
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ISBN: 978-1-63117-262-5
Chapter 3
DIGITAL TEXTILE PRINTING USING

COLOR MANAGEMENT
Dejana Javorek*, Primo Weingerl and Marica Stareini
University of Ljubljana, Faculty of Natural Sciences and Engineering,
Ljubljana, Slovenia
ABSTRACT
The chapter presents the possibilities and a correct procedure for a color
management application in the field of digital printing onto textile substrates. The
introduction of color management into the field of digital textile printing enables better
quality control, faster prepress, reduction in the use of material and better repeatable
color prints on textile substrates. Due to the high price of printing colors used in digital
textile printing, and the costs connected with the pre- and aftertreatment of printed
fabrics, an appropriate preparation of color patterns and simulated prints is of even
greater importance.
The aim of this chapter is hence to present how long-term and expensive pre- and
aftertreatments of textile substrates can be avoided with the help of an appropriate use of
printer color profiles for all print devices included in the workflow, e.g., print simulation
on paper printed with a laser or inkjet printer. On the basis of simulated prints on paper, a
customer can decide on the color that gives the best results on a selected pattern.
Digital printing on a textile substrate a banner made for indoor and outdoor
applications, using the color profiles is presented as well. This includes experimental data
and the methods for testing the lightfastness and weatherability of the substrate with a
Xenotest, and for defining the uniformity of prints mottling. The method for defining
the uniformity of prints is included in the draft of the standard ISO 15311 and is also
proposed by the German Printing Association FOGRA.
In addition, the importance of the optical brightener used for the improvement of
substrate whiteness in digital textile printing is discussed. Furthermore, the calculation of
the color inconstancy index CMCCON02 when defining the influence of different
illuminants on the color change of substrates is presented.
*
Corresponding author: Dejana Javorek, University of Ljubljana, Faculty of Natural Sciences and Engineering,
Snenika 5, 1000 Ljubljana, Slovenia, E-mail: dejana.javorsek@ntf.uni-lj.si.
54
Keywords: Color management, ICC profiles, digital textile printing, print simulation, color
inconstancy index CMCCON02
INTRODUCTION
The technology of digital printing is more and more established [1] in the field of textile
printing [25] as it allows unlimited color sampling and good durability of prints, as well as
in the field of pharmaceutical research [6,7], electronics and micro-engineering industries for
printing electronic materials, such as printed circuit boards (PCB) [8, 9] and a humidity
sensor directly printed on a textile using the inkjet printing technology [10], and even food
decorating uses the digital printing technique as a major working tool. Recently, the inkjet
technology has also been successfully applied in the biomedical field [11], where the DNA
molecules have been directly printed onto glass slides using commercially available inkjet
printers for the high-density DNA microarray fabrication [12], and inkjet printers were used
to print cells and biomaterials for 3D cellular scaffolds [13].
In the case of inkjet technology, printing on various substrates is performed by means of
non-impact printing or jetting drops of ink on a substrate. The most important component of
inkjet technologies is the printing ink alone, which greatly affects the quality and reliability of
the output [14]. Thus, in the digital textile printing, various inks that are designed for different
needs and requirements are used, including reactive, acid, disperse and pigment dyes [15].
Despite the advantages and widespread use of pigment dyes [1618], reactive dyes still
occupy an important position in the printing of textiles, especially with thermal (bubble)
inkjet printers. Reactive dyes are used for the printing on cotton fabrics and their blends, and
on linen and silk fabrics. Reactive dyes for the printing with inkjet printers are now widely
accessible to everyone yet relatively expensive. Therefore, a number of studies aimed at the
improvement of digital printing on cotton with reactive dyes. Yang and Naarani researched
the printing of cotton with reactive dyes using the inkjet printer. They studied the impact of
matting conditions on the cotton print and how to improve the lightfastness of printed cotton
with reactive dyes [19,20].
Digital textile printing with reactive dyes is different from conventional printing,
especially:
in the substrate pretreatment with appropriate chemicals, as ink due to viscosity and
stability does not contain chemicals that are necessary for the binding of the dye to
fibers, and
in the aftertreatment when a chemical bond between the fibers and the reactive dye is
formed, resulting in excellent wet fastness of color prints.
A lot of research has been conducted in this area [2123]. It is known that these two, preand post-processing treatments, are essential as they further influence the change in color tone
[24]. Moreover, the dimensional stability of the fabric patterned with the inkjet printer was
controlled as well [25]. Weiguo et al. also analyzed the color print on the cationic agent
printed cotton with reactive dyes and established that a color print is better on the cotton
which was treated with a cationic agent than on the cotton treated with alkali, urea and
55
thickener [26], while some other researchers preferred modified chitosan pretreatment of
polyester fabric for the printing with inkjet ink where the pretreated fabrics produced a much
better color quality than the untreated fabrics [27], and preferred the pretreatments of the silk
fabric with amino compounds for the inkjet printing where the amino compound
pretreatments held and fixed the additional ink on the fabric surfaces resulting in a wider
color gamut of the inks [28]. Kaimouz et al. provided a quantitative insight into the effect of
pretreatment chemicals on the color strength, dye fixation and ink penetration on the inkjet
printed Lyocell and cotton fibers, using a statistical analysis approach [29].
The trend in small print collections and unique products requires greater flexibility of
printing companies and a fast production of color patterns and products. By using graphic
programs, the expectations of textile and clothing designers and of small businesses are
growing. In most cases, they require that a specific color pattern or color sample presented on
paper be exactly reproduced on the textile substrate. However, the path from the model
presented on paper to the final product printed on a textile substrate is relatively complex.
Problems arise when discrepancies between the color patterns on paper, computer screen and
the textile substrate occur.
In graphic technology, color management and the use of ICC (International Color
Consortium) color profiles ensure a consistent color reproduction throughout the
technological process and on all kinds of devices, regardless of the color space, including the
original, scanner, digital camera, display screen and color printer. Color management has
been used in graphics for a number of years, which is evident from the literature [3035].
By introducing color management into the field of digital textile printing, the time
required for prepress could be shortened and the use of materials could be reduced, which
would lower the printing process costs [36]. Due to the high price of printing colors used in
the digital textile printing and the costs connected with the pre- and aftertreatment of printed
fabrics, an appropriate preparation of color patterns and simulated prints is very important. A
print simulation in textile printing can be observed on a screen (i.e., soft proof) or conducted
on another printer (i.e., hard proof), which enables with appropriately built profiles for any
device and their correct use a simulation of particular color patterns on a different output
device.
In one typical research [36], the linearization and characterization of three printers for
paper and textiles, two inkjet and one electrophotographic (laser) printer, were
implemented. It was demonstrated that an accurate creation of color profiles ensured the top
quality of prints and successful hard proof on both laser and inkjet printers. While digital
printing has become a link between the traditional and electronic media, the need for an
accurate color reproduction is increasing. The users expectations have risen, representing
new challenges for both, the color reproduction and manufacturers of a variety of substrates.
In the textile industry, more and more optical brightening agents (OBA) are used in order to
increase the whiteness of a fabric. With the same purpose, they are integrated in detergents,
wherein they optically increase the whiteness of washed goods. Nevertheless, the
performance of optical brighteners can be the source of incorrect and inaccurate
measurements caused by errors in the measurements. In one study, they assessed the impact
of the optical brightener in the fabric, before and after the treatment with washing agents [37].
This means that in addition to the initial treatment of the fabric with an optical brightener, the
perception of the fabric color and the printed colors is clearly affected by the amount of
optical brighteners in detergents that bond with the fabric during the washing process.
56
When color profiles for all devices involved in the process of printing (i.e., display
screen, printer and printer for hard proof) are generated, it is recommended to test the colors
under different illumination, since patterns are usually observed under various light
conditions. This can be predicted by calculating the color inconstancy index, which is
described below [38, 39]. The quality of prints can be controlled in different ways. One
possibility is the calculation of the heterogeneity footprint with the M-Score method [40].
EXPERIMENTAL
In our research, three substrates were used:
textile cotton fabric which was printed with the inkjet printer Mimaki Textile Jet
Tx2-1600 (Mimaki, Japan) using 8 reactive dyes [36], and
two textile synthetic fabrics, i.e., banner and textile banner made for indoor and
outdoor applications, which were printed with Canon Image Prograf W8400.
In the first case [36], we focused on hard proofing, where the matching between the
original colors and hard copy simulation of the colors was investigated using the color
difference equations E00. The purpose of the researches was to establish whether a print on a
textile made with a digital printer produced by Mimaki can be simulated with a print on a
paper with an inkjet (Canon Image Prograf W8400, Canon, Japan) and laser (Canon Image
Press C1+, Canon, Japan) printer.
In the second case, we focused on defining the print quality of presentational posters
substrate banner, using the color difference equations E00. This included experimental data
and methods for testing the lightfastness and weatherability of the substrate with a Xenotest
Alpha (Atlas, USA), and for defining the uniformity of prints mottling. The method for
defining the uniformity of prints is included in the draft of the standard ISO 15311 and is also
proposed by the German Printing Association FOGRA.
Materials
The cotton fabric used in the research was provided by Tekstina Plc, Ajdovina,
Slovenia. The basic fabric properties are as follows: raw material: 100% cotton, plain weave,
warp thread density: 54 threads/cm, weft thread density: 29 threads/cm, mass per square
meter: 130 g/m2, breaking force in warp direction: 38.0 daN, breaking force in weft direction:
26.0 daN, breaking elongation in warp direction: 17.6%, breaking elongation in weft
direction: 12.0% and fineness of warp and weft threads: 14 tex.
Two textile synthetic substrates, namely the high-impact, highly durable textile substrates
were used, i.e., a vinyl banner (in the text called banner) and a textile (in the text called
textile) produced in China. The basic fabric properties are as follows: material: PES
(polyester), plain weave, Sample 1: mass: 1.1213 g/dm2, thickness: base 0.180 mm, print
0.182 mm; Sample 2: material: PES (polyester), mass: 1.9526 g/dm2, thickness: base 0.321
mm, print 0.322 mm. Since the substrates were treated with a coating, only warp thread
57
density: 23 threads/cm, weft thread density: 30 threads/cm for Sample 1 (cf. Figures 1 and 3)
was defined.
The analysis performed under a stereomicroscope (Leica EZ 40) and SEM microscope
JEOL 6060LV is presented in Figures 14.
Figure 1. Sample 1, Print/Base, Leica EZ 40.
Figure 2. Sample 1, SEM microscope JEOL 6060LV.
Figure 3. Sample 2, Print/Base, Leica EZ 40.
58
Figure 4. Sample 2, SEM microscope JEOL 6060LV.
Color Measurements
After a few days of color stabilization, the measurements with the instrument EyeOne (XRite, USA) were performed. Instead of diffuse geometry, the measurement geometry 45/0
was used, as it is supported by the color management program (Texprint) for digital textile
printing.
The differences in the color between the original colors (print on inkjet printer Mimaki)
and simulated prints (prints on inkjet printer Canon and laser printer Canon), and the
differences between the prints made on a banner and textile were calculated with the E00
color differences equation [41]. The color differences between the original colors on a banner
and textile, and the colors after the treatment on a Xenotest were calculated using the E00
color differences equation. The results are presented as the calculated average color
differences of all samples. All calculations were performed using the program Octave 3.0.0
[42].
LINEARIZATION AND CHARACTERIZATION OF INKJET PRINTER

Defining Parameters
The first step was to define the substrate type (cotton, linen, blend of cotton and
polyester), the number and type of colors, and print quality. Each time, the type of substrate,
finishing and colors were changed to create a new color profile.
In one research [43], the quality of prints made with the inkjet printer Canon Image
Prograf W8400 using two different papers, matt coated and glossy photo paper, was
determined. In addition, the impact of Wasatch softRIP settings draft and high on the print
quality was researched. The software package ProfileMaker 5.0.8 was employed for the
creation of the ICC color profiles for both printing quality settings and both papers. The
results show that the changes in the RIP printing quality settings (draft vs. high) produced
only small differences in prints and when calculating color differences; it can hence be
59
concluded that the printing quality parameters, colorimetrically speaking, do not have any
special effect on the prints.
Achieving Repeatability and Optimal Color Gamut

In the second step, the printer was set to achieve the repeatability and optimal color
gamut:
A. Defining Ink Limit of Individual Color

The linearization chart (i.e., chart that contains color patches from 0 to 100% area
coverage of an individual CMYK color) was made in the ProfileMaker Pro 5.0 Measure Tool
(X-Rite, USA) and printed without color management. After the printing, spectral data were
measured using the spectrophotometer EyeOne, and the CIELAB and CIELCh values were
calculated. The CIELAB values were used to define the ink limit from the a*, b* diagram for
CMY (C cyan, M magenta and Y yellow) and from lightness L* in dependence of the
area coverage of K (K key, black ink) expressed in percent, L* (area coverage). An example
of the a*, b* diagram is represented in Figure 5. On the a*, b* diagram, the point (percent of
the area coverage) where the chromaticity C*ab stops increasing and the color hue hab starts
changing was determined, this point defining the ink limit. In the end, the ink limit was set on
Wasatch SoftRIP software (RIP Raster Image Processor). Figure 1 also represents the
difference in defining the ink limit on banner and textile substrates. It is evident that a banner
could accept more ink than the textile substrate.
B. Linearization
Afterwards, another linearization chart chosen from the Wasatch SoftRIP software was
printed and measured (Wasatch SoftRIP Setup Color Properties Halftone Properties
Calibration Calibration Curves). After the measuring and final linearization process, the
linearization chart was printed and measured once again to ensure that the linearization was
performed appropriately.
C. Defining Total Ink Limit (TIL)
This step included the printing of a chart with black patches printed with all four inks
(area coverage 0400%) and defining the color patch where the ink was not bleeding. In
general, this parameter was important when the test chart and the final ICC profile were
elaborated.
Creation of Test Chart

In the third step, the test chart was made in the program ProfileMaker Pro 5.0 Measure
Tool and printed.
The views of the professional public about how many patches are required for a quality
color description of devices vary; however, mostly there are generic test charts on which the
number of patches is related to the chosen type of print quality (draft, medium or high).
60
Figure 5. Defining maximum ink limit of cyan, magenta and yellow (above) and black (below).
The number of color patches also depends on the instrument used, since manually
measuring of test charts with a large number of color patches is very time consuming. There
are frequent speculations about the adequacy of too many color patches on generic color test
61
charts, which are used sometimes. The reflection in this direction is also triggered by the fact
that the process of the color profile creation is time consuming and expensive, as the creation
of the profile for a digital printer generally requires first pre- and then aftertreatments of the
textile substrate. At the same time, the digital printing technique, where it is necessary to
follow the customer requirements, results in frequent changes of textile substrates, which
should be followed by the color profiles. In practice, therefore, for the reasons described
above, color management is not yet fully implemented and most printers, instead of proper
color profiles for each substrate, use a color profile designed only for one type of textile
substrates. Accordingly, optimal results cannot be achieved and printers are only wasting their
time by editing colors in one of the programs. This method can be used in the case of very
small differences between the base substrate (for which the basic color profile was made) and
the new one.
In digital inkjet printing, a color test chart can be made, using programs which are
payable, e.g., ProfileMaker Pro 5.0 Measure Tool or free open source software, e.g., Argyll
CMS by Graeme Gill [44]. Although the creation of a color test chart and later the creation of
the ICC color profile using programs bring good results, the possibility to determine the
parameters and settings of the program is rather limited. With Argyll CMS, it is possible to
change a larger number of these parameters and, in this case, we know for certain, that the
algorithm used is OFPS (Optimized Farthest Point Sampling) for the production of the color
test chart with the help of which a point in the 4-dimensional space of the device (C, M, Y, K)
is allocated so that the distance between two individual points is minimized. The color test
charts differ in form, depending on the type of the instrument used for measuring. An
example of a color test chart for making the printer profile, made in the program
ProfileMaker, is shown in Figure 6.
Figure 6. Example of test chart for printer characterization.
62
For a color test chart made in one of the programs that make this possible (Measure Tool,
Argyll), we took into consideration the following:
number of colors with CMYK; we can also use other non-processing (spot) colors,
e.g., orange, green, blue (in case of additional colors, it is usually necessary to know
the CIELAB value),
maximum area coverage,
GCR (Gray Component Replacement),
black max maximum black (typically 100),
black start start adding black component (usually 10),
black width adding black component in saturated tones,
determine the number of fields of color on the color plate and
determination of the instrument used to measure the color test chart, as the layout and
size of the color patch depend on that.
After the color test chart is created, printing takes place the following day and the
measurement with the instrument which was set in its creation.
Figure 7. Comparison of color gamut for banner and textile in CIE a*, b* color diagram.
63
Creation of Color Profile

In the fourth step, the printed test chart was measured using the spectrophotometer
EyeOne and the ICC profile was made using ProfileMaker Pro 5.0. The generated color
profile has the extension.icc and contains information about the connection between the color
values of the device (in this case the printer), i.e., CMYK, and the color values independent of
the device, i.e., CIELAB or CIEXYZ.
The appropriately generated color profiles were used afterwards, for the print of a newly
designed plate with 725 color fields on the two media banner and textile. Figure 7 shows a
comparison of the color gamut for two different materials on which we wanted to achieve the
best possible reproduction by retaining all the details with the lowest optimal area coverage of
all colors (in both cases 100%). The details were controlled during the creation of a color
profile by adding extra color patches or boxes made of thin lines. Despite the same maximum
area coverage (TIL), i.e., 100%, the textile has a slightly larger color gamut, especially in the
area of blue and magenta (cf. Figure 7).
USE OF OPTICAL BRIGHTENERS
Figure 8. Reflection spectra of cotton fabrics, O1 treated with optical brightener, B bleached, O2
treated with optical brightener, instrument EyeOne, measured without UV-cut filter (O1 and B) and
with UV-cut filter (O2).
In the textile industry, optical brighteners (Optical Brightening Agents, OBAs or

fluorescent Brightening Agents, FBAs) colorless organic compound that fluoresces, are
used to enhance the whiteness on chemically bleached fabrics [47]. For the same reason, they
are used in detergents to optically increase the whiteness of laundered goods, in the
manufacture of plastics (added in the phase of polymer dissolution), in the fashion industry
64
and certain warning signs (emergency vehicles, buses, traffic signs etc) [46]. In one research,
a preparation of inkjet inks with fluorescent brighteners as antifraud markers for inkjet
printing on polyester and polyamide substrates was performed [47]. High whiteness of the
textile substrate enhances the contrast on the printed surface, allowing a more specific
appearance of the printed pattern and increases the color gamut of the print. Optical
brighteners absorb invisible ultraviolet light and convert it into visible light [48]. UV
radiation is near the blue area of the spectrum and therefore increases the reflection of light in
the blue area of the spectrum. Therefore, the substrate observed under natural daylight, which
also contains UV radiation, appears whiter. The most commonly used optical brighteners
absorb light at the wavelengths between 300 nm and 400 nm, and reflect it in the range of the
visible part between 400 nm and 480 nm [45], which results in increased reflection of blue.
The reflection spectra of the used materials are shown in Figure 9. The ISO whiteness (R
at 457 nm) for the banner is 87.69 and for the textile 95.84, measurements being made with
EyeOne without a UV-cut filter.
Figure 9. Reflection spectra of used materials.
Usually, spectrophotometers have a tungsten lamp with the color temperature of 2800 K.
A spectrophotometer measures the light reflected from the sample at selected wavelengths
and the result is given as a spectral reflection value between 0 and 100% (cf. Figure 8
Sample B). To produce an ICC color profile, the standard illuminant D50 is used. It is
therefore clear that the instrument measures the reflected light on a single type of light
(standard light A or white LED) and the result is given as the value of CIEXYZ under
different light (e.g., D50) with the use of a simple calculation.
65
The problem occurs when the measurement is performed on the substrate, which was
treated with optical brighteners. The latter disrupts the simple calculation, as the light is
reflected at a different wavelength than absorbed. This can lead to a shift in hue [49]. The
experiment results showed that the proportion of UV radiation of the light source affects the
color printed on the substrate which contains optical brighteners. Due to the impact of the
proportion of UV radiation, the color shade moves to the blue shade. The experiment results
also show that the proportion of UV radiation in the light source affects the colors close to
white and blue more than the colors close to yellow and black.
One solution is to use spectrophotometers containing a UV-cut filter, which can retain
UV radiation, whereas the second solution is to avoid the substrates with optical brighteners
for test prints the latter nowadays being almost impossible. A better solution is to use the
software which takes into account the effect of optical brighteners. To create a color profile in
ProfileMaker 5.0 (X-Rite), an optical brightener compensation (OBC) module is used to
compensate for optical brighteners in combination with the instrument i1iSis for an automatic
spectral measurement of color patches on the test chart with an included UV-cut filter, using
only UV radiation [50]. The Argyll program uses the algorithm FWA (Fluorescent Whitening
Agent) [51], which can successfully compensate for optical brighteners; however, it requires
the measurement of quantity and types of optical brighteners used on the substrate, and
sufficient information on the observation environment to predict the behavior/impact of
optical brighteners. To determine the amount of optical brighteners in the substrate, the
instrument must enable illumination of the sample with a certain level of UV radiation.
In the field of color management, for the creation of printer color profiles for a variety of
substrates that contain different amounts of optical brighteners, it is recommended to use
instruments which do not contain a UV-cut filter (cf. Figure 8) [51]. If the instrument contains
a UV-cut filter, it is not suitable to compensate for optical brighteners since they cannot be
activated. For this purpose, Greame Gill developed the algorithm to compensate for them.
The X-Rites compensation module (OBC) is the industrys first integrated module that takes
into account the amount of the optical brightener on various substrates [50].
The most common example of using the FWA compensation is the creation of test prints
(hard proof) when the two media contain a different level and type of optical brighteners, i.e.,
the paper on which the hard proof is performed and the print. The use of the FWA
compensation in the generation of color profiles for output devices and for the devices on
which we are going to perform a test print, and also the use of the absolute colorimetric
rendering intent can lead to very good colorimetric matching.
TEST PRINTS
A test print presents in the process of printing a very important step, since it accurately
displays the appearance of the final print. The test print can be seen on the display screen (soft
proof) or it can be printed on a different printer or on a dedicated printing machine (hard
proof). Using print simulations on a screen or test print allows us to simulate certain color
patterns on any other output device with a proper creation of color profiles for any device
both input and output. A simulation of the print on a screen is cheaper than the test print on a
66
printer. In this case, we encounter two media, i.e., observation on the screen and observation
of prints on paper [52, 53].
This could lead to variations in the color perception:
1
2
3
due to possible differences in the color gamut of devices a screen usually has a
larger color gamut than a printer or printing machine,
when performing the simulation of a print on the screen, only substrate whiteness can
be simulated and not the feel of the substrate,
simulation of the print on a screen depends on the screen light source, which means
that in this case, we are dealing with a self-luminous medium and in the case of the
print, with a reflective medium.
The introduction of color management in the field of textiles has increased the possibility
of faster and easier preparation of the color pattern for printing. Moreover, it can lead to
controlled, high quality and repeatable color print on a textile substrate. Due to the high price
of inks for digital textile printing and costs associated with the preparation and then
aftertreatment of printed textiles, especially when using reactive dyes, a simulation of the
print on a display screen and the execution of the test print on paper are even more important.
Figure 10. Comparison of color gamut of printers in CIE a*, b* diagram.
The simulation of prints was conducted with a laser printer (Canon Image Press C1+) and
an inkjet printer (Canon Image Prograf W8400), using CMYK [37]. For the color
transformations from the source printer (Mimaki) to proof printers (both Canon), an absolute
67
colorimetric rendering intent was used for the simulation of prints. This intent
colorimetrically transforms in-gamut colors from the source to the destination color space
taking into account the change of the media white point (using chromatic adaptation
transform to the standard illuminant D50), while the out-of-gamut colors are clipped to the
gamut boundary of the destination color space.
On the basis of the average values of color differences of all samples between the original
colors (print on inkjet printer Mimaki) and simulated prints (print on inkjet printer Canon and
laser printer Canon), it was established that a print simulation on an inkjet printer is better
than the simulation on a laser printer. The color gamut of the inkjet printer, i.e., Canon 1, is in
the whole color range larger than the color gamut of the laser printer, i.e., Canon 2, while it is
the smallest at the inkjet printer for textiles, i.e., Mimaki (cf. Figure 10). The CIELAB
diagram shows that the inkjet printer colors are more saturated than the colors from the laser
printer (cf. Figure 10).
Prior to the analysis, each sample was categorized according to the magnitude of its E00
value into one of the four groups: 01 (color difference undetectable with a human eye), 13
(small color difference between two patches) [54], 36 (perceivable difference) or > 6 (large
difference). At the average color differences for 0 < E00 < 1, it was established that both
printers simulate very well to approximately the same extent. Nevertheless, differences
occurred with regard to the number of colors, since the inkjet printer simulated well
(1 < E00 < 3) a larger number of samples (733) than the laser printer (457) (cf. Table 1).
Both printers simulated equally well a larger number of colors for 3 < E00 < 6.
Table 1. Number of color patches in dependence of E00, simulated with laser
and inkjet printer
E00
01
13
36
>6
laser Canon
32
457
983
400
inkjet Canon
40
733
914
185
COLOR INCONSTANCY INDEX CMCCON02

An important component that creates a visual impression of the color and color change,
apart from the observer, is light. To ensure the matching of two colors, samples should be
observed under a number of different light sources. While most offices have illuminations
that include fluorescent lights (illuminants from F1 to F12) and at home, the incandescent
light (illuminant A) is used most frequently, daylight is most important outdoors [55]. The
CIE recommended several standard daylight illuminants with the color temperatures at 5000
K (known as D50), 5500 K (D55), 6500 K (D65) and 7500 K (D75) [56]. A problem arises
when the colors of two materials with a different surface structure (textile substrate and
paper) should match under a particular illuminant. To determine the illuminant influence on
the change in the color appearance of samples, i.e., textile fabric and their proofs on paper
under different illumination, the color constancy of samples was defined as well. The color
constancy was computed using the color inconstancy index CMCCON02, which uses the
68
CAT02 chromatic adaptation transform and is the current recommendation by CIE [40, 57].
Furthermore, the recommendation has been incorporated into the ISO Standard 105 [40].
Calculation of CMCCON02
The color constancy of samples was investigated with the calculation of the color
inconstancy index CMCCON02. To calculate the color inconstancy index, R, G and B, which
describe cone responses, were calculated with Equation 1 [40, 41, 58]:
R
X
G M

CAT 02 Y

B
Z
(1)
where
M CAT 02
0.7328 0.4296 0.1624

0.7036 1.6975 0.0061
0.0030 0.0136 0.9834
(2)
Rw, Gw and Bw were calculated from tristimulus values under the test illuminant
(Equation 3):
Rw
X w
G M

CAT 02 Yw
w
Bw
Z w
(3)
Rc, Gc and Bc are cone responses for the reference illuminant (D65) (Equations 46):
R
Rc R D wr
Rw
1 D
(4)
G
Gc G D wr
Gw
1 D
(5)
B
Bc B D wr
Bw
1 D
(6)
69
where Rwr, Gwr and Bwr represent the cone responses to the reference white under D65
reference illumination. D is the degree of adaptation. The calculation of the CMCCON02
index for the samples of such textiles recommends that D be set to 1.
The calculation of tristimulus values of a corresponding color in the illuminant D65 is
represented in Equation 7:
Rc
Xc
Y M 1 G
CAT 02 c
c
Bc
Z c
(7)
where
1
CAT 02
1.096124 0.278869 0.182745

0.454369
0.473533 0.072098
0.009628 0.005698 1.015326
(8)
On the basis of the color difference (where the CMC (1 : 1) equation was used) between
the reference (XYZ values under reference illuminant D65) and chromatic adaptationtransformed values, the CMCCON02 index was computed. Usually, it is important to
calculate the CMCCON02 index, since the standard illuminants A (incandescent light), F2
(CWF cold white fluorescent light) and standard daylight illuminants, e.g., D50, D55 and
D75, are the most commonly used.
Figure 11. Average color inconstancy index for illuminants A, D50, F2, D55 and D75, reference
illuminant D65 for prints made on cotton fabric (Mimaki) and paper (laser and inkjet Canon).
70
Figure 12. Average color inconstancy index for illuminants A, D50, F2, D55 and D75, reference
illuminant D65 for prints made on banner and textile (inkjet Canon).
Figure 13. Spectral power distributions of A, D50, D55, D65, D75 and F2.
The results of the average CMCCON02 index lead to the conclusion that lower average
index values were obtained when using daylight D75 followed by D55, D50, while A and F2
had the highest CMCCON02 index (cf. Figures 11 and 12) [37]. The latter was also expected,
since the illuminants D50, D55 and D75 are according to the spectral power distribution fairly
similar to the illuminant D65 (cf. Figure 13), while the illuminants A and F2 have a
fundamentally different spectral power distribution. The highest average CMCCON02 index
was acquired when the transition from the fluorescent light F2 to D65 was performed.
In the case of prints made on the cotton fabric and Mimaki printer, the CMCCON02
index was lower than in the transition from A to D65, whereas in the case of prints made on
71
the textile and Canon inkjet printer, the CMCCON02 index was higher than in the transition
from A to D65. From the research results, it could be concluded that the illuminants A and F2
are not appropriate for the comparison of all colors, especially in the case of a simulation with
an inkjet printer Canon, since the average CMCCON02 index > 5 in the first case (cf. Figure
11) and > 3 in the second case (cf. Figure 12).
MOTTLING
Print mottle can be defined as perceived inhomogeneity in the solid print area due to the
variations in the reflectance of the printed surface. The emphasis is on perceived
inhomogeneity, since perception is often not in linear correlation with the physical
characteristics of the print.
Print mottle can be stochastic, with randomly distributed noise, or systematic, with
periodic and/or regular pattern (bands, streaks or even more complex textures). Both forms
are common on the prints made with inkjet printing systems. From the aspect of inkjet
printing, mottle is primarily caused by incompetent properties of the printing substrate or a
malfunction of the printing process (print head or substrate movement) [59].
In recent years, several methods have been proposed for the evaluation of print mottling
[6064]. In spite of the similarity in some segments, they differ from each other in basic
principles, their complexity and limitations. In this paper, the method proposed by the
German Printing Association FOGRA was used to determine the level of print mottle on both
materials. The M-Score (i.e., Melcer-Score) method is based on analyzing the color difference
(CIE DE2000 is recommended) in the vertical and horizontal direction. Despite M-Score not
taking the human visual system directly into account, the results correlate well with the
perception of mottling when mottling takes a systematic form [42].
For the sake of simplicity, M-Score computes a single value between 0 (poor
reproduction clearly visible mottling) and 100 (no mottling present). For more precise
interpretations of the obtained values confer Table 2.
Table 2. Interpretation of M-Score values
M-Score
> 95
Meaning
Perfect
> 80
Very Good
> 70
Good
> 60
Satisfactory
> 50
Adequate
< 50
Poor
Comments
No visible inhomogeneity
Print with slightly visible inhomogeneity. Randomly distributed noise,
no periodic or systematic structures.
Print with visible randomly distributed inhomogeneity, but almost no
visible periodic or systematic structures.
Visible randomly distributed and systematic inhomogeneity. Still
accepted by most observers.
Clearly visible randomly distributed and systematic inhomogeneity.
Acceptance is dependent on printed image.
Clearly visible randomly distributed and systematic inhomogeneity.
Not accepted as high quality print.
72
The test form used in this study was generated on the basis of ISO 12647-8 [65] and
consists of three large solid areas of sizes 29.2 18.4 cm. The following tone value
combinations were used (cf. Figure 14):
a).= C: 65%, M: 50%, Y: 50%, K: 50%;
b).= C: 40%, M: 30%, Y: 30%, K: 30%;
c).= C: 20%, M: 15%, Y: 15%, K: 15%.
Figure 14. Test form based on ISO 12647-8.
According to the size of solid area, 984 measurements (41 patches in the horizontal and
24 patches in the vertical direction) were performed by the spectrophotometer EyeOne Pro
and automated scanning table iO (X-Rite, USA).
Algorithm:
1
2
3
Print test forms with large solid (uniform tint) areas, using tone value combinations
defined in ISO 12647-8.
Measure all patches in each test form with a spectrophotometer and average CIELAB
measurements across the lines and columns to get vertical and horizontal profiles.
Compute CIELAB color differences (E00) between neighbor profiles and sum them
up separately for the vertical and horizontal projection, according to Equation 9:
73

n1
Evertical 10 Ei (LABi , LABi1 )

i1
m1
Ehorizontal 10 Ei (LABi , LABi1 )
(9)
i1
where m is the number of patches in the vertical direction and n is the number of patches in
the horizontal direction.
4
Normalize and sum up color differences to get general Egen (Equation 10):
Egen
5
Ehorizontal Evertical
m 1
n 1
(10)
Compute M-Score based on exponential transformation of general E00, as shown in

Equation 11:
M Score 100
2
2 Egen
15
(11)
Table 3. Computed M-Score values

Tone Value Combinations (%)
20/15/15/15
40/30/30/30
65/50/50/50
Average
Figure 15. Results of mottling analysis.
M-Score values
textile
70.42
75.59
84.16
76.72
banner
81.77
70.72
65.31
72.60
74
It is evident from the results that inhomogeneity occurred on both materials, commonly
as randomly distributed noise and rarely as periodic or systematic structures.
As it can be seen from Figure 15 and Table 3, inhomogeneity is slightly more visible on
the banner, especially on the prints with larger tone value combinations (darker area).
However, on the prints with small tone value combinations (light area), inhomogeneity is
more distinguishable on the prints made on the textile substrate.
It should be noted that the testing performance of the M-Score method (correlation
between results and visual perception) is not within the scope of this paper and could be
included in future work.
TESTS FOR COLOR FASTNESS

For the material printed on a textile substrate, for an indoor and outdoor presentation, to
be exposed to light for a longer period of time in various weather conditions sun and rain, it
makes sense to analyze the stability of color patterns to these conditions.
The tests for color fastness on both substrates banner and textile, were made on a
Xenotest Alpha (Atlas, USA) according to the standard SIST ISO 105-B02 [66], SIST ISO
105-B04 [67] under the following conditions:
measurement and control of irradiance (42 W/m),

temperature in test chamber (35C),
relative humidity (dry conditions: 70%, wet conditions: 35% for 29 min and 100%
water spray for 1 min),
filter: WINDOW GLASS (320 nm) in the case of SIST ISO 105-B02 and
XENOCHROME 300 (300 nm) in the case of SIST ISO 105-B04.
The results of color fastness are represented in Tables 47. Color measurements were
performed with the instrument EyeOne after 16 and 32 h in the case of exposure to water
spray, and after 30 and 72 h in the case of exposure to artificial light.
Table 4. Tests for color fastness after exposure to rain made on banner
Ink/area coverage (100%)
C/100
M/100
Y/100
K/100
C/50
M/50
Y/50
K/50
E00
after 16 h
2.78
1.95
1.24
1.56
2.71
2.62
1.00
3.01
after 32 h
2.74
2.28
1.66
1.78
2.76
2.95
1.47
3.15
75
The color differences in the case of the banner after the exposure to rain are within the
acceptable ranges (less than 6, maximum value is 3). The differences between 16 and 32 h are
very small, regardless of the coverage area (50 or 100%).
Table 5. Tests for color fastness after exposure to artificial light made on banner
C/100
M/100
Y/100
K/100
C/50
M/50
Y/50
K/50
E00
after 30 h
1.90
1.01
1.03
1.26
2.60
2.33
1.04
2.59
after 72 h
2.27
1.45
1.05
0.79
2.67
2.63
0.81
2.98
The color differences in the case of the banner after the exposure to artificial light are
acceptable, in the case of cyan, magenta and black with the area coverage of 50% being
slightly higher.
From the color differences calculated for the banner, it can be concluded that the printed
substrate, i.e., banner, is appropriate for both indoor and outdoor posters for promotional
purposes, since the color differences are still acceptable after 32 h of exposure to rain and
72 h of exposure to artificial light.
Table 6. Tests for color fastness after exposure to rain made on textile
C/100
M/100
Y/100
K/100
C/50
M/50
Y/50
K/50
E00
after 16 h
2.87
2.84
2.93
4.03
1.67
2.37
2.37
0.59
after 32 h
2.65
3.69
3.39
3.56
1.62
2.83
2.82
0.99
The color differences in the case of textiles after the exposure to rain are acceptable in all
cases. The maximum E00 is in the case of black (100%) after 16 h.
The color differences on textiles after the exposure to illumination after 30 h and 72 h are
acceptable (less than 6). The maximum value of E00 is 3.46 in the case of yellow (50%) after
72 h.
From these results, it can be concluded that the printed textile substrate is also suitable for
indoor and outdoor applications, the same as the banner. The results on the banner are slightly
better, as E00 is smaller.
76

Table 7. Tests for color fastness after exposure to artificial light made on textile

C/100
M/100
Y/100
K/100
C/50
M/50
Y/50
K/50
E00
after 30 h
1.81
1.76
1.83
2.16
1.50
2.05
2.15
0.31
after 72 h
3.03
1.90
1.96
2.75
2.41
2.80
3.46
0.51
CONCLUSION
In this work, we presented digital inkjet printing on textile substrates and the importance
of using color profiles made for a particular substrate, ink and pretreatment chemicals. The
reactive dyes are the most commonly used dyes that create the covalent chemical bond
between the dye and fibers, while the unreacted dye is washed off from the fabric with an
aftertreatment in various washing baths. On the paper itself and on the promotional substrates
printed with the inkjet printer Canon, the whole print remains on the surface; therefore, the
simulation procedure is a complex process, which requires apart from the knowledge on the
textile substrate and printing ink, and their physical-chemical characteristics also the
knowledge in the fields of color measuring, physical principles of the printing and the
knowledge of hardware and software.
By calculating the color inconstancy index CMCCON02, the illuminant influence on the
color change of the substrates under different illumination could be determined. From the
results of the CMCCON02 index, it could be concluded that simulated colors should be
compared with original colors under daylight illuminants (D50, D55 and D75), while the
indoor illuminants A and F2 are not appropriate for a comparison of all colors.
The research results of the print simulation on paper demonstrated that most colors from
the printer Mimaki (color difference up to 6) could be fairly successfully simulated on a
Canon laser and inkjet printer, whereby slightly better results were acquired with an inkjet
printer. The experimental prints on paper are cost- and time-saving, since the pre- and
aftertreatment of the textile substrate are in comparison with paper obligatory.
In order to determine the level of inhomogeneity on both materials, we examined test
charts with three different tone value combinations using the M-Score method, described in
the methodology section. It is evident from the results that inhomogeneity occurred on both
materials, commonly as randomly distributed noise and rarely as periodic or systematic
structures.
The results of testing the lightfastness and weatherability of the substrate with a Xenotest
shows that the printed substrate, banner and textile, are both appropriated for both indoor and
outdoor posters for the promotional purposes, the results of E00 being slightly better in the
case of the banner.
77
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ISBN: 978-1-63117-262-5
Chapter 4
INKJET PRINTED PHOTO-RESPONSIVE

TEXTILES FOR CONVENTIONAL AND
HIGH-TECH APPLICATIONS
Shah M. Reduwan Billah*
Department of Chemistry, Durham University, Durham, UK and
The School of Textiles and Design, Heriot-Watt University, Galashiels, UK
ABSTRACT
Inkjet printing technology, a modern non-impact printing technique, is in the process
of revolutionizing the whole printing industry, including textile printing, for producing
almost any print design on textiles within a very short time. It provides inkjet printing a
cutting edge over other conventional printing techniques. Photo-responsive inkjet printed
textiles have many applications, some of which include, fashion and design, selfindicating alert systems, anti-counterfeit, security and brand protection. Both
photochromic dispersed and photochromic acid dyes can be used to formulate inkjet inks
to produce photo-responsive inks for inkjet printing on different types of textiles (for
example, cotton, wool, silk, nylon) for potential conventional and high-technology
applications. Formulation of inkjet inks using functional dyes, such as, photochromic
dyes needs proper care for producing jettable inks which can retain functional behaviour
for a considerable period along with other desired properties (for instance, high print
quality and robust technical performances of printed textiles). In addition, the porosity of
the substrate plays a significant role on the absorption or penetration behaviour of an
inkjet ink or more simply regulates its spreading on a substrate thus controlling inkjet
printed image quality and the technical performances of an ink to some extent. As a
result, it is necessary to control a number of influencing factors to produce desired high
quality printed responsive substrates with good technical performances for various
applications. This chapter briefly point out some of these issues along with the
applications of inkjet printed textiles for a variety of conventional and high-tech
applications.
Dr. Shah M. Reduwan Billah, 7 Laurel Grove, Galashiels TD1 2LA, Scotland, UK, E-mail: reduwan.
shah@gmail.com or s.m.r.billah@durham.ac.uk.
82
Keywords: Inkjet printing, photo-responsive, printed-textile, conventional and high-tech

applications.
INTRODUCTION
Inkjet printing, a non-contact printing technology, allows deposition of ink droplets on
various substrates, such as, textiles, paper, leather, ceramic, glass and also on many other
substrates for different purposes [1-7]. It is capable to meet the market demand for producing
samples and product within a very short time compared to screen printing technology and also
suitable for mass customisation along with the scope of adaptation to unlimited design
possibilities with respect to repeat size and colour range. Inkjet printing techniques can also
be used for the digital dyeing of textiles using a very innovative technique where the
colorants and related additives can be applied on the substrates in the form of a jettable ink
disposing through the inkjet print head which is commonly used for inkjet printing
technology. Inkjet printing techniques are increasingly gaining the momentum to produce
very high quality printed substrates using a wide variety of materials, including, conventional
dyes, functional dyes, pigments to meet the demand for a wide variety of coloured substrates
for their different applications. Photochromic dyes are classed as functional dyes which
usually change the colour from a colourless state to a coloured state when exposed to UV
light or sunlight and the inks produced using these dyes also retain the same functional
character to impart this unique colour change behaviour to inkjet printed substrates making
them suitable for a huge range of applications. For a better understanding on the nature of
photo-responsive inkjet printed textiles which is the main concern of this chapter it is
important to briefly discuss different aspects of inkjet printing technology and also to analyse
its features which made it so important as a technique to draw very high attention both in
academia and in industry to replace conventional printing techniques with this technique.
A Brief Historical Overview on Inkjet Printing

The idea of inkjet printing goes back to the eighteenth century when Abb Nollet
published his experiments where he analysed the effect of static electricity on a stream of
droplets in 1749 [8]. After almost a century later, in 1833, Felix Savart found that an acoustic
energy could be used to break up a laminar flow-jet into a train of droplets and Joseph Plateau
investigated the formation of liquid jets from nozzles in 1856 which in turns forms the basis
of modern day inkjet printing technology [9]. However, it was only between 1858 and 1867
when Lord Kelvin at first developed inkjet like recording device for recording signal of the
Atlantic Cable [10]. The Belgian physicist Joseph Plateau (in 1856) and the English physicist
Lord Rayleigh (in 1878) studied the break-up of liquid streams and are, therefore, considered
as the founders of modern inkjet printing technology [11].
After these different pieces of theoretical work at different times, the first actual form of a
continuous inkjet printing device was patented by Elmqivist of Siemens-Elma in 1951 [12].
Then after a relative short period of time there was significant development in the field of
inkjet printing technology. In 1965, M. Naiman at first patented thermal inkjet where he
Inkjet Printed Photo-Responsive Textiles for Conventional and High-Tech
83
developed a sudden stream printer [13] and Richard G. Sweet patented device for direct
writing signal using fluid droplet recorder [14]. In 1972, Steven I. Zoltan of Clevite
Corporation, USA patented a squeeze mode piezoelectric inkjet print head for pulsed droplet
ejecting system [15]. After that in 1973 Nils Gustaf Erick Stemme of Sweden patented bend
mode piezoelectric inkjet print head which he used it for writing on paper with coloured
liquid using the device and also stated the detail mechanism of writing system [16]. In 1976,
Sears et al., patented certain method and apparatus for recording with writing fluids and drop
projection systems [17]. In 1984, Stuart D. Howkins of Exxon Research and Engineering,
USA patented push mode piezoelectric inkjet print head and explained the detail operating
principles of a push mode piezoelectric print head [18]. Since then there is a huge upsurge in
the development in the field of inkjet as a micro-disposal technique also as a technique for
inkjet printing on textiles. Figure 1 shows a brief history of different stages of development in
inkjet technology in the form of a chart presentation.
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History of Inkjet Printers for Textile Printing

Introducing colour in our surrounding environments and also into our life styles involves
a huge variety of arts, sciences, technologies, businesses and industries- where textile printing
for producing lucrative colourful design enjoys a significant importance. The findings during
different archaeological excavations to explore the nature of civilization in ancient Egypt bear
84
the hallmarks of textile printing which used to be carried out using curved wooden printing
blocks [19]. In Europe textile printing industry flourished in a much later date which is
evidenced by the discovery of first crafted textile printing samples in 15th century. During 18th
century there was a remarkable growth in textile printing particularly in the UK reaching at its
zenith just before the First World War which trend faced a gradual decline after the war and
this decline continued at a higher speed even after the Second World War [20].
The introduction of new fibres and also new colorants (such as, reactive and disperse
dyes) contributed for a significant development in textile printing during the second half of
the 20th century [21]. However, it is very interesting to observe that textile printing saw a
significant competition between different techniques at the last few decades of 20th century.
For example, screen printing, especially with rotary screens, has continued to replace roller
printing and during this period new machinery with level of sophisticated control was
introduced into the printing industry [22]. A precise alignment of screens using digitally
controlled electromechanical systems is a notable achievement of this time which at present
controls around 80% of all printed textiles which are produced by using flat o rotary screens
[23, 24].
Inkjet Printing of Textiles

Textile dyeing and printing industry is in the verge of new digital era where digital
solutions are increasingly playing an important role as the intensity in competition between
the level of versatility and flexibility available in different printing processes are intensified.
Digital printing and analogue printing use different type of techniques for representing data
and methods during print reproduction. In the analogue systems if the computer is used it is
used to make a variation in continuous phenomena such as voltage or pressure during the
transmission of print data, however, in the digital printing systems digital signals are
transmitted using computers which completely rely on discontinuous pattern transmission
using discrete amount of electricity or light for data communication [25]. In usual terms
digital printing covers a range of technologies including, inkjet printing, thermography,
electrophotography, electrostatic printing, ionography and magnetography. In all these cases
digital data may be used to produce images. Inkjet printing technique has the highest potential
compared to these other techniques for textile applications [26]. Table 1 demonstrates a brief
historical review on the significant development on the direct inkjet printing of textiles from
1975 till 2004 and after that period the inkjet printing of textiles has reached to maturity stage
in a number of areas which is beyond the scope of this current chapter.
It is important to note that relative contemporary developments from different companies
also contributed to the direct inkjet printing of textiles, some of which are, development of
Fast Jet single pass print head of Inca Digital, M class piezo MEMS and water tolerant
piezoelectric print head from Spectra, Xaar 1001 series print heads, Picojet 256 all stainless
piezoelectric print heads from Picojet and also the improvement of pigmented binder-less
inkjet inks by BASF have profound impacts on the total development process. Additionally,
developments in the areas of sublimation ink and sublimation transfer printing techniques
have significant contributions on the indirect digital printing of textiles. Some of the most
important developments are (a) Roy DeVries sublimation transfer printing method in 1974,
(b) Donal Hare T-shirt decoration method in 1978, (c) inkjet sublimation method by
85
Crompton and Knowles in 1982, (d) RPL-QLT inkjet sublimation method in 1988, (e) Saw
grass patent on sublimation ink in 1991, (f) development of Fotoware-Canon inkjet transfer
paper in 1994 and (g) soft link method by Hanes in 1999 [27].
Table 1. A brief historical overview on the significant developments on the direct inkjet
printing of textiles
Year
1975
1976
1990
1993
1996
1997
1998
2001
2002
2003
2004
Significant developments
Milliken-Millitron carpet printer
Zimmer-Carpet printer
Seiren-Parallel processing
Embleme-Water UV direct T-shirt
Perfecta/Zund-Flatbed
Rhome Revolution-Direct T-shirt
Encad and Mimaki-Textile proofing
L&P-UV-curable textiles and Dupont Artisti 3210
Mimaki-GP 0604
Mimaki TX 3, DupontArtisti 2020, L&P UV-cure dye, Robustelli
Mona Lisa,
Reggiani DReAM, Zimmer Chromotex
USSPI Fast T-Jet & USSPI Fast T-Jet Jombo,
Kornit 930 and Kornit 931
Inkjet Printers for Textiles

Inkjet printing systems are used different areas of textile printing, some of the most
widely used areas are fashion accessories, sports and swimwear, home textiles (e.g.,
curtains, sheets, towels, table settings, furniture upholstery), flags and banners, t-shirts and
specialties, automation and transportation upholstery, architectural textiles, medical textiles
(e.g., trans-dermal dosing) and also in some types of technical textiles. Some of the most
notable inkjet printers used for digital textile printings are Colorspan Display Maker XII,
Mimaki TX2 and TX3, Dupont Artisti 2020, Legget & Platt UV-dye, Robustelli Mona Lisa,
Reggiani DReAM, Zimmer Chromotex and Imaje-Osiris. For direct T-shirt printing different
types of inkjet printers are used, some of which are Mimaki (e.g., Mimaki GP-1810,
Mimaki GP 604) and Kornit (e.g., Kornit 930, Kornit 931) printers. Digital inkjet printing
of textiles can be divided into different categories, such as wide format direct, wide format
indirect, single pass printing and inkjet T-shirt printers [27, 28].
Inkjet Print Head Technologies

All inkjet technologies are basically precise micro-disposal techniques where digitally
controlled the fluid droplets (e.g., the inks) are ejected from the print head onto a substrate.
Various techniques can be used for a digital control on the fluid droplet ejection from the
print head to the substrates which are sometimes used as a basis for the classification of inkjet
86
print heads. For example, continuous inkjet printing technique or drop-on-demand inkjet
printing technique are two mostly used terms for a broader classification of industrial inkjet
printing technology (although there are variants within each class). The print head that uses
continuous inkjet technology ejects drops continuously (Figure 3) where the drops are either
directed to the substrate or to a collector for recirculation and reuse. On the other hand, the
print head which uses drop on demand type inkjet printing technology ejects drops only when
required (Figure 4). A brief classification of inkjet print heads are shown in Figure 2.
Continous inkjet print heads are of two type in terms of the use of inks continuous
inkjet print heads which uses aqueous inkjet inks (such as, Kodak, Versamark) and
continuous inkjet print heads which uses solvent or UV curable inks (such as, Danaher,
Dover, Domino, ITW, Mathews). In this same sense, drop-on-demand print heads can be
divided into different classes- (a) thermal inkjet print heads which only use aqueous inks
(e.g., Hewlett-Packard, Cannon, Lexmark, Kodak), (b) piezoelectric print heads which use all
types of inks (e.g., Epson, Dimatix, Xaar, Richoh, Konica-Minolta, Toshiba Tec, Panasonic)
and (c) valvejet print heads which mainly uses solvent based inks, however, they can be used
for all types of inks (e.g., VideoJet, Imaje, Crayon, Loveshaw, Kortho, Foxjet, Miliken,
Zimmer, Danaher, Dover, Domino, ITW, Mathews). However, based on deflection mode
continuous inkjet print heads can be divided into two categories (a) binary (such as, Stork,
Scitex, Iris, Siemens, Domino, Kodak, Versamark) and (b) multi-deflection (such as,
VideoJet, Danaher, Imaje, Dover, Linx, Willet). Based on printed head technologies,
piezoelectric print heads are of five types, they are push mode (e.g., Ricoh, Trident, Brother,
Epson), bend mode (e.g., Sharp, Epson, Xerox, PicoJet, Dimatix Samba & M-class, Kyocera),
squeeze mode (e.g., Siemens, Gould), shear wall shear mode (e.g., Xaar, Konica, Minolta,
Toshiba Tec, Seiko II, Brother, Kodak, Microfab) and shear mode (e.g., Dimatix) [27, 28].
Figure 2. A schematic representation of the classification of the inkjet print heads.
87
Continuous Inkjet (CIJ) Printing Technique

Continuous Inkjet printing is an amateur micro-disposal technique popularly used for
marking and coding of products and packages. In a CIJ disposal technique, a pump directs
fluid from a reservoir to small nozzles that eject a continuous stream of drops at high
frequency (in the range of roughly 50 kHz to 175 kHz) using a vibrating piezo crystal. In
addition, the drops are charged using an electrostatic field which are then allowed to pass
through a deflection field to determine landing position of the charged the drops while at the
same time the unprinted drops are collected and returned to the reservoir for reuse. The high
drop frequency of continuous inkjet micro-disposal system makes this technique suitable for a
direct translation into a very high speed printing system as evidenced by such applications as
the date coding of beverage cans using continuous inkjet printing technique. It also shows
very high drop velocity which allows micro-disposal at relatively (compared to other inkjet
technologies) large distances from the print head to the substrate for useful in industrial
environments. CIJ shows advantage over other inkjet technologies in its ability to use inks
based on volatile solvents that allow rapid drying and aiding in adhesion on different
substrates. However, CIJ shows relatively low print resolution but requires very high
maintenance and environmentally not friendly due to the use of volatile solvent-based fluids
which need to be charged for printing.
Figure 3. A schematic representation of a continuous inkjet printing system.
In principle, the continuous inkjet printers apply a pressure wave pattern to an orifice in
order to break a continuous liquid jet into droplets of equal size and spacing. During the
formation of droplets they are selectively charged and the stream of drops is passed through
an electric field to deflect the charged droplets. According to the nature of the printer either
the charged or uncharged drops are used for image generation while the unused drops are
collected for recirculation. Based on the mechanism of image generation, the continuous
inkjet printers may be of different types, such as, (a) the binary or multiple deflection, (b)
88
hertz, and (c) microdot types. The continuous printers are mostly used in industrial marking
processes and also in the field of graphic arts. These printers usually generate a smaller drop
size, a high drop velocity, and a higher drop generation rate (up to 1 MHz) compared to other
inkjet printers. However, they are expensive and difficult to control the satellite drop
formation. Figure 3 illustrates a schematic diagram of a continuous inkjet printing system [29,
30].
Drop-on-Demand Inkjet (DOD) Printing Technique

In broad terms it refers to an inkjet technology which allows the micro-disposal of inkjet
inks (in the form of droplets) when required using pressure pulse. In addition, DOD print
heads are classified in different sub-categories based on the technique which is used to
generate this pressure pulse and these are thermal, piezo and electrostatic. Besides these
print heads, MEMS print heads are also often merged into this drop-on-demand type of print
heads which are invariably still based on either piezo or thermal inkjet technology. In a drop
on demand type inkjet print head, it uses a vacuum method to control drops and eject only
when the drops are in demand. It applies a negative pressure in the print head to keep the ink
inside until a local pressure wave at the nozzle is generated which can eject a droplet. DOD
inkjet print heads are more advanced compared to continuous inkjet print heads as they are
free from some requirements which are highly required in the continuous print heads, such as,
starting up and shutting down, complicated charging, deflection hardware and also the need
for an ink recirculation unit. Different pieces of work for producing inkjet printed high
performance photo-responsive surfaces reported in this chapter has widely used piezoelectric
inkjet print head (DOD Xaar Omnidot 760) so this chapter will briefly cover different aspects
of piezoelectric printing technology along with other print head technologies [31, 32].
Thermal Inkjet Technology

In a thermal inkjet system, drops are generated from a rapid heating of a resistive element
(of the print head) in a small chamber containing the ink. During the heating of the resistive
element temperature rises very fast (such as, from 350C to 400C) that causes a vaporisation
of a thin film of ink above the heater for a rapid creation of a bubble that in turns creates a
pressure pulse to force the ink (in the form of a droplet) through the nozzle. When the drop is
ejected it leaves a void in the ink chamber which is subsequently replaced and filled by the
ink in preparation for the creation of the next drop for a continuation of this droplet formation
(in Figure 4A, illustrates a thermal inkjet print head).
Thermal inkjet print heads are comparatively cheaper and have the potential in producing
very small drop sizes along with higher nozzle density suitable for compact devices.
However, the print head must have to withstand the effects of ultra-high local temperature
which is usually used to vaporise the ink for the creation of ink droplet in the form of the
bubble. Thermal inkjet inks are usually based on aqueous systems and the ink formulation
needs significant level of accuracy; otherwise, there are chances to form a hard coating on the
resistive element which in turns limits the efficiency of the print head causing a total failure in
89
long term. This type of print head is not suitable to dispose most of functional inks because
the high temperature often has very high detrimental effect on the functionality [33, 34].
Principle of Operation for a Piezoelectric Print Head

A piezoelectric print head uses a piezoelectric element (such as, lead zirconate titanate or
PZT) to modulate a pressure based deformation on the ink flow for the physical displacement
of the ink droplet by the way of sending the electrical impulse. For printing an electrical
impulse is sent to a piezoelectric element of the print head to cause physical displacement by
way of changing the elongation or bends of the piezoelectric element. This physical
displacement creates a volumetric change in the nozzle chamber to produce a pressure wave
to push the droplet through the nozzle orifice. Figure 4 shows a schematic representation of
different print heads (A) thermal, (B) piezoelectric and (C) electrostatic.
Piezoelectric print heads have comparably higher manufacturing costs although they have
a long operation life. This high manufacturing cost is one of the main limitations of the
piezoelectric print heads which categorically hinders the miniaturisation of the nozzles. In
addition, piezoelectric print heads are also sensitive to the air bubbles trapped in the nozzles
which also limits their printing qualities. It is an important requirement for the inks to be used
the piezoelectric print heads that the ink must remain incompressible in order to maintain a
controllable propagation of mechanically generated pressure waves in the nozzle chamber.
Air bubbles in the nozzle disturb this condition and de-gassing operation should be carried out
to remove the air or dissolved gases before actual printing. It is commonly used technique to
purge a considerable amount of ink through the print head before printing in order for
ensuring the total removal the air or bubbles to produce high quality printing images or high
quality disposal of inks to a desired substrate [35, 36].
Piezoelectric drop-on-demand inkjet printers are usually used in graphic designs, textile
printing, commercial printing, industrial and digital fabrications and also in biomedical
applications. Thermal piezoelectric print heads are normally used as desktop printers and also
used in graphics, commercial and biomedical printings. Electrostatic drop-on-demand print
heads mostly used in the printing on beverage cans while valve jet printers most got their
applications for carpet printing, coating, marking and coding. In addition, continuous inkjet
print heads are widely used in proofing, marking, coding and sometimes also in textile
printing.
Figure 4. A schematic representation of different print heads (A) thermal, (B) piezoelectric and (C)
electrostatic.
90
Inkjet printing techniques can also be used for graphic designs which have been used in a
wide variety of fields some of which include textile printing, coding and marking,
carpeting, office inkjet printing, addressing direct mails, proofing, CAD, wide format
graphics (for billboards and signage), flags, T-shirts, wall covering, floor covering, ceramics,
photo finishing, food decorations, packaging, and also other types of commercial printings
[27, 28].
Choice of Technology and the Selection of Inkjet Print Heads

Inkjet printing technology as a micro-disposal technique has a wide range of applications
in different fields, including in electronics, photovoltaic, electronic displays, 3D additive
manufacturing, chemical formulations, tissue engineering, high-throughput screening,
biomedical applications. However, during the selection of an inkjet print head for a particular
application needs rigorous study on the different aspects of the inkjet print head, available
facilities, properly defined objectives of the project where the print head to be used, nature of
the substrates, nature of the inks to be used, technical performance, the market, costs and
related many other fundamentals issues. For example, during the selection of print heads
proper care and advices from different manufactures and others involved in the supply chain
is instrumental because one particular type does not necessarily meet or even suitable for all
desired applications. Briefly, some important characters of a print head needs careful
consideration (during matching it to different applications) include, (a) single-pass
throughput, (b) firing frequency, (c) fluid firing viscosity range, (d) types of fluids the print
head can tolerate (e.g., effective pH range for aqueous inks where print head can be operated),
(e) drop velocity, (f) native dpi (depth per inch) of printed image, (g) nature of crosstalk, (h)
print line length, (i) nozzle diameter, (j) nozzle pitch, (k) drop size, (l) drop firing
straightness, (m) greyscale capability, (n) drop through distance, (o) nature of the heater (in
the case of thermal inkjet print head and (p) maximum operating temperature [28,37-39].
There are different elements in inkjet technology which virtually control the whole
system, some of the main elements include (a) the nature of a print head, (b) firmware,
driver, RIP (raster image processing) and image generation software, (c) print controller
electronics, (d) print head monitoring and maintenance, (e) print head and/or substrate
movement, (f) substrate transport and handling, (g) the nature of an ink or a fluid, (h) the ink
delivery system, (i) colour control, (j) nature of pre-treatment or post treatment on the
substrate, (k) curing, fixing and drying processes, (l) the system integration and (m) tailoring
and tuning components to meet specific requirements. [40, 41].
Some recently introduced printers for textile application includes, Durst Kappa (Ricoh
Gen4), MS LaRio (Kyocera Kj4B), Konica Minolta Nassenger Pro 1000 (KM 1024 4 lines
for 256 nozzoles), SPG Prints (Stork), La Meccanica (Kyocera KJ4B), Kornit Allegro
(Dimatrix Nova AAA), D-gen Teleios Grande (Ricoh Gen4L), Shima Seiki new SIP flat bed
(Ricoh Gen 4L), AnaJetmPower (Ricoh Gen4). [27, 28].
91
Table 2. Types of inkjet inks

Different types of inks
Division based on solvent or and the method
Different types of inks Aqueous solution, dispersion or micro-emulsion
Non-aqueous inks
Oil based or solvent based
Phase change inks
Liquid to solid, liquid to gel
Reactive inks
UV curable inks
Division based on the colorants used in the ink formulation
Dye based inks
Acid, Reactive, Direct, Disperse, Vat, Sulphur, Solvent
Pigment based inks
Inorganic pigments (e.g., Carbon Black), and organic pigment based
Polymer based inks
Aqueous, Non-aqueous, Polymer blend based
Different Types of Inkjet Inks

There are different types of inkjet inks and a brief division is shown in Table 2 and the
inkjet print heads which suitable to certain types of inkjet inks are shown in Table 3.
Table 3. A brief presentation of different inkjet print heads suitable for specific
ink classes
Print head model
Oil
Xaar 1001
Trident 256Jet
Epson TFP
HP X2
Richo Gen 4
Fujifilm Dimatix PQ-512/15
Fujifilm Dimatix Scan PAQ QS-10

Fujifilm Dimatix QS-256/10
Fujifilm Dimatix Samba
Panasonic 600X600
Kyocera KJ4A
Kyocera KJ4B
Different types of inks

Water
Solvent
/ x
x
x
x
x
x
UV-cure
DESIGN AND DEVELOPMENT OF INKS AND TYPICAL

INK COMPONENTS
The ink and the print head are the two vital components of the inkjet printing system (in
exception to the nature of the substrates which have significant importance), because even
they are improved individually to an outstanding level, it is finally the cooperation of both,
which defines the printing performance. This section focuses on the challenges for designing
92
and developing inkjet inks. The composition of the inks is not trivial and the inks must fulfil
several essential requirements to be jettable also to produce high quality prints.
Design Requirements of Inkjet Inks

Sometimes specific requirements for certain print heads exert challenges in the design
and development of particular classes of inkjet ink formulations. These requirements define
the nature of inkjet inks, some of the important features are intrinsic characteristics of the
inks, ink performance in the printers and interaction of the ink with print media. Since all of
these requirements are intricately related to each other so during designing the ink a
compromise between these categories is important. The intrinsic ink characteristics are
basically the physicochemical properties of an ink particularly relating to the ink composition.
Other important properties which need rigorous considerations include, viscosity, surface
tension, pH, conductivity, purity of the components, drop velocity, dye solubility, visible
spectrum, density (specific gravity), solid content, and stability of the inks as well as health,
safety, and environmental considerations. As some these properties are more specifically
related to the print head technology (such as, the type or model of the print head) so these
properties must be optimised to meet the specific operation range of the print head used for
the printing purpose. Jettability and drop placement accuracy of the inkjet print head depend
on the interaction of inks with the print head and its components. It also important to note that
nature of ink plays a vital role in terms of technical performance which is defined by the level
of interactions between the inks and the substrates. A primary consideration is the ink must be
compatible with the printer print head and should not cause any corrosion to the metallic
parts, softening or swelling of the organic parts along and any type of contaminations. Inks
should be free from chemical reactions, biological or fungal growth, particle agglomeration or
precipitation or foaming must during the operation and storage. The ejected inkjet drops
should be of identical volume and velocity. The drop break off length should be uniform
without any satellite or secondary droplet formations. The ink should be resistant to any pH
changes, decomposition and evaporation. The ink should neither clog the orifice nor wet the
face plate. The ink droplets should show desired criteria when the printed on the substrates to
achieve desired print quality. It is expected that the ink drops should reveal proper wetting
and spreading on the substrate and dry reasonably quickly. When printing is carried out nonporous media (such as glass) the surface energy of the substrate and the surface tension of the
ink are most likely to define the spreading and the dot size. However, during the printing on
porous substrates (such as, a textile substrate), the ink vehicle usually wets the surface and
penetrates into it to set the correct dot size to provide a printed image. It is also expected that
during penetration and evaporation, errors like bleeding, feathering, mottling, or line banding
should not occur. Additionally, the printed patterns should have high print quality and high
technical performances. A quality inkjet ink is usually designed considering all the above
mentioned points [42, 43].
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REQUIREMENTS FOR DIFFERENT INKJET PRINTING TECHNOLOGIES

Different inkjet print heads uses different techniques to jet the inkjet inks onto different
substrates. Inkjet inks are required to meet certain criteria (such as, physical and chemical
requirements) to be jetted from a particular type of inkjet print head. So, in order for such inks
or fluid compositions to be deposed from a certain type of print head the compositions may be
formulated to meet the characteristics as specified in Table 4.
Rheological and Other Requirements for a Good Jettable Fluid

The nature of inkjet fluid is of immense importance which controlled the quality and
performances of both printed images as well as the productivity and printing performances of
the inkjet print heads. Different selected properties of the inkjet fluid is briefly summarised
here.
Table 4. Jet fluid property requirements for specific print head technologies
Property
Drop on demand (DOD)

Thermal (TIJ)
Piezo
Valvejet
Viscosity (cP) (at operating 1-4+/- 0.25*b

temp*a)
Surface tension(dynes/cm) 30-50
Conductivity (uS/cm)
0
2-15+/-0.25-0.5*b 2-20
25-45
0
25-50
0
Salt content Chlorides (ppm)

Particle size limit (um)
pH
% solids(residual)
Stable to shear rate of (s-1)
Dot diameter (um)
Droplet volume (pico-litre)
<10
0.5
4-10
<4
105
20-250
2-200
<100
1
4-10*d
<20*e
105
20-250
2-200
Droplet velocity (m/s)

Firing frequency (kHz)
15
30
5-10
30
<100
5
4-10
<20
105
100-5000
150100,000
10
<2
Continuous (CIJ)
Binary
Multideflection
deflection
1-2.5+/-0.25*b 2-4+/-0.5*b
20-50
20-50
>500+/- 20%*a >500+/20%*c
<100
<100
0.5
2
4-10
4-10
<4
<15
106
106
50-300
100-2000
50-250
50-750
20
64-1000
20
60
N. B. In this case, a*illustrates that DOD print heads may have temperature control where CIJ print
heads generally operate at ambient temperature, b* shows typical ink manufacturing batch to batch
tolerance, c* indicates the tolerance during operation (re-circulation of ink), d* shows the pH
profile unless a ceramic print head is used which can operate at any pH and lastly e* indicates the
exception for UV curing inks which may be up to 100% solids.
Viscosity
Inkjet requires low viscosity fluids compared to most dispensing techniques. In a thermal
print head, it is often heated to reduce the viscosity of a fluid to allow the print head to print.
However, this also reduces the effect of changes in ambient temperature on printing
reliability. It is an important feature of most modern DOD print heads which can regulate the
temperature of the print head to change the viscosity. It is important to note that the
temperature control of CIJ printers is not usually controlled by a thermal management system
94
and the printer is usually operated at ambient temperature. The viscosity of a fluid controls
the jettability (ability to be jetted from the print head), for example Newtonian fluids are
preferred for inkjet deposition; however shear thinning fluids may be used with care whereas
shear thickening fluids should be avoided. However, the assurance of a proper control on the
viscosity for a fluid does not necessarily guarantee inkjet printing success as other aspects of
the fluids flow properties are also important to the inkjet printing process. For example, a
highly viscoelastic fluid may not exhibit proper jet breakup even though it may appear to
have the correct viscosity for jetting.
Surface Tension
Surface tension plays an important role to control the wetting of the fluid inside the print
head. When the surface tension is too high, the fluid does not wet the internals of the print
head properly which may leave some air pockets to cause unreliable printing. However, a too
low surface tension of the fluid does not allow a proper meniscus formation in the print head
nozzle and in the case of DOD which causes the fluid to flow spontaneously onto the print
head face plate (also known as faceplate wetting) producing an unreliable jetting. In the case
of CIJ also, a droplet break-up becomes unreliable. In addition, surface tension has a tendency
to affect the drop size and satellite formation.
Conductivity
Conductivity is an important issue as the continuous inkjet printing technique requires
deflected charged droplets for printing using an electric field. However, for all other inkjet
techniques conductivity is undesirable as it may cause corrosion of metal components in
contact with the ink.
Salt Content
In different printing techniques (especially in continuous inkjet printing techniques)
sometimes salts are used mostly to control conductivity, however, some specific salts such as
chlorides are particularly undesirable as they are more corrosive compared to other salts. So, a
proper care is essential to select a salt during the formulation of inkjet inks for a continuous
inkjet printing system to minimize its corrosion effects. In addition, multi-valent metal salts
(such as, magnesium and calcium based salts) should be avoided during the formulation of
inks for thermal inkjet printing as these types of salts often cause kogation (crusting of the
print head heater element) eventually leading to a premature failure of the print head.
Particle Size
Particle size of the different ingredients of an inkjet ink formulation has a limiting effect
on printability since the inkjet nozzles are very narrow (typically of the range of 20-75
microns in diameter). So, to avoid higher particle sizes (usually over 2 microns in diameter)
repeated filtration is necessary to get rid of the maximum particle size or the aggregates
present in the fluid to prevent blocking of the print head nozzles.
pH
Usually a specific pH is used to control solubility or dispersion stability of active
components in the ink fluid. Additionally, the pH range where a print head can operate is
limited because of the chances of corrosion of the print head (since most of the print head are
95
usually made from steel). However, there are some piezoelectric drop-on demand ceramic
print heads which allow a reliable jetting of fluids from across the full range of pH.
Solids Percentage
Different factors such as viscosity, elasticity and the particle size directly control the
amount of solids which can be present in an ink fluid. Because, when the solids content of the
fluid is too high it may dampen the pressure pulse which is necessary to eject or break up the
inkjet drop and also may prevent reliable printing.
Shear
Inkjet printing is a high shear technique so proper cares are needed during the selection of
materials for inkjet ink formulations, in this case materials which can tolerate some level of
shear resistance is desired. Because, there are chances that materials that are not stable to high
shear may decompose in the print head nozzle to block it (or the return gutter for a continuous
inkjet printing system) and also may cease to provide the desired application or end user
properties on the printed substrate. Particularly for continuous inkjet printing technology, the
nozzle experiences a higher shear compared to the other inkjet techniques.
Dot Diameter
It is the diameter of a drop that the printed droplet provides when disposed from an inkjet
print head to the substrate. It is also a function of a number of things including, the nature of
interactions of the droplet with the substrate. Sometimes the substrates are pre-treated using
different techniques to modify their wetting behaviours such as hydrophobicity, absorbency
which have a direct impact on the levels of interactions of the ink droplet towards the printed
substrates which subsequently controls the dot diameter. In addition, shapes of the substrate
also have pronounced control on the nature of ink and substrates interactions.
Drop Volume
Drop volume (picoliter)
45
36
27
18
9
0
Kyocera
KJ4A
Kyocera Panasonic Xaar 1001

KJ4B
600X600
Trident Ricoh Gen Epson TFP HP X2

256Jet
4
Xaar 1001
Print heads
Figure 5. Average drop volume (in picoliter) of different inkjet print heads.
Trident
256Jet
Fujifilm Fujifilm Fujifilm

Dimatix Dimatix Dimatix
PQ Scan PAQ
QS 512/15
QS - 10
256/10
96
Figure 6. Average DPI (dot per inch) per drop volume (in picoliter) of different inkjet print heads.
The drop volume is usually determined by a number of influencing factors, including the
physical size of the nozzle that makes up the print head. Some other prominent factors are the
firing frequency and the force by which the drop is ejected also control drop volume. It is
important to note that the firing frequency is usually determined by the nature of waveform or
voltage used during firing (may also called disposing) from the print head. Figure 5 indicates
the average drop volume (in picoliter) of different inkjet print heads while Figure 6 shows the
average DPI (dot per inch) per drop volume (in picoliter) of different inkjet print heads
[27, 28].
Drop Velocity
The nature of drive electronics in combination with the physical parameters of the
disposing fluid usually determine the droplet velocity as it emerges from the print head.
Firing Frequency
It is an indication of the rate of the ability of a print head how much it can deliver in each
second when it disposes ink fluid onto a substrate which is usually counted by the number of
droplets ejected from a print head in one second.
Settling and Sedimentation
Settling and sedimentation are unexpected from an inkjet ink; however, in a functional
ink fluid sometimes it may contain particulate material. So, it is important to ensure that
settling or sedimentation is either eliminated or minimized using a proper control on the
maintenance regime to avoid both the blockage in the print head nozzles and unreliable
printing performance.
97
BASIC REQUIREMENTS IN THE COMPOSITION OF AN INKJET

INK FLUID
Table 5. Jet fluid disposing compositions
Different components
Solvent
Co-solvent
Humectant
Viscosity control agent
Conductivity agent
Surfactant
Biocide
pH modifier
Corrosion inhibitor
Wetting Agent
Active agent(s)
Binary CIJ Multi-deflection CIJ Thermal Inkjet

(TIJ)
70-95
50-90
70-95
0
0-20
0-3
0-3
0-5
10-30
0-2
0-25
0-0.5
0-0.5
0-0.5
0-0.5
0-0.5
0-0.5
0-0.5
0-1
0-1
0-1
0-0.2
0-0.2
0-0.2
0
0.01-0.3
5-20
5-30
1-5
Piezo DOD
60-90
0-5
10-35
0-25
0-0.5
0-1
0-0.2
0.01-0.3
5-30
N.B. In all the cases, compositions defined by the percentage (% ) of weight.
Some typical compositions of inkjet disposing fluids are given in Table 5 for each of the
print head technologies. The list shows the composition in the form of an example of the
number of components that may make up a formulation. However, it is important to note that
not all formulations may require each and every component to be present for successful
operation.
Effect of Components in the Formulation

The main aim of the inkjet ink composition described in Table 5 is to provide some
examples for a jettable composition by adjusting the parameters that have influence on the
ejection of the fluid from different types of print heads. There are complex inter-relationships
between these components in stabilizing the ink fluid and for a better understanding of the
role of each component is briefly described here.
Solvent
In most cases to apply functionality on printed textiles the solvent or vehicle used in the
inkjet ink formulation should preferably be de-ionized, de-mineralized water which provides
the ink a highly significant chemical basis for the interaction of the active agents or the
colorants with the textile after printing. Sometimes post treatment is required on inkjet printed
textiles for a number of reasons including the enhancement of technical performances. In this
type of cases sometimes alternative inkjet ink compositions using non-water based solvents
such as ethanol or lactates may also be used which fulfill the desired characteristics. There is
a wide range of solvents which can be used in different types of inkjet ink formulations which
can meet particular requirements which are expected from the inks.
98
Co-Solvent
A co-solvent can be used along with a main solvent in an ink formulation to address
certain desires aspect from the formulated ink. For instance, in a drying ink formulation a cosolvent is often required to provide solubility for the conductivity agent in which case a small
amount of ethanol is used to dissolve a conductivity agent that is not soluble in MEK alone.
Additionally, a co-solvent may also be used to improve the solubility of the active
component(s) and their compatibility with the conductivity agent (where the incompatibility
between these materials is a common formulation issue). More particularly, in continuous
inkjet printing systems the non-printing fluid is often mixed with air during the recirculation
process which has a tendency to lead to air entrapment related to foaming issues. In these
cases, co-solvents are usually used to control foaming in these systems.
Humectant
Usually a humectant is a low volatility, high boiling point liquid which is used in the
inkjet ink formulation to prevent crusting of the nozzle when the jet(s) are not active. During
different types of inkjet inks formulations humectants are generally selected from the group
consisting of polyhydric alcohols, glycols, especially polyethylene glycol (PEG), glycerol, nmethyl pyrrolidone (NMP). There is no hard and fast rule for this selection, for example,
during certain formulations it may appear that more than 5% humectant is being used,
however, it is in fact the case that the same material may also be present as a viscosity
modifier.
Viscosity Control Agent
Viscosity control agent is the most important component of ink. Because it has a
significant control on the inkjet printing reliability and the quality of droplet formation and
break up process. Additionally, sometimes it acts as an active component and provides some
of the end user properties particularly in the cases of functional inkjet inks. During the
selection of viscosity controlling agent high molecular weight polymers should be avoided,
because of their higher elastic nature sometimes they cause difficulty in jets breaking up of
inkjet inks. Some of the widely used viscosity control agents are, polyvinyl pyrrolidone,
polyethylene oxide, polyethylene glycol, polypropylene glycol, acrylics, styrene acrylics,
polyethyleneimine, polyacrylic acid.
Conductivity Agent
Particularly in the cases of inkjet ink formulations for continuous inkjet systems
conductivity imparting agents (such as, electrolytes) are used to produce charged ink droplets
which can be deflected during actual printing. An electrolyte is usually used when there is
insufficient conductivity in the ink. It is important to note that conductivity agents should be
compatible with the other components of the ink formulation and they should not promote
corrosion. Some commonly used conductivity agents are lithium nitrate, potassium
thiocyanate, dimethylamine hydrochloride, thiophene-based materials. These materials show
different level of conductivity, for example, it was observed that the use of a small amount of
potassium thiocyanate was sufficient to provide required level of conductivity to produce
uniformly jettable continuous inkjet inks.
99
Surfactant
In typical inkjet ink formulations, surfactants are usually used either to reduce foaming of
the formulation and release dissolved gases or to lower the surface tension of the droplet and
to improve wetting. Some usually used surfactants are Surfynol DF75, Surfynol 104E,
Dynol 604 (Air Products, USA) and Zonyl FSA (Du Pont, USA). Additionally, BYK 022
(BYK-Chemie) and Respumit S (Bayer, Germany) are both silicone based antifoam agents
that have proved very effective for smooth and uniform jetting purposes.
Biocide
Sometimes a small amount of biocide is usually used in an aqueous based inkjet ink
formulation to prevent bacterial growth in the inks when stored for a long time. However, in
the solvent based inkjet ink formulation biocides are not usually required, for example, when
solvent like isopropyl alcohol is present in the composition in sufficient amount it can prevent
bacterial growth.
pH Modifier
Different types of buffer solutions or pH modifiers are sometimes used in the inkjet ink
formulation to maintain a pH at which the components of the ink formulation are soluble or
make a stable dispersion. In typical formulation the pH is usually neutral (pH 7.0) or slightly
alkaline. Additionally, the pH modifier may also be used to modify the chemical interaction
between the different suitable components of the ink and the printed substrates (such as,
textile). Some usually used pH modifers are, ammonia, morpholine, diethanolamine,
triethanolamine and acetic acid. However, it is desirable from an inkjet perspective to use
relatively neutral solutions to reduce corrosion in the print heads.
Corrosion Inhibitor
A corrosion inhibitor is mostly used in an inkjet ink formulation to prevent unwanted ions
present in the ink fluid (as impurities coming from the active components) that may cause
corrosion to the printer.
Wetting Agent
Wetting agents are usually in ink formulations to improve the surface wetting of the fluid
on the internal capillaries of the digital nozzles. Some of the usually used wetting agents are
based on acetylinicdiols. In addition, sometimes, surfactants and co-solvents may also act as
wetting agents.
Active Ingredients
The active ingredients (such as in this case photochromic dyes) are the materials which
are usually used in the inkjet ink formulation to impart desired properties on the printed
substrates. For example, when the photochromic dye based inkjet inks were disposed onto the
textile substrates, all the printed substrates showed photochromic colour change under UV or
sunlight exposure, so in this particular case photochromic dyes played as active ingredients.
100
RECENT TRENDS IN HIGH PERFORMANCE INKJET

PRINTING TECHNOLOGIES
Recent studies indicates that there is very significantly increasing growing demand for
environmentally friendly high performance and technically robust inkjet ink system which
can be used for wide format inkjet printing on different substrates including textile printing.
So, a very precise discussion within the very limit of this chapter will focus on selective
important aspects of UV inks, inkjet technologies that use UV inks for wide format inkjet
printing systems is included here in the following subsequent sections.
UV Inks and Inkjet Printing

Ink Jet printing technologies that use UV inks need a UV curing set up to cure the printed
substrates. Industrial inkjet printing with UV inkjet inks requires the integration of inkjet print
heads, printing mechanisms along with the proper curing systems which have already been
effectively addressed by different inkjet print head manufacturers. UV-curable inks are
widely used for the decoration of the sheathing of wire and fibre optic cable, automotive
hoses and packaging for marking for high level of technical performances. There is a
significantly increasing demand of UV-curable inkjet inks and associated inkjet technologies
for high performance graphic arts printing systems on different substrates, including as PVC,
acrylics and textiles. It is also interesting to note that some analog printing equipment
manufacturers are also trying to incorporate UV-curable ink jet printing systems into analog
printing set up for an effective use of the ability of the digital printing system which can print
variable information with the high speed and quality. UV inkjet inks and related systems are
used for rapid prototyping, signage and other industrial applications. The recent advances in
UV-curable ink chemistry successfully mitigating different requirements and limitations of
UV-inkjet inks and ink jet technology for a wide range of industrial exploitations, including
wide format high performance inkjet printed textiles.
As some of them are already stated somewhere in an above section, there are many
advantages of using UV curable inks, some of which include - no VOCs (volatile organic
compounds), little or no air pollutants, high print quality, low odour after curing, reduced ink
wastage, constant ink composition, no print-head clogging, low energy requirements and the
ability to print on a wide range of substrates. UV inks are highly viscous and have limited
flow on the substrate. This particular nature when combined with the instant or spot fixation
offered by UV curing lamps provides an opportunity to have very high print quality and fast
overall operating speeds. It is an advantage of UV inkjet system that there is no evaporation
of volatile solvents in the print head which minimises waste and time spent on maintenance.
UV inks can provide good colour value and when optimised accurately. UV inks can be used
to produce a very clean colour gamut. An additional feature is that as the UV ink does not
cure before it is exposed to UV light there is minimum or no risk for a premature drying of
the ink which in turns extend the life of the print head to ensure less down time when the UV
inks are stored and managed properly. Usually UV inks are typically 100% solids which
imply that when they are printed on the substrate after curing they almost remain there. As
101
there are no volatile carbons they are more environment friendly making it a good green
technology option. However, there are situation which limits the uses of UV inks.
UV inks are typically highly viscous which limit their ability to print smooth consistent
thin films to meet certain application demands. The generation of heat from UV lamps used
during curing has the ability to damage thin or delicate substrates, however, with the
introduction of UV LED technology this issue mitigated to some extents. Additionally,
sometimes there is risk of over-curing which may reduce the adhesion of the ink to the
substrates and a drastic over-curing may turn the ink film to flake. Use of UV ink needs some
training for the effective uses of UV light where an inefficient use risks huge health problem
to the workers and also the handling uncured materials carries potential health hazards which
needs significant level of considerations. UV inkjet system needs UV system setup (such as,
UV lamps, devices to run the systems, ancillary devices to dissipate heat) for curing which
also involve an operational cost which is often expensive. There are still issues relating to
poor adhesion which sometimes require modification when printed on difficult substrates
(e.g., polypropylene) though UV inks have a wide variety of printing applications on nonporous substrates. In addition, UV light requires to reach all the way through the ink layer in
order for it to polymerise otherwise there are chances of improper curing causing a serious
issue of overall adhesion properties and printed image quality. It requires a careful
optimisation of ink chemistry, studying the absorption nature of the substrate along with the
modification UV intensity to ensure full curing [44-46].
Besides some of these limitations of UV inks, with the improvements in technology UV
inks are now in the road to capture new markets. For example, UV digital inkjet printing
systems are dominant in the printing of rigid substrates for the POP market and continue to
increase its market share in areas such as outdoor signage, film packaging and other areas.
Integration of UV Curable Inks and Inkjet Print Heads with Analog System
Some technical difficulties delay the progress to some extents in the current trend to
integrate screen printing with inkjet printing systems that use UV inks. The combined
systems have many advantages, some of which include (a) eliminating the cost and time for
making films, plates and screens and set up, (b) printing short-run images more economically,
(b) permitting variable information printing and customization, (c) printing for long term
outdoor durable images and (d) minimising the cost and waste associated with lamination
from many applications. For example, some of these types of printers are available from
Barco, Inca, Durst, Sias, Zund, Tampoprint or Leggett and Platt.
UV inkjet inks are suitable to use for printing a wide range of flexible substrates
including paper, textile fabrics, banner materials, vinyl, polyester, polycarbonate and other
plastics. It is important to note that the flatbed models have the capability to print on different
rigid substrates, for examples, rigid plastics, wood, glass, tile, metal, and foam and corrugated
board. There are scopes for the use of UV-curable inks and ink jet multi-colour printing
which will help to grow to supply an increasing part of the demand for advertising, display
graphics, posters, signs, banners, rigid boards, outdoor graphics, exhibition and stage
graphics, architectural graphics and murals, backlit displays, flags, fleet and vehicle graphics,
bus shelters graphics and bus wraps. Additionally, UV-curable inkjet inks are much less
substrate dependent compared to water, oil and solvent-based ink jet inks. For example,
102
Leggett and Platt showed the additional possibilities of fixing and curing textile dyes and
other colorants using UV curing system.
The Nature of UV Inkjet Inks

UV are prepared from a composition of different materials, where the main components
are (a) reactive monomers, (b) photo initiators, (c) oligomers, (d) colorants (such as, dyes or
pigments) and (e) other additives. In this case, the usual mechanism is, during the curing
process the ink reacts to UV light and the monomers polymerise to form a tough film. UV
curable inks are also used in different traditional printing methods as well, for example,
flexographic, lithographic, rotogravure and screen printing systems.
UV curable inks used in inkjet large-format printing mainly are of two types (a) free
radical and (b) cationic; however, the vast majority of UV-curable inks are used in the
industry today are based on free radical chemistry. One of the basic differences between free
radical and cationic systems is based on the solidification process when exposed to UV light.
Both free radical and cationic UV-curable inks are available in two forms (a) solvent
diluted and (b) 100% solids form. For example, HP Scitex UV-curable inks are based on free
radical chemistry and are formulated with 100% solids which mean they do not contain
solvents. It is important to note that the term 100% Solids should not be confused with a
hot-melt ink, also called a solid ink where the solid inks are a waxy solid at normal
temperatures. During printing, they are heated and melted for jetting, and then solidify by
freezing on the substrate.
UV Curable inks
Free
radical
Solventdiluted
Water
100%
solids
Organic
Figure 7. Classification of UV inkjet inks.
Cationic
Solventdiluted
Water
100%
solids
Organic
103
Wide Format Inkjet Printing

Recently there is an upsurge in wide format inkjet printing technology and it is making
more and more in-roads into print shops. This is mainly because there are significant
improvements in wide format inkjet technology in last few years which make the market
more stable and affordable. Thermal, piezoelectric and MEMS based wide format inkjet
printers are now available in the market.
Functional Inkjet Inks and Certain Selective Issues

The main objective of a functional inkjet ink is to retain its functional behaviour in the
pot life or ink life of the formulated inkjet and also the printed substrates should show this
functional behaviour for a long time. The technical performances of both the inks and inkjet
printed images are very important. Now this chapter will concentrate on different aspects of
photochromic dye based inkjet inks and analyse different functional behaviour of the inks and
also the inkjet printed textiles when exposed to UV light at different environmental conditions
after a brief discussion on coloured inkjet printed textiles.
COLOURED INKJET PRINTED TEXTILES

Colorants (such as, a dye or a pigment or a mixture different dyes or a mixture of
different pigments) are one of the main components for an ink formulation for the inkjet
printing of textiles. They can be divided into two groups - conventional colorants (such as,
acid dyes, basic dyes, direct dyes, vat dyes, reactive dyes, disperse dyes, pigments, etc.) and
functional colorants (such as, photochromic, thermochromic, ionochromic dyes, etc.).
Functional dyes are used for a variety of conventional and high-technology applications,
including, optical data storage, light harvesting, analytical detections, security printing and
anti-counterfeit applications [47]. Currently, these functional dyes are also used for the
coloration of textile and leather substrates using a variety of ways, including, inkjet printing,
conventional and digital dyeing (using inkjet print head) techniques to impart different
functionalities on the printed or dyed substrates for different specific applications [48-54].
Many functional dyes are stimuli responsive. The development of technology and devices
using of stimuli responsive surfaces to detect changes in the ambient environment by
applying sensoric materials is an active field of research with immense commercial potentials
[55].
There are some functional dyes which change their colour from a colourless or faintly
coloured state to another colour under the influence of different external stimuli.
Photochromic, thermochromic, ionochromic and electrochromic dyes are responsive to UV
irradiation or sunlight, thermal condition, pH and electrical field, respectively, and change
their colour from one state to another under appropriate influence of a certain stimulus or a
combination of different stimuli. [56] For example, some particular spirooxazine and
spiropyran based photochromic dyes give a colour change both under UV irradiation and also
by the application of appropriate thermal condition. Selective textile and leather substrates
104
which are dyed, printed or coated with specific functional dyes can be used as stimuli
responsive flexible matrices to produce controlled and measurable colour change with a
variety of potential applications, including, fashionable functional protective materials for
clothing or footwear. There are potentials for the integration of these functional materials with
digital warning systems by appropriate incorporation of the colour change mechanism on
their surfaces when exposed to different stimuli, such as, UV irradiation, temperature,
humidity and chemical exposure [57-60].
This current chapter will focus on the various aspects of selected functional dyes, such as,
photochromic dyes when they were applied for the coloration of different type of textiles
using inkjet printing technology. There are huge challenges to produce technically standard
textile based printed stimuli responsive surfaces using inkjet printing technology, this chapter
will also selectively highlight on some of these issues along with other selected aspects of
conventional and high-tech applications of these inkjet printed textiles.
Photo-Responsive Inkjet Printed Textiles

Photo-responsive inkjet printed substrates is usually produced by the formulation of
inkjet inks using a suitable photo-responsive material (such as a photochromic dye) as a
colorant where it can retains its colour change behaviour in the ink for a desired time.
However, the development of high performance photo-responsive stable inkjet ink through
the incorporation of appropriate photochromic dye in inkjet inks, and their subsequent
applications on to suitable textile or related substrates to produce photochromic colour change
under UV light or sunlight exposure is very challenging for a number of reasons. These
include (a) acceptable criteria for the inkjet ink to meet the requirements of the print head,
(b) good jettability, (c) storage stability of the ink, (d) appropriate reversible colour changing
capability of the printed image under UV light or sun light exposure and (e) good technical
performances (such as, wash fastness and light fastness properties). So, in order to understand
the photochromic nature of different types of photochromic dyes which have the potential for
inkjet ink formulation for textile applications the following sections briefly discuss the nature
of different types of photochromic systems.
Photochromic Dyes and Principles of Photo-Responsive Colour Changes

Photochromism is a reversible colour change phenomenon usually observed in
photochromic systems (such as, photochromic dyes and photochromic dye doped polymers).
For example, when a photochromic molecule A is exposed to UV light or sun light
transformed into B showing a different absorption spectra (Scheme 1). In some particular
photochromic system, this colour change is an obvious effect detectable without any scientific
tools and causes to generate difference in optical, physical and chemical properties [61-64].
Scheme 1. A reversible photo-induced transformation between two forms of a photochromic dye.
105
When a photochromic molecule undergoes a photochromic reaction when exposed to UV

light or sun light it also causes a significant change in the geometrical structure,
oxidation/reduction potential, refractive index and dielectric constant of two states of a
photochromic molecule. All these changes are the direct results of chemical transformations
observed in majority of the reversible photochromic systems with unimolecular reactions.
There are two main types of photochromic systems classified according to the nature of
thermal stability of the photochemically generated isomer(s). For example, T-type
photochromic compounds which comprise most photochromic dyes, show thermal reversion
whereas P-type photochromic compounds only show a reversion when irradiated with visible
light. Spirooxazines, one of the most commonly studied classes of T-type photochromic dyes,
show very high level of photochromic colour build up and technical performances so this
current chapter will concentrate on the different aspects of this dye class and its applications
in the formulation of inkjet inks along with other selective photochromic dye classes (for
example, naphthopyrans) for inkjet printing on textiles for different purposes.
Besides spirooxazines, azobenzenes (Scheme 2) and spiropyrans (Scheme 3) are the two
mostly studied compounds. Azobenzenes undergo a reversible photochemical cis-trans
photoisomerization during UV irradiation, however, the cis form of an azobenzene is more
unstable which goes back to the trans form by a thermal isomerization (or reversion). On the
other hand, when exposed to UV light on a spiropyran, it opens up the electrocyclic ring of
the pyran that generates a charge at the indoline nitrogen followed by a subsequent
rearomatization of the phenyl ring with an extensive change in the polarity of the zwitterionic
form [61-64].
Scheme 2. The reaction mechanism of a photochromic azobenzene (substituted).
Scheme 3. The reaction mechanism of a photochromic spiropyran (substituted).
106
Scheme 4. The reaction mechanism of a photochromic naphthopyran (substituted).
Photochromic napthopyrans are well-known for their commercial applications in lightsensitive ophthalmic lenses due to their ability to undergo a reversible colour change when
irradiated with ultraviolet (UV) light [61-64]. Naphthopyrans (also known as chromenes)
show thermal decolourization when UV irradiation is ceased and are usually used to develop
a broad range of intense colours depending on their electronic substitution and also
demonstrate a significant fatigue resistance when exposed to light. In a napthopyran the
photochromic reaction proceeds through a heterolytic cleavage when the C-O bond in the
pyran moiety is ruptured due to UV irradiation and produces isomeric open forms
(merocyanines) which are coloured due to their extended conjugation and quasi-planar
structures. During the conversion from a closed form to an open form the molecule undergoes
a large intramolecular rotation to form coplanar structure in its coloured (open or
merocyanine) form or orthogonal structure in its colourless (closed) form (Scheme 4).
Naphthopyrans have the potentials for textile applications. [60] Selectively several
naphthopyran dyes have been used for inkjet ink formulations.
Scheme 5. The reaction mechanism of a photochromic fulgide.
107
Scheme 6. The reaction mechanism of a photochromic diarylethene.
Photochromic furylfulgides (Scheme 5) and diarylethenes (Scheme 6) are P-type

photochromic molecular switches. In the cases of fulgides and diarylethenes the geometric
shape of molecule A as shown in Scheme 1 is open and B is closed. The thermally stable Ptype switches have potential for practical textile applications including, responsive surface,
brand protection, security, authentication, camouflage and in fashion and design. During UV
irradiations both of these classes of compounds show a electrocyclic photochromic reaction.
In this case, ring-closed isomer shows some types of stability where the reversible ringopening process proceeds with an irradiation using a visible light. Diarylethenes are the most
promising candidates for future applications due to the possibility of incorporating a huge
variety of substituents during the synthesis of these compounds [61-65].
Photoisomerization reactions of photochromic fulgides, fulgimides, diarylethenes based
on the molecular structures of these compounds may be divided into two major categories,
such as electrocyclic ring closed (coloured) and opened (colourless) structures. Fulgides,
fulgimides and diarylethenes show photochromic reaction due to photo-induced reversible
electrocyclization. The closed forms of fulgides, fulgimides and diarylethenes show an
absorption band in the visible spectral range so they are coloured in their closed forms (which
in contrast to spirooxazines and spiropyrans where closed forms are colourless), however, in
the open forms exhibit their first absorption band at significantly shorter wavelengths
resulting colourless forms. When these compounds are excited in the respective first
absorption bands, the molecules undergo reversible photoisomerization between their two
forms. However, spiropyrans and spirooxazines show a photo-induced heterolytic bond
cleavage on excitation with UV light leading to the amphoteric ionic structures of
merocyanines with an onset of absorbance in the visible region. The usual reaction time in
certain types of fulgides, fulgimides and diarylethenes is very fast which has a real impact on
the overall performance of these molecules when used as molecular switches. These
molecules are often judged in terms of their efficiency and photostability when exposed to
light (such as, UV light for forward reaction and visible light for reverse reaction) either
embedded in a solid matrix or dissolved in a solution. However, different studies also
revealed that photo-excited organic molecules very easily undergo unwanted side reactions
and also susceptive to quenching processes with other molecules along with radiative or nonradiative transitions. From a usual analysis, it is also observed that the photoisomerization
reactions of these photochromic compounds (such as fulgides and diarylethenes) take place
within a femtosecond time scale. In addition, on this fundamental femtosecond time scale, the
108
movement of atoms in a molecule takes place and side reactions are minimized, since a few
molecular degrees of freedom are involved in the photoreaction [66].
EVALUATION OF PHOTO-RESPONSIVE BEHAVIOURS OF INKJET

PRINTED TEXTILES
Photochromic colour build up and fading as well as the technical performances of a inkjet
printed photo-responsive textile substrate can be evaluated using a variety of ways, where
colour measurement is one of the most important techniques. Colour can be measured from a
solution by measuring the transmission properties of the liquid or in opaque material using
reflectance measurements. However, the colour of photochromic dyed, printed or coated
substrates may be assessed using reflectance measurements. These colorimetric attributes of
material can be used to calculate the difference in colour between samples before and after
UV irradiation [47-53]. In different studies, the Kubelka-Munk function shown in equation
(A) is has been used to determine the colour strength of dyed photochromic substrates [4753].
K/S = (1-R)2/2R
(A)
where, K is the co-efficient of absorption, S denotes the co-efficient of scattering, and R is

reflectance of an opaque object at a specific wavelength. In the case of inkjet printed photoresponsive textiles it is assumed that scattering is solely due to that from the substrate and
variations in the amount of dye in the substrate, up to an upper limit, have a linear
relationship with the K/S. However, in some cases it may be necessary to sum up the
individual K/S values over the visible spectrum to determine the effect of variation in
conditions on colour strength of the dyed substrate. During this study, the K/S function and
colour difference (E) have also been used to analyse the technical performance of inkjet
printed photo-responsive (also termed as photochromic) substrates (for detail procedure,
please see the references from 6-8).
BEHAVIOURS OF INKJET PRINTED PHOTO-RESPONSIVE TEXTILES

Photo-responsive printed textiles were produced by using inkjet printing technique (with
a piezoelectric drop on demand print head, e.g., Xaar Omnidot 760 print head) where
photochromic dyes were used as colorants during inkjet ink formulations. These
photochromic dyes were then printed on different textile substrates using the inkjet print head
and the printed substrates were dried in the open air. The printed textiles showed
photochromic colour change when exposed to UV light or sunlight which is described as the
photo-responsive behaviour of the inkjet printed textiles in this chapter. This photoresponsive behaviour of the inkjet printed textiles is only due to the presence of photochromic
dyes (which may also be called as photoswitches) in the inks. Photochromic dyes show
photoswitching which is the isomerisation of a photochromic compound resulting from
irradiation with UV light. While many photochromic molecules undergo electronic transitions
109
under UV/visible irradiation, only a few reversibly isomerise as a result of a transition. It is

highly desired that to fulfil the ideal molecular switching or photoswitching requirements, the
photoisomerisation process should have high quantum yield and proceed to completion
quickly without side reactions. In addition, the isomer formed should be stable to ambient
light conditions and to the initial isomerisation wavelength, but be readily isomerised back to
the initial state by isomerisation at a different wavelength. During the formulation of suitable
inkjet inks using photochromic dyes, several relatively effective photoswitches that fulfil
most of these criteria have been carefully studied and selectively some of them were used for
the ink formulations which are briefly discussed here.
Colour Build Up and Fading Behaviour of Spirooxazine Based Inks

on Cotton
Photochromic colour change in the solution state, such as, in the inkjet ink is very quick
which even active in visible light although in solid state (in the form of inkjet printed
substrate) it requires UV light to initiate this photochromic colour change reaction. It was
observed that during inkjet ink formulation just after the addition of photochromic colorants
into the ink compositions (such as, a humectant, a solvent and other additives) the ink were
colourless for about 1 to 15 seconds and then they started to become coloured absorbing the
photons of visible light [3]. This nature of the rate of colour change depends on the nature of
photochromic molecules and the surrounding environments. For examples, naphthopyran
(Scheme 4) based inkjet inks retain the yellow colour build up state in visible light within 5 to
7 seconds from a colourless state while spirooxazine (Scheme 7) based inkjet inks almost
instantly (within 1 to 3 seconds) convert into blue photochromic inkjet inks just after the
addition of the dye molecules into the ink formulations [3].
K/S
0.46
Before UV irradiation
After UV irradiation for 1'
0.23
0
400
450
500
550
600
Wavelength (nm)
650
700
Figure 8. Photochromic (photo-responsive) colour build up on photochromic spirooxazine based inkjet

ink printed cotton after UV irradiation for specific times (in min).
110
0.48
Before UV
After UV
irradiation for 3'
Fading after 1'
0.32
K/S
Fading after 2'
0.16
0
400 430 460 490 520 550 580 610 640 670 700
Wavelength (nm)
Figure 9. Gradual fading behaviour of inkjet ink printed cotton from the colour build up state (reached
after continuous UV irradiation for 3 min) after removal from the source of UV irradiation.
where, R = H (Spirooxazine 1) or -SO3 Na (Spirooxazine 2)
Scheme 7. Reaction mechanism of spirooxazines 1 and 2 when exposed to UV light and visible light.
0.7
After UV irradiation for 1 min
0.56
K/S
0.42
0.28
0.14
0
400
430
460
490
520 550 580 610

Wavelength (nm)
640
670
700
Figure 10. Photochromic (photo-responsive) colour build up on photochromic diarylethenes1 based

inkjet ink printed cotton after UV irradiation for specific times (in min).
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0.68
K/S
0.51
0.34
0.17
0
400
450
500
550
Wavelength (nm)
600
650
700
Colour builp up after continuous UV irradiation for 4 min
Fading (from colour build up state reached after continuos UV irradiation for 4 min) after 70 min of removal from the source of UV irradiation
Figure 11. Fading behaviour of inkjet ink printed cotton from the colour build up state (reached after
continuous UV irradiation for 4 min) and then after 70 min of removal from the source of UV
irradiation.
Figure 8 shows the photochromic colour build behaviour of inkjet printed cotton where a
spirooxazine 2 (see the structure and reaction mechanism in Scheme 7) based inkjet ink was
used during inkjet printing. It reaches to its highest level of colour up under continuous UV
irradiation for 3 min and further continuous irradiation causes a decrease in the colour build
up due to generation of heat which initiates the thermal back reaction thus resulting in lower
colour build up. Figure 9 demonstrates the fading behaviour from the colour build up state of
inkjet printed cotton after removal from UV light and it nearly regains its original colour just
within 5 min. So, it is clear from this study that spirooxazine based inkjet printed substrates,
such as, inkjet printedcotton shows photochromic colour build up when exposed to UV light
show a very intense photo-response in terms of a highly intense blue colour build up from an
almost colourless inkjet printed background and quickly regain (within couple of min
depending on the structure of photochromic spirooxazine used) the original colourless state
when the printed substrates are removed from the source of UV light. However, this
photochromic colour build up and fading (from the colour build up state when the substrate
removed from the source of UV light) behaviours are different when diarylethenes based
photochromic dyes are used for the formulation of inkjet inks for inkjet printing on textiles.
For example, Figure 10 indicates the photochromic (photo-responsive) colour build up (after
continuous UV irradiation for different times, such as, 1 minute to 4 min) on inkjet printed
cotton substrate using a photochromic diarylethene 1 based inkjet ink. It clearly establishes
that photochromic colour build up is a function of time of UV irradiation where the printed
cotton reaches to its maximum level of photochromic colour build up in terms of colour
intensity. However, in this case fading from the colour build up state takes a long time to
reach to the original colourless state (the colourless or weakly coloured state of the printed
substrate before UV irradiation) because of very slow relaxation process. Figure 11 indicates
the fading behaviour of inkjet ink printed cotton from the colour build up state (reached after
continuous UV irradiation for 4 min) and then after 70 min of removal from the source of UV
irradiation where the printed cotton substrate still retains nearly half of its colour build up
112
(reddish colour) while it usually takes couple of h to completely regain the original
background colourless state (which was before UV irradiation). Again, the rate of colour
build up and fading depends on the nature of diarylethene molecules used in the inkjet ink
formulations and also on the natures of printed substrates (such as, cotton, wool, silk, nylon,
polyester, lycra, polyester-viscose blend, polylactic acid based fabrics) along with many other
controlling factors, such as, nature of UV light, humidity, temperature of the surrounding
environment, etc. For instance, Figure 12 indicates, the matrix effect on photochromic colour
build up on different textile substrates inkjet printed with diarylethene 1 based inkjet ink
before and after exposure to UV irradiation.
It is important to note that the thermal decolouration is a unimolecular process, which in
solution follows a simple mono-exponential decay which can be stated using first-order
kinetics as shown in Equation (1):
A=A0 e-kt and ln[A] = -kt + ln[A]0 ..
Equation 1
(where, A = concentration of the coloured species decaying with rate constant k with time t).
However, when two different isomeric populations of open forms of a photochromic dye
(such as, a spirooxazine) are considered as decaying with two concurrent first-order
processes, the decay data normally needs to be fitted to the biexponential Equation (2).
Equation 2
The interpretation of photochromic kinetics in polymer media (where a very close

relation can be established with the inkjet printed photochromic textiles), is not straight
forward. This is because the collective influences of the surrounding matrix environment
introduce many complexities which need careful consideration. Some of these important
aspects are - chain segmental mobility, the available free volume of the matrix, polarity,
crystallinity, volume changes that accompany the structural changes involved in
photochromic process, how the photochromic molecules are distributed in the matrix, as well
as the behaviour of the different isomers. In addition, during the analysis of the photochromic
decolouration kinetics in non-uniform inkjet printed polymer matrices (such as, inkjet printed
cotton, wool, silk, nylon, polyester and their blend fabrics) a distinct departure from simple
exponential kinetics is to be expected. It is worth to mention here that Levitus et al. applied
two kinetic models to explain decolouration of photochromic films in the dark [67]. In this
case, when a Gaussian distribution model was used, the polymer matrix was found to affect
the width of the activation energy distribution while broader distributions were found for
media that were more rigid. This model provided a rather static picture of each polymer on
the basis of the assumption which does not change during the decay process. Besides this, a
relaxation model was also put forward to provide a mean value for the relaxation time of the
matrix, taking into account the possibility of change of the environment during the decay.
However, this model did not consider the micro-heterogeneity of solid samples, and was
deemed less appropriate for describing the kinetic behaviour of highly rigid media, as
compared to the intermediate range between a highly rigid polymer and a very labile, liquidlike environment. But these models have been applied to describe the thermal decolouration
113
behaviour of the photochromic dyes with reference to the complexities of the solid matrices
for a long time. On the contrary, a less absolute, yet a meaningful approach has been used by
different group to fit thermal decolouration data in solid media to the bi-exponential equation
(3) [68]. This allows quantitative comparisons to be made between decolouration kinetics in
different polymers as a means to optimize photochromic performance and by passes the
mathematical expertise that is required from the other described methods above.
Equation 3
In Equation 3, A(t) is the optical density at the maximum of coloured form at time t, A1
and A2 are the contributions to the initial absorption A0, Ath is the residual colouration,
accounting for residual coloured forms and it is assumed that molecules are decolourized with
different rate constants. If we consider a uniform distribution of free volume, the separated
constants k1 and k2 are understood as empirical mean values between the fast and the slow
constants, as opposed to absolute values of decolouration for the different isomers. In
addition, in some cases, the above equation permits some deductions regarding the
homogeneity of the environment around the photochromic substrates to be made by analyzing
the A1/A2 ratio. It is also observed that the photochromic kinetics of photochromic doped
hybrid organicinorganic matrices, have been quantified using both Gaussian and
biexponential models, the latter allowing a comparison of photodynamics with those of
organic polymers [68]. It was noted that different studies were carried out to analyse the
thermal decoloration kinetics of spirooxazine, spiropyran and naphthopyran-doped hybrid
organic-inorganic matrices using both mono and biexponential kinetics [69, 70].
Figure 12 illustrates that inkjet printed cotton shows the highest level of photo-responsive
colour change from a nearly colourless state to deep red colour build up when exposed to UV
light exposure for one minute which is closed followed by the photochromic colour build up
in polylactic acid (PLA) fabric. However, the photochromic colour build up in nylon, wool
and lycra is comparatively higher than the photochromic colour build up on silk, polyester
and polyester-viscose blend fabrics. The photochromic performance of the inkjet printed
substrates (such as, inkjet printed cotton, wool, silk, polyester, nylon fabrics) is strongly
connected to the nature of the photochromic molecule in many levels. Some of these most
important behaviours are - (a) the characteristics of the polymer and the mode of
incorporation (such as nature of pre-treatment or post-treatment on the printed substrates), (b)
the nature of physical or chemical attachments or dissolution into a fabric. These have very
significant influence on photochromic colour build up, fading and also on life-time of the
retention of the photochromic functionality of the printed substrates. Micro and nanoenvironmental properties of matrices, such as local rigidity, polarity and free volume, as well
as their intermolecular interactions may also affect the efficiency and properties of the
photochromicinter-conversions in the inkjet printed substrates. It is a general observation that
the photochromic transitions are usually slower in a polymer matrix, as compared to solution
which may be attributed to the reduced segmental motion of the macromolecular chains and
the limited free volume of a polymeric matrix, as compared to solution. In addition, the
matrix environment imposes steric restraints by limiting the mobility of the molecules and
therefore their ability to isomerize and also the aggregation of molecules within solid media
may influence kinetic and spectral properties to some extent. However, to understand the
114
nature of the thermal decolouration or fading kinetics of photochromic spirooxazine based

inkjet printed substrates a detail look into the impact of polymer dynamics on photochromic
switching is essential.
0.48
K/S
0.36
0.24
0.12
0
400
435
470
505
540
575
610
Wavelength (nm)
645
680
0 min (cotton)
1 min (cotton)
0 min (lycra)
1 min (lycra)
0 min (nylon)
1 min (nylon)
0 min (PLA)
1 min (PLA)
0 min (polyester)
1 min (polyester)
0 min (polyester-viscose blend)
1 min (polyester- viscose blend)
0 min (silk)
1 min (silk)
0 min (wool)
1 min (wool)
Figure 12. Matrix effect on photochromic colour build up on different textile substrates inkjet printed
with diarylethene 1 based inkjet ink, where 0 min indicates colour of the inkjet printed substrate (in
terms of K/S value plotted against wavelength from 400 700 nm) before exposure to UV irradiation
and 1 min indicates colour of the substrates after exposure to UV irradiation for one minute.
115
Effect of the Nature of Dye Molecules on Photochromic Colour Build Up

Figure 13 illustrates the result of a comparative study on the photochromic colour build
up performances of different photochromic dyes when inkjet printed on different substrates
and also on the matrix effect on photochromic colour build up in terms of the colour
difference from colour build up state after UV irradiation to nearly background colourless
state of inkjet printed substrates before UV irradiation on different textile substrates (cotton,
wool, silk, polyester, nylon, PLA, polyester-viscose blend and lycra) inkjet printed with three
diarylethenes 1, 2 and 3 (Scheme 8); two spirooxazines 1 and 2 (Scheme 7) and a
naphthopyran (Scheme 9) based inkjet inks. It indicates that diarylethenes 3 and spirooxazine
2 based inkjet printed cotton shows the highest level of photochromic colour build up which
closely followed bythe photochromic colour build up on polylactic acid (PLA) based inkjet
printed substrates which were printed with these two dyes based inks. UV light transmission
through cotton is more pronounced compared to other textiles which may have a positive
impact to stimulate more photochromic dye molecules within the inkjet printed area of cotton
allowing it to produce higher colour build up after UV irradiation. As a dye class spirooxazine
and naphthopyran based photochromic inkjet printed textiles show very quick response to
photochromic colour change under UV irradiation while this response is quite quick in the
cases of printed textiles printed with diarylethene 3 based inks while it is a bit slower in the
cases of other two diarylethenes (1 and 2) based inkjet printed substrates. So, this study
clearly establishes that the nature of individual dye molecule plays a very vital role on
determining the photochromic performances of inkjet printed substrates. Another important
point is the porosity; texture and other component of the fabric matrix also play a very
significant role because these properties are directly related to the adsorption and the
penetration behaviour of the inkjet inks onto the fabric surface and also inside the fabric
structure. A general observation is after UV irradiation on the printed substrates, diarylethene
1 based inkjet printed substrates showed red colour build up from a nearly colourless (with a
very pale reddish tone) state, diarylethene 3 based inkjet printed substrates showed very
highly intense reddish purple colour build up from an almost colourless state while
diarylethene 2 based inkjet printed substrates showed yellow colour build up from a
colourless state (with a pale yellow colour). However, after UV irradiation on both
spirooxazines 1 and 2 based inkjet printed substrates showed intense blue colour build up
from nearly colourless state (with a very pale bluish tone) while naphthopyran based inkjet
printed substrates showed yellow colour build up from a natural colourless background states
of different fabrics obtained after inkjet printing.
Different studies on the technical performances in terms of retention of photochromic
colour changing functionality of the inkjet printed substrates after exposure to simulated
environmental conditions (such as, exposure to light fastness and wash fastness test) revealed
that spirooxazine based inkjet printed substrates retained significant amount of original
photochromic colour change capability even after several of controlled washing cycles and
continuous exposure to continuous exposure to Xenotest (simulation of artificial day light
using Megasol based light fastness test) for 50 h. However, the technical performances of the
textile substrates inkjet printed with diarylethes or other classes of photochromic dyes (such
as, napthopyrans) based inkjet inks are not so pronounced as seen in the cases of spirooxazine
based inkjet printed substrates [3].
116
So it is understood from different studies that photochromic materials show

transformation from a colourless ground state to a coloured excited state during excitation
with light of different wavelengths as an external stimulus [3]. The two forms generally differ
in their physicochemical properties, for examples, the molecular geometry, electronic
delocalization, colour and reactivity. A better understanding on the nature of photochromic
molecules, the matrix where they would be used and also other very important influencing
factors, including methods of application, pre-treatment of the matrix before applying
photochromic dye and after treatment of techniques, nature of additives, surrounding
environment require a high level of consideration for any product developments, especially,
in inkjet printed photo-responsive textile based products. From a series of studies on different
types of photochromic dyes (such as, photochromic spirooxazine based disperse dyes and
water-soluble photochromic acid dyes) the author noticed that thermal degradation and acidic
decomposition restricted the practical utilisation of photochromic dyes for a variety of
potential applications. However, it was also observed that these barriers can be effectively
removed using a careful selection of suitable additives during inkjet ink formulations using
photochromic dyes, optimising the treatment techniques (such as, pre-treatment and posttreatment techniques to modify the nature of the substrate to be printed), selecting high
performing photochromic dyes with particular functionalities to retain the photochromic
funcationality on the inkjet printed substrates for a long period.
Scheme 8. Reaction mechanism of diarylethenes1, 2 and 3 when exposed to UV light and visible light.
117
Scheme 9. Reaction mechanism of naphthopyran when exposed to UV light and visible light.
54
45
36
27
18
9
0
Diarylethene 1
Diarylethene 2
Diarylethene 3
Inkjet printed textile substrates

Figure 13. Comparative study on the photochromic colour change of different photochromic dyes when
inkjet printed on different substrates and also on the matrix effect on photochromic colour build upin
terms of the colour difference from colour build up state after UV irradiation to nearly background
colourless state of inkjet printed substrates before UV irradiation on different textile substrates (cotton,
wool, silk, polyester, nylon, PLA, polyester-viscose blend and lycra) inkjet printed with three
diarylethenes1, 2 and 3 (Scheme 8); two spirooxazines1 and 2 (Scheme 7) and a naphthopyran (Scheme
9) based inkjet inks.
APPLICATIONS OF PHOTO-RESPONSIVE INKJET PRINTED TEXTILES

FOR CONVENTIONAL AND HIGH-TECH APPLICATIONS
A good quality inkjet printed photo-responsive textile show photochromic colour change
for a long time and show a substantial retention of its reversible photo-coloration behaviour
even after exposed to different environmental conditions. This behaviour make it suitable for
many potential applications, including in security, responsive surface, brand protection,
authentication, actinometry, self-indicating UV warning system, active and adaptive
camouflage, environmental warning system, electrophoretic textile based display, interior
design, exterior design and also in fashion and design applications. In addition, inkjet printed
photo-responsive textiles has the potential for healthcare applications as well. The possibility
to bind a photochromic molecule onto a naturally occurring receptors and enzymes which in
turn bind with an inkjet printed photo-responsive textile using certain techniques provides the
opportunity to photo-regulate their binding and catalytic activities. In future, this type of
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photo-responsive textiles may be used for different therapy, bio-sensing and also in wound
care along with their (already stated) applications [3, 47-53].
CONCLUSION AND PERSPECTIVE

Inkjet printing technology has been increasingly successful for producing almost any
print design on textiles within a very short time providing this technique a cutting edge over
other conventional printing techniques, for example, screen printing. For high performance
textiles which can ensure different functionalities (such as, sensing ambient environment and
also working as printed design based fashion items) at a relatively low cost have a strong
appeal to the users for a variety of reasons. Photo-responsive inkjet printed textiles have many
applications, some of which include, fashion and design, self-indicating alert systems, anticounterfeit, security and brand protection. Both photochromic dispersed and photochromic
acid dyes can be used to formulate inkjet inks to produce photo-responsive inks for inkjet
printing on different types of textiles (for example, cotton, wool, silk, nylon) for potential
conventional and high-technology applications. Formulation of functional inks using
functional dyes, such as, photochromic dyes needs proper care for producing jettable inks,
retaining functional behaviour for a considerable period along with other desired properties,
for instance, high print quality and robust technical performances of printed textiles. In
addition, the porosity of the substrate plays a significant role on the absorption or penetration
behaviour of an inkjet ink or more simply regulates its spreading on a substrate thus
controlling inkjet printed image quality and the technical performances of an ink to some
extent. As a result, it is necessary to control a number of influencing factors to produce
desired high quality printed responsive substrates with good technical performances for
various applications. A technically robust photochromic inkjet printed textile substrate would
be suitable for a huge variety of conventional and advanced applications.
The current inkjet print head technology are focused to ensure next generation of
developments in different aspects including, higher drop frequency, MEMS construction,
single-pass, higher aqueous tolerance, integrated system with multiple head types, LED-UV
curing system, efficient monitoring for drop-outs and fluid recirculation. Some of the main
objective of this advanced technologies are trying to ensure sustainability and eco-friendly
character, hybrid system with integration of analog and digital technologies, automatic
maintenance system along with higher temperature and humidity controls to ensure top
quality fluid disposal system. There are considerable trends in lowering the price of the print
heads in terms of lower cost per nozzle, larger arrays of print heads and lower cost per print.
Inkjet technology is evolving by the day, for example, it is going from binary to
grayscale, from macro to MEMS micro machining, from scanning heads to single pass, from
fitting application to match inkjet technology to designing inkjet technology to match
application requirements, from sub-boiling temperature operation to high temperature
performance and 2D graphic designs to 3D fabrications including high quality additive
manufacturing for a huge range of applications. So, the effective inclusion of required
functionalities (such as, in this case photochromic performances) on printed textiles using
appropriate inkjet printing techniques can provide a significant breakthrough in value
addition, fashion and design along with high-tech applications.
119
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application of commercial photochromic dyes as disperse dyes to polyester by exhaust
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J. Mater.Chem. 13, 727-730.

ISBN: 978-1-63117-262-5
Chapter 5
SYNTHESIS AND GRAFTING OF CELLULOSE

DERIVATIVES FROM CELLULOSIC WASTES
OF THE TEXTILE INDUSTRY
Md. Ibrahim H. Mondal* and A. B. M. Fakrul Alam
ABSTRACT
Wastes from cotton based garment and textile industries contain good quality of cellulose. These cellulosic wastes can easily be used to produce commercially valuable
cellulosic derivatives, viz. carboxymethyl cellulose (CMC), cellulose acetate (CA) and
cellulose nitrate (CN); and consequently reduce the pollution problem. Carboxymethyl
cellulose was synthesized by reaction with sodium hydroxide in aqueous ethanol
followed by reaction with mono-chloroacetic acid. The synthesized crude CMC was
washed with 80% ethanol and dried over P2O5 in a desiccator. CA was synthesized by
pretreatment with glacial acetic acid and then by reaction of acetic anhydride in presence
of concentrate H2SO4 followed by hydrolysis. The synthesized crude CA was washed
with distilled water, stabilized by Na2CO3 solution and then dried over P2O5 in a
desiccator. On the other hand, CN was synthesized by reaction in the P2O5 and HNO3
medium in an ice bath. The synthesized crude CN was washed with cold water, stabilized
with boiling water, rinsed with methanol and then dried in an oven at 50 oC for 1 h. Low
substituted to high substituted products were obtained from single to seven reaction steps
in all cases. These processes permit to produce low cost different grades of CMC, CA
and CN. The products were identified and their physical characteristics were determined.
Solubility, degree of substitution and molecular weight of the products were found to be
increased gradually with the increase of reaction steps, and the optimum levels were
obtained at the fourth step of synthesis in all cases. The structures of CMC, CA, CN and
grafted CMC, CA, CN were investigated by FTIR, 13C NMR and SEM test. Grafting of
prepared CMC, CA and CN films with methyl methacrylate (MMA) monomer was found
to increase their strengths to 86.11%, 73.61% and 71.43%, respectively. However,
decreased rigidity and moisture content due to the incorporation of hydrophobic MMA
*
E-mail: mihmondal@yahoo.com.
124

monomer were observed. The prepared CMC was also applied as a sizing agent to fabric
and yarn to develop the physico-chemical characteristics.
Keywords: Cellulose derivatives, carboxymethyl cellulose, cellulose acetate, cellulose

nitrate, knitted rag, textile wastes, degree of substitution, molecular weight, grafting
CARBOXYMETHYL CELLULOSE
Introduction
Carboxymethyl cellulose (CMC) is one of the most versatile cellulosic derivatives of the
present day world, and is tremendously used in textiles and many other industrial fields
including in food products, paper, cosmetics, pharmaceuticals, and adhesives [1]. Hence it is
most important in the textile manufacturing and in everyday life. It is true for present day that
Bangladesh is a textile industry-based country, and large amount of CMC is being imported
to meet its demand for textile sector in every year; and the demand of CMC is increasing day
by day. It has been reported that CMC was prepared from different cellulosic sources by
different researchers following different methods [2,3,4a,5-7]. The different cellulosic sources
considered by the researchers include paper sludge [2], hyacinth [3], wood residue [6], cotton
linters [7,8], bagasse [9] etc. No worth mentioning work has been performed on the synthesis
of CMC from knitted rag. Knitted rag contains high amount of good quality -cellulose which
is 9598 % [10]; and huge amount of knitted rags are deposited as textile wastes in different
garment industries that have virtually no use. The wastes contain both colored and noncolored rags. These are normally dumped in nearby area, and degraded naturally. Hence,
these create environmental pollution. As the rag contains high amount of good quality cellulose and as this can be easily collected with almost free of cost, it can act as a great raw
material source for the manufacture of CMC and other derivatives of cellulose.
The purpose of the present work is to explore the use of the knitted rags to synthesize
different grades of CMC by applying carboxymethylation techniques in multiple steps in
order to obtain lucrative CMC with good solubility and fair degree of substitution (DS). The
unique features of this report include the recycling of ethanol, attainment of high DS, grafting
ability and its application to textiles.
Experimental
Materials
The knitted rag as raw material was collected from Mozart Knit Ltd, Ashulia, Saver,
Dhaka. The analytical grade ethyl alcohol (Merck, Germany), hydrogen peroxide (BDH,
England) sodium hydroxide (Merck, India), mono-chloroacetic acid (BDH, England), sodium
carbonate (BDH, England), standard CMC (BDH, England), potassium bromide (Merck,
Germany), methyl methacrylate (MMA) (BDH, England) etc. were used without further
purifications.
Synthesis and Grafting of Cellulose Derivatives from Cellulosic Wastes
125
Preparation of Sample
The collected knitted rag contained both non-colored and colored rags which were hand
sorted. The non-colored knitted rag was washed with 1% Na2CO3 solution at 60 oC [8]. The
colored knitted rag was immersed in bleaching liquor consisting of 1.5% (w/w) hydrogen
peroxide, 2.5% sodium silicate and 1% sodium hydroxide on the basis of fiber in the ragliquor ratio of 1: 50 at 40 oC for 1 h. The temperature was gradually raised to 85 oC and held
for 3 h with occasional stirring [11]. Resulting non-colored knitted rag were washed with
sufficient fresh water and then dried in air. The non-colored knitted rag obtained by either
washing or bleaching was used as a source of cellulose in preparation of CMC, CA and CN.
Carboxymethylation
The CMC was synthesized by the conversion of cellulosic rag to alkali cellulose on
swelling by aqueous NaOH solution followed by reaction with mono-chloroacetic acid
(ClCH2COOH) in rectified spirit. The reaction conditions were as follows:
(a) Basification
In this step of reaction, alkali cellulose was formed. An aliquot of 1g knitted rag was
immersed in 18% NaOH solution in rectified spirit at 30 oC for 3 h in the rag-liquor ratio of
1:14 with occasionally stirring In the basification (also known as steeping ) step, the
following reaction was taken place:
[C6H7O2(OH)3]n + nNaOH = [C6H7O2(OH)2ONa]n + nH2O
(b) Etherification
In the second step, an aqueous 80% (w/v) mono-chloroacetic acid solution was added
drop by drop to the above mixture at 50 oC for 6 h; so that the final pulp volume in the
basification step to reagent solution volume ratio became 1:4. In etherification (also known as
carboxymethylation) step, the reaction of basified cellulose with sodium mono-chloroacetate
was taken place as indicated below:
nClCH2COOH + nNaOH = nClCH2COONa + nH2O
[C6H7O2(OH)2ONa]n + nClCH2COONa = [C6H7O2(OH)2OCH2COONa]n + nNaCl
Single step carboxymethylation only gave low substituted product. The highly substituted
CMC could however be prepared by the technique of multi-step carboxymethylation. For this
purpose, CMC obtained in the previous step was purified with aqueous 80% ethanol solution
and subjected to carboxymethylation by fresh addition of NaOH and ClCH2COOH solutions.
Finally the synthesized crude Na-CMC (the sodium form of carboxymethyl cellulose is
commonly known as CMC) was purified by water dissolution and precipitation by rectified
spirit method followed by washing with 80% ethanol solution, then filtered and dried over
P2O5 in a desiccator under vacuum.
126
Scheme 1. Flow chart for the preparation of Na- CMC from knitted rag.
Determination of Degree of Substitution

One gram of dried CMC was added to 100 ml of distilled water and 12.5 ml of 1 N
NaOH. After dissolving the mixture was titrated by 1 N HCl. The degree of substitution (DS)
in CMC was determined [3,12] as:
DS = 0.162A / (1 0.058A)
where, A is the milliequivalent of sodium hydroxide required per gram of sample.
Determination of Molecular Weight

On dissolving Na-CMC in aqueous 0.8 M NaOH solution, the intrinsic viscosity was
measured by an Ostwald viscometer at 35 oC. From the value of the intrinsic viscosity, the
molecular weight was calculated with the help of Mark-Houwink-Sakurada equation [13] as
given below:
[] = KMa,
127
where, [] is the intrinsic viscosity, M is the molecular weight of Na-CMC, K is a constant,

and a is the polymer shape factor.
Determination of CMC Content in Prepared Sample

An aliquot of exactly 1.5 g CMC was stirred with 100 mL of aqueous 80% methanol
solution for 10 min and filtered. The cake was washed by 100 mL of aqueous 80% methanol
solution, dried to constant weight [5]. The CMC content was calculated using the relation
below:
CMC content, % = 100M2 / M1
where, M1 and M2 are the weights (g) of samples before and after washings, respectively.
Determination of NaCl in Na-CMC

Two grams of Na-CMC was kept immersed in 250 mL of aqueous 65% methanol
solution for 5 h. On filtration, 100 mL of liquid phase was neutralized by 0.1 N HNO3 and
titrated with 0.1 N AgNO3 solution [5]. The NaCl content was calculated using the following
formula:
NaCl, % = 1.461V / M
where, V (mL) is the amount of AgNO3 solution required in titration and M (g) is the weight
of dried sample used.
Grafting Procedure
Graft polymerization of CMC was carried out with 80% methyl methacrylate (MMA),
5% K2S2O8, 5% FeSO4 at 60 oC for 90 min in the CMC-liquor ratio of 1:30. Graft yield and
grafting efficiency were calculated according to the following formulas [14,15]:
Grafting yield, % = [(W1 W0) / W0] 100
Grafting efficiency, % = [(W1 - W0) / W2] 100
where, W0, W1 and W2 are the weights of non-grafted CMC film, MMA-grafted CMC film
and total monomer used, respectively.
Moisture Content
The grafted and non-grafted 2% CMC films were weighed accurately and dried at 105 oC
for 2 h in a forced convection oven (FC-610, Toyo Seisakusho Co. Ltd., Tokyo, Japan). These
were then cooled in a desiccator over silica for about 30 min and weighed again. Moisture
content was determined using the equation given below [14]:
Moisture content, % = [(W0 W1) / W0] 100
where, W0 and W1 are weights of air and oven dried films, respectively.
128
Water Absorption
The grafted and non-grafted 2% CMC films (6 cm 4 cm) were weighed out accurately
and immersed in distilled water for 15 h at 30 oC. The films were then taken out and wiped
using tissue paper and weighed again. Water absorption was determined using the relation
[16]:
Water absorption, % = [(W1 W0) / W0] 100
where, W0 and W1 are weights before and after immersion, respectively.
Gel Content
Gel content of the grafted and non-grafted 2% CMC films was determined by dissolution
of gel in hot toluene. The weighted film (6 cm 4 cm) was subjected to extraction using a
Soxhlet apparatus with 250 mL toluene for 6 h. After that, the sample was taken out for
vacuum drying and weighed to a constant weight. Gel content of grafted and non-grafted
CMC films was calculated accordingly [16] as:
Gel content, % = (W1 / W0) 100
where, W0 and W1 are weights before and after extraction, respectively.
Tensile Strength
To determine the tensile strength of CMC and modified CMC films (2 cm 1 cm) was
used and measured by a Tensile Strength Tester (Harada Co. Ltd. Nagano-ken, Japan). The
distance between jaws of the film was 1 cm.
FTIR Spectroscopy
The washed knitted rag and prepared CMC were dried at 50 oC and powdered by a motarpastle. The powder was mixed with KBr in the ratio of 1:125, and a pellet was prepared. IRspectra of the KBr pellet were recorded with a FTIR Spectrophotometer (Model: FTIR-8900,
Shimadju, Japan) within 4000400 cm-1.
Application of CMC to Cotton Fabric as Sizing Agent
The cotton fabric was washed with 1% Na2CO3 solution at 60 oC for 2 h. After drying,
this was immersed in 3% CMC solution as sizing agent at 60 oC for 2 h. Then the CMC sized
fabric was dried and calendered.
13
C NMR Spectroscopy
The non-grafted CMC film was dissolved in D2O and MMA-grafted CMC film was
dissolved in dimethyl sulfoxide (DMSO). Then the non-grafted and grafted CMC films were
examined by 13C NMR spectra with proton decoupling at 25 oC by a Bruker AV400 NMR
Spectrometer (Switzerland) at a frequency of 400 MHz and with 14536 scans. The spectrum
range carried out was from 0 to 200 ppm.
129
Scanning Electron Microscopy

The surface morphology of washed and CMC-sized cotton fabrics was examined by a
Scanning Electron Microscope (SEM, Hitachi, Model-S 3400N, VP SEM, Japan). The
micrographs were taken at magnifications of 500 and 1000 times using accelerating voltage
(kV).
Results and Discussion

The synthesis of Na-CMC from knitted rag (1 g) was carried out according to the Scheme
1. The potentiality of the process was the re-use of ethanol after washing of the crude NaCMC. Effects of solvent system, alkali concentration in basification, concentration of monochloroacetic acid for etherification, time and temperature of each reaction step on the degree
of substitution (DS) were optimized.
Table 1. Preparation of Na-CMC by multi-step carboxymethylation method
No. of
Reaction step
1
2
3
4
5
6
7
Amount of
NaOH, g
2.52
2.52
2.52
2.52
2.52
2.52
2.52
Amount of
ClCH2COOH, g
3.2
3.2
3.2
3.2
3.2
3.2
3.2
Yield of
Na-CMC, %
360
751
1052
1231
1304
1404
1494
Remark
Partially soluble in water
Soluble in water
Highly soluble in water
The yields of Na-CMC obtained in carboxymethylation process from first to seventh step
are shown in Table 1. The optimized condition for the synthesis of Na-CMC was established
as ethanol to cellulose ratio of 12:1 (v/w), water to cellulose ratio of 2:1 (v/w), overall NaOH
concentration of 18% (w/v), steeping time of 3 h, steeping temperature of 30 oC, monochloroacetic acid concentration of 80% (w/v), carboxymethylation time of 6 h and
carboxymethylation temperature of 50 oC. It can be seen from Table 1 that yield of CMC is
increased with increasing number of reaction step used in carboxymethylation. The 360%
yield of Na-CMC in the 1st step is increased to 751%, 1052%, 1231%, 1304%, 1404% and
1494% in the 2nd, 3rd, 4th, 5th, 6th and 7th steps, respectively. Solubilities of produced Na-CMC
samples has been tested in water. The Na-CMC obtained by the multi-step
carboxymethylation showed a high water solubility. The role of solvent in
carboxymethylation is to provide accessibility of the etherifying reagent to the reaction site of
cellulose chain [17].
The DS of the prepared Na-CMC has been determined by the acid-base titration method
[3,12]. The step wise DS data are given in Table 2. It can be seen from Table 2 that DS is
increased rapidly at the initial steps and then almost levelled off at the 6th step. The DS
achieved in the 1st step is 0.91 which is increased to 2.72 at the 4th step and 2.84 at the 8th
step. The reason of this phenomenon is due to the fast substitution reaction for initial steps
under alkaline conditions. The hydroxyl group of cellulose in rag fiber is very active, and to
130
be replaced by carboxymethyl group in the initial stages; but decreased the number of OH
group in later stages decreases substitution rate.
Table 2. Determination of DS in CMC prepared from knitted rag at different
etherification steps
No. of reaction step
1
2
3
4
5
6
7
Milliequivalent of NaOH required

per gram of sample, A
4.21
6.07
7.93
8.49
8.63
8.68
8.70
Degree of substitution
0.91
1.52
2.38
2.72
2.82
2.83
2.84
Figure 1 shows that the yield of CMC is increased gradually with the increase of DS.
Complete carboxymethylation of cellulose (DS=3) is not possible. That is why above the 4th
reaction step, the increase in DS is slowed down. It might have occurred that successive
treatment with NaOH generated activated hydroxyl groups for substitution. The
carboxymethylation depends upon the accessibility of reagent and the availability of the
activated hydroxyl groups. Increase of DS by successive treatment with alkali clearly shows
activation of the free secondary hydroxyl groups.
Yield of Na-CMC, gm
16
12
0
0.5
1.5
2.5
Degree of substitution (DS)

Figure 1. Plot of yield of Na-CMC vs DS.
Table 3 represents the intrinsic viscosity and molecular weight of CMC obtained at
different etherification steps. Table 3 shows that the molecular weight of the prepared NaCMC is increased gradually with the increase of reaction step. The reason is obvious that as
the DS increased with successive steps, number of OH groups attached to cellulose molecule
131
is replaced by carboxymethyl groups. As the molecular weight of carboxymethyl group is

higher than that of the OH group, the molecular weight of final product Na-CMC is also
increased with the reaction steps. Table 3 shows that increase of DS and molecular weight is
string down with the number of successive steps indicating the DS of Na-CMC went on to the
completeness of the substitution reaction.
Table 3. The intrinsic viscosity and molecular weight of Na-CMC obtained at different
etherification steps (K = 37 10-5 dl/g and a = 0.61 at 35 oC) [13]
No. of reaction step Degree of substitution
Intrinsic viscosity
Molecular weight
1
2
3
4
5
6
7
0.54
0.61
0.66
0.68
0.71
0.72
0.73
153886
187888
213796
224543
241046
246603
252231
0.91
1.64
2.46
2.72
2.80
2.82
2.84
The amount of CMC, NaCl and others contents in Na-CMC are listed in Table 4. From
Table 4 it can be seen that percentages of CMC and NaCl are increased gradually with the
increase of DS (or, number of reaction steps) and at the same time percentage of other
materials is decreased. This result confirms the increased yield of CMC with increase of
reaction step.
Table 4. The contents of CMC, NaCl and others in synthesized Na-CMC samples
No. of reaction
step
1
2
3
4
5
6
7
Degree of
substitution
0.91
1.64
2.46
2.72
2.80
2.82
2.84
Na-CMC, %
NaCl, %
Others, %
72.60
76.80
79.00
81.40
82.80
83.80
85.00
3.07
3.29
3.44
3.51
3.58
3.65
3.65
24.33
19.91
17.56
15.09
13.62
12.55
11.35
Table 5. Effect of MMA concentration on modification of CMC film (DS=2.72)

No. of
experiment
1
2
3
4
5
MMA
concentration, %
40
60
80
90
100
Grafting
yield, %
10.29
12.76
20.58
13.51
12.35
Grafting
efficiency, %
25.74
19.60
19.40
15.15
12.35
132
Table 5 shows that maximum graft yield is obtained at 80% MMA concentration and then
decreases with further increase of MMA concentration due to homopolymer formation at the
higher concentration of MMA.
The moisture content, water absorption, gel content, tensile strength and elongation at
break of CMC and grafted CMC are listed in Table 6. It can be seen from Table 6 that
moisture content and water absorption value of CMC are 2.86% and 7.69%, respectively.
These values are much higher than the value of MMA-grafted CMC. This indicates that
MMA has been grafted successfully with the prepared CMC film, and due to the
incorporation of MMA, the grafted film losses its moisture absorption capacity. The gel
content of grafted film is 97.03% which is lower than that in the CMC film. The high gel
content means the high reactivity [14-16]. It is proved that MMA has been successfully
grafted to the prepared CMC film. Table 6 indicates also that the breaking load and
elongation of CMC film are 0.72 MPa and 2.6 %, respectively; and those of grafted-CMC
film are 1.34 MPa and 1.7%, respectively. It is seen that the tensile strength is increased but
the elongation percentage at break is decreased on grafting. The tensile strength of grafted
CMC film is higher due to the incorporation of MMA monomer to CMC film and this
reasonably increased the rigidity of the grafted film and hence lowered elongation at break.
Table 6. Comparison of physical properties of CMC (DS=2.72) and MMA-grafted CMC
film (3% CMC film)
Name of
sample
CMC film
Grafted
CMC film
Moisture
content,
%
2.86
1.08
Water
absorption, %
7.69
1.78
Gel
content,
%
99.47
97.03
Tensile
strength,
MPa
0.72
1.34
Elongation
at break,%
2.6
1.7
FTIR Analysis of CMC and Grafted CMC Films

The FTIR spectra of standard CMC film (DS = 0.8), prepared CMC film (DS = 2.72),
and MMA-grafted CMC film powder pelleted with excessive KBr are shown in Figure 2. It
can be seen from Figure 2 that the peaks assigned at 1630 cm-1 and 1420 cm-1 indicate the
presence of carboxymethyl substituent in both standard CMC and prepared CMC films
[Figures 2b and 2c]. The carboxylate ion [18] gives rises to two bands: a strong asymmetrical
stretching band near 16501550 cm-1 and a weaker symmetrical stretching band near 1400
cm-1. Two weak peaks near 1630 cm-1 and 1420 cm-1 in cellulose are observed which are due
to absorbed water and CH2, respectively. Hence the occurrence of strong peaks in CMC films
confirms the formation of CMC by the process of etherification between knitted rag and
mono-chloroacetic acid in strong alkaline alcoholic medium. An extra absorption band at
1741 cm-1 is observed in grafted CMC film indicating the stretching of C = O group, which is
due to the introduction of ester carbonyl group of the grafted MMA [19,20]. So the
appearance of new peak in the spectrum of MMA-grafted CMC film suggests that MMA has
been successfully grafted to prepared CMC film.
133
Figure 2. FTIR Spectra of (a) knitted rag (cellulose), (b) standard CMC film (DS = 0.8), (c) prepared
CMC film (DS = 2.72) and (d) MMA-grafted CMC film.
Application of CMC to Textiles

CMC is extensively used as protective coating solution for textiles and in many other
fields. The prepared CMC was applied as sizing agent to develop the physico-chemical
characteristics of both fabric and yarn which was investigated by FTIR and SEM tests.
Figure 3. FTIR spectra of (a) washed cotton fabric, (b) 3% CMC modified (DS = 2.46) cotton fabric.
134
FTIR Analysis of Cotton and CMC Modified Cotton Fabrics

FTIR spectra of washed and CMC-modified cotton fabrics are shown in Figure 3. From
Figure 3b it can be observed that an absorption band at 1638 cm-1 is assigned to the stretching
vibration of C = O in CMC modified cotton fabric. The spectra suggest that CMC has been
successfully deposited on the modified cotton fabric.
13
C NMR Analysis of CMC and Grafted CMC Films
Figure 4. 13C NMR spectra of (a) prepared CMC film (DS = 2.72) recorded in D2O at 25 oC (number of
scans 13223) and (b) MMA-grafted CMC film (DS = 2.72) recorded in DMSO at 25 oC (number of
scans 13223).
13
C NMR spectra of prepared CMC film and MMA-grafted CMC film are shown in
Figure 4. The molecular structure of CMC was analysed by means of 13C NMR spectroscopy
of the intact polymer. Figure 4a shows a 13C NMR spectra of CMC film with a DS value of
2.72, and the typical signals with their chemical shifts of the modified anhydroglucose unit
are in the range of 60-105 ppm as well as peaks assigned for carboxymethyl groups at
C8=178.9 (C=O) and C7=70.2 ppm respectively [21,22]. Here new peaks are due to the
esterification of hydroxyl groups of C2, C3 and C6. From Figure 4b, it can be observed that
the chemical shift of ester C=O and CH3-groups (which come from carbonyl bearing
monomer MMA) are at 179.7 ppm and 21.8 ppm respectively. The appearances of these two
strong sharp signals in the NMR spectra of MMA-grafted CMC film give the supporting
evidence on the success of grafting.
135
SEM Analysis of Cotton and CMC Modified Cotton Fabrics
Figure 6. Scanning electron micrograph of (a) washed cotton fabric (magnified 500 times), (b) washed
cotton fabric (magnified 1000 times), (c) washed cotton fabric after 3% CMC treatment (magnified 500
times), (d) washed cotton fabric after 3% CMC treatment (magnified 1000 times).
136
Washing with soda ash was done to remove impurities and adventitious dirt. The surface
morphologies of washed and CMC modified cotton fabrics was examined by SEM and are
shown in Figure 6. Figures 6a and 6b show SEM image of washed cotton fabric at two
magnifications. From the Figures 6a and 6b it can be seen that the image of cotton fiber
surface is loosened, ruptured, and cracked for washing with soda ash. Figures 6c and 6d show
SEM images of 3% CMC-modified cotton fabric at two magnifications and it is noticed that
the surface of the fiber is very smooth and no rupture is visible as the surface of yarns were
sized with CMC and projecting fibers are not noticed on the surface. This indicates deposition
of CMC on the fabric fiber. The deposited CMC might form probably chemical bond by
abstracting a hydrogen atom from the fabric fiber backbone.
CELLULOSE ACETATE
Introduction
Cellulose acetate (CA) is one of the most common cellulosic derivative of the present day
world. It is widely used in textiles and many other industrial fields including fibers, films,
sheets, coatings and plastic moldings. It is also extensively used in wearing apparel, such as
woven fabrics, knits, braids, woven fashion etc. and is often blended with other fibers to make
combination yarns [23]. Hence it is a very useful ingredient in textile manufacturing and in
everyday life. The importance of CA is increasing day by day. CA is prepared from different
cellulosic sources by different methods [24-26]. As Bangladesh is textile industry based
country, a large amount of CA is required to meet its demand for textile sectors. Textile
industries of Bangladesh produce huge amount of cellulosic rags that have virtually no use.
The purpose of the present part is to explore the possibility of synthesis of a high grade
CA from the rags by applying multiple steps acetylation method. As the rags, especially
knitted rag contains high amount of good quality -cellulose, it will be a great source for the
manufacture of CA and acetyl derivatives of other polysaccharides. In the present research
work, a lucrative method for producing novel CA with good solubility and fair degree of
substitution at a low cost from knitted rag has been explored to satisfy its need in Bangladesh.
Experimental
Materials
The knitted rag was collected from Mozart Knit Limited, Ashulia, Saver, Dhaka. Glacial
acetic acid (GAA; BDH, England), acetic anhydride (AA; BDH, England), hydrogen
peroxide (Merck, India), sulfuric acid (Merck, India), standard cellulose acetate (Fluka,
Switzerland) etc. were purchased as analytical grade and used without further purification.
Preparation of sample from both non-colored and colored knitted rag for acetylation has
been discussed in the CMC Part.
137
Preparation of Cellulose Acetate

The CA was synthesized by the conversion of dry knitted rag swollen in glacial acetic
acid with acetic anhydride in presence of conc. H2SO4. The production of CA was carried out
by the following three steps [4b]:
(a) Pretreatment
In the first step,1g knitted rag was immersed successively in distilled water and glacial
acetic acid (GAA) at 30 oC for 30 min with occasional stirring. Then, it was filtered and
dewatered by washing with the GAA.
(b) Acetylation
In the second step, a mixture of GAA and conc. H2SO4 was added to the above wet
sample and was shaken vigorously for 5 min. Then acetic anhydride (Ac2O) was added to the
mixture and shaken vigorously for another 5 min and then the system was continuously
shaken for further 1 h at 30 oC.
(c) Hydrolysis
In the third step, a mixture of distilled water and GAA at the ratio of 1:2 was added to the
system obtained on acetylation with high speed stirring for 5 min at 30 oC. Then the
temperature was raised to 55 oC and continued the reaction for 30 min with occasional
stirring. The product was precipitated in distilled water and held overnight. Then the CA was
carefully filtered with a Buckner funnel.
Single step acetylation gave only low substituted product. Highly substituted CA can be
prepared by performing multi-step acetylation. In each step, acetylation was done with fresh
addition of GAA and Ac2O. The synthesized crude CA was washed with distilled water,
stabilized with Na2CO3 and then dried over P2O5 in a desiccator.
138
Scheme 2. Flow chart for the preparation of CA from knitted rag.
Determination of Acetyl Content, Acetic Acid Content and Degree of Substitution

Acetyl content, acetic acid content and degree of substitution (DS) of the products were
determined by the alkali saponification method. In aliquot of 1 g dried sample was put into a
flask containing 40 mL of 75% ethanol, heated at 50 oC for 30 min followed by addition of 40
mL of 0.5 N NaOH solution and saponified at 30 oC for 24 h. The excess alkali was back
titrated with 0.5 N HCl. The acetyl content, acetic acid content and DS of CA were calculated
by the following equations [4b]:
Acetyl content, % = [(A - B) Nb (C - D) Na] 4.3 / W
Acetic acid content, % = % Acetyl 1.395
and DS = 3.86 % acetyl / (102.4 - % acetyl)
139
where, A, B, C, D Na and Nb are mL of NaOH added to sample, mL of NaOH added to blank,

mL of HCl added to sample, mL of HCl added to blank, normality of HCl solution and
normality of NaOH solution, respectively; and W is weight of sample (g). Factor 4.3 is %
acetyl, equivalent to CH3CO group.

Cellulose acetate was dissolved in dimethyl sulfoxide (DMSO) and the molecular weight
was determined by the viscosity measurement method. The procedure was as in CMC part.
Grafting Procedure
The procedure for graft polymerization of CA was as in CMC part.
Moisture Content, Water Absorption and Gel Content
The procedure for determination of moisture content, water absorption and gel content
were as in CMC Part.
Tensile Strength
The procedure for tensile strength is similar to CMC part.
FTIR Spectroscopy
The procedure is similar to CMC Part.
13
C NMR Spectroscopy
The non-grafted CA film was dissolved in acetone and MMA-grafted CA film was
dissolved in dimethyl sulfoxide (DMSO). Then 13C NMR spectra of non-grafted and grafted
films were determined as in CMC part.

The synthesis of CA from knitted rag (1 g) was carried out according to the Scheme 2.
The potentiality of the process is the recovery of GAA by distillation method and its reuse.
The parameters investigated were the effect of solvent system, GAA concentration for
pretreatment, concentration of Ac2O in presence of conc. H2SO4 for acetylation, and GAA
concentration for hydrolysis, time and temperature of the reaction for the acetyl content and
degree of substitution. The acetylation reaction was optimized with respect to the DS by
varying each parameter.
140

Table 7. Preparation of CA by multi-step acetylation
No. of
reaction steps
1
2
3
4
Volume of
GAA, ml
20
20
20
20
Volume of
Ac2O, ml
6
6
6
6
Yield of
CA, %
158.6
172.1
176.0
180.3
20
182.0
20
182.8
20
183.2
Solubility
Insoluble in CHCl3 but soluble in acetone
Soluble in both CHCl3 and acetone
Soluble in CHCl3 but insoluble in acetone
Highly soluble in CHCl3 but insoluble in
acetone
acetone
acetone
acetone
The yield of CA obtained from acetylation process for one to seven steps is shown in
Table 7. The optimized condition for the synthesis of CA was established as GAA to
cellulose ratio of 20:1 (v/w), acetic anhydride to cellulose ratio of 6:1 (v/w), pretreatment
time of 30 min, pretreatment temperature of 30 oC, acetylation time of 1 h, acetylation
temperature of 30 oC, hydrolysis time of 30 min, hydrolysis temperature of 55 oC and H2SO4
to cellulose ratio of 0.1:1 (v/w). It can be seen from Table 7 that yield of CA is increased with
the increase of the number of reaction step in the optimized condition of acetylation. The
yield of product of CA in first step of acetylation after hydrolysis is 158.6%, but for the
second to seventh successive steps, yields are between 172.1% and 183.2% respectively.
Solubilities of the produced CA samples was tested in CHCl3 and acetone. The CA obtained
from multiple steps acetylation shows a high solubility in CHCl3 than the product of single
step. The role of the solvent in the acetylation reaction is to provide accessibility of
esterifying reagent to the reaction centre of the cellulose chain [16].
Table 8. Determination of DS in CA prepared from knitted
rag at different acetylation steps
No. of reaction
step
1
2
3
4
5
6
7
Yield of CA,
%
158.6
172.1
176.0
180.3
182.0
182.8
183.2
Acetyl content,
%
39.95
41.87
43.14
43.96
44.14
44.24
44.25
Acetic acid content,

%
55.73
58.41
60.18
61.32
61.57
61.71
61.73
Degree of
substitution
2.47
2.67
2.81
2.90
2.92
2.93
2.94
The DS of the prepared CA was determined by the acetyl method [4b]. The acetyl
content, acetic acid content and DS data of all steps are listed in Table 8. It can be seen from
Table 8 that DS is increased considerably at the initial steps, but after the 4th step the
141
increasing rate is slowed down. Hence fourth step is considered as optimum. The reason of
this phenomenon is due to the fast substitution reaction for initial steps under acetic
conditions. The hydroxyl groups of cellulose in knitted rag are very active and can be
replaced by acetyl group, which decreases the number of OH groups rapidly. Table 8 also
shows that the yields of CA and acetyl content in CA is increased gradually from the initial
steps to the successive steps with the increase of DS. Acetyl content and acetic acid content
are directly related to DS, and hence this increasing rate is very harmonic to each other.
Complete acetylation of cellulose is practically not possible. That is why above the 4th
reaction step, the increase in DS as well as yield of CA is slowed down. The acetylation
depends upon the accessibility of reagent into cellulose and the availability of the activated
hydroxyl groups on the cellulose surface. DS increased more than one by successive
treatment with GAA clearly shows activation of the free secondary hydroxyl groups.
Table 9 shows that the molecular weight of the prepared CA is increased gradually with
the increase of reaction steps. The reason is that as the DS increased with successive steps,
number of OH groups attached to cellulose molecule was replaced by acetyl groups. As the
molecular weight of acetyl group is higher than that of the OH group, the molecular weight of
final CA product is also increased with the reaction steps. Table 9 shows that increase of DS
and molecular weight is string down with the number of successive steps indicating the DS of
CA went on to the completeness of the substitution reaction.
Table 9. Determination of molecular weight of CA products at different acetylation
steps using DMSO as (K= 171 10-5 dl/g and a = 0.61 at 25 oC) [13]
No. of reaction step
1
2
3
4
5
6
7
2.47
2.67
2.81
2.90
2.92
2.93
2.94
Intrinsic viscosity
1.6
1.8
1.95
2.05
2.1
2.15
2.16
Molecular weight
74,249
90,063
102,691
111,465
115,956
120,517
121,437
From Table 10 it can be seen that high graft yield is obtained at 80% MMA
concentration, whereas high grafting efficiency is found at 40% MMA concentration. The
graft yield is decreased at the high MMA concentration due to the formation of
homopolymer. With the increase of monomer concentration, grafting efficiency is decreased.
Table 10. Effect of MMA concentration on modification of cellulose acetate film
(DS=2.90)
No. of experiment
1
2
3
4
5
MMA concentration, %
40
60
80
90
100
Grafting yield, %
10.29
12.76
18.50
13.51
12.35
Grafting efficiency, %
25.74
19.60
19.40
15.15
12.35
142
The moisture content, water absorption, gel content, tensile strength and elongation at
break of CA and grafted CA are listed in Table 11. It can be seen from the Table 11 that the
moisture content and water absorption value of CA film are lower than those of grafted CA
film. These values for CA film are 1.71% and 1.22%, and those for grafted CA film are
0.98% and 0.87%, respectively. It proves that MMA has been successfully grafted with
prepared CA film, and due to the incorporation of MMA in grafted CA film a somewhat
hydrophobic nature is developed. The percentage of gel content of grafted film is less than
CA film. The high gel content means high reactivity. It is also proved that MMA has been
fruitfully grafted to the prepared CA film. Breaking load and elongation at break of CA film
are 1.00 MPa and 3% (Table 11), and those of grafted CA film are 1.73 MPa and 2%,
respectively. This result shows that the tensile strength of grafted CA film is higher than CA
film and the elongation of grafted CA film is lower than CA film. The higher tensile strength
of grafted CA film is due to the incorporation of MMA to CA film. This reasonably increased
the rigidity of the grafted film, and hence lowered elongation at break.
Table 11. Comparison of physical properties of CA film (DS=2.90) and grafted CA film
(2% CA film)
Name
sample
CA film
Grafted
CA film
Moisture
content, %
1.71
0.98
Water
absorption, %
1.22
0.87
Gel content,
%
99.18
96.77
Tensile
strength, MPa
1.00
1.73
Elongation
at break,%
3
2
Figure 6. FTIR spectra of (a) cellulose, (b) standard CA film (DS=2.47), (c) prepared CA film (DS=
2.90) and (d) MMA-grafted CA film.
143
FTIR Analysis of CA and Grafted CA Films

The FTIR spectra of knitted rag (cellulose), standard CA film (DS=2.47), prepared CA
film (DS=2.90) and prepared MMA-grafted CA film are shown in Figure 6. From Figure 6, it
can be observed that the characteristic broad absorption bands of OH and C-O groups are at
around 3430-3470 cm-1 and 1051-1057 cm-1 respectively [19,27,28]. However, the graft
copolymer prepared with carbonyl-bearing monomer MMA shows an ester C=O group
stretching band near 1751 cm-1, in addition to the original bands associated with cellulose
[29] such as OH and bound water [14]. Here the appearances of strong sharp peak in the
spectrum of prepared MMA-grafted CA film supports the evidence for the grafting, and
suggests that MMA has been successfully grafted to prepared CA film.
13
C NMR Analysis of CA and Grafted CA Films
Figure 7. 13C NMR spectrum of (a) prepared CA film (DS=2.90) recorded in CHCl3 at 25 oC (number of
scans 13417) and (b) MMA-grafted CA film (DS=2.90) recorded in DMSO at 25 oC (number of scans
13417).
13
C NMR spectrum of prepared CA film and MMA-grafted CA film are shown in Figure
7. From Figure 7(a) it can be seen that the two new peaks at C7 and C8 are appeared in
addition to the typical peaks of anhydroglucose unit. This spectrum proves the molecular
structure of CA. The chemical shift of C8 (acetyl methyl) and C7 (carbonyl) are in the range
of 20.1 20.8 ppm and 169.3 - 170.4 ppm respectively [30-32]. It can be observed from
Figure 7(b) that the chemical shift of ester C=O group (which come from carbonyl bearing
monomer MMA) is at 170.5 ppm. Here the appearance of strong sharp signal in the NMR
spectra of prepared MMA-grafted CA film give the supporting evidence for the successful
grafting.
144
SEM Analysis of Cotton and CA Modified Cotton Fabrics
cotton fabric (magnified 1000 times), (c) washed cotton fabric after 3% CA treatment (magnified 500
times and scale 100 m), (d) washed cotton fabric after 3% CMC treatment (Magnified 1000 times and
scale 50 m).
Figures 8a and 8b show SEM images of washed cotton fabric and its magnified image,
respectively. It can be seen from the Figures 8a and 8b that the image of cotton fiber surface
is loosened, ruptured and cracked, which are due to washing with Na2CO3 solution. Figure 8c
145
and 8d show SEM images of 3% CA treated cotton fabric. It can be seen from the Figures 8c
and 8d that the surface of the single fiber is very smooth, and no rupture is visible in the
images, because surface of the yarns are sized with CA and projecting fibers are not the
visible on surface. This indicates the CA deposition to the fabric fiber surface occurred, and
this is a good agreement with the FTIR results.
CELLULOSE NITRATE
Introduction
Cellulose nitrate (CN) is also one of the important cellulosic derivative used in textiles
and many other industrial fields including films, sheets, safety glass, thermoplastic materials,
composite materials, and coating agents in metal industry. It is also extensively used in
cellulose nitrate membrane, art conservation, pottery reconstructions, diagnostic test,
immobilization of proteins, adhesive for stone and ceramics [33-37]. Hence it is vastly
important in everyday life, and the demand is increasing day by day. Like CMC and CA, the
purpose of the present part is to explore the possibility of synthesis of high grade CN from the
knitted rags by applying multi-steps nitration method.
Experimental
Materials
The knitted rag was collected from Mozart Knit Limited, Ashulia, Saver, Dhaka.
Phosphorus pentaoxide (BDH, England), nitric acid (BDH, England), methanol (Merck,
India), ethanol (Merck, India), sulfuric acid (Merck, India), sodium thiosulfate pentahydrate
(BDH, England), salicylic acid (Merck, India) etc. were used without further purification.
Preparation of sample from both non-colored and colored knitted rag for nitration has
been discussed in CMC Part.
Preparation of Cellulose Nitrate
1. Preparation of the reagent
200 g of P2O5 was slowly added to 100 g of cold 70% nitric acid in an ice bath. After the
reaction, the composition of the mixture was 64% of nitric acid, 26% of phosphoric acid and
10% of phosphorus pentaoxide.
146
2. Nitration
In this step, 1 g dry knitted rag was added to 50 ml of the above prepared reagent at 0 oC
for 2 h with occasional stirring. After nitration the CN was carefully filtered on a fritted glass
crucible. The reaction for the synthesis of CN was taken place mentioned below:
Single step nitration only gave low substituted product. Highly substituted CN could be
prepared by multi-step nitration. In each step, nitration was done with fresh addition of the
reagent.
3. Washing and stabilization
The synthesized crude CN was washed with cold distilled water, stabilized with boiling
water, rinsed with methanol and then dried in an oven at 50 oC.
Scheme 3. Flow chart for the preparation of CN from knitted rag.
147
Determination of Yield, Nitrogen Content and Degree of Substitution

Yield of CN at the different steps was calculated by the following equation:
Yield, % = (wt. of product / wt. of cellulose) 54.6
Nitrogen content and degree of substitution of the products were determined by the
Kjeldahl method. 25 mg dried CN was weighed out and put into a Kjeldahl flask containing 2
mL of conc. H2SO4 and 0.1 g of salicylic acid. After overnight immersion 0.3 g of sodium
thiosulfate pentahydrate, 0.6g of K2SO4 were added. The mixture was warmed gently for 10
min and finally refluxed for about 6 h. The solution was diluted with 15 mL of water and
made alkaline by the addition of 20 ml of 35% NaOH, then distilled with 25 mL of 0.8%
boric acid solution containing indicator. After 10 min, the boric acid solution was titrated with
0.03 N HCl. The nitrogen content and DS of CN are determined by the following equation
[4c]:
Nitrogen, % = (meq. of acid 1400) / mg of sample
and DS = (1.62 % N) / (14 - 0.45 % N)

Cellulose nitrate was dissolved in dimethyl sulfoxide (DMSO) and the molecular weight
was determined as in CMC part.
Grafting Procedure
The procedure for graft polymerization of CN was as in CMC part.
Moisture Content, Water Absorption and Gel Content
The procedure for determination of moisture content, water absorption and gel content
was as in CMC Part.
Tensile Strength
The procedure for tensile strength was as in CMC part.
FTIR Spectroscopy
The procedure of identification of CN and graft were similar to those of CMC Part.
13
C NMR Spectroscopy
The procedure is similar to CA Part.

148

The synthesis of CN from knitted rag (1 g) was carried out according to the Scheme 3.
The potentiality of the process is the re-use of reagent after washing of crude CN. Effects of
solvent system, preparation of the reagent, preparation of the sample, concentration of reagent
for nitration, time and temperature of reaction for nitration step on the degree of substitution
were optimized.
Table 12. Preparation of CN by multi-steps nitration method
No. of
reaction step
1
Volume of
reagent, mL
50
Yield of
CN, %
169.26
50
182.36
3
4
50
50
197.00
208.14
50
212.06
50
214.04
50
215.56
Solubility
Insoluble in pyridine but soluble in
acetone
Insoluble in pyridine but soluble in
acetone
Soluble in both pyridine and acetone
Highly soluble in both pyridine and
acetone
acetone
acetone
acetone
The yield of CN obtained by nitration process from 1st to 7th steps is shown in Table 12.
The optimized condition for the synthesis of CN was established as preparation of the
reagent, cellulose to reagent ratio of 1:50 (w/v), nitration time of 2 h and nitration temperature
of 0 oC. It can be seen from Table 12 that yield of CN is increased with increasing number of
reaction step in nitration. The yield of product of CN in the first step of nitration is 169.26 %,
but for the 2nd to 7th successive steps these values are between 182.36 % and 215.56 %
respectively. Solubilities of the produced CN has been tested in pyridine and acetone, and is
listed in Table 12. The CN obtained by multi-steps nitration showed a higher solubility in
pyridine than the product of initial step. The role of solvent in nitration reaction is to provide
accessibility of esterifying reagent to the reaction site of the cellulose chain [16,38].
The DS of the prepared CN was determined by the Kjeldahl method [4c]. The % nitrogen
content and the corresponding stepwise DS data are given in Table 13. It can be seen from
Table 13 that DS is increased rapidly at the initial step but after the 4th step, the increasing
rate of DS is slowed down. Hence, the DS value obtained at the fourth step is considered as
optimum. The reason of this phenomenon is due to the fast substitution reaction for initial
steps under acetic conditions. The hydroxyl group of cellulose in knitted rag fiber are very
active; and can be replaced by NO2 group in the initial stages, as a result decreased the
number of OH groups very fast in the latter stages. Table 13 also shows that the yield of CN
and nitrogen content in CN are increased gradually from the initial to the successive steps
with the increase of DS. Nitrogen content is directly related to DS, and hence this increasing
149
rate is very harmonic to each other. The nitration is dependent upon the accessibility of
reagent and the availability of the activated hydroxyl groups in cellulose. Increase of DS by
successive treatment with reagent mixture clearly shows activation of the free secondary
hydroxyl groups.
Table 13. Determination of DS in prepared CN from knitted rag at different nitration
steps by the Kjeldahl methods
No. of reaction
step
1
2
3
4
No. of reaction
step
5
6
7
Yield of CN,
%
169.26
182.36
197.00
208.14
Yield of CN,
%
212.06
214.04
215.56
Nitrogen content,
%
12.49
13.20
13.70
13.96
Nitrogen content,
%
14.02
14.03
14.04
2.41
2.65
2.83
2.93
2.95
2.96
2.96
The molecular weight of the prepared CN is increased gradually with the increase of
reaction steps and the results are listed in Table 14. The reason is that as the DS increased
with successive steps, number of OH groups attached to cellulose molecule is replaced by
NO2 groups. As the molecular weight of NO2 group is higher than the OH group, the
molecular weight of final CN product is also increased with the nitration reaction. Table 14
shows that increase of DS and molecular weight is string down with the number of successive
steps indicating the DS of CN went on to the completeness of the substitution reaction.
Table 14. Determination of molecular weight of CN obtained at different steps using
acetone as solvent (K = 6.93 10-5 dl/g and a = 0.91 at 25 oC) [13]
No. of reaction
step
1
2
3
4
5
6
7
Degree of
substitution
2.41
2.65
2.83
2.93
2.95
2.96
2.96
Intrinsic viscosity Molecular weight

2.50
2.70
2.88
3.03
3.10
3.15
3.18
101,841
110,829
118,974
125,801
128,998
131,287
132,661
From Table 15 it can be seen that high graft yield is obtained at 80% MMA
concentration, whereas high grafting efficiency is found at 40% MMA concentration. The
graft yield is decreased at the higher MMA concentration as homopolymer is formed at the
higher concentration of MMA. The grafting efficiency is decreased with the increase of
monomer concentration.
150

Table 15. Effect of MMA concentration on modification of CN film (DS=2.93)
No. of
experiment
1
2
3
4
5
MMA
concentration, %
40
60
80
90
100
Grafting
yield, %
10.29
11.76
15.50
13.51
12.35
Grafting
efficiency, %
25.74
19.60
19.40
15.15
12.35
The physical properties, viz. moisture content, water absorption, gel content and tensile
strength of CN and grafted CN are listed in Table 16. It can be seen from the Table 16 that the
moisture content and water absorption value of CN film are lower than those of grafted CN
film. These values for CN film are 2.11% and 1.29%, and those for grafted CN film are
1.06% and 0.88%, respectively. It is proved that MMA has been successfully grafted to the
prepared CN film and due to the incorporation of MMA in grafted CN film hydrophobic
nature is developed. The percentage of gel content of grafted film is less than CN film. The
high gel content shows high reactivity. It is also proved that MMA has been fruitfully grafted
to prepared CN film. Breaking load and elongation of CN film are 0.72 MPa and 2.6%, and
those for grafted CN film are 1.25 MPa and 1.8% respectively (Table 16). This result shows
that the tensile strength of grafted CN film is higher than CN film, and elongation at break of
grafted CN film is lower than CN film. The higher tensile strength of grafted CN film is due
to the incorporation of MMA to CN film, and thus reasonably increased the rigidity of the
grafted film; and hence lowered elongation at break.
Table 16. Comparison of physical properties of CN (DS=2.93) and MMA-grafted CN
films (2% CN film)
Name of
sample
CN film
Grafted CN
film
Moisture
content,
%
2.11
1.06
Water
absorption, %
Gel content,
%
Tensile
strength, MPa
Elongation
at break, %
1.29
0.88
99.21
96.90
0.72
1.25
2.5
1.8
FTIR Analysis of CN and Grafted CN Films

The FTIR spectra of knitted rag cellulose, prepared CN film (DS=2.93) and MMAgrafted CN film are shown in Figure 9. It can be observed from Figure 9 that the
characteristic broad absorption bands of CH2, ONO2 and C-C-O groups stretching are at
around 2968 cm-1, 1651 cm-1 and 1069 cm-1 respectively [39]. However, the graft copolymer
prepared with carbonyl-bearing monomer MMA showed an ester carbonyl group stretching
band near 1756 cm-1 in addition to the original bands associated with cellulose [14,29]. Here
the appearances of strong sharp peak in the spectra of MMA-grafted CN film give supporting
evidence for the grafting and suggests that MMA has been successfully grafted to prepared
CN film.
151
Figure 9. FTIR spectra of (a) cellulose, (b) prepared CN film (DS= 2.93) and (c) MMA-grafted CN
film.
13
C NMR Analysis of CN and Grafted CN Films
Figure 10. 13C NMR spectra of (a) prepared CN film (DS = 2.93) recorded in acetone at 25oC (number
of scans 14536) and (b) MMA-grafted CN film (DS = 2.93) recorded in DMSO at 25 oC (number of
scans 14536).
152
cotton fabric (magnified 1000 times), (c) washed cotton fabric after 3% CN treatment (magnified 500
times and scale 100 m), (d) washed cotton fabric after 3% CN treatment (Magnified 1000 times and
scale 50 m).
13
C NMR spectra of prepared CN film and MMA-grafted CN film are shown in Figure
10. As the number of carbon atom in anhydroglucose unit and cellulose nitrate are same, i.e.,
6, the chemical shift of the anomeric carbon is sensitive to the presence or absence of a nitro
group after nitration of cellulose hydroxyl groups at C2, C3 and C6 positions, because the
electron attracting induced effect of nitro group is stronger than that of hydroxyl group. It can
be seen from Figure 10a that the chemical shift of C1 appeared at 101.5 ppm, and that of C6
appeared at 69.3 ppm. The upfield signal of C1 and the downfield signal of C5 and C6 as well
as weaker signals (peaks) of C2, C3 and C6 of typical anhydroglucose unit prove the
153
molecular structure of CN [38,39). From Figure 10b it can be observed that the chemical
shifts of ester C=O and CH3 groups (which come from carbonyl bearing monomer MMA) are
at 178.2 ppm and 21.3 ppm respectively. Here the appearances of strong sharp signal in the
NMR spectrum of MMA-grafted CN film suggest that MMA has been successfully grafted
onto prepared CN film.
SEM Analysis of Cotton and CN Modified Cotton Fabrics

Figures 11a and 11b show SEM images of washed cotton fabric and its magnified
images, respectively. From the Figures 11a and 11b, it can be seen that the image of cotton
fiber surface is loosened, ruptured, and cracked which are produced due to washing with
Na2CO3 solution. Figure 11c and 11d show SEM images of 3% CN treated cotton fabric and
its magnified images, respectively. It can be seen from Figures 11c and 11d that the surface of
the single fiber is very smooth, and no rupture is visible in the images; because yarn surfaces
are sized with CN as sizing materials and projecting fibers are not visible on surface. This
indicates that the CN deposition to the fabric fiber surface is occurred, and the formation of
bond between CN and fiber backbone is observed by FTIR spectra.
CONCLUSION
Huge amount of knitted rag are dumped as textile wastes by different garment and textile
industries, those have virtually no use. High performance carboxymethyl cellulose, cellulose
acetate and cellulose nitrate (high degree of substitution, purity and molecular weight) were
successfully synthesized from knitted rag, a cellulosic waste, which contains high amount of
good quality -cellulose. Hence, production of different grades CMC, CA and CN using
cellulosic wastes of garment and textile industries can be considered as a feasible alternative
way for generating value-added products, and those will be ultimately helped to reduce the
pollution problems.
ACKNOWLEDGMENTS
The authors would like to acknowledge the Ministry of Education in Bangladesh for
funding the project as Higher Education Research Grant in 2011 (Project no. MoE/Branch 17/
10 M-15/ 2007 (Part-2)/40(36). We also would like to thank to Professor C. M. Mustafa of
Department of Applied Chemistry and Chemical Engineering, Rajshahi University,
Bangladesh and Dr. Jacqualyn Eales of Bangor University, UK for checking the language and
technical points.
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M.A., Jalil, M.A. (1997). Preparation of sodium-carboxymethyl cellulose from bagasse,
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ASTM (1961). Tentative methods of testing sodium carboxymethyl cellulose. ASTM:
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acrylonitrile onto jute fiber with permanganate ion initiator system in presence of air. J.
Appl. Polym. Sci. 55, 1673-1682.
Lin, O.H., Kumar, R.N., Rozman, H.D., Noor, M.A.M. (2005). Grafting of sodium
carboxymethylcellulose (CMC) with glycidyl methacrylate and development of UV
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Ethers, in cellulose and cellulose Derivatives (Vol.II). Interscience Publishers, Inc.,
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procedure for analysis of cellulose and modified cellulose. Anal. Chem. 29, 998.
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[20] Adinugraha, M.P., Marseno, D.W., Haryadi, (2005). Synthesis and characterization of
sodium carboxymethyl cellulose from cavendish banana pseudo stem (Musa cavendishi
LAMBERK), Carbohydr. Polym. 62, 164-169.
[20] Aguir, C., MHenni, M.F. (2006). Experimental Study on Carboxymethylation of
Cellulose Extracted from Posidonia Oceanica. J. Appl. Polym. Sci. 99, 1808-1816.
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new solvent dimethyl sulfoxide/tetrabutylammonium fluoride, Carbohydr. Polym. 60,
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cellulose acetate from wood in concentrated acetic acid. Cellulose 10, 397-404.
[24] Saka, S. (2004). Wood as natural raw materials for cellulose acetate production,
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[25] Saka, S. (2004). Cotton fibers as natural raw materials for cellulose acetate production,
Macromol. Symp. 208, 29-35.
[26] Mondal, Md.I.H., Farouque, F.I., Salam, M.A. (2006). Graft copolymerization of
acrylate monomers onto sulfonated jute-cotton blended fabric. J. Applied Polym. Sci.
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diffraction study of the polymorphism of native celluloses. Macromolecules 24, 2461
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[28] Marchessault, R.H., Liang, C.Y. (1960). Infrared spectra of crystalline polysaccharides,
III, Mercerized cellulose. J. Polym. Sci. 43, 71-84.
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acetylation of cellulose in new ionic liquid. Biomacromolecules 5, 266-268.
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cellulose acetate by means of a 13C NMR study on its propanoated derivative.
Carbohydr. Res. 273, 83-91.
[31] Buchanan, C.M., Edger, K.J., Hyatt, J.A., Wilson, A.K. (1991). Preparation of cellulose
acetate and determination of monomer composition by NMR spectroscopy.
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[32] Shari, Li. X., Glen, E. F., Chongin, W., James, Y. (2007). Templating mesoporous
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156
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studies of cellulose nitrates. Applied Spectroscopy 45(4), 604-610.

ISBN: 978-1-63117-262-5
Chapter 6
HISTORY, SYNTHESIS AND PROPERTIES

OF AZO PYRIDONE DYES
Faculty of Technology and Metallurgy, University of Belgrade,
Belgrade, Serbia
ABSTRACT
Azo dyes are synthetic organic colorants bearing chromophoric azo group. Over 50%
of the colorants used belong to the azo compounds. Such a wide range of usage of azo
dyes is due to the number of variations in chemical structure and methods of application
which are generally not complex. Cotton, paper, silk, leather, and wool can be dyed by
azo dyes. Also, there are azo dyes for dying polyamides, polyesters, acrylics, polyolefins,
viscose rayon, and cellulose acetate. They can be used for the coloring of paints,
varnishes, plastics, printing inks, rubber, foods, drugs, and cosmetics. Azo colorants are
also used in diazo printing and color photography.
Among azo colorants arylazo pyridone dyes have become important in the last
several decades. The high molar extinction coefficient, the medium to high light and wet
fastness properties are very favourable. They find application generally as disperse dyes.
Disperse dyes are characterized by low aqueous solubility and are applied to hydrophobic
fibers from an aqueous system, in which the dye is present in a highly dispersed state.
The importance of disperse dyes increased in the 1970s and 1980s due to the use of
polyester and nylon as the main synthetic fibers. Also, disperse dyes were used rapidly
since 1970. in inks for the heat-transfer printing of polyester as well as for other
applications including hot-melt inks, ink-jet inks and color filters for liquid-crystal
display panels.
Pyrydone azo dyes generally produce yellow shades on fabrics but other shades were
also reported. Dye structure affects the intensity of color and fastness properties. Azo
pyridone dyes which have OH or NH group in ortho position to azo group show an azohydrazone tautomerism which was investigated in a number of papers. Azo-hydrazone
tautomerism was studied in solvents as well as by crystallography. Generally, azo
E-mail: kavur@tmf.bg.ac.rs
158

pyridone dyes exist in hydrazone form in the solid state while in solvents azo-hydrazone
equilibrium can be found.
1. INTRODUCTION
A hundred years ago, the usual way to apply dyes to cotton, wool, silk etc. (natural fibers)
is to make an aqueous dye solution. When after the First World War a man-made fiber,
cellulose acetate, was introduced, only a few available dyes had affinity for the new fiber due
to its hydrophobic nature. This led to development of disperse dyes [1].
The first dyes developed for the application to acetate fibers were the Ionamine dyes [13]. They are characterized by the presence of hydroxyl and amino groups and a relatively low
molar mass. These dyes which are water soluble were hydrolyzed to produce the sparingly
soluble free base in the form of a very fine suspension which was then absorbed by the fiber.
The use of disperse dyes was increased when new man-made fibers as nylon and acrylic
were introduced in the late thirties and early forties. The real boom in disperse dyestuff
development was not until late forties when polyester fibers were commercially
introduced [1].
Disperse dyes are non-ionic compounds which have very limited solubility in water at
room temperature and have substantivity for hydrophobic fibers such polyester, nylon and
acetate. To achieve efficient diffusion into fibers these dyes are usually applied as a fine
aqueous dispersion. The molar mass of dyes should be in the range 400-600. Also, disperse
dyes should be able to withstand various dyeing conditions, pH and temperature [1,4,5]. In
thermofixation and heat transfer printing the dyes must first sublime into single molecules
before diffusion into the fiber.
Usually, disperse dyes contain no water solubilising groups and they are marketed in the
form of either an easily dispersible powder or a concentrated aqueous dispersion. A surfaceactive agent is needed in order to keep dye particles in dispersion [1].
There are several methods for the classification of disperse dyes. In the 1970s, ICI
(Imperial Chemical Industries) divided disperse dyes according to their sublimation fastness
and dyeing properties. The dyes were placed into categories from A to D, where dyes in class
A had low relative molar masses and hence poor sublimation fastness. Dyes in class D had
high relative molar masses and good sublimation fastness. Therefore dyes in class A had
desirable dyeing properties while dyes in class D had poorer dyeing properties. Dyes in
classes B and C were between these two border classes. Other dye manufacturing companies
also introduced their own similar systems of disperse dye classification [1].
The Disperse Dye Committee of the Society of Dyers and Colourists has classified the
dyeing characteristics of disperse dyes according to the results of several tests (the build up,
leveling properties, rate of dyeing and temperature range properties). The dyes are divided in
two classes: low energy and high energy disperse dyes. The low energy disperse dyes
comprise small dye molecules with low polarity. They are levelling, rapid dyeing dyes with
poor heat resistance. The high energy disperse dyes are more polar, higher molar mass dyes.
They have low dyeing rates, poor migration during dyeing but good heat and sublimation
fastness [6].
Acording to Koh [1] the Colour Index in 1992 listed around 1,150 disperse dyes. Among
them monoazo dyes of relatively low molar mass were the majority. They are generally
159
nonionic, although they may be quite polar. Anthraquinone derivatives made a significant
portion of the disperse dyes, but they are being gradually replaced (because of cost and
environmental problems). In the last several decades newer disperse dyes were developed
based on the heterocyclic components [5].
Disperse dyes can be divided by chemical structure as: monoazo, anthraquinone,
benzodifurane, methine, nitrodiphenylamine, naphthalimide and quinoline derivatives.
Azo dyes are synthetic organic colorants bearing the chromophoric azo group. On one
side the azo group is attached to an aromatic or heterocyclic nucleus and on the other, to an
unsaturated molecule of the carbocyclic, heterocyclic, or aliphatic type [7]. IUPAC defines
azo compounds as: "Derivatives of diazene (diimide), HN=NH, wherein both hydrogens are
substituted by hydrocarbyl groups, e.g., PhN=NPh azobenzene or diphenyldiazene" [8].
Commercially, azo colorants are the largest and most versatile class of organic dyestuffs.
As published in Kirk-Othmer Encyclopedia of Chemical Technology [7] in 2003, there were
more than 10,000 Colour Index (C.I.) generic names assigned to commercial colorants.
Approximately 4,500 of them are in use, and over 50% of these belong to the azo compounds.
Azo dyes can be divided according to the number of azo groups to monoazo, disazo, trisazo
and polyazo, and also further subdivision can be achieved according to the solubility or
according to the types of component used. The wide range of usage of azo dyes is due to the
number of variations in chemical structure and methods of application which are generally
not complex. Cotton, paper, silk, leather, and wool can be dyed by azo dyes. Also, there are
azo dyes for dying polyamides, polyesters, acrylics, polyolefins, viscose rayon, and cellulose
acetate. They can be used for the coloring of paints, varnishes, plastics, printing inks, rubber,
foods, drugs, and cosmetics. Azo colorants are also used in diazo printing and color
photography. The shades of azo dyes cover the whole spectrum [7].
Monoazo disperse dyes are largely based on the parent compound aminoazobenzene, C.I.
Solvent Yellow 1 (Figure 1). Aminoazobenzene dye polyester of yellow with such poor
fastness so it is not used as a disperse dye. By introduction of different groups in
aminobenzene molecule a number of monoazo disperse dyes with different properties can be
obtained. Some of them are listed in Figure 2. In comparison to anthraquinone dyes the azo
group is usually 2 or 3 times stronger in tinctorial strength. Due to their simplicity and the
ease of manufacturing, the cost of manufacturing of azo dyes is comparatively lower than the
expensive anthraquinone dyes. On the other hand, they have duller shades, lower fastness to
light and breakdown into carcinogenic amines. Nevertheless, the cost effectiveness
compensates the drawbacks [1,5].
H2N
N
N
Figure 1. C.I. Solvent Yellow 1.
The color ranges of disperse dyes based on aminoazobenzene are very broad, but the
color of aminoazobenzene derivatives do not extend into the area of greenish yellows. These
dyes are with high extinction coefficients, but are not noted for their brightness [5].
160

O
HO
CH3CN
O2N
CH2CH2CN
CH3
CN
Cl
O2N
CH2CH3
O2N
N
N
CH3CN
N(CH2CH2COCH3)2
N(CH2CH2COCH3)2
H3C
Br
OMe
O2N
N
N
O
NO2
CH3CN
H
N(CH2CH2COCH3)2
5
Figure 2. Monoazo disperse dyes: C.I. Disperse Yellow 3 (1), C.I. Disperse Orange 25 (2), C.I.
Disperse Red 167 (3), C.I. Disperse Violet 33 (4), C.I. Disperse Blue 79 (5).
NH2
NH2
O
OH
NHCH3
OH
NH2
O
O
NH2
NH2
Figure 3. Anthraquinone disperse dyes: C.I. Disperse Red 15 (6), C.I. Disperse Red 60 (7), C.I.
Disperse Violet 4 (8), C.I. Disperse Violet 26 (9).
Anthraquinone disperse dyes (Figure 3) are among dyes which were used for cellulose
acetate as well as for polyester fibers. They produce bright dyeings with color shades from
yellow to even turquoise blue depending on substituents and their position. Also these dyes
show high light fastness and no dye stability problems during dyeing [1].
Benzodifurane disperse dyes gives hues that range from yellow to blue [5]. The example
is C.I. Disperse Red 356 a bright red disperse dye (Figure 4).
161
O
O
O
O
O(CH2)3CH3
Figure 4. C.I. Disperse Red 356.
Coumarin disperse dyes are principally bright fluorescent yellows such as C.I. Disperse
Yellow 82 (Figure 5). Among these dyes some derivatives are used as fluorescent
brighteners [5].
H
N
CH2CH3
CH3CH2
N
N
O
Figure 5. C.I. Disperse Yellow 82.
Although methine based disperse dyes give brilliant yellows [5], the brightest blue
disperse dye available, C.I. Disperse Blue 354 belongs to these disperse dyes (Figure 6).
H 3C
CN H
N(C6H13)2
NC
SO2
Figure 6. C.I. Disperse Blue 354.
Disperse dyes which are naphthalimide derivatives include some brilliant, fluorescent
compounds [5]. C.I. Disperse Yellow 11 is an example of such dyes (Figure 7).
O
H2N
CH3
N
O
Figure 7. C.I. Disperse Yellow 11.
CH3
162
Nitrodiphenylamine disperse dyes are yellow dyes. They have high light fastness on
polyester but poor on nylon. Also they have low extinction coefficients [5]. Examples are C.I.
Disperse Yellow 42 and C.I. Disperse Yellow 59 (Figure 8).
H
N
H
N
O
O
N
NO2
S
O
CH3(CH2)3-N-S
10
NO2
11
Figure 8. C.I. Disperse Yellow 42 (10) and C.I. Disperse Yellow 59 (11).
Quinoline disperse dyes are also yellow dyes (Figure 9). C.I. Disperse Yellow 54 is the
unsubstituted parent compound and is suitable for many general applications. This is a low
energy dye while C.I. Disperse Yellow 64 has higher energy and better resistance to
sublimation [5].
Br
OH
OH
12
13
Figure 9. C.I. Disperse Yellow 54 (12) and C.I. Disperse Yellow 64 (13)
In order to improve further brightness, color range, and economics chemists have
prepared new azo disperse (mono, dis, tris) using different heterocyclic components. Many
heterocycles have been used; some of them are azothiophenes, azobenzothiazoles,
azopyrazolone and azopyridones, or aryl azo pyridone dyes.
-O
-O
+
N O
Et
H O
Cl
Me
14
Et
H O
+
N O
N
O
Me
15
Me
H O
CN
Me
CN
CN
16
Figure 10. Structure of C.I. Disperse Yellow 119 (14), C.I. Disperse Yellow 211 (15) and C.I. Disperse
Yellow 114 (16). (Reproduced from Hemijska Industrija Journal with permission by Association of
Chemical Engineers of Serbia).
163
Among azo colorants arylazo pyridone dyes (Figure 10) have become important in last
several decades. The high molar extinction coefficient and the medium to high light and wet
fastness properties are very favourable. They find application generally as disperse dyes. The
importance of disperse dyes increased in the 1970s and 1980s due to the use of polyester and
nylon as the main synthetic fibers. Also, disperse dyes were used rapidly since 1970 in inks
for the heat-transfer printing of polyester [7]. They can be used in the production of color
filters using them with excellent light and heat resistance [9]. Also, there are basic and
reactive azo pyridone dyes as well as dyes and pigments for usage in printing inks [10].
In the following text synthesis of azo pyridone dyes is illustrated on certain examples
including mono, dis and tris azo dyes. After the overview of synthesis discussion of fastness
and tautomerism is given.
2. SYNTHESIS
2.1. Synthesis of Monoazo Dyes
The main synthetic route for the preparation of azo dyes is the coupling reaction between
an aromatic diazo compound and a coupling component. Of all dyes manufactured, about
60% are produced by this reaction [7]. The success of azo colorants is due to the simplicity of
their synthesis by diazotization and azo coupling, and to the almost innumerable possibilities
presented by variation on the diazo compounds and coupling components [11]. All coupling
components used to prepare azo dyes have the common feature of an active hydrogen atom
bound to a carbon atom.
Generally, arylazo pyridone dyes can be prepared with pyridone moiety as a coupling
component along with various diazonium salts using a well known reaction [11]. Pyridones
can be also prepared using known procedures [12-15]. Figure 11 show the general synthesis
of monoazo pyridone dyes. 3-Cyano-6-hydroxy-4-methyl-2-pyridone (19), prepared from
ethyl cyanoacetate (acetoacetic ester, AAE (17)) and cyanoacetamide (18), is coupled with
diazonim salts derived from 4-nitroaniline (21).
O
O
CN
1. KOH,
2. HCl
NH2
CH3CH2O
17
CH3
NC
H3C
HO
H 19
+
18
NH2
N2
NaNO2, HCl
H2O, 0-5 oC
NO2
NO2
O2N
20
CH3
N
HO
21
CN
N
Figure 11. Synthesis of arylazo pyridone dye from pyridone. (Reproduced from Hemijska Industrija
Journal with permission by Association of Chemical Engineers of Serbia).
164
As a result 3-cyano-6-hydroxy-4-methyl-5-(4-nitrophenylazo)-2-pyridone (21) is formed

[16]. For the preparation of diazonium salts different substituted anilines or other heterocyclic
derivatives can be used.
Different monoazo pyridone dyes were prepared from 3-cyano-6-hydroxy-4-methyl-2pyridone or 1-substituted 3-cyano-6-hydroxy-4-methyl-2-pyridones [17-32]. Disperse azo
dyes useful for dyeing polyester fibers fast brilliant yellow shades were described in 1972 by
Burkhard et al. These dyes were prepared by coupling diazotized anilines with 3-cyano-6hydroxy-4-methyl-2-pyridones in AcOH at 0-5 oC and pH 4.5 [17]. Starting from different
anilines disperse dyes were prepared and used in dyeing or printing polyester fibers with fast,
yellow [18,19] to greenish yellow shades [20]. In addition, disperse azo dyes were
manufactured and used to dye synthetic fibers fast greenish yellow to red shades, by further
modification of amino component (e.g., 5-amino-4,6-dicyanoindan) [20]. Lightfast yellow
shades were obtained by dyeing poly(ethylene terephthalate) (PTT) fibers with azo dyes
where molecules like decyl 4-aminobenzoate was diazotized and coupled with 3-cyano-6hydroxy-4-methyl-2-pyridone [33]. Besides yellow shades, polyester fibers were dyed fast
orange shades [21]. It was shown that dye prepared from p-toluidine and 3-cyano-6-hydroxy4-methyl-2-pyridone is useful for dyeing and printing hydrophobic synthetic fibers, e.g.,
polyester, in a mixture with Disperse Yellow 54 and/or Disperse Yellow 64 [34].
By coupling diazotized 2,4,3,5-(NC)2Me2C6HNH2 with 3-cyano-6-hydroxy-1,4-dimethyl2-pyridone in aqueous NaOH, the yellow azo dye was prepared and used for dyeing polyester
fibers light- and sublimation fast yellow shades [22]. Another azo dye was prepared by
coupling diazotized 3-H2NC6H4SO3Ph with 3-cyano-6-hydroxy-1,4-dimethyl-2-pyridone and
used for dyeing polyester fibers a fast greenish yellow shade [23]. In addition, azo dyes
prepared by coupling diazotized 2,4-O2N(RO)C6H3NH2 (R = Me(CH2)3CHEtCH2,
Me(OCH2CH2)2, Me(CH2)9) with the same pyridone, were used to dye polyester fibers fast
orange shades from aqueous dispersions and from tetrachloroethylene [24].
Dyes were also prepared from 3-cyano-1-ethyl-2-hydroxy-4-methyl-6-pyridone [25-27],
3-cyano-2-hydroxy-4-methyl-1-propyl-6-pyridone [26,27] and 1-butyl-3-cyano-2-hydroxy-4methyl-6-pyridone [26-28]. These dyes dye polyester fabric fast yellow to greenish yellow
shades.
Other 1-substituted 3-cyano-6-hydroxy-4-methyl-2-pyridones were used as coupling
components. When 1-substituents were: (un)substituted Ph, C3-4 alkenyloxy, C3-4 alkynyloxy,
PhO and (un)substituted C1-8 alkoxy, azo dyes were obtained with different substituents in
arylazo part of dye. Thus, 4-H2NC6H4CO2CH2CO2CH2Ph was diazotized and coupled with 1butyl-3-cyano-6-hydroxy-4-methyl-2-pyridone to give dye that gave brilliant greenish yellow
on polyester fibers, both in polyester fabrics and in polyester-cotton blends [29]. By coupling
diazotized 2-nitroaniline with 3-cyano-1-(2-ethylhexyl)-6-hydroxy-4-methyl-2-pyridone an
azo dye insoluble in water was obtained which produce heat- and wetfast greenish yellow on
polyester fibers [30].
The water-soluble disperse azo dyes series including light yellow, yellow, orange, red,
violet and blue colors were obtained by introduction of methyl, methoxy and HOOCCH2SO2
group [31] or methyl, HOCH2CH2, Me2NCH2CH2, dodecyl [32] in position 1 of pyridone
ring. Reactive azo dyes for cotton as well as a cationic azo dye for polyacrylonitrile fiber, a
disperse azo dye for hydrophobic fibers, and an acid azo dye for nylon were prepared from 1(2-aminoethyl)-3-cyano-2-hydroxy-4-methyl-6-pyridone [35]. The yellow dyes were prepared
from 1-(alkoxyalkyl)-3-cyano-6-hydroxy-4-methyl-2-pyridones, and used to produce ink
165
which was used for thermal-transfer recording [36]. Also, azo disperse dyes based on
pyridone moiety which contain -sulfatoethylsulfonyl group were used to dye
poly(trimethylene terephtalate). The dyes showed alkali-clearing property and exhibited good
to excellent fastness on the PTT fabric [37]. Pyridone component was further modified by
introduction of phenyl group in position 4 or 2. So, azo dyes were prepared from 3-cyano-4hydroxy-2-phenyl-2-pyridone as well as from 3-cyano-6-hydroxy-4-phenyl-2-pyridone, and
coupling with diazotized aniline and 4-substituted anilines (Me, OMe, Cl) [38]. Cyano group
in position 3 of pyridone ring can be substituted by pyridinium group. Basic dyes can be
prepared from 1-substituted 6-hydroxy-4-methyl-3-pyridinium-2-pyridones using above
mentioned procedure and used to dye acrylic fibers fast yellow shades [39] or used in ink-jet
inks [40]. In addition, pyridone azo dyes were prepared from 2-pyridones with a
trifluoromethyl [41,42] or a carboxy group in position 4 of pyridone ring [42].
A series of new aryl azo pyridone disperse dyes were derived by the reaction of 5-cyano6-hydroxy-4-methyl-2-pyridone with POCl3. The obtained 3-cyano-2,6-dichloro-4methylpyridine were further transformed by the reaction with ethanolamine and then another
primary amine. The dyeing ability of such dyes toward polyester fiber was generally poor,
while wash and rubbing fastness were excellent and light and sublimation fastness were good
[43]. Synthesis of 5-arylazo-2,6-dichloro-3-cyano-4-methylpyridines and their application on
polyamide fiber as disperse reactive dyes were also reported [44].
Reactive pyridone monoazo dyes were prepared from (disulfoanilino)dihalotriazine and
the appropriate azo pyridine, which are useful in dyeing or printing of cotton or polyamide
fibers. Synthesis of one such dye is given in Figure 12 [45]. Diazonium salt was prepared
from 4-acetylamino-2-aminobenzensulphonic acid (22) and coupled with 3-amido-1-ethyl-6hydroxy-4-methyl-2-pyridone (23) to give compound (24). The compound (24) then reacts
with (disulfoanilino) dihalotriazine (27) prepared from 1-amino-3,4-benzendisulphonic acid
(25) and 2,4,6-trichlorotriazine (26). The obtained monoazo pyridone dye (28) dyes cotton to
a greenish yellow shades. The printings exhibit excellent light and wet fastness properties.
More yellow reactive dyes were prepared when instead of 2,4,6-trichlorotriazine, 2,4,6trifluorotriazine was used [46].
When the amino component is concerned, it should be pointed out that disperse azo dyes
prepared from 5-amino-isoindole-1,3-dione and pyridone had improved wash fastness in
dyeing of hydrophobic fibers [47]. Also, disperse dyes were prepared from 2-aminothiophene
derivatives, such as 2-amino-3-cyano-4,5,6,7-tetrahydrobenzo[b]tiofene and ethyl 2-amino4,5,6,7-tetrahydrobenzo[b]tiofene-3-carboxylate, and 5-cyano-1-ethyl-6-hydroxy-4-methyl-2pyridone [48,49].
Basic dyes were obtained from [-(4-aminobenzenesulfonamido)ethyl]pyridinium
chloride which was diazotized and coupled with 3-cyano-1-ethyl-2-hydroxy-4-methyl-6pyridone. The dyes were used to dye polyacrylonitrile fast yellow shades [50].
Disperse azo dyes were also prepared from cumarin derivatives and used in dyeing and in
jet and hot-melt printing. These dyes are suited for application to hydrophobic and synthetic
textiles with good fastness [51]. In addition, acid dyes containing silver can be used to
prepare anti-bacterially functional fiber [52]. Another group of pyridone azo dyes which
contains the quaternary ammonium salt was used to stain acrylic fibers and can kill or inhibit
both Gram positive and Gram negative bacteria [53].
166

O
NH2
CH3CN
NaNO2, HCl
N2
HO3S
H2O, 0-5 oC
SO3H
SO3H
22
CH3
CONH2
1. NaOH,
SO3H
Cl
Cl
HO3S
NH2
HO
C2H5 23
N
2. HCl, 75-80 oC
Cl
25
26
H2N
CH3
NaNO2, HCl, H2O, 0-5 oC
N
HO3S
HO3S
H
N
N
HO3S
27
CONH2
HO
C2H5
24
Cl
N
Cl
NaOH, pH=7, 5-10 oC
HO3S
HO3S
H
N
Cl
N
N
HN
CH3
HO3S
28
N N
HO
CONH2
N
C2H5
Figure 12. Synthesis of reactive dye from (disulfoanilino) dihalotriazines. (Reproduced from Hemijska
Industrija Journal with permission by Association of Chemical Engineers of Serbia).
Azo pyridone dye derived from substituted 2-amino benzothiazole was used for dyeing
and/or printing leather, cellulose materials (e.g., paper, wood, cardboard), and for producing
inks and formulations for contactless printing (e.g., inkjet printing) [54].
Azo pyridone dyes were used in order to provide an optical recording medium. This
medium had a recording layer improved in light stability capable of recording and
regeneration of high-density optical information by short-wavelength laser beams. The
recording layer contained a metal complex of pyridone azo compounds which was obtained
from a 6-hydroxy-2-pyridone structure as a coupler component and an isoxazole, 1,2,4-
167
triazole or pyrazole structure as a diazo component and an ion of bivalent metal, such as Ni,
Co, Fe, Zn, Cu or Mn [55]. Also, Cr-complex azo dyes were obtained from o,o'dihydroxyphenylazopyridone intermediates and ammonium chromium sulfate [56].
Azo pyridine thermally stable yellow pigments were obtained by coupling diazotized 2,51
R CO(R2CO)C6H3NH2 (R1, R2 = MeO, NH2) with 5-cyano-2-hydroxy-4-methyl-6-pyridone.
The pigments were stable up to 350 C and resistant to organic solvents and suitable for
plastics and baking varnishes [57]. Also, by treatment of azo pyridone dye, obtained from 2pyridones (e.g., 3-cyano-6-hydroxy-4-methyl-2-pyridone), with BaCl2 yellow azo pigments
were obtained and used in printing inks [58].
Arylazo dyes containing pyridone ring can also be prepared from arylazo diketones or
arylazo ketoesters (obtained by coupling -diketones or -ketoesters with diazonim salts) by
condensation with cyanoacetamide. The synthesis of 3-cyano-4,6-dimethyl-5-(4nitrophenylazo)-2-pyridone (31) is presented in Figure 13. Diketo arylazo compound (30),
produced by the reaction of acetylacetone (29) and diazonium salt, reacts with
cyanoacetamide in the presence of sodium ethoxide to give arylazo pyridone dye (31) [59,60].
Instead of diketone keto esters can be used, e.g., ethyl acetoacetate [61]. In the same manner
arylazo pyridone dyes were prepared with Me or Ph group in position 4 and with OH or
C6H5NH in position 6 of pyridine ring [62]. In addition, azo dyes were prepared from
thiopyridones which were obtained by the reaction of thiocyanoacetamide with
MeCOC(COMe)=NNHPh and sodium ethoxide [59].
+
N2
H 3C
O
5-10 oC, CH3COONa,

CH3CH2OH
H3 C
O 2N
N
N
O
H 3C
NO2
30
H 3C
29
NC
, CH3CH2ONa,
NH2
O 2N
CH3
N
H3 C
31
CN
N
Figure 13. Synthesis of arylazo pyridone dye from arylazo intermediate. (Reproduced from Hemijska
Recently, a new procedure for the synthesis of arylazo pyridones, according to Figure 13,
using microwave irradiation was reported. The advantages of this procedure are short reaction
times, high yields and aplication in the synthesis of azo dyes from different 2-pyridones [63].
168
The synthesized derivatives of 3-cyano-4,6-dimethyl-2-pyridone (Table 1, entry 1-6) were

obtained with nearly quantitative yield, while the derivatives of 3-cyano-4,6-diphenyl-2pyridones (Table 1, entry 7-9) were obtained in a lower yields. Synthesis of 3-cyano-4,6dimethyl-5-phenylazo-2-pyridone in a conventional manner [60] also takes place in the
presence of a base in ethanol, except that this synthesis occurred during 3 h with somewhat
lower yields (70 80 %).
Table 1. Synthesized arylazo 3-cyano-4,6-dimethyl-2-pyridone, 3-cyano-4,6-diphenyl-2pyridone, 3-cyano-6-hydroxy-4-methyl-2-pyridone and 3-cyano-6-hydroxy-4-phenyl-2pyridone dyes with their yields (Reproduced from Hemijska Industrija Journal with
permission by Association of Chemical Engineers of Serbia)
R1
R2
N
R3
R4
CN
N
5
Entry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
R4
R5
Yield (%)
H
H
Br
Br
H
H
H
Br
H
H
Br
Br
H
H
H
H
H
Me
Me
H
H
Me
Me
H
H
Me
Me
H
H
NO2
H
Me
Me
I
H
Me
Me
H
H
Me
Me
H
Me
Me
Me
Me
Me
Me
Ph
Ph
Ph
Me
Me
Me
Me
Ph
Me
Me
Me
Me
Me
Me
Ph
Ph
Ph
OH
OH
OH
OH
OH
99
100
92
100
100
100
72
72
83
47
93
80
50
78
Another microwave procedure for the synthesis of arylazo pyridone dyes was reported.
Arylazo pyridone dyes (Figure 14) were synthesized from cyanoacetamide and azodisperse
dye obtained from the reaction of corresponding dianalides with diazotized aromatic amines.
The microwave synthesis gave dyes with yields of around 60 % for 3-5 min, while
conventional heating gave dyes with yield of around 80 % but after 4 h.
The fastness properties of silk screen printed polyester using these synthesized dyes have
been investigated and it was concluded that the prints posses very good washing, rubbing,
perspiration and light fastness [64].
169
Cl
H
X
N
H
N
CN
N
N
Cl
Figure 14. A recent new class of arylazo pyridone dyes.

OH
NH2
HO3S
33
SO3H
1. 0-5 oC, pH=7, KOH
SO2CH2CH2OSO3H
SO2CH2CH2OSO3H
2.
NaNO2, HCl
0-5 oC
+
H 2N
N2
32
HO3SOCH2CH2O2S
OH
N N
HO3S
34
HO3S
NH2
1. NaNO2, HCl, 0-5 oC
CH3
CONH2
2.
HO
HO3SOCH2CH2O2S
C 2H 5
35
OH
N N
HO3S
CH3
HO3S
N N
HO
36
CONH2
N
C2H5
Figure 15. Synthesis of a reactive disazo pyridone dye from 2-[(4-aminophenyl)sulfonyl] ethyl
hydrogen sulfate and 6-amino-1-hydroxy-3,5-disulfonaphthalene. (Reproduced from Hemijska
170
2.2. Synthesis of Disazo Dyes

Disazo pyridone dyes can be prepared in different ways using diazo coupling reaction.
One example is shown in Figure 15. Synthesis of disazo dye (36) starts with the diazotization
reaction of 2-[(4-aminophenyl)sulfonyl]ethyl hydrogen sulfate (32), and the resulting
diazonium salt is coupling with 6-amino-1-hydroxy-3,5-disulfonaphtalene (33). The resulting
azo compound (34) is then diazotized and coupled with 3-amido-1-ethyl-6-hydroxy-4-methyl2-pyridone (35) to form a disazo dye (36). The reactive azo dyes prepared can be used for
dyeing cellulosic and polyamide fibers [65]. In a similar manner 5-[(4-arylazophenyl)azo]-3cyano-6-hydroxy-4-methyl-2-pyridones were obtained [66].
New disazo dyes were prepared by successive reactions of diazo coupling. The starting
amino compounds were 5-amino-4-hetarylazo-3-methyl-1H-pyrazole and 5-amino-4hetarylazo-3-methyl-1-phenylpyrazole, and their diazonium salts were coupled with 3-cyano6-hydroxy-4-methyl-2-pyridone [67]. This synthesis is shown in Figure 16.
N
S
NH2
37
NaNO2, H2SO4, 0-5 oC
NC
N2
NH2
+
H
CN
CH3COONa, pH=5-6, 0-5 oC
CH3
38
NH
N N
H
39
CH3
1. PhNHNH2
2.
CH3
CN
N
HO
N N
NH2
H 19
H3C
1. KOH, 0-5 oC,

CH3COONa, pH=5-6
40
NaNO2, H2SO4, H2O, 0-5 oC
N
S
N N
N2
2.
H3C
CN
H3C
N
S
N N
N N
O
N
OH
H3C
N
41
Figure 16. Synthesis of disazo pyridone dye from 5-amino-4-benzothiazole-2-ylazo-3-methyl-1phenylpyrazole and 3-cyano-6-hidroxy-4-methyl-2-pyridone. (Reproduced from Hemijska Industrija
171
The starting 2-aminobenzothiazole (37) is diazotized and the resulting diazonium salt is
coupled
with
3-aminocrotonitrile
(38)
giving
2-benzothiazolylhydrazon-3ketiminobutyronitrile (39). In the next step nitrile (39) reacts with phenylhydrazine to give 5amino-4-benzothiazole-2-ylazo-3-methyl-1-phenylpyrazole (40). Finaly, the compound (24)
is diazotized and coupled with 3-cyano-6-hydroxy-4-methyl-2-pyridone (19).
The disazo compound can be also synthesized by the diazotization reaction of diamino
compound (42) and coupling of diazonium salt with 1-substituted pyridone (43), as given in
Figure 17 [68]. The produced disazo pyridone compound (44) was used in the production of
colored plastics or polymeric color particles. Dyes had good heat resistance, migration
resistance, tinctorial strength, and fastness when used for bulk coloration. In the same manner
different disazo pyridone colorants can be prepared for use in phase change inks [69-72].
CH3
O3S
SO3
CH3
CH3
NH2
CN
H2N
42
HO
CH3COOH, HCl, H2O,

NaNO2, 0-5 oC
(CH2)3O(CH2)2O 43
1. NaOH, H2O,
pH=4-5, 0-5oC
CH3
O3S
+
N2
2.
SO3
CH3
N2
CH3
O3S
SO3
CH3
CH3
NC
CN
HO
N
OH
N
O(CH2)2O(CH2)3
H3C
N
O
(CH2)3O(CH2)2O
44
Figure 17. Synthesis of disazo pyridone dye by coupling of diazotized diamino compound with 1substituted pyridone. (Reproduced from Hemijska Industrija Journal with permission by Association of
Chemical Engineers of Serbia).
Another reaction pathway for the preparation of disazo pyridone compounds is the
synthesis of compound (51) shown in Figure 18. The disazo pyridone compound was
prepared here from bispyridone derivative. Specifically, in this synthesis dodecamethylen
dipyridone (50) is synthesized first, starting from 1,12-diaminododecane (48), ethyl
cyanoacetate (49) and acetoacetic ester. The diazonium salt prepared from octadecyl-2-
172
aminobenzoate (47) is then coupled with synthesized dodecamethylen dipyridone (50) to

yield disazo compound (51). Octadecyl-2-aminobenzoate was obtained by the reaction of 1octadecanole (45) and isatoic anhydride (46). The resulting green-yellow disazo pyridone
colorants were used in phase change inks [72-74]. In a similar manner disazo colorants were
prepared for dyeing or printing cotton and polyamide materials [75]. The dipyridone structure
can be obtained by the reaction of two moles of 1-ethyl-6-hydroxy-2-pyridone with one mole
of glutaraldehyde sodium hydrogen sulphite. Obtained dipyridone is then coupled with two
mole of diazotized 4-(2-sulfatoethylsulfonyl)aniline to form reactive disazo yellow dye [76].
CH3(CH2)17OH
45
NH2
100-150 oC
COO(CH2)17CH3
N2
1. CH3COOH
2. NSA, 0-5 oC
COO(CH2)17CH3
47
N
46 H
H2N(CH2)12NH2
48
CNCH2COOCH2CH3
49
NC
1. 150 oC
H3C
2. AAE, piperazine,
DMF, 120 oC
3. 25 oC, HNO3
OH
CN
O
(CH2)12
CH3
N
HO
50
1. H2O, NaOH, CH3COONa,

iPrOH
2.
NC
H3C
N
N
CH3(CH2)17OOC
CN
O
(CH2)12
CH3
N
HO
OH
COO(CH2)17CH3
51
Figure 18. Synthesis of disazo pyridone dye from bispyridone derivative. (Reproduced from Hemijska
Disazo reactive dyes, which dye cotton in yellow shades, containing hydroxyl pyridone
and fluorotriazine groups were also prepared. Thus, pyridone dye (53) was obtained from 5[(3-amino-6-sulfophenyl)azo]-1-ethyl-6-hydroxy-4-methyl-3-(sulfomethyl)-2-pyridone (52),
2,4,6-trifluorotriazine and 1,4-diphenylamine [77].
173
HO3S
CH3
HO3SH2C
O
NH2
N N
N
OH
CH2CH3
52
1. NaOH, H2O
2. 0 oC, 2,4,6-trifluorotriazine, NaOH
3. 0 oC, 1,4-diphenylamine
HO3S
CH3
HO3SH2C
O
NH
N N
N
OH
CH2CH3
NH
CH2CH3
NH
HO3SH2C
OH
N N
N
NH
CH3
HO3S
53
Figure 19. Synthesis of a reactive disazo dye from 2,4,6-trifluorotriazine and 1,4-diphenylamine.
(Reproduced from Hemijska Industrija Journal with permission by Association of Chemical Engineers
of Serbia).
2.3. Synthesis of Trisazo Dyes

Synthesis of trisazo pyridone colorants is given in Figures 20 and 21. Synthesis of trisazo
pyridone dye (56) is similar to the synthesis of disazo pyridone dye (51) given in Figure 18.
Here, diazonium salt obtained from substitute aniline (47) is coupled with tripyridone (55).
Tripyridone was prepared from tris(aminoethyl)amine (54), ethyl cyanoacetate (49) and
ecetoacetic ester [78]. The obtained trisazo azo pyridone dye is used in yellow hot-melt inks.
174
CH3(CH2)17OH
45
2. NSA, 0-5 oC
47
CN
46 H
HO
+
CNCH2COOCH2CH3
49
COO(CH2)17CH3
CH3
N(CH3CH2NH2)3
54
N2
1. CH3COOH
COO(CH2)17CH3
O
N
NH2
100-150 oC
CH2CH2
1. 150 oC
CH2CH2
2. AAE, piperazine,
DMF, 120 oC
3. H2O, HNO3, CH3OH
HO
N
CH2CH2
O
O
OH
CN
CH3
NC
CH3
55
1. H2O, NaOH, CH3COONa,

iPrOH
2.
CH3
CN
N N
CH3(CH2)17OOC
HO
CH2CH2
CH2CH2
HO
N
CH2CH2
O
O
OH
CN
N
CH3
NC
COO(CH2)17CH3
CH3
COO(CH2)17CH3
56
Figure 20. Synthesis of trisazo pyridone dye from tripyridone. (Reproduced from Hemijska Industrija
The trisazo pyridone dye can be prepared using the procedure presented in Figure 21.
First, triazine derivate (58) is prepared from 2,4-diaminobenzensulfonic acid (57) i 2,4,6trichlorotriazine (26). The obtained intermediate (58) is then diazotized and coupled with
pyridone (59). Trisazo pyridone dye (60) is used for dyeing poliamide fibers such as nylon 6
[79].
175

SO3H
NH2
Cl
SO3H
NH2
3
+
Cl
NH2
NH
N
N
Cl
26
H2 N
N
H
N
H
N
57
58
HO3S
SO3H
NH2
1. NaNO2, HCl, H2O, 0-5 oC
CH3
CN
2. NaOH, pH=6,
HO
CH2CH3
59
CN
H 3C
SO3H
N N
CH2CH3
OH
CN
CH3CH2
NH
CH3
O
N
N
OH
N
H
N
N
H
N
HO3S
SO3H
N
HO
CH3CH2
N
CH3
CN
O
60
Figure 21. Synthesis of trisazo pyridone dye from 2,4,6-trichlorotriazine. (Reproduced from Hemijska
3. PROPERTIES
3.1. Fastness
A number of authors have studied the fastness properties of azo pyridone dyes on
different materials [43,47-49,51,65,66,68,80]. For example, Helal have published the
synthesis of monoazo pyridone dyes given in Figure 13 [81]. This azo dyes were mono and
disubstituted on arylazo component, and pyridones were 3-cyano-6-hydroxy-4,6-dimethyl-2-
176
pyridone or 3-cyano-6-hydroxy-4-methyl-6-phenyl-2-pyridone. The synthesised dyes were

used to dye polyamide and polyester fabrics, and the color characteristics of the dyed fabrics
varied due to the difference in the nature of substituents present on the dye molecules. The
study revealed that the synthesised compounds, on polyester and polyamide fabrics, have high
color strength, good wash fastness, good rub fastness, good perspiration fastness as well as
good light fastness. Dyes from 3-cyano-6-hydroxy-4-methyl-6-phenyl-2-pyridone showed
better fastness than dyes from 3-cyano-6-hydroxy-4,6-dimethyl-2-pyridone.
Wang and Wang have studied the photofading kinetics of 5-(4- and 2-substituted
arylazo)-5-cyano-2-hydroxy-4-methyl-6-pyridone dyes in amide solvents (DMF, HCONH2,
and AcNMe2) and n-hexane [82]. It was established that a fair linear correlation existed
between the observed rate constant and the free energies of transfer, suggesting the possibility
that the photofading rate increased with increasing solvation of dyes. The rate was increased
by the presence of two electron-withdrawing substituents (NO2 and Cl) on the benzene ring.
The same authors have also studied photostability of 3-(mono- and disubstituted arylazo)-5cyano-2-hydroxy-4-methyl-6-pyridones in N,N-dimethylformamide [83]. Photodegradation
was observed when dyes were irradiated by 254 nm light. It was established that the primary
photochemical reaction with pyridone azo dyes involved hydrogen abstraction from the amide
solvent. Also, it was found that the simultaneous presence of two electron-withdrawing
substituents in diazo component of dyes caused a bathochromic effect and an increase of
fading rate, while introduction of a alkylol group to coupling component resulted in
hypsochromic shifts and in decrease of fading rate. In addition, Wang and Wang [84] applied
synthesized monoazo pyridone dyes to polyester fabrics and studied dyeing properties,
fastness of dyed fabrics, fading rate of the dyes, and their color parameters. They found out
that electron-withdrawing substituents on aniline increased the photostability and improved
the sublimation fastness of the azo dyes on polyester, while the -hydroxyethyl group
increased the fading rate. When the dye had a 1st-order fading rate curve, its light fastness
was very low.
In another work, a yellow disperse azo dye was synthesized from 2,6-dichloro-4nitroaniline and 3-cyano-6-hydroxy-1,4-dimethyl-2-pyridone and its dyeing, fastness, and
photodegradation behavior on polyester fabric was investigated. It was found that the buildup and light fastness of the dye derived from pyridone was not good [85]. Introduction of
various substituents can have different impact on dye properties. So when in dyes presented
in Figure 22 a long perfluoroalkyl group was introduced a lowered film-forming ability and
sensitivity but good photostability was achieved [86]. When 5-(2-benzothiazolylazo)-3cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridone was compared to other asymmetrical and
symmetrical bis(hetaryl)azo dyes it was found that only the pyridone derivative showed
remarkable difference of decomposition temperature [87].
R3
R2
CN
N N
N
HO
R1
61
Figure 22. Azo pyridone dyes with good photostability (R1 = H, Me, C3H7, C4H9, C6H13, C8H17, Ph; R2
= Me, CF3; R3 = CF3, C4F9, C6F13, C8F17).
177
Besides direct photodegradation, photocatalytic degradation of 3-cyano-6-hydroxy-4methyl-5-(4-sulphophenylazo)-2-pyridone in the presence of commercial TiO2 (Degussa P25), in aqueous solutions by simulated sunlight was studied [88]. It was found that the
optimal catalyst concentration was 1.0 g dm3. Concerning the initial dye concentration, it
was observed that the increase in the initial dye concentration lead to decrease in
photodegradation. The photodegradation is favored in acidic and basic media. Measurement
of the total organic compound loss during the reaction showed that under investigated
conditions (dye concentration 20 mg dm3, catalyst concentration 1 g dm3) almost complete
dye mineralization occurred within 240 min. Results indicate that 54% of total organic
compound remained when 100% of the dye was decolorized. Further optimization showed
that after 240 min, the TOC loss was larger than 90%, revealing that the dye could be
efficiently demineralized using TiO2 photocatalytic degradation [89].
3.2. Tautomerism
A number of studies can be found in literature in which substituent and/or solvents effects
were discussed in a series of arylazo 177yridines. So, dyes derived from 3-cyano-6-hydroxy4-methyl-2-pyridone [90,91], 3-amino-5-cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridone [92],
4-amino-6-hydroxy-2-pyridones, 4,6-diamino-3-cyano-2-pyridone and 2,4-diamino-3-cyano6-pyridone [93], 5-(2-pyrido-5-yl)azo-thiophene derivatives [94], 4-(p-substituted) phenyl-2(2-pyrido-5-yl)azo-thiazole derivatives [95], 5-(arylazo)-3-cyano-4-methyl-6-methyl/phenyl2-pyridinones [81] and 1-butyl-3-cyano-6-hydroxy-4-methyl-2-pyridone [96] were studied
among others. In these studies, often azo-hydrazone tautomerism was investigated. Thus,
three series of dyes were prepared by coupling diazonium salts to 2-(ethylthio) and 2(butylthio)-4,6-diaminopyrimidine as well as to 3-cyano-6-hydroxy-1,4-dimethyl-2-pyridone.
IR spectra and visible absorption spectroscopy indicated that the arylazopyrimidines existed
in the azo tautomeric form, while the 177yridine dyes existed as hydrazones [97]. Also,
absorption spectra of ten 5-(4-substituted arylazo)-3-cyano-6-hydroxy-4-methyl-2-pyridones
have been recorded in fifteen solvents in the range 200-600 nm. Besides the effects of the
substituents on the absorption spectra and the effects of solvent polarity and solvent/solute
hydrogen bonding interactions, azo-hydrazone tautomerism (Figure 23, X = OH, OCH3, CH3,
C2H5, H, Cl, Br, I, COOH, NO2) was studied and it was concluded that equilibrium depends
on the substituents as well as the solvents [16]. The significant role of substituent effects on
azo-hydrazone tautomerism was observed since the azo group is stabilized by the more
electron-donating substituents, while an electron-accepting group stabilizes the hydrazone
form. This is in accordance with canonical structures of hydrazone and azo form of these dyes
(Figure 23, structures 5 and 6). It was also shown that 5-(substituted arylazo)-3-cyano-6hydroxy-4-methyl-2-pyridones exist in solid and in DMSO-d6 in hydrazone form, while in
solvents there is an azo-hydrazon equilibrium [16,98]. Song et al. [99] prepared azo dyes
from 5-amino-3-cyano-1-ethyl-6-hydroxy-4-methyl-2-piridone as diazo component and find
that dyes exist in solid in hydrazone form, while in solvents there is azo-hydrazon
equilibrium.
Ertan I Gurkan [90] have concluded that azo 177yridine dyes obtained from 3-cyano-6hydroxy-4-methyl-2-pyridone and substituted anilines exist in solid in hydrazone form as well
as in CF3COOD/CDCl3 mixture. When NMR spectra of 177yridine azo dyes obtained from 1-
178
alkyl-3-cyano-6-hydroxy-4-methyl-2-pyridone were recorded in CDCl3 and DMSO-d6 it was

also confirmed that dyes exist in hydrazone form [100]. Cheng et al. [101] have shown earlier
that arylazo 178yridine dyes prepared from 3-cyano-6-hydroxy-1,4-dimethyl-2-pyridone exist
in hydrazone form.
Generally, arylazo 178yridine dyes have different color in solutions of different pH.
Color change is caused by the presence of acidic hydrogen. In acidic and neutral solutions
arylazo 178yridine dyes are dominantly in hydrazon form and in basic solution as an azo
anion [102-104].
It was shown that hydrazon-azo anion equilibrium exists in solutions according to UV-vis
spectra [105]. Thiadiazolazopyridones easily dissociate in polar solvents and proton-accepting
solvents (ethanol, dimethylformamide, dymethyl sulfoxide, pyridine) and in these solvents
dyes are in azo anion form (Figure 23, structure 3).
- ..
X
..
:
+H O
N ..
N
N
O
..
H O
.. _ ..
N ..
N
..
CN
H3C
H
N
O
CN
H 3C
(6)
(5)
..
H :O
..
N ..
N
N
O
..
H O
..
..
N ..
N
CN
H 3C
..
N
.. ..
N
OH
H
N
O
(2)
CN
(4)
..
:O
H 3C
H 3C
(1)
OH
H
N
CN
..
:O
..
..
N ..
N
H 3C
(3)
H
N
O
CN
Figure 23. The equilibrium between hydrazone form (1) and azo form (2) of 5-(4-substituted arylazo)3-cyano-6-hydroxy-4-methyl-2-pyridones, azo (3) and hydrazone anion form (4) and canonical
structures (5) and (6).
179
In proton-donating solvents (chloroform and glacial acetic acid) dyes are dominantly in
hydrazon form, while in acetone, cyclohexanone benzene there is equilibrium between these
two forms. Hydrazon form is dominant in all solvents in substituted phenylazo 179yridines.
In organic solvent-water mixture, by the addition of a base, there is an equilibrium
between hydroxyl anion and hydroxyazo form (Figure 23, structures 3 and 4) [106].
Azo-hydrazone tautomerism was also studied by crystallography. So 2-(2methoxyethoxy)ethyl
4-[(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,2,3,6-tetrahydropyridin-3ylidene)hydrazino]benzoate crystallizes in the hydrazone form [107]. The same conclusion
was obtained for C.I. Disperse Yellow 114 (5-cyano-2-hydroxy-1,4-dimethyl-6-pyridone
component) [108]. C.I. Disperse Yellow 119 and C.I. Disperse Yellow 211 (pyridine-3cyano-1-ethyl-4-methyl-2,6-dione backbone) (Figure 10) also crystallize in the hydrazone
form [109].
Besides azo-hydrazon tautomerism, pyridone azo dyes exibit another type of
tautomerism, naimely 2-pyridone/2-hydroxypyridine. Examples of such tautomerism were
found in 5-(3- and 4-substituted arylazo)-3-cyano-4,6-dimethyl-2-pyridones and 3-cyano-4,6diphenyl-5-(3- and 4-substituted phenylazo)-2-pyridones [60,110,111]. It was found that 2pyridone/2-hydroxypiridine tautomeric equilibration depends on the substituents as well as on
the solvents.
On the basis of the above results, it may be concluded that the azo colorants containing
hydroxyl and amino substituents ortho or para to the azo groups can in principle exist as
mixtures of azo and hydazone tautomers. While azohydrazone tautomerism is quite
interesting from a theoretical viewpoint, it is also important from a practical standpoint
because the two tautomers have different technical properties and dyeing performances
[103,112].
CONCLUSION
Arylazo pyridone dyes were intensively synthesized from the early 1970s and first used
as disperse dyes for polyesters. The synthesis of these dyes is based on coupling reaction of
various diazonium salts with pyridones or on cyclization of azo compound with
cyanoacetamide or substituted cyanoacetamide to obtaine pyridone moity. Due to variety in
the synthesis of amino as well as pyridone parts of dye, a large number of arylazo pyridone
dyes were prepared. These dyes give, usually, yellow shades with generally good fastness.
Besides disperse dyes, basic and reactive dyes were prepared. Arylazo pyridone dyes were
also used in printing inks, hot-melt inks and in phase change inks as well as in the production
of color filters. Arylazo pyridone dyes can show azohydrazone tautomerism which is
important from a practical point of view because the two tautomers have different technical
properties and dyeing performances. The azohydrazone equilibrium depends on the
substituents as well as the solvents used.
The significant role of substituent effects on azo-hydrazone tautomerism was observed
since the azo group is stabilized by the more electron-donating substituents, while an
electron-accepting group stabilizes the hydrazone form. In acidic and neutral solutions
arylazo pyridone dyes are dominantly in hydrazon form and in basic solutions as an azo
anion.
180
ACKNOWLEDGMENTS
The authors are grateful to the Ministry of Education, Science and Technological
Development for financial assistance (project 172013).
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ISBN: 978-1-63117-262-5
Chapter 7
SMART TEXTILES AND THE EFFECTIVE USES

OF PHOTOCHROMIC, THERMOCHROMIC,
IONOCHROMIC AND ELECTROCHROMIC
MOLECULAR SWITCHES
Shah M. Reduwan Billah*
Department of Chemistry, Durham University, Durham, UK and
The School of Textiles and Design, Heriot-Watt University, Galashiels, UK
ABSTRACT
Smart textiles have been successful to draw very high levels of active current
research interests within different areas of research on textiles and related fields. The
wide range of application potentials of smart textiles made them a hub for a variety of
interdisciplinary research fields. There are various ways for producing smart textiles; one
of the methods is to incorporate environmentally stimuli responsive switches which can
sense the surrounding environment. These types of stimuli-responsive smart textiles have
numerous application potentials, including, safety, security, comfort, fashion, health care,
remote sensing, along with a variety of other biomedical and intelligent applications. This
current chapter briefly focuses on different aspects of smart textiles and the method of
production of these textiles using different types of stimuli-responsive molecular
switches, such as, photochromic, thermochromic, ionochromic and electrochromic
molecular switches. As the successful incorporation of these stimuli-responsive switches
into smart textiles needs certain level of basic understandings on the nature of these
molecular switches, a brief discussion is also included to highlight different features on
different types of stimuli-responsive systems and their mode of application for producing
high performance stimuli-responsive smart textiles for a variety of applications.
Keywords: Smart textiles, molecular switches, photochromic switches, thermochromic

switches, ionochromic switches, electrochromic switches
*
Address for correspondence: Dr. Shah M. Reduwan Billah, 7 Laurel Grove, Galashiels TD1 2LA, Scotland, UK, Email: reduwan.shah@gmail.com or s.m.r.billah@durham.ac.uk.
188
INTRODUCTION
In last two decades, there have been many multi-disciplinary approaches in textile
research to incorporate multi-level of functionalities along with other distinct features
generally expected from usual as well as special types of clothing based on smart and
intelligent textiles along with other useful features sometimes expected from ordinary textiles.
With the advancements in different related technologies (such as, nanotechnology,
information technology, biotechnology, flexible display techniques, etc.) now there are scopes
for new possibilities to enhance textiles with a variety of new functionalities. Some of these
possibilities including the production of multifunctional new fibre structures, composite
materials and coatings at the nano and micro levels to the visible integration of wearable
electronic assemblies into clothing system. Currently, there is a high level of convergence of
different sophisticated technologies, for example, biochemistry, polymer chemistry and
computer processor based techniques which are miniaturised to produce lab-on-achip
diagnostics, and new forms of textile sensors, actuators and other components that are now
available. As a result, many high quality previous efforts to produce high performance
functional and intuitively wearable computing systems based on textiles are slowly becoming
a practical reality. [1-10]
Smart textiles incorporated with different functionalities have many uses in a variety of
fields; some of them are widely used in the fields of biomedical or healthcare applications.
For more specific information, some of the important fields of applications are briefly
summarized here:(a) medical textiles (in general), (b) smart wound-care materials, (c) textilebased drug release systems, (d) phase change and shape memory based smart textiles for
different applications, (e) textile based sensors for healthcare, (f) smart medical textiles for
particular types of patient (e.g., intelligent garments for pre-hospital emergency care), (g)
smart medical textiles in rehabilitation, (h) smart medical textiles for monitoring pregnancy,
(i) smart textiles for monitoring children in hospital, (j) wearable textiles for rehabilitation of
disabled patients using pneumatic systems, (k) wearable assistants for mobile health
monitoring, (l) smart medical textiles for monitoring patients with heart conditions, and (m)
textiles in surgical implants, tissue engineering and wound care. [11-22]
Advanced Materials Used in Different Technologies for Smart or

Intelligent Textiles
Current trends in the manufacture of smart or intelligent textiles involve a variety of
established and also emerging technologies with different level of adaptations in different
areas. As a result, now-a-days it is extremely important to have meaningful interdisciplinary
collaboration for high quality product development. For example, the electronics industry is
concentrating on required level of knowledge on different types of textiles (where electronics
are increasingly incorporated into clothing systems to produce specific products) to solve
problems in wearable electronics. So, it is important to have fundamental knowledge on
standard commercial textile production methods along with the knowledge of wearable
electronics for an effective adaptation of new developments in both electronics and in textile
Smart Textiles and the Effective Uses of Photochromic, Thermochromic
189
to produce high quality textile based electronics for specific applications in different target
areas within affordable costs. [23]
In recent years, different materialshave been incorporated into the structure of textile or
related materials used in the clothing systems to serve different purposes, some other
advanced materials and techniques have also been used to improve the performance of smart
(to some cases also for biomedical) textiles, some of the most important materials and method
are (a) phase change materials, (b) photochromic materials, (c) thermochromic materials,
(d) shape memory alloys and polymers, (e) conductive fibres and yarns metals, wires and
conductive polymers, (f) quantum tunnelling composites for switching devices, (g)
piezoelectric resistance, (h) organic or plastic electronics, (i) biomaterials, (j) light-emitting
polymers, (k) light-emitting diodes, (l) fibre optics, (m) photovoltaic and solar cells, (n)
photoluminescence, (o) holography, (p) plasma technologies, (q) nano technologies for fibre
and fabric coating, (r) micro encapsulation for therapy delivery, (s) global positioning and
wireless communications, (t) radio frequency identification (RFID) tags, and (u) microelectronic mechanical systems (MEMS). [24-27] Some of the selected basic features of smart
textiles produced by using certain types of molecular switches are briefly covered in this
chapter.
SMART TEXTILES
It is a new field in textile research with no universally accepted definition, however,
different terms, such as intelligent, smart or active materials and textiles are mostly used
in the expression of different aspects of this types of textile which are sometimes inter
changeable and also obviously not confined within the very frame of these different words.
With the progress of active research in this area there have been different approaches to
define these words into moreacceptable forms. Here is an attempt to show the differences in
different definitions which have been used by some famous scholars of smart textiles, some
of the selected definitions are:
a) Smart materials and structures can be defined as the materials and structures that
sense and react to environmental conditions or stimuli, such as those from
mechanical, thermal, chemical, electrical, magnetic or other sources a definition
by Tao. Then she extended her approach by adding divisions ofsmart materials into
different groups, such as- (i) passive smart (sensitive to environmental conditions or
stimuli), (ii) active smart (sense and react to the conditions or stimuli) and (iii) very
smart materials (sense, react and adapt themselves accordingly); [27]
b) smart is a term used to define a material that reacts in a particular way when
exposed to stimuli such as environmental changes, for example, temperature or
electronic currents Baurley adopted this to define smart textiles; [11]
c) smart textiles utilise integrated or applied electronics such as sensors, actuators,
etc., whereas intelligent textiles produce predictable effects and phenomena by
interacting with the environment and the wearer; [28]
d) textiles with integrated electronics and microsystems which could be in clothes and
in technical textiles are smart textiles as defined by Strese, et al. They further define
190

three levels of integration but without specific names, such as, (i) solutions adapted
to clothes, e.g., mobile phone in a pocket, (ii) electronics and micro systems
integrated into clothes or textiles withconnectable modules (e.g., with textile
conductors) and (iii) functions integrated into the textile via direct insertion into
textile fibres (e.g., woven displays); [29]
e) fabrics and textiles that cognitively respond or interact to environmental or electrical
stimuli a definition endorsed by the Venture Development Corporation, a USAbased technology market research company (on the definition of smart fabrics and
intelligent textiles in their report of January 2005). They also concentrate on
applications that utilise electrical stimuli further outline these responses as (i)
conducting, transferring or distributing various properties through the material or
across the materials membrane; such properties include electrical current, light
energy, molecular or particulate matter, and thermal energy and (ii) changing
physical characteristics or phase, such as colour, permeability, porosity, rigidity,
shape, size (VDC 2005); [30]
f) smart materials are materials that form part of a smart structural system that has
capability to sense its environment and the effects thereof, and if truly smart, to
respond to that external stimulus via an active control mechanism this is a definition
given by the Foresight Smart Materials taskforce, a UK government initiative, which
recently reviewed the potential for wealth creation and strategies for UK industry and
academia, which concludes that competitive advantage will depend on products with
increasing levels of functionality. In this report degrees of smartness is defined for
different materials which can be transposed to a textile system. The Foresight report
also includes that the terms smart, functional, multifunctional, and intelligent
are often used interchangeably. In this context this is reasonable, if confusing, for the
first three terms but the last certainly suggests a degree of consciousness that does
not exist in any non-biological system. Additionally, there is arguably no such thing
as a smart material only materials that exhibit interesting intrinsic characteristics
which can be exploited within systems or structures that, in turn, can exhibit smart
behaviour; [31]
g) smart textiles are an interesting class of electronic and photonic textiles which are
capable of monitoring their own health conditions and structural behaviour, as well
as sensing external environmental conditions and sending the information to other
locations,a definition given by El-Sherif. [16, 27]
As we see it is not easy to categories the stimuli-responsive materials based textiles

whether they are smart or intelligent or smart and intelligent textiles. Because, it is possible to
use some members of photochromic, thermochromic, ionochromic and almost all members of
electrochromic switches to produce different types of colour change (both passive and active
types) when used in different suitable systems or device constructions based on textile media.
In depth discussion on the device constructions using these switches is beyond the scope of
current chapter, as a result it only focuses on the general aspects of the nature of these
switches and also on their uses in textiles for smart or intelligent applications to serve
different purposes. This chapter also concentrates on different aspects of certain types of
selective environmental stimuli-responsive materials or more simply selective stimuliresponsive molecular switches (such as, photochromic, thermochromic, ionochromic and
191
electrochromic material based stimuli responsive switches) and their potential uses in the
production of smart textiles. Before going to in-depth discussion on molecular switches a few
related aspects of smart textiles in smart clothing system and smart clothing design are briefly
discussed here.
Smart Textiles in Smart Clothing System

Smart textiles are mainly focused for their important inclusion during smart clothing
design to serve certain specific purposes along with usually expected particular aspects from
some distinctive clothing which is usually designed to fulfil required desired features. Smart
clothing, a new type of apparel, usually uses a fusion technology to combine electronic
engineering and apparel design. It requires a combination of several generically distinctive
features, for examples - electronic efficiency, electrical safety, physical comfort and
aesthetics of a garment. As a result, the multi-faceted factors are of significant importance
during smart clothing design. Sometimes there are practical difficulties for the apparel
designers to avoid confronting fatal limitations in reflecting their vision into the design
process when they apply the traditional apparel design process to the creation of an apparel
line of smart clothing. In some cases one of the main reasons for this situation is simply
because many of the steps for a very novel design may have never been used before even
when the multivariate consideration is not uncommon to be included in the traditional design
process. For successful smart clothing design it is a prerequisite to modify the traditional
apparel design process to combine some appropriate steps for interdisciplinary creation. [712, 27]
Variables during the Inclusion of Smart Textiles in Smart Clothing Design

In industrial design, a design refers to a process that usually starts from an analysis of
design requirements and ends with the synthesis into some visualized forms. In this process
design requirements are devised by the expectations held by consumers and manufacturers
toward the object to be designed in the contexts of aesthetics, functionality, ergonomics,
safety, and price. These fundamental design requirements usually modify different features to
producea harmonious reflection in most of the high quality designed products. In many times,
there are critical changes in the design process when it requires accommodating new design
features to fulfil certain specific needs. The territory of design needs for apparel in the case of
smart clothing sometimes needs widening to include new categories, for example, embedding
digital functions or the interaction between parts of digital function and human body. In the
field of smart clothing, some researchers have analysed design needs (or requirements)
according to their varying definitions. There are a number of analyses on design requirements
in the field of smart clothing when we see the varying nature of these design aspects. There
are many considerations during the design of smart clothing, however, some of the important
aspects for the design include (a) functionality, (b) connectability, (c) durability, (d)
maintainability, (e) usability in combat (especially, for defence uses), (f) manufacturability,
(g) wearability, and also (h) affordability. [27] In another point of view, thermal and moisture
management, along with other aspects, for examples (a) mobility, (b) flexibility, (c) sizing
192
and fit, (d) durability, and (e) garment care are of significant importance. [32] Additionally,
smart clothing is also defined as digital clothing and categorized the requirements into
different features, some of which include (i) durability, (ii) easy care, (iii) comfort, (iv)
safety and also (v) aesthetic satisfaction. [33]
As a result when we think about safety, fashion, warning system along with other
different features of smart clothing, it is sometime possible to attain these features by the
judicious utilisation of molecular switches in terms of their applications on textiles using
dyeing, printing (both screen printing and inkjet printing), coating, dipping techniques to
produce smart textiles. In this case, one of their main goals is to incorporate into smart
clothing systems to serve specific desired purposes. In a series of publications we have shown
that molecular switches have many important application potentials for smart textile
applications. So, in successive sections different features of molecular switches within the
clear boundary of the main objectives of the chapter are briefly discussed here.
MOLECULAR SWITCHES
A molecular switch is a switch which can exist in more than one (usually two or more)
stable states (more specifically metastable states) where it shows significant difference in
physical, chemical or biological properties. These properties can be reversibly shifted
between these metastable states in response to external stimuli, such as, change in pH, light,
temperature, electrical current or potential. As for instance, pH indicators are well-known
examples of synthetic molecular switches which show distinct colours as a function of a
change in pH (for detail classification of molecular switches, see Table 2). As a result, a
simple molecular switch has a potential (when incorporated in a complex molecular system)
to act as a trigger to turn off and on important physical, chemical or biological properties of
the system, such as surface wettability, polymer elasticity, host-guest recognition, catalysis,
enzyme activity, fluorescence, neural activity and membrane activity for intracellular drug
delivery. [33] However, for this current chapter a particular emphasis is given on the nature of
colour changes of a molecular switch when exposed to different environmental stimuli (such
as, light, pH, temperature, electrical potential, etc.) with a specific aim to integrate the system
in terms of textile applications for environmental sensing (more specifically producing a
notable colour change) for a variety of purposes. In this context, a very brief discussion will
highlight selected fundamental mechanisms of colour production using different systems.
FUNDAMENTAL MECHANISM OF COLOUR PRODUCTION AND THE

NATURE OF MOLECULAR SWITCHES
Our eyes are stimulated with rays of light with wavelengths ranging from the ultra-violet
to infra-red regions of electromagnetic wave spectrum, which is popularly termed as the
visible region. However, within this visible region, different wavelength ranges give rise to
different colours. In collective term they produce a white effect which is usually composed of
seven basic colours violet, indigo, blue, green, yellow, orange and red. The production of
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colour can be divided into five broad fundamental mechanisms which are summarized in
Table 1. [34]
Table 1. Major fundamental mechanisms of colour production
Effects
Vibrations and excitations
Ligand field effects
Transitions between molecular orbitals
Transitions between energy bands

Geometrical and physical optics
Causes and examples

External heat or energy transfer within molecules
(such as, in vapour lamps, incandescence and a
few lasers)
Usually caused by single electrons in ions and
complexes of transition metals (for examples, in
phosphorescence and lasers)
This is usually observed from dyes and pigments
of both organic and inorganic origin, and also
from some fluorescent molecules (e.g., dyes,
pigments, etc.)
Usually seen in metals and semi-conductors
(such as, in WO3, TiO2, etc.)
Observed due to the interference phenomenon,
iridescence diffraction and liquid crystals (such as,
photonic crystals, liquid crystals)
Different types of molecular switches show colour change due to a number of

reasons(detail discussion on the mechanism is beyond the scope of the chapter), some of the
important reasons are, change in conjugation in molecular structures (for example,
spirooxazine, spiropyan, naphthopyran based photochromic molecular switches, when
exposed to certain stimuli, such as, light and heat they show change in conjugation when
exposed to these stimuli and show the colour change), vibrations and excitations, transitions
between molecular orbitals, transitions between energy bands, change in geometrical and
physical properties. Molecular switches show their presence in different metastable state
when exposed to different environmental stimuli, so they can also be term as chromic
switches which is briefly covered in next sections.
Chromism from the Colour Change Behaviours of Molecular Switches

Chromism refers to colour change phenomena of different substances and the materials
show this behaviour are usually called chromic materials. In general terms, chromic
phenomena are related to different processes that cause reversible colour change, absorption
and reflection of light, absorption of energy and emission of light, absorption of light and
energy transfer or a conversion and manipulation of light. [34] It is a general observation that
a reversible colour change is usually observed when there is a change of the electronic state,
especially involving pi-electrons (-electrons), physical change of the material or
rearrangement of molecules in a matrix. In all these cases, these type of colour changes are
stimuli-responsive which means these materials show a distinctive colour change when they
are exposed to a suitable stimulus or even sometimes responsive to a combination of different
stimuli (such as, light, heat, pH, gas, time, sound, mechanical force, electrical force, magnetic
force, etc.). A brief classification of selective chromic materials is shown in Table 2.
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Table 2. Different major types of molecular switches (or materials)
Materials or switches
Photochromic
Thermochromic
Usual responsive
stimulus
Light (and heat in
some cases)
Temperature
Ionochromic/Halochromic pH, ions

Electrochromic
Electrical field
Usual nature of
changes
Colour, geometric
shape, dipole
moment, refractive
index, etc.
Colour, geometric
shape, refractive
index, etc.
Colour, producing
different ionic form
Colour, producing
different ionic form
Example
Spiropyrans,
spirooxazines,
diarylethenes,
chromenes, fulgides
Spirolactones,
bianthrones, etc.
Phenol Red, Cresol
Red, Bromocresol
Green, etc.
Viologens
As already stated previously, there are many uses of different molecular switches in the
production of smart textiles for a variety of applications. Among different molecular switches
photochromic, thermochromic, ionochromic and electrochromic switches are most frequently
used in variety of smart textiles. So, most discussion on this chapter will concentrate on these
four types of molecular switches along with their possible effective utilisation on smart textile
productions.
PHOTOCHROMIC MOLECULAR SWITCHES AND THEIR

APPLICATIONS IN SMART TEXTILES
A photochromic molecular switch is a photochromic dye or pigment or material which
changes colour reversibly under the effect of ultra-violet irradiation. Photochromic materials
(especially, spirooxazines, spiropyrans, naphthopyrans, fulgides, diarylethenes) have attracted
intensive current research interest due to their variety of applications including sun-screening,
security printing and optical data storage. Photochromic dyes are commonly applied in a
polymer matrix. There are numerous potential applications of photochromic dyes on textiles
and leather to produce novelty or fashionable colour change design effects, intelligent textiles
for sensing exposure to sunlight and other sources of UV light, in camouflage, for military
purposes, and for security purposes such as in brand protection.
Photochromism is a chemical phenomenon, in which a chemical species transforms
reversibly from one form to another form under electromagnetic radiation. [35-45] The word
photochromic originates from the Greek word phos (light) and chroma (colour). In 1950,
Hirshbergh proposed to use the word photochromism for light- induced colour changes in
non-biological systems. [37] Photochromism may also be termed as a reversible change of a
single compound between two molecular states that show different absorption or emission
spectra under electromagnetic radiation. Photochromic materials show reversible
transformation under photoexcitation between two forms A and B, absorbing photons at
different wavelengths (Amax, Bmax). Besides the different absorption spectra of the isomers,
they also show different chemical and physical properties, such as refractive indices,
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dielectric constants, oxidation-reduction potential and geometrical structures. In addition,

most photochromic systems are unimolecular as shown in Scheme 1.
Chemical species
(max1)
External stimulus (h1)
Removal of stimulus (or h2)
Chemical species
(max2)
Scheme 1. Transformation of chemical species in a unimolecular photochromic system.
Photochromism and its various aspects are used for variety of purposes. These
applications can be classed into several general categories:
1) Applications depending on the colour change due to the molecular and electronic
structures of the two species (A and B) and their corresponding absorption or
emission spectra: (a) variable-transmission optical materials (such as photochromic
ophthalmic lenses or camera filters), (b) fluid flow visualization, (c) optical
information storage, (d) novelty items (toys, T-shirts), (e) authentication systems
(security printing inks), (f) cosmetics.
2) Applications depending on the changes in the physical or chemical properties that
occur along with the easily perceivable colour change at the time of photochromic
reaction. Some examples of these properties are conductivity, refractive index,
electrical moment, dielectric constant, chelate formation, ion dissociation, phase
transitions, solubility and viscosity.
3) Potential applications using the physical and chemical changes due to the shift in the
absorption maxima, such as, optoelectronic systems (modulated by photochromic
pigments), reversible holographic systems, optical switches, optical information
storage, photochemically switchable enzymatic systems, nonlinear optical devices.
Among all of these potential applications, some of them are more demonstrably
commercially successful (such as photochromic glasses, opto-electronic applications), some
of them are gaining access into commercial markets (novelty items and security printing inks)
or demonstrated to be useful (fluid flow visualization). [38-44] In the cases of printing these
photochromic materials are commonly used in the form of microcapsules. Photochromic dyes
can be applied on textiles using different techniques, including dyeing, printing (e.g., screen
printing, inkjet printing), coating, dipping techniques for producing photo-responsive textile
for a huge range of potential applications. [46-57] Different types of photochromic dyes can
be used for producing photochromic textile based smart textiles for their various applications
so a proper selection of photochromic dyes is a very important step.
Selection of Photochromic Dyes for Producing Photochromic Smart Textiles

An effective selection of a photochromic dye and understanding its behaviour in different
matrices is one of the most important issues relating to the photochromic phenomena of dyed,
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printed or coated photochromic textiles. One of the most important fundamental requirements
for a photochromic dye to be used for dyeing, printing or coating of photochromic textiles is
that the photochromic molecule (or switch) must have a photoisomerisable chromophore to
show a clearly visible and reversible colour change for a long time. The molecule should have
enough resistance to degradations (degradation due to oxidation, air, heat, light) during
dyeing, printing, coating operations and it should not produce a clearly observable
background colour (because for a pure photochromic dye, it should produce colourless
dyed/printed/coated substrates). The behaviour of a photochromic molecule is analogous to a
switch, for example, similar to a switch it has two states on and off. If this rationale is
applied to a textile substrate which is dyed with a photochromic spirooxazine dye, the
coloured state under UV light can be considered as on state and normal colourless state can
be considered as off state. There are many requirements to select a high quality
photochromic dye or photochromic molecular switch suitable to be used for producing
photochromic smart textiles and some of these requirements are - (i) the dipole moment of the
dye and also its excited state or merocyanine structure which should exhibit significant
difference between the on and off states, (ii) the thermal back reaction is sufficiently slow
that the molecule can have a lasting effect to show an observable colour change in a dyed
photochromic textile, (iii) very higher fatigue resistance or technical properties (such as,
higher photostability, good affinity or adhesion properties), (iv) the colourless or the ground
state (off form)on the dyed photochromic textile (before UV irradiation) contains no or very
insignificant amounts of the colour after dyeing, printing or coatingand also (v) the relative
simplicity to synthesize the photochromic dye or photochromic molecular switch.
The Ideal Behaviour of Textiles Dyed, Printed or Coated with a High Quality
Photochromic Molecular Switch
It is expected from a high-quality photochromic molecular switch (or simply
photochromic dye) that it shows enough resistance to degradation, a quick colour change
from a photochromic dyed, printed or coated textiles; retains its photochromic colour build up
for a long time along with other high level of technical performances. The evaluation of
photochromic colour build up and to enhance the photochromic life of the dyed, printed or
coated photochromic textiles is very important to understand the nature of the photochromic
dye. Additionally, the nature of the dyed, printed or coated photochromic substrates clearly is
a function of a number of things, including, the nature of the dye or photochromic molecular
switch, concentration, nature of the light source, time of UV irradiation, surrounding
environments, nature of the matrices, the method used to apply photochromic switch on the
substrates. So, it is highly recommended that dyeing, printing or coating techniques must be
carefully adjusted to promote the nature of photochromic dyed substrates to show
photochromic colour build up for a long time for practical useful applications. So, some
important points of many additional features expected from a dyed, printed or coated
photochromic textile are - good colour build up on exposure to UV light, a controlled fading
behaviour (return to colourless state from a coloured state), producing a colourless
background state after dyeing, printing or coating and also a long product life along with the
retention of the colour changing performance for many cycles. [46-57]
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Photochromic Molecular Switches Relevant to Smart Textiles

Some of the most important photochromic molecular switches relevant to smart textile
applications are (a) spirooxazines, (b) spiropyrans, (c) naphthopyrans, (d) diarylethenes, (e)
fulgides, (f) fulgimides, (g) azulenes (dihydroindolyzenes) and some particular types of
photochromic supra-molecular switches. The behaviour of spirooxazines, spiropyrans,
naphthopyrans and diarylethenes basedmolecular switches are discussed in the chapter on
Inkjet printed photo-responsive textiles for conventional and high-tech applications by this
author so in this section some unique features of these photochromic molecular switches will
be selectively discussed (in successive sections on photochromic molecular switches) here.
Brief History of Selected Molecular Switches and Their Potential

Applications in Smart Textile Production
In 1960, Feyman introduced the concept of artificial molecular machine and also
highlighted their different application potentials (such as, their uses in molecular devices).
[58] Shinkai et al., at first synthesised molecular machines with having crown, azacrown
ethers and azo groups in their structures. Azo group present in this system has the capability
to photoisomerize to show reversible switching behaviour for inducing a conformational
change, for example, Azacrown Acontains two crown ether linked to one another by an
azobenzene hinge which is illustrated in Scheme 2. This system shows reversible change
when irradiated UV light and then with visible light. [58, 59]
Scheme 2. One of the first examples of a molecular switch.
There is no report of using photochromic azacrown in textile coloration. Additionally,

one of the main limitations of azobenzene based photochromic switches is some of them
revert back to original state (from where they switched to another state on exposure to UV
light) at room temperature and also at wavelength below 390 nm. As a result, there is no
observable colour change from many of the azobenzene species when used on textile
application. [60] However, spirooxazines, spiropyrans, naphthopyrans are suitable molecular
switches for a variety of textile applications. [46-57] Diarylethenes and fulgides are important
photochromic molecular switches which have high potential for textile applications. As a
result a few aspects of diarylethenes and fulgide based selected photochromic molecular
switches are described here. Usually, diarylethenes show photoisomerization and cyclization
when exposed to UV irradiation and return to their original form after exposure to visible
light. For example, diarylethene A is colourless (ring open form) in hexane solution before
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exposure to UV light, however, it retains a blue colour when irradiated with a UV light (at
313 nm) (Scheme 3). [61]
Scheme 3. The nature of photo-induced switching behaviour of diarylethene Afrom ring open form
(colourless) to ring close form (coloured) to give a photochromic colour change.
It is important to note that generally the ring close form of a diarylethene is thermally
stable and does not revert to the ring open form. Irie et al., concluded that this thermal
stability is due to the low aromatic stabilization energy when the aryl groups are furanes,
thiophenes or thiazole rings. [62] On the other hand, when the ring- close form of a
diarylethene contains a pyrrole, indole or phenyl ring, it shows high aromatic stabilization
energy and is therefore thermally unstable. [63]Scheme 4 shows the photochromic switching
behaviour of diarylethene B (a pyrrole containing diarylethene) and itreverts back to its
original colourless ring open form in a very short time (e.g., 37 seconds) at 25C.
Additionally, this thermal behavior is closely related to the aromatic stabilization energy of
the aryl groups.
Scheme 4. Photochromic switching behaviour of a thermally unstable diarylethene B.
So, from this two examples (as in Schemes 3 and 4) it is clearly understood that
diarylethene A is suitable for application to textiles while diarylethene B is not suitable for
textile application because it will not show a desired stable and observable photochromic
colour change since it starts to return to the original colourless state even at a temperature
(25C) very close to the room temperature.
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Diarylethene Based Photochromic Molecular Switches for Smart Textiles

Different varieties of diarylethene based photochromic switches are now available. As
mentioned above not all of them are suitable for producing stable photochromic colour
change on textiles when targeted for smart textile applications. There are huge variety of
approaches to produce photochromic diarylethenes using different techniques mainly focused
on their application as memories and switches, [63] and one of them is based on host-guest
interactions. For example, a crown ether in a diarylethene unit may participate in host-guest
guest interaction to show photochromic switching behaviours as shown in Scheme 5. In this
reaction, Takeshita showed that the ring open form of diarylethene C forms a sandwich
complex with large metal ions. [64-66] This system have different applications and one of
which is the active transport of molecules and metal ions that may be suitable for photoinduced drug delivery when incorporated with a suitable system and applied in the
preparation of photo-responsive dyed, printed or coated textiles for smart textile based health
care applications. Using the same logic as shown in Scheme 5, a glucose molecule can be
captured and released by modified diarylethene bearing boronic acid moieties by using photoirradiation. [67]
Scheme 5. A conceptual demonstration of photoswitchable cesium ion tweezers (diarylethene C based

on a diarylethene functionalised with crown ether) which acts like a tweezers where metal ions are
controlled by light.
So far we have seen diarylethenes which show different types of thermal behaviours
(such as some are thermally stable and some are unstable) and we have also seen the
feasibility of using diarylethene based system for their potential applications in photocontrolled drug release when incorporated in different substrates (such, smart textiles and
other suitable systems). Now we would like to focus on a few selected features of some
particular types of diarylethenes, fulgides and couple of other selected members of photoinduced molecular switches which may be considered for smart textile applications apart from
their usual applications in a variety of fields. Some diarylethenes are electrically responsive,
for example diarylethene D shows electrically responsive behaviours (Scheme 6). [68,69] In
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this case, the two positively charged pyridinium ion moieties interact only weakly in the ringopen form (colourless state), this colourless state can be considered as off state.
Scheme 6. Control of the electron flow through photoisomerization of diarylethene Din this figure.
However, on the other hand, the two pyridinium ion groups in the ring close form
(coloured state) this interaction is more strong due to the delocalization of pi-electrons
producing a coloured form, so this state can be considered as on state. These types of
systems are suitable for their potential uses as switchable molecular wires in which electron
flow is controlled by light irradiation. This type of switch is also suitable for electrochromic
display on smart textiles for a wide variety of applications.
Selection of Diarylethene Based Molecular Switches

Most of the diarylethene based molecular switches are photo-responsive even when
applied in textiles using dyeing, printing or coating process. In these cases, light acts as an
attractive physical stimulus which can be easily used in various media with short response
times. Among a variety of molecular photo-responsive switches, dithienylethene derivatives
are very prominent. These compounds show very high fatigue resistance and the
coloration/decoloration cycle could be repeated more than 104 times without loss of their
spectral features due to side reactions or decomposition. [63] Because of their absorption
properties along with stability features, they are excellent materials which are suitable for
showing photo-induced changes of physical properties. For a further example of a simple
diarylethene based small photochromic molecule E, it shows repeated colouration/
decoloration switching behaviour in solution (i.e., the ring-open isomer is colourless or very
pale coloured isomer when irradiated with UV light, it transforms into ring closed isomer that
show a deeply coloured form and it again regains its colourless or very pale coloured ring
open form when exposed to visible light, this continues for many times) (Scheme 7).
Scheme 7 shows the two different absorption spectra (one for ring open form and another
for the ring closed form) of diarylethene E, it indicates that the delocalisation of the
electrons in closed form extends towards longer wavelengths up to the visible region
spreading over the entire structure in the closering form. However, in ring open (colourless)
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form, the delocalization of electrons is restricted to each half of the molecule and electronic
communication through the unsaturated bond of the middle ring is interrupted. In terms of an
explanation similar to electrical switches, if we consider that a diarylethene E is
functionalized with suitable anchor groups and immobilized between two electrodes in a
junction, the coloured form or ring closed form would then correspond to the ON state while
the less conducting form ring open (or colourless) form would be referred to the OFF state
(Scheme 7). These types of diarylethene based molecular switches are suitable for smart
textile applications. Apart from diarylethenes, spirooxazines, spiropyrans, naphthopyrans,
some particular types of fulgides, azulene based photochromic molecular switches (to some
extent) and some particular types of molecular chiroptical molecular motors and supramolecular switches are potentially suitable for smart textile applications. So, this following
section will very briefly discuss some very selective features of these systems with a view to
their potential applications in smart textiles.
Scheme 7. Principle of reversible photo-switching between the ring open form (colourless) and the ring
closed form (coloured) of dithienylethene E in solution.
Fulgides
Fulgides are bismethylenesuccinic anhydrides, they usually contain a phenyl ring on the
methylene carbon atom. They were first synthesized and studied early in the 20th century by
Stobbe. [70] Scheme 8 indicates the photochromic switching behaviour of a fulgide. In this
case, ring open E-isomeric form of this fulgide undergoes cyclization when exposed to UV
light turns into a deeply coloured ring closed form (of this fulgide). Additionally, there is
concomitant transformation from the E-form to Z-form which are always colourless and when
all these forms absorb UV light, inter conversions between them occur until a photostationary
state is reached. Besides this, as the coloured ring closed form is the only form which can
absorb visible light, so when it is exposed to visible light it disappears completely and returns
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to its original colourless form due to a change in conjugation of pi-electron systems of the
fulgide molecular switch.
Scheme 8. Photochromic switching behaviour of a fulgide.
There are different types of fulgides used in various applications. [71] A wide variety of
photochromic fulgides can be produced from the anhydride derivatives. Most of the fulgides
produced in this usual system are mostly thermally reversible. However, in 1981, Heller et
al.,, at first produced thermally stable fulgides by introducing furane derivatives instead of the
phenyl group. [72, 73] This type of thermally stable fulgide (furylfulgide) is shown in
Scheme 9.
Scheme 9. Photochromic switching behaviour of a thermally stable fulgide (a furylfulgide).
Thermally stable fulgides are more suitable for producing photochromic textiles. There
are some fulgides which also show fluorescence behaviours. Scheme 10 shows the
photoswitching behaviour of a fulgide. In this case, ring open form of furylfulgide rarely
emits fluorescence unless it contains a fluorescent moiety. However, on the other hand,
cyclized closed form of this compound usually shows fluorescence at low temperatures. Port
et al., prepared a types of fulgides (more specifically fulgimides), where fluorescence is
photo-controlled (i.e., a particular photo-isomer of a fulgimide shows fluorescence). [74, 75]
Figure 9 shows a fulgimide which contains an anthracene, this anthracene acts as an antenna
(or as an energy donor) on the thiophene ring. Additionally, in this molecule, the nitrogen
atom of fulgimide is attached with an aminocoumarin with an aim to use it to work as a
luminescent moiety (or as an energy acceptor). So, when the ring open form of this fulgimide
203
is irradiated with a light of 320 nm wavelength, the anthracene group is excited to a higher
energy level and this energy is transferred through the core of the ring open form through the
coumarin and shows fluorescence. On the contrary, this fluorescence behaviour is
significantly reduced when this molecule is exposed to a visible light of 520 nm due to
photocyclization.
Scheme 10. Photochromic switching behaviour of a particular type of fulgide.
This type of molecular switch has the potential to apply in textiles for producing
photochromic fluorescent fabrics for smart textile applications to work as multi-functional
items.
MULTIFUNCTIONAL PHOTOCHROMIC MOLECULAR SWITCHES

Some photochromic systems also have the capability to work as multi-functional
switches. Azulenes and supra-molecular switches are some of the important types of
multifunctional molecular switches which are very briefly discussed here.
Azulenes
Photochromic azulenes shows photochromic colour changes when exposed to UV light.
This photochromic behaviour is due to the change in the electronic structure of molecule
which originates from a rearrangement molecular structure when exposed to a suitable actinic
radiation (such as, UV light). Generally, this type of molecule is not thermally stable. Scheme
11 shows a precise schematic illustration of the photochromic switching behaviour of a
dihydroazulene (or diamidotriazine) type photochromic azulene. The structure of this
molecules also indicates that this type of azulenes have influence in the complex properties of
the diamidotriazine moiety. This system is one of the good examples of a photochromically
controlled supra-molecular interaction. It is important to mention here that some
photochromic azulenes to multimode photochromic behaviours. For example, Scheme 12
indicates a multi-mode photochromic system of an azulene based photochromic switch where
it shows a multi-addressable system with different inputs of stimuli (such as, light, heat and
pH). Several multimode photochromic systems based on dihydroazulene have been reported.
[76, 77] Diederich et al., have published results [43] about composing system based on
dihydroazulene (DHA)/vinylheptafulvene (VHF) photochromism with a three-way molecular
204
switch, which may be controlled by several different types of inputs, such as, pH, light, and
heat. It is very interesting to note that all three subunits are individually addressable and have
the ability to undergo individual, reversible switching cycles (Scheme 12).
Scheme 11.A precise schematic illustration of the photochromic switching behaviour of a

dihydroazulene (or diamidotriazine) type photochromic azulene.
Scheme 12. Multi-mode photochromic behaviour of an azulene based photochromic switch (i.e., multiaddressable system with different input types).
Additionally, some members of photochromic azulene based molecular switches also

show photo-controlled fluorescence behaviour. For example, Scheme 13 illustrates a
schematic representation of photo-responsive fluorescence behaviour of a particular type of
photochromic azulene based molecular switch. In this case, a light-controlled fluorescent
switch has been prepared from a boron-dipyrromethene dye which acts as a fluorescent sensor
and the photochromic DHA/VHF as a photochromic switch (Scheme 13). [78] So far there is
no report of using photochromic azulene based molecular switches for textile applications,
however, these type of molecular switches have some potential applications when considered
them as photochromic disperse dye type molecular switch which may be used in polyester,
nylon and other related textile in terms of dyeing, printing and coating techniques for a
variety of smart textile applications. Besides this, there are some leuco-derivatives (one
example is shown in Scheme 14) which show photo-induced ionisation and are useful
205
candidate for hydrogels or polymers where there shapes can be controlled using actinic
radiation (such as, UV light). [79] This type of materials are suitable for producing healthcare
materials, photo-controlled drug release and have the potentials to be incorporated in
healthcare based smart textiles for a wide variety of biomedical applications.
Scheme 13. Schematic representation of a photo-responsive fluorescence behaviour of a photochromic

azulene based molecular switch.
Scheme 14. Photo-induced switching behaviour of a leuco-derivative which also shows thermal back
reaction to regain its original state (which was before exposure to UV light).
The photo-induced ionisation of compounds which contain leuco-derivatives, for

example, bis(4-(dimethyl amino) phenyl) (4-vinylphenyl)methyl leuco cyanide, is useful to be
206
used to produce expansion and shrinkage on different polymers or gels. Scheme 14 shows the
photo-induced switching behaviour of a leuco-derivative which also shows thermal back
reaction to regain its original state (which was before exposure to UV irradiation). The
changes in the material arise due to the change in electrostatic repulsion between the charges
and the ionisation of the compound is mainly due to the effect of UV irradiation (of an UV
light of wavelength 270 nm or more). In this context, cyclobutanes are other types of
materials which are widely used for photo-induced shape controls in gels, hydrogels or
similar types of systems which have many applications in biomedical textiles. Cyclobutanes
are usually produced from cinnamic acid and also from its different derivatives. In this type of
system, two cinnamic acid molecules dimerise to form a cyclobutane when irradiated with
UV-light (of wavelength 300 nm or more). Scheme 15 illustrates a photo-induced
dimerisation reaction of cinnamic acid when exposed to UV-light of wavelength 300 nm, or
more. It also indicates that there is a reverse reaction from the changed state when it is
irradiated with an UV light of shorter wavelength (such as, 254 nm) and regains its original
form. [79]
Scheme 15. Photo-induced dimerisation of cinnamic acid on exposure to UV-light (of wavelength 300
nm, or more); however, when irradiate with an UV light of shorter wavelength (such as, 254nm) it
shows a reversion to its original form.
These types of photo-responsive switch are particularly important for producing photoresponsive shape memory polymers which have some potential applications in healthcare
based smart textiles. Finally, there are some molecular motors based on chiroptical molecular
switches and some particular types of supra-molecular switches have many potential
applications in smart textile applications. So, they are briefly discussed here.
MOLECULAR MOTORS
Some unidirectional chiral molecular motors have the capability to mimic the rotational
motion of ATP synthase and flagella motors. [81] Scheme 16 indicates the photo-switching
behaviour of a unidirectional molecular motor A which work as a function of the nature of
wavelength of UV light and the nature of heat. This molecular motor A (in E-form, I)
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contains a tetra-substituted photo-isomerizable alkene which has two phenanthrene

derivatives. The steric hindrance of the phenanthrene substituents of the alkene introduces
helical chirality in the system. In the first phase, the alkene adopts a trans-conformation
which is isomerized into a highly strained cis-isomer (molecular motor A in Z-form, II) when
irradiated with a UV light (>280 nm) at -55C.
Scheme 16. Photo-switching behaviour of a unidirectional molecular motor A which work as a function
of the nature of wavelength of UV light and also according to the nature of heat.
In the second phase, there is a concomitant move of the methyl substituents of the
cyclohexane ring from the axial position to the equatorial position. In the third phase, when
the molecular motor A (in Z-form, II) is heated at 20C it undergoes a flipping motion of the
aromatic rings around the alkene to give an oppositely twisted helicalmolecular motor A III
isomer. In the fourth phase, when the molecular motor A III isomer is exposed to photoirradiation with a UV light of >380 nm, it undergoes a conformational change into a highly
strained trans-isomer (molecular motor A IV isomer). In addition, at 60C, the molecule
flips back to its original form to end the rotation cycle. The unidirectionality of this motor is
made possible due to the chiral properties of this molecular motor A. There are a number of
improved forms of these molecular motors. [80-84] There is no reports of using these type
molecular motors in textiles; however, they have the potentials for multi-functional switches
based high performance smart textiles for many advanced applications. Some supramolecular switches, such as, catenanes also have the potential for multi-functional switches
based high performance smart textiles for a wide variety of advanced applications. The nature
208
of a particular type of a catenane based supra-molecular switch is described here to conclude

this section on photochromic molecular switches.
Catenanes and Rotaxanes Based Supra-Molecular Switches

Interlocked molecular switches, such as, catenanes and rotaxanes are of great interest
because of significant importance because of their many potential applications in different
fields, for examples, sensors, memories, switches, etc. They attain some unique properties due
to the cooperative or synergistic effect of each component present in the interlocked system.
In last two decades different types of catenanes and rotaxanes have been prepared and their
structural and dynamic properties have been investigated both in solid and solution states.
[85] Stoddart et al. have prepared a variety of self-assembled catenane and rotaxane using the
intermolecular charge transfer interaction between viologen and dialkoxybenzene derivatives.
[86] They are based on the ability of the tetracationic cyclic viologen derivative or parabenzo-crown-ether to form inclusion complexes with pi-electron donating compounds or
linear viologen units, respectively. These catenane and rotaxane showed excellent
performances as the molecular machines which are driven by the chemical or electrochemical
stimulus. [87] There are a few reports on the photo-induced spectroscopic properties of
photochromic supra-molecular switches. [88] A recent report on the supra-molecular
regulation of the photochromism by the additives shows that it is possible to interact with the
photochromic molecule using inter-molecular interactions. There is an increase in the
quantum yield for the photochromic reaction of diarylethenes by the complexation with the
cyclodextrin. [89] It is also possible to add metal ions switched on the trans-cis isomerization
of azobenzene derivatives. [90] Addition of metal ions improves the thermal stability of
coloured merocyanine form of spirobenzopyran derivatives. [91] So, from this brief
discussion it is clear that photochromic supra-molecular switches can be produced in various
ways for a wide range of applications. There are also wide variety of catenanes which act
aselectrochromic switches, for example, Scheme 17 shows electrochemically induced
rearrangements of catenane (from form A to D). The detail nature of electrochromic switches
are discussed later in this chapter.
Usually some particular types of catenanes are interlocked with two different rings. [92,
93] In this system, one of the loops includes two coordinating units - a bidentate and a
tridentate terpyridine. On the other hand, the second loop has only one bidentate
complexation site. In the beginning, catenane A is immobilized on a copper (I) metal ion and
adopts a 4-coordinate tetrahedral geometry which is shown in Scheme 17. Upon oxidation of
the copper to the divalent state, A produces an intense green colour and transformed into
structure Bspecies (which gives an absorption band at 670 nm in acetonitrile). It is important
to note that this process can be triggered either by using chemical or electrochemical
oxidation. In addition, due to a rotational rearrangement form B turns into a pale olive-green
coloured species and takes the shape of form C. At this stage, the system includes
decomplexation followed by rotation and recomplexation at the terpyridine binding site. The
5-coordinate copper (II) shows an absorption band at 636 nm which corresponds to 5coordinated copper complex. Form B has a slightly distorted tetrahedral geometry whereas
form C is square pyramidal. After reduction of form C into D, rotation of the terpyridine
group leads to the starting original catenane form A. This type of gliding of the ring takes
209
place in a few seconds at room temperature regardless of the solvent. On the other hand, the
speed of rearrangement after oxidation from B to C depends mostly on the solvent and the
counter-anion. This type of device can be regarded as a molecular motor as the loop activates
a complete 360 rotary motion around the copper ions. This type of systems are suitable for
site specific drug delivery on human skin using particular types of high performance
biomedical textiles which may be incorporated into smart textiles for multi-purpose
applications.
Scheme 17. Electrochemically induced rearrangements of catenane (from form A to D).
APPLICATION OF PHOTOCHROMIC SMART TEXTILES

A good quality photochromic smart textile is expected to show photochromic colour
change for a long time and will retain of its reversible photo-coloration behaviour even after
exposed to different environmental conditions. This behaviour makes it a suitable candidate
for many potential applications. Some of the selected important application field are (a)
security, (b) responsive surface, (c) brand protection, (d) authentication, (e) actinometry, (f)
self-indicating UV warning system, (g) active and adaptive camouflage, (h) environmental
warning system, (i) electrophoretic textile based display, (j) interior design, (k) exterior
design and also in (l) fashion and design applications. In this context, photochromic smart
textiles have the potential for healthcare applications as well. It important to note that the
possibility to bind a photochromic molecule onto a naturally occurring receptors and enzymes
which can be bonded with a photochromic smart textile using certain techniques provides the
opportunity to photo-regulate their binding and catalytic activities. Hopefully, in future, this
type of photo-responsive textiles may be used for different therapy, bio-sensing and also in
wound care along with their other already stated applications. [46-57]
210
THERMOCHROMIC MOLECULAR SWITCHES AND THEIR

APPLICATIONS IN SMART TEXTILES
Thermochromic molecular switches (such as, thermochromic dyes, pigments, materials)
change colour as a function of temperature either reversibly or irreversibly. The molecular
switcheswhich show a reversible thermochromic colour change have their potential
application in textiles, such as, leuco dyes (in appropriate composition with other additives)
and cholesteric liquid crystal based thermochromic pigments. Usually a leuco dye based
thermochromic switch shows a colour change from coloured to colourless or to another
colour with an increase in temperature. However, a cholesteric liquid crystal based
thermochromic switch exhibits a vivid range of colour change (may also be termed as a
colour play) by passing through the whole spectrum with an increase in temperature. The
leuco dye based active thermochromic switch usually consists of a colour former, a developer
and a solvent in a specific combination where the colour former is a pH sensitive dye (e.g., a
spirolactone ora fluoran) and the developer is a proton donor (e.g., an week acid like
Bisphenol A). The solvent suitable for this thermochromic composition is usually a low
melting hydrophobic, long aliphatic chain fatty acid, amide or alcohol and its melting point is
used to associate the system with a specific temperature at which the colour former and
developer can easily interact. On the other hand, the liquid crystals with a chiral centre (also
known as cholesteric liquid crystals) show colour change in response to a suitable change in
temperature in the surrounding environment. In the preliminary stage most liquid crystals
were cholesterol derivatives, however, now-a-days synthetic chiral molecules (also known as
chiral nematic liquid crystals) are also available. The cholesteric liquid crystals are usually
used against a black background for the manipulation of the incident light and also for the
reflection of light of selected wavelengths which vary with change in temperature. In this
case, the particular reflected wavelengths are dependent on the pitch length of the helix
formed by the liquid crystals and these parameters show a change with a change in
surrounding temperature. Microencapsulation is a widely used technique for the integration
and application of the leuco dye based and liquid crystal thermochromic pigments. For clarity
and better understanding the word thermochromic material or dye or pigment used in this
chapter will be used in place of a thermochromic molecular switch when necessary, which
has similar type of meaning but not necessarily the same. [94-95]
Commercial thermochromic pigments are available since the late 1960s for a variety of
applications, including, thermographic recording materials, temperature indicators (e.g., to
measure body temperature), recording thermal history (such as, to determine the temperature
or history of the food storage when used in a food container). These materials also have other
wide ranging applications, some of which are (a) in medical thermography for diagnosis
purposes, (b) in thermal mapping of engineering materials to diagnose faults in product
design and in mechanical performance, (c)in the cosmetic industry for moisturizing and as a
carrier for vitamins, (d) in memory devices for date storage,(e) in batteries for life indication,
(f) in the architecture field for decoration or for its functionality, (g) authentication, (h) brand
protection, and also in (i) anti-counterfeit applications. Thermochromic materials are also
used as novelty materials in the manufacture of toys, ornaments, kettles, umbrellas, toilet
seats, etc. However, in textiles, thermochromic materials are usually applied by printing,
coating and extrusion methods. Thermochromic textiles produced from using thermochromic
211
materials have many applications, including in T shirts, children clothing, jeans, electronic
heat profiling circuitry, in man-made cellulose fibres and also in acrylic fibres. Although
thermochromic materials have been used in textiles relatively for a longer time compared to
photochromic materials but the extent of application is still not that much wide ranging. [9499]
CLASSIFICATION OF THERMOCHROMIC MOLECULAR SWITCHES

In broad classification thermochromic materials are divided into two groups and they are
inorganic and organic thermochromic molecular switches (or materials).
Inorganic Thermochromic Systems

There are a number of inorganic molecules which show thermochromic colour change in
solid or solution states. For this type of molecules which show temperature dependent
thermochromic colour changes, there are a number of mechanisms, some of which are (a)
phase transitions, (b) changes in ligand geometry,(c) equilibria between different molecular
structures and also (d) changes in the number of solvent molecules in the coordination sphere
(for example involving dehydration). [98] Most of the inorganic thermochromic systems are
originated from transition metals and organo-metallic compounds. Generally, most of the
inorganic thermochromic systems show intrinsic colour changes which are direct heat
dependent in nature. Some examples of inorganic thermochromic materialsare - (a) Cu2HgI4
is red at 20C but black at 70C,(b) ZnO is white at room temperature but yellow at higher
temperatures; (c) In2O3 is yellow at a lower temperature but yellow-brown at a high
temperature; (d) Cr2O3-Al2O3 is red at 20C but grey at 400C; (e) (Et2NH2)2CuCl4 is bright
green at 20C but yellow at 43C; (f) CoCl2 is pink at 25C but blue at 75C; (g) VO2 at
about 68C changes from transmissive semiconductor to an infrared reflecting metallic
conductor. [40, 95-101]
Inorganic thermochromic materials/systems have some limitations for textile
applications. Because these materials often show their thermochromic behaviour at a high
temperature or in solution form and sometimes the colour change is irreversible. [102]
However, it is an important requirement for the thermochromic materials to be suitable for
textile applications that they show heat dependent colour changes at close to ambient
temperatures, as for instance, around -10C for ski wear and around body temperature at 35C
for apparel and smart textiles. [98] As a result, most of inorganic and organometallic
materials based thermochromic systems are mostly used in temperature indicating paints and
crayons for the identification of temperature change and also for providing a permanent
record of thermal data.
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ORGANIC THERMOCHROMIC SYSTEMS

A stark difference of organic thermochromic systems from the inorganic one is that they
show reversible thermochromic colour change involving both intrinsic and indirect systems.
So, now a brief discussion will concentrate on different systems involved in organic
thermochromic systems.
Reversible Intrinsic Thermochromic Organic Systems

Usually reversible intrinsic thermochromic organic systems show colour change when
exposed to heat without depending on anything else (such as the environment) and they revert
to the more stable state as they cool down after removal from the heat source. There are four
different types of mechanisms generally used to explain the colour change phenomena of
different thermochromic systems; they are - (a) molecular rearrangement, (b)
stereoisomerism, (c) macromolecular systems and (d) supra-molecular systems.
Thermochromic Colour Change Based on Molecular Rearrangement

Sometimes molecular rearrangement is observed in some of organic thermochromic
systems which are mostly due to the result of tautomerism. This tautomerism may originate
from acid-base, keto-enol or lactim-lactam equilibria, which lead to an increase or decrease in
the electron conjugation in molecules, to form different types of chromophores. [90, 103] For
example, due to hydrogen transfer Schiff bases (usually produced by the condensation of
salicylaldehydes and anilines) show enol-keto tautomeric structures. [104, 105] In this case,
in the tautomeric equilibrium the keto form is more favoured and the Schiff bases are planar
in stucture and at this stage they show thermochromic colour changes from yellow to orange
or red as shown in Scheme 18.
Scheme 18. Tautomeric forms of a Schiff base.
213
Sometimes, some photochromic molecules such as, spiropyrans and spirooxazines may
also show thermochromic colour change. In this case, in solid or liquid form, both
spirooxazines or spiropyans may show heat induced transformation from their colourless
ground state (closed form) (at lower temperature, such as, room temperature or below) to their
coloured merocyanine (or ring opened) format high temperature. Additionally, these
compounds also show solvatochromism in polar solvents may be due to the formation of the
polar merocyanine structure. [106] Another similar example of this type of compound is bisspiropyran (as shown in Scheme 19) is colourless at lower temperature, however, it shows a
red colour in n-propanol at 60C and blue colour at 70C. This phenomenon is mainly due to
the structural formation of mono-merocyanine and bis-merocyanine respectively. [40]
Scheme 19. Sequential coloration of a bis-spiropyran with temperature.
214
Thermochromic Colour Change Due to Stereoisomerism

Sometimes stereoisomerism also causes thermochromic colour change which usually
observed in the compounds which have at least one ethylene group, a number of aromatic
rings and one hetero-atom (such as, nitrogen or oxygen) in their structure. In this case, the
ethylene group present in the structure restricts a molecular orientation which in effect causes
the difference in energy levels in different isomeric forms. When the type of system exposed
to heating, the molecule adopts different stereoisomeric forms which eventually produces
colour changes. Some particular examples of these materials are overcrowded ethylenes, such
as, bianthrone, dixanthylene, and xanthylideneanthrone. [98-106] Bianthrones exhibit
reversible colour change from yellow (as shown in A ) at room temperature to green (as
illustrated in B) at high temperature when heated in solution (as shown in Scheme 20). [40]
These types of stereoisomers based thermochromic materials are not suitable for textiles
application. Because, they only show thermochromic colour changes in their molten states
which commonly occur at higher temperatures.
Scheme 20. Schematic representation of thermochromic bianthrones where 1 is a folded structure and 2
represents a twisted structure of a bianthrone.
Thermochromism in Macromolecular Systems

Some types of macromolecules, such as, poly(3-alkylthiophenes) and poly(3alkoxythiophenes) show thermochromic colour change in solid and solution form due to the
change in conjugation. Some of them also show other types of chromism (such as,
photochromism, electrochromism) when exposed to suitable environmental stimuli.
Sometimes a hypsochromic reversible colour change is observed in some macromolecular
systems which is usually termed as negative thermochromism. As for instance, poly[3oligo(oxyethylene)-4-methylthiophene] is violet at room temperature and yellow at 100C
due to a change in conjugation at high temperature from its molecular planarity at room
temperature (as shown in Scheme 21).
215
Scheme 21. A planar (violet coloured) form of poly[3-oligo(oxyethylene)-4-methylthiophene] at room

temperature with a non-planar (yellow coloured) form at high temperature (e.g., 100C) where a shift in
conjugation is clearly visible.
Thermochromism in Supra-Molecular Systems

Liquid crystals are some types of materials which have a special type of character that
they can exist in a state between solid and isotropic liquid, in which they exhibit the
properties of a liquid (e.g., the ability to flow), however, they also have a crystalline like
molecular arrangement (which are usually termed as liquid crystals). Liquid crystals are
anisotropic in nature usually derived from calamitic molecules and also they have a very large
length to breadth ratio (which means the molecules are long and narrow in size). [107,108]
Liquid crystals are usually divided into three main groups and they are (a) smectic, (b)
nematic and (c) cholesteric or chiral nematic. They can also be divided into sub groups. [107,
109, 110] However, most reversible intrinsic thermochromic systems operate at a high
temperature which is not suitable for the application on textiles (with an exception to some
particular types of liquid crystals). Additionally, there are significant technical problems to
cover all the colours in visible spectrum which need the synthesis of many compounds.
Reversible Indirect Thermochromism in Organic Systems

The chromophore responds to a change in its environment when exposed to heat in the
case of reversible indirect thermochromic organic systems. The colours used using these
systems are not thermochromic by themselves, however, they show change in colour due to
the difference in the physical environment by the increase or decrease in surrounding
temperature. Usually, the chromophores in these systems are also responsive to pH (similar to
216
the features of dyes which are usually acidochromic or ionochromic in nature). Generally,
indirect systems operate within an ambient temperature range which mostly matches the
temperature range usually used in textile products during their life time. Some of these types
of compounds are also pH sensitive and modifications are possible using suitable synthesis
techniques to provide a range of colours. Thermochromic materials based from this system
have a wide range of textile applications where they can be used to provide precise and
predetermined colour changes at specific temperatures which is in contrast to intrinsic
systems. So, in this stage a brief discussion is given to the nature of usually used organic
thermochromic systems containing colour formers, their versatility and also different aspects
of their compositions.
Usually Used Organic Thermochromic Systems for Specific Purposes

Usually used organic thermochromic systems for specific purposes are generally prepared
by judicious mixtures (in specific proportions) of three essential components which are: (a)
colour formers, (b) developers and (c) co-solvents. In usual terms, these systems are coloured
in their solid form but when there is a suitable rise in surrounding temperature they become
colourless and also regain their original coloured state on cooling. In this case the colour
former is a pH sensitive compound which accepts a proton to convert from a colourless state
to a coloured state. It is a popular practice that they are applied in the form of microcapsules
to avoid any change or damage to the system or variation in the proportion of components.
There are versatile features of this type of organic thermochromic systems (which sometime
referred to as leuco dye systems), some of which include:
a) a sharp transition in colour intensity -over a few degrees temperature difference
where a change from intense or deep colour to colourless is often possible;
b) flexibility of temperature switching -colour changing effects can be obtained at
different temperatures using a proper selection of different co-solvents with
appropriate melting points;
c) a wide variety of colour changing effects it allows to produce colour change from
the coloured (across whole visible spectrum available) state to colourless state, from
one coloured state to another coloured state (is possible by the incorporation of pHinsensitive dyes as a base colour or by using colour formers with a secondary
chromophore).
Compositions of Usually Used Thermochromic Mixtures

The usual colour formers used in organic thermochromic pigments are N-acyl
leucomethylene blue derivatives, fluoran dyes, diarylphthalide compounds, diphenylmethane
compounds or spiropyrans compounds. In this case, crystal violet lactone analogues
(diarylphthalide compounds) and fluoran dyes are mostly used compounds. [111] The ringclosed forms of these compounds are colourless and show colour after conversion to their
coloured ring-opened forms which are obtained by protonation using weak acids as
developers (e.g., phenolic compounds). Sometimes, this type of compounds are often referred
217
to as catalysts or electron acceptors, however, they are mostly proton donors. [98] Mostly
phenolic or nitrogen-containing heterocycles (such as, bisphenol B and bisphenol A) are used
as developers and the latter class provides deep and high contrast colours. Bisphenol A and
phenol have the same acidity level but have different effects which indicate the involvement
of other factors in the efficiency of developers. [97] There are different types of materials are
also used as developers during thermochromic compositions, some of the most popularly used
ones are (a) 1,2,3-triazoles (e.g., 1,2,3-benzotriazole, dibenzotriazole), (b) thioureas, (c)
saccharin and its derivatives, (d) halohydrins, (e) boric acid and its derivatives, (f) guanidine
derivatives (e.g., phenyl diguanide) and (g) 4-hydroxycoumarin derivatives. Some of these
compounds help to improve lightfastness because phenol compounds give rise to quick fading
when exposed to light. [98] There are different types of organic hydrophobic solvents which
are generally used as the co-solvents in thermochromic systems and some of the important cosolvents belong to different groups, some of which are (a) alcohols, (b) hydrocarbons, (c)
esters, (d) ethers, (e) ketones, (f) fatty acids, (g) amides, (h) acid amides, (i) thiols, (j)
sulphides and disulphides and (k) alcohol acrylonitrile mixtures. In most cases aliphatic
solvents are widely used and are effective solvents for thermochromic systems which provide
good desensitising effect at relatively low concentrations which improve the rate of colour
development and also provide more complete colour change. [98] A schematic representation
is shown in Scheme 22, where colour formers and developers interact in the solid form of the
co-solvent and separate in the molten form.
Scheme 22. Coloured and colourless microcapsule.
218
IONOCHROMIC MATERIALS AND SMART TEXTILES

Recently, smart textiles have become the subject of many studies all over the world.
Among the different group of smart textiles, there is a growing interest in colour change
materials for the production of textiles that will produce colour change on exposure to certain
stimulus, some of which are already discussed in the previous sections. In this case
ionochromic materials are a distinct class of materials they change their colour on exposure to
suitable ionic or pH conditions. There are many ways of incorporating ionochromic materials
on textiles, some of which are (a) dyeing, (b) printing, (c) coating, (d) extrusion, (e)
microencapsulation.[40, 55, 56]
Nature of Ionochromic Materials

Ionochromism is the reversible colour change caused by the addition of ions which is
nearly similar to halochromism where there is a colour change due to a change in pH in the
surrounding environment. The materials show this type of colour changes are usually called
ionochromic materials. It is important to note that when the main ionic species is the solvated
hydrogen ion, in which case the terms halochromic, or pH sensitive are often used. There are
other different types of ions also produced by this class of materials and some of the most
commonly observed ionsare (a) metal ions, (b) onium cations (e.g., tertiary ammonium and
phosphonium). In this case the usual reversible colour change is from colourless to coloured
state or from one coloured state to another coloured state. There are different types of
ionochromic materials, some of the important ones are (a) phthalides, (b) triarylmethanes
and (c) fluorans. Most of the commercially available pH sensitive dyes belong to these three
classes. The pH sensitive dyes from natural sources, some of them known as anthocyanines,
also show potentially effective forms of ionochromism.
Classification and Method of Application of Selective pH Sensitive Dyes

Phthalides based commercially available indicator dyes which show a colour change due
to a change in pH of the surrounding environment can be divided into two groups, they are
(a)the phthaleins (e.g., which are mostly available in their lactone form) and (b) the
sulfophthaleins. [40] A number of commercially available indicator dyes (such as, phenol red,
cresol red) can be used for the dyeing, printing, coating of different types of textiles although
very rigorous studies are needed to improve different technical performances (such as,
washfastness, lightfastness, abrasion resistance, perspiration resistance).
Ionochromic Dyes from Natural Sources

Some natural plants based colorants show stimuli-responsive colour changes;
anthocyanines (a sub class of flavinoids) are most prominent in this case. They are also
available in different colours from different parts of plants, vegetables and flowers.
219
Anthocyanines show a range of colour changes when exposed to suitable pH conditions in

aqueous environment. A table of ionochromic materials is shown in Appendix 1, it shows the
nature of pH responsive colour change of some selected synthetic indicator dyes and a few
natural dyes based ionochromic molecular switches. [40, 54, 55, 150]
APPLICATIONS OF IONOCHROMIC TEXTILES

Ionochromic materials have many important practical technological applications.
Ionochromic textiles can be produced by using the ionochromic materials (such as, natural
anthocyanines or synthetic indicator dyes). They are suitable for many practical applications;
some of them are (a) to detect noxious gases, (b) to assess humidity, (c) detect toxic metals,
and (d) to monitor deterioration of functionality. They are also useful for many applications in
healthcare textile products when incorporated into smart textiles along with other required
suitable functionalities when used as hydrogels, ionogels or similar other types of materials.
[54, 55]
ELECTROCHROMIC MOLECULAR SWITCHES AND

THEIR APPLICATIONS IN SMART TEXTILES
Different types of electrochromic materials (or molecular switches) are practically in use
to produce electrochromic smart textiles which have many applications and one of the most
obviously important one is for wearable displays. [111-115] Some of other important
applications include adaptive camouflage and biomimetic systems. [116-121] There are a
number of ways to incorporate electrochromic materials into textiles, such as, using
conductive metal threads along with textile fabrics using knitting or weaving or coating with
conductive oxides. There are some reports which showed that high conductivities of the
underlying conductive fabric are not always necessary for electrochromic function to produce
textile based electrochromic device architectures. In one such report it has been illustrated
using spandex electrodes prepared by a method having low conductivity (such as, 0.1 S/cm)
which electrochemically convert precursor polymers into conjugated forms to show
electrochromic response. [122-128] It is a significant achievement because it illustrates the
way how some other suitable conductors can possibly be used to prepare similar electrically
responsive systems. [129-134] In this context, it is important to note that the electrochromic
fabric system is not transparent and difficult to rely on reflected light to get them assembled
into reflective-type devices. As a consequence, displays are an obvious extension to this
situation [135-139] where informational patches can be used for the infrared (IR) attenuation
capability of electrochromic materials. In this case, the preparation of user-controlled active
colour changing fabric is an extension to passive colour change from photochromic textiles.
As for instance, PEDOT:PSS type conductive polymers can be used for electrochromic textile
production. Now different aspects of electrochromic materials are precisely covered in this
chapter along with their applications for their potential uses in smart electrochromic textile
production for a wide variety of potential applications. There are many applications of
220
electrochromic textiles, some of which are -(a) adaptive camouflage, (b) coatings and
additives, (c) on carpets, curtains, wallpapers, T-shirts, smart uniforms, etc. [139 - 141]
Methods of Applicationsof Electrochromic Molecular Switches in

SmartTextiles
Electrochromic materials can be doped in different fibres used in textile production (such
as, extrusion, electrospinning, melt spinning, etc.) which show dynamic colour change when
exposed to suitable electrical potentials. Some intrinsically conductive polymers (ICPs) and
materials (such as, metal oxides, viologens, some particular type of phthalocyanines) are
suitable to be doped in the textile fibres for producing electrical stimulus responsive
electrochromic textiles to show dynamic colour changes. In this case, intrinsically conductive
polymers (such as, polythiophene, polyannilne, polypyrrole, etc.) are easy to be processed
using solution media to print them using screen printing or inkjet printing to produce
electrochromic images or circuits on printed textiles; they can be even used to produce
electrochromic fibres using electrospinning technique. Additionally, there are many other
techniques to incorporate these materials to textile fibres, such as, coating, dipping, dyeing,
weaving or knitting with conductive electrochromic threads, graft copolymerisation of
conductive polymer based textile fibres with electrochromic molecules, etc.
ELECTROCHROMISM AND ELECTROCHROMIC DEVICES

Electrochromism is a reversible change in optical properties of a material due to
electrochemical oxidation or reduction in response to an electrical stimulus (e.g., electric
current). Usually an electrochromic device is composed of three layers, such as, (a) an ion
storage film, (b) the electrolyte and (c) the electrochromic layer. When a voltage difference is
applied, electrons enter into the electrochromic layer while the positive ions move towards the
electrochromic material to maintain charge neutrality. There are a number of materials which
show electrochromic colour changes; some of these materials are (i) transition metal oxides
(e.g., WO3, V2O5), viologens (e.g., 1,1-disubstituted-4,4-bipyridinium dications) and
conducting polymers (such as, polydioxythiophene-polystyrene sulphonates and their
derivatives). A detail classification of different types of electrochromic materials are shown in
Table 3.
Table 3. Classification of electrochromic materials
Electrochromic materials Examples
Transition metal oxides
WO3, V2O5, TiO2,and also transition metal oxides (such as, oxides of
tungsten, nickel, iridium, vanadium, titanium)
Conductive polymers
Polypyrrole, polyaniline, polythiophene
Viologens
1,1-disubstituted-4,4-bipyridinium dications, methyl viologens
Prusian blue analogues
Prusian blue, prussian brown
Certain phthalocyanines
Lutetium bis (phthalocyanine)
Certain carbazoles
Polyethylcarbozole
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ELECTROCHROMIC MATERIALS AND THEIR PROPERTIES

A large number of electrochromic materials can be broadly grouped into different groups
as shown in Table 3 some important groups which are briefly discussed here.
Transition Metal Oxides

There are a number of transition metal oxides which show electrically responsive colour
changes and some these types of materials are WO3, V2O5, MoO3, TiO2. However, WO3 is
by far, the mostly studied metal oxide based electrochromic material. [142] As a direct effect
of electrical field when a transition metal oxide (present in a suitable set up) is reduced it
shows a colour change and the small metal ions (Li+, H+, Na+, etc.) are intercalated into the
lattice. For example, the electrochromic colour change of WO3 is due to the new electronic
transitions raised along the intercalation process; however, the exact mechanism how it works
is not fully understood. [143]
WO3 (colourless) + xM+ + xe+
MxW+5xW(1-x)O3 (blue)
The rate limiting process of this reaction is usually the ion diffusion inside the metal
oxide lattice, what slows down the switching time of the devices. It is important to note that
in comparison to other electrochromic materials, metal oxides have excellent durability,
stability and reliability but deficient in response times, narrow colour variations and relative
higher cost. [141-143] Additionally, different types of transition metal oxides (TMOs) show
electrochromic properties. There are many inorganic oxide based compounds which contain
transition metals in their structures (some of the metals are iridium, ruthenium, tungsten,
manganese, cobalt), some of them can be used as high quality inorganic oxide based
electrochromic materials. [143]
Prusian Blue Analogues

Prussian blue analogues show electrochromic changes. In usual practice, Prussian blue
films are prepared through electrochemical reduction of a solution containing Fe+3 and
hexaferrocyanate (III) ions. The resultant aqueous solution of Prussian brown,
[(Fe+3Fe+3(CN)6] is reduced to give a Prussian blue [(Fe+3Fe+2(CN)6]- which is deposited in
the form of a blue film. In this case the electro-neutrality is balanced due to the presence of
K+ present in the electrolyte.
[(Fe+3Fe+3(CN)6]0 + ePrussian brown
[(Fe+3Fe+2(CN)6]Prussian blue
Prussian blue is negative in charge and shows maximum absorbance at 690 nm. When
there is a gradual increase in oxidation state the absorbance from 690 nm shows a gradual
decrease whereas the absorbance at 425 nm starts to increase which correspond to
222
[(Fe+3Fe+3(CN)6]0. The combination of these two types of absorbance generates the second
coloured state- the Prussian green (a combination of Prussian blue and Prussian brown).
Prussian green has a fixed anion composition ([Fe+33{Fe+3(CN)6}2{Fe+2(CN)6}]-). However, it
is directly in contrast to the relative gradual change in the absorbance observed for Prussian
blue towards Prussian green (during the increase in oxidation), the reduction of Prussian blue
results in a rapid colour change to give Prussian white as an optically transparent film.
[(Fe+3Fe+2(CN)6]- + ePrussian blue
[(Fe+2Fe+2(CN)6]-2
Prussian white
Potentially Electrochromic Conducting Polymers

Conductive polymers used for a variety of purposes as shown in Figure 1. Some of them
are useful to be used for the generation of electrochromic colour change as they are
responsive to the electrical potentials. Table 4 illustrates the nature of electrochromic colour
change of some selected electro-active polymers in their oxidised and reduced states. The
conductivity of a conductive polymer can be adjusted which can vary over a very wide range,
for example, it may start as insulating and moves towards a more conductive form (metallic
form) with the variations of the concentrations of adopant. Although the conduction
mechanism of conductive polymers sometimes are not well understood, it was noticed that
their behaviour is similar to a semiconductor where electrons under thermal excitation jump
from the valence band to the conduction band to give rise to conductivity. This is true for a
narrow band-gap, but if the band-gap is very wide, then the electrons under thermal excitation
at room temperature do not have enough energy to travel across the gap. So, in addition to
band theory, it is essential to also study the properties of charge carriers. Most of the known
conductive polymers are p-type doped and this involves formation of an abundance of mobile
or carrier holes in the material, while in n-type doping the carriers are electrons. The model
for the conduction mechanism of conductive polymers can be explained using band theory.
[144]
Table 4. Behaviour of certain electroactive polymers in different forms
Electroactive polymers
Colour in
Oxidised form
Polyaniline
Emeraldine: blue/green
Perigraniline: blue/violet
Poly(3,4-ethylenedioxythiophene) Almost transparent blue
Poly(3-methylthiophene)
Blue
Polythiophene
Blue
Polypyrrole
Dark grey
Reduced form
Leucoemeraldine: white/clear
Colourless
Dark blue
Red/purple
Red
Yellow
Data
storage
Super
capasitor
Surface
protections
223
Photovoltaic
cells
Electrochromic
devices
Conductive
polymers
Chemical
sensors and
biosensors
Transistor
and switch
Field
emission
display
Actuators
Figure 1. Different primary uses of conductive polymers.
Figure 2 shows a schematic representation of the band structure in an electronically

conducting polymer. In this case, the energy difference between two frontier orbitals, such as,
the energy difference of HOMO (highest occupied molecular orbital) and LUMO (lowest
unoccupied molecular orbital) orbitals, is also termed as the band-gap. This band gap is very
important as the intrinsic optical property of a conductive polymer is directly related to this
band gap or energy difference (which is usually expressed by the energy gap between the
highest occupied -electrons of valence band and to that of the lowest unoccupied conduction
band). [145] When there is a reduction in the band gap, it makes the material more conductive
so there is active research in this area to find polymers with very low band gap (close to that
of metals). Examples of a few most commonly used conducting polymers include
polypyrrole, polythiophene, and polyaniline (Scheme 23). [141-143]
Figure 2.A schematic representation of the band structure in an electronically conducting polymer.
224
Scheme 23. Structures of some common conducting polymers.
The thin films of all conducting polymers are potentially electrochromic, they show
redox switching which gives rise to new optical absorption bands associated with electron
transfer. The oxidised state of a conducting polymer is doped with a counter anion (p-doping)
and retains a delocalised -electron band structure, while the HOMO-LUMO energy gap
provides a first estimation of the electronic excitation energy which in turn can be measured
by UV/Vis spectroscopy and provides the colours in the materials. [146, 147]
ELECTROCHROMIC MATERIALS FOR SMART TEXTILES

As already stated above that electrochromism is the phenomenon displayed by some
materials in which colour can reversibly change when a certain electrical potential is applied.
Electrochromic colour change is observed from an electrochromic material, when it is
oxidized or reduced that causes a change in the band-gap of this electrochromic material
which is induced by a suitable change in the electrical potential. A large number of
electrochromic materials are available from almost all branches of synthetic chemistry.
Organic electrochromic materials represent a major class of materials used for electrochromic
devices and they can be grouped into follow three categories:
a) type I electrochromic materials -they are soluble in both reduced and oxidized states,
and remains in solution at all times during electrochromic usage (such as, a methyl
viologen, it changes its colour from colourless to intense blue during reduction on
electrode); [148]
b) type II electrochromic materials they are soluble in one redox state, but form a
solid film on the surface of an electrode during electron transfer (e.g., heptyl or
benzyl viologens, three redox states of this type of viololgens is shown in Scheme 24,
where the dicationic state is most stable and the solid form of 1,1'-di-n-heptyl4,4'bipyridilium (heptyl viologen) shows an intense yellow colour in its dicationic state,
but in solution it appears as a pale yellow/or colourless material); [ 143, 149]
c) type III electrochromic materials usually they are conducting polymers.
Intrinsically conducting and electrochemically active nature of most of these types of
polymers are promising candidates for numerous applications, including in textile
based electrochromic colour change and also on display applications. [143]
Metal oxide based electrochromic materials, viologens and conjugated electrochromic
polymers can be used in electrochromic textile production. However, conjugated
electrochromic polymers are increasingly targeted because they provide more practical
advantages over others in many areas.
225
Scheme 24. A schematic representation of three common redox states of a viologen (where form I is
colourless, form II is blue-violet and form III shows very little coloration).
CONCLUSION AND PERSPECTIVES

This current chapter has briefly concentrated on different aspects of smart textiles and the
method of production of these textiles using different types of stimuli-responsive molecular
switches, such as, photochromic, thermochromic, ionochromic and electrochromic molecular
switches. It has also briefly highlighted selected features on different types of stimuliresponsive systems and the mode of application for producing high performance stimuliresponsive smart textiles for a variety of applications. Because, certain level of basic
understandings on the nature of these molecular switches are of utmost importance for a
successful incorporation of these stimuli-responsive switches into the textile materials for
their effective high-performance utilization in smart textiles for a wide range of applications.
As already stated at different places of this chapter that stimuli-responsive smart textiles have
numerous application potentials, including in safety, security, comfort, fashion, health care,
remote sensing, along with a variety of other biomedical and intelligent applications. It may
take some time to reach at its maturity level since there are many issues still need to be
addressed properly. There is active research going on in the different fields of molecular
switches as well to enhance their different properties, so in future perhaps we will see new
range of molecular switches which may overcome many of the current limiting issues.
However, it is possible to overcome many of the limiting factors (very selectively some of
which have been stated in this chapter at different places) of the molecular switches available
226
today for their effective utilization in smart textile applications for a wide range of uses in
different fields.
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APPENDIX 1. THE NATURE OF PH RESPONSIVE COLOUR CHANGE OF

SOME SELECTED SYNTHETIC INDICATOR DYES AND A FEW NATURAL
DYES. [40, 54, 55, 150]
Serial
No.
1
2
3
4
5
6
7
8
9
10
Indicator dyes
Methyl Violet
Crystal Violet
Ethyl Violet
Malachite Green
Methyl Green
2-(p-diethylamino
phenylazo)pyridine
o-Cresolsulfonephthalein
(Cresol Red)
Quinaldine Red
p-(p-diethylamino
phenylazo)-benzoic acid, Na salt
(Paramethyl Red)
m-(p-diethylamino
phenylazo)-benzene sulfonic acid,
Na salt (Metanil Yellow)
pH range
(approx.)
0.0-1.6
0.0-1.8
0.0-2.4
Colour change
Preparation
yellow to blue
yellow to blue
yellow to blue
02-1.8
0.2-1.8
4.4-5.6
0.05% in water
0.02% in water
0.1g in 50 cm3
Methanol + 50 cm3
water
yellow to blue green Water
yellow to blue
0.1% in water
red to yellow
0.4-1.8
7.0-8.8
1.0-2.2
1.0-3.0
yellow to red
yellow to red
colourless to red
red to yellow
0.1g in (0.01N) NaoH

water (26.2 cm3 )
1% in Ethanol
Ethanol
(EtOH)
1.2-2.4
red to yellow
0.01% in water
236

Appendix 1. (Continued)
Serial Indicator dyes

No.
11
4-Phenylazodiphenylamine
pH range Colour change

(approx.)
1.2-2.6
red to yellow
12
Thymolsulfonephthalein
(Thymol Blue)
1.2 2.8
8.0-9.6
red to yellow
yellow to blue
13
m-Cresolsulfonephthalein
(Metacresol Purple)
1.2-2.8
7.4-9.0
red to yellow
yellow to purple
14
p-(p-anilinophenylazo)
1.4-2.8
benzenesulfonic acid, Na-salt
(Orange IV)
4-o-Tolylazo-o-toluidine
1.4-2.8
Erythrosine, disodiumsalt
2.2-3.6
Benzopurpurine 48
2.2-4.2
N,N-dimethyl-p-(m-tolylazo)aniline 2.6-4.8
3.0-4.0
4,4-Bix(2-amino-1naphthylazo)2,2-stilbenedisulfonic
acid
red to yellow
Tetrabromophenolphthaleinethyl
ester, K-salt
3, 3, 5, 5tetrabromophenolsulfoephthalein
(Bromophenol Blue)
2,4-Dinitrophenol
3.0-4.2
yellow to blue
3.0-4.6
yellow to blue
15
16
17
18
19
20
21
22
23
24
25
26
27
28
N,N-Dimethyl-p-phenyl-azoaniline
(p-Dimethyl
aminoazobenzene)
Congo Red
Methyl Orange-Xylene
Cyanole solution
Methyl orange
Ethyl orange
4-(4-Dimethylamino-1naphtholazo)-3methoxybenzenesulfonic acid
No.
29
3, 3, 5, 5-tetrabromo-mcresolsulfonephthalein
(Bromocresol Green)
30
Resaurin
31
4-Phenylazo-1-naphthylamine
orange to yellow
orange to red
violet to red
red to yellow
purple to red
Preparation
0.01 g in HCl 1N, 1
cm3) + EtOH (50
cm3) + Water (49
cm3)
0.1g in NaOH
(0.01N, 21.5 cm3) and
Water (229.5
cm3)
0.1 g in NaOH
(0.101N, 26.2 cm3)
and water (223.8 cm3)
0.01% in water
Water
0.1% in water
0.1% in water
0.1% in water
0.1 g in NaOH
(0.05N NaOH, 5.9
cm3) and water (94.1
cm3)
0.1% in EtOH
3.0-5.0
3.2-4.2
0.1 g in NaOH
(0.01N, 14.9 cm3) and
water (235.1 cm3)
colourless to yellow saturated water
solution
red to yellow
g in EtOH
(90 cm3) and water
(10 cm3)
blue to red
0.1% in water
purple to green
ready solution
3.2-4.4
3.4-4.8
red to yellow
red to yellow
3.5-4.8
violet to yellow
2.8-4.0
2.8-4.4

(approx.)
3.8-5.4
yellow to blue
3.8-6.4
4.0-5.6
orange to violet
red to yellow
0.01% in water
0.05-0.2% in water or
aqueous EtOH
0.1% in EtOH (60%)
Preparation
0.1g in NaOH
(0.01N, 14.3 cm3) and
water (235.7 cm3)
water
0.1% in EtOH

No.
32
Ethyl Red

(approx.)
4.0-5.8
colourless to red
33
0.2-1.8
4.4-5.6
4.4-5.8
yellow to red
red to yellow
orange to yellow
0.1% in water
35
2-(p-Dimethylamino
phenylazo)-pyrodine
4-p-ethoxyphenylazo)-mphenylenediaminemonohydrochlori
de
Lacmoid
4.4-6.2
red to blue
0.2% in EtOH
36
Alizarin Red S
4.6-6.0
yellow to red
37
38
Propyl Red
5, 5-Dibromo-ocresolsulfonephthalein
(Bromocresol Purple)
3, 3-Dichlorophenol
-sulfonephthalein (Chlorophenol
red)
p-Nitrophenol
Alizarin
6.0-7.6
yellow to blue
34
39
40
41
42
43
44
2-(2,4-Dinitrophenylazo)-1naphthol-3,6-disulfonic acid, disodium salt

3, 3-Dibromothymol
sulfonephthalein (Bromothymol
blue)
6,8-Dinitro-2,4(1H)quinazolinedione(mDinitrobenzoylene urea)
237
Preparation
0.1g in MeOH
(50 cm3) and water
(50 cm3)
0.1% in EtOH
dilute solution in
water
4.8-6.6
red to yellow
EtOH
5.2-6.8
yellow to purple
0.1g in NaOH
(0.01N, 18.5 cm3) and
water (231.5 cm3)
5.2-6.8
yellow to red
0.1g in NaOH
(0.01N, 23.6 cm3) and
water (226.4 cm3)
5.4-6.6
colourless to yellow 0.1% in water
5.4-6.6
5.6-7.2
yellow to red
0.1% in MeOH
11.0-12.4 red to purple
6.0-7.0
yellow to blue
0.1% in water
6.4-8.0
45
46
Brilliant yellow
Phelonsulfonephthalein
(Phenol red)
6.6-7.8
6.6-8.0
47
Natural red
6.8-8.0
48
49
m-Nitrophenol
o-Cresolsulfonaphthalein
(Cresol red)
6.8-8.6
0.0-1.0
7.0 -8.8
50
Curcumin
7.4-8.6
10.2-11.8
0.1g in NaOH
(0.01N, 16 cm3) and
water (234 cm3)
colourless to yellow 25 g in NaOH, 1M,
115 cm3) and boiling
waterorin 0.292g
NaCl in water (100
cm3)
yellow to orange
1% in water
yellow to orange
0.1g in NaOH
(0.01N, 28.2 cm3) and
water (221.8 cm3)
red to amber
0.1g in EtOH
(50 cm3) and water
(50 cm3)
red to yellow
0.1g in NaOH
yellow to red
(0.01N, 26.2 cm3) and
water (223.8 cm3)
yellow to red
EtOH
238

Appendix 1. (Continued)

No.
51
m-Cresolsulnaphthalein
(Metacresol purple)

(approx.)
1.2-2.8
red to yellow
7.4-9.0
yellow to purple
52
4, 4-Bis(4-amino-1-naphthylazo)2,2stibene disulfonic acid

(Thylmol blue)
o-Cresolphthalein
p-Naphtholbenzene
Phenolphthalein
1.2-2.8
8.0-9.6
red to yellow
8.2-9.8
8.2-10.0
8.2-10.0
colourless to red
orange to blue
colourless to pink
Ethyl-bis(2,4dimethylphenyl)acetate
Thymolphthalein
8.4-9.6
colourless to blue
9.4-10.6
colourless to blue
5-(p-Nitrophenylazo)salicylic acid,
Na-salt
(Alizarin Yellow R)
p-(2,4-dihydroxyphenylazo)
benzenesulfonic acid,
Na-salt
5,5-Indigodisulfonic acid, di-Nasalt
2,4,6-Trinitrotoluene
1,3,5-Trinitrobenzene
Clayton yellow
10.1-12.0 yellow to red
0.1g in NaOH
(0.01N, 26.2 cm3) and
water (223.8 cm3)
0.1g in NaOH
(0.01N, 21.5 cm3) and
water (228.5 cm3)
0.04% in EtOH
1% dil. alkali
0.05 g in EtOH
(50 cm3) and water
(50 cm3)
Saturated solution in
50% acetone/ alcohol
0.04 g in EtOH
(50 cm3) and water
(50 cm3)
0.01% in water
11.4-12.6 yellow to orange
0.1% in water
11.4-13.0 blue to yellow
water
53
54
55
56
57
58
59
60
61
62
63
Preparation
11.5-13.0 colourless to orange 0.1-0.5% in EtOH

12.0-14.0 colourless to orange 0.1-0.5% in EtOH
12.2-13.2 Yellow to amber
0.1% in water

ISBN: 978-1-63117-262-5
Chapter 8
SMART TEXTILES
Ali Akbar Merati
Advanced Textile Materials and Technology Research Institute (ATMT),
Amirkabir University of Technology, Tehran, Iran
ABSTRACT
The smart textile is a convergence of different sciences such as materials, physics,
chemistry, electrical engineering, wireless and mobile telecommunication and
nanotechnologies. This chapter introduces the phase change materials (PCM), shape
memory materials (SMM), chromic materials (color change), optical fibers and
conductive materials and their application in the functionalized smart textiles. Then the
important key issues for the design of a smart textile system such as working conditions,
effective alarm generation, and energy constraints are presented. The components of an
electronic smart textile that provide several functions such as sensors unit, network unit,
processing unit, actuator unit and power unit are then discussed. The conductive fibers,
yarns and fabrics are defined and explain how textile materials and structures can be used
as sensors, actuators, communication devices, energy sources and storage tools, and even
processors. Finally, the formation of the flexible electrical circuits in smart textile
structures and different device attachment methods are explained.
Keywords: Chromic materials, conductive materials, fabric, fiber, phase change materials,
shape memory materials, smart textile, yarn
INTRODUCTION
Textiles are defined as drapeable structures made of fine and flexible fibers and yarns that
have a high length/diameter ratio. Fibers and fabrics have to meet special requirements
concerning processability and wearability. In order to be comfortable to wear, the fibers of
fabrics have to be fine and elastic. They should be able to withstand handling that is typical
E-mail: merati@aut.ac.ir.
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Ali Akbar Merati
for textiles, for example weaving, washing and wrinkling, without damaging functionality.
Therefore, fabrics need to have a low mechanical resistance to bending and shearing so that
they can be easily deformed and draped. The closer the textiles are to the body, the more
flexible and lightweight they have to be.
The multifunctional textiles such as fashion and environmental protection, ballistic and
chemical protection, flame protection are all passive systems. The smart textiles are a new
generation of fibers, yarns, fabrics and garments that are able to sense stimuli and changes in
their environments, such as mechanical, thermal, chemical, electrical, magnetic and optical
changes, and then respond to these changes in predetermined ways [1-3]. They are
multifunctional textile systems that can be classified into three categories of passive smart
textiles, active smart textiles and very smart textiles [4]. Smart textiles is a new aspect in
textile that is a multidiscipline field of research in many sciences and technologies such as
textile,
physics,
chemistry,
medicine,
electronics,
polymers,
biotechnology,
telecommunications, information technology, microelectronics, wearable computers,
nanotechnology and micro-electromechanical machines. Shape memory materials (SMMs),
conductive materials, phase change materials (PCMs), chromic materials, photonic fibers,
mechanical responsive materials, intelligent coating/membranes, micro and nanomaterials and
piezoelectric materials are applied in smart textiles.
The objective of smart textile is to absorb a series of active components essentially
without changing its characteristics of flexibility and comfort. In order to make a smart
textile, firstly, conventional components such as sensors, devices and wires are being
reshaped in order to fit in the textile, ultimately the research activities trend to manufacture
active elements made of fibers, yarns and fabrics structures. Smart textiles are ideal vehicle
for carrying active elements that permanently monitor our body and the environment,
providing adequate reaction should something happen.
The smart textiles have some of the capabilities such as biological and chemical sensing
and responding, power and data transmission from wearable computers and polymeric
batteries, transmitting and receiving RF signals and automatic voice warning systems as to
dangers ahead that may be appropriate in military applications. Other than military
applications of smart textiles, mountain climbers, sportsmen, businessmen, healthcare and
medical personnel, police, and firemen will be benefitted from the smart textiles technologies.
A smart textile can be active in many other fields. Smart textiles as a carrier of sensor
systems can measure heart rate, temperature, respiration, gesture and many other body
parameters that can provide useful information on the health status of a person. The smart
textiles can support the rehabilitation process and react adequately on hazardous conditions
that may have been detected. The reaction can consist of warning, prevention or active
protection. After an event has happened, the smart textile is able to analyze the situation and
to provide first aid.
Wearable electronics and photonics, adaptive and responsive structures, biomimetics,
bioprocessing, tissue engineering and chemical/drug releasing are some of the research areas
in integrated processes and products of smart textiles. There are some areas that the research
activities have reached the industrial application. Optical fibers, shape memory polymers,
conductive polymers, textile fabrics and composites integrated with optical fiber sensors have
been used to monitor the health of major bridges and buildings. The first generation of
wearable motherboards has been developed, which has sensors integrated inside garments and
is capable of detecting injury and health information of the wearer and transmitting such
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information remotely to a hospital. Shape memory polymers have been applied to textiles in
fiber, film and foam forms, resulting in a range of high performance fabrics and garments,
especially sea-going garments. Fiber sensors, which are capable of measuring temperature,
strain/stress, gas, biological species and smell, are typical smart fibers that can be directly
applied to textiles. Conductive polymer-based actuators have achieved very high levels of
energy density. Clothing with its own senses and brain, like shoes and snow coats which are
integrated with Global Positioning System (GPS) and mobile phone technology, can tell the
position of the wearer and give him/her directions. Biological tissues and organs, like ears and
noses, can be grown from textile scaffolds made from biodegradable fibers.
PHASE CHANGE MATERIALS

Phase change materials (PCM) are thermal storage materials that are used to regulate
temperature fluctuations. The thermal energy transfer occurs when a material changes from a
solid to a liquid or from a liquid to a solid. This is called a change in state, or phase.
Incorporating microcapsules of PCM into textile structures improves the thermal performance
of the textiles. Phase change materials store energy when they change from solid to liquid and
dissipate it when they change back from liquid to solid. It would be most ideal, if the excess
heat a person produces could be stored intermediately somewhere in the clothing system and
then, according to the requirement, activated again when it starts to get chilly.
The most widespread PCMs in textiles are paraffin-waxes with various phase change
temperatures (melting and crystallization) depending on their carbon numbers. The
characteristics of some of these PCMs are summarized in Table 1. These phase change
materials are enclosed in microcapsules, which are 130 m in diameter. Hydrated inorganic
salts have also been used in clothes for cooling applications. PCM elements containing
Glaubers salt (sodium sulphate) have been packed in the pockets of cooling vests [5].
PCM can be applied to fibers in a wet-spinning process, incorporated into foam or
embedded into a binder and applied to fabric topically, or contained in a cell structure made
of a textile reinforced synthetic material.
In manufacturing the fiber, the selected PCM microcapsules are added to the liquid
polymer or polymer solution, and the fiber is then expanded according to the conventional
methods such as dry or wet spinning of polymer solutions and extrusion of polymer melts.
Fabrics can be formed from the fibers containing PCM by conventional weaving, knitting or
nonwoven methods, and these fabrics can be applied to numerous clothing applications.
Table 1. Phase change materials
Phase change
material
Eicosane
Nonadecane
Octadecane
Heptadecane
Hexadecane
Melting
temperature C
36.1
32.1
28.2
22.5
18.5
Crystallization
temperature C
30.6
26.4
25.4
21.5
16.2
Heat storage
capacity in J/g
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In this method, the PCMs are permanently locked within the fibers, the fiber is processed
with no need for variations in yarn spinning, fabric knitting or dyeing and properties of
fabrics (drape, softness, tenacity, etc.) are not altered in comparison with fabrics made from
conventional fibers. The microcapsules incorporated into the fibers in this method have an
upper loading limit of 510% because the physical properties of the fibers begin to suffer
above that limit, and the finest fiber available is about 2.2 dtex. Due to the small content of
microcapsules within the fibers, their thermal capacity is rather modest, about 812 J/g.
Usually PCM microcapsules are coated on the textile surface. Microcapsules are
embedded in a coating compound such as acrylic, polyurethane and rubber latex, and applied
to a fabric or foam. In lamination of foam containing PCMs onto a fabric, the selected PCMs
microcapsules can be mixed into a polyurethane foam matrix, from which moisture is
removed, and then the foam is laminated on a fabric [6]. Typical concentrations of PCMs
range from 20% to 60% by weight. Microcapsules should be added to the liquid polymer or
elastomer prior to hardening. After foaming (fabricated from polyurethane) microcapsules
will be embedded within the base material matrix. The application of the foam pad is
particularly recommended because a greater amount of microcapsules can be introduced into
the smart textile. In spite of this, different PCMs can be used, giving a broader range of
regulation temperatures. Additionally, microcapsules may be anisotropically distributed in the
layer of foam. The foam pad with PCMs may be used as a lining in a variety of clothing such
as gloves, shoes, hats and outerwear. Before incorporation into clothing or footwear the foam
pad is usually attached to the fabric, knitted or woven, by any conventional means such as
glue, fusion or lamination.
The PCM microcapsules are also applied to a fibrous substrate using a binder (e.g.,
acrylic resin). All common coating processes such as knife over roll, knife over air, screenprinting, gravure printing, dip coating may be adapted to apply the PCM microcapsules
dispersed throughout a polymer binder to fabric. The conventional padmangle systems are
also suitable for applying PCM microcapsules to fabrics. The formulation containing PCMs
can be applied to the fabric by the direct nozzle spray technique.
There are many thermal benefits of treating textile structures with PCM microcapsules
such as cooling, insulation and thermo regulating effect. Without phase change materials the
thermal insulation capacity of clothing depends on the thickness and the density of the fabric
(passive insulation). The application of PCM to a garment provides an active thermal
insulation effect acting in addition to the passive thermal insulation effect of the garment
system. The active thermal insulation of the PCM controls the heat flux through the garment
layers and adjusts the heat flux to the thermal circumstances. The active thermal insulation
effect of the PCM results in a substantial improvement of the garments thermo-physiological
wearing comfort [7]. Intensity and duration of the PCMs active thermal insulation effect
depend mainly on the heat-storage capacity of the PCM microcapsules and their applied
quantity. In order to ensure a suitable and durable effect of the PCM, it is necessary to apply
proper PCM in sufficient quantity into the appropriate fibrous substrates of proper design.
The PCM quantity applied to the active wear garment should be matched with the level of
activity and the duration of the garment use. Furthermore, the garment construction needs to
be designed in a way which assists the desired thermo-regulating effect [7]. Thinner textiles
with higher densities readily support the cooling process. In contrast, the use of thicker and
less dense textile structures leads to a delayed and therefore more efficient heat release of the
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PCM. Further requirements on the textile substrate in a garment application include sufficient
breathability, high flexibility, and mechanical stability.
In order to determine a sufficient PCM quantity, the heat generated by the human body
has to be taken into account carrying out strenuous activities under which the active wear
garments are worn. The heat generated by the body needs to be entirely released through the
garment layers into the environment. The necessary PCM quantity is determined according to
the amount of heat which should be absorbed by the PCM to keep the heat balance equalized
[7]. It is mostly not necessary to put PCM in all parts of the garment. Applying PCM
microcapsules to the areas that provide problems from a thermal standpoint and thermoregulating the heat flux through these areas is often enough. It is also advisable to use
different PCM microcapsules in different quantities in distinct garment locations.
APPLICATIONS OF TEXTILES CONTAINING PCMS

Fabrics containing PCMs have been used in a variety of applications including apparel,
home textiles and technical textiles (Table 2) [8].
Phase change materials are used both in winter and summer clothing. PCM is used not
only in high-quality outerwear and footwear, but also in the underwear, socks, gloves,
helmets and bedding of world-wide brand leaders. Seat covers in cars and chairs in offices
can consist of phase change materials.
Currently, phase change materials are being used in a variety of outdoor apparel items
such as smart jackets, vests, mens and womens hats and rainwear, outdoor active-wear
jackets and jacket lining, golf shoes, trekking shoes, ski and snowboard gloves, boots,
earmuffs and protective garments. In protective garments, the absorption of body heat
surplus, insulation effect caused by heat emission of the PCM into the fibrous structure and
thermo-regulating effect, which maintains the microclimate temperature nearly constant are
the specified functions of PCM contained smart textile.
The addition of PCMs to a fabric-backed foam significantly increases the weight,
thickness, stiffness, flammability, insulation value, and evaporative resistance value of the
material. It is more effective to have one layer of PCM on the outside of a tight-fitting, two
layer ensemble than to have it as the inside layer. This may be because the PCMs closest to
the body did not change phase.
Table 2. Application of PCMs in Textiles [8]
Casual clothing:
Professional clothing:
Medical uses:
Shoe linings:
Building materials:
Life style apparel:
Other uses:
Underwear, Jackets, sports garments

Fire fighters protective clothing, Bullet proof fabrics, Space suits,
Sailor suits
Surgical gauze, Bandage, Nappies, Bed linings, Gloves, Gowns
Caps, Blankets
Ski boots, Golf shoes
In proof, In concrete
Elegant fleece vests, Mens and womens hats, Rain wear
Automative interiors, Battery warmers
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Ali Akbar Merati
PCM protective garments should improve the comfort of workers as they go through these
environmental step changes (e.g., warm to cold to warm, etc.). For these applications, the
PCM transition temperature should be set so that the PCMs are in the liquid phase when worn
in the warm environment and in the solid phase in the cold environment [9]. The effect of
phase change materials in clothing on the physiological and subjective thermal responses of
people would probably be maximized if the wearer was repeatedly going through temperature
transients (i.e., going back and forth between a warm and cold environment) or intermittently
touching hot or cold objects with PCM gloves [9].
One example of practical application of PCM smart textile is cooling vest (TST Sweden
Ab) [5]. This is a comfort garment developed to prevent elevated body temperatures in people
who work in hot environments or use extreme physical exertion. The cooling effect is
obtained from the vests 21 PCM elements containing Glaubers salt which start absorbing
heat at a particular temperature (28 C). Heat absorption from the body or from an external
source continues until the elements have melted. After use the cooling vest has to be charged
at room temperature (24 C) or lower. When all the PCMs are solidified the cooling vest is
ready for further use [5].
A new generation of military fabrics feature PCMs which are able to absorb, store and
release excess body heat when the body needs it resulting in less sweating and freezing, while
the microclimate of the skin is influenced in a positive way and efficiency and performance
are enhanced.
In the medical textiles field, a blanket with PCM can be useful for gently and controllably
reheating hypothermia patients. Also, using PCMs in bed covers regulates the micro climate
of the patient.
In domestic textiles, blinds and curtains with PCMs can be used for reduction of the heat
flux through windows. In the summer months large amounts of heat penetrate the buildings
through windows during the day. At night in the winter months the windows are the main
source of thermal loss. Results of the test carried out by Pause [10] on curtains containing
PCM have indicated a 30% reduction of the heat flux in comparison to curtains without PCM.
SHAPE MEMORY MATERIALS

Shape memory materials (SMMs) are able to remember a shape, and return to it when
stimulated, e.g., with temperature, magnetic field, electric field, pH-value and UV light [11
15]. An example of natural shape memory textile material is cotton, which expands when
exposed to humidity and shrinks back when dried. Such behavior has not been used for
aesthetic effects because the changes, though physical, are in general not noticeable to the
naked eye. The most common types of such SMMs materials are shape memory alloys and
polymers, but ceramics and gels have also been developed. When sensing this material
specific stimulus, SMMs can exhibit dramatic deformations in a stress free recovery. On the
other hand, if the SMM is prevented from recovering this initial strain, a recovery stress
(tensile stress) is induced, and the SMM actuator can perform work. This situation where
SMM deforms under load is called restrained recovery [16].
Because of the wide variety of different activation stimuli and the ability to exhibit
actuation or some other pre-determined response, SMMs can be utilized to control or tune
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many technical parameters in smart material systems in response to environmental changes

such as shape, position, strain, stiffness, natural frequency, damping, friction and water vapor
penetration [11, 12]. Both the fundamental theories and engineering aspects of SMMs have
been investigated extensively and a rather wide variety of different SMMs are presently
commercial materials. Commercialized shape memory products have been based mainly on
metallic shape memory alloys (SMAs), either taking advantage of the shape change due the
shape memory effect or the super-elasticity of the material, the two main phenomena of
SMAs. Shape memory polymers (SMPs) and shape memory gels are developed at a quick
rate, and within the last few years also some products based on magnetic shape memory
alloys have been commercialized. Shape memory ceramic (SMC) materials, which can be
activated not only by temperature but also by elastic energy, electric or magnetic field, are
mainly at the research stage.
Applications of Textiles Containing SMMs

There are many potential applications of shape memory polymers in industrial
components like automotive parts, building and construction products, intelligent packing,
implantable medical devices, sensors and actuators, etc. SMPs are used in toys, handgrips of
spoons, toothbrushes, razors and kitchen knives, also as an automatic choking device in
small-size engines [17]. One of the most well known examples of SMP is a clothing
application, a membrane called Diaplex. The membrane is based on polyurethane based shape
memory polymers developed by Mitsubishi Heavy Industries.
Polyurethane is an example of shape memory polymers which is based on the formation
of a physical cross-linked network as a result of entanglements of the high molecular weight
linear chains, and on the transition from the glassy state to the rubber-elastic state [18]. Shape
memory polyurethane (SMPU) is a class of polyurethane that is different from conventional
polyurethane in that these have a segmented structure and a wide range of glass transition
temperature (Tg). The long polymer chains entangle each other and a three-dimensional
network is formed. The polymer network keeps the original shape even above Tg in the
absence of stress. Under stress, the shape is deformed and the deformed shape is fixed when
cooled below Tg. Above the glass transition temperature polymers show rubber-like behavior.
The material softens abruptly above the glass transition temperature Tg. If the chains are
stretched quickly in this state and the material is rapidly cooled down again below the glass
transition temperature the polynorbornene chains can neither slip over each other rapidly
enough nor become disentangled. It is possible to freeze the induced elastic stress within the
material by rapid cooling. The shape can be changed at will. In the glassy state the strain is
frozen and the deformed shape is fixed. The decrease in the mobility of polymer chains in the
glassy state maintains the transient shape in polynorbornene. The recovery of the materials
original shape can be observed by heating again to a temperature above Tg. This occurs
because of the thermally induced shape-memory effect [18]. The disadvantage of this
polymer is the difficulty of processing because of its high molecular weight [15]. Some of the
shape memory polymers are suitable for textiles applications (Table 3).
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Ali Akbar Merati

Table 3. Shape memory polymers and mechanisms [11, 15]
Polymers
Polynorbornene
Polyurethane
Polyethylene/nylon-6 graft copolymer
Styrene-1, 4-butadiene block
copolymer
Ethylene oxide-ethylene terphethalate
block copolymer
Polymethylene-1, 3-cyclopentane)
polyethylene block copolymer
Physical interactions
Original shape
Chain entanglement
Microcrystal
Crosslinkig
Microcrystal/Glassy
state of polystyrene
Microcrystal of PET
Microcrystal of PE
Transient shape
Glassy state
Glassy state
Microcrystal
Microcrystal of poly(1,4butadiene)
Microcrystal of PEO
Glassy state/microcrystal
of PMCP
Shape memory polymers can be laminated, coated, foamed, and even straight converted
to fibers. There are many possible end uses of these smart textiles. The smart fiber made from
the shape memory polymer can be applied as stents, and screws for holding bones together.
Shape memory polymer coated or laminated materials can improve the thermophysiological
comfort of surgical protective garments, bedding and incontinence products because of their
temperature adaptive moisture management features.
Films of shape memory polymer can be incorporated in multilayer garments, such as
those that are often used in the protective clothing or leisurewear industry. The shape memory
polymer reverts within wide range temperatures. This offers great promise for making
clothing with adaptable features. Using a composite film of shape memory polymer as an
inter-liner in multilayer garments, outdoor clothing could have adaptable thermal insulation
and be used as protective clothing. A shape memory polymer membrane and insulation
materials keep the wearer warm. Molecular pores open and close in response to air or water
temperature to increase or minimize heat loss. Apparel could be made with shape memory
fiber. Forming the shape at a high temperature provides creases and pleats in such apparel as
slacks and skirts. Other applications include fishing yarn, shirt neck bands, cap edges, casual
clothing and sportswear. Also, using a composite film of shape memory polymers as an
interlining provides apparel systems with variable tog values to protect against a variety of
weather conditions.
CHROMIC MATERIALS
Chromic materials are the general term referring to materials, which their color changes
by the external stimulus. Due to color changing properties, chromic materials are also called
chameleon materials. This color changing phenomenon is caused by the external stimulus and
chromic materials can be classified depending on the external stimulus of induction.
Photochromic, thermochromic, electrochromic, piezochromic, solvatechromic and
carsolchromic are chromic materials that change their color by the external stimulus of heat,
electricity, pressure, liquid and an electron beam, respectively. Photochromic materials are
suitable for sun lens applications [19]. Most photochromic materials are based on organic
materials or silver particles. Thermochromic materials change color reversibly with changes
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in temperature. The liquid crystal type and the molecular rearrangement type are
thermochromic systems in textiles. The thermochromic materials can be made as semiconductor compounds, from liquid crystals or metal compounds. The change in color occurs
at a pre-determined temperature, which can be varied. Electrochromic materials are capable
of changing their optical properties (transmittance and/or reflectance) under applied electric
potentials. The variation of the optical properties is caused by insertion/extraction of cations
in the electrochromic film. Piezochromism is the phenomenon where crystals undergo a
major change of color due to mechanical grinding. The induced color reverts to the original
color when the fractured crystals are kept in the dark or dissolved in an organic solvent [19].
Solvatechromism is the phenomenon, where color changes when it makes contact with a
liquid, for example, water. Materials that respond to water by changing color are also called
hydrochromic and this kind of textile material can be used, e.g., for swimsuits.
Applications of Textiles Containing Chromic Materials

The majority of applications for chromic materials in the textile sector today are in the
fashion and design area, in leisure and sports garments. In workwear and the furnishing sector
a variety of studies and investigations are in the process by industrial companies, universities
and research centers. Chromic materials are one of the challenging material groups when
thinking about future textiles. Color changing textiles are interesting, not only in fashion,
where color changing phenomena will exploit for fun all the rainbow colors, but also in useful
and significant applications in soldier and weapons camouflage, workwear and in technical
and medical textiles. The combination of SMM and thermochromic coating is an interesting
area which produces shape and color changes of the textile material at the same time [9].
OPTICAL FIBERS IN SMART TEXTILES

Optical fibers are currently being used in textile structures for several different
applications. Optic sensors are attracting considerable interest for a number of sensing
applications [20, 21] There is great interest in the multiplexed sensing of smart structures and
materials, particularly for the real-time evaluation of physical measurements (e.g.,
temperature, strain) at critical monitoring points. One of the applications of the optical fibers
in textile structures is to create flexible textile-based displays based on fabrics made of optical
fibers and classic yarns [22]. The screen matrix is created during weaving, using the texture
of the fabric. Integrated into the system is a small electronics interface that controls the LEDs
that light groups of fibers. Each group provides light to one given area of the matrix. Specific
control of the LEDs then enables various patterns to be displayed in a static or dynamic
manner. This flexible textile-based displays are very thin size and ultra lightweight. This
leads one to believe that such a device could quickly enable innovative solutions for
numerous applications. Bending in optical fibers is a major concern since this causes signal
attenuation at bending points. Integrating optical fibers into a woven perform requires
bending because of the crimping that occurs as a result of weave interlacing. However,
standard plastic optical fiber (POF) materials like polymethylmethacrylate, polycarbonate and
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Ali Akbar Merati
polystyrene are rather stiff compared to standard textile fibers and therefore their integration
into textiles usually leads to stiffen of the woven fabric and the textile touch is getting lost
[23]. Alternative fibers with appropriate flexibility and transparency are not commercially
available yet.
CONDUCTIVE MATERIALS IN SMART TEXTILES

Several conductive materials are in use in smart textiles. Conductive textiles include
electrically conductive fibers fabrics and articles made from them [24]. Flexible electrically
conducting and semi-conducting materials, such as conductive polymers, conductive fibers,
threads, yarns, coatings and ink are playing an important role in realizing lightweight,
wireless and wearable interactive electronic textiles. Generally, conductive fibers can be
divided into two categories such as naturally conductive fibers and treated conductive fibers.
Naturally, conductive fibers can be produced purely from inherently conductive
materials, such as metals, metal alloys, carbon sources, and conjugated polymers (ICPs).
Highly conductive flexible textiles can be prepared by weaving thin wires of various metals
such as brass and aluminum. These textiles have been developed for higher degrees of
conductivity.
Metal conductive fibers are very thin filaments with diameters ranging from 1 to 80 m
produced from conductive metals such as ferrous alloys, nickel, stainless steel, titanium,
aluminum and copper. Since they are different from polymeric fibers, they may be hard to
process and have problems of long term stability. These highly conductive fibers are
expensive, brittle, heavier and lower processability than most textile fibers.
Treated conductive fibers can be produced by the combination of two or more materials,
such as non-conductive and conductive materials. This conductive textiles can be produced in
various ways, such as by impregnating textile substrates with conductive carbon or metal
powders, patterned printing, and so forth. Conducting polymers, such as polyacetylene (PA),
polypyrrole (PPy), polythiophene (PTh) and polyaniline (PAn), offer an interesting
alternative. Among them, polypyrrole has been widely investigated owing to its easy
preparation, good electrical conductivity, good environmental stability in ambient conditions
and because it poses few toxicological problems [25, 26]. PPy is formed by the oxidation of
pyrrole or substituted pyrrole monomers. Electrical conductivity in PPy involves the
movement of positively charged carriers or electrons along polymer chains and the hopping
of these carriers between chains. The conductivity of PPy can reach the range 102 S cm-1,
which is next only to PA and PAn. With inherently versatile molecular structures, PPys are
capable of undergoing many interactions.
The conductive fibers obtained through special treatments such as mixing, blending, or
coating are also known as conductive polymer composites (CPCs), can have a combination of
the electrical and mechanical properties of the treated materials [23]. Fibers containing metal,
metal oxides and metal salts are a proper alternative for metal fibers. Polymer fibers may be
coated with a conductive layer such as polypyrrole, copper or gold [27]. The conductivity will
be maintained as long as the layer is intact and adhering to the fiber. Chemical plating and
dispersing metallic particles at a high concentration in a resin are two general methods of
coating fibers with conductive metals.
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The brittleness of PPy has limited the practical applications of it. The processability and
mechanical properties of PPy can be improved by incorporating some polymers into PPy [28,
29]. However, the incorporation of a sufficient amount of filler generally causes a significant
deterioration in the mechanical properties of the conducting polymer, in order to exceed the
percolation threshold of conductivity [30]. Another route to overcoming this deficiency is by
coating the conducting polymer on flexible textile substrates to obtain a smooth and uniform
electrically conductive coating that is relatively stable and can be easily handled [31, 32].
Thus, PPy-based composites may overcome the deficiency in the mechanical properties of
PPy, without adversely affecting the excellent physical properties of the substrate material,
such as its mechanical strength and flexibility. The resulting products combine the usefulness
of a textile substrate with electrical properties that are similar to metals or semi-conductors.
Due to electron-transport characteristics of Conjugated polymers or ICPs, they are regarded
as semi conductors or even sometimes conductors. Due to their high conductivity, lower
weight, and environmental stability, they have a very important place in the field of smart and
interactive textiles [33].
The conductivity of materials is often affected by several parameters which may be
exploitable mechanisms for use as a sensor. Extension, heating, wetting and absorption of
chemical compounds in general may increase or decrease conductivity. Swelling or shrinkage
of composite fibers of carbon nanotubes alters the distance between the nanoparticles in the
fibers, causing the conductivity to change.
Fibers containing conductive carbon are produced with several methods such as loading
the whole fibers with a high concentration of carbon, incorporating the carbon into the core of
a sheathcore bicomponent fiber, incorporating the carbon into one component of a sideside
or modified sideside bicomponent fiber, suffusing the carbon into the surface of a fiber.
Nanoparticles such as carbon nanotubes can be added to the matrix for achieving
conductivity.
Semi-conducting metal oxides are often nearly colorless, so their use as conducting
elements in fibers has been considered likely to lead to fewer problems with visibility than the
use of conducting carbon. The oxide particles can be embedded in surfaces, or incorporated
into sheathcore fibers, or react chemically with the material on the surface layer of fibers.
Conductive fibers can also be produced by coating fibers with metal salts such as copper
sulfide and copper iodide. Metallic coatings produce highly conductive fibers; however
adhesion and corrosion resistance can present problems. It is also possible to coat and
impregnate conventional fibers with conductive polymers, or to produce fibers from
conductive polymers alone or in blends with other polymers.
Conductive fibers/yarns can be produced in filament or staple lengths and can be spun
with traditional non-conductive fibers to create yarns that possess varying wearable
electronics and photonics degrees of conductivity. Also, conductive yarns can be created by
wrapping a nonconductive yarn with metallic copper, silver or gold foil and be used to
produce electrically conductive textiles.
Conductive threads can be sewn to develop smart electronic textiles. Through processes
such as electrodeless plating, evaporative deposition, sputtering, coating with a conductive
polymer, filling or loading fibers and carbonising, a conductive coating can be applied to the
surface of fibers, yarns or fabrics. Electrodeless plating produces a uniform conductive
coating, but is expensive. Evaporative deposition can produce a wide range of thicknesses of
coating for varying levels of conductivity. Sputtering can achieve a uniform coating with
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good adhesion. Textiles coated with a conductive polymer, such as polyaniline and
polypyrrole, are more conductive than metal and have good adhesion, but are difficult to
process using conventional methods.
Adding metals to traditional printing inks creates conductive inks that can be printed onto
various substrates to create electrically active patterns. The printed circuits on flexible textiles
result in improvements in durability, reliability and circuit speeds and in a reduction in the
size of the circuits. The printed conductive textiles exhibit good electrical properties after
printing and abrading. The inks withstand bending without losing conductivity. However,
after twenty washing cycles, the conductivity decreases considerably. Therefore, in order to
improve washability, a protective polyurethane layer is put on top of the printed samples,
which resulted in the good conductivity of the fabrics, even after washing [34]. Currently,
digital printing technologies promote the application of conductive inks on textiles.
Applications of Conductive Smart Textile

Electrically conductive textiles make it possible to produce interactive electronic textiles.
They can be used for communication, entertainment, health care, safety, homeland security,
computation, thermal purposes, protective clothing, wearable electronics and fashion. The
application of conductive smart textile in combination with electronic advices is very
widespread. In location and positioning, they can be used for child monitoring, geriatric
monitoring, integrated GPS (global positioning system) monitoring, livestock monitoring,
asset tracking, etc.
In infotainment, they can be used for integrated compact disc players, MP3 players, cell
phones and pagers, electronic game panels, digital cameras, and video devices, etc.
In health and biophysical monitoring, they can be used for cardiovascular monitoring,
monitoring the vital signs of infants, monitoring clinical trials, health and fitness, home
healthcare, hospitals, medical centers, assisted-living units, etc.
They can be used for soldiers and personal support of them in the battlefield, space
programs, protective textiles and public safety (fire fighting, law enforcement), automotive,
exposure-indicating textiles, etc.
They can be also used to show the environmental response such as color change, density
change, heating change, etc. Fashion, gaming, residential interior design, commercial interior
design and retail sites are other application of conductive smart textiles.
DESIGNING THE SMART TEXTILE SYSTEMS

Comfort is very important in textiles because stresses lead to increased fatigue. The
potential of smart textiles is to measure a number of body parameters such as skin
temperature, humidity and conductivity and show the level of comfort through the textile
sensors. To keep the comfort of textiles, adequate actuators are needed that can heat, cool,
insulate, ventilate and regulate moisture. The use of the smart system should not require any
additional effort. The weight of a smart textile system should not reduce operation time of the
rescue worker.
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251
Other key issues for the design of a smart textile system are [35]:
Working conditions relevant parameters: only relevant information should be

provided in order to avoid additional workload; this includes indication of danger and
need for help.
Effective alarm generation: the rescue worker or a responsible person should be
informed adequately on what needs to be done.
System maintenance: it must be possible to treat the suit using usual maintenance
procedures.
Cost must be justified
Robustness
Energy constraints: energy requirements must be optimized
Long range transmission: transmission range must be adjusted to the situation of use.
Fighting a fire in a building is different from fighting one in an open field.
A wearable smart textile system basically comprises following components [36]:
Sensors to detect body or environmental parameters;

A data processing unit to collect and process the obtained data;
An actuator that can give a signal to the wearer;
An energy supply that enables working of the entire system;
Interconnections that connect the different components;
A communication device that establishes a wireless communication link with a
nearby base station.
The main layers concerned with smart clothing are the skin layer and two clothing layers.
Physically the closest clothing layer for a human user is an underwear layer, which transports
perspiration away from the skin area. The function of this layer is to keep the interface
between a user and the clothes comfortable and thus improve the overall wearing comfort.
The second closest layer is an intermediate clothing layer, which consists of the clothes that
are between the underclothes and outdoor clothing. The main purpose of this layer is
considered to be an insulation layer for warming up the body. The outermost layer is an
outerwear layer, which protects a human against hard weather conditions.
The skin layer is located in close proximity to the skin. In this layer we place components
that need direct contact with skin or need to be very close to the skin. Therefore, the layer
consists of different user interface devices and physiological measurement sensors. The
number of the additional components in underwear is limited owing to the light structure of
the clothing.
An inner clothing layer contains intermediate clothing equipped with electronic devices
that do not need direct contact with skin and, on the other hand, do not need to be close to the
surrounding environment. These components may also be larger in size and heavier in weight
compared to components associated with underclothes.
It is often beneficial to fasten components to the inner clothing layer, as they can be
easily hidden. Surrounding clothes also protect electronic modules against cold, dirt and hard
knocks.
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Generally, the majority of electronic components can be placed on the inner clothing
layer. These components include various sensors, a central processing unit (CPU) and
communication equipment. Analogous to ordinary clothing, additional heating to warming up
a person in cold weather conditions is also associated with this layer. Thus, the inner layer is
the most suitable for batteries and power regulating equipment, which are also sources of
heat.
The outer clothing layer contains sensors needed for environment measurements,
positioning equipment that may need information from the surrounding environment and
numerous other accessories. The physical surroundings of smart clothing components
measure the environment and the virtual environment accessed by communication
technologies. Soldier and weapons camouflage is possible by using chromic materials in outer
layer of smart textiles.
SMART FABRICS FOR HEALTH CARE

The continuous monitoring of vital signs of some patients and elderly people is an
emerging concept of health care to provide assistance to patients as soon as possible either
online or offline. A wearable smart textile can provide continuous remote monitoring of the
health status of the patient. Wearable sensing systems will allow the user to perform everyday
activities without discomfort. The simultaneous recording of vital signs would allow
parameter extrapolation and inter-signal elaboration, contributing to the generation of alert
messages and synoptic patient tables. In spite of this, a smart fabric is capable of recording
body kinematic maps with no discomfort for several fields of application such as
rehabilitation and sports [37].
ELECTRONIC SMART TEXTILES

The components of an electronic smart textile that provide several functions are sensors
unit, network unit, processing unit, actuator unit and power unit. On the smart textile, several
of these functions are combined to form services. Providing information, communication or
assistance are possible services. Because mobility is now a fundamental aspect of many
services and devices, these smart textiles can be used for health applications such as
monitoring of vital signs of high-risk patients and elderly people, therapy and rehabilitee,
knowledge applications such as instructions and navigation and entertainment applications
such as audio and video devices [38].
For communication between the different components of smart textile applications, both
wired and wireless technologies are applicable. An applied solution for data transferring is
often a compromise based on application requirements, operational environment, available
and known technologies, and costs.
Smart Textiles
253
Data Transfer Requirements in Smart Textiles

The data transfer requirements can be divided into internal and external. The internal
transfer services are divided into local health and security related measurements. Many of the
services require or result in external communications between the smart clothing and its
environment. Wired data transfer is in many cases a practical and straightforward solution.
Thin wires routed through fabric are an inexpensive and high capacity medium for
information and power transfer. The embedded wires inside clothing do not affect its
appearance. However, wires form inflexible parts of clothing and the detaching and
reconnecting of wires decrease user comfort and the usability of clothes [39]. The cold winter
environment especially stiffens the plastic shielding of wires. In hard usage and in cold
weather conditions, cracking of wires also becomes a problem [39]. The connections between
the electrical components placed on different pieces of clothing are another challenge when
using wires. During dressing and undressing, connectors should be attached or detached,
decreasing the usability of clothing. Connectors should be easily fastened, resulting in the
need for new connector technologies.
A potential alternative to plastic shielded wires is to replace them with electrically
conductive fibers. Conductive yarns twisted from fibers form a soft cable that naturally
integrates in the clothings structure keeping the system as clothing-like as possible. Fiber
yarns provide durable, flexible and washable solutions. Also lightweight optical fibers are
used in wearable applications, but their function has been closer to a sensor than a
communication medium [40, 41]. The problem of conductive fibers is due to the reliable
connections of them. Ordinary wires can be soldered directly to printed circuit boards, but the
structure of the fiber yarn is more sensitive to breakage near the solder connections.
Protection materials that prevent the movement of the fiber yarn at the interface of the hard
solder and the soft yarn must be used. Optical fibers are commonly used for health monitoring
applications and also for lighting purposes [42].
Low-power wireless connections provide increased flexibility and also enable external
data transfer within the personal space. Different existing and emerging WLAN and WPAN
types of technologies are general purpose solutions for the external communications,
providing both high speed transfer and low costs. For wider area communications and full
mobility, cellular data networks are currently the only practical possibility.
Electrical Circuits in Smart Textile Structures

In order to form flexible circuit boards, printing of circuit patterns is carried out on
polymeric substrates such as films. Fabric based circuits potentially offer additional benefits
of higher flexibility in bending and shear, higher tear resistance, as well as better fatigue
resistance in case of repeated deformation. Different processes that have been described in
literature for the fabrication of fabric based circuits include embroidery of conductive threads
on fabric substrates, weaving and knitting of conductive threads along with nonconductive
threads, printing or deposition and chemical patterning of conductive elements on textile
substrates.
The insulating fabric could be woven, non-woven, or knitted. The conductive threads can
be embroidered in any shape on the insulating fabric irrespective of the constituent yarn path
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in a fabric. One of the primary disadvantages of embroidery as a means of circuit formation is

that it does not allow formation of multi-layered circuits involving conductive threads
traversing through different layers as is possible in the case of woven circuits.
Conductive threads can be either woven or knitted into a fabric structure along with
nonconductive threads to form an electrical circuit. One of the limitations of using weaving
for making electrical circuits is that the conductive threads have to be placed at predetermined
locations in the warp direction while forming the warp beam or from a creel during set up of
the machine. Different kinds of conductive threads can be supplied in the weft or filling
direction and inserted using the weft selectors provided on a weaving machine. Some
modifications to the yarn supply system of the machine may be needed in order to process the
conductive threads that are more rigid.
In most conventional weft knitting machines, like a flatbed machine, the conductive
threads can be knitted in the fabric only in one direction, i.e., the course (or cross) direction.
In order to keep the conductive element in a knit structure straight, one can insert a
conductive thread in the course direction such that the conductive thread is embedded into the
fabric between two courses formed from non-conductive threads.
Processes that have been employed to form a patterned conductive path on fabric surfaces
include deposition of polymeric or nonpolymeric conducting materials and subsequent
etching, reducing, or physical removal of the conductive materials from certain regions. Thus,
the conductive material that is not removed forms a patterned electrical circuit or a region of
higher conductivity. The biggest problem associated with patterning of circuits from thin
conductive films (polymeric or metallic) deposited on fabric substrates is that use of an
etching agent for forming a circuit pattern leads to non-uniform etching, as some of the
etching liquid is absorbed by the threads of the underlying substrate fabric [43-45]. Another
problem with deposition of conductive films on fabric substrates is that bending the fabric
may lead to discontinuities in conductivity at certain points.
There are different device attachment methods like raised wire connectors, solders, snap
connectors, and ribbon cable connectors in electronic smart textiles. Soldering produces
reliable electrical connections to conductive threads of an electronic textile fabric but has the
disadvantage of not being compatible with several conductive threads or materials like
stainless steel. Moreover, soldering of electronic devices to threads that are insulated is a
more complex process involving an initial step of removal of insulation from the conductive
threads in the regions where the device attachments are desired and insulation of the soldered
region after completion of the soldering process. The main advantage of employing snap
connectors is the ease of attachment or removal of electronic devices from these connectors,
whereas the main disadvantages are the large size of the device and the weak physical
connection formed between the snap connectors and the devices. Ribbon cable connectors
employ insulation displacement in order to form an interconnection with insulated conductor
elements integrated into the textiles. A v-shaped contact cuts through the insulation to form a
connection to the conductor. Firstly, the ribbon cable connector is attached to the conductive
threads in an e-textile fabric and subsequent electronic devices and printed circuit boards are
attached to the ribbon cable connector. One of the advantages of employing ribbon cable
connectors for device attachment is the ease of attachment and removal of the electronic
devices to form the electronic textiles.
Smart Textiles
255
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ISBN: 978-1-63117-262-5
Chapter 9
OVERVIEW OF TEXTILES EXCAVATED IN GREECE

Christina Margariti*, Stavroula Moraitou and Maria Retsa
Hellenic Ministry of Culture, Athens, Greece
ABSTRACT
Research was conducted through the Archives of the Hellenic Ministry of Culture
and Tourism, the literature, and a questionnaire sent to museums, and regional services of
the Ministry in order to provide an overview of the condition of excavated textiles. A
preliminary statistical analysis of the data collected identified four types of preservation:
1) in association with a metal present (which for the vast majority of the finds is copper);
2) in association with salts (such as calcium salts); 3) incomplete burning (carbonisation);
and 4) inhumation burials. It also showed that only 56% of the finds have received a
conservation treatment that has been properly recorded. In addition, there were only three
cases where conservators, archaeologists and textile historians had produced a common
publication, indicating that collaboration between them was limited. In general, this
review showed that, in contrary to the general notion, a considerable number of textiles
have been preserved (90), in an excavation context, in Greece.
ABBREVIATIONS
AIC
CTR
ECCO
IIC
JAIC
NATCC
UKIC
American Institute for Conservation

Centre for Textile Research
European Confederation of Conservator-Restorers Organizations
International Institute for Conservation
Journal of the American Institute for Conservation
North American Textile Conservation Conference
United Kingdom Institute for Conservation
E-mail: chmargariti@culture.gr.
260
INTRODUCTION
Textiles have been indissolubly connected with numerous aspects of human life and
culture. They have been records of everyday life conditions, products of technology, social,
religious, and cultural symbols, exchangeable commodities, and works of art and crafts, and
hence worth conserving as evidence of the evolution of human culture. Conservation is the
comprehensively documented action taken by adequately qualified professionals, to diagnose
the condition of cultural property in order to retard or prevent deterioration or damage, and to
retain its significance as primary evidence, by control of the environment, whether in store,
display or transport, and/or treatment of the structure, and/or research that conforms to
established legal, ethical and academic practices, in order to maintain it as nearly as possible
in an unchanging state, accessible to present and future generations [1,2,3].
Archaeology is a highly esteemed, prolific science, in Greece. Extensive research has
been and still is conducted in areas such as, architecture, ceramics, metalsmithing, and
sculpting but this is not the case with textiles. There is the general notion in Greece, that
survival of textiles in a burial context is rare, a fact that inhibits a comprehensive research.
The scope of this paper is, therefore, to identify the current condition of textiles excavated in
Greece. The term condition is more generally used here, to include the physical condition of
the finds as this has been recorded, and the general situation concerning these textiles on
issues such as, location, analysis, conservation and publication. This research aimed to
determine their present location and storage and/or display environments, whether they had
been conserved, whether the finds had been published, and finally to provide the approximate
number of excavated textiles retrieved within Greece.
CHRONOLOGICAL TABLE OF TEXTILES EXCAVATED IN GREECE

Information was collected from several different sources such as, the General and
Sampling Archives of the Hellenic Ministry of Culture, the literature, archaeological journals,
symposia and conferences, a questionnaire distributed around the museums and regional
services of the Ministry, and personal communication with conservators, archaeologists and
textile researchers.
The fields included in the table were: 1) Reference Name, according to which the finds
are known, for easier reference; 2) Period and Area of Origin, to achieve a chronological
order; 3) Type and Date of Excavation, to record whether the finds were from a recent or old
and a systematic or rescue excavation; 4) Type and State of Preservation, to identify how
textiles have been preserved in Greece, in an excavation context; 5) Type of Fibre/Dye/Other
Decoration, to record any information on previous analyses of the finds; 6) Conservation, to
present an overview of the conservation of excavated textiles in Greece; 7) Present Location,
to locate the finds; 8) Study, and 9) Publication Conservation/Archaeological/Technological,
to determine the level of collaboration between conservators, archaeologists and textile
researchers in Greece.
The finds were put in order by the period of origin, thus putting them in a chronological
order, which was thought to be the simplest and most objective way.
261
The total number of textiles recorded was ninety (90) at the time of writing, hence a
considerable number of textiles have been excavated, which is in contrast to the general
notion, that textiles do not survive in an excavation context in Greece. Moreover, the number
90 is not representing the actual number of textiles preserved, but the homogeneous groups of
textiles that have survived under certain conditions. More often than not, there are indications
that the fragments, though numbered as one, come from different textiles. However, the aim
of this table was to identify the different cases where textiles have been preserved, rather than
the actual number of different textiles.
In the following sections approximate percentages are used to present the preliminary
statistical analysis results. The percentages are calculated and quoted to the nearest integer
according to the ratio of the number of finds falling under the same category to the total
number of finds present in the table.
Types of Preservation of Textiles Excavated in Greece

Four types of preservation were identified: 1) in association with a metal present (66%);
2) inhumation burials (14%); 3) in association with salts from a ceramic and/or stone
container (7%); and 4) carbonisation (8%). High Relative Humidity (RH) values, elimination
of oxygen or a combination of the above seem to be the reasons for preservation in
inhumation burials. For 5% of the finds the type of preservation is unknown. Note that these
are the types of preservation as recorded in the sources. The condition of several of the finds
has never been comprehensively studied and assessed. The results are better illustrated in the
pie chart (Figure 1).
Figure 1. Pie chart showing the percentages of the types of preservation of textiles excavated in Greece.
262
Different Metals Responsible for the Preservation of Textiles Excavated in Greece

The cases where textiles have been preserved in association with metals can be further
analysed according to the type of metal present. Copper was the metal present in 76% of the
cases, gold 5%, iron 5%, lead 5%, silver 2%, combination of metals 5%, and unidentified
metal 2% (Figure 2).
Figure 2. Pie chart showing the percentages of the different metals responsible for the preservation of
textiles excavated in Greece.
A considerable amount of textiles (76%) have been preserved due to the presence of
copper in their burial environment. This may indicate that if copper was present in a burial
environment there is high likelihood that any textiles in its proximity would be preserved.
Textile Preservation in Association with Metals

The preservation of textiles in association with metals is one of the most important
methods of preservation with abundant examples worldwide. Textiles have been recovered
from sites all over the world, which have been preserved through their association with metals
such as copper, iron, silver or lead [4]. Of particular interest is the fact that these textiles may
have been preserved under conditions which would otherwise have detrimental effects on
them [5]. The exact mechanisms of textile preservation in association with metal are not yet
understood [6].
The process of textile preservation in association with a metal is known as mineralisation.
The process of mineralisation begins when the organic fibres of a textile, which is in close
contact with a metal object, are gradually replaced by the metal corrosion products [7]. At a
molecular level, it means that the atoms of the fibres are replaced by metal ions or the spaces
between the molecular chains are filled with metal ion complexes. The progress of this
process may terminate at any time or continue until the replacement is complete [8]. In any
case, the physical shape of the fibre is preserved [9].
The mineralisation process could be broken down into three stages: 1) the corrosion of
the metal, which is dependent on factors such as, the amount of water, oxygen, carbon
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dioxide, micro-organism and organic matter, temperature, salts, acids, and soil porosity.
Corrosion is an electrochemical reaction, that is a reaction between negatively (organic fibres)
and positively (metal ions) charged atoms [10]; 2) the migration of the metal ions, when they
move towards the organic fibre, and; 3) the precipitation of the metal ions on the textile fibre.
For precipitation, and finally replacement, to occur the organic fibre must be preserved.
Certain metal ions, such as copper, nickel, mercury and lead, act as micro-organisms
inhibitors, hence the fibres are not attacked by bacteria [4, 11].
The environmental factors prevailing, the amount of textile fibres and metal present, even
the position of the textile in relation to the metal are of crucial importance to the
mineralisation of the fibres. Hence, not all fibres, or even the whole fibre, of a textile may be
mineralised, if at all, at the same stage. Indeed, Mannering and Peacock [6] when analysing
mineralised samples, found that in several cases, areas of the same object had reached
different stages of mineralisation. It is possible that the partially replaced fibres are at an
intermediate stage of being fully replaced by the corrosion products [8].
The total replacement of the organic matter of the textile fibre by the metal corrosion
products results in the formation of a pseudomorph. The term literally describes the formation
of an object, which looks like a fibre but chemically speaking, it is not a fibre. Meaning that it
retains all the morphological characteristics of the fibre, and in consequence of the textile, but
none of the original constructive organic elements is present, since they have been replaced
by the inorganic metal corrosion products. The fibre formations in pseudomorphs are solidly
filled with inorganic material and have bigger dimensions than their organic predecessors
[4,12]. Nevertheless, Gillard et al. [9] when reporting the results of the experiments they
conducted indicate that total replacement is rarely achieved and that true pseudomorphs are
uncommon.
In spite of the fact that the mineralisation process is not fully understood, thus not
providing an adequate answer as to why the textiles have been preserved, the excavated finds
are evidence of how textiles have been preserved. There is a marked difference in the
preservation of textiles in association with metals. There are either positive casts formed,
where the metal corrosion products precipitate within the fibre, and negative casts, where
metal corrosion products deposit on the fibre surface [4,9,13].
In order for a positive cast to be formed, the concentration of the metal ions needs to be
high enough for its biocidal action to be effective, yet low enough for the ions to penetrate the
fibre rather than to deposit on its surface in the form of encrustations. Copper has biocidal
properties, because of the toxicity of its salts to micro-organisms [7], hence the fibre is
preserved long enough to be impregnated by the copper corrosion products. Even small-scale
degradation, other than that occurring by micro-organisms, promotes mineralisation, since
even the crystalline regions of the fibres are more susceptible to impregnation by copper
corrosion products [9]. Thus copper is commonly associated with the formation of positive
casts. In certain cases even evidence of the original colour of the fibre has been preserved
[14]. Although copper has been found to act as a catalyst in cellulosic degradation, it also
forms a barrier around and/or within the fibre, which protects it from the micro-organisms.
The kinetics of these contradictory actions of copper have not yet been identified.
Nevertheless, it has been suggested that when the biocidal action of the copper corrosion
products is predominant, then partially mineralised fibres are formed. In contrast, when the
catalysis of cellulose hydrolysis by copper corrosion products is predominant, then
pseudomorphs are formed [4,8].
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Lead and silver have been reported to have a similar action to copper in the process of
mineralisation. Meaning that the corrosion products of these two metals have biocidal
properties and are able to impregnate the textile fibres to form positive casts [6,13,14].
Iron on the other hand, does not have marked biocidal properties and its rate of corrosion
is much faster than that of copper. As a result, there is not sufficient time for the iron
corrosion products, which are readily formed, to penetrate the fibre before this is degraded by
micro-organisms. In addition, Iron (III), which is one of the main forms of iron corrosion
products is highly insoluble, thus even harder to penetrate the fibre. Nevertheless, due to the
fast rate of iron corrosion there is plenty of time for the corrosion products to precipitate on
the surface of the fibre before this is perished due to the action of micro-organisms. Hence
iron corrosion products precipitate on the fibres surface, forming negative casts [9,10,15].
The fibre inside the cast could be either totally perished or preserved in varying stages of
degradation [14]. Whether the imprint on the cast is recognisable depends on the rate of fibre
degradation compared to the rate of metal corrosion. In essence, it depends on whether there
was sufficient time for the metal corrosion products to encapsulate the fibre before this had
decayed to an unrecognisable degree [15].
Only rarely casts which are partly positive and partly negative have been detected on the
same object [4, 6].
Textile Preservation in Association with Salts

Sodium chloride (common salt) has been reported to preserve skin and cloth from the
Iron Age salt mines at Halstatt in Austria due to its property of inhibiting the growth of
micro-organisms [16]. Calcium salts from sources such as limestone, shell and bone have
been reported to be responsible for the preservation of plants and invertebrates by mineral
replacement [17].
Textile Preservation by Carbonisation
In carbonisation, similarly to mineralisation, the nature of the textile fibres changes
irreversibly, though not from organic to inorganic, but from cellulosic or proteinaceous
material to carbon. It is the irreversible chemical reaction of incomplete burning, similar to
that of wood becoming charcoal. The carbonised textiles are black and very brittle, but short
lengths of fibre may remain virtually intact [16].
Several articles have been found in the literature review, where carbonised textiles are
reported. Nevertheless, none of them offers an explanation or even raises hypotheses as to
why these textiles have been preserved. Wild [13] presents the case of a 60 AD Roman
legionary base in Colchester, where the rebel forces set fire to timber buildings. A mattress
was not consumed by the heat, but carbonised. The diamond twill weave is still recognisable,
although the fibres are distorted. Excavations at the cities around Vesuvius, buried by the
eruption of the volcano in AD 79, have brought many textile fragments to light. These have
been preserved in various degrees of carbonisation [18].
Textile Preservation in High Moisture Content and Low Oxygen Levels
The growth of micro-organisms is a major factor for the destruction of textiles in burial
environments. Low oxygen levels inhibit the growth of micro-organisms providing a
favourable environment for the preservation of textiles, and organic materials in general [19].
265
In Northern and Central Europe, textiles are usually preserved due to the combination of high
moisture and low oxygen levels [13, 16]. In Greece, the low oxygen levels have usually been
achieved in combination with a metal present, in the form of a sealed metal vessel that had
been preserved intact, and in sealed inhumation burials.
States of Preservation of Textiles Excavated in Greece

Four states of preservation were identified: 1) object/s 11% (a complete or incomplete
find with a defined shape, even if there are numerous areas of loss); 2) Fragment/s 56% (one
or more loose parts of one or more textiles, with no attachment between them); 3) Remains
28% (textile yarns/threads/fibres that are loose and/or deposited on a foreign surface); 4)
Traces 2% (imprint of a textile and/or yarns/threads/fibres on another surface); and unknown
3% (Figure 3).
Figure 3. Pie chart showing the percentages of the states of preservation of textiles excavated in Greece.
The majority of the finds have been preserved as fragments. Remains are fewer than
fragments and whole objects even less. Preservation in the form of traces, is extremely low.
An obvious question is whether the recording methods traditionally used and the tight time
limits of especially rescue excavations, are inadequate for the salvation of obscured and
extremely vulnerable traces of textiles.
TEXTILE FINDS PRESERVED AS COMPLETE OBJECTS

In the case of textile finds preserved as complete objects, the percentage (11%) represents
ten case studies.
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Five of the finds have been preserved enclosed in copper vessels, one enclosed in lead,
one in gold, two in contact with a copper vessel, and two have been preserved in inhumation
burials. It is interesting that the aforementioned finds cover a wide date range from the 8th c.
BC to the 15th c. AD. Hence, the time length of the burial does not correspond to the
condition of the find. Achievement of favourable conditions is far more important. Seven out
of the ten finds that have been preserved as whole objects were found inside sealed metal
containers, i.e., in association with a metal in combination with limited amounts of oxygen
present. Five out of these seven containers were made of copper. Therefore, the combination
of copper with oxygen elimination provides the most favourable environment for the
preservation of textiles within Greece.
Types of Fibres
Both cellulosic and proteinaceous fibres have been identified. In most of the cases fibre
identification has been achieved by the means of an optical microscope or a Scanning
Electron Microscope. In one case study TLC analysis confirmed by HPLC analysis identified
the remains of wool fibres.
In more detail, the types of fibres identified were: cellulosic (20%), flax (23%), cotton
(4%), hemp (3%), silk (7%), wool (8%), combination of fibres (8%) and unidentified fibres
(27%). These results are better illustrated in the following pie chart (Figure 4). The largest
percentage represents unidentified fibres. This indicated that either the majority of the finds
have not been adequately analysed or their condition does not allow for conclusive fibre
identification.
Figure 4. Pie chart showing the percentages of the types of fibres found in textiles excavated in Greece.
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ASSOCIATING THE TYPE OF FIBRE WITH

THE TYPE OF PRESERVATION
Some observations were made according to the type of fibre and the type of preservation,
and are presented below (Table I).
Table 1. Preservation of certain types of fibres according to the type of preservation
Type of fibre
Cellulosic
Total
percentage
20%
Flax
23%
Cotton
4%
Hemp
3%
Silk
7%
Wool
8%
Combination of
fibres
8%
Unidentified
fibres
27%
Percentage according to type preservation

15% in association with copper
1% in association with gold
1% in association with silver
1% carbonisation
1% inhumation burial
1% unknown
1% in association with a combination of metals
1% unknown
1% carbonisation
3% - in association with copper
1% unknown
1% in association with lead
3% carbonisation
2% in association with salts
1% carbonisation
3% in association with iron
1% in association with silver
3% - in association with salts
3% carbonisation
2% - unknown
Cellulosic finds represent 50% of the total, unidentified fibres 27%, proteinaceous fibres
15%, and combination of fibres 8%. Forty-one percent (41%) of the cellulosic fibres have
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been preserved in association with copper and 21% of that is flax fibres preserved in
association with copper. There are three possible explanations. First, flax is more resistant
than cotton due to its higher proportion of crystalline regions within the fibre. Hence, it has
greatest chances of survival in an excavation context [20]. Second, cotton cultivation is
believed to have reached Greece through India and Egypt at a later date than flax, hence the
use of cotton textiles in ancient Greece was rare [21]. Third, flax is a cellulosic bast fibre.
Fibres belonging to that type, such as hemp and nettle, share common morphological
characteristics, such as nodular thickening along their length, polygonal cross-sections, thick
cell walls and narrow lumens and they occur in bundles [21, 22, 23, 24]. It could be possible
that some of the fibres identified as flax were other cellulosic bast fibres.
As far as proteinaceous fibres are concerned, they are almost equally divided in silk (7%)
and wool (8%). Four percent (4%) of the silk finds have been preserved in inhumation
burials. Inhumations are in general alkaline environments due to the body decomposition
products. Silk is relatively resistant to alkalis [20], due to the absence of disulphide bonds in
its proteins and high crystallinity, i.e., decreased accessibility [9]. Wool on the other hand, is
markedly affected by alkalis [20], because they are responsible for the breakdown of the
disulphide bonds within the wool proteins [9]. Indeed, only two (2%) of the woolen fibres
identified have been preserved in an inhumation burial.
There are certain methods of preservation which are mainly associated with unidentified
fibres, such as: in association with iron (3%); in association with silver (1%); in association
with salts (3%); and inhumation burial (7%). For the cases with the iron and salts, a possible
explanation could be that, as mentioned before, they tend to precipitate on the surface of the
fibres rather than penetrating them [9,10,15], which would account for severe masking of the
fibres morphology, hence increased difficulty in identifying them. For the cases of silver and
inhumation burials, possibly the preservation of fibres is not as good for their morphological
characteristics to be retained, again inhibiting identification.
CONSERVATION
Four methods of treatment were identified: 1) First Aid (29%, which is mainly
consolidation); 2) Preventive (8%); 3) Interventive (9%); and 4) Combination of treatments
(10%). In 44% of the cases no treatment has been applied or this has never been recorded.
These results are better shown in a pie chart (Figure 5).
A preliminary observation of the type of treatment applied to the finds, according to the
date when this was applied and the dates (middle 1990s) when a more systematic technical
examination initiated, revealed the following. Consolidation has been traditionally used as
means of First Aid treatment from the first half of the 20th century until the end of the 1990s.
At this point the results of technical examination started being published [e.g., 25,26,27].
However, consolidants may obscure and/or confuse the results of such investigations, and this
may have prompted the coincidental change in conservation approach. The first interventive
treatments recorded, took place in the first half of the 1950s and continued through the late
1970s and 1980s. Another interventive method of treatment has been recorded later in 2000
[28]. Preventive conservation, i.e., the provision of a controlled environment and/or
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appropriate storage, started being applied in the second half of the 1990s beginning of
2000s.
Figure 5. Pie chart showing the percentages of the types of conservation treatments applied to textiles
excavated in Greece.
Collaboration
Recording the studies and publications of the analysis and/or conservation of the finds
afforded the opportunity to make observations on the collaboration between conservators,
archaeologists and textile historians, in Greece.
Almost 50% of the finds have been studied. Half of that percentage has been studied by
conservators in the process of treatment. As far as publications are concerned, 40% of the
finds have been published by archaeologists [e.g., 29,30,31], 20% by textile historians [e.g.,
26,27,32,33] and only 4% have been published by conservators [e.g., 28]. There are only
three joint publications of conservators, archaeologists and textile historians [28,34,35],
indicating that collaboration between the aforementioned professionals has been limited but is
now growing.
It is in the authors belief that the educational background of a professional is reflected in
their conduct. In Greece, archaeology is a highly esteemed science and has been taught at a
University level since 1837. On the other hand, the National School of Conservation was
founded in 1985 at a Technological and not a University level. Even today this School has not
been upgraded to a University level. Moreover, Art History studies have only been available
in Greece, at a University level, since 2006. Consequently, in Greece, archaeologists are
always in charge of any potential collaboration between these professionals, conservators are
more often than not considered to be technicians, and art historians are rare and usually their
270
role is taken by the archaeologist. As a result, collaboration between them becomes a thorny
issue.
Collaboration between Conservators, Archaeologists and Textile Historians

Archaeology is the science that studies the material culture of the past, in order to
reconstruct it. Studying the material culture means interpreting the evidence held within
objects [36]. In the past, the predominant notion was that very rarely textiles survive in a
burial context, therefore archaeological interest in them was limited [37]. At present this
situation has changed. An interest of the archaeologists in more social and economic
questions along with the fact that a considerable amount of textile finds has been retrieved,
has raised the awareness of archaeologists about excavated textiles [38].
Conservators are the professionals responsible for the long-term preservation of objects.
To them, the objects life continues after excavation, it just changes form. It is still considered
to be an information recipient and care is taken not to undertake a treatment that would
interfere with its new history. Conservation goes beyond the application of the appropriate
treatment. The presence of a specialised conservator would not only ensure the welfare of the
finds but also aid the yielding of information held within them. Conservation enables,
increases and clarifies the interpretation of objects, and this is attributed to two main reasons:
One reason is the examination methods used in conservation, which can unlock
information held within a degraded object. Odegaard [39] presented a case where the
application of technical analysis used in conservation, on extremely fragile, fragmentary
painted clay-covered basketry, lead to the recovery of important ethnological information.
The second reason lies with the fact that the close contact and continuous observation of
the find afforded by the conservation process allows for a level of study otherwise
inaccessible. The conservator has the opportunity to analyse and understand the
characteristics of the constituent materials of the object and to reveal details in its
construction that would otherwise remain concealed. When that is combined with the
conservators knowledge of the archaeological/historical context of the object it ensures a
justified interpretation [36,40].
The earlier a conservator is involved in an excavation project the better, both for the
preservation and the interpretation of the finds. Since the conservator is the one responsible
for treating and examining, hence interpreting, the fragile excavated finds, it would be of
utmost importance for them to have been present at the time when the find was first brought
to light. In that way they would be able to record evidence such as, the exact positioning of
the find, its condition and the environmental parameters prevailing. Cruickshank et al. [41]
argued that considerable information was retrieved by the conservator (Cruickshank) involved
in the excavation project of the 1st-3rd century AD Nabataean/Roman cemetery in Jordan,
from the initial stage of planning. For the conservator was able to observe the undisturbed
graves and textiles within them in-situ, hence a significant amount of information on burial
practices was transported back to the conservation laboratory to be combined with the
analytical examination results and provide guidance to the treatment decision-making.
One could argue that archaeologists are adequately trained to record in detail the way an
object was found and its exact position. Nevertheless, the conservator still has to offer
additional input. First, they would be able to record the environmental parameters, which
would provide necessary evidence for the future treatment and preservation of the actual
object. Second, archaeological conservators are trained in lifting the objects in a way that they
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are safe for transport to the laboratory and all information is retained. Third, the combination
of the expert knowledge of the archaeologist on the context of the find, with that of the
conservator on its materials and condition would ensure the correct completion of the
archaeological record, which is the first and very important stage of its interpretation [39].
Mathias et al. [42] added that the examination of the Ferryland site in Newfoundland
would be incomplete without the combined input of a conservator, conservation scientists and
archaeologists in researching the excavated finds, original documents of the period and other
contemporary costumes.
As far as the preservation of the finds is concerned, archaeologists do not usually
appreciate the sensitivity of their nature, and the fact that although they may have been
preserved for thousands of years in burial, the extreme changes in the environmental
conditions could lead to their complete destruction in less than a few days even hours. Hence,
the services of the conservator are essential when the object is to be treated for either storage
or display.
Rotroff [43] presented the case of the Agora excavations, conducted by the American
School of Classical Studies in Athens (ASCSA). As time passed, the accumulated finds
(mainly ceramics and stone) started to deteriorate. This alerted the archaeologists to the
involvement of trained conservators at the excavation project, which according to Rotroffs:
meant profound changes in the attitude of archaeologists toward the objects of their study: a
sharper awareness of their fragile nature and our responsibility, and ability, through
collaboration with conservators, to take decisive action to pass these objects on to future
generations intact [43].
In the case of excavated textiles, the need for a conservator to be involved in their
retrieval is even more pressing. The sensitive, unique, and sometimes obscured nature of
excavated textiles are the main reasons for seeking the assistance of a specialist conservator.
Textiles preserved in either damp, or very dry and anaerobic conditions are susceptible to
rapid deterioration from the moment they are brought to light. As Glover [44] wrote, the only
way to suspend deterioration and to retain the value of textiles as archaeological/historic
documents, is to seek advice and practical assistance from a specialist textile conservator as
soon as possible.
There are similar considerations for mineralised textiles, which especially in the form of
pseudomorphs, are not only very sensitive to handle, but often not recognisable to the
untrained eye of the archaeologist. An adequately trained conservator should be present to
identify the mineralised textile, hence preventing its accidental removal from the metal/host
object and finally to ensure its safe retrieval and transport to the laboratory [8, 38, 45].
Glover [44] presented two case studies to illustrate how the prompt contribution of a
specialised textile conservator would have improved the condition of textile finds
dramatically. The first one is that of an excavated burial, where deleterious interventive action
was taken by non-specialists. Once lifted, the damp textile was transported to the local
Museum to be examined by archaeologists and other specialists. Two weeks passed before it
was assigned to a specialist textile conservator (Glover). By that time it had dried and to the
conservators astonishment it had not only been washed but two quite large triangular pieces
had been cut off from its corners for the sake of analysis. One of the pieces bore evidence of
selvedge while the other a section of braided edge. Without the removal of these pieces, the
outline of the object would have been complete. A textile conservator would have not washed
the find unless absolutely necessary, and in that case they would have kept a detailed record
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of the characteristics (such as dimensions and weave count) of the object before treatment. In
the case of analysis a textile conservator would be aware of the fact that the same information
could be extracted from already detached fragments and/or other damaged areas, and would
have never cut pieces from the object.
The second case study presented is that of another inhumation burial where the damp
textiles excavated were moved to the Conservation Department of the local University for
storage. They were folded, wrapped in polythene and refrigerated without first seeking the
advice and guidance of a textile conservator. Eight months later, when the textiles were
removed from the refrigerator to be opened at the presence of the textile conservator (Glover)
they had been extensively attacked by green and fluffy white mould. A textile conservator
would have been prompt in freezing the objects before mould growth; they would have made
sure the textiles were not so tightly folded for the centre to cool at very slow rates [44], and
would have ensured that a sufficiently low temperature was reached to prevent mould growth.
Textile historians are the professionals primarily interested in the analysis and research of
textiles. They constantly compare and evaluate the results of the analysis on one object with
these from other groups of objects, seeking to create an all round body of knowledge. Hence,
they have adapted an inherent hesitation towards conservation remedial treatments, which
they, more often than not, consider them to be an obstacle to this retrieval of information.
Objects on display in a museum need to be accessible and unaltered, even after conservation
treatment, for a textile researcher to be able to retrieve information [38]. Although recording
and analysis ideally takes place before conservation, this is not always the case [46] and in
addition there are still many questions to be answered in the future, hence an object needs to
remain accessible [38].
Excavated textiles, even those in the poorest condition or obscured state of preservation,
can yield a substantial amount of valuable information. A specialised textile conservator is the
one entrusted with preserving both the tangible and intangible evidence of past history and
technology enclosed in textile finds. Archaeologists should appreciate that the sooner a
conservator is involved at an excavation the better for the welfare of the finds. Conservators,
in turn, should always take care not to inhibit the work of textile analysts and historical
researchers by using inappropriate treatments and materials.
Apparently good collaboration between conservators, archaeologists and textile
researchers is of crucial importance to the welfare, long-term preservation and understanding
of excavated finds [47]. There are four ways to aid a successful collaboration between
representatives of the three aforementioned professions: the use of a common language and
terminology, which would enable better understanding between them; joint publications in
journals of interest to their professions, which would promote the fact that they are all
partners sharing the common goal of preserving material culture and its evidence for future
generations; close contact, which would enable the appreciation of each professions
contribution and restrictions; and continuous dialogue, which would secure the transfer of
information between them [38, 41, 43, 46].
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CONCLUSION
Compiling a chronological table of textiles excavated in Greece and analysing the
information gathered, provided an overview of the present condition of these finds. Ninety
(90) different finds were identified, which indicates that in contrary to the general notion,
textiles could survive in a burial context in Greece, should favourable environmental
conditions prevail. These conditions, which are not unique to Greece, were identified as: in
association with a metal present (66%), in association with salts (7%); carbonisation (8%),
and inhumation burials (14%). In certain cases (5%) the method of preservation was
unknown.
The presence of a metal in a burial context was found to be primarily responsible for the
preservation of textiles. Different metals have been recorded in association with textiles:
copper (76%), lead (5%), silver (2%), gold (5%), iron (5%), and combination of metals (5%).
The kind of metal is unknown in very few cases (2%). The high percentage of copper showed
that its presence in a burial environment greatly increases the chances of textile preservation,
which was in accordance with the findings of the literature review. Excavated textiles in
Greece have been found in different states of preservation: object/s (11%), fragment/s (56%),
remains (28%), and traces (2%). In certain cases (3%) the state of preservation was unknown.
The fact that fewer textiles have been retrieved in the state of remains and/or traces could
indicate a lack of experience in identifying textiles in such a poor state of preservation during
the excavation process. The actual number of textiles found as whole objects is ten. Seven of
them have been preserved by the combination of a metal present and elimination of oxygen.
This could mean that the presence of a metal in association with elimination of oxygen
provides optimum conditions for the preservation of textiles in a burial context in Greece.
Different types of fibres have been identified: cellulosic (50%), proteinaceous (15%), and
combination (8%). The majority of cellulosic fibres have been preserved in association with a
metal present, whereas the majority of the proteinaceous fibres have been preserved in
inhumation burials. This indicated that the former method of preservation is favourable to the
preservation of cellulosic fibres, while the latter is favourable to the preservation of
proteinaceous fibres, which was in accordance with the findings of the literature review. The
small percentage of a combination of different types of fibres preserved (8%), futher indicated
preferential preservation of cellulosic and proteinaceous fibres under different conditions. The
type of fibre was not identified in certain cases (27%), indicating the lack of comprehensive
analysis of textiles excavated in Greece.
As far as conservation of the finds is concerned, first aid treatment by the means of
consolidation was the usual conduct of practice (29%) up to the late 1990s / beginning of
2000. The beginning of a more systematic study and analysis of the finds at that period might
have been responsible for the discontinuation of this practice. Interventive treatment (9%)
was similarly discontinued at the same period, giving way to preventive conservation (8%).
The employment of specialist textile conservators by the Hellenic Ministry of Culture at that
period, probably affected that change in attitude.
The literature review showed that a good and continuous collaboration of conservators,
archaeologists and textile historians would be most beneficial to the preservation of the
information and physical existence of excavated textiles. The small number (3) and dates
(2000; 2011) of joint studies and publications of the aforementioned professionals, indicated
274
that their collaboration may have been limited, but is now growing. There are two possible
reasons for the limited collaboration: either the interest in excavated textiles is generally low,
or these professionals lack a common ground. Open communication, continuous dialogue
using a common language and joint publications from excavation to conservation, storage,
display and analysis, is required between conservators, archaeologists and analysts to secure a
successful collaboration.
In conclusion, this research showed that a significant number of excavated textiles have
survived in Greece, the study of which would greatly contribute to the body of knowledge on
archaeology, technological advancements and material culture, and it would be enabled by a
good collaboration established between the professionals involved.
ACKNOWLEDGEMENTS
To all the conservators and archaeologists of the Hellenic Ministry of Culture who
collaborated for this research project.
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Conservation and its Consequences 16-21.

ISBN: 978-1-63117-262-5
Chapter 10
INNOVATIVE Ag-TEXTILES PREPARED

BY COLLOIDAL, CONVENTIONAL SPUTTERING
AND HIPIMS INCLUDING FAST BACTERIAL
INACTIVATION: CRITICAL ISSUES
Sami Rtimi1,*, Cesar Pulgarin1, Rosendo Sanjines2
and John Kiwi3
1
EPFL-SB-ISIC-GPAO, Ecole Polytechnique Fdrale de Lausanne, Lausanne,

Switzerland
2
EPFL-SB-IPMC-LNNME Ecole Polytechnique Fdrale de Lausanne, Bat PH,
Lausanne, Switzerland
3
EPFL-SB-ISIC-LPI, Ecole Polytechnique Fdrale de Lausanne, Btiment Chimie,
Lausanne, Switzerland
ABSTRACT
The bacteria inactivation of E. coli by Ag colloidal loaded cotton and polyester was
investigated. Textile surfaces were pretreated by RF-plasma and UVC to introduce
organic-polar groups containing oxygen functionalities binding/complexing/chelating
Ag-clusters. Since sol-gel films are not mechanically stable, only exhibit low adhesion
and can be wiped off by a cloth or thumb, we present in this study the Ag-sputtering of
semiconductors and metal films to avoid the lack of reproducibility attained by colloidal
preparations on textiles. Films sputtered by the DC-magnetron sputtering (DC) and
pulsed direct magnetron sputtering (DCP) were compared with films sputtered by highly
ionized pulse plasma power magnetron sputtering (HIPIMS). The amounts of Ag needed
to inactivate E. coli by HIPIMS were an order of magnitude lower than films loaded with
DC. The more compact microstructure obtained by HIPIMS seems to lead to a significant
saving of noble metal compared to the DC/DCP sputtering. The antibacterial kinetics
evaluated for the Ag-sputtered films are estimated to be sufficient to decrease
E-mail: sami.rtimi@epfl.ch.
278
Sami Rtimi, Cesar Pulgarin, Rosendo Sanjines et al.

significantly the bacteria in hospital rooms besides precluding the formation of
pathogenic biofilms on textile surface.
The sputtering by (DC) and surface characterization of TiN, TiON, TiN-Ag and
TiON/Ag textiles are reported addressing disinfection in the dark and under light, either
solar or actinic. The TiN and TiON films presented semiconductor properties leading to
the formation of TiO2. These TiN and TiON textile samples induced bacterial
inactivation within acceptable times without leaching of Ag into the natural environment.
ZrN/Ag and ZrNO/Ag nanofilms were deposited on textiles by DCP in Ar+N2 and/or
O2 atmosphere. These nitride films were more active for E. coli inactivation compared to
Zr/Ag-films. ZrO2-Ag2O was formed during the co-sputtering of ZrNO and Ag. Finally,
the coupling narrow and wide band-gap semiconductorswas investigated on TaON/Ag
sputtered sample. The mechanism of interfacial charge transfer (IFCT) due to the electron
injection from the Ag2O conduction band (cb) to the lower laying Ta2O5 (cb) is discussed.
A beneficial effect for the e-injection from Ag2O clusters into Ta2O5 is suggested.
Keywords: Textiles pretreatment, sol-gel, sputtering, Ag, Ag-nitrides, Ag-oxynitrides, IFTC
INTRODUCTION
Silver has been recognized as antibacterial agent in various material forms: colloids,
powders and supported on natural textiles fibers like cotton and artificial fibres like polyester,
polyamide and wound-pads, thin polymer films like polyethylene, polypropylene,
polyurethane. The silver ion release kinetics and extended operational time and cytotoxicity
(biocompatibility) will determine its effective use when deposited on antibacterial surfaces.
In this review we address the description/discussion of the preparation of Ag on textile
surface by different methods, the evaluation of their antibacterial activity in the dark and
under light irradiation and the characterization of the Ag-textile surfaces by up-to-date surface
techniques. The content of this review is warranted since silver biocidal surfaces are the
strongest growth segment in the medical and health care applications. The advantage of using
Ag-disinfection is that it will not cause bacteria to become resistant to antibiotics and that Ag
surface will prevent the formation of harmful biofims since this is the main source of human
infections. Textiles presenting a faster bacterial inactivation are needed at the present time
due to the increasing resistance of pathogenic bacteria to synthetic antibiotics when
administered for long-times.
If Ag-textiles would be optimized and attain a more widespread use in hospital textiles,
gloves, rugs, curtains, medical devices and catheters, an effective reduction or elimination of
infections can be expected [1-3]. This review describes the current search for more efficient,
stable and adhesive antimicrobial Ag-nanoparticulate films on textiles to preclude the
formation of biofilms leading to hospital acquired infections (HAI) [4]. These biofilms
remain stable for long periods spreading bacteria by contact in public places or confined to
hospital or school-rooms and could only be precluded by Ag-ion release in a slow and steady
way by a favorable ionic transfer rate regulated by the ambient environmental conditions.
The nanoparticles of Ag exhibit bacterial and fungicidal properties. They can accumulate
on the cell wall of bacteria and release Ag-ions that due to their small size penetrate into the
cells through the wall porins [5]. Ag-nanoparticles affect the bacteria respiratory enzyme due
to the production of reactive oxygen species (ROS) and associated DNA damage leading to
Innovative Ag-Textiles Prepared by Colloidal, Conventional Sputtering ...
279
death [6,7,8] and the antimicrobial effect of the potentials of Ag-solutions have been recently
reported [9]. The release of Ag-ions from Ag-grafted surfaces involves Ag-oxidation
reactions due to the oxygen available to the Ag-clusters, protons, salts and are directly
dependent on the Ag-particle size that for large particles is effective only when releasing Agions in sufficient concentrations in a sustained way during relatively long periods [10].
Recently, the advances in Ag-nanoparticle preparations nanotechnology led to Ag nanocrystalline structures with a markedly improved biological value and efficiency. Agformulations in solution or embedded in humid wound-pads pass the Ag-ions/radicals and
have been in use since 1920. Silver atoms are in itself no disinfectant and are considered nontoxic to in vivo human cells [11]. Decreasing the Ag particle size increases the particle
surface area available for surface reactions to take place over shorter time periods. The large
surface of the nano-Ag crystals contain a higher amount of oxidized surface Ag-species, some
of them soluble leading to an enhanced disinfectant reactivity. The Ag-nanoparticles will
release Ag-ions for days compared to the Ag-salts and complexes releasing in the hours range
[12-13]. Sulfadiazine by itself does not show antibacterial action but due to its synergy with
Ag+ a slow release from Ag-ions occurs from the sulfadiazine-Ag salt presenting low
solubility [14].
Many studies have appeared over the last three decades involving the preparation of
colloidal/powder Ag [15-18]. More recently, Ag/TiO2 dispersions or colloids prepared by
different routes in the dark and in some cases under light have been leading to a bacterial
inactivation [19-21]. When applying solar or visible light Ag2O (bg 1.5-1.7) has been
observed to act as a semiconductor enhancing bacterial inactivation [22]. Recently, Ag photoswitching processes by finely divided dispersed Ag 2nm in size has been reported relating the
hydrophobic Ag initial surface kinetics when the surfaces changed to super-hydrophilic under
light concomitant to E. coli and Staphylococcus aureus inactivation. In this way the contact
angle and surface energy were investigated during the light induced and dark reversible
process after bacterial disinfection [23].
Recently, some reviews have appeared on the cell killing mechanism by semiconductor
TiO2 and by metal nanoparticles on E. coli and other bacteria [24-28]. These reviews report
and efficient processes by nanoparticle dispersions leading to the loss of bacterial viability or
inducing the lack of bacterial cultivability.
METHODS AND RESULTS

RF-plasma and UVC Pre-treatment of Surfaces/textiles Loaded
with Colloidal Ag
Microbial colonization with the consequent biofilm formation is a widespread
complication on implants, catheters and textiles used in hospitals, health facilities and
laboratories. Colloidal Ag film deposition on non-heat resistant surfaces attached weakly on
the textile surface. The colloidal Ag-deposits were not uniform, hardly reproducible and no
heating could be applied to diffuse them into the substrate [29]. This lead us to pre-treat
textiles in the presence of residual O2 to introduce O-containing negative polar groups like:
280
COO-, -O-O- and other -O-C- containing functionalities. These sites introduce additional
bonding functionalities able to attach the Ag found in colloidal suspension.
a) Functionalization of fibers by RF-plasma pretreatment: this fabric was pretreated in a
RF-plasma cavity (Harrick Corp. 13.56 MHz, power 100 W). Generally for RF-plasma
formation low pressures are used to increase the capture length of the electrons generated in
the electric field generated in the RF-chamber. Vacuum at 1 torr avoids the collisions between
the electrons when allowing the electrons to react with residual O2. The RFplasma is created
when a gas is exposed an electromagnetic field within radio frequencies. In the low
temperature plasma the gaseous ions present temperature ranges between ambient and few
hundred degrees, but the electrons have transient energies corresponding to high temperature
values. The system is not under thermal equilibrium.
The activated RF-plasma interacts with oxygen leading to atomic, excited O*, anionic Oand cationic O+, giving rise to carboxyl, per-carboxylic, peroxides, lactam etc able to
chelate/complex or/and attach by electrostatic attraction with the partial positive Ag-species.
The Ag-salt/colloid are reduced by isopropanol and precipitated by ammonia on the textile
surface. Without vacuum, the RF-plasma induces a localized heating breaking intermolecular
H-bonds and generating for very short times temperatures > 160C able to segment the textile
[30].
b) Functionalization of fibers by atmospheric or vacuum UVC: the textile polymer
surface can also be functionalized by UVC light irradiation using the 185 nm line (6W) from
a 25W (254 nm + 185 nm light) low-pressure mercury lamp (Ebara Corp. Tokyo, Japan).
UVC activation having a lower energy than the RF-plasma, does not lead to cationic or
anionic oxygen species in the gas phase. Only atomic (O) and excited oxygen (O*) species
under UVC are obtained. The energy necessary for the O2 2O* reaction is at the
wavelength 241 nm (495 kJ/mole). The absence of cationic or anionic oxygen species when
pre-treating with UVC lead to a more uniform TiO2 layer of the textile surfaces and has been
reported in the literature [30]. Figures 1a and 1b below report the loading of Ag and the
bacterial inactivation time on textile pretreated in the UVC cavity and positioned at 3 mm of
the UVC source. The O2 cross section is 10-20 cm2 and the molar absorption coefficient O2
(185 nm) ~26M/cm-1 [31]. The cross section of N2 is about 10 times smaller than for O2 at
this wavelength. Therefore, the N2(185 nm) would negligible. At 185 nm the extinction
coefficients of O2 and N2 are so low, that practically no UVC-radiation is lost in the optical
pathway between the light source and the sample even at atmospheric pressures.
The control fabric in Figure 1b shows a modest reduction of the number of initial bacteria
concentration on the fabric surface due to bacterial adsorption on the textile surface [30]. The
inactivation performance was observed to be dependent on the amount of silver on the textile
surface. By XPS the Ag2O and AgO species were identified on the cotton surface.
Continuing the preceding study, Ag-colloidal clusters were fixed on cotton to investigate
the fabric antibacterial kinetics [32]. Figure 2a shows that in the dark bacteria are inactivated
by contact with the Ag-cotton surface.
The bactericidal activity of the Ag-TiO2-cotton in the dark is shown in Figure 2b. It is
readily seen that the addition of TiO2 to the colloid under diffused laboratory light increases
the bacterial inactivation time with respect to the Ag-cotton samples.
281
inhibition of airborne bacteria (%)
100
80
60
40
20
0
0.0
0.2
0.4
0.6
AgNO3 (g/200 ml solution)
0.8
1.0
Figure 1a. Inhibition of airborne bacterial growth by textile fabrics activated by vacuum-UVC as a
function of the textile Ag-loading. Total inhibition occurs of E. coli activity at concentrations 0.5 g
AgNO3/200 ml solution.
4
Bacterial survival (CFU/ml)
10
10
control
10
sample with Ag
10
10
10
15
20
Time (h)
Figure 1b. Bacterial survival in CFU/ml of a vacuum-UV activated textile surface as a function of time
for a) control textile and b) textile loaded by using an AgNO3 solution (1g/200 ml).
TiO2 e-cb + h+vb
(1)
Ag+ + e-cb Ag0
(2)
Since Ag0 is not bactericidal. The results presented in Figure 2b compared to Figure 2a
can be understood due to the lower amount of Ag+ responsible for the bacterial inactivation
available in Ag-TiO2 compared to the Ag by itself on the cotton surface (Figure 2a). Reaction
282
10
(2) is possible since the conduction band of TiO2 (-0.1 V) is more negative than the Ag+/Ag0
potential of around 0.70 (V) and this reaction partially occurs under diffused laboratory
conditions.
10
10
10
10
3 min
10
10
50
100 150 200 250
time (min)
10
10
10
10
10
10
10
20
30
40
50
time (min)
(a)
(b)
(c)
Figure 2. (a) E. coli survival on Ag-cotton, samples in the dark. (b). E. coli survival on Ag-TiO2 cotton,
samples in the dark. (c). TEM of the Ag-clusters on the cotton textile deposited as described before.
Figure 2c shows the Ag-clusters on the cotton textiles and also in the topmost layers
where they have penetrated by diffusion. Figure 2c has been obtained after the cotton sample
has been cross-sectioned with an ultra-microtome. Particle sizes 3-10 nm imparted a brownish
color to the Ag-cotton presented in Figure 2c. The presence of Ag2O and AgO were detected
and identified later by XPS [33]. Leaching of Ag-ion clusters with a minimal dissolution of
Ag is responsible for the E. coli inactivation (1-4, 15-16, 23-28).
283
Sputtering of Ag-textile Presenting Uniformity, Adhesion and Fast

Bacterial Inactivation
(i) The Ag-deposition on cotton is important since cotton has the property to adsorb a
large amount of moisture making this textile prone to microbial attack. With ambient
temperature and humidity, cotton is a nutrient for bacterial and fungal growth. To preclude
bacterial growth we reported the preparation of Ag on wound pads by wet
impregnation/reduction of AgNO3 to inactivate airborne bacteria induced infections [30,32].
By direct current magnetron sputtering (DC) we sputter Ag-films having a strong adhesion,
fast kinetic bacterial inactivation and would not smear under friction [33]. XPS analysis of
cotton samples loaded at 15, 60 and 600 s present a surface atomic percentage concentration
of 7.31, 23.36 and 37.76 % of Ag, respectively. We used XPS and Auger lines to follow the
changes in the oxidation state of Ag [34]. The highest Ag-oxidation state was found after the
shortest deposition time of 15s. In this case, the Auger parameter was 725.15 eV and the Agcontent for the cotton sample was low. But at longer deposition times, a significant shift of
Auger parameter from 725.15 to 725.65 eV indicates a higher deposition for the AgO at 60s
and 600s sputtered samples. The amount of oxidized silver was observed to be similar for
samples sputtered during 60s and 600s (Fig. 9c, d) while at the same time the total amount of
Ag was almost two times higher after 600s DC-sputtering. This indicates that the Ag-ions are
located mainly at the silver interface and provides the evidence that Ag-ions and not Ag0 is
responsible for the bacterial inactivation. While the presence of Ag0 and Ag2+ seems to be
documented, the assignment to Ag+1 is less clear [35]. The reason for that is that O1s line at
530.71 eV and for this reason cannot be used for clear identification of the Ag-oxidation state.
Sputtering from an Ag-target for 60s produced thin semi-transparent coatings with 4-5 layers
showing strong adherence, bactericide activity and did not affect the handle or touch of the
cotton textile. The Ag wt % Ag/wt cotton to for a bactericide film on the cotton was found to
be 0.054% and could be sputtered in 60s, this time is short and shows that Ag-sputtering on
cotton makes an economic use of Ag.
(ii) In a more recent study [36] the deposition of active, uniform nano-particulate Ag-thin
films on polyester textiles by DC-magnetron sputtering (DC) and pulsed DC-magnetron
sputtering (DCP) has been reported. The deposition of Ag on the polyester fiber was observed
to be function of the type of sputtering used either DC or DCP directly determining the E. coli
inactivation kinetics. In the magnetron sputtering chamber the reaction Ar Ar+ + e- lead in
a subsequent steps to the collision of the electron with Ag0: e- + Ag0 Ag+ + 2e-. The Ag0
kick-off a second electron. The Ag ionization increased when higher currents (mA) were
applied during the DC or DCP-sputtering. The ratio of Ag+/Ag0 was higher for DCP (up to
10%) than in the case of the DC presenting Ag+/Ag0 1% [37].
The shortest E. coli inactivation was attained within 2 hours DCP. The results are shown
in Figure 3a. Pulse trains of 3 pulses each of 10 microseconds with a recovery time of 7 ms to
avoid overheating of the Ag-target was used during in the DCP mode. When sputtering DC
with 300 mA the bacterial inactivation was complete after 5 hours. Samples sputtered by DCP
for 160s inactivated E. coli within 2 hours with an equivalent loading of ~1018 atoms/cm2.
The threshold Ag-loading by DCP in Figure 3a was attained after sputtering for 20s and led to
inactivation of E. coli only after 9 hours.
284

polyster alone (1)
300 mA DC-Pulse Magnetron Sputtering
Ag-20s (2)
1.0E+08
Ag-40s (3)
E. coli (CFU mL-1)
Ag-80s (4)
Ag-160s (5)
1.0E+06
(1)
1.0E+04
(4)
(5)
(2)
(3)
1.0E+02
1.0E+00
0
10
time (h)
Figure 3a. E. coli inactivation kinetics as a function of time on Ag-polyester DCP-sputtered at different
times applying currents of 300 mA.
Figure 3b. Electron microscopy of Ag-polyester fiber DCP sputtered for 160s at 300 Ma..
285
By electron microscopy (TEM) Ag-polyester fibers it was found that Ag sputtered by

DCP penetrated more deeply into the polyester fiber compared to DC-sputtering. Figure 3b
shows the composite TEM results for an Ag-polyester fiber sputtered by DCP for 160s. The
arrow on the lower side in Figure 3b indicates the direction of incidence of the Ag-particles
on the polyester in the sputtering chamber. A dark continuous Ag-deposit ~80-90 nm thick
was observed. But only 5-15 nm thick Ag-layer was found on the other end. About 65-70% of
the full polyester fiber perimeter was covered by a 50-90 nm thick Ag-deposit. The DCP ionenergies are much higher than the DC energies and DCP sputtering ion-energies of 10-100 eV
have been recently reported with a small number of ions exceeding 100 eV and electron
densities of ~1016 e-/m3 [37].
The E. coli inactivation process has been described to proceed by Ag-ionic states using
the ambient kT energy and ambient humidity leads to the formation of highly oxidative
radicals HO2 and OH necessary for E. coli inactivation. The Ag-crystals in air are covered
by layer(s) of AgOH and the kT energy at room temperature leads to bacteria oxidation via
the surface AgOH groups [38].
16000
DCMSP 20s 300 mA

DCMSP 160s 300 mA
12000
6000
5000
36
8000
4000
36
HIPIMS 13s 1 Amp

HIPIMS 75s 5 Amps
Intensity [counts]
Intensity [counts]
7000
37
38
39
40
41
37
38
39
40
41
Figure 4. X-ray diffraction of DCMS and HIPIMS sputtered Ag-polyester fibers under different
conditions. For other details see text.
Figure 4 shows the XRD for Ag-nanoparticle films on polyester sputtered by DCP for 20s
and 160s. The cluster formation occurs when Ag-atoms bind to other metal-atoms rather than
to polyester. The growth of Ag-atoms into clusters at 20s in Figure 4 leads to near spherical
but not necessarily crystallographic Ag-clusters [39]. At longer sputtering time of 160s, a
steep peak is observed in Figure 4 assigned to the Ag-metal peak at 2=38.
Ag-metal nanoparticles have been reported with dimensions > 1 nm [40]. HIPIMS sputtering
286
for 13s at 1A indicate a low Ag-cluster formation in the insert to Figure 4. The Ag-clusters
grow into bigger aggregates when sputtered for 75s at 5A, but did not lead to Ag-metal
formation. We have not looked in a detailed way in Figure 4 into the effect of the
microstructure changes introduced in the Ag-nanoparticles by the HIPIMS sputtering during
75s at 5 A leading to the formation of a 40 nm film compared to a thinner 4 nm film sputtered
during only 13s at 1 A.
(iii) In a separate study we addressed the DC-magnetron sputtering (DC) by Ag-films on
polyester and compared the results obtained with (HIPIMS) for bacterial inactivation [41].
HIPIMS deposition of Ag-films was carried out in a CMS-18 vacuum system from Kurt
Lesker Ltd. evacuated to 10-2 Pa by a turbomolecular pump using Ag-target was 5 cm in
diameter, 99.99% pure from K. Lesker Ltd. UK.
The HIPIMS unit was operated at 100 Hz with pulses of 100 microseconds separated by 10
ms. The HIPIMS short pulses avoid a glow-to-arc transition during plasma particle
deposition. The applied power was varied between 1 and 5 A and no glow-to-arc transition
was detected during the plasma deposition. The pressure was the same as the one used in the
DC chamber. The mass spectrometry measurements were carried out in a Hiden Analytical
Ltd PSM003 unit to determine the ion-composition of the ions in the plasma Ar-atmosphere.
The polyester used was a polyester Dacron polyethylene-terephthalate; type 54 spun,
plain weave ISO 105-F04 used for color fastness determinations. The nominal calibration of
the Ag-film thickness on the polyester was carried out on Si-wafers. The film thickness was
determined with a profilometer (Alphastep500, TENCOR) as shown in Figure 5a for DC and
Figure 5b for HIPIMS samples. Figure 5a shows that DC sputtering applying 0.3 A increases
the Ag-deposition rate by a factor of 8 with respect to Ag-deposition at a lower current of
0.05 A. Figure 5b shows that a thinner Ag-coating is deposited within the same times by
HIPIMS compared to DC- sputtering shown in Figure 5a. Since the lattice distance between
Ag-atoms can be estimated at 0.3 nm, a monolayer of Ag contains ~1015/atoms/cm2. DC
sputtering at 0.3 A deposits a coating 100 nm thick after 80s, and if each Ag-layer is about 0.2
nm thick, then the silver deposition rate was ~6x1015 atoms/cm2s.
Film Thickness (nm)
500
Ag - DCMS
50 mA
300 mA
400
300
200
100
0
0
100
200
300
400
Deposition time (s)

Figure 5a. Nominal calibration of the Ag-thickness obtained by DC at 50 mA and 300 mA on Siwafers.
Film Thickness (nm)
250
HIPIMS
5A
1A
2A
200
150
100
50
0
0
100
200
300
400
Deposition time (s)

Figure 5b. Ag thickness obtained by HIPIMS at 1, 2 and 5A on Si-wafers.
10
10
Polyester alone (1)

Ag 1.5 s 1A (2)
Ag 13 s 1A (3)
Ag 03 s 2A (4)
1 A - HIPIMS
-1
E. Coli (CFU mL )
10
10
(1)
(2)
10
(3)
(4)
10
10
Time (h)
Figure 6a. E. coli inactivation kinetics induced by HIPIMS Ag-polyester sputtered at 1A.
10
10
Polyester alone (1)

Ag 13 s (2)
Ag 37 s (3)
Ag 75 s (4)
Ag 150 s (5)
5 A - HIPIMS
-1
E. Coli (CFU mL )
10
10
(1)
4
10
(5)
(3)
(4)
(2)
10
10
Time (h)
Figure 6b. E. coli inactivation kinetics at a current of 5A.
287
288
Inactivation Time (h)
10
8
6
DCMS
4
2
HIPIMS
0
0
50
100
150
200
250
Nominal thickness (nm)

Figure 6c. Times of E. coli inactivation times as a function of nominal thickness of Ag-layers deposited
by DC and by HIPIMS sputtering.
Figure 6a presents the results for HIPIMS sputtering at 1A and 2A. HIPIMS sputtering
for 3s at 2A lead to the most effective E. coli inactivation having a relatively low Ag-content.
The initial CFU decrease in Figure 6a for Ag-polyester at time zero with respect to polyester
alone is due to a quasi-instantaneous redox process taking place between Ag and E. coli. The
Ag-layer thickness and the % Ag wt/ wt polyester for the samples prepared by HIPIMS at 1 A
or 2 A with respect to DC samples Ag-sputtered for 160s was observed.
Figure 6b presents the results for the E. coli inactivation with HIPIMS sputtering with
5A. Trace (2) shows that sputtering for 13 s at 5A leads to bacterial inactivation within 5
hours. The threshold polyester Ag-loading was 0.0029% wt Ag/wt polyester. Sputtering times
shorter than 13 s did not induce complete bacterial inactivation. HIPIMS sputtering for 37s
lead to an Ag-film 20 nm thick with 0.0086 Ag wt% / wt polyester able to inactivate E. coli
within 4 hours. DC sputtering for 80s lead to E. coli inactivation within 5 hours. In this case
the Ag wt% / wt polyester was 0.118 and the Ag-layers were 105 nm thick. DC-sputtering
required >10 times higher loading when compared to HIPIMS and led layers more than 5
times thicker compared to the HIPIMS. This shows the significant saving in Ag-metal and
sputtering time introduced by HIPIMS compared to more traditional DC sputtering.
Figure 6c presents the trends for the inactivation time of E. coli vs the Ag-layer thickness
deposited by DC and HIPIMS sputtering and shows the significant reduction of the Ag-layer
thickness required to completely inactive E. coli by HIPIMS compared to DC.
Issues related to the basis of Ag and Au and Ag/TiO2 and Ag/SiO2/TiO2 colloidal films
have been reported recently by Daoud et al., [42] focusing on self-cleaning issues on cotton,
wool and synthetic fibers [43] involving the discussion of mechanism, photocatalytic
efficiency and material stability during long operational times. These considerations are also
valid for Ag-antibacterial surfaces when addressing the basic science related to Agdisinfection. An active group in Belgrade (Saponjic, Radetic) has recently published
consistent work on Ag-sputtering and colloidal deposition on natural and artificial fibers to
optimize their antibacterial performance in the dark and under light irradiation [44-47]. Other
289
workers are reporting studies on Ag-textiles like Ag-Nylon [48], Ag-cotton [49], and Agcellulose [50].
The search for more efficient, stable and adhesive antimicrobial nanoparticulate films is a
valid research topic. These films are directed to preclude the formation of biofilms leading to
hospital acquired infections (HAI) [1-4]. Films presenting a faster bacterial inactivation are
needed at the present time due to the increasing resistance of pathogenic bacteria to synthetic
antibiotics when administered for long-times. These bacterial biofilms remain stable for very
long periods on a variety of surfaces spreading bacteria by contact in public places or
confined to hospital or schools.
To cover heat resistance surfaces with uniform thin antibacterial films has by Physical
Vapor Deposition (PVD) where the materials are heated in vacuum until they decompose.
The released atoms/species condense on the substrate being this surface at a lower
temperature mainly on heat resistant materials. TiO2, Ag, and Cu films from 6 to 50 nm have
been reported and these thicknesses have been shown to lead an effective bacterial
inactivation under UV and under visible light irradiation. The disadvantages of the PVD
deposition approach are the high investment costs, the high temperatures needed precluding
film deposition on textiles like the polyester and the amount of heat used requiring costly
cooling systems.
By spin-coating semiconductor and metals films with a uniform structure have been
deposited on a variety of substrates using volatile molecular precursors. By CVD Ag-films
have been deposited by Page et al., [50-51] Foster et al., [52] and Dunlop et al. [53].
More recently the application of diverse sputtering methods have become widely spread
to deposit thin metal or oxides (by reactive sputtering) on non-heat resistant substrates like
textiles or thin polymer films like polyethylene (PE) since these substrates resist temperatures
up to about 120C. The sputtering approach to deposited Ag-antibacterial films has been
addresses with the objective to produce surfaces decreasing/eliminating the leaching of Ag
from textiles. There is a growing concern that Ag-nanoparticles in commercial textiles will
spread the Ag-nanoparticles into the environment. Geranio et al., [54] shows that a significant
release of Ag-cations was observed after addition of oxidants to washing formulations of
textile containing Ag. This was investigated also after several washing cycles. Since the
further environmental chain transformation of these Ag-nanoparticles and their toxicity is not
entirely known [55]. Work in this direction addressing the solubility and reactivity of the Agleachates is necessary.
Antimicrobial silver films/textiles have been produced by magnetron sputtering processes
in chamber where traces of H2O/O2 are available. The crystals of Ag present point defects,
crystal impurities and dangling bonds in low or high-density imperfections acting as a pump
for elusive Ag-ions able to inactivate bacteria, fungi and algae. Most of the magnetron
sputtered Ag-films present an effective antibacterial action with coatings < 1 micron [56].
Sputtering silver textiles research is warranted since it aims to reduce or eliminate the
Ag-leaching during washings keeping at the same time the Ag-disinfection performance. Aghospital textiles are in principle able to reduce/eliminate the contamination of public hospitals
from E. coli and MRSA. The level found for these bacteria in many UK hospitals is higher
than the allowed level for the hospital rooms. For example, the contamination of 105
CFU/cm2 was observed in a diabetic wound dressing. But in the vicinity of the patient, a
microbial density of about 102 CFU/cm2 was found. The use of Ag-textiles as described
290
above should be sufficient to decrease significantly the bacterial concentration, since we do

not deal with a high bacterial concentration [57].
Sputtering of Textiles by TiN and TiN/Ag: Kinetics of the Dark and Light
Induced Bacterial Inactivation
(i) To avoid environmental Ag-contamination by bactericide surfaces we have sputtered
TiN films on polyester and evaluated the bacterial inactivation kinetics. Ti was sputtered in
the plasma chamber in N2 atmosphere depositing TiN films loaded on polyester fibers. These
films present absorption in the visible region as shown in Figure 7a. A TiN layer of 50 nm
sputtered for 3 min under low intensity/actinic visible light led to the inactivation within 120
min of 99.99% of bacteria [58].
XPS measurements were carried out on an AXIS NOVA photoelectron spectrometer
(Kratos Analytical, Manchester, UK). The surface atomic concentration was determined from
the peak areas using sensitivity factors [34]. Spectrum background was subtracted according
to Shirley [59]. The XPS peaks of the Ti-species were analyzed by the spectra deconvolution
software (CasaXPS-Vision 2, Kratos Analytical UK).
The formation of TiO2 can be understood in terms of: a) the partial oxidation of TiN takes
place in the presence of an oxygen source due to the residual H2O vapor in the sputtering
chamber at the residual pressure Pr=10-4 Pa. This pressure is representative of about 1015
molecules/cm2, there are sufficient O-radicals available to induce partial oxidation of TiN
films and b) the films also oxidize after the deposition when exposed to air and during the
sterilization process when autoclaving at 121C.
Figure 7a. Diffuse reflectance spectroscopy of TiN-polyester for the sputtering times shown in the
figure captions.
291
Figure 8. X-ray photoelectron spectroscopy (XPS) of the TiN (3 min) in contact with bacteria for 3s: a)
at time = 0 min and b) at time 120 min, showing the shift in the deconvoluted peaks after bacterial
inactivation.
292
Figure 8 presents the TiO2 (Ti2p3/2 doublet) for the polyester when sputtering TiN for 3
min. The peaks in Figure 8a assigned to TiN and Ti2O3 (Ti3+ in the net sense) have been
deconvoluted and TiN shows a peak at 455.62 eV, the Ti3+ doublet at 456.22 eV and the the
Ti4+ doublet at 458.43 eV. Figure 8b) presents the XPS deconvoluted spectra for the TiN
sample at the end of the bacterial inactivation process (120 min). The TiO2 (Ti2p3/2 doublet)
BE shifted to 459.01 eV. Peak shifts 0.2 eV are due to changes in the oxidation states
Ti4+/Ti3+ during bacterial inactivation. The shift of the Ti2O3/Ti3+ doublet to 457.13 eV at 120
min reflects an increase in the reduced Ti3+-species at the end of the bacterial inactivation.
The surface atomic concentration of the fastest TiN (3min) sample at time zero was
determined by XPS as: O1s 10.2%; Ti2p 44.7% N1s 3.5 % and C1s 22.31%.
(ii) In a separate study TiN and TiN-Ag nanoparticulate films on polyester induce
photocatalytic and catalytic inactivation of E. coli [60]. For TiN-Ag samples, bacterial
inactivation was attained within ~15 min. The absorption of the TiN-Ag samples in KubelkaMunk (KM) units was directly proportional to the E. coli inactivation kinetics.
The TiN and TiN-Ag thin films have been sputtered onto polyester heating <130C using two
confocal magnetron-sputtering systems. The polyester samples were 2x2 cm in size. Before
the deposition of the films, the residual pressure Pr in the sputtering chamber was typically Pr
10-4 Pa. The substrate-to-target distance was fixed at 10 cm. The TiN thin films have been
deposited by reactive DC magnetron sputtering (DC) using a 5 cm diameter Ti target 99.99 at.
% (Kurt J. Lesker, East Sussex, UK) in an Ar + N2 atmosphere. The total working pressure
PT=(PAr+PN2) was fixed at 0.5 Pa and the ratio PN2/PT= 4.5 %.
Figure 9 shows the bacterial inactivation of E. coli for TiN/Ag films. The deposition time
of the TiN under layer film was fixed at 3 min while the deposited amount of the Ag was
tuned by changing the deposition time from 10 s to 30 s. A 15 min irradiation period led to a
3log10 reduction (99.9%) of the initial E. coli concentration as shown in the insert. Complete
bacterial inactivation was observed within ~60-90 min. A darker-grey metallic Ag-color was
observed on the polyester with increasing sputtering time. Migration/aggregation of the Agparticles leads to stable agglomerates. The dark grey color corresponds to the Ag2O/Ag0 with
a band-gap (bg) 0.7-1.0 eV and an absorption edge of ~1000 nm.
Figure 10 presents the release of ions from polyester samples sputtered with Ag, TiN-Ag
and TiN. For Ag-sputtered samples up to the 8th cycle the level of Ag-release is seen to be 6
and 8 ppb/cm2. In the case of TiN-Ag samples the Ag-release was observed to decrease with
the number of cycling down to 5 ppb/cm2. Ag-ions were formed by oxidation of the Agloaded polyester surface in contact with reaction media. The release of Ag-ions > 0.1 ppb has
shown significant antimicrobial effect and higher Ag-ions >35 ppb can be toxic to human
cells [1]. The TiN polyester samples maintained a release of ~14 ppb/cm2 of Ti-ions. The
excellent intrinsic biocompatibility of TiN has been well documented in biomedical
applications [51, 61, 62]. A fast bactericidal kinetics and a low cytotoxicity are the two
essential requirements for bactericide surfaces and this is referred to the oligodynamic effect
[1].
293
Figure 9. E. coli survival on TiN-Ag polyester sputtered for different times under light irradiation.
Traces (1): TiN-Ag 3 min/ 20s; (2): TiN-Ag 3 min/ 30s; (3): TiN-Ag 3 min/ 10s; (4): TiN-Ag 3 min/
20s in dark and (5): polyester alone. The inset shows the time for bacterial reduction of 3log10.
20
ion concentration (ppb/cm )
(1) Ag sputtered for 20 s on polyester

(2) Ag sputterd for 20 s on polyester-TiN (3 min)
(3) Ti sputtered for 3 min on polyester
15
(3)
(Ti)
(2)
10
(Ag)
(1)
(Ag)
10
recycling cycles
Figure 10. Ion-coupled plasma spectrometry (ICPS) determination of Ag- ions and Ti-ions released
during the recycling of a) sample sputtered with Ag for 30s (trace 1), b) TiN-Ag (3min-20s) sputtered
sample and c) TiN sample sputtered sample for 3 min (trace 3).
294
Figure 11 shows the ratio found for the XPS signals for the oxidative species (C-O) and
the reduced initial polyester groups (C=C) during the bacterial inactivation/oxidation on a
TiN-Ag (3min-20s) and a TiN sputtered sample. The increase of the surface O is due to the
appearance C-OH, C-O-C and carboxyl species as the E. coli inactivation time progresses
[63]. At the same time, the total C-content decreases with reaction time due to bacterial
inactivation and this is monitored by the progressive decrease of the C-C signals as a function
of time. The ratio of the peaks area of the C-C species including the reduced C-forms C=C,
C-H) at 285 eV and the deconvoluted oxidized C-forms of C-OH, C-O-C and carboxyl
functionalities at 286.1 eV, 287.0 eV and 289.1 eV respectively [64] is plotted a s a function
of time in Figure 11. The increase of this ratio C-OH + C-O-C + carboxyl/C-C is shown in
traces 1 and 2 up to 180 min.
Figure 11. Ratio of oxidized carbon and reduced carbon (C-O/C=C) on TiN-Ag (3min-20s) and TiN (3
min) during E. coli inactivation under actinic light.
Sputtering of Textiles by TiON and TiON/Ag Composite Antibacterial

Surfaces, Testing and Surface Characterization
(i) New evidence has been reported for TiON sputtered polyester surfaces activated by
sunlight irradiation leading to the accelerated bacterial inactivation in the minute range [65].
The objective of the present study is to report on solar induced bacterial inactivation by
sputtered TiON films using a laboratory scale solar simulator. These TiON films avoid the
adverse environmental effects caused by Ag leaching out of silver films as reported by
Geranio et al., [54].
295
Irradiation of the samples during the bacterial inactivation was carried out with a Suntest
cavity provided with Xenon lamp with an emission spectrum between 320 and 700 nm.
Figure 12 shows the bacterial inactivation kinetics as a function of the TiON sputtering time.
The bacterial inactivation becomes faster at longer sputtering times up to 4 min. Beyond 4
minutes sputtering time the reverse trend is observed in Figure 12 for sputtering times of 5
and 10 min. The slowing down in the bacterial inactivation for samples sputtered above 4 min
presenting a 70 nm layer thickness may be due to thicker coatings leading to bulk inward
diffusion of the charge carriers diffusing from the TiON decreasing the amount of active sites
held on the surface in exposed positions interacting with the bacteria. Besides these
considerations, longer sputtering times induce TiON inter-particle growth decreasing the
TiON contact surface area with bacteria. A solar simulator for Hereaus GmbH, Hanau,
Germany was used to irradiate the samples with an overall power of 92 mW/cm2 with light
distribution wavelength distribution resembling solar irradiation emitting at wavelengths
between 320-800 nm.
10
10
10
10
10
10
10
(7)
E. coli (CFU/ml)
(6)
(1) (2) (3) (4)
(1) TiON 4 min

(2) TiON 5 min
(3) TiON 10 min
(4) TiON 3 min
(5) TiON 2 min
(6) TiON in dark
(7) polyester alone
(5)
60
120
180
time (min)
Figure 12. E. coli inactivation on TiON sputtered on polyester for: (1) 4 min, (2) 5 min, (3) 10 min, (4)
2 min, (5) 1 min, (6) TiON 4 min in dark and (7) polyester alone and irradiated by a Suntest Xenon
lamp (320-700 nm). The reactive gas flow composition: Ar 90%: N2 5%: O2 5% and total P = 0.5 Pa.
E. coli was obtained from the Deutsche Sammlung GmbH (DSMZ) ATCC23716,
Germany. The polyester fabrics were sterilized by autoclaving at 121C for 2h. The 20 L
aliquots of the bacterial culture with a concentration of ~106 CFU mL-1 in NaCl/KCl were
placed on the polyester fabric. These polyester samples were placed on Petri dish provided
with a lid to prevent evaporation. After each determination, the fabric was transferred into a
sterile 2 mL Eppendorf tube containing 1 mL autoclaved NaCl/KCl saline solution. This
solution was subsequently mixed thoroughly using a Vortex for 3 min. Serial dilutions were
made in NaCl/KCl solution. The 100 l sample of each dilution was pipetted onto a nutrient
296
agar plate and then spread over the surface of the plate using the standard plate method. Agar
plates were incubated lid down, at 37C for 24h prior to the counting of the bacterial colonies.
The bacterial data reported were replicated three times. The statistical analysis of the
experimental values was compared by one-way analysis of variance and with the value of
statistical significance.
Figure 13 shows the TiON plasmon resonance occurring in the UV region in agreement
with a recent study recently by Subramaniam et al., [66] The optical absorption of the TiON
samples increases with longer sputtering times up to 4, 5 min. Increasing the sputtering times
from 1 to 5 min in Figure 13 lead to TiON samples with a higher optical absorption due to the
introduction of N-interstitial sites doping the TiO2 with O-vacancies. This in turn leads to a
larger amount charge transfer sites in the visible region [67]. Samples sputtered for 4 ad 5 min
are seen to present a similar optical absorption indicating saturation of the polyester surface
by the sputtered TiON layers. This suggestion seems to be confirmed by the lack of further
growth in the optical absorption by the samples sputtered for 10 minutes showing additionally
a different shape for the TiON spectra. This is due to the non-linear optics introduced by the
high density of TiON layers on the polyester surface not following quantitatively the normal
optical absorption increase beyond the saturation concentration [68]. Diffuse reflectance
spectroscopy (DRS) was determined using a Perkin Elmer Lambda 900 UV-VIS-NIR
spectrometer. The absorption of the samples was plotted in Kubelka-Munk (KM/S) units.
0.8
(4)
(5)
0.6
(3)
KM/S
0.4
(2)
0.2
(1)
0.0
-0.2
200
300
400
500
600
700
Wavelengh (nm)
Figure 13. Diffuse reflectance spectra of TiON samples sputtered on polyester for different times: (1) 1
min, (2) 2 min, (3) 4 min, (4) 5 min and (5) 10 min.
By Inductively coupled plasma mass spectrometry (ICP-MS) spectrometry, the K, Naions released by the bacteria within the 40 min inactivation time was determined and the
results shown in Figure 14. The K+-ions leak at a relative low concentration through the
297
2.5
ions concentrations (ppb/cm )
2.0
(1) K -ions release

+
(2) Na -ions release
Ti-ion concentration (ppb/cm2)
bacterial cell wall membrane becoming more permeable up to 30 min. These K+-ions are
known to be important regulators of the cell-wall redox potential. The Na+-ions present at a
higher initial concentration leaked at a higher rate up to 40 min due to their smaller size
compared to the K+-ions [69]. The cell wall permeability increase of E. coli preceding
inactivation occurs within 40 min, the time of bacteria inactivation as shown in Figure 12
[70]. A FinniganTM ICPMS was used for these experiments equipped with a double focusing
reverse geometry mass spectrometer presenting an extremely low background signal and high
ion-transmission coefficient. The spectral signal resolution for the Na, K and Ti-ions was
1.2x105 cps/ppb and the detection limit of 0.2 ng/L.
Ti-release
4.5
3.0
1.5
1.5
1.0
(2)
0.0
0
recycling cycles
0.5
(1)
0.0
10
20
30
40
time (min)
Figure 14. Ion-coupled plasma mass spectrometry (ICP-MS) determination of the leakage of 1) K+ and
2) Na+-ions through the E. coli cell wall during bacterial inactivation by a TiON 4 min samples
irradiated by a Suntest solar simulator. The insert shows the Ti-ions release during the sample recycling
after 1, 3, 5, and 8 E. coli inactivation cycles.
(ii) A further study involving E. coli inactivation on TiON-Ag films sputtered on

polyester by DC and DCP has been reported out of our laboratory [71]. A photo-induced
charge transfer from Ag2O and TiO2 is suggested for the interfacial charge transfer
mechanism (IFCT) between Ag2O and TiO2 formed after the oxidation of the top-most-layers
of the sputtered TiON-Ag. Figure 15 shows the atomic deposition rate of TiON films as a
function of the O2/N2 ratio. The total pressure PT = (PAr+ PN2 + PO2) was fixed at 0.5 Pa and
after optimization the fastest bacterial inactivation kinetics and under a gas flow Ar 90%: N2
5%: O2 5%. Sputtering for 4 min leads to layers ~70 nm thick. This is equivalent to 350 layers
each containing 1015 atoms/cm2 being deposited at a rate of ~1.5x1015 atom/cm2s. The TiON
was sputtered first for 4 min followed by Ag-sputtering for 30s. The atomic deposition rate
was observed to be a function of the O2/N2 ratio.
298
16
Atomic rate deposition (atom/cm .s)
9.0x10
16
8.5x10
16
8.0x10
16
7.5x10
16
7.0x10
16
6.5x10
0.0
0.5
1.0
1.5
2.0
2.5
O2/N2 ratio
Figure 15. Atomic deposition rate of TiON films on polyester as a function of the O2/N2 ratio. Ar gas
flow was 90% at a working pressure 0.5 Pa.
Figure 16. Visual presentation of the samples of sputtered TiON and TiON-Ag textiles within 4
minutes: A) color variation as a function of the distance of the Ti-target and the polyester sample, B)
color variation as a function O2/N2 ratio for TiON samples C) color variation of TiON-Ag samples with
different Ag wt%/ wt polyester.
299
The colors of the TiON samples sputtered for 4 min are shown in Figure 16, row A.
These colors are seen to be a function of O2/N2 ratio. A higher content of O2 has been
reported also to increase the biocompatibility of the TiON samples.
The samples TiON 4 min sputtered with Ag for 20-40s in Figure 16(B) became darker for
TiON samples sputtered for longer times. The wt% Ag /wt polyester of the TiON-Ag of
samples sputtered Ag for 20, 30 and 40s are shown in Figure 16(C).
Figure 17a presents in the left hand side the almost continuous dark TiON-Ag (4min-30s)
deposit on the polyester fiber. The right hand side image with a higher magnification of 100
nm shows the immiscibility of the Ag-dark coating and the TiON coating grey layers. The
Ag-particles present sizes between 20-40 nm within a TiON-Ag layer with a width of 70 10
nm. Ag/Ag2O particles of 20-40 nm will not pass through the bacterial cell wall having
protein porin pores with a diameter of 1.1-1.5 nm [72]. This confirms once more that
Ag bacterial inactivation is due the Ag-ions having sizes <1 nm, and not to the Agnanoparticules.
Figure 17a. Left hand side: Transmission electron microscopy of a TiON-Ag (4min-30s) DC-sputtered
sample showing the continuity of the sputtered TiON-Ag layer around the polyester fiber. Right hand
side: dense continuous Ag-layers being immiscible with the grey TiON layer. (P=polyester and
E=epoxide).
Figure 17b. Surface of the TiON-Ag (4min-30s) sample taken by Bright Field (BF) showing Ti and Ag
at the current beam position.
300
Figure 17b shows the image of a TiON-Ag (4min-30s) sample in Bright Field (BF). The
immiscibility of the Ag and Ti on the sample surface is readily seen at the current beam
position.
Figure 18 presents the release of Na+ and K+ during the bacterial inactivation from a
TiON-Ag (4 min-30s) sample. The K+-ion exists universally in bacteria regulating the
potential for the transfer of-ions across the bilayer membranes. The K-ions leak at a low rate
from the bacterial cell as the cell wall becomes more permeable up to 30 min. The Na+-ions in
Figure 18 are seen to leak at a faster rate compared to K+-ions due to their smaller size. The
rate and pattern of the leaking in Figure 18 is different to the Ti and Ag-leakage reported
during bacterial inactivation for the same system in Figure 12. The leakage of K+ and Na+
increases after 30 min due to the more advanced state of decomposition of the cell bacterial
envelope [73]. The loss of cell viability is consistent with the decomposition of the cell-wall
membrane and the time of the leakage of intracellular K+ and Na+. Cell walls are repaired
during the culture of cells on the agar plates. This leads to a different rate of decomposition of
the outer cell membrane [74].
The possible mechanism of bacterial inactivation for the TiON-Ag film can be suggested:
AgOH on the film surface by contact with air. The AgOH decomposes spontaneously to
Ag2O (eq3):
2AgOH Ag2O + H2O (pk= 2.87)
(3)
This Ag2O is stable at pH 6-7 where the inactivation of E. coli proceeds. Light irradiation
photo-activates Ag2O with 1.46 < bg < 2.25 eV (77) as noted next in eq(4):
4.0
(1) Na
+
(2) K
3.5
3.0
(1)
2.5
2.0
1.5
1.0
(2)
0.5
0.0
10
20
30
40
50
60
time (min)
Figure 18. Ion-coupled plasma mass spectrometry (ICP-Ms) determination of the leakage of 1) Na+ and
2) K+- ions through the E. coli cell-wall envelope during bacterial inactivation by a TiON-Ag (4min30s) sample under light.

Ag2O + light Ag2O h+ + Ag2O e-
301
(4)
The Ag2O/TiO2 transfer of charges we have to consider the position of the energy bands
of Ag2O and TiO2. Under visible light irradiation, the transfer of charge from Ag2O to TiO2 is
thermodynamically favorable because the position of the Ag2Ocb at 1.3 eV NHE at pH 0 and
the vb of Ag2O +0.2 V NHE at pH 0 [75] lies above the TiO2cb at -0.1 V vs NHE and the vb
at +3.2 V. Under light an interfacial charge transfer process (IFCT) may proceed between
Ag2O and TiON [75,76]. The Ag2Ocb transfer electrons to the TiO2cb in an energetic
favorable process and this will hinder the electron-hole recombination in Ag2O. We suggest
that the transfer of Ag2O electrons to O2 due to this increased charge separation plays an
important role in the photocatalytic activity leading to bacterial inactivation.
We suggest a mechanism in which the Ag2O in eq(1) reacts as shown below in eq(5):
Ag2O- 2Ag0 + O2-
(5)
The O2 in eq(5) would promote at later stages reactions (5,6) producing highly oxidative
radicals, while the h+ in eq(4) reacts with H2O as noted in eq(6). This reaction runs parallel
with eq(5) generating OH radicals or other highly reactive oxidative radicals by way of the
Ag2Ovb h+ (see eq(4))
h+ + H2O OH + H+
(6)
2e- + 2H2O + O2 2OH + 2OH-
(7)
ZrN/Ag Textiles and ZrNO/Ag Composite Antibacterial Textiles;

Design, Sputtering, Testing, and Characterization
Ag-ZrN films were deposited on polyester by direct current pulsed magnetron sputtering
(DCP) in Ar+N2 atmosphere. ZrN on the polyester surface interacts with Ag leading to AgZrN films. These composite films were more active in E. coli inactivation compared to the
Ag-films by themselves. Sputtering Zr in N2 atmosphere presented no antibacterial activity by
itself when applied for short times < 1 min.
Figure 19 shows an E. coli inactivation time of 1.5 h on Ag/Zr polyester sputtered for 20s
presenting a wt %Ag / wt polyester of 0.0105 and a Zr wt% / wt polyester of 0.0012 as
determined by XRF The pattern of trace 5 in Figure 19 indicates that E. coli inactivation is a
complex process. This is sample presented the optimal ratio of Ag wt/Ag particle size. The
Ag-sites held in exposed positions active in the E. coli inactivation were above other
sputtering formulations. Ag sputtered alone as a control experiment in Figure 19 indicates an
E. coli required an inactivation time of ~9 h.
Figure 20 shows that for samples sputtered > 20s, the E. coli inactivation kinetics became
larger compared to samples sputtered for times above 20s since the Ag-agglomerates becomes
bigger but the catalytic activity per exposed atom decreased due to the Ag-agglomeration
process. At times < 20s, there was not enough Ag on the polyester to mediate the E. coli
inactivation as detected on the polyester by the X-ray fluorescence data (XRF).
302
Figure 21 presents the contact angle for different Ag-ZrN samples on Si-wafers. No
polyester was used for the contact angle measurements since the water droplet disappeared at
zero time. Figure 21 shows that samples sputtered for 5 s at 50 mA presented a contact angle
of 64.4 at time zero. This contact angle decreased with the contact time on the Si-wafer
surface due to the hydrophobic to hydrophilic transition ending up after15 min and leading to
an hydphobic-hydrophilic type of surface. The second row in Figure 21 shows that Ag-ZrN
samples become more hydrophobic at time zero after 20s sputtering (initial contact angle of
73.3). A contact angle of 101 was observed at time zero for 80 s sputtered samples, since
the samples became more hydrophobic due to the higher amount of Ag on the Si-wafers.
Figure 19. E. coli inactivation by a Ag-ZrN confocal sputtered DCP catalyst in an Ar 10% N2 gas
mixture and applying 300 mA.
Figure 20. Inactivation time of E. coli on Ag-ZrN polyester as a function of the deposition time by DCP
sputtered at 300 mA.
303
Ag-ZrN, 50 mA, 5s
0 min: 64.4
10 min: 43.8
15 min: 36.7
10 min: 46.2
15 min: 25.9
10 min: 63.6
15 min: 42.1
Ag-ZrN, 50 mA, 20s
0 min: 77.3
Ag-ZrN, 50 mA, 80s
0 min: 101.0
Figure 21. Contact angle (CA) for Ag-ZrN composites on polyester.
(ii) In a more recent study [77] the co-sputtering of ZrNO and Ag2O was seen to enhance
the E. coli bacterial inactivation kinetics compared to the sequential sputtering of ZrNO and
Ag addressed above when sputtering ZrN-Ag composites. The amounts of Ag-ions released
during bacterial inactivation were < 5 ppb/cm2 and well below the Ag cytotoxic levels. Since
no cytotoxicity was introduced during the bacterial inactivation process when a ZrNO-Ag
sputtered with Zr for 90s and Ag for 10s in an N2+O2 atmosphere, the disinfection was seen
to proceed within 45 min through an oligodynamic effect.
Figure 22 presents the sample DRS spectra in Kubelka-Munk units. The UV-vis
reflectance rough data cannot be used directly to assess the absorption of the loaded polyester
because of the large scattering contribution of polyester to the reflectance spectra. Normally it
is assumed a weak dependence of the scattering (S) on the wavelength when taking DRS
spectra. The KM/S values in Figure 22 allow the correlation of the spectral intensity of the
ZrNO-Ag co-sputtered and of the ZrNO samples spectra with the bacterial inactivation
kinetics. The increase in reflectance in the co-sputtered spectra compared to the sequentially
sputtered layers in Figure 22 is due to the different microstructure of the ZrNO-Ag
photocatalyst in both cases as shown next in Figure 23 by TEM.
The red shifted absorption in the nanoparticles of ZrNO-Ag leads to a red tail in the DRS
spectra of the nanoparticles in Figure 22 at ~400 nm due to the localized surface resonance of
the Ag-plasmons. Gunawan et al., [23] recently reported that the oxidation of Ag0 to Ag2O
(Ag+) is a reversible reaction increasing the surface plasmon resonance.
The electron microscopy (TEM) of ZrNO-Ag (90 s) co-sputtered sample is discussed
next. Figure 23 presents the TEM of a co-sputtered ZrNO-Ag (90 s) sample on polyester. In
the left-hand side the Zr and Ag are shown to be immiscible when co-sputtered on the
polyester fibers. The right-hand side in Figure 23a shows the Zr and Ag-nanoparticles
contrasted by high angular annular dark field (HAADF). The sizes of the ZrO2 and Ag
304
nanoparticles in the co-sputtered ZrNO-Ag (90 s) sample were respectively 80-130 nm and 815 nm.
(1) ZrNO-Ag cosputtered for 150 s
3
(1)
KM/S
2
(2)
(3)
(4)
0
0.75
(1)
(1) ZrNO sputtered for 150 s

(2)
KM/S
0.50
0.25
(3)
(4)
0.00
200
300
400
500
600
700
800
Wavelengh (nm)
Figure 22. Diffuse reflectance spectra for ZrNO and ZrNO-Ag sputtered on polyester for times as
indicated in
the Figure legends.
Figure 23. Left-hand side: Transmission electron microscopy of a co-sputtered ZrON-Ag (90 s) sample
(amplification 28k) Right side: the same sample in high angular annular dark field (HAADF)
representation.
305
Due to its size, the Ag-nanoparticles are not able to penetrate to bacteria core through the
bacterial porins with diameters of 1-1.3 nm and only Ag-ions are able to diffuse through
bacterial porins leading to DNA damage and finally to bacterial inactivation [72,77].
Figure 24 shows the Ag- and Zr-ions concentrations released during the reuse of ZrNOAg (90 s) sputtered samples. The Ag-ions release during 8 cycles was < 5 ppb/cm2, which is
below the allowed cytotoxicity levels of 35-90 ppb/cm2 for Ag[79]. Therefore, the bacterial
inactivation mediated by ZrNO-Ag (90 s) sample does not introduce cytotoxicity but proceeds
through an oligodynamic effect comprising fast bacterial inactivation kinetics and acceptable
cytotoxycity [1].
The surface atomic percentage concentration of elements in the ZrNO-Ag (90s) sputtered
samples after being contacted 3s with bacteria were: O1s 8.8%; N1s 2.3%; C1s 54.9%; Zr3d
2.8% and Ag3d 35.4%. These percentages did vary less than 10% during the 45 min reaction
leading to the total bacterial loss of viability. Therefore, the rapid destruction of
decomposition products during the photocatalysis allows for repeated bacterial inactivation by
the ZrNO-Ag (90s) sputtered samples.
TaON and TaON/Ag Composite Antibacterial Surfaces

This study reports the design, preparation, testing and surface characterization of uniform
films deposited by sputtering Ag and Ta on polyester in the presence on N2 and O2 to evaluate
the E. coli inactivation. Co-sputtering for 120s Ta and Ag in the presence led to the faster E.
coli inactivation by a TaON/Ag sample within ~40 min under visible light irradiation. A
mechanism of interfacial charge transfer (IFCT) from the Ag2O conduction band (cb) to the
lower laying Ta2O5 (cb) is suggested. The TaON/Ag sample microstructure was characterized
by contact angle (CA) and by atomic force microscopy (AFM) [78].
7.5
(1) Zr ions
(2) Ag ions
6.0
4.5
(1)
(2)
3.0
1.5
0.0
reusing cycles
Figure 24. Ion-coupled plasma mass spectrometry (ICP-MS) determination of Ag-ions and Zr-ions
released from a co-sputtered ZrNO-Ag (90 s) sample within the E. coli loss of bacterial viability.
306
The bacterial inactivation becomes faster for increasing TaN-sputtering times. Figure 25a
shows that sputtering TaN for 120 s inactivated bacteria within 300 min. Figure 25a, trace 5)
shows that in the dark no bacterial inactivation on TaN/Ag-polyester. TaN/Ag shows a faster
bacterial inactivation compared to TaN films and inactivate E. coli within 120 min for a 120s
co-sputtered sample. Figure 25a, traces 3) shows bacterial inactivation for TaN/Ag surfaces
co-sputtered for 60s. Since the E. coli inactivation time for samples sputtered for 120s
becomes shorter, a 60s sputtering time did not deposit sufficient TaN/Ag layers or did not
allow a full light absorption of the incident visible light. A sample of TaN/Ag co-sputtered for
120 shows an inactivation time of 120 min. The co-sputtered TaN/Ag (150 s) sample (Figure
25a, trace 2) is seen to inactivate E. coli at longer times compared to the TaN/Ag co-sputtered
sample for 120 s (Figure 25a, trace 1). This is due probably to: a) bigger Ag-clusters
hindering the diffusion of charges between TaN and the Ag layers, b) a decrease in the
number of surface catalytic sites available for bacterial inactivation, and c) an excess of Ag
acting as recombination centers for the photo-induced charges on the sample surface.
Figure 25b shows the bacterial inactivation kinetics on TaON/Ag-polyester under
O2/N2/Ar atmosphere. A 6log10 (99.99%) reduction in the bacterial concentration was
observed within ~40 min for the TaON/Ag co-sputtered sample for 120s. Sequential
sputtering of Ta and Ag lead to a slower bacterial inactivation than the co-sputtered samples
as shown in Figure 25b, trace 4). The shorter bacterial inactivation kinetics reported on Figure
25b compared to Figure 25a can be rationalized considering that reactive sputtering in the
presence of O2 introduces in the TaN ionic metal-oxygen species in a matrix of covalent
metal-nitrogen bonds [80]. The polarity introduced by these metal-oxygen species is due to
the van der Waals forces comprising: permanent dipoles, induced dipoles and hydrogen
bonds. The surface energy of the TaON-Ag surfaces (Figure 25b) is higher than the one
available on the TaN/Ag (Figure 25a) surface due to the presence of ionic Ag-O metal oxygen
species. Figure 2c shows that Ag sputtered on polyester does not lead to complete bacterial
inactivation even after 6 h of irradiation. Figure 25d shows that TaON samples sputtered on
polyester for 120 s inactivated bacteria within 90 min. This is two times longer than the time
required by TaON/Ag due to an interfacial charge transfer between Ag and TaON. E. coli
inactivation time as a function of the TaON/Ag layer thickness showed that a 130 nm coating
leads to the shortest bacterial inactivation. For very thin TaON/Ag thicknesses below 50 nm,
the microstructure of the film seems not to be effective in inducing fast bacterial inactivation
kinetics.
Figure 26a shows the atomic force microscopy (AFM) for a sputtered TaON (120 s)
sample. Non-uniform TaON grains with sizes of 40-60 nm are observed. Figure 26b shows
the AFM image for a co-sputtered TaON/Ag (120 s) sample with grain sizes of 70-100 nm.
The root mean square (rms) roughness for the samples TaON and TaON/Ag were
respectively 2.2 and 2.7 nm. An increase in roughness leads to higher contact angle reducing
the polarity and the total surface energy. Increased sample rugosity allows for a better
adhesion of the Ag-ions leading to the bacterial inactivation [28,29].
b)
a)
6
10
10
10
10
10
10
E. coli (CFU/ml)
(5)
10
10
10
(4)
10
(3)
(2)
(1)
(4)
10
(3)
(1) (2)
10
10
60
120
180
240
10
300
60
120
180
c)
6
10
10
10
10
E. coli (CFU/ml)
240
(6)
300
d)
(5)
10
10
10
10
Ag sputtered on polyester for 120 s in dark

Ag sputtered on polyester for 20 s
10
10
10
(1)
10
(2)
(3)
(4)
10
307
60
120
180
time (min)
240
300
10
60
120
180
240
300
time (min)
Figure 25. E. coli inactivation on TaN, TaN/Ag, TaON and TaON/Ag sputtered on polyester for
different times under light (360-700 nm) with an output of 4 mW/cm2. 25a: (1): TaN/Ag co-sputtered
for 120 s, (2): for 150 s, (3): for 60 s, (4): TaN sputtered for 120 s and (5): TaN/Ag co-sputtered for
120s in dark, 25b (1): TaON/Ag co-sputtered for 120 s, (2): for 150 s, (3): for 60 s, (4): TaON/Ag
sequential sputtered for 120 s TaON / 40 s Ag and (5) TaON/Ag co-sputtered for 120 s in dark. 25c: Ag
sputtered on polyester for different times under light. 25d: (1): TaON for 120 s, (2): TaON for 150 s,
(3): TaON for 60 s, (4): TaON for 20s, (5): TaON sputtered on polyester for 120 s in dark and (6)
polyester alone irradiated under visible light.
The contact angles (CA) with TaON and TaON/Ag polyester as a function of time after
the bacterial inactivation are shown in Figures 27a and 27b. The TaON sample after 2s shows
a CA of 80 and after 6s of 12. The water droplet disappeared after 10s. This means that the
TaON-sample becomes completely hydrophilic after 10s and eliminates any hydrophobic
residues left by bacterial inactivation.
A water droplet on the polyester alone was observed to disappear by contact with the
fabric. Although the polyester is hydrophobic, the polyester has a high amount of void
areas/porosity promoting water penetration through the polyester microstructure. The
sputtering TaON decreases the void areas leading to water penetration and concomitantly
increasing the sample hydrophobicity. The amount of O2 plays a role in the contact angle of
the surface. Studies on nitrides/oxynitrides have reported that O2 photo-adsorption introduces
highly polar and electronegative groups compared to N2 changing the electro-negativity and
electron density of nitrides [78,79].
308
Figure 26. Atomic force microscopy for polyester samples: a) sputtered with TaON for 120s time and
b) co- sputtered TaON/Ag for 120 s.
Figure 27b shows the CA of the water droplet on the surface of co-sputtered TaON/Ag
polyester samples. A slower decrease of the CA with time was observed on the TaON sample
in Figure 6a. The CA varied from an initial value of 108 at 10s to 14 within 300s and
disappears completely after 310s. The surface energy of Ta2O5 controls the surface CA. The
addition of Ag increases the hydrophobicity in the TaON/Ag film surface leading to a longer
to attain complete hydrohilicity.
The photo-induced interfacial charge transfer from the Ag-layers to the TaON layers will
be discussed in this section. Visible light is absorbed by the narrow band semiconductor
Ag2O up to 880 nm and the wideband semiconductor Ta2O5 absorbs UV-light < 310 nm (4
eV). In Figure 28, a mechanism for electron injection for the charge transfer from Ag2O into
Ta2O5 is suggested. This mechanism considers the potential energy of the semiconductor
bands. When the sputtered Ag layer is exposed to air, the water vapor in the air leads to the
formation of surface AgOH. The AgOH has been reported to decompose spontaneously to
Ag2O as shown before in eq(3).
The electron injection from Ag2O to the Ta2O5 is thermodynamically favorable. The
Ag2Ocb at -1.3 eV NHE lays above the Ta2O5 cb at 0.4 eV NHE. The potential 1.7 eV
difference in provides a considerable driving force inducing a fast electron injection from
Ag2O into Ta2O5. The Ag2O transfers the majority of the electrons to the Ta2O5cb hindering
309
the e-/h+ recombination in Ag2O. The values for the potentials for the cb for both
semiconductors are only indicative, since in quantum size nanoparticles, the band energy
shifts have been reported to higher potentials [80]. The reductive character in the quantum
size Ag2O particles proceeds at a higher energy level than -1.3 eV NHE.
80
108
12
94
14
Figure 27. Contact angle water-droplets as a function of contact time for: a) TaON sputtered on
polyester for 120s and b) TaON/Ag co-sputtered on polyester for 120 s.
Under visible light irradiation Ag2O gives raise to the charge separation
Ag2O + visible light h+ + e-
(8)
Ag2O + e- 2Ag0 + O-
(9)
Figure 28. Scheme for the photoinduced interfacial charge transfer (IFCT) from Ag2O to Ta2O5 under
visible light irradiation.
310

Ag2O + e- 2Ag0 + 1/2O2
(10)
The cbe- become available to reduce oxygen in eq.(9). The photo-induced electron
eq.(10) lead to silver atoms and additionally produce O2- eq(11): e- + O2 O2-
ACKNOWLEDGMENTS
We thank the EPFL for financial support of this work and COST Actions MP1106 and
MP1101for interactive discussions during the course of this study.
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ISBN: 978-1-63117-262-5
Chapter 11
FUNGAL DETERIORATION OF AGED TEXTILES

Katja Kavkler1,*, Nina Gunde-Cimerman2,3, Polona Zalar2
and Andrej Demar4
1
Restoration Centre, Institute for the Protection of Cultural Heritage of Slovenia,

Ljubljana, Slovenia
2
Department of Biology, Biotechnical Faculty, University of Ljubljana,
Ljubljana, Slovenia
3
Centre of Excellence for Integrated Approaches in Chemistry and Biology of Proteins
(CIPKeBiP), Jamova, Ljubljana, Slovenia
4
Faculty of Natural Sciences and Engineering, University of Ljubljana, Ljubljana,
Slovenia
ABSTRACT
Preservation of historical objects is of the utmost importance for future generations,
as such objects have great social, historical, cultural and educational value. However, the
preservation of organic materials often causes problems, as those involved can have little
knowledge of biological decay. Fungal contaminations in particular can alter the
appearance, and the structural and mechanical properties of an object, which can
consequently prove difficult to conserve or to return to its former state. Most museums
are aware of the importance of the maintenance of the correct environmental conditions
in storage rooms, such as low temperature and low relative humidity. However, some
fungi can still thrive under such conditions, and thus result in long-term contamination
and severe damage to materials. Some fungi can also remain viable in a dormant phase.
The present chapter describes an interdisciplinary approach for mycologists, textile
scientists, and art restorers to better understand the impact of fungi on historical textile
objects. The diversity and frequency of occurrence of different fungal species for each
selected material (cotton, linen, silk, wool) is here investigated, and the available
literature is reviewed. Additionally, there is often a lack of complete information about
the history of many objects, and a limit to the sample size that can be available for
analysis. On this basis, the impacts of selected fungal species are further examined here
*
E-mail: katja.kavkler@rescen.si.
316
Katja Kavkler, Nina Gunde-Cimerman, Polona Zalar et al.

by inoculation of pure cultures on artificially prepared laboratory samples, with
incubation in a controlled environment. Cotton is used as a representative of cellulose
material, and wool as a representative of proteinaceous material, and these are analysed
using non-destructive analytical methodologies, including tensile tests, scanning electron
microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy. An
overview of the textile changes detected at the levels of the surface morphology and the
supermolecular structure of these textile fibres is thus presented. It can be concluded that
in comparison to non-aged textiles, aged textiles are at greater risk when exposed to
fungal contaminations, and so they require additional care at the conserving institutions.
As changes in the structure and properties of textile fibres increase with longer incubation
periods after fungal contamination has occurred, museum workers need to regularly
examine stored objects for uncommon stains or visible fungal growth. As well as such
visual inspections, nano- and microtechnologies need to be implemented as new
standards of damage documentation.
INTRODUCTION
Conservation of objects that define our cultural heritage is the main aim of museums and
related institutions. This work is of great importance, as the objects can have social, historical,
cultural and/or educational value [1]. Cultural heritage is a crucial source of the common
identity for mankind. Specifically in Europe, the cultural development through the centuries
has left a heritage that is nowadays often kept in indoor and outdoor facilities at
archaeological sites and museums.
Artwork textiles are usually preserved and stored in museums, and these are common to
all human societies, and represent an important aspect of the cultural heritage. Historical
textile objects that are conserved in museums include clothing, accessories, furnishings,
tapestries, decorations, and many more. Although these were used by people in historical
times, they were not designed to last a long time, and thus often only a few pieces have
remained in their original state from different historical periods. More objects have remained
preserved since the baroque times than from earlier times, while few conserved objects are
recovered from several-thousand-year-old archaeological finds. Therefore these are precious,
and they need to be conserved for future generations, without allowing major changes to the
materials, or to their appearance and mechanical characteristics.
Deterioration of materials is an unavoidable part of the life-cycle of preserved objects,
although people working in the field of conservation of cultural heritage attempt to interrupt,
or at least to slow down, this process. Fungi are the most significant invaders of materials,
and they can cause major changes as a consequence of their growth. The aim of the present
chapter is to better define the influence of fungi on textile materials, from the perspective of
three different fields of science: textile sciences, mycology, and conservation. To present this
interdisciplinary approach, this chapter is divided into four main sub-chapters, which include:
(i) an introduction to the theme; (ii) the fungal deterioration of museum textiles; (iii) an
analysis of laboratory textile samples that have been artificially inoculated by fungi; and (iv)
short concluding remarks.
317
2. FUNGAL DETERIORATION OF MUSEUM TEXTILES

2.1. Fungi on Historical Textiles
Objects stored and displayed in museums and in similar institutions have different
histories and are therefore in different states of preservation. In the several decades, or maybe
hundreds of years, of their existence, they have been subjected to the influences of different
and various external factors, such as UV irradiation, oscillations in temperature and relative
humidity, mechanical and chemical damage, and (micro)biological influences. As organic
polymers, textile objects are prone to deterioration through different processes that can occur
during long-term storage, due to the above-mentioned external factors. All of these factors
can cause oxidation, hydrolysis, polymer-chain scission, and breaking of intramolecular
bonds [2-5]. Through these processes, objects lose their value as historical specimens, and can
finally completely disintegrate. Oxidative processes and hydrolysis of the polymers in natural
fibres result in the breakage of intermolecular and intramolecular bonds, and this facilitates
the penetration of microbes or their enzymes.
The above-mentioned changes influence the structure of a fibre and can allow its
decomposition by enzymes that are secreted by different types of microorganisms [6,7].
Organic materials are especially affected. Fungi represent one of the most important risk
factors for degradation and damage of textile objects that are part of our cultural heritage
(e.g., museum artifacts), as they are important decomposers of textile fibres of different
origins (i.e., plant, animal) and they can attack all kinds of macromolecules, such as cellulose
and protein, and even synthetic fibres [2]. Cellulosic fibres are supposed to be very sensitive,
whereas proteinaceous fibres, especially silk, tend to be more resistant to microbial attack [2,
8, 9].
Fungi are transmitted via spores. For their germination and further growth, spores need a
source of nutrition and oxygen, and appropriate temperatures and humidity. The growth of
fungi is the most important aspect here, and it involves secretion of enzymes into the fibres
and absorption of the resulting degraded products through the hyphae [10,11]. The
degradation of textiles by fungi can be the result of different processes, which include: (i)
various enzymes can breakdown the macromolecules, and subsequently metabolise the
products; (ii) fungi also produce various kinds of primary and secondary metabolites, such as
acids, oligopeptides, dyes and volatile organic compounds, and these can damage textiles or
change their appearance; (iii) fungi can cause physical disruption of the material via hyphal
penetration; and (iv) fungi can increase the water retention of a material, subsequently
allowing other microbes to colonise it. In summary, fungal colonisation not only leads to an
unpleasant mouldy odour, but also to changed appearance, pigmentation and texture, and/or
altered mechanical and structural characteristics, which will reduce the historical value of an
object [1,2,12,13].
Fungi that can infest cultural heritage objects have been relatively well documented over
the last decades, and particularly those involved with stone, wood, paintings and paper
biodeterioration (reviewed by [14]). However, there are only a few reports on fungi that can
cause deterioration of historical textiles [9,15-20]. Amongst these studies, there are also a few
reports on fungal species on archaeological textiles [17,18,20] and historical textiles
[9,16,17], and recently also on synthetic textiles stored as museum exhibits of modern times
318
[2]. Fungi have mainly been isolated from cellulosic substrates. Fungal genera reported in
these studies have included: Alternaria, Aspergillus, Chaetomium, Ctenomyces, Fusarium,
Memnoniella, Myrothecium, Neurospora, Penicillium, Scopulariopsis and Stachybotrys [1619]. Most of these can grow on historical cellulosic fibres; however, Aspergillus,
Chrysosporium, Ctenomyces, Fusarium, Penicillium, and Trichoderma have been reported
from historical proteinaceous fibres [17,19], and dermatophytic fungi (Trichophyton and
Microsporum) from historical wool [19].
To the best of our knowledge, only a few investigations have been performed on fungal
deterioration of historical textiles. These have mainly been part of more extensive
investigations of historical and archaeological textile objects [17,18,21-24]. Only a limited
number of investigations have been carried out on buried contemporary materials [20,25,26].
The fungi that have been isolated belong mainly to xerophilic species of the genera
Aspergillus and Penicillium. Additionally Cladosporium species have been commonly
isolated, as well as Alternaria spp., Chaetomium spp. and Trichoderma spp. (Table 1).
Table 1. Cultural heritage objects infected by fungi and organised according to
substrate material, as an overview of the literature. The period of the origin is given,
if known
Object
COTTON
Wooden statue in
textile
dress
Embroidered napkin
FLAX
Painting on canvas
with
a paper patch on the
back
Painting on canvas
Painting on canvas
(original canvas)
Painting on canvas
(original canvas)
Painting on canvas
(original canvas)
Painting on canvas
(original canvas)
Painting on canvas
(lining)
Painting on canvas
(lining)
Painting on canvas
Date
Fungal species
Literature
source
1850
Penicillium chrysogenum
[15]
1906
Aspergillus versicolor
[15]
Unknown
white filamentous hyphae
[15]
Unknown
Mid-19th
century
[15]
[15]
1729
Alternaria sp., Penicillium corylophilum

Penicillium corylophilum, Penicillium
bialowizense, Aspergillus proliferans,
Cladosporium tenuissimum, Penicillium
crustosum
Penicillium cf. corylophilum
17th century
Chaetomium globosum
[15]
1821
[15]
Unknown
Penicillium palitans
[15]
Unknown
Aspergillus sydowii, Aspergillus clavatus,

[15]
Unknown
[15]
[15]
319

Object
Date
Fungal species
Literature
source
(lining)
Coptic and Egyptian
textiles
Unknown
Aspergillus sp., Penicillium sp.,

Chaetomium sp., Alternaria sp.,
Trichoderma sp.
Chaetomium sp.
[16]
Alternaria alternata, Alternaria sp.,

Aspergillus candidus, Aspergillus sp.,
Aspergillus versicolor, Aureobasidium
pullulans, Cladosporium cladosporioides,
Cladosporium sp., Cladosporiun
herbarum, Drechslera sp., Epicoccum
purpurascens, sterile mycelium,
Penicillium cyclopium., Penicillium sp.,
Rhizopus stolonifer, Trichoderma viride,
Ulocladium chartarum, Ulocladium
oedemansii, Ulocladium sp.
[24]
Mid-20th
century
Cladosporium cf. cladosporioides
[15]
End of 19th or
beginning of
20th century
End of 19th or
beginning of
20th century
Aspergillus versicolor
[15]
Fomes fomentarius, Penicillium

chrysogenum
[15]
WOOL
Military coat
Coptic textiles
20th century
Unknown
[15]
[16]
Bedouin belts
Unknown
Cladosporium cf. cladosporioides

Aspergillus sp., Penicillium sp.,
Chaetomium sp., Alternaria sp.
Aspergillus sp., Chaetomium sp.,
Pencillium sp.
Archaeological
remains
in Georgia
Painting canvasses
from
Serbia
Unknown
Painting on canvas
HEMP
Painting on canvas
16th century
SILK
Embroidery
Embroidery
Unknown
[18]
[22]
In the framework of the studies performed by the authors of this chapter, the most
frequently occurring species has been Penicillium chrysogenum, as isolated from seven
different objects of various historical periods from Roman times to the 20th century and of
different fibre compositions cellulosic and proteinaceous. P. chrysogenum secretes
proteases [27] as well as cellulases [28]. The second-most frequently occurring species has
been Cladosporium cf. cladosporioides, as isolated from both cellulosic and proteinaceous
substrates that originate from the 19th and 20th centuries. C. cladosporioides has been reported
for its cellulolytic [29] and proteolytic [30] activities, and for its secretion of large amounts of
succinic acid [31], all of which can cause hydrolytic degradation. Species belonging to the
320
genus Cladosporium represent an important threat for historical objects, due to its ability to
survive relatively unfavourable conditions, such as low temperatures and low humidity [32].
The third and fourth most frequently occurring species are the cellulolytically active
Aspergillus clavatus and Penicillium corylophilum [33,34], which have both been isolated
from cellulosic objects: A. clavatus from cotton and flax, and P. corylophilum only from flax
(Table 1).
2.2. Environmental Conditions in Institutions Storing Historical Textiles

The environmental conditions in the storage and exhibition rooms of museums are of
great importance for the conservation of objects of high cultural and historical value [9].
Objects stored in buildings where conditions cannot be controlled are endangered and need to
be either preventively protected (e.g., chemical protection) or cured after infection. For
archaeological objects, the problem is even greater, as these objects have been exposed to
numerous environmental and microbial degradation factors for a long time [35]. Museum
guidelines on storage conditions, which to some extent diminish these degradation processes,
have been known for decades. They include controlled temperature (from 20 to 25 C), and
relative humidity (from 45% to 50%) [4,36]. Application of these conditions in many
instances does not suffice, however, as they do not prevent growth of many fungi, and
particularly airborne and xerotolerant fungi [37,38]. Additionally, reduction of the relative
humidity to below 45% can dry out stored materials, which can become brittle as a
consequence [4]. In summary, biodeterioration has to be controlled with additional
precautions, which include expensive air-filtering systems [9].
As mentioned above, fungal growth is related to the appropriate environmental
conditions; i.e., high room temperature and humidity, especially in non-ventilated storage
areas [7]. Storage conditions in the institutions selected for a study of biodeteriorated
historical textiles in Slovenia are mainly uncontrolled [15].
Generally, all of the objects investigated in our recent study [15] were until recently
exposed to inappropriate conditions. The most extreme case is the Slovene Museum of
Christianity, where the storage rooms are in an attic of a convent and the conditions changed
according to the seasonal weather. In spite of these adverse conditions, only a relatively small
number of the objects investigated was infected by fungi [15], which indicates that fungal
infections are not exclusively connected to environmental conditions. The objects might have
become infected before the acquisition by museums, as observed in the case of a painting
[15]. In some museums with controlled environmental conditions, the surfaces of objects are
cleaned before moving them to renovated storage rooms, to prevent further fungal growth, but
this does not destroy fungal spores, which remained viable and germinated on solid laboratory
medium.
According to these cases, it can be concluded that storage of objects under the
appropriate conditions (20 to 25 C, 45% to 50% relative humidity); [4,36] can temporarily
prevent active fungal growth, although this can be reactivated as soon as the objects are
exposed to humid and warm conditions again.
In the case of xerotolerant species of the genera Aspergillus and Penicillium,
environmental conditions have less important roles, as these fungi do not need high relative
humidity [2,39]. Therefore, lowering of the relative humidity in storage rooms is not a
321
sufficient measure, especially keeping in mind that historical textiles need to be kept in
environments that are humid enough to prevent them becoming brittle.
2.3. Influences of Substrate Type

The main constituents of most of infected objects are cellulosic fibres, and the most
infected cellulosic material is flax (Table 1). The possible reasons include a higher content of
non-cellulosic substances; e.g., hemicelluloses, pectins and pentosans make up 15% of flax,
in comparison to 5% of cotton [2,40], and the more complete supermolecular structure of
cotton in comparison to flax. Additionally, the objects made from flax include mainly
paintings that are stored or displayed in religious institutions where there is no control of the
environmental conditions, and often in contact with easily degradable materials, such as
protein glues [15].
Surprisingly, many objects composed of wool and silk fibres are also infected by fungi
(Table 1). One of the species that has been isolated from wool is C. cladosporioides, which to
the best of our knowledge, has not been isolated previously from wool. Within the study in
the Slovene museums, half of the objects made from silk that were analysed were infected.
The species isolated were Aspergillus protuberus, Fomes fomentarius and P. chrysogenum
[15]. According to the previous literature, only A. niger has been reported so far from silk
objects [17,41]. Rare fungal infections of silk objects are due to silk being the natural fibre
that is most resistant to biodeterioration [2]. As the sericin that is susceptible to
biodeterioration is mainly removed during processing, the remaining resistant fibroin
becomes susceptible only when exposed to light, heat or bacterial growth [41].
Many objects are composed of additional organic materials that can promote fungal
growth [19, 42]. In particular, non-fibrous protein (e.g., animal glues, which are used as
sizing of paintings) are easily affected by fungi [19]. Indeed, many of the objects we
investigated recently were paintings, where the textile carrier was in contact with other
organic materials. Some of these were identified using Fourier transform infrared (FTIR)
spectroscopy, as proteins, acrylic resins, and organic calcium salts.
2.4. Structural and Mechanical Properties of Historical Textiles Infected

by Fungi
The main structural changes due to fungal inestation that have been determined from
biodeteriorated textiles in previous reports were loss of tensile strength and/or weight, and
visual changes [16,20,43]. The methods already used for chemical and physicochemical
analyses of the raw materials and other components of archaeological and historical textiles
have included optical microscopy, scanning electron microscopy, inductively coupled plasma
mass spectrometry, attenuated total reflection FTIR spectroscopy, dispersive and Fourier
transform Raman spectroscopy, and atomic absorption spectroscopy, as well as high-pressure
liquid chromatography for colour analyses [17,44,45]. However, due to limited sample sizes,
and therefore limited choice of analytical methods, as well as insufficient information
regarding the history of selected objects, satisfactory interpretation of the results is often
difficult.
322
Figure 1. Representative scanning electron microscopy photograph of canvas painting RCS01, showing
extensive mycelium growth covering the surface of the flax fibres (magnification, 1900).
In our recent study on biodeteriorated historical textiles from Slovene museums and
religious institutions, various objects were selected for analysis of their structural and
mechanical properties after suspected fungal infections. These objects varied in terms of their
age, composition, purpose of use, history of use, and storage conditions (Table 1). FTIR and
Raman spectroscopy were used for the analysis of the structural properties of the fibres, and
scanning electron microscopy for determination of mechanical damage to the fibres [15].
These analyses were performed on textile materials that were taken as loosened fibres or
threads, or pieces of fabric. In general, they show that fungal growth was mostly limited to
the surface of the fibres (Figure 1), and did not influence their inner structure. Analysis of the
structural properties of infected textile fibres showed the most intensive changes in the
cellulosic fibres, and especially the flax fibres, and less distinctive structural changes to
proteinaceous materials.
For the structural changes analysed using FTIR and Raman spectroscopy, the spectra of
contemporary unaffected textiles were compared with those of inoculated and non-inoculated
historical fibres from the museums and religious institutions. The Raman spectroscopy was
used to assess the skeletal and supermolecular structure of the cellulosic fibres [46].
When analysing historical samples, a strong luminescent background can disturb the
analysis, especially when analysing bast fibres, which contain more non-cellulosic substances
than cotton [47]. This luminescence can be caused by non-cellulosic materials in fibres, by
fungal hyphae, or by deterioration products on the surface of the materials analysed [48]. In
several cases, only the two strongest bands could be identified specifically (at 1096 cm-1 and
1122 cm-1), which are typical of asymmetric and symmetric vibrations of glycoside bonds,
respectively [49]. By using prolonged exposure to low laser power (known as the signal
quenching method), the quality of the spectra was improved, thus allowing their better
interpretation, to obtain further information on the structures of the specimens selected. In the
most deteriorated samples, there were two bands in the Raman spectra, at 435 cm-1 and 520
323
cm-1, that are typical of crystalline cellulose [50], and these completely disappeared. Fewer
bands in the region between 300 cm-1 and 600 cm-1, which are typical of different ring
vibrations [49], is an indication of cellulose deterioration [44].
The most visible changes in the spectra of flax fibres were observed for a painting, which
was on the reverse side, with the sample visibly covered with mycelia (Figure 1) [46].
Although the strong luminescent background made interpretation of the spectrum difficult,
the decreased ratio between the two most intense bands at 1096 cm-1 and 1122 cm-1 (Figure 2)
was indicative of the hydrolysis of cellulose chains and the scission of glycoside bonds [45].
Figure 2. Comparison of the Raman spectra bands in the region between 950 cm-1 and 1250 cm-1 of the
reference flax sample (dotted line) and the sample of the inoculated canvas (RCS01; solid line), which
was severely affected by fungal growth.
FTIR spectroscopy is another efficient method that enables observations of changes that
have occurred at the molecular and supermolecular scale (e.g., depolymerisation,
crystallinity), as caused by either fungi or other external influences. FTIR spectroscopy
measures the vibrations of the molecular bonds of functional groups. When used as FTIR
micro-spectroscopy, this has a microscope attached to the IR source in transmission mode,
and changes throughout the whole thickness of a fibre can be identified [51]. Our recent FTIR
micro-spectroscopy revealed changes in the spectra of cellulose fibres, while no structural
changes were observed for the inoculated proteinaceous fibres (Table 1). Several spectral
features also showed decreases in the cellulose crystallinity in both inoculated and nonaffected samples, primarily as a decrease in the bands at 1430 cm-1 (typical of CH2 and OCH
vibrations, and intramolecular hydrogen bonds;) [3,52], 1371 cm-1 (COH and HCC vibrations
of cellulose and hemicellulose) [3], and 1335 cm-1 (OH and CH2 vibrations) [53]. This was
seen in the cotton and flax specimens, along with a shift in the bands at 1430 cm-1 and 1111
cm-1 (asymmetric vibrations of glycoside rings) [52] in the flax specimens (Figure 3). In the
spectra of the objects composed of bast fibres, a band at 1735 cm-1 was observed, which is
typical of carbonyl bonds [54], and probably arose as a consequence of depolymerisation [55]
324
due to fungal infection. Using these selected analytical methods, this enabled us to reveal and
qualify the extent of the changes arising from the deterioration of the fibres, although they did
not allow the clear attribution of the causative external factors, such as fungi, temperature,
humidity and/or time.
Figure 3. Comparison of the FTIR spectra of different flax samples (a-e) in the region typical of
crystalline cellulose vibrations. The peaks at 1430 cm-1, 1371 cm-1, 1335 cm-1 and 1111 cm-1 (from left)
are indicated (arrows).
Additional information can be obtained using attenuated total reflection FTIR

spectroscopy, which enables the analysis of only the surface properties of the fibres. In two
flax painting-canvass samples, two bands at 1335 cm-1 and 1316 cm-1 were joined into a
single peak at 1320 cm-1 as a consequence of the cellulose deterioration [56].
As well as the qualitative interpretation of the spectra, FTIR spectroscopy also provides
(semi)quantitative analysis [52,57]. As the intensities of certain bands change according to the
crystallinity of the cellulose, height ratios can be used as a cellulose crystallinity index.
Nelson and O'Connor [57] indicated two band ratios as measures of the Total Crystallinity
Index (TCI) (ratio of the bands at 1372 cm-1 and 2900 cm-1), which expresses the overall
arrangement of the cellulose macromolecules, and the Lateral Order Index (LOI) (ratio of the
bands 1430 cm-1 and 900 cm-1), which indicates the crystallinity. However, researchers still
differ in their views as to the use of these two ratios [58-60]. In our study of inoculated
textiles from Slovene museums and religious institutions, in most cases the TCI was lower for
bio-deteriorated samples than for non-infected samples (Figure 4) [51], while the LOI, which
can be affected by alkaline treatment of materials, did not give any clear results.
325
Figure 4. Total crystallinity indices of (A) hemp, (B) flax and (C) cotton samples.
3. IN VITRO TESTS OF FUNGAL DETERIORATION

OF NATURAL TEXTILES
Due to their cultural importance and conservation, historical textiles are endangered by
extensive sampling. To understand and to explain the processes of deterioration caused to
historical textiles by different fungal species, laboratory samples can be prepared under
controlled conditions. Fabrics can differ in composition and structure, and can be either
freshly prepared or artificially aged. In our study, the materials were selected according to the
composition of the museum objects investigated [21]. On this basis, cotton and wool fabrics
were selected for laboratory experiments. Cotton was selected as representative of a cellulose
material, as the second most often occurring fibre type among historical textile objects, and as
the most often used natural fibre in the world nowadays [61]. The selection criterion for wool
fabric was as representative of proteinaceous material, which is less resistant to fungal
infection than silk [2]. Both of the selected fabric types were neither dyed nor sized, to
minimise possible influences of added materials. Half specimens of each fabric type were
326
artificially aged at increased temperature (80 C) and relative humidity (65%), as previously
shown using different analytical techniques [21]. Six different fungal species were selected
for inoculation, four of which are those most often isolated from historical textiles. The most
frequently occurring species were A. clavatus, C. cf. cladosporioides, P. chrysogenum and P.
corylophilum. Two additional species, Hypoxylon fragiforme and F. fomentarius, were
included due to their wood-degrading abilities. The inoculation of samples and the
experimental set-up was described in detail in [21,62]. The specimens were incubated for
either 8 weeks or 20 weeks, and later autoclaved to prevent further deterioration. The samples
were analysed using scanning electron microscopy, Raman spectroscopy, and FTIR, with
tensile strength tests performed on a tensile testing machine.
3.1. Molecular and Supermolecular Structures and Mechanical Properties of

Contemporary Non-aged and Artificially Aged Cotton and Wool Specimens,
inoculated with Selected Fungal Species
3.1.1. Cotton
Fungal growth on cotton samples differed according to the species inoculated. Mycelia
were already observed by the naked eye after eight weeks of incubation in all cases, but
particularly with C. cf. cladosporioides, F. fomentarius and H. fragiforme inoculations, while
after 20 weeks, the mycelia had spread throughout the samples in almost all cases.
Scanning electron microscopy was used for observation of the morphological changes to
the fibre surface. Prolonged incubation led to more damage, which was more obvious in
artificially aged samples than in non-aged samples. The most extreme damage was observed
with C. cf. cladosporioides in both aged and non-aged samples. Longitudinal cracks are
typical of cellulosic fibres that are exposed to microbial influences [26], and breaks were seen
in brittle amorphous regions of the fibres [63] (Figure 5). As the cellulolytic activity of this
fungus is relatively low [64], the high amounts of secreted succinic acid [31] was probably
responsible for the deterioration seen.
The least invasive fungal species were F. fomentarius and P. chrysogenum. F.
fomentarius belongs to primarily lignolytic white rot fungi [65], while P. chrysogenum is
known for its strong cellulolytic activity [66]. Nevertheless, only occasional longitudinal
creases were observed.
The structural properties of the surface layers of the textiles investigated were analysed
using Raman and FTIR spectroscopies. Molecular and supermolecular changes in the cotton
fibre structure were more clearly visible in samples incubated for the longer time, and with
the aged samples. Using FTIR spectroscopy, there were no structural changes seen at eight
weeks for the non-aged samples and the artificially aged samples inoculated with A. clavatus,
C. cf. cladosporioides and F. fomentarius, which are all known for their weak cellulolytic
activity [29,65]. As with the Raman spectroscopy, changes in the cotton structure were
visible, and with the scanning electron microscopy, changes to surface morphology were
observed. It can therefore be concluded that A. clavatus, C. cf. cladosporioides and F.
fomentarius do not influence the functional groups and depolymerisation of cellulose chains
in the early stages of deterioration of cotton fibres [21].
327
Figure 5. Representative scanning electron microscopy photograph showing a crease and a broken fibre
in a non-aged cotton sample inoculated with C. cf. cladosporioides, after 20 weeks of incubation
(magnification 1500).
Figure 6. Comparison of Raman spectra of a reference non-aged cotton sample (a), and a non-aged
cotton sample inoculated with C. cf. cladosporioides (b). The bands at 435 cm-1, 520 cm-1, 1096 cm-1,
1122 cm-1 and 1180 cm-1 are indicated (arrows).
328
Figure 7. FTIR spectra of an artificially aged reference cotton sample (a), and an artificially aged cotton
sample inoculated with F. fomentarius (b). The shift at 1430 cm-1 and the joining of two bands with a
new peak at 1320 cm-1 are indicated (vertical dotted lines).
When compared to reference samples, the fewest visible differences in the Raman spectra
were seen with H. fragiforme and both of the Penicillium species. For H. fragiforme and P.
corylophilum this was as predicted, [67], while this behaviour was not expected for P.
chrysogenum. The Raman spectra of the inoculated samples after 20 weeks of incubation
showed decreased crystallinity and depolymerisation in the cotton fibres. For most of the
spectra analysed, there was a decrease in the band at 435 cm-1 relative to the band at 457 cm-1,
which indicates cellulose deterioration and a decrease in the crystallinity [50]. Both of these
bands are typical of the CCC and CCO vibrations of glucose rings [49,50]. The most visible
changes appeared in the non-aged specimens inoculated with C. cf. cladosporioides (Figure
6). Another sign of a crystallinity decrease [68] was the decrease in the band at 380 cm-1
(CCC vibrations of glucose rings) [49] for the non-aged specimens inoculated with H.
fragiforme and P. corylophilum. The ratio between the bands at 1096 cm-1 and 1122 cm-1
[45,49] increased in the non-aged specimens inoculated with A. clavatus, C. cf.
cladosporioides and H. fragiforme, as well as for the artificially aged samples inoculated with
C. cf. cladosporioides, as a consequence of the deterioration of the cellulose chain [49,69].
For samples inoculated with C. cf. cladosporioides, deterioration of the cellulose was
observed as decreased intensity of the band at 1380 cm-1 (CH2 bending and skeletal
vibrations) [70,71], and as the joining of the band at 1057 cm-1 with that at 1034 cm-1, which
are typical of CO vibrations of secondary and primary alcohols, respectively [48].
The FTIR analysis showed that in most cases the band at 900 cm-1, which is typical of glycoside bonds [52], broadened, and its intensity increased as a result of cellulose
deterioration. For non-aged samples inoculated with H. fragiforme and for the artificially
aged samples inoculated with P. chrysogenum, the band at 900 cm-1 decreased, as a sign of
329
increased crystallinity of the samples. Increased crystallinity in these samples was also
confirmed by an increase in the band at 1372 cm-1, which is typical of COH and HCC
vibrations of cellulose and hemicellulose [3,72]. For all of the other inoculated specimens, the
band at 1372 cm-1 decreased due to a decrease in the crystallinity. This decrease in
crystallinity was seen for the non-aged samples inoculated with A. clavatus and H.
fragiforme, as well as for the non-aged and artificially aged samples inoculated with F.
fomentarius (Figure 7). Here there was a shift of the band at 1430 cm-1 to lower
wavenumbers, which is typical of CH2 and hydrogen bond vibrations [52,73]. The
deterioration of the cellulose in the cotton fibres inoculated with F. fomentarius and the
decrease in crystallinity also results in the joining of the bands at 1335 cm-1 and 1316 cm-1,
which are typical of OH and CH2 [56] and COH and HCC vibrations [3], respectively; these
then showed a single band with a peak at 1320 cm-1 [56,74] (Figure 7).
Depolymerisation of cellulose in cotton fibres was confirmed also with the Raman
spectroscopy, as a decrease in the band at 520 cm-1 (CCC vibrations of glucose rings and
glycoside bonds) [44] for non-aged and artificially aged samples inoculated with C. cf.
cladosporioides and A. clavatus, and aged samples inoculated with P. corylophilum. This
shows that P. corylophilum can degrade previously deteriorated cellulose, although it is not a
typical cellulolytic species. Even clearer signs of depolymerisation were seen by the
appearance of a band in the region between 1710 cm-1 and 1750 cm-1 in the FTIR spectra.
This band is typical of vibrations of carbonyl groups [54,73,74]. Here, the depolymerisation
of the cellulose chains is caused either by hydrolysis or by oxidation [54,55,75], which leads
to the appearance of carbonyl groups at the depolymerised ends of the cellulose chains.
Although carbonyl bands mainly occur around 1730 cm-1, they were observed at higher
wavenumbers in the spectra of samples inoculated with P. corylophilum, due to changes in
the hydrogen bonding as a consequence of the deterioration [76]. The intensity of the band
increased with longer incubation times (Figure 8). In spectra inoculated with H. fragiforme,
the carbonyl band had already appeared after eight weeks of incubation, whereas in the
samples inoculated with C. cf. cladosporioides and P. corylophilum, the carbonyl band
occurred only after 20 weeks of incubation. It should be noted that none of these three species
has strong cellulolytic activity [64,67].
On the basis of the FTIR and Raman spectroscopy analyses of these inoculated samples,
it can be concluded that most of the fungi caused depolymerisation of the sample, and a
decrease in the crystallinity, which means that the fungi influenced the crystalline regions of
the cotton fibres. A few features suggested that certain fungi attack the amorphous regions
first. The luminiscence seen in some of the Raman spectra (non-aged samples inoculated with
F. fomentarius and P. chrysogenum, as well as artificially aged samples inoculated with C. cf.
cladosporioides and F. fomentarius) is a consequence of hyphae or deteriorated cellulose on
the surface of the fibres [48], which makes the interpretation of the spectra more difficult, as
the low intensity bands completely disappear into this background.
The mechanical properties of selected samples of the cotton specimens inoculated (i.e.,
weft yarns of the fabric) were analysed in terms of their tensile behaviour. The stressstrain
curves of these cotton yarns were monitored over the whole deformation range (from the
beginning of the deformation, until the break). The tensile behaviour of the cotton yarns
during this tensile analysis depended on the yarn properties (e.g., linear density, twist), as
well as on the fibre properties (e.g., degree of polymerisation, intramolecular bonding,
macromolecule orientation). Changes in the tensile properties occurred as a consequence of
330
changes in both the yarn and the fibre structures. Here, as all of the cotton specimens were
from the same textile material with the same initial textile properties, conclusions about the
structural changes to the cotton fibres can be drawn from the results of the tensile analysis.
Therefore, the differences in the tensile properties between the samples might be related to
the changes in the fibre structures as a consequence of the aging of the cotton specimens and
the inoculation of the samples with different fungi. The initial parts of the stressstrain curves
showed their initial resistance to stretching (initial modulus) [21].
Figure 8. FTIR spectra of an aged cotton reference sample (a), and samples inoculated with C. cf.
cladosporioides and incubated for 8 weeks (b) and 20 weeks (c). The band around 1730 cm-1, which is
typical for carbonyl group vibration, is indicated (arrow).
Figure 9 shows the stress-strain curves of the non-aged and artificially aged samples
inoculated with C. cf. cladosporioides. Comparisons of the stressstrain behaviours of the
non-inoculated aged and non-aged reference cotton specimens showed that the artificial
ageing resulted in severe changes to the tensile properties of the cotton yarns analysed. These
were seen as much lower breaking elongation, slightly lower breaking stress, and higher
elastic modulus. These changes in the tensile properties of the aged samples can be attributed
to the depolymerisation of the cellulose macromolecules and the higher crystallinity, as
observed by the spectroscopic methods. The aging significantly influenced the structure of the
cotton fibres, and consequently also the stressstrain behaviour, such that the stressstrain
curves were much lower for the aged samples than for the non-aged samples [21].
In all of the inoculated samples tested, there was a distinctive rise in the resistance to
stretching, which was seen as a steep rise at the beginning of the curve when compared to the
reference samples. The higher initial modulus of the yarn can be attributed to the fungal
growth between the fibres of the yarn, which can act as a yarn filler that increases the initial
modulus. The lower breaking strain, and in some cases the lower breaking stress, can be
attributed to the depolymerisation of the cellulose macromolecules in the fibres of the yarn,
331
while the higher initial modulus of the yarns was due to the depolymerisation of the cellulose
macromolecules in the fibres, which can form greater numbers of intermolecular bonds. This
phenomenon can be seen at the beginning of the stressstrain curves as a higher initial
modulus, and in some cases, also as a relatively high specific breaking stress and lower
breaking strain. When the initial modulus of the non-aged samples was compared with that of
the artificially aged samples, it could be seen that the initial modulus of the non-aged samples
was higher compared to that of the aged samples. This behaviour can be explained by the
much more severe degradation of the fibres in the aged samples, compared to the non-aged
samples. In the aged samples, the fibres were already degraded to such an extent that the
filling effect of the fungi on the yarn was overcome. The factors affecting the stressstrain
behaviour of the non-aged and the inoculated samples acted synergistically. These were:
depolymerisation of the cellulosic macromolecules in the cotton fibres, the filling effect of the
fungi between the fibres in the yarn, and the C. cf. cladosporioides secretion of succinic
acid [21].
Figure 9. Stress-strain curves of (A) a non-aged sample inoculated with C. cf. cladosporioides, and (B)
an artificially aged sample inoculated with C. cf. cladosporioides. Each panel shows the reference
sample (a) and samples incubated for 8 weeks (b) and 20 weeks (c).
3.1.2. Wool
For the wool samples, the infection with fungi was barely visible on the surface of the
samples. Deeper inspection of the material revealed more widespread mycelia between the
yarns of the fabric. The growth of all of the fungal species was also less intense on the wool
samples, in comparison to the cotton, in agreement with the literature data [2]. The least
intensive growth was observed with A. clavatus and P. chrysogenum, and the most intensive
with C. cf. cladosporioides,.
Most of the wool fibres analysed remained undamaged after inoculation with the fungi,
and especially the non-aged fibres. The frequency of occurrence and the intensity of the
surface morphological changes increased with the time of incubation. The most frequent
change was damage to the scales (Figure 10a), which already started during the processing in
the non-inoculated samples. The most intensive changes, which were seen as damaged scales,
longitudinal creases, fibrillation, and breaks, were observed with the non-aged samples
inoculated with H. fragiforme. In the non-aged samples inoculated with C. cf.
cladosporioides and F. fomentarius, there were some longitudinal creases seen.
332
Figure 10. Scanning electron microscopy photographs of deteriorated wool fibres. (A) Non-aged fibres
inoculated with P. chrysogenum, showing surface damage. (B) Artificially aged sample inoculated with
C. cf. cladosporioides, showing severe deterioration of cortical cells. (C) Artificially aged sample
inoculated with A. clavatus, showing a break in a fibre.
More surface changes were observed for the aged samples, where all of the fungal
species grew more intensively than on the non-aged samples. For example, C. cf.
cladosporioides completely destroyed the cuticle and cortex fibrils (Figure 10b), and caused
breaks in the fibres (Figure 10c).
It was not possible to analyse these wool fibres with Raman spectroscopy, as the
luminiscent background of the infected samples was so strong that no spectral bands could be
seen.
FTIR analysis anabled the evaluation of the intensity of the wool deterioration, by
comparing the intensity and positions of the amide I and II bands in the FTIR spectra [77]. No
clear changes were seen in the FTIR spectra of the inoculated wool samples, which indicated
that the fungi selected did not cause any intensive changes to the peptide bonds. The only
exception was an artificially aged sample that was inoculated with F. fomentarius, which
secretes proteases [78], with a decrease in the amide II band (1540 cm-1) (Figure 11). This
band is typical of the HN and CN vibrations [79], and it is sensitive to the molecular
conformation [80]. Its decrease is a consequence of changes in H-bonds, the steric
arrangement of the proteins, and the changes in the supermolecular structure [81].
333
Figure 11. FTIR spectra of an artificially aged wool reference sample (a) and an artificially aged wool
sample inoculated with F. fomentarius (b). In the amide II region (arrow) there is a slight decrease in
the band of the inoculated sample.
For the non-aged samples inoculated with F. fomentarius and P. chrysogenum, as well as
for the artificially aged samples inoculated with A. clavatus, H. fragiforme and P.
corylophilum, a carbonyl band was observed after 20 weeks of incubation (Figure 12). This
appeared mainly as a shoulder, which suggests that the depolymerisation process had just
started. Carbonyl bands are a consequence of oxidation of polypeptide chains, which leads to
crosslinking and interruptions to the macromolecules [81]; this can cause brittleness of the
fibres and less resistance to mechanical influences [63]. Carbonyl groups occur mainly on
depolymerised chain ends [82]. As the band occurred in samples inoculated with the various
fungal species, the depolymerisation is probably not directly connected with the fungal
proteolytic activities.
Deterioration of polypeptide chains can be observed as a decrease in the band at 1450
cm1, which is typical of skeletal CC vibrations [83]. This decrease in the 1450 cm-1 band was
seen for non-aged samples inoculated with P. corylophilum. In the region between 1170 cm-1
and 1000 cm-1, the vibrations of oxidised cysteine residues can be seen at 1075 cm-1 for CysO and at 1120 cm-1 for Cys-O2 [82]. The appearance of the 1075 cm-1 band is a consequence
of keratin oxidation [84]. This decreased in the non-aged samples inoculated with A. clavatus,
which shows that the deterioration of cysteine and its oxides leads to the formation of cysteic
acid [83].
The intensity of the amide III band (1235 cm-1) decreased only for the non-aged sample
inoculated with A. clavatus, which showed the more ordered structure of the molecules [82].
According to the literature, A. clavatus secretes proteases [85] and attacks the amorphous
regions first.
334
Figure 12. FTIR spectra of an artificially aged wool reference sample (a) and an artificially aged wool
sample inoculated with H. fragiforme (b). The carbonyl band is indicated (arrow).
The mechanical properties of selected samples of the inoculated wool specimens (weft
yarns of the fabric) were also analysed according to their tensile behaviour. The stressstrain
curves of these wool yarns were monitored over the whole deformation range (from the
beginning of the deformation, until the break). Figure 13 shows the stressstrain curves of
these non-aged samples inoculated with P. corylophilum and artificially aged samples
inoculated with P. chrysogenum. Different fungal species affected different mechanical
properties of the wool fibres. The fungi did not influence the mechanical properties of the
wool fibres to any large extent, and especially in the non-aged samples, the differences from
the reference samples were small.
Comparison of the stressstrain behaviour of the non-inoculated aged and non-aged
reference wool samples was seen as lower breaking elongation, slightly lower breaking stress,
and higher elastic modulus for the artificial ageing. These changes in the tensile properties of
the aged samples can be attributed to the depolymerisation of the macromolecules and the
higher number of intermolecular interactions. The changes caused by aging of the wool fibres
was the same as for the cotton fibres, but to a lesser extent. In the non-aged samples
inoculated with P. corylophilum, the breaking strain was only a little lower than with the
reference sample. The breaking stress significantly decreased after eight weeks of incubation,
and then increased after 20 weeks of incubation (Figure 13a). In the aged samples inoculated
with P. chrysogenum, the breaking stress increased after both the shorter and longer
incubation times (Figure 13b). The stressstrain behaviour of all of the inoculated samples
showed that the initial modulus and breaking strain are lower compared to the reference
sample. The changes related to ageing, inoculation and incubation appear to be as a
consequence of the lower crystallinity and the higher number of intramolecular interactions
[63].
335
Figure 13. Stress-strain curves of (A) non-aged samples inoculated with P. corylophilum, and (B)
artificially aged samples inoculated with P. chrysogenum. Each panel shows the reference sample (a)
and samples incubated for 8 weeks (b) and 20 weeks (c).
CONCLUSION
This chapter has focused on fungal deterioration of historical and modern, aged and nonaged, textiles through an interdisciplinary approach. The review of the literature and our
analyses performed on historical textiles stored in several Slovene museums and religious
institutions reveal that the history of each artefact has to be carefully considered, as many
factors can influence the structure and properties of historical materials, from the growing and
processing of the fibres, and the making and application of the object, to the storage
conditions. The combination of these factors can change the fibre properties in terms of the
physical and chemical structures, thus affecting further the chemical changes, and promoting
336
microbial infestation. Biodeterioration of historical textile objects is most often caused by

fungi, which do not necessarily change the structure and properties of the fibres to any large
extent; however, they can nevertheless have a considerably effect on the visual image of the
object, and most importantly, pose a latent danger to later fungal reactivation and growth.
The analysis performed on the diversity of the fungal species that can contaminate
historical textiles cannot be linked to certain historical periods and institutions, as the same
genera were isolated from historical objects that originated from different periods and
environments. However, the genera Alternaria, Aspergillus, Chaetomium, Cladosporium,
Penicillium and Trichoderma were most often the infecting agents in our analysis of historical
textile objects, as they were repeatedly isolated. These can thus be considered as ubiquitous
museum mycoflora.
The structural, surface and mechanical properties were also analysed for historical
textiles, as contemporary non-aged and artificially aged textiles, composed of cotton and
wool, and inoculated with the six selected species of fungi. The structural and morphological
changes were more pronounced for the cellulosic than proteinaceous textiles. The most
intensive changes in the structure (e.g., depolymerisation, decrease in crystallinity) and the
mechanical properties (e.g., breaks in the fibres, tensile properties) of the cellulosic fibres
were caused by C. cf. cladosporioides, while they were least affected by P. chrysogenum.
Wool fibres showed their greatest deterioration with H. fragiforme, and their least with A.
clavatus and P. corylophilum.
The most pronounced surface changes in the cellulosic fibres were longitudinal creases
between the fibrils, while for the wool fibres, the surface scales were mostly damaged. At the
level of the structural changes, depolymerisation, and disordering of the macromolecular
structures of the fibres, this occurred for both cellulose and proteinaceous fibres. The intensity
of these changes increased with the prolonged incubation time following the fungal infection,
and with the aging of the samples.
Those in charge of taking care of historical textiles (e.g., curators, conservators) must be
aware of the possible influences of fungi on the visual, mechanical and structural properties
of these objects. The best measure is prevention, so storage of the objects in environments
with low humidity and cool temperatures, with regular ventilation of the rooms. As infections
with different fungal species can nevertheless occur and cause different structural changes, it
is important to correctly identify the infecting fungal species, to take appropriate curative
measures.
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ISBN: 978-1-63117-262-5
Chapter 12
DURABILITY OF FUNCTIONALIZED
TEXTILES BY MICROCAPSULES
Lucia Capablanca, Pablo Monllor, Pablo Daz and
Maria ngeles Bonet*
Departamento de Ingeniera Textil y Papelera,
Universitat Politcnica de Valncia, Alcoy, Spain
ABSTRACT
Nowadays textiles are required to have extra properties, they should offer active
functionality. Microcapsules applied on textiles have become a way of modifying textiles
properties.
Microencapsulated products can be applied on fabrics by impregnation, bath
exhaustion, foam, spraying and coating. The most extended industrial application is by
padding. To paste microcapsules to fabrics, they should be in contact with a bath, which
contains microcapsules, resin and water. The resin allows the microcapsules adhesion to
the fabrics fibers because no affinity between them.
Textiles in their useful life are submitted to washing, drying, ironing, abrasion, etc.
These processes affect the stability of microencapsulated products. The aim of the textile
industry is to achieve greater permanence of microcapsules on fabrics.
In this chapter we study microcapsules useful life on plain fabrics applied by
impregnation. Washing treatments allow us to study the behavior and permanence of the
microencapsulated commercial products on fabrics. The aim of this work is to provide to
the textile industry a study about the microcapsules behavior on washing treatments in
order to ensure the major durability of microcapsules.
Scanning electron microscopy (SEM) has been used in order to determinate the
quantity of microencapsulated products that remains on fabrics after washing treatments.
We concluded that washing treatments affect the microcapsules stability and permanence.
To sum up, we can indicate that depending on the washing treatment conditions
microcapsules behavior can differ from one fabric to other.
E-mail: maboar@txp.upv.es
344
Lucia Capablanca, Pablo Monllor, Pablo Daz et al.
1. INTRODUCTION
Nowadays textiles are required to have extra properties; they should offer active
functionality, and in recent years some textiles have come to be known as smart textiles. It is
very common to think that smart textiles contain electronic devices, but this is not necessarily
so. The term smart textile refers to textiles that are able to react when an external effect is
present.
Nanotechnology processes are present into the textile field. One of these processes
involves encapsulated nanoparticles or nanoproducts, know as microcapsules.
Microencapsulated products are very common in some fields, such as pharmacy [1-19],
cosmetics [20-25], food [26-40], insecticides [33,41-43], adhesives [44,45], medicine [8,23],
and the textile industry has recently incorporated them into their products. They are used by
the more developed countries into textiles to confer new properties and added value, for
example into medical and technical textiles. It has encouraged the industry to use
microencapsulation processes as a means of imparting finishing and properties on textiles
which were not possible or cost-effective using other technologies [46].
Textile manufacturers are demonstrating an increasing interest in the application of
durable fragrances and skin softeners to textiles [42,46,47]. Other potential application
include insect repellents, dyes, vitamins, antimicrobials, phase change materials and specific
medical applications, antibiotics, hormones, and other drugs [42,46-54].
Microcapsules present an active core, which is protected by means of an external
polymer. The composition of microencapsulated products can be different because they are
made of different shell materials and diverse core materials. The core material will define the
use, i.e., medicine, food, etc. The cosmetic industry uses fragrances in liquid cores, and
although they can be used in aromatherapy, they are not as important as in medicine. The
nature of the shell is considerably wide nevertheless, it is not common to find reactive
polymers that can react with fibers surface. The effect of microcapsules is usually measured
by the presence of a property such as odor measurements when flavors are encapsulated.
Nevertheless, some properties such as hydration, antibacterial, insect repellents, etc., cant be
tested without analytical methods. Some characterization techniques have been applied in
order to study microcapsules products, presence and state [42,46,47,49,55-60].
Fragrance encapsulation is one of the applications of microencapsulation technology in
the textile sector. Microencapsulation technology allows us an opportunity that can flavor its
durability on fabrics. Some papers have been published on fragrance microcapsules
[42,46,47,61-64], where they were studied in relation to their final use on textiles or other
materials and their effect. When microcapsules are applied to textiles, commonly used shells
are not reactive; otherwise, they would stick together. As a result of that chemical stability, no
chemical reaction can be applied between microcapsule and fiber. Thus, in order to improve
durability to washing or handle some auxiliary products, it is required to join microcapsules
to the fiber surface [42], they are usually based on acrylic, polyurethanes or silicone resins
[65].
Knowing there is not enough affinity between microcapsules and fibers, a resin is needed
to adhere them to the fiber and a mechanical process to help microcapsules to get into the
fabric. In the textile sector the most extended microcapsules industrial application is by
345
padding; however commercial brands suggest some recipes depending on the procedure
mainly padding or bath exhaustion, although foam is also an application system.
In all application processes, the control of variables is essential to achieve increased
deposition and retention of microencapsulated products on fabrics. Fabric structure is an
important parameter to consider in the microcapsules application on fabrics [66]. Furthermore
application procedure, bath composition, fibers nature (hydrophobic vs hydrophilic
character), cross section, fabric weight and fabric wave, are variables to consider in the
application of microencapsulated products into textile substrates [67,68] in order to ensuring
the stability and durability of microencapsulated.
Textiles in their useful life are submitted to washing, drying, ironing, abrasion, etc. These
processes affect the stability of microencapsulated products [68-70]. The aim of the research
is to evaluate the durability of fragrance microcapsules deposited on plain fabrics.
Normalized washing treatments have been carried out on fabrics with an active substance to
evaluate their effects on the maintenance of fabrics conditions and the state of commercial
products. Scanning electron microscopy (SEM) has been used to check their presence, surface
distribution, preferred join position in textile fibers and washing effects.
2. EXPERIMENTAL
2.1. Materials
Lavender fragrance microcapsules were supplied by COLOR CENTER (Tarrasa, Spain).
The wall material was melamine formaldehyde. An acrylic resin was applied in order to bond
the microcapsules to the fabric, also supplied by COLOR CENTER.
The plain fabrics used were a 100 % cotton twill 210 g/m2, which have been chemically
bleached with peroxide in an industrial process.
2.2. Fabric Treatment

Fragrances microcapsules were applied to the surface of the fabrics by impregnation. An
acrylic resin was used as a binder. For the process, a horizontal foulard (2608 TEPA foulard;
Barcelona, Spain) was used. Bath treatment was composed of 10g/L of resin and 60g/L of
commercial microcapsules, it had been studied previously [68]. Pick-up (bath absorption)
obtained was about 90-95%.
All the samples were thermally dried and fixed in a scale pin stenter at 110C for 10 min
in an air forced heater (WTC BINDER 030;Wisconsi, USA). Previously, it has been
demonstrated that this temperature was high enough to polymerize the binder without
evaporating the fragrance [69].
346
2.3. Washing Treatment

Washing treatments were applied in order to study microcapsules behavior and durability.
One of them was carried out in a Heraeus Linitest; Frankfurt, Germany applying the standard
ISO 105 C10. Samples were dried on a horizontal surface. The other was carried out in a
Domestic Washing Machine Fagor Innova; Guikuzpoa, Spain applying the standard ISO
6330. Samples were dried on a horizontal surface according to the standard.
All samples were examined by scanning electron microscopy (SEM) (Phenom
Microscope FEI Company, Hillsboro, OR, USA) after 1 and 10 washing cycles.
2.4. Organoleptic Analysis

Qualitative and subjective analysis, for implementation is not available or used no
standardized method or instrumental technique. Organoleptic analysis is always performed by
specialists in order to counter the results. In turn, these results are corroborated by scanning
electron microscopy in order to ascertain the presence or absence of microencapsulated
products between the fabrics fibers.
This analysis is performed in fabrics after being subjected to washing cycles. After drying
is checked if fabrics off the scent used as active material or if it is necessary to appreciate that
rub aroma. If the fabric contains microcapsules the friction will cause membrane rupture and
the release of the active ingredient.
2.5. Instrumental Techniques

In order to observe fabric surface, a scanning electron microscopy (Phenom Microscope
FEI Company, Hillsboro, OR, USA) was used. Each sample was fixed on a standard sample
holder and sputtered with gold and palladium.
3. RESULTS
3.1. Application Procedure
Figure 1 shows a SEM microphotograph of cotton fabric with microcapsules applied by
impregnation. It was not possible quantify microcapsules presence using this technique. SEM
only allowed us to observe the fabrics surface detecting the microcapsules presence, location
and condition.
It can be observed that microcapsules have a spherical shape with the fragrance inside. In
the same commercial product there are microcapsules with different sizes. Microcapsules tend
to be in the grooves that forming the kidney section of the cotton fibers.
Resin presence can be observed in SEM micrographs. If the encapsulated fragrance is
applicated only onto a substrate and dried, the microcapsules could be lost during a hot, wet,
347
frictional washing because there is no affinity between the microcapsules and the fabric. The
resin enables to fix the microcapsules to the fabric.
Figure 1. Cotton fabric with microcapsules.
3.2. Washing Effect
Figure 2. SEM micrographs of cotton fabrics with microcapsules and after one washing cycle. Cotton
fabric with microcapsules. Cotton fabric after 1 washing cycle ISO 105 C10. Cotton fabric after 1
washing cycle ISO 6330.
348
It can be observed in Figure 2 that larger microcapsules have lost the core partially, and
cannot be observed as spheres. A previous work [70] demonstrated that larger microcapsules
are washed out of the fabric more quickly (in the first washing cycles) than the smaller
microcapsules that remain on the fabric for more washing cycles. Moreover, larger
microcapsules deflate rather than smaller microcapsules.
After five washing cycles (Figure 3) the microcapsules presence decreases on the fabric.
Washing cycles affect the microcapsules stability.
Figure 3. SEM micrographs of cotton fabrics after five washing cycles. Washing process according to
ISO 105 C10. Washing proces according to ISO 6330.
In Figure 3 the SEM images from ISO C10 (linitest machine) and from ISO 6330
(domestic washing process) are compared, it can be observed differences between the number
and the state of microcapsules that remaining on the fabrics. Resin remains on the cotton
fibers after five washing cycles.
When the standard ISO 6330 is used less microcapsules were observed between cotton
fibers and most have lost their spherical shape and therefore the fragrance inside. These
microcapsules do not provide any property to the cotton fabric.
Washing cycles with standard ISO 6330 are the most similar to those made at home with
textiles.
3.2.1. Organoleptic Analysis

In Figure 1 it can be observed that microcapsules tend to be in the grooves that forming
the kidney section of the cotton fibers. Microcapsules located at these positions will be more
protected against washing action.
If one compares the results of organoleptic analysis between washing processes it can be
observed again differences. These differences are shown in Table 1.
Table 1 shows the organoleptic analysis results, "Yes" has been typed when it is
necessary to rub the fabric to appreciate the fragrance and No when appreciated the
fragrance without rub. Before the analysis, fabrics with microcapsules have been washed (1, 5
or 10 washing cycles) according to the standards and dried.
349
Table 1. Results of Organoleptic Analysis, cotton fabric with microcapsules

Washing Cycles
1
5
10
ISO C10
No
No
No
Standards
ISO 6330
No
Yes
Yes
Organoleptic analysis results coincide with the micrographs of Figure 3. After five
washing cycles, in the cotton fabric washed according to ISO 6330 (domestic washing) is
necessary to rub the fabric to appreciate the fragrance. In Figure 3b it can be observed less
microcapsules between cotton fibers.
Microcapsules located in the grooves that forming the kidney section of the cotton fibers
are more protected from the washing action and retain their spherical shape with the fragrance
inside after five washing cycles. Rub action breaks the membrane and the fragrance can be
appreciated.
Cotton fabrics washed according to ISO C10 maintain the fragrance without rubbing after
five and ten washing cycles. Washing conditions influence the microcapsules permanence and
stability.
CONCLUSION
The present study compares the stability and durability of microcapsules on plain fabrics
surfaces after washing treatments. Certain differences can be observed. The number of
microcapsules that remain on the fabrics after washing cycles is different depending on the
washing process.
When the standard ISO 6330 is used, less microcapsules were observed between cotton
fibers and it is necessary the rub action to appreciate the lavender fragrance after five and ten
washing cycles.
After 5 and 10 washing cycles according to ISO C10 we can confirm some odor intensity
remained on fabrics. This means that there are small microcapsules partially filled on the
fabric, the active material is still on the fabric and we can appreciate the odor without the
rubbing action.
Washing process according to the standard ISO 6330 is stronger than standard ISO C10,
therefore, it affects microcapsules stability and permanence. Washing cycles with standard
ISO 6330 are more similar to those made at home with textiles.
Process conditions and substantial quantities of products are parameters to consider in
order to ensure the stability and durability of microencapsulated products. Regardless of the
standards used, the continuous washing cycles affect the microcapsules durability to fabrics,
thus, optimizing product baths is necessary to achieve textile articles with a long life.
350
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ISBN: 978-1-63117-262-5
Chapter 13
NEW APPROACHES AND APPLICATIONS

ON CELLULOSIC FABRIC CROSSLINKING
Eva Bou-Belda, Maria ngeles Bonet, Pablo Monllor,
Pablo Daz, Ignacio Montava and Jaime Gisbert
Departamento de Ingeniera Textil y Papelera,
Universitat Politcnica de Valncia, Alcoy, Spain
ABSTRACT
Shrinkage and wrinkling are the major undesirable properties of cotton fabric. Those
fibers are generally treated with crosslinking agents to further provide new properties to
cotton fabric such as durable press property. Generally, in a cross-linked cotton fabric,
cellulose chains are bridged across through chemical reaction with certain compounds.
Cellulose cross-linking can be traced back more than eighty years and is still being
actively researched. In this paper, literature on cotton cross-linking was reviewed from
the past to the present. In this paper, possibilities offered by these type of acids in the
textile, the experimental techniques used to characterize the treated fabric, new
approaches and applications are discussed.
Keywords: Polycarboxylic acids, durable press, cotton, fabric, crosslinking
INTRODUCTION
Cellulosic textiles are finished in order to improve their properties, dimensional stability
and crease resistance play a considerably important role. These properties can be
satisfactorily achieved by crosslinking agents, which react with hydroxyl groups of cellulose
fibers. Esterification between polycarboxylic acids and cotton cellulosic has been investigated
since 1960s [1, 2].
Corresponding author: Maria Bonet. Departamento de Ingeniera Textil y Papelera, Universitat Politcnica de
Valncia, Plaza Ferrandiz y Carbonell s/n, 03801 Alcoy, Spain. E-mail: maboar@txp.upv.es.
356
Eva Bou-Belda, Maria ngeles Bonet, Pablo Monllor et al.
Some finishing treatments such as wrinkle-free, wrinkle-resistant and crease recovery

confer very important properties to cotton fabrics. There are many cross-linking agents which
are effective to this type of textile finishing, these have been studied for years in the past,
such as urea/formaldehyde, melamine/formaldehyde, tetramethyllolacethylenediurea, dimethyleneurea and dimethyloldihydroxyethylene-urea (DMDHEU) [3, 4]. Although dimethyloldroxylethyleneurea was the most widely reactant for the production of durable press
garments, its use resulted in fabrics that were chlorine retentive and also prone to some degree
of yellowing [5].
N-methylol agents have long been used by the textile industry as durable press finishes
producing wrinkle-resistant cotton fabrics. However, as they release formaldehyde either
from treated fabrics or during finishing processes, their use in textile industry is limited.
Formaldehyde has been identified to have impact on human health and the environment. For
this purpose, in recent years extensive efforts have been made to develop polycarboxylic
acids (PCAs) as new crosslinking finishing agents for cotton fabrics to replace the traditional
reagents [5].
Over the past few years, there has been an attention on application of nanoparticles with
crosslinking agents to impart other properties to the fabric, such as antimicrobial, flame
retardant, water repellency or UV protective. In this work, literature on cellulosic fabric
crosslinking have been reviewed from the past to the present. Publications refer to the
possibilities which can offer these type of acids in the textile product, the experimental
techniques used to characterize the treated fabric, new approaches and applications are
discussed.
POLYCARBOXYLIC ACIDS AGENTS

Some of the most used and studied in different works are reviewed briefly.
Citric acid (CA), is a tri-functional carboxylic acid known as a cost-effective and
environmentally friendly cotton crosslinking agent but it was not satisfactory with its
performance due to its tendency to discolor the treated fabric. Among the various effective
polycarboxylic acids, 1,2,3,4-butanetetracarboxylic acid (BTCA) has proved to be the most
efficient cross-linking agent for cotton fabrics [6, 7]. Esterification of cotton cellulose with
BTCA in order to form crosslinking is believed to proceed through a mechanism involving
formation of an intermediate cyclic anhydride, which reacts with the cellulosic hydroxyl to
complete the ester linkage. [5]
Peng et al. [8] suggested the combination of maleic acid (MA) and sodium hypophosphite
as a formaldehyde-free and cost-effective durable press finishing system with superior fabric
strength retention. Yang et al. [9] found that acid maleic was less effective than 1,2,3,4butanetetracarboxylic acid (BTCA) due to the low mobility of the anhydride intermediates to
access the cellulosic hydroxyl during a curing process. For this reason, some works suggested
the combination of maleic acid with another polycarboxylic acid, for example citric acid or
the combination of maleic and itaconic acid.
Research has been done by Yang et al. in 2001 [10] on the effectiveness of poly itaconic
acid (PITA) synthesized in an aqueous solution and ITA polymerizing in situ for crosslinking cellulose and imparting wrinkle resistance to the cotton fabric.
New Approaches and Applications on Cellulosic Fabric Crosslinking
357
They reported that despite the fact that the tensile strength loss of the cotton fabric crosslinked by ITA polymerizing in situ is very similar to that cross-linked by PITA applied as a
polymer, ITA is more effective in esterifying cotton cellulose. In 2003 [11], they reported that
the cotton fabric treated with ITA, lost more tensile strength than that treated with PITA due
to cellulose degradation and the tensile strength loss caused by cross-linking for PITA treated
fabric is significantly higher than that for ITA treated fabric. This was believed to be due to
more concentrated cross-linkages formed on the nearest surface of the fabric treated with
PITA.
Succinic acid (SUA) is used as a crosslinking agent as well. For example, Chen Chi Che
et al. [12] used succinic acid as crosslinking agents in the presence of nanometer TiO2 as
catalyst under the irradiation of UV light whose wavelength is 254 nm. They found that the
carboxylic acid group of succinic acid can be photo-reduced to form the aldehyde group. The
crystalline structure of SUA adsorbed on nanometer TiO2 particles can be changed under UV
irradiation. The photo-reduction of succinic acid in the presence of nanometer titanium
dioxide solved in water under UV irradiation can increase the values of conductivity and
improve the creation of free radicals. In this study they suggested that the crosslinking
reactions were due to the reaction between aldehyde group from succinic acid and the
hydroxyl group on cellulose and the reaction between free radical of succinic acid and the
free radical of cellulose. The stress concentration caused by crosslinks and the damage caused
by the photo-reduction are the main factors to decrease the tensile strength of the treated
fibers.
In a previous work [13], we evaluated the yellowing of the treated samples with different
acid. We could observe whiteness index differences, which were compared with the untreated
cotton fabrics whiteness. We could observe different behaviour depending on the acid used.
Using PCA as a crosslinking agent for cotton causes fabric yellowing. This yellowness can be
increased by the increase of curing temperature and acid concentration, however, when
BTCA and SA-treated cotton are used it can be obtained a gradual decrease in whiteness
index. It could be noticed that while untreated samples whiteness decreases exponentially as
the curing temperatures increases, the same sample treated with BTCA or SA showed a
reduction in yellowness at higher temperatures above at 170C.
EXPERIMENTAL TECHNIQUES
FTIR
Yang et al. [14] indicated, using FTIR, that PCA esterifies cellulose in two steps: the
formation of a 5-membered cyclic anhydride intermediate to form an ester linkage [14-16]. In
another research these authors used FTIR and Fourier transform Raman spectroscopy to study
the formation of cyclic anhydride intermediates by BTCA and other polycarboxylic acids.
The reaction between cellulose and BTCA with catalyst and high cured temperatures. They
found that BTCA and other polycarboxylic acids in a crystalline state start to form 5membered cyclic carboxylic anhydride when the temperature reaches the vicinity of their
melting point with the exception of bifunctional acids, which form cyclic anhydrides at
temperatures much higher than their melting point.
358
Intermolecular hydrogen bonding between carboxylic acid prevents the formation of the
cyclic anhydride intermediates at lower temperatures [17].
Authors to confirm the crosslinking reactions of different PCAs on cotton use FTIR
spectroscopic studies. The formation of ester crosslinking between the hydroxyl groups of
PCAs can be witnessed in the spectra of PCAs treated fabrics.
For example, Figure 1 shows the spectra of the BTCA cotton treated samples studied in a
previous work [18]. The spectra of untreated cotton fabric was compared with the one from
the treated fabric with 80 g/L of BTCA and 40 g/L of catalyst. An FTIR spectrum of
untreated sample shows absorption in the region 3010-3750 cm-1 due to the hydroxyl groups
present in the cotton fabric.
Spectra of the BTCA treated fabric sample shows absorption in the band 1725 cm-1 due
to the ester carbonyl groups formed (which confirm the covalent bond between the cellulose
and BTCA) [14].
Scanning Electron Microscope

Some researches such as Lam et al. [3] examined the surface morphology of cotton
specimens by the scanning electron microscope (SEM). The untreated samples picture shows
the normal spiral structure of the cotton sample, which was clearly defined (Figure 2).
Treating the cotton samples with 5% BTCA evidenced a damaged surface as shown in
Figure 3. Figure 4 illustrates the SEM image of the cotton sample treated with 10% BTCA in
the presence of 10% SHP.
0,6
0,5
0,3
0,2
0,1
0
3600
3100
2600
2100
Wavenumber (cm1)
CO_210
80BTCA+40SPH
Figure 1. Infrared spectra of the untreated and treated samples.
1600
1100
600
Absorbance
0,4
Figure 2. SEM image of control cotton sample by YL Lam et al. [3].
Figure 3. SEM image of cotton sample treated with 5% BTCA [3].
Figure 4. SEM image of cotton sample treated with 10% BTCA and 10% SHP [3].
359
360
It was obvious that fibers were severely damaged when 10% BTCA was applied to the
cotton samples. It was concluded that the surface was damaged after undergoing the treatment
and the deterioration of fibers might be caused by the attack of BTCA at extremely low pH
value, i.e., pH 12.
Whiteness Index
Another experimental technique used is the spectrophotometer applied in order to
compare objectively samples whiteness index. In a previous study [13], cotton fabrics
yellowing was studied when different carboxylic acids were used at high temperature. The
study was conducted with four acids: 1,2,3,4-butane-tetracarboxilyc acid (BTCA), citric acid
(CA), maleic acid (MA) and succinic acid (SA) and different response were obtained
depending on the acid used. Using carboxylic acids as a crosslinking agent for cotton causes
fabric yellowing. This yellowing can be increased by the increase of curing temperature and
acid concentration, but if BTCA and SA-treated cotton are used, it can be obtained a gradual
decrease in whiteness index.
Wrinkle Recovery Angle

In the past, workers studied the relationship between cotton fabric strength and the chain
lengths of crosslinking agents [19-23]. In 2000, Yang and Wei [24] studied the relationship
between fabrics tensile strength loss and the molecular structures of crosslinking agents.
Crosslinking between cellulose molecules causes stiffening of the cellulosic
macromolecular network and fiber embrittlement thus, reducing the mechanical strength of
the treated cotton. Authors used a linear tetracarboxylic acid (BTCA) and a cyclic one
(CPTA) to treat cotton at different concentrations and different temperatures, and compare the
tensile strength loss from the crosslinked fabric as a function of wrinkle recovery angle
(WRA). It was also compared the tensile strength loss of cotton treated with DMDHEU and
DHDMI.
Results indicate that BTCA is more effective as a crosslinking agent for cotton cellulose
and imparts higher levels of wrinkle resistance to the treated cotton than CPTA. The
relationship between tensile strength loss and wrinkle recovery angle for the cotton treated
with BTCA and CPTA is essentially equivalent. Cottons treated with DMDHEU and DHDMI
showed the similar phenomenon. Therefore, all the studies evaluated indicate that the tensile
strength loss of crosslinked cottons fabric is independent of differences in the molecular
structure and reactivity of the crosslinking agents.
Thermal Analysis
In order to investigate the effect of performed treatment on cellulose pyrolysis process,
thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out
by several researches. For instance, Lessan et al. [25] studied the effect of SHP and nano TiO2
as a novel flame retardant for cotton fabric.
361
Some analysis including char length, char yield, LOI, TGA and DTA were studied in
order to evaluate flame retardant properties from treated samples. They concluded that the
presence of phosphorus deposited on the SHP treated samples is the most effective parameter
in the char forming and decreasing the treated fabrics flammability.
Furthermore, nano TiO2 is an effective compound in increasing the char formation.
Moreover, the performed treatment helps to form more non-flammable char residue and
increases char formation after heating. Thermal gravimetric analysis (TGA) and differential
thermal analysis (DTA) were employed to investigate the thermal decomposition from the
treated samples.
NEW APLICATIONS
Flame Retardant
Polycarboxylic acids are able to reduce the flammability of cotton as reported by
Blanchard and Graves [26]. For example, phosphorus-containing oligomers of maleic acid
reduce flammability through increases of char formation in cotton. The combination of an
insaturated bifunctional acid, for example maleic acid, and a phosphorus-containing inorganic
compound, such as sodium hypophosphite, can reduce the flammability of cotton fleece [27].
Other polycarboxylic acids like succinic acid, tartaric acid, citric acid and 1,2,3,4butanetetracarboxylic acid have been used as flame retardant. These polycarboxylic acids in
combination with sodium hypophosphite reduce the flammability of cotton fabrics [26, 27].
The most successful and effective durable flame retardant systems of cellulosic textile are
based on phosphorus-containing and nitrogen-containing compounds. The mechanism of
flame retardancy in these systems is based on cellulose crosslinking, making more char and
preventing the formation of undesirable levoglucosan and flammable volatiles [28]. The
phosphorus-nitrogen synergism plays an important role in these compounds [29].
Dehabadi et al. [30] use polyamino carboxylics acids (PACAs) and their combination
with sodium hypophosphite (NaH2PO2) as a novel flame retardant finishing for cotton fabrics.
To evaluate its flammability 45 flammability test and differential scanning calorimetry were
used.
Antimicrobial Property
Chitosan is the deacetylated derivative of chitin, which is the main component of the
shells of crustaceans such as shrimps, crabs and lobsters [31]. Large quantities of chitin are
produced as a byproduct of the seafood industry. Chitosan has been found to inhibit the
growth of microbes in a large body of work that has been extensively reviewed by Lim and
Hudson [32].
The antimicrobial mechanism is not clear but is generally accepted that the primary
amine groups provide positive charges which interact with negatively charged residues on the
surface of microbes. Such interaction causes extensive changes in the cell surface and cell
permeability, leading to leakage of intracelular substances.
362
This antimicrobial ability, coupled with its non-toxicity, biodegradability and

biocompatibility, is facilitating chitosans emerging applications in food science, agriculture,
medicine, pharmaceuticals and textiles. The prime focus for chitosan as an antimicrobial
treatment has been on cotton.
Ancient works, indicated that the antimicrobial effect was potent against a range of
microbes, but the finishing was not durable at all. To improve durability, chitosan has been
crosslinked to cotton using chemicals such as dimethyloldihydroxyethyleneurea (DMDHEU),
citric acid, 1,2,3,4-butanetetracarboxylic acid (BTCA) or glutaric dialdehyde [33, 34]. Eltahlawy et al. [33] demonstrated that cotton fabrics treated with two different crosslinking
agents BTCA and Arcofix NEC (low formaldehyde content) in the presence of chitosan
provide the cotton fabrics a durable press finishing and antimicrobial properties by chemical
linking of chitosan to the cellulose structure. Orhan et al. [35] used citric acid and BTCA to
improve the effect antimicrobial of the cotton fabric and Chung et al. [36] used Citric acid
(CA) and chitosan as durable press and antimicrobial finishing agents on cotton fibers. They
showed that cotton fabric treated with no more products than CA shows antimicrobial
properties and strength retention improvement is higher when CA is used with chitosan.
Grafting of Micro and Nano Particles on Fabric

Polycarboxylic acids are used to improve the adhesion of nano and micro particles onto
cotton fabric, thereby to increase washing durability. It is known that carboxylic acids could
esterify with celluloseOH, and also could co-condense with SiOH groups, leading to the
formation of interfacial ester bonds. When one of the carboxylic acid groups in
polycarboxylic acid binds to cellulose with ester bond, there would still be free carboxylic
acid group(s) available to form ester bonds with SiOH [37]. As a result, polycarboxylic acids
could act as ester-bridge to connect cellulose and heterogeneous silica functional layer.
Huang et al. [38] used different polycarboxylic acids to fix hydrophobic cellulose fabric
finished by solgel method combining SiO2 nanoparticles and with hexadecyltrimethoxysilane modification. They concluded that among various polycarboxylic acids, BTCA gave
the best performance. One of the main disadvantages of using film-forming binders in
application of microcapsules onto textile materials is possible hindrance of the active
substances release. To avoid this problem, microcapsules can be covalently linked onto textile
substrate by using bi/ polyfunctional crosslinking reagents. The most agent crosslinking used
in the literature is BTCA. Badulescu et al. [39] used BTCA with cyanamide (CA) and N,Ndicyclohexylcarbo-diimide (DCC) as catalyst and shown that esterification between BTCA,
ethylcellulose microcapsules and hydroxyl groups of cellulose can occur simultaneously. The
same authors linked supramolecular compound (-cyclodextrin) onto cotton cellulose via
grafting or crosslinking with BTCA [40].
Water Repellency
Fluorocarbon resin is the most effective treating agent for making fabrics water
repellant [41].
363
To improve the washing durability of water repellency, some cross-linking agents are
usually used along with the water repellent agents. Montazer [42] applied BTCA, with the
optimum concentration of 5 g/L, and different concentrations of fluorocarbon agent for water
repellent finishing of cotton fabrics. BTCA is confirmed to be an effective cross-linking agent
with sodium hypophosphite (SHP) catalyst for washing durability improvement of cotton
fabrics treated with fluorocarbon resin. It has been reported that the water repellency of the
sample treated with fluorocarbon resin and 8% BTCA is higher than the sample treated only
with fluorocarbon resin [43]. This kind of difference can be seen especially after fifty
washing cycles and subsequent heat treatments [5].
CONCLUSION
In years past, significant progress has been made in introducing cross-linking
nonformaldehyde agents to cotton fabrics in order to obtain a durable press fabric, being
BTCA the most used as it is one of the more efficient PCAs. To study the mechanism of the
reaction between the PCA and cellulose FTIR is used. Moreover, this technique is used to
study and evaluate the effectiveness of the crosslinking agent used.
Nowadays, this type of finishing is being studied by many researchers as we have shown
in this work due to the fact that they provide new properties to the cellulosic fabric, such as
flame retardant and antimicrobial. Moreover, these acids are used to improve the adhesion of
nano and micro particles onto cotton fabric, thereby to increase washing durability.
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ISBN: 978-1-63117-262-5
Chapter 14
WRINKLE RESISTANT AND COMFORT FINISHING

OF COTTON TEXTILES
Vahid Ameri Dehabadi* and Hans-Jrgen Buschmann
NETZ / DTNW GmbH, Duisburg, Germany
ABSTRACT
The Cotton fiber is the most important fiber in the apparel industry, since it can
readily absorb moisture. Cotton made clothes are the most comfortable garments.
However, easy wrinkling of cotton fabrics is their main disadvantage. Therefore, wrinkle
resistant cotton is one of the consumers demands in the textile market and durable press
finishing is still an interesting field in chemical processing textiles. On the other hand,
there is always an increasing request for those clothes and garments with high
specifications and more performance, such as easy-care garments and more comfort.
Durable press (DP) or easy care finishing is the special treatment to defeat the easy
wrinkling of cotton textiles. This process provides resistance against shrinkage and
improved wrinkle recovery to cellulosic textiles. The mechanism of durable press finish
is inhibition of easy movement of the cellulose chains via crosslinking with appropriate
resins/polymers. During this finishing process other molecules can be simultaneously
bonded to improve the wear comfort. In this chapter, after presenting a short historical
background of DP finishing, the general strategies and the most recent advances of easycare finishes will be discussed.
Keywords: Cotton, easy-care, comfort, finishing
INTRODUCTION
Finishing is a process to add extra value such as fashion aspects and new functions into
the textile materials. In other words, the aim of finishing is completing the fabrics
*
Corresponding author: E-mail: vahid.ameri@dtnw.de.
368
performance through providing special functions, such as anti-microbial activity, odourresistance and easy-care. In contrast to the traditional usage of textiles, which are restricted to
their primary performances as covering and protecting of the human body against
environmental influences, finishing brings extra values and functions in a direct response to
market demand. For instance, it has been always a growing request for wrinkle-free apparel,
known also as wrinkle resistant, easy-care, durable press or easy-ironing clothes. Among the
fibers used in apparels, cotton fabrics show the most problems with wrinkling. The main
cause of easy wrinkling of cotton originates from its chemical/physical structure. As a matter
of fact, crushing of fabrics during use and care generates wrinkles. By considering the
chemical structure of cellulose as the main component of cotton we can see lots of
hydrogen bonds between molecular chains (see Figure 1). Water or moisture absorption
during washing and wearing (from environment or body perspiration) by hydroxyl groups of
cellulose chains leads to the easy moving of the molecular chains in amorphous and
intermediate (non-crystalline) regions of cellulose (see Figure 2). Then, cellulose chains will
be newly arranged and fixed by the hydrogen bonds between the adjacent hydrogen
groups [1].
Figure 1. Hydrogen bonds between cellulose chains.
Figure 2. Moving of cellulose chains in amorphous and non-crystalline regions of cotton (right) due to
the deformation and new-formation of hydrogen bonds (left).
369
Therefore, inhibiting the movement of cellulose chains by crosslinking of with

resins/polymers is the appropriate way to overcome this problem [2-3]. The crosslinking
agents can be principally divided into two main groups: formaldehyde-based chemicals (the
oldest crosslinkers) and formaldehyde-free compounds.
PRIMARY EASY CARE FINISHING AGENTS BASED ON

FORMALDEHYDE RESINS
N-methylol compounds, namely urea-formaldehyde or melamine-formaldehyde (see
Figure 3), were introduced as the primary easy-care finishing agents at the end of 1920s [4-5].
In 1947 dimethylolethylen urea compounds, in particular N, N-dimethylol-4,5dihydroxyethylen urea (DMDHEU), were employed as the main crosslinking agents [6-7].
DMDHEU as the final product of the reaction between urea, glyoxal and formaldehyde reacts
with the cellulose and form a crosslinking net [8-11] (Figure 4).
O
C
HO
H2C
HN
NH
CH2 OH
H3C
H2C
HN
NH
CH2 O
H
NCH2OCH3
N
CH3OCH2N
N(CH2OCH3) 2
N
NCH2OCH3
(CH3OCH2)2N
N
N(CH2OCH3) 2
Figure 3. Resins of urea-formaldehyde (A) and melamine-formaldehyde (B).

O
C
Cell
OH
HOH2C
CH2OH
HO
OH
+ 2H2O
- 2H2O
C
Cell
H2C
CH2 O
HO
OH
Figure 4. Reaction of DMDHEU (A) with cellulose and resulting crosslinked cellulose (B).
Cell
CH3
370
H C C H
H C C3H6
O O
glyoxal
C H
O
glutaraldehyde
Figure 5. Chemical structures of glyoxal and glutaraldehyde.
The main problem of the above-described compounds was release of formaldehyde

during washing and use. Formaldehyde has lots of potential hazards: it can irritate mucous
membranes, cause teary eyes, cough, headache and difficulties in breathing. Furthermore,
eczema and allergic responses may be evoked through direct contact of skin with the textiles
containing of high levels of [12-15].
Due to the release of formaldehyde during production of easy care textiles with
DMDHEU or even during the storage and use of the treated cotton fabrics N-methylol
compounds, since 1960s it has been tried to develop the formaldehyde-free easy care agents
or the finishes with low amount of formaldehyde release [16-17].
PRIMARY FORMALDEHYDE-FREE EASY CARE FINISHING AGENTS

The early formaldehyde-free compounds were nitrogen-free finishes, including aldehydes
such as glyoxal and glutaraldehyde (see Figure 5) [18-19]. Apart from high costs of glyoxal
and glutaraldehyde, application of these compounds on cotton textiles cause more strength
loss (in comparison to N-methylol compounds), yellowing and discoloring the fabric [20-22].
Acetals such as 2,5-dimethoxyfuran, 2,3-dihydroxy-1,1,4,4-tetramethoxybutane, 3,4dihydroxy-2,5 dimethoxytetra-hydrofuran, and glyceraldehyde dimethylacetal have been used
as formaldehyde-free crosslinking agents. Treatment of cotton textiles with acetals reduces
the fabric strength dramatically and therefore they are not applied in industrial scales [23-26].
Reaction products of amides and aldehydes, mainly N, N-dimethyl-4,5dihydroxyethxylen urea (DMeDHEU) or 4,5-dihydroxy-2-imidazolin (see Figure 6) have
been considered as effective formaldehyde-free finishes, which produce enough easy-care
performance with a good durability against washing [26-27].
O
C
H3CN
HO
NCH3
OH
Figure 6. Chemical structure of N, N-dimethyl-4,5-dihydroxyethxylen urea (DMeDHEU).
371
CURRENT TREND IN EASY-CARE IN EASY-CARE FINISHING

OF FINISHING COTTON FABRICS
Polycarboxylic Acids
Among the formaldehyde-free crosslinking agents for providing wrinkle resistant textiles
and considering the limits of the primary finishes in practical applications (yellowing of
textiles, reduce of tensile strength and in some cases high costs of chemicals), it can be said
that polycarboxylic acids are the most promising compounds [28-33]. The benefits of
finishing with polycarboxylic acids are: high quality crosslinking, high fabric strength
retention and good durability against laundering [34-37].
The presence of at least three carboxylic groups in polycarboxylic acids is necessary to
create an acceptable wrinkle-resistant effect on cotton textiles. Therefore, 1, 2, 3, 4butanetetracarboxylic acid (BTCA), citric acid (CA) and succinic acid (SUA) (see Figure 7)
are the most conventional polycarboxylic acid [38-43]. Except from BTCA, the other
mentioned polycarboxylic acids have some limitations in practice and BTCA shows the best
results [44-48].
Cotton fabric is crosslinked by polycarboxylic acids through the formation of 5- or 6member cyclic anhydride intermediates and finally esterification of the hydroxyl groups in the
cellulosic chains (see Figure 8) [49-51].
In Figure 9 formation of the cyclic dianhydride intermediate of BTCA and final
esterification of cellulose chains is shown [52].
HO
HO
HO
OH
O
O
HO
OH
OH
O
OH
OH
OH
BTCA
SUA
CA
Figure 7. Chemical structure of the conventional polycarboxylic acids used for easy-care finish of
cotton textiles: 1,2,3,4-butanetetracarboxylic acid (BTCA), succinic acid (SUA) and citric acid (CA).
R1 O
R1 O
HC
HC
OH
OH
R2 O
Polycarboxylic acid
HC
R1 O
- H2O
O
HC
R2 O
Cyclic anhydride
+ HO
Cell
HC
Cell
HC
R2 O
Polycarboxylic acid bonded to cellulose
through ester linkage
Figure 8. Esterification of cellulose chains by polycarboxylic acids via formation of cyclic anhydride
intermediates.
372

O
HO
HO
O
HO
OH
- H2O
O
O
O
O
+ H2O
+Cell
CH2OH
Cell
H2C
O
CH2 Cell
O
O
OH
OH
O
a
Figure 9. Crosslinking of cellulose (c) with BTCA (a) via formation of cyclic anhydride
intermediate (b).
Application of a proper catalyst accelerates the esterification reaction and reduces the
time and temperature of process. Several catalysts have been used and their advantages and
disadvantages were studied by researchers. Most of the used catalysts belong to the sodium
salts of phosphoric acids, such as sodium hypophosphite (NaH2PO2), monosodium phosphate
(NaH2PO4), disodium phosphate (Na2HPO4), and trisodium phosphate (Na3PO4) [29, 46, 5354]. It has been shown that sodium hypophosphite (NaH2PO2) is the best catalyst for the
crosslinking of cotton with polycarboxylic acids, especially BTCA. By application of sodium
hypophosphite in durable press finishing of cotton highest levels of durable press rating and
wrinkle recovery angle, reduction in cure temperature, increase of tensile strength retention
and the most satisfactory whiteness are obtained [54-60]. The action mechanism of sodium
hypophosphite as catalyst in reaction of polycarboxylic acid and cellulose is shown in Figure
10 [51, 60]. Beside to the phosphorus catalysts, nonphosphorus catalysts have been also
investigated, including aromatic N-heterocyclic compounds such as imidazole and its
derivatives to improve the retention of mechanical properties of the treated fabric [61], base
catalysts such as sodium carbonate and tertiary amines to minimize degradation of treated
cotton fabric, and other compounds like mono- or disodium salts of -hydroxy acids such as
tartaric, malic, or citric acid [33].
In addition to the role of catalyst in easy care finish of cellulosic textiles, pH value of
finishing bath and the molecular weight of polycarboxylic acid have an important effect in
final result. The number of ester linkages and the effectiveness of the bonded polycarboxylic
acid molecules decrease by increase of pH from 1.5 to 5.5. As a matter of fact, by decrease of
the pH the number of cyclic anhydride intermediate increases. In the other words, forming of
cyclic anhydride is accelerated by increase the concentration of proton in the finish bath [6263]. Polycarboxylic acids with lower molecular weights cause easy mobility of cyclic
anhydride intermediate to access hydroxyl groups of cellulose chains [39-40,64].
R1 O
HC
R1 O
O
C
O
HC
R2 O
HC
HC
ONa
OH
ONa
R1 O
R2 O
Cell
OH
HC
HC
OH
Cell
+
ONa
R2 O
Figure 10. Crosslinking of cellulose by polycarboxylic acids in the presence of sodium hypophosphite
as catalyst.
373
High cost, requirement of large amount of catalystsand loss of the mechanical strength
are general limits of finishing with the conventional polycarboxylic acids [65-66].
The last progress in polycarboxylic acids, we can mention to polyamino carboxylic acids
(PACAs) [67-68]. PACAs can be easily synthesized by carboxylation of polyvinylamine
(PVAm) or polyethyleneimine (PEIm), via reaction of the primary amino groups (Figure 11a)
with halocarboxylic acids, such as bromoacetic acid (Figure 11b). The resulting substance can
esterify the hydroxyl groups in cellulose and make crosslinking net (Figure 12).
PACAs have less negative impact on tensile strength and whiteness of the cotton
compared to the conventional polycarboxylic acids such BTCA and citric acid [67-68]. On
the other hand, cotton finished with PACAs shows biostatic properties [69], and has a better
dyeability due to the presence of the free amino groups [70]. PACAs in a combination with
sodium hypophosphite reduce the flammability of the cotton, as well [71].
Figure 11. Synthesis of polyaminocarboxylic acids (b) via carboxylation of polyvinylamine (a) with
bromoacetic acid under alkaline condition.
Figure 12. Covalent crosslinking of cellulose chains with PACAs.
374
Ionic Crosslinking Agents

Another approach to impart wrinkle resistance effect is ionic crosslinking, in which a
preionized cotton fabric (either cationic or anionic) can adsorb an opposite charged substance
and form a crosslinking net [72]. For instance, a precationized cotton fabric can be
crosslinked with a citric acid [73]. In Figure 13, cellulose is precationized with 3-chlorohydroxypropyl trimethyl ammonium chloride (CHTAC) and then crosslinked in the presence
of citric acid.
OH
Cell
CH2 CH
CH2 N (CH3)3 Cl +
HO
OH
O
OH
O
Cell
CH2 CH
CH2 N (CH3)3 OOC
CH2 + HCl
HOOC
OH
HOOC
CH2
Figure 13. Ionic crosslinking of cotton precationized with 3-chloro-hydroxypropyl trimethyl

ammonium chloride (CHTAC) in the presence of citric acid.
H3C
CH3 H3C
Si
O
CH3 H3C
Si
O
NH3
Si
O
Si
Si
O
OH
CH3
Si
O
O
COO
CH3 H3C
H3C
Si
O
CH3
CH3
NH3
CH3
Cotton or CMC fabric

Figure 14. Crosslinking of cellulose using an aminosilicone softener with partially protonated amino
groups on negatively charged cotton (e.g., carboxymethylated cotton-CMC).
375
Using of an aminosilicone softener with partially protonated amino groups on negatively

charged cotton (e.g., carboxymethylated cotton), wrinkle resistant and soft-hand effects will
be simultaneously created [74] (see Figure 14).
Two basic reactions occur between amino-silicones and cellulose chains in cotton: the
ionic interaction between protonated amino groups of in amino-silicone molecule and
negatively charged cotton, and self-polymerization of silicone molecules through their
respective reactive groups. Incorporation of amine functional silicone softeners in the
ionically crosslinked cotton includes coulomb and dipole-dipole forces, hydrogen bond, van
der Waals interaction and ether crosslinking. The nitrogen atoms in amino-silicone molecule
are protonated under acidic condition. The negatively charged carboxymethylated cotton
(CMC) and the positively charged amino-silicone make a crosslinking when these groups are
localized at two adjacent cellulose chains.
Nanotechnology in Easy-Care Finish of Cotton Textiles

The first use of nanotechnology particularly nanoparticles in easy care finish of cotton
textiles is employing of titanium dioxide (TiO2) nanoparticles as catalyst to improve the
wrinkle resistance properties of silk fabrics treated with maleic anhydride as crosslinking
agent [75]. Nanoparticles of titanium dioxide have been used as photo catalyst for finish of
cotton with polycarboxylic acids: BTCA, maleic acid, succinic acid and citric acids [76]. The
action mechanism of nanoparticles of titanium dioxide can be explained in this way: electron
of TiO2nanoparticles is excited at the valence bond under UV radiation with a wavelength
lower than 400 nm for a few microseconds (s) and moves to the surface of the nanometer
particles and therefore water molecules and hydroxyl ions can be reduced by this process
(known as photo reduction) [77]. As a result, the carboxylic acid groups and vinyl double
bond of the polycarboxylic acids react with the cellulose molecules (crosslinking) [78].
In the case of crosslinking with polycarboxylic acids, e.g., succinic acid, and
nanoparticles of titanium dioxide, the mechanism of reaction can be supposed as following
(see Figure 15): the molecules of succinic acid are adsorbed on the surface of the
nanoparticles and exposed to the UV photo-reduction under to form free radicals of succinic
acid (Figure 15a) and an aldehyde group (Figure 15b). The contact between the succinic
acids free radicals and the cellulose molecules complete the crosslinking reaction (Figure
15c).
Another well-known technique in nanotechnology is sol-gel processes, which involve the
hydrolysis of inorganic precursors such as organo-silicates, organo-titanates-aluminates, etc.
and forming a 3D molecular network [79]. Finishes based on sol-gel technique have been
investigated to improve performance of cotton finished with polycarboxylic acids [79].
Cotton can be finished in two steps with BTCA, sodium hypophosphite and TEOS
(tetraethoxysilane)/GPTMS (glycidylpropyloxytrimethoxysilane)-based solutions with
different amounts of GPTMS [80]. Dry wrinkle recovery angle can be fairly improved;
meanwhile abrasion resistance increases greatly.
376
2 HOOC
CH2 CH2 COOH
HOOC
CH2 CH COOH
HOOC
CH2 CH2 CHO
(a)
H2O2
(b)
TiO2, H2O
UV irradiation
Cell
TiO2
OH
Cell
(c)
UV irradiation
COOH
Cell
HOOC
CH2 CH
COOH
Cell
CH
(d)
CH2
COOH
O
Cell
OH
OHC
CH2 CH2 COOH
Cell
CH2
H2O
(e)
CH2
COOH
Figure 15. Crosslinking of cellulose with succinic acid catalyzed by nanoparticles of titanium dioxide
under UV irradiation.
Figure 16. Chemical structures of the different cyclodxetrins and their dimensions.
377
Comfort Finishing of Cotton Textiles

Due to their chemical structure cotton fabrics easily adsorb water molecules. Therefore,
the consumer judges the comfort of cotton fabrics high. However, due to the permanent
contact of the textile with the human skin also the organic sweat components are incorporated
within the cellulosic fiber. Due to the coincidence of humidity and the adsorbed organic
substances from the sweat microorganism decompose these organic substances. This may
result in some unpleasant odour released from the textiles. It is also well-known that textile
materials act as reservoir for odour adsorbed from the neighborhood. These substances e.g.,
tobacco smoke are slowly released. To achieve a permanent fresh impression the desorption
or release of substances from the textile have to been avoided. This effect can be realized by
the use of cyclodextrins.
Cyclodextrins are formed during the enzymatic degradation of starch. They are
polysaccharides built from six to eight (=6, =7, =8) D-glucose units. The D-glucose units
are covalently linked at the carbon atoms C1 and C4.. The glucose units form a torus shaped
molecule with a cavity. In these cavities guest molecules can be enclosed. Cyclodextrins are
already used in pharmaceutical and cosmetic applications [81]. The chemical structures of the
different cyclodextrins are given in Figure 16.
Unfortunately the cyclodextrin molecules do not show any affinity to any fibre material.
Thus, a permanent fixation of the cyclodextrins on cotton fibers has to be done using
chemical reactions. A cyclodextrin derivate with a reactive group (e.g., the
monochlorotriazinyl group) is able to react with the hydroxyl groups of a cotton fiber [82-83].
Since the hydroxyl groups of the cotton and of the cyclodextrin molecules behave chemically
nearly identical any crosslinking reaction can be used for the permanent fixation of
cyclodextrins on the cotton fiber. Using bifunctional or polyfunctional reactants cyclodextrins
have already successfully bound on cotton fibers [84-88]. Thus, it is very simple to combine
an easy care finishing with an additional wearing comfort.
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ISBN: 978-1-63117-262-5
Chapter 15
EVALUATION OF PHYSICAL
AND THERMAL COMFORT PROPERTIES
OF COPPER/ALGINATE TREATED WOOL FABRICS
BY USING ULTRASONIC ENERGY
Muhammet Uzun*
1
Institute for Materials Research and Innovation, University of Bolton, Bolton, UK.
Goztepe, Istanbul, Turkey
ABSTRACT
The aim of this study is to treat wool fibre based woven fabric with sodium alginate
and copper sulphate by using ultrasonic energy, and then test and analyse the treated
fabrics physical and thermal comfort properties including: tensile properties, abrasion
behaviour, flexural rigidity, and thermo physiological properties. The fabrics were
immersed in 5%, 10% and 15% w/v copper solution and subsequently the fabric
specimens were subjected to 10 min and 20 min ultrasonic energy treatment. The results
clearly demonstrated that the wool fabric was successfully treated with the copper and the
coated fabrics showed significant changes as compared to their untreated forms. The
tensile strength of the treated fabrics was strongly affected by the volume of copper in the
solution. The abrasion test was performed for up to 50.000 rubs due to the standard test
method and there were no considerable differences between the untreated and the treated
fabrics. The treatment lowered the flexural rigidity values. The fabrics thermal
conductivities and thermal resistances were increased significantly after the treatment. It
was also observed that the conductivity of the fabrics increased gradually. Furthermore,
the treated fabrics had lower thermal absorbtivity values. The treated fabrics showed
considerably lower water vapour permeability compared to the untreated fabrics. The
ultrasonic energy application times did not affect any of the measured fabric properties
significantly.
E-mail: m.uzun@marmara.edu.tr and muzun46@hotmail.com.
384
Muhammet Uzun
Keywords: Wool fabric, alginate, copper treatment, thermal comfort, physical properties,
ultrasonic energy
INTRODUCTION
Recently, there have been a number of studies carried out detailing the converting of
conventional textile materials to novel smart, responsive and high value-added products. The
textile surface structure of the fabric can be modified by appropriate chemical method for the
required functions and features. A wide range of smart products have been successfully
commercialised which include fire-retardant fabrics, waterproof fabrics, biomedical
applications such as silver treated wound dressings. Some coated products have been
developed to minimise the risk of the bacteria which occurs in a hospital environment. To
prevent forming of reservoirs of bacteria, surfaces such as bed rails, bedside tables and door
handles, must be cleaned and disinfected properly. However, some bacteria now have the
ability to survive even after thorough treatment with disinfectant [1]. Thus there is a greater
need for biocidal surfaces to help reduce cross-contamination. This has led researchers to
investigate antimicrobial agents such as copper to produce biocidal surfaces. Copper has been
identified as being effective against a broad spectrum of microorganisms such as Clostridium
difficile [2], Escherichia coli O157:H7 [3], Influenza A(H1N1) [4], Listeria monocytogenes
[5], and methicillin-resistant Staphylococcus aureus.
Sodium alginate can form a hydrophilic gel when in the presence of divalent cations such
as copper (Cu2+) via a unique ion exchange mechanism whereby the sodium ions attached to
the carboxyl groups on the uronic acid monomers are exchanged by the copper ions, which
subsequently cross-links the alginate chains together, forming a crystalline structure [6]. A
number of studies have shown that the ultrasonic energy has many advantages over
alternative treatment methods such as superior cleaning, a reduction in the textile processing
time, and reduced energy and chemicals [7-9].
Thermo physical comfort has been described as the garments ability to keep the wearer
dry whilst maintaining body temperature, even when the wearer is subject to varying
surrounding temperatures and humidity. The thermal comfort properties of a textile fabric are
advantageous characteristics for the end-product [10-12]. The comforts of a garment mainly
depend on its thermal properties, water vapour permeability and air permeability [13, 14].
Garment comfort characteristics are based on fibre types (natural, synthetic), yarn production
method (ring, open-end), yarn properties (count, twist), fabric structures (woven, knitted,
nonwoven), fabrics physical features (thickness, warp-weft number) and also textile finishing
process (bleaching, dyeing), etc [15-17].
In this study, a novel technique of incorporating copper into100% wool fabric using
sodium alginate, cupric sulphate and ultrasonic energy has been effectively established. The
main idea is to take advantage of alginates unique ion exchange mechanism to form copper
alginate soaked wool fabric by incorporating ultrasonic energy. In order to investigate the
effect of the copperon the wool fabric, three different concentrations (5%, 10% and 15%) of
cupric sulphate solution were prepared and the fabric specimens were soaked for two hours
and then the fabrics were subjected to 10 min and 20 min of ultrasonic energy. The untreated
(control, 0%) and the treated fabrics were tested and analysed for tensile properties, abrasive
properties, flexural rigidity, thermo physiological properties including; thermal conductivity,
thermal resistance, thermal absorbtivity, water vapour permeability, and heat loss. Analysis of
385
Evaluation of Physical and Thermal Comfort Properties
variance (ANOVA) was employed to determine the significance of the tested properties for
assessing the statistical significance of the differences between i) the untreated and the treated
fabrics; ii) ultrasonic energy application times; and iii) dry and wet states of the comfort test
results.
MATERIALS AND METHODS

Materials
100% plain wool fabric was purchased from the UK market. The plain weave, being the
fundamental weave, was chosen as the fabric structure where each filling yarn passes
successively over and under each warp yarn, alternating each row. The fabric dimensional
properties were tested and the results are given in Table 1. Sodium alginate, MANUCOL
DH, was obtained from Ashland Ltd., U.K., (formerly ISP) (SA, medium viscosity 40-90
mPas (1%), M: G ratio 61/39). Copper (II) sulphate, pentahydrate was obtained from Fisher
Bioreagents Ltd., U.K.
Table 1. Dimensional property of wool based woven fabric
Fabric
Area density Thickness

(gm-2)
(mm)
171
0.5
Bulk density
(gm-3)
0.343
Warp no.
(per cm)
28
Weft no.
(per cm)
19
Figure 1. Plain woven fabric structure.
Methods
Copper/Alginate Treatment
20cm 20cm fabric specimens were prepared and the specimens were fully immersed
into the sodium alginate solution (2.5% w/v) for 24 h and then they were rinsed thoroughly
with distilled water. After rinsing, the fabrics were then bathed in the copper sulphate
solutions of different concentrations, (5%, 10% and 15% (w/v)) for two hours. Ultrasonic
energy was applied to the fabrics under a 25C bathing temperature at different application
386
Muhammet Uzun
times, 10 and 20 min. For the ultrasonic application, the ultrasonic bath (Bamdelim Sonorex
Digital, UK 10P, 220 volt and 205 watt) was employed using a 1010% power. The treated
fabrics were rinsed three times in distilled water and finally, the fabrics were left to dry at
room temperature for 24 h.
Tensile Properties
The specimens were prepared in 20cm length x 5cm width in both weft and warp
direction of the fabrics. The specimens were then mounted in the grips of an Instron universal
tester 3300, UK, with 100 mm gauge length and 300mm/minute extension rate. Five
measurements were carried out for each fabric combinations and the mean values of the
readings were calculated.
Abrasive Testing
The abrasion test was performed with Martindale Abrasion and Pilling Tester M235/3,
USA, using the established standard Martindale abrasion test method. The abrasive wear
testing determines the resistance to abrasion of textile fabrics. The measurement of the
resistance to abrasion of textile fabrics relies on several parameters such as the mechanical
properties of the fibres, the dimensions of the fibres, the structure of the yarns, the
construction of the fabrics, the type and kind of finishing material etc. The fabric specimens
were cut using press cutters into circular specimens of 38mm diameter and placed on the
specimen holder. The test was performed while applying a pressure of 9kPa, and the machine
speed was maintained at 50 rubs per minute. After performing every 5000 rubs, the specimens
were inspected for abrasion.
Flexural Rigidity Testing
The stiffness depending on bending length and flexural rigidity of fabrics were done
using Shirley stiffness tester, UK, in accordance with BS 3356:1961. The test specimen size
was prepared in 25mm width and 200mm length. Three specimens in warp directions and
three weft directions were tested and the mean values were calculated.
Thermo Physiological Testing
The thermophysiological properties of the woven fabrics were determined by using an
Alambeta instrument (Sensora Instruments, Czech Republic). The Alambeta instrument
provides values for thermal conductivity, thermal resistance (insulation) and thermal
absorbtivity (warmth-to-touch), fabric thickness and thermal diffusion. The test instrument
was used to conclude the transient and steady state thermophysical properties of the fabrics.
The specimens size of 20cm 20cm were prepared and placed in between two plates. The
heat flow through the fabric due to the difference in temperature between the bottom
measuring plate (at ambient temperature) and the top measuring plate which is heated to
40C. The thermal absorbtivity of the textile structure is a measure of the amount of heat
conducted away from structure surface per unit time [18-20]. The test was performed on dry
and wet specimens. The wet specimens were wetted with 0.2mL of water on the centre of the
fabrics and allowed 4 min of thermal recovery before testing. For each side (front and back
side of fabric) of the untreated and treated fabric measurements were made, and the mean
values of the measured parameters were calculated.
387
Water vapour permeability and the resistance to evaporative heat loss of the fabrics were
tested using the Permetest instrument (Sensora Instruments, Czech Republic). This instrument
is based on a skin model, which simulates dry and wet human skin in terms of its thermal
feeling. The instrument uses the same principle as specified in ISO 11092 developed by
Hohenstein Institute, Germany, whereby a heated porous membrane is used to simulate
sweating skin. The heat required for the water to evaporate from the membrane, with and
without a fabric covering, is measured [18].
RESULTS AND DISCUSSION

Tensile Properties of Wool Fabrics
The tensile properties of the fabrics are presented in Table 3. The tensile test results of
the warp and weft direction of the fabrics were found to be different. It can be seen in Figure2
the warp directions of treated fabrics lost their tensile strength properties gradually when the
copper volume increased. On the other hand, it is shown in Figure3 that the copper treatment
had different impact on the tensile properties in weft direction.
Table 2. Tensile properties of the treated and untreated wool fabrics
Copper
Concretions
Warp
Weft
0%
5%
10%
15%
0%
5%
10%
15%
10 min
20 min
Tensile strengthBreaking extensionTensile
(N)
(mm)
(N)
341
5.4
341
263
8.5
261
253
6.9
263
170
6.4
177
257
7.9
252
348
6.9
342
366
6.7
366
143
6.9
156
strengthBreaking extension
(mm)
5.4
7.2
6.2
7.2
5.9
6.4
7.2
6.2
The tensile strength of warp direction for the untreated (0%) fabric was 341 N which was
the highest strength value compared to the treated fabrics and 15% copper treatment applied
fabric had the lowest tensile strength of 170 N. It can be observed that the copper treatment
has a noticeable impact on the tensile strength in warp direction of the wool fabrics.
Moreover, comparing the data sets by analysis of variance ANOVA demonstrates that the
difference between the untreated and the copper treated ones is statistically significant (F ratio
= 25.08 > F critical = 5.93; = 0.01). In both 10 min and 20 min ultrasonic energy
application times, the tensile strength values of copper treated fabrics were much lower than
their untreated counterparts. Furthermore, the effect of the ultrasonic energy application times
on the tensile properties did not find to be significant (F critical = 7.39 > F ratio = 0.023; =
0.01). The breaking extension of the warp direction was increased by the copper treatment.
For the all cases, the copper treated fabrics had higher breaking extension compared to the
untreated fabric.
388
Muhammet Uzun
Figure 2. Tensile strength properties of warp direction.
Some variations were observed in tensile strength results of weft direction. The fabrics
that were treated with 5 % and 10 % copper solution, improved the tensile strength in the weft
direction significantly (F ratio = 119.1 > F critical = 5.95; = 0.01), nevertheless; 15% copper
treatment decreased the tensile strength of weft considerably. 10 % copper treated fabrics for
both application times, 10 min and 20 min, had 366 N which was the highest tensile strength
value compared to all the tested combinations. Conversely, 15% copper treated fabric had the
lowest tensile strength (143 N) in this study. Besides, the effect of the ultrasonic energy times
on the tensile properties in weft direction was not found to be noteworthy and ANOVA
analysis showed that the differences are not statistically significant (F critical = 13.75 > F ratio =
5.11E-05; = 0.01). The breaking extension values decreased with 10 min application time
and increased with 20 min time.
Figure 3. Tensile strength properties of weft direction.
389
There are two scenarios that could explain this decrease. The first scenario, the tensile
strength could be affected because of the interaction between the metal ions and the polymer
structure. The metal ions could cause the fibres to become more brittle and this can have a
negative impact on the physical properties of the fibre. The second scenario could be that the
presence of silver could make the fabrics more dry which also could cause a reduction in the
tensile behaviour. These findings require further in-depth study, in order to establish the true
impact of silver and how it can cause a decrease in fabric tensile properties. Wasif and Laga
treated cotton fabric with nanosilver and they found that silver treatment decreased the tensile
strength of the fabrics [24].
Abrasive Test Results

The plain woven woollen fabrics resistance to abrasion were tested and compared for a
total of 35 fabrics (5 controls, 30 treated fabrics with different copper volume). Each tested
specimen was inspected to analyse its abrasion behaviour after every 5.000 rubs. After the
initial 50.000 rubs, none of the fabrics exhibited any sign of damage or wear. This result
indicates that all the fabrics were not subject to significant abrasion after 50.000 rubs;
however, 15% copper treated fabrics showed some minor weak points. Overall there were no
considerable differences found between the treated and untreated fabrics after 50.000 rubs.
This study proves that there is no noteworthy difference between the particular amounts of
copper alginate treated wool fabrics and control fabric.
Figure 4. SEM photograph (100) of treated fabrics A) 0%, B) 5%, C) 10% and D) 15%.
390
Muhammet Uzun
Flexural Rigidity Test Results

The flexural rigidity is the ratio of the small change in bending moment per unit width of
the material to the corresponding small change in curvature:
Flexural rigidity; G = M X C3 X 9.807 X 10-6inNm
Eq. (1)
where:
C = bending length (mm);
M = fabric mass per unit area (g/m2).
The flexural rigidity values of the untreated and the treated fabrics are given in Table 3.
The higher flexural rigidity of fabric can be caused by the compactness of the structures
which affects the freedom of movement during bending. This reduction in freedom of
movement is an undesirable property for clothing. Lower flexural rigidity value is preferred
for apparel fabrics [21]. In all cases, the flexural rigidity values of the fabrics decreased after
the copper treatment. This decrease increases gradually with higher copper volumes. The
fabrics which were treated with 15% copper solution had the lowest flexural rigidity values.
This could be attributed to the surface deformation of the wool fabrics by the copper
treatment. The ultrasonic energy application times did not have any significant impact on the
flexural rigidity properties.
Table 3. Average values of weft and warp flexural rigidity of woven fabrics (Nm)
0%
6.03
5.99
10 min
20 min
5%
5.87
5.89
10%
5.55
5.62
15%
5.17
5.25
Thermal Comfort Properties

Table 4. Thermal comfort properties of untreated and treated wool fabrics in dry state
10 min
20 min
0%
5%
10%
15%
0%
5%
10%
15%
Thermal conductivity
(W/mK10-3)
32.4
33.8
33.7
35.1
33.1
34.2
34.5
35.5
Thermal resistance
(W-1K m210-3)
25.4
57.6
67.4
77.8
26.5
60.1
71.3
82.1
Thermal absorbtivity
(W m-2 s 0.5 K -1)
129
87.5
83.1
78.8
129
85.1
81.3
77.1
391
Table 4 and 5 show the thermal conductivity, thermal resistance and thermal absorbtivity
for dry and wet states of fabrics, respectively. The thermal properties of the fabrics were
measured using an Alambeta instrument. The wet state was investigated separately due to the
importance of fabric application areas and to determine wet performance of the treated
fabrics.
Table 5. Thermal comfort properties of untreated and treated wool fabrics in wet state
0%
10 min. 5%
10%
15%
0%
20
5%
min.
10%
15%
Thermal conductivity
(W/mK10-3)
53.1
61.7
64.8
65.7
53.9
61.6
65.6
66.1
Thermal resistance
(W-1K m210-3)
15.0
29.5
39.2
50.9
17.1
30.9
40.1
51.7
Thermal absorbtivity
(W m-2 s 0.5 K -1)
289
229
218
179
289
220
213
180
Thermal Conductivity of Woven Fabrics in Dry and Wet State

The thermal conductivity basically gives the amount of heat, which passes from 1 m2 area
of tested structure through the distance 1 m within 1 s and create the temperature difference of
1 K. The thermal conductivity can be calculated by using the following expression [22,23],
= Q/ FT/ in Wm-1 K-1
Eq. (2)
where:
Q = amount of conducted heat,
F = area through which the heat is conducted,
= time of heat conducting
T = drop of temperature,
= fabric thickness
The thermal conductivity results are presented in Table 4 and Table 5 for dry and wet
states, respectively. The thermal conductivity values ranged from 32.4 to 35.5 Wm-1 K-1 in its
dry state and 53.1 to 65.6 Wm-1 K-1 in its wet state. The copper treatment increased the
thermal conductivity of the wool fabric in dry and wet states for all the test combinations
(Fig.5). 15% copper treated fabric had the highest thermal conductivity values in its dry and
wet states. Moreover, comparing the data sets by analysis of variance ANOVA
demonstrates that the difference between the untreated and the copper treated ones is
392
Muhammet Uzun
statistically significant (F ratio = 130.9 > F critical = 16.69; = 0.01). The fabrics which were
subjected to 20 min of ultrasonic energy had slightly higher conductivity than those applied
for 10 min. The application times were found to have an inconsiderable effect on the thermal
conductivity of wool fabrics (F critical = 8.10 > F ratio = 1.86; = 0.01). In wet state, the fabrics
exhibited higher conductivity values than dry state and the difference is statistically
significant (F ratio = 291.16 > F critical = 9.33; = 0.01).
Figure 5. Thermal conductivity () of woven fabrics in dry and wet state (W/mK10-3).
Thermal Resistance of Woven Fabrics in Dry and Wet States

The thermal resistance of the fabrics depends on thickness and thermal conductivity
value. The thermal resistance has to be known due to the fabrics application areas and
seasons. For the winter garments, it is higher resistance value is preferred. The resistance is
expressed by the following relationship.
R(m2kW-1) = h(m)/ inW-1K m210-3
Eq. (3)
where:
h = fabric thickness
= thermal conductivity
The thermal resistance values of dry and wet states are given in Table 4 and Table 5,
respectively. The resistance results are also illustrated in Fig.6. The resistance of the fabrics
ranged from 25.4 to 82.1 W-1K m210-3 for the dry state and from 15.0 to 51.7 W-1K m2103
for the wet state. The differences between the groups were found to be highly significant (F
ratio = 51323.7 > F critical = 16.69; = 0.01). As seen in F values (F critical = 8.09 > F ratio = 0.14;
393
= 0.01) the ultrasonic application periods did not have significant effect on the resistance
properties of the fabrics. In wet state most of the fabrics had up to two times lower values of
thermal resistance than dry state. The difference between dry and wet states is considerable
and it is statistically significant (F ratio = 9.76> F critical = 9.33; = 0.01). The fabrics thermal
resistance behaviour improved gradually with the copper treatment and the application times
also affect the measured property positively.
Figure 6. Thermal resistance (r) of woven fabrics in dry and wet state (W-1K m210-3).
The percentage recovery of the fabrics after 4 min of wetting is presented in Table 6. Any
textile fabrics which have a 75% recovery value can dry quicker than any lower % values. All
the fabric combinations had lower than 75% percentage recovery value after 4 min of wetting.
Only 15% copper treated fabric had slightly higher percentage recovery values in comparison
to the rest of the fabrics. The ultrasonic treatment did not have any significant effect on the
tested recovery values.
Table 6. % recovery after 4 min wetting (%)
10 min.
20 min.
0%
59.1
64.5
5%
51.2
51.4
10%
58.2
56.2
15%
65.4
62.9
Thermal Absorbtivity of Woven Fabrics in Dry and Wet States

Warm-cool feeling (thermal absorbtivity) of fabric is one of the prior characteristics for
textile garments and this feature is the first sensation that is felt when any customer touches
the garments, this is a kind of heat transfer between the skin and the fabric surface. A fabrics
394
Muhammet Uzun
warm-cool characteristic can be modified during the textile finishing processes. Lower
thermal absorbtivity causes a warm feeling and a diametrically higher thermal absorbtivity
value tends to give a cooler feeling. The thermal absorbtivity is calculated by the following
equation.
b = c in Ws1/2 m-2 K-1
Eq. (4)
where:
= thermal conductivity;
= fabric density;
c = specific heat of the fabric.
The treated fabrics had lower thermal absorption values in comparison with the untreated
fabrics, furthermore; the treated fabrics absorbtivity slightly decreased when they were
treated with 20 minutes of ultrasonic energy (Table 4, Table 5 and Figure7). The differences
between the untreated and the treated fabrics were found to be significant (F ratio = 1657.1 > F
critical = 16.69; = 0.01). The 15% copper treated fabric had the lowest absorbtivity value. The
copper treatment increases the warm feeling of the fabrics due to the lower absoptivity.
Important differences in thermal absorbtivity of the fabrics were observed when the
specimens were wetted with 0.2 ml of water and the statistical analysis showed that there is a
significant differences (F ratio = 69.59 > F critical = 9.33; = 0.01). The thermal absorbtivity
values of fabrics in their wet states are considerably higher than the dry state fabrics. The
ultrasonic application times were found to be insignificant (F critical = 21.20 > F ratio = 0.33; =
0.01).
Figure 7. Thermal absorbtivity (b) of woven fabrics in dry and wet state (W m-2 s 0.5 K -1).
395
Water Vapour Permeability and Resistance to Evaporative Heat

Loss (Permetest)
The water vapour permeability (WVP) depends on the water vapour resistance which
indicates the amount of resistance against the transport of water through the fabric structure.
The amount of water present in a garment (which has crucial importance in the degree of
comfort) must be minimal. The relative WVP is expressed using the following formula.
WVR = Qs(Wm-2)/Q0(Wm-2)100in %
Eq.(5)
where;
Qs = the heat flow with the fabric specimen
Q0 = the heat flow without the fabric specimen
The WVP and resistance to evaporative heat loss results are summarized in Table 7. The
study of WVP was performed by using Permetest instrument. According to the test results
there are noticeable differences between the untreated and the treated fabrics, all the treated
fabrics had reduced WVP value compared to the untreated counterparts. It can be clearly seen
that the copper treatment enhances WVP properties of the wool fabrics and ANOVA results
showed that it is of significant level (F ratio = 262.1 > F critical = 7.59; = 0.01). The ultrasonic
energy treatment times did not have any determinable influence on the WVP property of the
fabrics (F critical = 13.75 > F ratio = 0.009; = 0.01).
Table 7. Water vapour permeability (%) and Resistance to evaporative heat loss (m2Pa
W-1)
10 min.
20 min.
Water vapour permeability (%)

0%
5%
10%
15%
63
49
47.9
40.7
64
50
48.9
41.5
Resistance to evaporative heat loss (m2 Pa W-1)

0%
5%
10%
15%
2.8
4.8
5.2
6.1
2.9
5.0
5.2
6.3
As seen in Table7, the copper treated fabrics had higher resistance to evaporative heat
loss values than the untreated fabric. The treated fabrics resistance to evaporative heat loss
values increased gradually and the change is statistically significant (F ratio = 582.8 > F critical =
7.59; = 0.01). The ultrasonic energy treatment times did not have any considerable effect on
the fabric heat loss values (F critical = 13.75 > F ratio = 0.016; = 0.01).
CONCLUSION
Copper is considered as an antimicrobial agent with useful medical applications in order
to develop protection against the risk of the bacteria which occurs hospital environment. In
this study, the physical and thermal comfort properties of 100% wool fabric coated with
sodium alginate via a copper sulphate interaction, incorporating with ultrasonic energy has
396
Muhammet Uzun
been studied. The coated fabrics demonstrated lower tensile strength values and it was found
that the differences between the control and the treated fabrics were statistically significant.
The coating did not have considerable effect on the abrasive properties of the fabrics up to
50.000 rubs, however; the fabrics which were treated with 15% copper volume had some
weak points after the 50.000 rubs, nevertheless; the fabrics was not abraded. The flexural
rigidity of the coated fabrics was lower than the control fabric. The fabrics thermal
conductivities were changed after the treatment. The fabrics coated with copper had higher
thermal conductivities in comparison with the control fabrics for the both dry and wet states.
The thermal resistance of the coated fabrics was found to be significantly higher than the
control fabrics. The coated fabrics have lower thermal absorbtivity values when compared to
the control fabrics. In the wet state, the thermal absorbtivity is considerably higher than in the
dry state for all cases. According to the Permetest results, the differences between the control
and the coated fabrics are considerable. The coated fabrics had reduced water vapour
permeability. Heat loss increased when the fabrics are coated with copper. In general, the
ultrasonic energy application times have no significant effect on most of the tested properties.
ACKNOWLEDGEMENTS
The author would like to thank Dr. India Rose Sweeney and Dr. Vijay Parikh for supports
during the project.
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AUTEX Research Journal 9, 5-13.

ISBN: 978-1-63117-262-5
Chapter 16
HEMP FIBERS: OLD FIBERS NEW APPLICATIONS

Mirjana Kostic1, Marija Vukcevic*1, Biljana Pejic1
and Ana Kalijadis2
1
Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia

2
Laboratory of Physics, Vinca Institute of Nuclear Sciences,
University of Belgrade, Belgrade, Serbia
ABSTRACT
Hemp (Cannabis sativa) was most likely the first plant cultivated by mankind for its
textile use. Currently, the interest in hemp is focused on its use as a raw material for the
production of environmentally friendly clothes, technical textiles and composite
materials. The increased production of hemp fibers in textile industry brings the
considerable amount of waste in the form of short and entangled fibers. The cost of waste
disposal can be minimized by recycling the waste in the way of producing useful lowcost products. Following the general trend of finding low-cost and easily available
adsorbent, waste short and entangled hemp fibers were utilized as a heavy metal
biosorbents. Due to the specific structure and heterogenous chemical composition
(cellulose, hemicelluloses, lignin, pectin), short hemp fibers as biosorbent offer an
effective way to decrease Pb2+, Cd2+ and Zn2+ ion concentration in wastewaters. The
influence of hemp fiber chemical composition on their heavy metal ions sorption
potential, were assessed by evaluating the water and metal ions uptake capacities of
differently modified hemp fibers. The process of heavy metal ions biosorption on short
hemp fibers was clarified by mathematical model development. Proposed mathematical
model provides a better insight into phenomena of different ions transport through porous
fiber matrices, and possibility of optimization of the complex process of biosorption. This
is from great importance in the case of using short hemp fibers as filter material for
removing the heavy metal ions from polluted water. Furthermore, there is a growing
interest in using different type of waste biomass for production of carbon materials as a
sorbents for water purification. From that aspect, short and entangled hemp fibers were
used as low-cost precursor for production of carbon materials. Chemical modification of
hemp fibers, prior to carbonization, affects the specific surface area, amount of surface
*
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia, E-mail:
marijab@tmf.bg.ac.rs.
400
Mirjana Kostic, Marija Vukcevic, Biljana Pejic et al.

oxygen groups and morphology of carbonized hemp fibers. Furthermore, activation of
carbonized materials with potassium hydroxide improves sorption properties of
carbonized hemp fibers by increasing the specific surface area (up to 2192 m2/g) and
amount of surface oxygen groups. Due to the good adsorption properties toward heavy
metals and pesticides, carbonized and activated hemp fibers were successfully used as a
sorbent for the purification of water polluted with pesticides and heavy metals. Also,
activated hemp fiber sorbent used for analyte preconcentration in the solid-phase
extraction procedure (SPE) for pesticide analysis in water samples, showed even higher
efficiency in pesticides preconcentration than expensive commercial cartridges. Sorption
process of heavy metal ions and structural parameters of carbonized hemp fibers were
described by upgrading already proposed mathematical model. A good agreement
between model prediction and the experimental data indicates that the proposed
mathematical model can be used for optimization of heavy metal ions adsorption process
by correlating the model parameters to the carbonized hemp fibers performances.
Keywords: hemp fibers, chemical modification, biosorption, carbonization and activation,

mathematical modeling
INTRODUCTION
Hemp (Cannabis Sativa), an old and controversial plant, was harvested by the Chinese
8500 years ago. Hemp was most likely the first plant cultivated by man kind for its textile
use. However, the decline of hemp began in 1925, when hemp was included in the prohibition
list due to its hallucinogenic properties, which resulted in an almost total ban of the plant.
Also, chemical fibers and their intensive development after the Second World War had an
influence on the total textile fiber situation characterized by the significant elimination of
natural fibers from textile products. Among the fibers, which suffered the most, were flax,
hemp, wool and silk. Such situation was caused by relatively cheep, simple and efficient
chemical fibers production technology and foremost by the possibility of their adaptation to
the existing technologies. However, in the 1990s, due to the exhaustion of major organic
chemicals resources (coal, gas, oil) necessary for chemical fibers production, the attention
was paid to the renewable and biodegradable raw materials. At this point, production of hemp
fiber is experiencing a renaissance again. After quite a long period of intensive application,
synthetic fibers, created to replace natural fibers, are today considered inferior to natural ones,
especially in respect to comfort and ecological properties. From this point, the total
substitution of natural with synthetic fibers is not desirable. These facts, together with limits
in the yield of cotton, the main comfort providing fibers, were main reasons for the beginning
of an unexpected, worldwide return to almost forgotten bast fibers, among them hemp [1-5].
Intensive growth of world population imposes the need for comfortable, biodegradable,
biocompatible and ecological fibers. Textile fibers and textile materials are in continuous
contact with consumer bodies during their use and comfort of clothing materials, among the
other things, implies hygienic materials with good sorption properties and low values of
electric resistance. As a textile fiber, hemp fiber has the specific properties, namely aseptic
properties, high absorbency and hygroscopicity, good thermal and electrostatic properties, as
well as good UV protection properties and lack of any allergenic effect, that make them
different from other fibers. However, high quantity of noncellulosic components in hemp
Hemp Fibers: Old Fibers New Applications
401
fibers (hemicelluloses, lignin, pectin and waxes) and impurities negatively influence further
fiber processing and fiber properties (fineness, elasticity, evenness, and sorption properties).
In order to make them finer, cleaner, softer, and more suitable for processing on machines of
higher efficiency than traditional hemp machines, numerous chemical, mechanical, enzymatic
and combined treatments of hemp fibers are applied which are mostly directed towards
elimination of hemicelluloses, lignin and pectin. Modification of hemp fibers has to be
performed in such way that attaining the desired goal is not followed by decreasing the most
important positive properties of hemp fiber, especially very important comfort properties of
fibers their relation to water (vapor or liquid) and low static electricity charges, which
defines their physiological properties [1,6-11].
The increased production of hemp fibers in textile industry brings the considerable
amount of waste in the form of short and entangled fibers. The cost of waste disposal can be
minimized by recycling the waste in the way of producing useful low-cost products.
Following the general trend of finding low-cost and easily available adsorbent, waste short
and entangled hemp fibers were utilized as a heavy metal biosorbents. Due to the specific
structure and heterogenous chemical composition, short hemp fibers as biosorbent offer an
effective way to decrease Pb2+, Cd2+ and Zn2+ ion concentration in wastewaters [12].
Furthermore, short and entangled hemp fibers can be used as low-cost precursor for
production of carbon materials, as a sorbent for water purification [13].
HEMP FIBERS CHEMICAL COMPOSITION

Technical (multi-cellular) hemp fibers, obtained from hemp plant, are characterized with
extremely complicated microstructure and heterogonous chemical composition. Generally,
hemp fibers contain about 67.0 - 78.3 % cellulose, 5.5 - 16.1 % hemicelluloses, 0.8 - 2.5 %
pectin, 2.9 - 3.3 % lignin, and some fats and waxes in the fibers [12,14].
The main component of hemp fiber structure is cellulosic macromolecule. Cellulose is a
natural polymer consisting of D-anhydro-glucoside repeating units held together by -(1,4)glycosidic linkages at C1 and C4 position [15]. The degree of polymerization (DP) is around
10,000 [16]. Each repeating unit contains three hydroxyl groups, which have ability to form
intramolecular and intermolecular hydrogen bond within the same cellulose chain and the
surrounding cellulose chains. In that way, chains tend to be arranged parallel and form a
crystalline supermolecular structure, with regions of high order, i.e., crystalline regions, and
regions of low order, i.e., amorphous regions. Then, bundles of linear cellulose chains (in the
longitudinal direction) form a microfibril which is oriented in the cell wall structure [17].
Cellulose is insoluble in most solvents and has a low accessibility to acid and enzymatic
hydrolysis [14].
Unlike cellulose, hemicelluloses comprise a group of polysaccharides composed of
different monosaccharide units, such as combination of 5- and 6-carbon ring sugars.
Hemicelluloses are derived mainly from chains of pentose sugars, and act as supportive
matrix for cellulose microfibrils. Hemicelluloses differ from cellulose in three aspects. Firstly,
they contain several different sugar units whereas cellulose contains only 1,4--Dglucopyranose units. Secondly, they exhibit a considerable degree of chain branching
containing pendant side groups giving rise to its noncrystalline nature, whereas cellulose is a
402
linear polymer. Thirdly, DP of hemicelluloses is around 50300, whereas that of native

cellulose is 10100 times higher than that of hemicelluloses. Among the most important sugar
of the hemicelluloses component is xylose. In hardwood xylan, the backbone chain consists
of xylose units which are linked by -(1,4)-glycosidic bonds and branched by -(1,2)glycosidic bonds with 4-O-methylglucuronic acid groups [17]. In addition, O-acetyl groups
sometime replace the OH groups in position C2 and C3. For softwood xylan, the acetyl
groups are fewer in the backbone chain. However, softwood xylan has additional branches
consisting of arabinofuranose units linked by -(1,3)-glycosidic bonds to the backbone.
Hemicelluloses are very hydrophilic, soluble in alkali, and easily hydrolyzed in acids [14].
Lignin is a hydrocarbon polymer with a complex three-dimensional structure and very
high molecular weight, consisting of both aliphatic and aromatic constituents. Lignin is
covalently linked with xylans in the case of hardwoods and with galactoglucomannans in
softwoods. The basic chemical phenylpropane units of lignin (primarily, syringyl, guaiacyl
and p-hydroxy phenol) are bonded together by a set of linkages to form a very complex
matrix. This matrix comprises a variety of functional groups, such as hydroxyl, methoxyl and
carbonyl, which impart a high polarity to the lignin macromolecule [15,17,18]. Lignin has
been found to contain five hydroxyl and five methoxyl groups per building unit. It is believed
that the structural units of lignin molecule are derivatives of 4-hydroxy-3-methoxy
phenylpropane. Lignin is totally amorphous and hydrophobic in nature. It is totally insoluble
in most solvents and cannot be broken down to monomeric units. It is not hydrolyzed by
acids, but soluble in hot alkali, readily oxidized, and easily condensable with phenol [19-22].
Pectins are complex polysaccharides consisting mainly of esterified D-galacturonic acid
resides in an alpha-(1-4) chain. Pectins may also contain rhamnogalacturonan II side chains
containing other residues such as D-xylose, L-fucose, D-glucuronic acid, D-apiose, 3-deoxyD-manno-2-octulosonic acid and 3-deoxy-D-lyxo-2-heptulosonic acid attached to poly--(1
4)-D-galacturonic acid regions [23]. D-galacturonic acid residues form most of the
molecules, in blocks of 'smooth' and 'hairy' regions. The molecule does not adopt a straight
conformation in solution, but is extended and curved ('worm like') with a large amount of
flexibility. The `hairy' regions of pectins are even more flexible and may have pendant
arabinogalactans. The carboxylate groups tend to expand the structure of pectins as a result of
their charge, unless they interact through divalent cationic bridging (their pKa of about 2.9
[24] ensuring considerable negative charge under most circumstances). Methylation of these
carboxylic acid groups forms their methyl esters, which take up a similar space but are much
more hydrophobic and consequently have a different effect on the structuring of the
surrounding water. The properties of pectins depend on the degree of esterification, which is
normally about 70 %.
STRUCTURE AND MORPHOLOGY OF HEMP FIBERS

The hemp fibers are characterized with cross section complexity and specific surface
morphology. It can be considered as composites of hollow cellulose fibrils held together by a
lignin and hemicelluloses matrix. The cell wall in a fiber is not a homogenous membrane.
Structure of hemp fibers is presented in Figure 1. Each fiber has a complex, layered structure
consisting of a thin primary wall which is the first layer deposited during cell growth
403
encircling a secondary wall. The secondary wall is made up of three layers and the thick
middle layer determines the mechanical properties of the fiber. In the secondary cell wall, the
cellulose molecules are synthesized by enzymes that float around in the cell membrane,
spinning off primary fibrils of about 5 nm in diameter, each containing about 40 molecules.
These primary fibrils are assembled into microfibrils of about 2040 nm in diameter, which
have hemicelluloses decorating the outside. These hemicelluloses act as the connection
between the microfibrils, creating the primary structural network. Lignin can be deposited
within this network in two ways: either as isolated lumps (when it acts to limit the movement
of the microfibers, thus increasing stiffness by steric hindrance) or (later) as a continuous
matrix, which then supplements and presumably replaces the hemicelluloses in importance as
a linker of the cellulose microfibrils The hydrophobic lignin network affects the properties of
other network in a way that it acts as a coupling agent and increases the stiffness of the
cellulose/hemicelluloses composite [25].
Figure 1. Structure of hemp fibers.
Complex structure and heterogeneous chemical composition of hemp fibers are the
crucial factors that affect their specific characteristics. As a textile fiber, hemp possesses a
range of extraordinary properties as: antimicrobial properties, extremely quick absorption of
humidity accompanied with quick drying, good thermal and electrical properties (increased
heat of sorption and low static electricity charges), outstanding tenacity (5090 cN/tex), lack
of allergenic effects, biodegradability and protection against UV radiation [3,26-28].
However, high quantity of noncellulosic components in hemp fibers (hemicelluloses, lignin,
pectin and waxes) and impurities negatively influence further fiber processing and fiber
properties (fineness, elasticity, evenness, and sorption properties). In order to make them
finer, cleaner, softer, and more suitable for processing on machines of higher efficiency than
traditional hemp machines, numerous chemical, mechanical, enzymatic and combined
treatments of hemp fibers are applied which are mostly directed towards elimination of
hemicelluloses, lignin and pectin. The predominant task in preparing hemp fibers for further
404
fiber processing is to remove these noncellulosic components with improving fiber properties
and without damage to the fiber cellulose [2,6-11].
CHEMICAL MODIFICATION OF HEMP FIBERS

The most commonly used methods for hemp fiber modification are different chemical
treatments, such as: alkaline, oxidative, silane, benzoylation, acetylation of natural fibers, etc.
[29]. The appropriate chemical treatment is generally selected regarding the future hemp fiber
usage and desired characteristics. This chapter will be focused on using alkaline and oxidative
treatments for hemp fibers modification.
Alkaline Treatment
Alkaline treatment or mercerization is one of the commonly used chemical treatments of
natural cellulose fibers. Mercerization is usually carried out in the presence of NaOH, KOH
and LiOH, and by varying the chemical agent concentration, temperature and time of
treatment. The alkaline treatment with 17.5 % NaOH at room temperature, leads to changes in
the chemical composition: the level of hemicelluloses removal from hemp fibers is high,
while lignin content is almost unchanged. Content of hemicelluloses decreases up to 70 % in
relation to unmodified fibers. In contrast to hemicelluloses, lignin shows low reactivity during
the alkaline treatment, mainly because of strong carboncarbon linkages and aromatic groups
and rings, which were very resistant to chemical attack. Changes in chemical composition
occurred during the alkaline treatment affects the structure of lignocellulosic fibers. The main
structural modification is the disruption of hydrogen bonding in the network structure which
induces the cellulose depolymerization and increases the amorphous cellulose content at the
expense of crystalline cellulose. Additionally, alkaline treatment increases the amount of
cellulose exposed on the fiber surface and thereby increase the surface roughness
[8,10,12,30].
The NaOH usage affects the swelling of lignocellulosic fibers, during which the natural
crystalline structure of the cellulose relaxes. Native cellulose (i.e., cellulose as it occurs in
nature) shows a monoclinic crystalline lattice of cellulose I, which can be changed into
different polymorphous forms through chemical or thermal treatments. The type of alkali and
its concentration will influence the degree of swelling, and hence the degree of lattice
transformation into cellulose II [31-33]. Sodium hydroxide treatment results in a higher
amount of swelling, due to formation of new Nacellulose I lattice with relatively large
distances between the cellulose molecules. Additionally, the sodium hydroxide promotes the
ionization of the hydroxyl group to the alkoxide [15]. The OH-groups of the cellulose are
converted into ONa-groups, expanding the dimensions of molecules. Subsequent rinsing with
water will remove the linked Na ions and convert the cellulose to a new crystalline structure,
i.e., cellulose II, which is thermodynamically more stable than cellulose I. In contrast to other
alkalis which produce only partial lattice transformation, NaOH can cause a complete lattice
transformation from cellulose I to the cellulose II. The alkali solution influences not only the
405
cellulosic components inside the plant fiber but also the noncellulosic components
(hemicelluloses, lignin, and pectin) [2,8,12].
Oxidative Treatments
The usage of different oxidative agents in order to modified hemp fibers become one of
the significant chemical treatments. The factors that may influence the hemp fibers
characteristics during the oxidative treatments are concentration and type of oxidative agent,
time and temperature of treatment. The most significant change emerged as a result of
oxidative treatment, is selective removal of lignin accompanied by decrease in amounts of
hemicelluloses, pectines and waxes. Removal of lignin and hemicelluloses induce the
fibrillation of hemp fibers which is accompanied by changes in physical and chemical
characteristics. The hemp fibers major component, cellulose, which is a polyhydric alcohol, is
very sensitive to oxidizing media. The chemical structure of cellulose is altered in a way that
hydroxyl groups are oxidized into the corresponding carbonyl structures, i.e., an aldehyde at
C-6 and ketone at C-2 and C-3, or carboxyl moiety (at C-6). Oxidation can also be
accompanied by a change in the carbon skeleton of the cellulose backbone: a carbon-carbon
bond cleavage between C-2 and C-3, for instance, allows for the introduction of aldehyde or
carboxyl structures also at C-2 and C-3, which otherwise would not be possible. Cellulose
degradation (chain cleavage) often accompanies the oxidation, but is actually caused by
subsequent reactions and not by the oxidation itself [15].
Oxidative treatment of lignocellulosic fibers can be carried out through the selective or
non-selective cellulose oxidation.
Selective Oxidation
Frequently applied procedures for selective cellulose oxidation are TEMPO and periodate
treatment. TEMPO oxidation process implied conversion of glucans by the system 2,2,6,6tertramethylpiperidine-1-oxyl (TEMPO) / sodium hypochlorite / potassium bromide [15, 34].
This reaction takes place through the selective oxidation at C-6 of the anhydroglucose units to
carboxylic groups via the intermediate aldehyde stage, finally producing water soluble
polyglucuronic acids. The nitroxyl radical affects the oxidation from the alcohol to the
aldehyde oxidation state, while the hyperbromide generated in situ from hypochloride and
bromide performs the further oxidation of the aldehyde to the carboxylic acid. TEMPO
oxidation is usually accompanied by a drastic change of the molecular weight, due to elimination starting from C-6 aldehyde. This oxidative process is carried out around pH 1011, since at lower pH hypochlorite becomes an overly aggressive and non-selective oxidant,
and TEMPO reactivity is decreased. The selective oxidation of hemp fibers, using TEMPO,
introduces new functionalities, removes lignin and hemicelluloses, and improves sorption
properties of hemp fibers. By changing the parameters of the oxidation (HClO concentration
and treatment time), it is possible to obtain hemp fibers with a different amount of cation
exchange functions (0.09 to 0.80 mmol of carboxylic groups per gram of fibers). Amount of
cation exchange functions into the fibers depends directly on the time of modification, as well
as concentration of oxidizing agents [35].
Another type of selective oxidation is periodate oxidation [15,36]. This type of cellulose
oxidation induces bond cleavage between C-2 and C-3 of the anhydroglucose units with
406
concomitant introduction of aldehyde functionalities at those two positions. The reaction is

thought to proceed via a cyclic diester of per-iodic acid with geminal hydroxyls, which
subsequently undergoes an intramolecular redox process with simultaneous C-C bond
cleavage according to a concerted mechanism. The reaction is quite selective for cellulosics
as the only geminal hydroxyls available at C-2 and C-3 of the anhydroglucose units.
Non-Selective Oxidation
Non-selective oxidation of hemp fibers is usually performed by permanganate, peroxide
and chlorite treatments. Hydrogen peroxide and potassium permanganate are well known
bleaching agents, capable of oxidizing low molecular impurities on natural fiber surfaces,
thus obtaining not only greater whiteness but also eventual surface cleaning and oxidation of
available functional groups of fibers [37].
In the area of hemp fibers modification, the treatments with chlorine derivatives take
precedence. The most frequently used chlorine derivatives are chlor-dioxide and sodium
chlorite. Depending of the concentration of oxidizing agent used and treatments parameters,
hemp fiber can be fibrillated in that level to obtain the fibrils of micro and nano dimension.
Chlorine derivatives (NaClO2) usage in the hemp fibers modification induced the fibrillation
and decrease in the fiber diameter from 22-25 m, for unmodified fiber, to 5-90 nm, for
oxidized fibers [38,39]. This fiber diameter decrease is a result of lignin oxidation followed
by its degradation and thereby decreases in hemp fibers lignin content.
The sodium chlorite modification is commonly used after the sodium hydroxide or
sodium periodate treatments. Sodium periodate selectively oxidizes the C-2 and C-3 hydroxyl
groups of cellulose into cellulose dialdehyde, which on further reaction with sodium chlorite
in the presence of acetic acid forms dicarboxylic groups at C-2 and C-3 position.
Hemicelluloses, which consist mainly of pentoses, may react with sodium periodate in a
similar way to cellulose. On the other hand, lignin (phenyl propane-based polymer) may be
oxidized by the sodium periodate and sodium chlorite. Sodium periodate oxidation of lignin
results in demethylation of methoxy groups of lignin and formation of Ph-OH groups, while
sodium chlorite oxidation causes benzene ring cleavage and formation of dicarboxylic groups
[40].
As it is shown, chemical treatments used for hemp fiber modification leads to changes in
chemical structure of cellulose and accompanying compounds and thereby to the changes in
hemp fiber structure and morphology. These changes directly affect the hemp fiber properties,
such as: physical, mechanical and sorption properties.
INFLUENCE OF SODIUM HYDROXIDE AND SODIUM

CHLORITE CHEMICAL TREATMENTS ON HEMP FIBERS
CHEMICAL COMPOSITION
The alkaline and oxidative treatments used for hemp fiber modification [12,41,42] are
schematically presented in the Figure 2.
407
Figure 2. The scheme of hemp fiber chemical modification.
The chemical compositions of modified hemp fibers and those of the control, unmodified
sample, weight loss and fineness are given in Table 1. From the obtained results, it is obvious
that during hemp fibers treatment with 17.5 % NaOH hemicelluloses were progressively
removed, their content decreased for approximately 70 % in relation to unmodified fibers.
Lignin content decreased slightly, because of its low reactivity. Namely, degradation of lignin
during the alkaline treatment is impeded by the presence of strong carboncarbon linkages
and other chemical groups such as aromatic groups, which are very resistant to chemical
attack [10]. On the other hand, treatment of hemp fibers with 0.7 % NaClO2 progressively
removed lignin for about 50 % in relation to unmodified fibers. It has to be mentioned that, in
this case, the content of hemicelluloses in modified hemp fibers decreased for about 17 %.
During both types of hemp fibers modification, noncellulosic component content in modified
fibers decreased in relation to unmodified hemp fibers, proportionally to the increase of
modification time. Removing different amounts of hemicelluloses and lignin by chemical
modification changed both chemical and physical properties of hemp fibers. The severity of
the treatment is generally characterized by weight loss. Loss in weight, as result of chemical
treatment (Table 1), in both cases increased with the increase of time of treatment. Also, the
alkaline treatment of hemp fibers results in higher weight loss, in comparison to the sodium
chlorite treatment. Additionally, as result of removing noncellulosic substances, hemp fibers
acquired a high level of divisibility, which determines important properties of hemp fibers
their fineness (Table 1). Hemicelluloses removal leads to higher extent of fiber liberation than
lignin removal; fiber fineness was reduced from 21.5 tex for unmodified to 1.8 tex for H45
sample.
Table 1. The chemical composition, weight loss and fineness of unmodified
and modified hemp fibers
Sample
C
H5
H45
L5
L60
-Cellulose
content
(%)
78.15
80.59
79.70
80.03
79.15
Hemicelluloses
Content
Removed
(%)
(%)
10.72
4.69
56.25
3.59
66.51
8.89
17.07
8.99
16.14
Lignin
Content
(%)
6.06
5.66
5.41
4.09
3.09
Removed
(%)
Weight
loss
(%)
6.60
10.73
32.51
49.01
8.15
9.90
4.16
6.17
Fineness
(tex)
21.5
4.2
1.8
9.2
8.0
408
STRUCTURAL CHANGES INDUCED BY CHEMICAL MODIFICATION

OF HEMP FIBERS
Figure 3. SEM images of unmodified and modified hemp fiber samples: a) C, b) L5, c) L60, d) H5 and
e) H45.
Changes in hemicelluloses and lignin content which are result of chemical treatment by
alkaline or sodium chlorite, have influence on hemp fibers structure (surface pore structure,
morphology and crystallinity) and sorption properties [12]. Changes in fiber surface and
structure can be ascribed not only to the decrease of lignin or hemicelluloses content, but also
to the location of these components in the hemp fiber. Lignin is located in the middle lamellae
and secondary wall of hemp fibers and with pectins can be more or less strongly associated
with the cellulose microfibrils. During the oxidation treatment lignin is selectively removed,
resulting in more homogenous middle lamella due to the gradual elimination of micro-pores
and the less rigid cell wall. Removal of lignin is accompanied by fibrillation and formation of
new capillary spaces in inter-surfacial layer between completely or partially separated
elementary fibers. In the other hand, hemicelluloses are deposited in amorphous areas of fiber
structure and occupy spaces between the fibrils in primary and secondary walls. When the
hemicelluloses were gradually removed, by alkaline treatment, inter-fibrillar regions become
less dense and rigid and thereby make the fibrils more capable for rearrangement [2,6,10].
Removal of hemicelluloses and lignin from hemp fibers were followed by peeling of their
surface and fiber fibrillation. The SEM photographs of unmodified (sample C) and modified
(samples L5, L60, H5 and H45) hemp fibers surfaces, are presented on Figure 3.
Surface of unmodified hemp fibers is relatively uneven and fibril bundles within the fiber
seems to be embedded in resinous substances (matrix of hemicelluloses, lignin and some
pectins) (Figure 3a). Through the progressive removal of lignin, surface peeling of fibers is
very intensive and roughness of fiber surface was increased (Figure 3b and 3c). After the
alkali treatment, there was uneven surface peeling in various areas along the fiber (Figure 3c
and 3d). Also, both treatments lead to liberation of elementary fibers, which is slightly more
pronounced in the case of alkaline treatment.
409
EVALUATION OF TENSILE PROPERTIES AND FLEXIBILITY

OF UNMODIFIED AND MODIFIED HEMP FIBERS
In order to obtain usable strength information many aspects of hemp fibers morphology
should be considered. As a natural bast fiber, hemp shows great variation in fiber diameter
even within a single fiber. The fiber surface appears relatively rough and uneven, with small
fibrillar ends pointing away from the surface. Due to these irregularities, there are large
variations in breaking strength data and assessing tensile strength is a multidimensional
problem. Measuring tenacity of single fibers gives the most precise results, but the process is
laborious and time-consuming. Many fibers should be tested to obtain representative values,
because of wide variations in the tenacity of single fibers (coefficient of variation range up to
30 % after 200 tested fibers [2]). Keeping in mind the all above mentioned, it is reasonable to
measure the tenacity of fiber bundles, which give average values. However, an important
effect must be taken into consideration: the fibers with shortest elongation will break first,
decreasing the size of the bundle cross-section. This effect results in too low tenacity values.
For better understanding of this effect, different fineness bundles (bundles containing
different number of fibers) and different lengths should be tested. The bundle tenacities
decrease with reducing of bundle fineness and increasing test length. These are consequence
of two reasons. First, the fiber strength is related to the number of weak places along the axis
in the bundle. Second, with increased test length, the number of fibers held only at one end
will increase. In order to obtain numeric values which require much less time and skill, and,
in the same time, permit good description and comparison of the tensile properties of
unmodified and modified hemp fibers, as result of investigated influence of measuring
conditions on the tensile properties of hemp fibers, an original method based on the use of
tenacity of 500 tex fiber bundle extrapolated to zero-test length was developed and applied by
Kostic and co-workers [2]. It is very important to note that values obtained for flat bundle
tenacity extrapolated to the zero test length show a high correlation with values measured on
single fibers.
The bundle strength of unmodified and modified hemp fibers is shown in Table 2.
Presented results show the decrease in tensile strength of the modified hemp fibers with
increasing time of treatment, which is more pronounced for the alkali treated samples. This
pronounced drop in tenacity of alkali treated hemp fibers can be explained by the removal of
hemicelluloses accompanied by swelling and shrinkage of the ultimate cells, which result in
some disorientation of the fibrils. Such a loss in fibrillar orientation is mainly responsible for
the observed significant decrease in tenacity, as well as a poor and ineffective stress transfer
among disoriented fibrillar network. The same decrease in tenacity of chemically textured
fibers was also observed during chemical texturing of jute fibers by Mukherjee and coworkers
[43]. Hemp fibers oxidation induce only slight drop in tensile strength which is the
consequence of the middle lamella homogenization.
The both oxidative and alkali treatment yielded higher flexibility of modified than
unmodified fibers (Table 2). Changes in flexibility with certain treatments reflect changes in
chemical composition (part-removing of lignin and other noncellulosic substances) and
structure (fibrils rearranging) [2].
410

Table 2. Mean tenacity and flexibility of unmodified and modified hemp fibers
Samples
C
H5
H45
L5
L60
Tenacity (cN/tex)
23.97
12.35
8.11
20.69
17.68
Flexibility (cm)
3.51
5.48
7.13
7.00
6.92
INFLUENCE OF HEMICELLULOSES AND LIGNIN REMOVAL ON

VOLUME ELECTRIC RESISTANCE OF HEMP FIBERS
Unmodified hemp fibers have exceptionally low electric resistance in comparison with
other natural and synthetic fibers [44]. Data obtained during the experiments (Figure 4)
showed that with increase of modification times (i.e., degree of hemicelluloses and lignin
removal), the volume electric resistance of all samples of modified fibers increased in
comparison with the volume electric resistance of unmodified fibers. Increase of volume
electric resistance of hemp fibers modified with sodium hydroxide (i.e., hemicelluloses
removal) was higher than for fibers modified with sodium chlorite (i.e., lignin removal).
Values of volume electric resistance, at standard relative humidity (65 %), were 34285 times
and 33.5 times higher for hemp fibers modified with alkali and chlorite, respectively, than
for unmodified fibers. In the case of lower relative humidity, increase of volume electric
resistance for modified hemp fibers in comparison to unmodified fibers is more pronounce.
Volume electric resistance of alkali modified fibers for all modification time, at 45% relative
humidity, was about 5758 % higher in comparison with values obtained for the same
samples at 65 % relative humidity (Figure 4). Volume electric resistance for samples, from
which lignin was gradually removed, was higher about 5666 % at 45 % relative humidity
than at 65 % relative humidity (Figure 4). This can be explained by influence of relative
humidity on partly ionization of water molecules, which were around the fibers, and
neutralization of electric charges on fibers surface by these molecules. Furthermore,
according to literature data [45,46] moisture and amorphous regions of the fibers are the most
important factor in determining their resistance. Hemp fibers with higher moisture content
and greater amorphous fraction, i.e., hemp fibers from which hemicelluloses were removed
(H5 and H45), have higher volume electric resistance in comparison with unmodified or
fibers from which lignin was removed gradually (L5 and L60) [30]. This indicates that
electric resistance of hemp fibers is mainly determined by their chemical composition, i.e.,
content of noncellulosic substances, namely hemicelluloses. Furthermore, detailed
comparison of the results from the literature [44] for cotton, viscose, flax and hemp shows
that they are in reasonable agreement with the assumption that the low electric resistance
values of hemp fibers are consequence of deposited noncellulosic substances (i.e.,
hemicelluloses, lignin). Obtained results show that hemp fibers with good levels of the
comfort properties are acquired as a result of the noncellulosic substances removal.
411
Figure 4. Dependence of volume electric resistance on relative humidity of unmodified and modified
hemp fibers.
SURFACE PROPERTIES OF UNMODIFIED AND

CHEMICALLY MODIFIED HEMP FIBERS
The alteration of hemp fibers chemical composition also affects specific surface area and
the amount and accessibility of functional groups present at the hemp fiber surface. Table 3
summarized the values of specific surface area, amount of carboxyl, Q(COOH), and carbonyl,
Q(COH), groups, as well the pH values of the point of zero charge for all, unmodified and
modified, samples. Although, hemp fiber samples do not have a developed specific surface
area (Table 3), pronounced fibrillation induced by longer oxidative and alkali treatment leads
to specific surface area increase.
Both chemical treatments used, at first, remove the accompanying components from the
fiber surfaces, which lead to the liberation of the functional groups, and increasing their
amount. Therefore, samples L5 and H5, obtained by shorter treatments, have increased
amount of functional groups (Table 3). On the contrary, samples L60 and H45 contain
reduced amount of functional groups, compared to L5 and H5. As the hemicelluloses and
lignin contain a considerable amount of functional groups, pronounced removal of these
components by increased modification time, as in the case of samples L60 and H45, leads to
decrease in the amount of functional groups.
Additionally, the influence of chemical modification on the acid-base behavior of tested
hemp fiber samples was examined through the PZC determination. Point of zero charge pH is
a pH of the solution at which the overall observed charge on the hemp fibers surface is zero.
When the sorbent is kept in a solution having pH less then pHPZC, the protonation of
functional groups occurs and the sorbent behaves as positively charged. At this point
functional groups repel the positive ions. An increase in pH above pHPZC makes the
functional groups deprotonated, they act as negative species and attracts and binds positive
ions. The PZC pH values of the short hemp fiber samples were found to be in the range
412
between 3.8 for L5 and 4.6 for L60 (Table 3). These results are in agreement with the amount
of surface functional groups hence the highest amount of acidic functional groups leads to the
more acidic surface of short hemp fiber sample. Furthermore, for all tested samples the PZC
is below pH 5.0, demonstrating the predominantly negative surface charges that will attract
the positive ions, i.e., hemp fibers can be used as a sorbent for metal ions [41].
Table 3. Surface characteristics of short hemp fiber samples
Sample
SBET (m2/g)
C
L5
L60
H5
H45
0.236
0.217
0.312
0.185
0.258
Amount of functional groups (mmol/g)

Q(COOH)
Q(CHO)
Q(COOH)+Q(CHO)
0.535
0.052
0.587
0.606
0.031
0.637
0.525
0.021
0.546
0.571
0.048
0.619
0.527
0.071
0.598
pHPZC
4.4
3.8
4.6
4.1
4.3
DEGREE OF SWELLING AND WATER RETENTION CAPACITY OF

HEMP FIBERS
Lignocellulosic fibers are, generally, hygroscopic and have an affinity to water. Water is
able to permeate into the non-crystalline portion of cellulose and all of the hemicelluloses and
lignin. Thus, through adsorption and absorption, aqueous solution comes into contact with a
very large surface area of different cell wall components [12,47]. Accessibility of the cell wall
components to aqueous solutions is very important for the adsorption from aqueous solutions,
and can be assessed by determining the degree of fiber swelling and water retention value.
The degree of fiber swelling yields information on the extent of areas accessible to aqueous
solutions within hemp fiber. Changes in the degree of fiber swelling of modified hemp fibers
reflect changes in chemical composition, crystallinity and pore structure. According to the
literature [12], oxidized and alkali modified hemp fibers swell faster than unmodified.
Maximum swelling of unmodified hemp fibers is attained after 10 min from immersing in
water, while all modified hemp fibers attained maximum swelling already after 5min. Also,
from the results presented in Table 4, it is evident that the degree of swelling of all modified
samples is higher in relation to the unmodified hemp fibers. The increase of the degree of
swelling of hemp fibers modified with 17.5 % NaOH is the most likely consequence of
removing the hemicelluloses from interfibrillar regions, followed by swelling and shrinkage
of ultimate cells, which result in some disorientation of the fibrils and changes of amorphous
and crystalline regions ratio, in favor of amorphous ones [8,12]. Also, during alkaline
treatment of hemp fibers, lignin content decreased for 711 % (Table 1), which together with
the removal of fats and waxes, influences to a certain degree the increase of modified hemp
fibers swelling. The degree of swelling of hemp fibers samples H5 and H45 is higher for 77
% and 130 %, respectively, in relation to the unmodified fibers. The increase of degree of
hemp fiber swelling with the increase of time of treatment is very pronounced, and can be
explained by removing the hemicelluloses and hydrophobic components during the alkaline
treatment. Once when hemicellulosic components have been progressively removed,
interfibrillar regions become less dense and less rigid, which with the greater content of
413
amorphous regions enable easier penetration of larger quantity of water molecules into hemp
fiber structure. The degree of swelling of hemp fiber samples treated with 0.7 % NaClO2
samples, L5 and L60, is higher for about 68 % and 78 %, respectively, in relation to the
unmodified fibers. In hemp fibers modified with 0.7 % NaClO2 progressive removal of lignin
occurred mostly in the middle lamella. The decrease of lignin content for almost 50 % and of
hemicelluloses for approximately 17 % influenced changes in hemp fiber structure; these
changes influence an increase of degree of swelling in relation to the unmodified fibers. In
this case the duration of hemp fiber treatment did not influence the change of degree of
swelling to a large extent. It can be noted that the degree of swelling of oxidized samples, is
lower in relation to the alkali treated fibers degree of swelling. That could be ascribed to the
fact that in this case a greater part of hemicelluloses remained in the interfibrillar regions and
their densities have not been reduced as in fibers treated with 17.5 % NaOH, which caused
more difficult penetration of water molecules in these regions [8,42].
Table 4. Degree of swelling (DS), water retention (WRV) and iodine sorption values
(ISV) for unmodified and modified hemp fibers
Sample
C
H5
H45
L5
L60
DSeq (%)
35.61
54.17
70.48
51.27
53.17
ISV (mg/g)
69.09
58.72
44.91
252.2
212.4
WRV (%)
59.67
72.41
78.42
60.67
50.67
When hemp fibers are immersed in water they swell and imbibe considerably more water
than they are capable to hold. The total water holding capacity of a fiber can be estimated by
determining water retention values. All water absorbing and holding surfaces, cracks, and
cavities are included with the water retention measurement. Water retention values for all
samples tested are shown in Table 4. Compared to the unmodified samples, the alkali
treatment (hemicelluloses removal) yielded the same or lower water retention values. Hemp
fiber sample H5 has an almost unchanged water retention capacity in relation to unmodified
fiber (sample C). With an increase of modification time, water retention value decreases so
that the sample H45 has approximately 15 % lower water retention value in relation to the
unmodified sample. The decrease of water retention value of hemp fibers modified with 17.5
% NaOH with an increase of modification time is a consequence of structure changes, i.e.,
changes in the size and number of pores and microcracks in fibers during their modification.
It is also worth to mention that this treatment reduces the content of hydrophilic components,
hemicelluloses and pectins. The effect of lignin removal on water retention value was
significant, since removing about 50 % of lignin results in 20 % more water kept by modified
hemp fibers in comparison with unmodified fibers. The higher water retention values of hemp
fibers with lower lignin content can be explained by lignin removal from the middle lamella
followed by fibrillation. Occurred fibrillation increased the roughness of hemp fiber surfaces
and induced new capillary spaces in inter-surfacial layer between completely or partially
separated fibers within the modified technical hemp fiber [8,13,42].
The iodine sorption value is empirical measure of cellulose accessibility to aqueous
solutions in the fiber amorphous areas due to the fact that the mechanism of iodine sorption
414
differs from water sorption, i.e., three-iodide ions (built up when an iodide ion is added to an
iodine molecule) are preferentially adsorbed in a monomolecular layer, whereas additional
water molecules are bound to the water monomolecular layer by hydrogen bounds. Therefore,
the iodine sorption value is inversely proportional to the fiber crystalline phase (crystallinity
index-CrI) [48].
The obtained data showed that hemicelluloses removal increased the iodine sorption of
H5 and H45 samples for more than two times, compared to unmodified fibers (sample C). On
the other hand, after the removal of lignin from hemp fibers by chlorite treatment (samples L5
and L60), value for iodine sorption decreased for 15-35 %, compared to sample C (Table 4).
This suggests that removing the hemicelluloses leads to an increase in the amorphous area in
the structure of hemp fiber, while the progressive removal of lignin leads to increased
crystallinity index.
INFLUENCE OF CHEMICAL COMPOSITION OF

HEMP FIBERS ON THEIR CAPILLARITY
Capillary properties of hemp fibers may have importance when selecting the use of end
products. Good capillarity of fibers can be of advantage in products in which a good
absorption capacity and/or speed is needed. Also it allows the fiber to absorb moisture,
liquids, lubricants, finishes, and stem, permitting faster bleaching, dyeing, impregnating, etc.
[49,50]. Capillarity can be defined as the macroscopic movement of a fluid system under the
influence of their own surface, difference in pressures and interfacial forces. Equilibrium will
happen when the capillary action is balanced by gravity, that is, by the weight of the raised
liquid [50]. The evaluation of capillarity of fibers depends to a large extent on the measuring
conditions. Also, as a natural bast fiber, hemp showed great variation in chemical
composition and fiber diameter even within a single fiber. For this reason, several series of
experiments have been done using different number of fibers (single fibers and fiber bundles)
and wetting liquid (0.1 % aqueous solution of eosin (viscosity 1.03 x 10-3 Pa s) and
transformer oil (viscosity 28.84 x 10-3 Pa s)). The wetting liquids were chosen based on their
different polarity and affinity towards hemp fibers. Measuring capillarity of single hemp
fibers gives the high coefficient of variation [8] because of the fact that hemp fiber as a
natural bast fiber, showed great variation in fiber diameter even within a single fiber, and the
fiber surface appeared relatively rough and uneven, with small fibrillar ends pointing away
from the surface. These irregularities affect the liquid front movement, i.e., the flow in a
capillary space may stop when geometric irregularities allow the meniscus to reach an edge
and flatten. From the data presented in Table 5 it is evident that the value of equilibrium
height (heq) of capillary rise is different for single fibers and fiber bundles, but the tendency is
the same.
The increase of heq in the hemp fibers bundles, in relation to the single fibers, is caused
by an additional capillary effect, which appears as a consequence of interfacial capillary
forces formed between fibers within the bundle. Taking this in consideration and in order to
obtain numeric values which permit good description and comparison of the capillarity of
unmodified and modified hemp fibers, it is very important to prepare fiber bundles in the
same manner, which will minimize influence of fibers alignment and spaces between fibers in
415
the bundle on the obtained results. The applied capillary rise method provides the collective
measurements of simultaneous wetting of the fiber surface, liquid uptake in the pore
structures capillary penetration, adsorption on the fiber surface, and liquid absorption within
the fibers [50]. The sorption of the liquid into the fibers can cause their swelling, reduce
capillary spaces into the fibers and close smaller pores, and complicate kinetics. Influence of
chemical composition changes on the fiber capillarity can be misinterpreted if the effects of
sorption into the fibers are overlooked. By the removing hemicelluloses and lignin, the fiber
bulk structure and moisture sorption (Table 5) were changed, and it is expected that both
untreated and treated fibers have different swelling tendency [8]. In order to quantify the
individual contributions of wettability, sorption properties and pore structure to liquid
transport and retention properties of hemp fibers, two series of experiments using different
wetting liquids: 0.1 % aqueous solution of eosin and transformer oil, were set up.
Transformer oil was selected because it has no affinity towards hemp fibers and under these
measuring conditions the rise of the liquid can be attributed only to capillary effect caused by
the fiber surface properties and fiber micro-porosity.
Results of capillary rise in single fiber and fiber bundles of unmodified and modified
hemp fibers are shown in Table 5. Evidently, the capillary rise is strongly enhanced by fiber
modification (i.e., hemicelluloses and lignin removal). According to the literature [8], in the
case of eosin solution, the equilibrium value is attained up to 2000 s, and for transformer oil
up to 120 s. The capillary rise of eosin solution for modified fibers is increased in relation to
initial fibers. The oil capillary rise in modified fibers also manifests a trend of growth, in
relation to unmodified fibers. For the aqueous solution of eosin, it is obvious that we have
sorption of the liquid into the fibers and fibers swelling, leading to reducing capillary spaces
into the fibers and higher capillary pressure in smaller pores, i.e., higher equilibrium capillary
rise of water in comparison with transformer oil [8]. The capillary principles dictate that the
distance of liquid advancement is greater in a smaller pore because of the higher capillary
pressure, smaller pores are filled first and are responsible for the liquid front movement, i.e.,
the smaller the pore radius, the equilibrium height is greater, and the more time is needed for
liquid to reach the equilibrium height. Considering presented results, together with the
capillary principles, it is obvious that gradual removal of lignin leads to faster liquid
spreading in fibers facilitated by small, uniformly distributed and interconnected pores.
Table 5. Capillary rise data for single hemp fibers and fiber bundles and moisture
content of unmodified and modified hemp fibers
Sample
C
H5
H45
L5
L60
*
0.1 % eosin
heq (mm)
s.f.
8.8
29.2
40.4
29.6
29.4
f.b.
28.4
49.4
43.6
62.0
76.4
s.f. single fiber; f.b. fiber bundle.
Oil
heq (mm)
s.f.
9.8
13.2
24.8
25.0
35.8
f.b.
17.0
17.6
30.4
22.4
40.4
Moisture content
(%)
8.40
8.76
9.22
7.17
6.91
416
From the liquid capillary rise height time dependence, coefficient of capillary diffusion
can be determined on the basis of the general wettability relationships [51], as it is described
below. In the equilibrium, the maximum height heq of the front of capillary rise is defined by
heq
2 coseq
g RS
(1)
where is the surface tension and the density of the liquid, Rs the average static radius of
pores, g the acceleration due to gravity (9.81 m/s2), and heq is the equilibrium, static contact
angle, which is generally smaller than the dynamic contact angle. At the beginning of the
process, when the height reached by the liquid h is much smaller than heq, the hydrostatic
pressure can be neglected and h2 is proportional to time
h2 D t
(2)
where the slope D presents the coefficient of capillary diffusion, directly related to the
average equivalent radius of the capillaries in porous fiber structure, chemical composition of
fiber surface and physico-chemical characteristics of the liquid [51].
In the case when h is close to heq, the hydrostatic pressure cannot be neglected and by
introducing the approximation that = eq, the following equation is obtained:
heq ln
heq
eq
RD2 g
t
8
(3)
where RD is the average hydrodynamic radius of pores, and the liquid viscosity. This
equation can be presented, as [51] suggested, in a simplified form
H C t
(4)
Graphical presentation of the function H = f(t) is the straight line with the slope C being
dependent only on the size of the capillaries in fibers and to the nature of the liquid. As the
measure of validity of the assumption = eq the following ratio can be used:
cos
D
cos eq 2 C heq
(5)
This ratio is always smaller than 1, because of the fact that is generally larger than eq.
By processing of obtained data, i.e., the liquid capillary rise height vs. time up to the
equlibrium height is reached, through Eqs. (2), (4), and (5), and drawing corresponding
curves, all three parameters of wettability (D, C and R) were determined.
The coefficient of capillary diffusion D is clearly affected by the removing either
hemicelluloses or lignin. For modified hemp fibers, the value of coefficient D significantly
increases in relation to the unmodified fibers, and this increase is more pronounced in the case
417
of fibers with lower lignin content. The results of coefficient C, that can be made equal to the
wetting rate, are spread in a range from 0.02 to 1.26 mm/s (Table 6), suggesting some
influence of the lignin and hemicelluloses removal on the wetting rate of modified hemp
fibers. It is also obvious that the increase of coefficient C of modified hemp fibers, in relation
to the unmodified fibers, is much smaller in the case of hemicelluloses removal than lignin
removal.
Table 6. Values of coefficients D, C and R for unmodified and modified hemp fibers
Sample
C
H5
H45
L5
L60
0.1 % eosin
D (mm2/s)
1.03
5.49
1.68
13.82
25.37
C (mm/s)
0.02
0.07
0.03
0.16
0.25
R
0.91
0.79
0.77
0.69
0.66
Oil
D (mm2/s)
4.55
7.45
12.89
15.46
17.42
C (mm/s)
0.27
0.49
0.39
1.26
0.34
R
0.49
0.43
0.54
0.27
0.64
The trend of coefficients D and C of hemp fibers modified with sodium hydroxide listed
in Table 6 most likely can be ascribed to the greater influence of structural changes in hemp
fibers, in comparison to the changes in the hemicelluloses content. The R values, mostly
range from 0.71.0, confirm well enough the validity of assumption = eq in the case of
wetting with eosin solution, while the values of R are lower and more scattered in the case of
transformer oil. From results obtained, it is clear that changing hemp fiber chemical
compositions alter its porous structure and capillarity properties. These changes can be
ascribed not only to the decrease of lignin or hemicelluloses content, but also to the influence
of the location of these components in the hemp fiber structure. Treatments directed towards
modification of fiber surfaces bring about changes of pore diameter and of the contact angle,
both of them influencing variation of capillary rise heights and capillary diffusion
coefficients. These changes are more pronounce in the case of lignin removal and impose the
conclusion that gradual removal of hemicelluloses most likely induces smaller changes of the
fiber surface than gradual removal of lignin. This circumstance can be explained by the facts
that removed hemicelluloses were located in the inter-fibrillar regions inside ultimate cells
and that lignin which was partly removed with 0.7 % NaClO2 fulfilled the middle lamella
joining ultimate cells. Also, reason for this probably lies in the fact that when hemp fibers are
treated with 17.5 % NaOH, hemicelluloses are progressively removed, making the interfibrillar regions less dense and rigid and thereby make the fibrils more capable to
rearrangement. The removal of hemicelluloses is accompanied by swelling and shrinkage of
ultimate cells, which result in some disorientation of the fibrils and texturing of hemp fibers
[2,6,10]. In the case of lignin removal, occurred fibrillation induced new capillary spaces in
inter-surfacial layer between completely or partially separated fibers within the technical
modified hemp fiber. Due to fibrillation increased the roughness of hemp fiber surfaces can
promote wetting by decreasing apparent contact angle, even the intrinsic wettability of the
fibers remains the same. From the other side, when hemp fibers are treated with 0.7 %
NaClO2 and lignin is removed gradually; the middle lamella joining the ultimate cells is
expected to be more homogenous due to the gradual elimination of micro-pores, while the
418
ultimate cells themselves are affected only slightly. According to the literature [6,10] there is
no appreciable loss in molecular orientation in delignificated hemp fibers.
BIOSORPTION OF HEAVY METAL IONS FROM AQUEOUS

SOLUTIONS BY SHORT HEMP FIBERS
The increased production of hemp fibers brought about an increase in the amount of
waste, namely shives, short and entangled fibers. Due to the good sorption properties of hemp
fibers, it is very convenient to use these waste fibers as biosorbents. The biosorbents have
proved to be an efficient alternative to conventional sorbent [52-57]. The term biosorbent
includes the usage of dead biomass (such as fibers, peat and rice hulls) as well as living plants
and bacteria as sorbents. Biosorbents represent cheap filter materials often with high sorption
affinity and capacity, and they are already available in most places. Some types of biosorbents
are broad range with no specific priority of metal ion bonding, while others can be specific
for certain types of metal ions. There are some limitations pertaining to the usage of living
organisms as sorbents, e.g., they cannot function at low pH level, or at toxic levels of metal
ions, while plant fibers on the contrary are chemically and physically more robust [52,53,58].
Hemp fibers consist mainly of cellulose, hemicelluloses, lignin, some pectin and extractives
(fat, waxes, etc.). Strong bonding of metal ions by carboxylic (primarily present in
hemicelluloses, pectin and lignin), phenolic (lignin and extractives) and to some extent
hydroxylic (cellulose, hemicelluloses, lignin, extractives and pectin) and carbonyl groups
(lignin) often involves complexation and ion exchange [12,42]. Biosorption is not restricted
to one sorption mechanism only, but comprises several mechanisms such as ion exchange,
chelation, precipitation, sorption by physical forces, and ion entrapment in inter- and
intrafibrillar capillaries and spaces of structural lignin and polysaccharide networks.
Therefore, biosorption of heavy metal ions by lignocellulosics is affected by several factors
such as initial pH, initial metal ion concentration, contact time, temperature, fiber
pretreatment, etc. [12].
The pH value of the heavy metal ions solution is one of the key parameters that may
influence sorption process. The pH of the biosorption medium affects the solubility of metal
ions and the ionization state of the functional groups of the hemp fibers. Because of high
proton concentration at lower pH, heavy metal biosorption decreases due to the positive
charge density on metal binding sites (i.e., hydrogen ions compete effectively with metal ions
in binding to the sites) and at a low pH, of almost 2.0, all binding sites may be protonated,
thereby desorbing all originally bounded metals from the fibers. The negative charge density
on the fiber surface increases with increasing pH due to deprotonation of the metal binding
sites. The metal ions then compete more effectively for available binding sites, which
increase biosorption. The high sorption levels for the short hemp fibers between pH 4.0 and
5.5 indicate that a high affinity for Pb2+, Zn2+ and Cd2+ predominates in this pH region, with
maximum sorption at pH 5.5 [12].
Biosorption capacity is also affected by concentration of the metal ions in the sorption
medium, and the time of contact between biosorbent and metal ions solution. Maximum metal
ions uptake of unmodified (C) and modified hemp fibers (H5, H45, L5 and L60) increases
approximately 4 times, with increase of the initial metal ion concentration from 0.05 to 0.2
419
mmol/L [12]. The biosorption of Cd2+, Pb2+ and Zn2+ ions is very fast in the beginning, since
approximately more than 80 % of ions are sorbed in the first 5 minutes, after which sorption
process slows down and the amount of sorbed metal ions do not change significantly with an
increase in contact time. The generally fast sorptions indicate that reactions at outer surfaces
are important [12].
Also, the total uptake capacity of Cd2+ and Zn2+ ions is increased by hemp fibers
modification (i.e., the separate removal of hemicelluloses and lignin), while at the same time
the total uptake capacity of Pb2+ ions is almost unchanged.
The maximum sorption capacity of 0.078 mmol/g for all tested ions was obtained for
sample L60 (Figure 5). Data obtained from modification experiments indicated that
modification with sodium chlorite (i.e., removal of lignin) resulted in better improvement in
biosorption capacities compared to alkali modification. This can be explained by the
domination of sorption at outer surfaces of fibers, as we mentioned earlier, and increased the
roughness of hemp fiber surfaces and induced new capillary spaces in inter-surfacial layer
between completely or partially separated fibers due to the removal of lignin from the middle
lamella, followed by fibrillation. Also, sodium chlorite oxidation of residual lignin that
caused benzene ring cleavage and formation of dicarboxylic groups [40] should not be
neglected. Taking in consideration all above mentioned and complexity of the structure and
composition of hemp fibers, a simple relation between the lignin and hemicelluloses contents
and the sorption capacity could not be demonstrated. The results of the total uptake capacity
of Cd2+, Pb2+ and Zn2+ ions for non-competitive conditions indicate that all samples exhibit
capacities which are influenced by the investigated metal ion, but these differences are
significant only at the highest ions concentration (0.2 mmol/L). This is because the ratio of
the initial quantity of metal ions moles to the available binding sites is low at lower
concentration and subsequently the sorption is less dependent on metal ion affinity. The
exception is the sodium chlorite modified sample (L60) with the same affinity for Cd2+, Pb2+
and Zn2+ ions.
The selectivity of unmodified and modified hemp fibers for metal ions is more
pronounced and can be easily seen in the case of simultaneous biosorption of the ternary
mixture, in which three metal ions compete for a limited number of binding sites (Figure 5).
The biosorption capacities of hemp fibers in the presence of the ternary mixture were lower
for Cd2+ and Zn2+ ions than those for noncompetitive conditions, and almost the same for Pb2+
ions. Also, an increase in metal ions concentration from 0.1 to 0.2 mmol/L in the competitive
conditions caused about a twofold increase in the total uptake capacity of Pb2+ ions, while the
total uptake capacities of Cd2+ and Zn2+ ions stayed almost unchanged (Figure. 5). The order
of the affinity for competitive conditions was as follows: Pb2+ >Cd2+ >Zn2+ [12]. The
maximum uptake capacity and efficiency of metal ions removal from the ternary mixture was
obtained for the sample L5. Nevertheless, it can be noted that sorption capacity of all tested
samples is proportional to the amount of functional groups (see Table 3). This suggests that
amount of hemp fibers acidic functional groups have dominant influence on the metal ions
biosorption, since they act as an active cites for adsorption. Beside the amount and
accessibility of functional groups, the process of biosorption is also influenced by their
surface distribution i.e., surface homogeneity [41].
420
Figure 5. Total heavy metals uptake capacity of unmodified and modified hemp fibers.
For the better understanding of biosorption process, sorption equilibrium data were
treated with Langmuir and Freundlich adsorption isotherms. In order to calculate isotherm
parameters, the linear regression analysis was the most commonly used method. However,
linearization of such data distorts the experimental error, and the suitability of isotherm
models to describe experimental data, is determined only on the marginal differences between
correlation coefficients. Therefore, the non-linear form of Langmuir and Freundlich
adsorption isotherms were used for isotherm parameters calculation, and the model which is
best supported by experimental data is selected by model selection criteria e.g., Akaike
information criterion (AIC). AIC is able to answer the question: which model is better for
mathematical description of experimental data.
On the bases of the results presented in Table 7 we can conclude that shorter time of
modification, favor higher values of adsorption capacity and greater homogeneous
distribution of active sites for adsorption on the surface of hemp fiber. For all tested samples
values of 1/n were less than unity which indicates that the biosorption of zinc on short hemp
fibers is a chemical process. This also suggests that biosorption of zinc is predominantly
occur through the ion exchange reaction on the functional groups.
Adsorption kinetic data obtained using zinc ions as a model of heavy metal ion were
analyzed by pseudo-first and pseudo-second order kinetic models, and the best fitting model
is chosen using Akaike information criterion [41]. In order to determine the rate-controlling
421
step in the overall process of biosorption, kinetic data were examined by intraparticle
diffusion model.
The values of the equilibrium amount of zinc adsorbed calculated by pseudo-first and
pseudo-second order models, are compared with the experimental data (Table 8.). The
calculated values were fitted with the experimental data by minimizing the squared magnitude
of the residuals of the amount of zinc adsorbed. The optimal model parameters: qe.cal and k1
for the pseudo-first, and qe.cal and k2 for the pseudo-second order models, obtained by this
fitting procedure, have enabled the best comparison with the experimental data. The values of
the model parameters, Akaike information criterion and the standard deviation are shown in
Table 8. These results show that biosorption of zinc ions on all tested short hemp fiber
samples predominantly follows the pseudo-second order kinetic model indicating that
adsorption/binding of zinc ions on hemp fibers is mediated by chemical forces rather than
physical forces of attraction.
Table 7. Corrected Akaike information criterion, standard deviation and Langmuir and
Freundlich isotherm parameters for zinc ions adsorption on unmodified and modified
hemp fibers samples
Sample
C
L5
L60
H5
H45
Langmuir
Q0 (mg/g)
8.0
8.3
7.1
8.1
7.4
b (l/mg)
0.200
0.164
0.322
0.226
0.231
AICc
3.317
6.474
-2.166
5.169
4.109
std
0.135
0.365
0.053
0.333
0.254
Freundlich
1/n
Kf
0.390 2.100
0.470 1.606
0.331 2.300
0.420 2.101
0.381 2.046
AICc
5.487
6.995
5.679
6.085
3.362
std
0.253
0.328
0.3228
0.393
0.211
Table 8. Corrected Akaike information criterion, standard deviation and kinetic

parameters obtained by pseudo-first order and the pseudo-second order kinetic models
for zinc ions adsorption on unmodified and modified hemp fibers samples, for initial
zinc ion concentration of 0.1 mmol/l
Sample
C
H5
H45
L5
L60
Pseudo-first order
k1, (min-1) qe. cal, (mg/ g)
0.30
2.210
0.20
2.500
0.21
2.378
0.28
2.431
0.30
2.353
AICc
-1.352
1.281
1.051
-0.141
-0.206
std
0.147
0.265
0.257
0.190
0.181
Pseudo-second order
k2, (min-1) qe. cal, (mg /g)
0.51
2.195
0.40
2.479
0.38
2.400
0.42
2.453
0.55
2.350
AICc
-8.336
-5.168
-8.308
-4.548
-6.027
std
0.027
0.054
0.026
0.057
0.029
qe. exp, (mg /g)

2.193
2.454
2.393
2.505
2.444
In order to investigate the diffusion mechanism during the biosorption process,

experimental data was tested by the intraparticle diffusion model. Figure 6 shows the plots of
qt versus t1/2 for sample H5 and for zinc initial concentrations of 0.1 and 0.2 mmol/dm3.
422
Figure 6. Intraparticle diffusion plots of the zinc ions onto sample H5 at various initial zinc ions
concentration.
The initial stage, addressed to external surface adsorption is quite fast, which is expected
in the well shaken system. The second step is assigned to moderate intraparticle diffusion
while final slow step corresponds to the equilibrium adsorption process, where the
intraparticle diffusion starts to slow down due to the extremely low solute concentration in
solution. The rates of adsorption observed at different stages of the process indicated that the
adsorption rate was initially very fast and then slowed down as time progressed. Obtained
multi-linearity in the intraparticle diffusion curves and the fact that the second and the third
linear part of the curves did not pass through the origin, suggests that the intraparticle
diffusion is not the only rate-controlling step in the overall adsorption process.
As the external mass transport is much faster than the diffusion of heavy metal ions
through the fibers, the adsorption rate mainly depends on the diffusion of metal ions through
the porous structure of hemp fibers and adsorption at interior active sites. In order to describe
the mechanism of adsorption and ion transport from water solution through the hemp fibers,
mathematical model has been developed [42] and used for modeling the heavy metal ions
adsorption on hemp fibers.
(CD
MATHEMATICAL MODELING OF HEAVY METAL IONS

, ZN2+AND PB2+) BIOSORPTION BY CHEMICALLY MODIFIED
SHORT HEMP FIBERS
2+
Mathematical model that describes phenomena of different ions (Pb2+, Cd2+ and Zn2+)
transport through the porous fiber matrices was developed to determine the profile of heavy
metal ion concentration in fibers and optimize the biosorption of heavy metal ions by short
hemp fibers. Since the hemp fibers sample L5 showed the highest efficiency in heavy metals
removal [12], the mathematical model was developed based on the adsorption results
obtained for this fiber sample.
423
Mathematical model, formulated for the phenomenological description of the biosorption

of metal ions from the aqueous solution by the fibers, is based on the second Ficks low, and
represents the modification of the model developed by Medovic et al. [59]. Diffusion process
into the fibers was approximated as mass transport process in the very long cylindrical body
with radius R. The model of biosorption process describes the change of metal ions
concentration in swollen fibers. The last one is due to the fact that the fiber swelling process
is much faster than the biosorption of the ions based on our experimental observation.
Maximum swelling of fiber sample L5 was attained already after less than 5 min while the
highest sorption efficiency for all the three ions from mixture was attained after 60 min [12].
The experimental data of ion concentrations in solution are introduced into the model in order
to: (1) determine the effective diffusion coefficient for metal ions within the fibers and (2)
predict the profiles of heavy metal ion concentration within the fibers.
Balance equation of metal ion concentration change in the fiber is:
1 CF r , t
CF r , t
r
Deff
r r
t
r
(6)
where:
CF r, t is ion concentration difference, i.e., C F r, t C F eq C F r, t ,

C F r, t is local ion concentration,
CF eq is the equilibrium ion concentration,
Deff is effective diffusion coefficient of ions in fibers.
Deff corresponds to the Stokes-Einsteind diffusion coefficient for the diluted systems (the
single ion solutions). In the case of the concentrated system (the aqueous ion mixture) it
represents the temporally averaged collective diffusion coefficient.
Balance equation of metal ion concentration change in the solution is:
VS
CS t
CF r , t
Deff
t
r
Peff
r R
where:
CS r, t is ion concentration difference, i.e., C S t C S t CSeq ,
CS t is ion concentration in the solution,
(7)
424
C S eq is the equilibrium ion concentration in the solution,
VS is volume of the solution,

Peff is the effective interface between fibers and the solution, i.e.,
Peff
2VF
( R is the radius of already swollen fiber, V F is total volume of the already
R
swollen fibers).
The boundary conditions for sorption of metal ions from the solution to the fibers are:
1) At t 0 , the initial concentration of metal ion in the solution is CS 0 CS 0 .
2) At t 0 , the initial concentration of metal ion in the fibers for r R is
C F R, 0 C S 0 .
3) At every t the concentration of metal ion in the fibers for r R is equal to
C F R, t t C S t , where parameter t represents the effectiveness of
sorption.
4) The initial value of parameter
is 0 1 based on the condition (1).
5) At t t eq (where the equilibrium time for sorption of metal ions was t eq 60 min
the equilibrium concentration of metal ion in solution is C S t eq C S eq .
6) At t t eq the equilibrium concentration of metal ion in fibers was C F t eq C F eq

(where
C F eq
the
S0
equilibrium
C Seq VS
VF
ion
concentration
in
fibers
is
equal
to
).
Model balance equation, Eq. (6) is solved analytically by Fouriers dividing of the
variables and using Bessel functions. The general solution of Eq. (6) determines the profile of
the metal ion concentration within the fibers. It is expressed as:
CF r, t CF eq e t C1 J 0 ra C2 N 0 ra
2
(8)
Where:
J 0 ra and N 0 ra are the Bessel functions, while the parameter a is equal to

a
2
Deff
425
Deff is the effective diffusion coefficient of metal ions through the fibers,
2 is the specific rate of changes of metal ions concentration.

Only the Bessel function J 0 ra
1 ra
2
k 0 k! 2
2k
has the exact value for r 0 equal
to J 0 0 1 . On that base, we formulate the particular solution of Eq. (6) as:
ra 2 ra 4 ra 6
2
C F r , t C F eq e t C1 1
4
64
2304
(9)
where C1 is the constant which is determined starting from the boundary condition (2) and
Eq. (9). The value of C1 is expressed as:
C1
C Feq C S 0
(10)
Ra 2 Ra 4 Ra 6
1
4
64
2304
After introducing Eq. (10) into Eq. (9) for r R we obtain:
C F R, t C F eq C Feq C S 0 e t
2
(11)
The temporal change of the ion concentration in the solution is expressed from Eq. (11)
and the boundary condition (3) as:
C S t t
The parameter
C F eq C Feq C S 0 e t
2
(12)
t is expressed in accordance with the boundary condition (4). It is
formulated as:
C Feq C Feq C S 0 e t
2
C S 0 C S 0 C Seq 1 e t
2
(13)
After introducing Eq. (13) into Eq. (12), following relationship for the concentration of
metal ions in the solution is expressed:
426
C S t C S 0 C S 0 C Seq 1 e t
2
(14)
Eq. (9) is in the accordance with the boundary conditions 1 and 6.

After introducing Eqs. (9), (10) and (12) into Eq. (7) we obtain:
R R 3a 2 R 5a 4
VS C S 0 C Feq
2
16
384
2
4
Peff C Feq C S 0
Ra Ra Ra 6
1
4
64
384
(15)
Effective diffusion coefficient is obtained from Eq. (15) for all experimental conditions
using iterative procedure. The procedure is expressed by introducing the error function from
Eq. (15) as:
R R 3a 2 R 5a 4
VS C S 0 C Feq
2
16
384
a
2
4
Peff C Feq C S 0
Ra 6
Ra
Ra
1
4
64
384
(16)
The optimal value of diffusion coefficient is calculated from the condition
2
a
/ a aeff 0 such that Deff 2 .
a
a eff
Mathematical model enables the estimation of metal ion effective diffusion coefficient
value and the prediction of the change of the metal ion concentration in the fiber as the
function of time and fiber radial distance (profiles of metal ions concentration in fiber). The
model prediction values of ion concentration in solution are calculated from Eq. (14). The
predicted values are fitted with the experimental data by non-linear least-squares regression,
minimizing the squared magnitude of the residuals of the heavy metal ion concentrations in
solution. The experimental data and model prediction of Pb2+ ion concentration in single ion
solution, the initial ion concentration 0.1 mmol/L, are shown in Figure 7. The similar
agreement between experimental data and model prediction of ion concentration in solution
for Zn2+ and Cd2+ in the single ion solutions and for all three ions in the ternary mixture was
obtained (data not shown here).
The optimal model parameter 2 obtained by this fitting procedure that enables the best
agreement with the experimental data is given in Table 9. The values of the model parameter
2 are introduced into Eq. (15) in order to estimate the corresponding values of the effective
diffusion coefficients. The effective diffusion coefficients are calculated using the iterative
procedure described by Eq. (16) and given in Table 9. Additionally, the equilibrium ion
concentrations in fibers (CFeq) obtained as a model prediction are shown in Table 9.
427
Figure 7. The change of Pb2+ ion concentration in single ion solution during the biosorption obtained by
experiment and by mathematical model.
Table 9. Value for effective diffusion coefficient (De), specific rate of changes the
concentration of metal ions (2) and equilibrium ion concentration in fibers (CFeq) for
Cd2+, Pb2+ and Zn2+ ions in the single ion solutions and ternary mixture of ions
Metal
ion
Cd2+
Zn2+
Pb2+
Single ion solution

Deffx1012
2
2
(m /s)
(min -1)
10.10
0.179
10.80
0.228
22.80
0.419
CFeqx10-3
(mmol/m3)
16.87
16.35
16.00
Ternary mixture of ions

Deffx1012
2
2
(m /s)
(min -1)
9.40
0.131
9.45
0.199
9.71
0.205
CFeqx10-3
(mmol/m3)
14.10
12.90
16.00
Both, specific rate of changes the concentration of metal ions (2) and effective diffusion
coefficient (Deff) in the single ion solution have the highest value for the lead ions. The
effective diffusion coefficient value is affected by thickness of the metal ions solvation layer
in aqueous solution, ion-ion (same and different species of ion) and ion-fiber interactions, the
surface microporosity and oxidized hemp fibers structure. In the aqueous solution metal ions
are surrounded by solvation layer, whose thickness affects the ion transport through the
solution. Ions with smaller radius have thicker solvation layer [60], therefore their transport
toward the biosorbent surface is slower. Consequently, the diffusion coefficient of these ions
is smaller. Also, in the single ion solution initial concentration of metal ions is low enough
that mutual ion interaction can be neglected, so the ions keep the solvation layer when
entering the fibers. Considering fact that the dimension and share of the interfibrillar spaces in
the fiber structure is much higher than the dimension and share of micropores, microcavities
and microcracks, further transport of ions through the fiber can be approximated with the
transport through the interfibrillar spaces. The interfibrillar spaces are filled with a solution so
it can be assumed that the ions keep almost unchanged salvation layer during the transport.
Therefore, the ion transport through the fiber and effective diffusion coefficient is affected by
428
thickness of the solvation layer. Lead ions that have larger radius compared to cadmium and
zinc, and thinner solvation layer, need the shorter time to reach the hemp fibers surface. This
is in agreement with the highest value for the lead ion diffusion coefficient in the infinite
diluted solution (D0(Pb2+)=10.00x10-10 m2/s, D0(Cd2+)=7.19x10-10 m2/s, D0(Zn2+)=7.10x10-10
m2/s), obtained from the literature [61,62].
In the case of ternary mixture lead ion also has the highest effective diffusion coefficient,
but in this case the values of Deff are similar for all three examined ions. Though the initial
concentration of each metal ion was the same as in the single ion solution, there were a three
times more particles. This is the reason for an intensive collision between the same and
different type of ions, during the transport of these ions through the solution and fiber. As a
consequence of the mutual interactions, ions lose solvation layer and change the path of
transport. Mechanism of ions transport was partially changed compared to the single ion
solution, and now it mostly depends from the efficiency of collision.
Lead ions have the highest effective diffusion coefficient in both cases. Therefore, lead
ions faster reach the surface of the hemp fiber then other two ions, and have a priority of
deposition in micropores and microcracks of fibers and penetration into interfibrillar space in
fibers structure. Sorbed lead ions can represent the steric obstruction for sorption of other
ions.
In the next step of mathematical modeling, calculated values of effective diffusion
coefficient are introduced into Eq. (9) to determine concentration profiles of heavy metal ions
in fiber: for the single-ion solutions and for the mixture of all three ions in solutions. The
profiles of zinc ion concentrations in fibers are shown in Figure 8. The similar trend of ion
concentration in fibers was obtained for lead and cadmium ions [42].
Effectiveness of sorption (model parameter ), given by Eq (13), could be explained as
the measure of biosorption efficiency in regard to increased ion concentration in fibers
(Figure 9).
Figure 8. Profile of Zn2+ ions concentration in the fibers depending on time of biosorption for the single
ion solution and ternary mixture.
429
Figure 9. The dependence between the effectiveness and time of sorption for the single ion solution and
ternary mixture.
The biosorption of metal ions depends on: (1) the transport phenomena within the fibers
and (2) the resistance effects which arise as the result of the electrostatic interactions between
ions within the fibers. The effectiveness of sorption ((t)) represents the influence of both
processes. The effectiveness of sorption ((t)) is primarily influenced by the transport of ions
within the fibers in first 15 min (regime I). However, the resistance of the further transport of
metal ions within fibers increases with the increase of the ion concentration in fibers. The
resistance of the transport of metal ions within the fibers dominantly influences the
biosorption in next 45 min (regime II). During the regime I effectiveness of sorption is higher
for the lead ions then for cadmium and zinc, in both single ion solution and in mixture of
ions. In the single ion solution the effectiveness of sorption is changed in regime II in favor to
the cadmium and zinc ions. On the other hand, effectiveness of sorption value retained the
same order for all three ions (Pb2+>Cd2+>Zn2+) in the mixture during the both regime. The
effectiveness of sorption of Cd2+ and Zn2+ ions is higher for the single ion solution then for
the mixture of ions, while for Pb2+ ion is the similar in both cases. As it is explained earlier
[12], in the competitive condition (mixture of ions) short hemp fibers have a best affinity
towards lead ions. Therefore, effectiveness of sorption for lead ions will have the similar
value in both single ion solution and in the mixture of ions. In the same time, the
effectiveness of sorption for Cd2+ and Zn2+ will decrease in the mixture of ions.
Proposed mathematical model provides a better insight into phenomena of different ions
transport through porous fiber matrices. Consequently, this model may be considered useful
in the optimization of the complex process of biosorption. This is from great importance in
the case of using short hemp fibers as filter material for removing the heavy metal ions from
polluted water.
430
HEMP FIBERS WASTE AS A PRECURSOR FOR CARBON MATERIALS

Carbon materials with high surface area and pore volumes can be prepared from a variety
of carbonaceous materials such as coal, coconut shell, wood, agricultural or industrial wastes.
In the recent years, there is a growing interest in utilization of the low-cost and abundantly
available waste materials and biomass as precursors for the preparation of carbon materials
[63]. The usage of the waste materials represents a special way of recycling and producing
useful products. At the same time the cost of waste disposal are minimized. Additionally,
carbon sorbents obtained from waste can be used for water purification by removal of specific
pollutants, like dyes [64-66], heavy metals [67-69], pesticides [70,71] and phenols [72]. The
possibility of using different type of biomass has already been tested for production of the
carbon materials [63,65,72-80]. Among other biomass types, Reed and Williams [81] have
used hemp fibers for obtaining activated carbon. Hemp fiber is a lignocellulosic material that
contains celluloses, hemicelluloses and lignin which are rich in carbon, and therefore presents
a good precursor for carbon materials production.
CARBONIZATION OF CELLULOSIC MATERIALS

Celluloses based carbon materials are obtained by controlled thermal decomposition of
celluloses in the inert atmosphere and undergoes through the two phases. During the pyrolysis
of celluloses, that represents the first phase and ends around 400 oC, the large amount of
different compounds (CO, CO2, H2O and resinous products) are released. Therefore the
weight loss is very high and obtained carbonaceous material contains 60 70 % of carbon.
Carbonization represents the second phase with the ending temperatures over the 900 oC.
During the carbonization the defect graphitic structure is formed and the carbon content is
increased over the 90 %.
Although the full mechanism of carbonization of cellulose is not understood completely,
a summary of some of the chemical aspects of the process given by Bacon and Tang [82] is
shown in Figure 10.
The pyrolysis of cellulose is controlled mainly by two predominant reactions,
dehydration and depolymerization (cleavage). Physical desorption of water is the first
processes during pyrolisys, and take place between 25 and 150 oC, followed by dehydration
of the cellulosic unit which continues between 150 and 240 oC. The dehydration reaction
stabilizes the cellulose structure: during the dehydration, elimination of the hydroxyl groups
results in double bonds, conjugated double bonds, and subsequently, in an aromatic structure.
The polymeric structure is basically retained through dehydration and at this temperature
range weight loss is usually limited to the evaporation of water.
Degradation of native cellulose fibers starts at 200 oC and ends around 380 oC, under inert
atmosphere. Although the physicochemical processes taking place during the transformation
of cellulose into carbon are complex, it is certain that depolymerisation of the
macromolecular chains produces a variety of oxygenated compounds. This leads to the major
mass loss of the solid residue through the production of volatile substances. Based on the
molecular stoichiometry (C6H10O5)n the theoretical carbon yield of carbonization process of
cellulose structure is 44.4 %. However, the actual yield is only between 10 and 30 %. During
431
the depolymerisation of the macromolecular chains, the carbon content is decreased due to
releasing of carbon monoxide (CO) and carbon dioxide (CO2), aldehydes, organic acids and
tars [83].
Figure 10. Mechanism of celluloses controlled thermal decomposition, proposed by Bacon and Tang
[82].
432
Carbonization is the second step of controlled thermal decomposition of celluloses and

represents the conversion of depolymerized structure into graphite-like layers through the repolymerization. Depolymerization to monosaccharide derivatives occurs through the thermal
cleavage of the glycosidic linkage and ether bonds which is followed by decrease in degree of
polymerization. These derivates are re-polymerized by forming condensed, aromatic
structures and releasing gases containing non-carbon atoms (O, H). Subsequently, in the
temperature range of 400 900 oC, the carbonaceous residue is converted into a more ordered
carbon structure. The heat treatment up to 900 oC, under an inert atmosphere, leads to
formation of semi-ordered carbonaceous structures. Further heating, above 900 oC, initiate
graphitization, and generally amorphous carbonaceous structures converts to a turbostratic
carbon structure containing graphene layers. A remarkable feature is that the carbon structure
formed via pyrolysis retains some memory of the starting structure through the entire process
[83]. Additionally, characteristics of obtained carbon materials depend of the carbon
precursor structure and parameters of carbonization process [13].
THE INFLUENCE OF PREPARATION PROCESS PARAMETERS ON

THE CARBONIZED HEMP FIBERS SURFACE CHARACTERISTICS
Chemical modification of short hemp fibers prior to carbonization was used to examine
the influence of carbon precursor chemical structure and morphology on carbonized material
characteristics. The amount of hemp fibers structural components, especially lignin,
hemicelluloses and cellulose, may affect surface characteristics of carbonized materials,
especially specific surface area and amount and nature of surface functional groups [84]. In
order to obtain a row material with different characteristics, short hemp fibers were
chemically modified as it is described in the literature [12]. The progressive removal of the
hemicelluloses was brought by treating the fibers with 17.5 % NaOH solution, while the
lignin was progressively removed by treating hemp fibers with 0.7 % NaClO2. The samples
obtained by chemical modification along with the original (as received) hemp fiber were then
carbonized at 1000 oC under constant nitrogen flow (150 cm3/min), with the heating rate of
5 oC/min. The isothermal time at maximum carbonization temperature was 30 min. After
carbonization, five samples denoted Ch1, ChL5, ChL60, ChH5 and ChH45 (as it is shown on
the Figure 11), were obtained [13].
The changes in both chemical and structural properties of the hemp fibers incurred as a
result of alkali and oxidative chemical treatment are already explained in this Chapter. After
carbonization all samples retain fibrous structure of the precursor fibers. Compared to the
carbonized hemp fibers obtained from unmodified fibers (Ch1, Figure 12a), the carbonized
hemp fibers modified prior to the carbonization (ChL5, ChL60 and ChH5, Figure 12b, 12c
and 12d)) are characterized by visible surface fibrillation. In the case of sample ChH45
(Figure 12e) the fibrillation is even more pronounced.
The amount of lignin, hemicelluloses and cellulose in the carbon precursor affects the
specific surface area of carbonized materials [84]. Lignin has been found to be effective in
creating pores, as evident from the work by Kennedy et al. [85]. Furthermore, the BET
surface area was found to be highest for the carbon materials obtained from carbon precursors
with highest lignin content [81]. In view of that, short hemp fiber modified by removing the
433
lignin, after carbonization gave samples ChL5 and ChL60 with lower specific surface area
(Table 10) [13].
Figure 11. The scheme of carbonized hemp fibers production.
Figure 12. SEM photographs of carbonized hemp fibers: a) Ch1, b) ChL5, c) ChL60, d) ChH5 and e)
ChH45.
Table 10. Specific surface area and amounts of CO and CO2 evolving surface oxygen
groups of carbonized short hemp fibers samples
Sample
Ch1
ChL5
ChL60
ChH5
ChH45
SBET
(m2/g)
518.5
428.6
388.6
425.9
573.5
CO evolving groups
(mmol/g)
1.718
2.641
4.364
3.513
2.054
CO2 evolving groups

(mmol/g)
2.192
0.812
1.851
1.119
0.613
CO + CO2
(mmol/g)
3.910
3.453
6.215
4.632
2.667
434
During the alkali treatment of origin short hemp fibers, the crystal structure of cellulose,
named as cellulose I (Cell I), is transformed in to cellulose II (Cell II) [31,32]. The
polymorphic transformation of Cell I to Cell II depends on alkali concentration and the time
of treatment [33]. In the chemical treatment used for obtaining the carbon precursor for
sample ChH45 the concentration of NaOH and the time of treatment was high enough to
provide appropriate conditions for this polymorphic transformation. This transformation of
cellulose I in to more reactive cellulose II is probably the reason for high specific surface area
of sample ChH45 [13].
Surface oxygen complexes on carbon materials can be quantified by temperatureprogrammed desorption (TPD), as they decompose upon heating by releasing CO and CO2.
TPD peaks of CO and CO2 at different temperatures are related to the bond strength of the
specific oxygen groups. Thus, the position of the peak maximum at a defined temperature
corresponds to a specific oxygen complex at the surface. For example, CO2 is released by
decomposition of carboxylic groups at 373673 K or lactone groups at 463923 K. Both CO
and CO2 peaks originate from the decomposition of carboxylic anhydrides in the temperature
range of 623900 K. Phenols, ethers, carbonyls and quinones give rise to CO at 9731253 K
[86-89]. The quantities of CO and CO2 released during the TPD experiments correspond to
the total amount of oxygen groups present at the carbonized hemp fibers samples surface
(Table 10). For all samples modified prior to carbonization amount of CO evolving groups
increase while amount of CO2 evolving groups decrease compared to sample Ch1. It is
interesting that sample ChL60 has the highest amount of surface oxygen groups and sample
ChH45 the lowest, which are totally opposite to the values of their specific surface area. Also,
the extension of the oxidation treatment time leads to the increased amount of the surface
oxygen groups, while the extension of alkali treatment time leads to the reduced amounts of
the functional groups.
Figure 13. The scheme of activated hemp fibers production.
Specific surface area and the amount of surface oxygen groups can be increased by
activation of carbon material surface [13,86]. Activation of carbonized hemp fibers using
different amounts of potassium hydroxide, as activating agent, is schematically presented in
435
Figure 13. During the activation process, decomposition of KOH molecules is followed by
gasification process under high temperature:
2KOH K2O+H2O
H2O+C CO+H2
Stronger activation, i.e., increased ratio of KOH, open up the porous structure and
increases specific surface area up to 673 m2/g for sample ACh1 and 2192m2/g for sample
ACh2 [13].
Figure 14. TPD spectra of carbonized short hemp fibers samples: (a) CO and (b) CO2 desorption
profile.
436
Potassium hydroxide activation increases the amount of both CO and CO2 evolving
groups with increased amount of KOH used. TPD profiles of CO and CO2 evolution for all
tested samples are shown in Figure 14.
The TPD spectra of CO2 desorption profiles of all tested samples show an intensive peak
at relatively high temperature (from 890 K to 1073 K). For the sample ACh2 this peak is most
intensive and shifted to the higher temperatures. It can be noted that activation process as well
as the increased amount of activating agent increase the intensity of the peak and shifts it to
the higher temperature, which suggests the stabilization of surface oxygen groups. For all
tested samples, CO desorption profiles have a maximum at the temperature which coincides
with the maximum in CO2 desorption profile indicating the existence of anhydride groups,
which decompose upon heating by releasing both CO and CO2. The increase of this peak
area, with increased amount of KOH used for activation, suggest that high amount of
anhydride groups on the surface of activated hemp fibers samples is probably consequence of
the KOH activation process [86].
CARBONIZED AND ACTIVATED HEMP FIBERS APPLICATION AS

SORBENT MATERIALS
The possibility of producing carbon materials with high specific surface areas,
microporous structure, high adsorption capacity and degree of surface reactivity brings the
variety of application for these materials.
The carbonaceous materials have been proved to be effective sorbents for removal of
metal ions as well as their complexes. Their large sorption capacity is linked to well develop
internal pore structures, a large specific surface area, and the presence of a wide spectrum of
surface functional groups [87]. In the past decade, there is a growing interest in using
different type of biomass for production of carbon materials [68,69,90], as a low cost and
ecologically acceptable alternative to activated carbon. Carbonized hemp fibers obtained by
carbonization of origin and chemically modified waste hemp fibers was used as an efficient,
low-cost sorbent for heavy metals removal.
Sorption properties of carbonized hemp fiber samples tested through the heavy metal ions
adsorption are presented in Figure 15.
The increase of the heavy metal ions initial concentration leads to the increase of the
adsorbed equilibrium amount. For the initial concentration of 50 mg/dm3 all samples obtained
by chemical modification of carbon precursor have similar sorption capacity, which are
considerably higher compared to the sample obtained by carbonization of unmodified
precursor (Ch1). With increasing the initial concentration up to 100 mg/dm3, the sample Ch1
shows the lowest sorption capacity for lead ions, while its sorption capacities toward
cadmium and zinc ions have comparable values. Also, obtained results (Figure 15) suggest
that changes in carbon precursor morphology, caused by chemical treatment, affect the
sorption process and sorption capacity of examined samples.
437
Figure 15. Sorption capacity of carbonized hemp fiber toward a) Cd2+, b) Pb2+ and c) Zn2+.
In order to connect sorption process of heavy metal ions with structural parameters of
carbonized hemp fibers (CHF), mathematical model previously developed for prediction of
heavy metals biosorption, and described in this Chapter, was upgraded. For this purpose
adsorption of lead ions, which is proved to be the most concurrent ion during the adsorption
from the mixture of heavy metal ions [91], was used. Since, transport of ions depends on ion
concentration in water solution and structure of fibers, model consideration included two
successive steps: analysis of ion transport from water solution through CHF and
characterization of CHF structure. For ion transport analysis, developed model was upgraded
[92] by introducing the damping coefficient that quantifies the influence of fibers morphology
and surface porosity on ion transport, while ion transport through the porous matrices is
characterized by the effective diffusion coefficient. Additionally, structure of carbonized
hemp is described by: the pore volume as function of pore diameter, the porosity and the
average tortuosity.
Effective diffusion coefficient, damping coefficient and the lead ion concentration profile
within the carbonized hemp fibers, obtained as results of proposed mathematical model, give
the insight in the mechanism and the rate of adsorption process, while average tortuosity
connected the sorbent structure and ions transport through the sorbent. Figure 16 shows the
correlation between model prediction and experimental data obtained for lead ions
concentration within the sample Ch1.
438
Figure 16. Correlation between model prediction and experimental data obtained for lead ions
concentration within the sample Ch1.
As it was shown in Figure 16, model prediction is well fitted with the experimental data
for the initial concentration up to 200 mg/dm3. With further increase of initial ion
concentration in solution data obtained by model prediction and experiment starts to differ,
but remaining in good correlation. A good agreement between model prediction for both
structural and ion transport model parameters and the experimental data, indicates that the
proposed mathematical model can be successfully used for optimization of heavy metal ions
adsorption process.
Different carbon materials have been widely used as sorbents in the solid phase
extraction (SPE) which is an efficient and economical sample preparation technique for
preconcentation of the target analyte. This method has been previously applied to the
determination of many pesticides in natural water and crops due to its substantial advantages
such as providing higher concentration factors, decreasing sample preparation time, reducing
costs, and requiring less solvent [93,94].
Following the standard SPE procedure, carbonized and activated hemp fibers described
previously in this chapter were used as a sorbent in the solid-phase extraction for pesticide
analysis in water samples. Extracts, obtained after SPE procedure, were analyzed by liquid
chromatographytandem mass spectrometry technique. The pesticides belonging to the
different chemical classes as triazine (atrazine, simazine, propazine), neonicotinoid
(imidocloprid, acetamiprid, thiamethoxam), carbamate (carbofuran, methomyl),
organophosphate (monocrotophos, dimethoate, malathion, acephate), hydroxyanilide
(fenhexamid), diacylhydrazine (tebufenozide) and phenylurea (linuron) were chosen. The
method recoveries obtained using carbonized hemp fibers as a sorbent in SPE procedure is
presented in Table 11 and Figure 17.
439
Table 11. Recoveries of selected pesticides obtained using different carbonized hemp
fibers as SPE cartridges
Pesticide
Thiamethoxam
Monocrotophos
Imidocloprid
Acetamiprid
Tebufenozide
Fenhexamid
*
Ch1
ChL5
Recovery (%) (RSD (%))
62.9 (0)
93.1 (8)
14.3 (11)
57.2 (17)
64.2 (7)
88.8 (19)
61.9 (14)
105.8 (12)
61.4 (10)
95.3 (1)
40.4 (13)
71.1 (0)
ChL60
ChH5
ChH45
90.7 (13)
73.9 (0)
95.2 (7)
87.6 (15)
100.7 (15)
84.3 (0)
89.5 (5)
37.8 (20)
95.2 (7)
89.4 (0)
91.7 (12)
62.5 (3)
91.9 (2)
70.7 (10)
85.3 (7)
96.0 (18)
86.2 (1)
81.8 (13)
RSD relative standard deviation.
Sample Ch1 could not be used as a sorbent for SPE cartridges due to low recoveries
(under 70 %). Carbonized hemp fibers modified prior to the carbonization can be used for
preconcentration of few pesticides: thiamethoxam, imidocloprid, acetamiprid, tebufenozide
and fenhexamid. Additionally, samples ChL60 and ChH45 can be used for preconcentration
of monocrotophos.
Activated hemp fibers sample ACh1 can be used for preconcentration of all examined
pesticides except for methomyl, imidocloprid, linuron and fenhexamide (Figure 17).
Activated sample ACh2, can be used for all examined pesticides except for acephate,
methomyl, linuron and fenhexamide. Recoveries obtained for activated samples are
comparable with those obtained for commercial cartridges [13]. In the case of acephate,
dimethoate, simazine, carbofuran, propazine, malation and tebufenozide recoveries obtained
by activated hemp fibers was even better than those obtained with commercial cartridges.
Figure 17. Recoveries of selected pesticides obtained using activated hemp fibers as SPE cartridges.
440
Comparing the results obtained in the SPE experiments with the surface properties and
morphology of the carbonized and activated samples, it can be noted that the best SPE
efficiency was achieved with activated hemp fibers samples with the highest specific surface
area and the amount of surface oxygen groups.
CONCLUSION
The research summarized in this chapter represents an attempt to explain the influence of
chemical modification on hemp fibers structure and consequently on their properties.
Hemicelluloses and lignin removal, induced by oxidative and alkaline treatment, affects the
fiber structure and improves the fiber properties that are of great importance for their usage
for clothing, working and protection textile materials.
The influence of hemp fiber chemical composition on their heavy metal ions sorption
potential, were assessed by evaluating the water and metal ions uptake capacities of
differently modified hemp fibers. The process of heavy metal ions biosorption on short hemp
fibers was clarified by mathematical model development. Proposed mathematical model
provides a better insight into phenomena of different ions transport through porous fiber
matrices, and possibility of optimization of the complex process of biosorption.
Also, chemical modification of hemp fibers, prior to carbonization, affects the specific
surface area, amount of surface oxygen groups and morphology of carbonized hemp fibers.
Furthermore, activation of carbonized materials with potassium hydroxide improves sorption
properties of carbonized hemp fibers by increasing the specific surface area (up to 2192 m2/g)
and amount of surface oxygen groups.
Good sorption properties of short hemp fibers, obtained as the waste material from textile
industry, and therefore their very low price in comparison with commercial sorbents highly
recommends their use for purification of wastewater.
On the other hand, short hemp fibers represent an attractive low cost precursor for carbon
material production. Due to the good adsorption properties toward heavy metals and
pesticides, carbonized and activated hemp fibers were successfully used as a sorbent for the
purification of water polluted with pesticides and heavy metals. Also, activated hemp fiber
sorbent used for analyte preconcentration in the solid-phase extraction procedure for pesticide
analysis in water samples, showed even higher efficiency in pesticides preconcentration than
expensive commercial cartridges.
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855865.

ISBN: 978-1-63117-262-5
Chapter 17
TEXTILES USING ELECTRONIC APPLICATIONS

University of Ljubljana, Faculty of Natural Sciences and Engineering,
Ljubljana, Slovenia
ABSTRACT
Textiles, from fibers to fabric, with integrated special electronics are more and more
used as special materials in newly developed smart clothing. Simple systems are based on
electronic elements integrated in pockets and connected with soft wires, while in more
developed systems, conductive fibers are used to connect sensors, processors, LED
lighting, photovoltaic cells, communication elements and more. Hybrid systems, with
permanently integrated electronics, are developed with the elements that are washable
and can be used in extreme weather conditions. Different microcontrollers (ATMEL
ATmega, ATtiny etc.) used in the products of wearable electronics LilyPad Arduino,
are already available. These textiles can be used as protective clothing due to their
material properties for heat, fire, increased visibility and UV protection. For such a
protection, electronic sensors can be integrated in combination with integrated batteries
and photovoltaic cells that generate electricity, which is stored in batteries. Special fibers
can generate power when in motion or when exposed to light and this can be used for the
power or reversed, to light the integrated OLED lights. Such textiles can be used in all
kinds of activities in different terrain and weather conditions as sports and free time
activities as well as in different accidents, natural or transportation, to save lives. These
technologies are also used in medicinal applications, when the clothing with integrated
sensors can measure patients conditions and transmit the data to doctors.
In this chapter, textile applications with integrated electronic elements are presented
on several examples. The safety vest that was presented at the LOPE-C conference in
Frankfurt, with integrated photovoltaic cells and LED lights, can be used in conditions
for better visibility on roads and in the case of accidents. Another example is textiles with
integrated microcontrollers in the combination with different sensors, e.g., temperature or
light, as well as LED lights, which enable numerous combinations of their usage, for
protection or decoration, or simply for the color/lighting effect. The integration of a
Email: marica.staresinic@ntf.uni-lj.si.
448

custom made printed circuit board and designed program for a different action of LED is
represented.
The research shows that the knowledge from various fields, e.g., textiles, chemistry,
electronics and programming, can lead to the creation of textile applications with
electronic elements.
Keywords: Wearable electronics, LED light, microcontroller, printed circuit boards
INTRODUCTION
Smart textiles, from fibers to fabrics, with integrated special electronics are nowadays
used to develop smart clothing. In this paper, some examples for future designs and
development are presented, as well as the safety vest that was presented at the LOPE-C
conference in Frankfurt with integrated photovoltaic cells and LED lights.
Smart textiles are, by definition, textiles which respond to the changes in the environment
as a result of mechanical, thermal, chemical or electromagnetic influences [1]. Interactive
textiles [2] represent textiles that have built-in into their structure the elements to control
(sensors, switches, communication components, batteries). Most commonly, these elements
control the health care functions (pulse, temperature, blood sugar etc), enable communication
or represent the security and entertainment systems, as well as they allow the power supply
thereof.
The development of textiles with electronic components can be subdivided into:
Simple systems: electronic components are incorporated into pockets sewn-in or

attached over soft cables and should be removed before cleaning, e.g., LED lighting
devices;
Hybrid systems: the elements are a part of permanent fabrics, woven or embroidered,
using conductive yarns;
Complete integration: the elements are integrated, using the fibers with special
properties that act as electronic textiles (sensors etc).
The functions [3] of textiles using electronic applications are:

Passive functions: as a result of material properties, they can sense the environment
(sensors);
Active functions: as a result of installed sensors, they can act to the environment
actuators, and can work to supply energy (work actively to changes in temperature
hot/cold), for protection (inflatable elements for protection against impact, missiles),
protection from water floating clothing, increased active visibility, communication
a cry for help, protection from hazardous substances, chemicals, gas, alarm and
protection against radiation, measurement of vital signals (pulse, temperature etc),
integrated antennas for communication and embedded components for the
photovoltaic generation of electricity for the operation independent of batteries.
449
Embedded components that measure the heart function and enable monitoring of the user
throughout the day, the data being transferred to a medical institution, are already used for
medical purposes. After the surgery, patients wear clothing with integrated elements of
control, thus allowing the movement and they avoid the pain for the installation of
measurement probes for their medical condition control.
For communication [4], the developed elements can be washed and are a part of the
clothing, where they operate as touch screens (touch-pad), are flexible, lightweight, durable
and allow interactivity.
Smart textiles, which include safety clothing, are materials that allow the installation of a
variety of technologies, e.g., various electronic components, in clothing. Such fabrics permit
the perception of the environment and thus the adaptation to different conditions.
The main functions enabled in smart textiles are integrated sensors [5] that measure vital
functions (medical textiles), enable communication, processing and storage of data,
acquisition and transmission of energy (including PCM materials Phase Change Materials)
[6].
Electronic components can be fitted directly into textile fibers, e.g., conductive materials
and conductive textile fibers, diodes, transistors and photovoltaic fibers. Current electronic
components prepared on a silicon base are not flexible whereas the new elements developed
on the base of organic polymers are.
The fibers that are made from materials which convert light into electricity or electricity
is the result of the fiber movement [7] enable the production of electricity. The energy is
stored in batteries and when necessary, it powers the built-in OLED lighting. At MIT
(Massachusetts Institute of Technology), dyes have been developed for the print of solar cells
[8] on different materials, including textiles.
USE OF SMART TEXTILES

Smart textile [9] products have been used in various fields, as smart textiles SFIT Smart
Fabrics and Interactive Textiles, as wearable technology (wearable tech), and as interactive
textiles. The areas of application range from the clothing for personal protection, e.g., work
clothes for special environments, for the protection of the health of workers and for the
protection in extreme sports in a variety of environments (hot, cold, wet, dry etc). Smart
textiles are intended for everyday use, heated/cooled clothing, for entertainment (clubs,
concerts, public events) and special effects with fashionable elements such as built-in
lighting, changing colors, as well as for communication.
Many of these technologies are being used or planned for use for the elderly who need
active assistance or protection in everyday life (control and communication garments with
wearable physiological sensors) in order to reduce the costs of care and treatment. The
research is conducted in the areas of direct installation in the clothing, enabling easy
maintenance (washing) and increased generation of energy or lower consumption to operate.
Energy can be produced on the basis of photovoltaic cells that can be a part of the garment
as a fashion accessory or using piezo crystals, based on the movement of MEMS (MicroElectronic Mechanical Systems). It also works in the field of storage and use of heat energy
that is released in the movement walking user. For all these cases of energy generation, it is
450
necessary to develop more storage options to be able to use printed batteries that are smaller
and can be incorporated into products.
All of the above results in increased consumption and increased amount of post-consumer
textile waste. Development can take place in the direction of one time use large quantities
of waste, or multiple uses problems of maintenance, but less waste.
The ecology [10] of smart textiles is still at the beginning, which means that there is still
a lot of work to be done and the need for deciding whether to use better and more expensive
organic materials or recycled towards the development of smart textiles. Of course, these
problems are also the opportunity for smaller companies which could focus on the
development and manufacture of tailor-made eco-smart clothes. This could lead to the
development of products with high added value, with added knowledge and the use of novel
developed materials.
In todays world, when electronics become a part of clothing, with embedded
microcontrollers and variety of sensors (e.g., temperature or light) and LED lighting, endless
combinations for use in both protective and decorative purposes are allowed. Microcontrollers
that can be washed, which is their major advantage, allow various connections between the
LED elements that can be programmed for any application, which is extremely important for
the use in textiles.
On the market, there are different microcontrollers (e.g., ATMEL ATmega, ATtiny etc)
which can be used in the products of wearable electronics, e.g., LilyPad Arduino [11]. By
using these microcontrollers, different applications can be developed, with custom made
circuits with arbitrary shape and at reduced price.
In our research, the design of printed circuit boards and programs for different behaviors
of LED lighting (gradual or simultaneous switched LED lighting) was performed [12]. The
final product represents a warning-decorative LED light arrow that lights up differently.
The research showed that the knowledge in the field of textiles, chemistry, electronics
and programming contributes to the manufacture of high quality applications that in addition
to textile components also includes the elements of electronics.
EXAMPLES OF SMART TEXTILES

PLED Dress
Clothes are changing every day, not only on the basis of fashion trends, but also to follow
the research in the field of technology, new materials and innovations from other fields.
Predicting the future has never been easy, people have predicted flying cars, peace, a diseasefree world etc which has not (yet) happened, while nobody foresaw the use of mobile
phones, 3D printed food and invisible clothes.
At fashion events, we can see clothing equipped with the LED technology and
micromotors that change dimensions and act as a light show. Chalayan [13] presented hightech dresses that transform on the body and translated them into wearable, commercially
viable pieces. The models, when walking, activated the application at the collar and the fabric
unraveled to reveal an entirely different look. Figure 1 shows the clothes illuminated by LED
lights, which is interesting from the design point of view.
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Figure 1. Dress with integrated PLED (Polymeric Light Emitting Diode) (Source: Museum of Science
and Industry in Chicago, online: http://www.crunchwear.com/cute-circuit-galaxy-led-dress). Cute
Circuit Galaxy LED Dress.
Figure 2. Schematic drawing of photovoltaic fiber.
Figure 3. Photovoltaic fibers [17] and single fiber [18].
452
Figure 4. Printing dress and detail of keyboard.
For the production of such garments, fabrics with special properties are necessary, e.g.,
photovoltaic fibers [14], which act as photovoltaic cells for generating electrical energy.
Figure 2 shows a scheme of such fibers.
Fibers can under the influence of light, wind or rain generate electric potential energy and
act as a hybrid photovoltaic-piezoelectric device. Hybrid films are constructed by depositing
an organic photovoltaic cell on a commercial PVDF film, while hybrid fibers are developed
by depositing an organic solar cell on a piezoelectric [15] polymer fiber. When the hybrid
film/fiber is subjected to mechanical vibrations from the wind, rain or tide, the piezoelectric
part produces an electrical voltage that is converted to a constant DC voltage by a rectifier.
The photovoltaic part of the hybrid film produces constant DC voltage from the solar energy.
Electrical energy can then either be used online or stored in a battery. These materials are
now available as an energy harvesting device for the use in various e-textile [16] applications.
Materials can be fitted on textiles as added materials on the surface or integrated as a part
of the material itself, e.g., photovoltaic fiber [19].
An interesting example of this technology is the printed dress which acts as a screen
Printing Dress [20]. The dress integrates different technologies. It consists of three main
parts of the upper corset and a skirt. The corset has fitted four elements LilyPad Arduino 11,
a USB port for connecting to a laptop computer, keyboard, a built-in corset and wires to
connect. The skirt is made up of a material with incorporated aluminum wires and hangs over
the projector which projects images directly onto the skirt. Each time the user presses a key, it
communicates with the processor to display the animation typewritten text on the skirt. In
Figure 4, the dress [21] is presented.
The dress is presented as a prototype of the concept and application of printed electronics
in the clothing purposes. The experience will contribute to the creation and development of
smart clothing. Nowadays, the dress can be used as a tool to communicate or tweet.
453
Safety Vest
In the more and more changing climate on the planet, we have to be able to work and
travel in the most challenging situations. The weather pattern can change very fast from hot to
cold, from draught to floods, so there is a need for the clothing to protect us. The advances in
new textiles and printed electronics on flexible substrates can together offer some interesting
possibilities.
The OE-A association (Organic Electronic Association, Germany), organizer of LOPE-C,
presented an international competition for student projects in order to present the possibilities
of using printed electronics, they offered a set of elements that had to be assembled in
working demonstrator. Safety clothing the safety vest presented in Figure 5, with printed
solar cells on the back and LED lights was developed at our department. The generated
energy was stored in the built-in battery and when necessary, the LED lights that are on the
back can be used. The basic concept (cf. Figure 6) is to use polymer solar cells to generate the
power that is stored in the built-in batteries and used for better visibility on the roads or in
nature. The polymer solar cells (Konarka), batteries and LED (Light Emitting Diode) lights
are linked by the special built-in softwire, the switch, battery and operation button being in
the pocket. In the sunlight, solar cells convert light into electricity, the energy is stored in the
batteries and when it gets dark, the LED lights, which are integrated on the back, give light.
Previous applications based on reflection, in our case the LED, give light in the dark. LED
lights are semiconductor diodes that emit light under the influence of electricity. Photovoltaic
cells are the elements that unlike LED lights emit electricity when under light.
Unlike past examples of safety clothing that acted on the principle of reflective elements
[22] embedded in clothing, our safety vest in Figure 5 has built-in LED lights that are
powered by photovoltaic cells. Figure 7 presents the details of the links which are located in
the inner side. The basic elements consist of polymer photovoltaic solar cells, LED lighting
and batteries. The safety vest represents the beginning of the research in the field of clothing
and the added value represented by the elements of printed electronics. Photovoltaic polymer
cells printed on a flexible substrate are suitable for the use on textile substrates.
Figure 5. Safety vest on model of conference LOPE-C 2011.
454
Figure 6. Basic concept and developed model.
Figure 7. Integration of polymer photovoltaic solar cells, LED lighting and batteries.
Figure 8. Power plastic photovoltaic cells.
455
Decorative Arrow with Custom Made Printed Circuit Board

In addition to the development of high-tech fabrics for the manufacture of sports clothing
[23], it is always possible to achieve better sports results with the incorporation of different
elements into fibers and fabrics, which is becoming more and more popular. Some of these
elements are microcapsules. Back in the early 1980s, NASA developed the technology for
embedding microencapsulated phase change materials into textiles for their temperature
control [24], [25]. In the printing and graphic arts industry, the microcapsules are used for
pharmaceutical and medical purposes, in cosmetic and food industries, for agricultural
products, as well as in the chemical, textile and construction industries, biotechnology,
photography, electronics and waste management [26, 27, 28].
In addition to the microcapsules integrated into fibers, there can be different electronic
elements, interlacing for the protective or decorative purposes. Electronic components can be
fitted directly into textile fibers (hybrid systems) or integrated in pockets connected via
flexible cables, e.g., batteries connected to LED lights (simple systems) [29]. Different
integrated sensors can be used for a variety of medical purposes, e.g., for the control of
respiration or the measurement of respiratory signals [30]. One study presented the usage of
sensors and a printed circuit board embedded in textiles, which enables the detection of the
changes in the basic life functions for infants, e.g., breathing and heart rate [31], while
another study improved the integration of sensors and electronics into textiles enabling the
control of the ECG combined with wireless communication [32]. Ultrasonic sensors in
combination with a printed circuit board in textiles can be used to detect the obstacles in
helping people with impaired vision [33]. The sensors are small, use little power, can be
installed internally and can be washed.
Embedded microcontrollers, in combination with a variety of sensors (e.g., temperature
or light sensors) and LED lighting, can be programmed and used for any purpose. Their
advantage lies in the fact that they can be washed, which is for the use in textile applications
extremely important. On the market, there are different microcontrollers available (e.g.,
ATMEL ATmega, ATtiny etc), which are used in the products of wearable electronics such as
LilyPad Arduino 11. LilyPad Arduino was designed and developed by Leah Buechley in
collaboration with the company SparkFun Electronics. Wearable electronics LilyPad consist
of different components (LED light, processor board, light sensor etc). LilyPad electronics are
well suited for prototypes and unique design products, while their size (processor board is
approx. 50 mm in diameter and approx. 3 mm in thickness) and price make them unsuitable
for the mass production or very small items.
Some researchers design their own printed circuit boards, while others use LilyPad
Arduino microcontrollers, e.g., for an immediate determination of the pH value of the sweat
that is excreted in sporting activities. In that case, Arduino controls the operation of LED
lights that change color according to the measured pH value of the sweat [34, 35].
The advantage of self-made decorative-protective applications is that they are made as a
separate element which can be integrated into various garments or fashion accessories, that
they are affordable, and their size and purpose is adjusted to the application.
Another example of our work presents a design of wearable electronics that consists of
LED lights, a processor, circuit board and custom written program for different behaviors of
these LED lights (gradually or simultaneously switched LED lights). The final product
represents a warning-decorative arrow shaped with LED lights that light up differently.
456
Figure 9. Printing template of circuit board.
Figure 10. Printed circuit board.
Figure 11. Insertion of electronic components a) side view, b) back view.
457
Figure 12. Soldering.
For that case, a printed circuit board was designed using the program EAGLE (Easily
Applicable Graphical Summary Layout Editor) from CadSoft, in which we made a printed
circuit diagram which represents the logical symbols and signs of electronic components and
their connections. In Figure 9, the printing template of the circuit board is represented.
The manufacturing of a printed circuit board (cf. Figure 10) was followed by the drilling
of holes for the insertion of electronic components (cf. Figure 11) and solder (cf. Figure 12)
electronic components into the pre-prepared printed circuit board.
The software that is run by a microcontroller was designed in the C programming
language in the program Arduino 11 1.0 and is shown in Table 1.
Figure 13 presents the operation of LED lights for the final application warning-decorative
arrow. The presented program code allows a gradual or simultaneous ignition of LED lights.
In Figure 14, the final product is presented. The advantages of our applications are that they
still present the most inexpensive option of the relevant microcontroller in our case
ATtiny13 and a precise adjustment for the desired final product with a manufactured printed
circuit board is allowed. The presented application (cf. Figure 14) can be used for various
purposes, e.g.:
for clothing (sportswear, roller skaters and cyclists on the road, for sports activities in
low-light conditions, as well as for clothing for entertainment in nightclubs),
for fashion accessories (brooch, add-on bag),
for warning safety margin for pets on walk and
for marking and identification of luggage when traveling.
Possible uses depend only on the imagination of the users. The advantage of the
application is in the fact that it can be washed, which is especially for sportswear of extreme
importance and it is only necessary to remove the battery before washing. Due to the battery,
such products are not suitable for use under water, whereas if the application is well protected
with waterproof elements, it can be used in the case of water sports, or in other extreme wet
conditions.
458

Table 1. C program code for microcontroller
#include <avr/pgmspace.h>
uint32_t GUT = 0;
uint32_t STEP_DELAY=0;
uint8_t U=0;
void setup() {
DDRB = 0b00011111;
// all ports on the controller are output
PORTB=0x00;
// when initialized all ports turned off
}
void loop() {
GUT=millis();
// assignment of system time
if(GUT-STEP_DELAY>300){ // delay for 300 ms before next step
if (U < 5){
// during first five steps turn on the port with corresponding number
PORTB |= _BV(U);
U++;
// increase step
}
else if(U == 5){
// in step 5
PORTB = 0x00;
// turn off all ports
U++;
// increase step
}
else if(U == 6){
// in step 6
PORTB=0xff;
// turn on all ports
U++;
// increase step
}
else if(U == 7){
PORTB = 0x00;
U++;
// increase step
}
else if(U == 8){
PORTB=0xff;
// turn on all ports
U++;
// increase step
}
else if(U == 9){
PORTB = 0x00;
U++;
// increase step
}
else if(U == 10){
PORTB = 0b00010001; // turn on first and fifth port
U++;
// increase step
}
else if(U == 11){
459
PORTB = 0b00011011; // turn on first, second, fourth and fifth port

U++;
// increase step
}
else if(U == 12){
PORTB = 0xff; // turn on all ports
U++;
// increase step
}
else{
PORTB = 0x00;
// in the last step turn off all ports
U=0;
// reset step to the firs one
}
STEP_DELAY=GUT;
// set the time of step delay
}
}
Figure 13. Operation of warning-decorative arrow; a)f) turning on additional two LED lights at the
same time in five steps; A) and C) all LED lights are turned off; B), D) and F) all LED lights are turned
on; E) gradually turning on four LED lights (two from front and two from back).
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Figure 14. Warning-decorative arrow.
In our case, we used only LED lights as the integral part of the application, while for
other applications, a variety of sensors can be used. Examples are the sensors for sensing
different lighting conditions in the environment or temperature sensors, force sensors, flex
sensors etc.
CONCLUSION
Clothes are changing every day, not only due to fashion trends, but also to follow the
research in the field of technology, new materials and innovations. Predicting the future has
never been easy, people have predicted flying cars, peace in the world without diseases etc
which has not (yet) happened, while nobody foresaw the use of mobile phones, 3D printed
food and invisible clothes.
At fashion events, clothing equipped with the LED technology and micromotors that
transform dimensions and act as a light show are nowadays presented. Some of the materials
shrink under the influence of temperature; consequently, when our surroundings get warmer,
we no longer need to turn up the sleeves, since they roll up themselves.
Development takes place in the direction of specific materials that can be cut with
ordinary tools, and can protect against electromagnetic and infrared radiation.
For medical purposes, the materials containing nanocapsules with colors that burst in the
presence of infection with bacteria have been developed and with the use of UV light, doctors
can quickly check for the presence of infection, as clothes change color. Furthermore, textile
products are being developed that can detect the presence of infection on the skin which has
been burned faster than enabled by the standard tests, which is especially important in the
therapy for children.
For safety purposes, the presented safety vest can be used in difficult conditions as it has
integrated power-lighting system (photovoltaic cells-batteries-lights), hence making the user
independent. The designed printed circuit board in combination with LED lights can be
shaped into decorative-protective applications of different sizes with an optional LED lights
effect, e.g., special lighting effects.
461
For the production of these quality applications, in addition to textile components with
integrated electronics items, we must combine the knowledge of textiles, chemicals,
electronics, programming and ultimately, of ecology. The research in this area is opening up
new possibilities for the development of new products in combination with the technologies
in various fields.
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ISBN: 978-1-63117-262-5
Chapter 18
TEXTILES FOR CARDIAC CARE

Narayanan Gokarneshan, Palaniappan P. Gopalakrishnan,
Venkatachalam Rajendran and Dharmarajan Anita Rachel
NIFT TEA College of knitwear fashion, Tirupur, India
ABSTRACT
This chapter highlights the developments in textile materials used for cardiac care.
Blood flow has been analyzed through a polyester vascular prosthesis. Woven bifurcated
vascular prosthesis has been developed that has good biocompatibility. The mechanical
behavior of knitted vascular graft has been analyzed. Weaving technique has been
developed for making small diameter blood vessels that are found very useful in
cardiovascular surgeries. A fabric prosthesis has been manufactured that is expected to
respect haemo-dynamics, with a central opening, and that is associated with good fatigue
resistance for long-term durability. Research has been focused to study the long term
fatigue behavior of woven polyester fabrics of different yarns and construction factors to
find whether they are suitable for heart valve replacement. Recent developments have
focused on developing a stent that minimizes the occurrence of retenosis (blocking of
artery). Weft knits have found suitability as stents for arterial implants, and have proved
to be more advantageous than their metallic counterparts.
Keywords: Artery, Hemodynamic, Grafts, Prosthesis, Stent
1. INTRODUCTION
The textile materials have found varied technical applications and medical textiles is one
such emerging area. This chapter specifically focuses on the technological advances with
regard to development of textiles for cardiology purpose. A good deal of research has been
reported over the past decade and this has revolutionized the surgical procedures in cardiac
care. Experimental studies on blood flow have enabled to design better artificial textile
E-mail: advaitcbe@rediffmail.com.
466
N. Gokarneshan, P. P. Gopalakrishnan, V. Rajendran et al.
prosthesis. Bifurcated prosthesis has been woven adopting 3D weaving technique, and the
prosthesis so woven is found to be versatile in its function. The underlying technology has
been highlighted. Textile implants have saved millions of people, but they are not yet perfect
because of the complexity of arterial biology and textile mechanics. Biocompatibility has
been achieved but the problems of compliance and resistance to the blood flow remain.
Textile vascular prosthesis made of polyester have been used in crimped form and these
exhibit better mechanical properties and resist deformation, and thereby show promise.
Technology has been developed for weaving small diameter blood vessels that would render
vascular surgery successful. Grafts of desired size can be engineered and their properties
predicted. A textile heart valve manufacturing process has been developed, consisting of
forming a fabric tube in a concentric way. The process minimizes fabric deformation,
especially in the zones that will experience the greatest stress when the valve is functioning.
This work already shows that the textile material can be used to manufacture a tricuspid heart
valve with performance that is close to that expected for such kinds of replacement
prostheses. Recent research trends indicate that one can use to develop criteria for designing a
fabric most highly suited for use in heart valve application.
2. ANALYSIS OF BLOOD FLOW IN POLYESTER PROSTHESIS

2.1. Review of the Earlier Prostheses Types
During the earlier days progress in vascular surgery has been closely linked to the use of
synthetic woven and knitted prostheses. Textile vascular prostheses made of
Polyethyleneterapthalate (PET), which was porous, had been used as substitutes. This
permitted good clinical performance with regard to satisfactory tissue ingrowths and biostability. The first generation of textile prostheses consisted of hand sewn woven structures.
Such devices exhibited practical difficulties after implantation due to lack of compression
resistance and tendency to kink. Thus crimping (imparting waviness) was suggested to give
the grafts radial resistance and longitudinal compliance. The crimping had been obtained by
fixation of an accordion pleat deformation, permitting easier implantation of prosthesis and
allowing the surgeon to control the longitudinal tension. Crimping also improved the
resistance of the prosthesis to kinking when crossing the knee and, also to external
compression. The graft was tunnelised subcutaneously.
2.2. The Analysis Method

Blood flow has been analyzed in impregnated polyester prostheses commonly used in
vascular surgery [1]. Gelatin and collagen are generally used to make the prosthesis
impermeable. Experimental investigations have been carried out to assess the impact of their
crimping on the flow. Flow velocity profiles measured with a laser doppler anemometer
reveal that crimping yields to decrease in flow velocity, particularly near the surface of the
prosthesis.
467
This has been followed by a numerical simulation of the blood flow in vascular prosthesis
using specific computer code, which adopts finite element method. The flow has been
investigated in both stationary and pulsatile cases, considering the most crucial physical
parameters of the blood namely, relative density and viscosity. In literature, haemodynamics
has been widely associated with pathological effects related to the vascular wall [2, 3].
2.3. Discussions and Findings of the Study

Experimental measurements and numerical simulations of the blood flow in textile
prostheses characterized by the wavy form of their wall under steady and pulsatile regimes
have revealed the presence of two distinct zones: an undisturbed central zone that preserves
the properties of the Poiseuille flow, and a disturbed zone near the wall characterized by
recirculation of the fluid inside crimping associated with very low velocities and shear stress.
These perturbations linked to the crimping lead to a braking of the flow detected in the
experimental and numerical studies.
From all haemodynamic factors, wall shear rate is the most frequently cited parameter
affecting the pathobiology of arterial walls [4, 5]. The low shear stress observed in wall
crimping can explain the deposit of particles and excessive cell development, which might
affect prostheses. Thrombosis, the formation of clots in sanguine vessels from blood
constituents, is induced by the wall alteration linked to the slowing of the sanguine current.
The zones near crimping could facilitate the adherence of platelets to the wall, releasing the
coagulation in the prosthesis. In this area, multiplication of endothelial cells can be explained
by the low shear stresses in crimping zones. This mechanical factor can also be responsible
for the haemolysis phenomenon characterized by red cell destruction under high shear rates.
Several researchers, e.g., Siegel el al. [6], Blustein et al. [7], Siouffi [8], Stergiopulosel al
[9] have used laser doppler anemometry, ultrasonic anemometry, or magnetic resonance
imaging to measure arterial flow velocity. They attempted to study the impact of particular
shapes of artery walls, like stenosis or aneurysm, on flow properties. They agree about the
implication of those shapes for decreased downstream shear stress and associate the deposit
of particles causing thrombosis to low shear stress.
The in-vitro study led by Moore and Ku [10] on unsteady flow in a blown glass
abdominal aorta model observed by magnetic resonance imaging shows that at the end of the
cardiac pulsation, although the debit remains positive, low negative velocities are recorded in
zones close to the wall. They have established a correlation between low shear stress
measured in the anterior wall of the aorta and the progression of atherosclerosis and
hyperplasia.
The numerical analysis of steady and pulsatile blood flows in a vascular prosthesis have
been studied. The design of textile artificial vessels requires knowledge of prosthesis flow
properties, especially near the wall. These data are of great interest to manufacturers of
prostheses who model the architecture of the implant as a function of local mechanical causes
of physiological and physic-pathological processes.
Quantitative and qualitative studies of flow fields could provide solutions for some
pathology linked to haemodynamic factors in prostheses. The low wall shear stress observed
in the crimping area can explain some problems that could affect prosthesis, such as particle
deposit and cell wall development.
468
Further work will add additional realism to blood flow-simulation. The next factor to be
considered is wall motion under arterial pressure. A specific computer code presents a module
solving Napier-Stokes equations for deformable mesh, which can be used for simulations in
moving wall flow fields.
3. WOVEN BIFURCATED PROSTHESIS

Three-dimensional fabrics have recently entered the medical field. Their specific area of
application is in the weaving of vascular prosthesis. Vascular prostheses are surgically
implantable materials. They are used to replace the defective blood vessels in patients so as to
improve blood circulation. Conventional types of prosthesis were made from air corps
parachute cloth, vignon sailcloth and other types of clothing materials. Materials such as
nylon, teflon, orlon, stainless steel, glass and dacron polyester fiber have been found to be
highly suitable for the manufacture of prosthesis. These materials were found to be
significantly stable with regard to resistance towards degradation, and were not adversely
affected by other factors [11]. Dacron polyester, which has bio-compatibility and high tensile
strength, is being used over a period of time as suture thread or artificial ligaments [1214].
3.1. Comparison of Woven and Knitted Grafts

Vascular grafts are manufactured on a very small scale as woven and knitted grafts, and
also as Velour and Gore Tex. Knitted grafts may be of warp or weft knitted types [15]. Velour
is a fabric made from textured yarns, wherein the filaments are exposed on either or both
sides of the velour grafts. The woven grafts have been used earlier. Gore Tex grafts are made
of polytetrafluoroethylene and molded as one single piece. Woven grafts have a good bursting
strength and resistance to fatigue. They can be woven compact enough to make them least
permeable to water and blood. They are manufactured as seamless tubes on special tape
looms with shuttles.
Knitted grafts are comparatively more porous than woven grafts. In the case of grafts
with weft-knitted structures, the mobility of yarn is higher in the course direction than in the
wale direction. This is a drawback since it leads to increase in diameter with time. Such a
problem ultimately leads to rupture of the graft. Hence, weft-knitted structures are not
preferred in the manufacture of grafts. Conversely, warp-knitted fabrics are highly versatile
since they can imitate woven- or weft-knitted fabrics with regard to mechanical performance.
Also, they are dimensionally stable comparatively and show higher compliance in the course
direction than in the wale direction.
Woven grafts are manufactured on tape looms with shuttle, specially designed for
vascular prosthesis. The grafts are made as tubes without seams. Single jersey grafts are
manufactured on flat knitting machines with very fine gauge and specifically designed for
producing grafts. Tubular warp-knitted structures are produced on warp knitting machines
equipped with two needle bars.
469
3.2. Manufacturing Technology

A prototype of a manually operated loom has been developed, which is suitable for
weaving of straight as well as bifurcated vascular prosthesis [15]. It is based upon the
principle of 3D weaving. A separate warp yarn selection device is incorporated. The main
trunk of the bifurcated prosthesis has been woven as a tubular structure using weft from the
same pirn. The filling yarn is inserted in the top layer of the warp shed and then the bottom
layer of the warp shed. The bifurcated branches are more difficult to make as they are
individually woven.
The warp sheet is split into two layers so as to weave a tubular structure. Both the layers
of warp sheet are manually wound around a warp beam. After string up, the warp yarns are
passed through the dents of the reed and then wound onto the cloth roll. The two branches of
the bifurcated prosthesis are woven by using two weft pirns in succession. For weaving one
branch of the prosthesis, the weft from a pirn is passed from the selvedge to the centre of the
top layer of warp shed and then inserted from the centre of the bottom layer of warp shed to
the same selvedge. The second branch is woven by repeating the operation with the second
weft pirn.
It is to be noted that the weft yarns do not cross the entire width of the warp shed. This
requires special selection of heald frames. Hence, the warp sheets have been divided
longitudinally into two equal sections. Each half of the warp sheet corresponding to one
branch of the prosthesis has been selected with a special heald frame group. Eight heald
frames have been used for weaving. Each of the heald frame can be placed in three different
positions, namely, higher, middle and lower positions.
Figure 1. Flow chart indicating weaving of prosthesis main trunk.
470
The middle position is used for weaving the branches. The two branches of the prosthesis
have been woven simultaneously. The first filling yarn is inserted successively in the top
layer and then the bottom layer warp sheds of the right branch and the second filling yarn is
inserted in the top layer and bottom layer warp sheds of the left branch.
Figure 2. Flow chart indicating weaving cycle of prosthesis branches.
471
During the first selection, the odd numbered warp threads are lifted, and during the
second selection, the even numbered warp threads are lifted.
The woven bifurcated prosthesis thus has the following technical particulars:
Type of material Texturised dacron polyester yarns (circular cross-section).

Linear density warp and weft 16 tex (34 fibres per yarn cross-section).
Number of yarns per warp sheet 160 (for right branch).160 (for left branch).
Reed particulars 20 dents/cm.
4 ends/dent 2 yarns for top warp sheet.
2 yarns for bottom warp sheet.
Dacron polyester yarn has been found suitable as it has sufficient resistance to be woven
without ruptures. Mechanical treatments comprising of compaction and crimping and also
thermal finishing treatments impart the desired tubular shape to the prosthesis. The weaving
of the branches of the bifurcated prosthesis requires special heald frames so as to enable
selection of the two sections of the warp sheets individually. The heald frames have been set
in the intermediate position and the filling yarn has been inserted manually to the middle of
the warp sheet so as to perform this special weaving. Such an arrangement is not found on
existing looms weaving narrow width fabrics. The 3D weaving machine could also be utilized
for the manufacture of thick ribbons consisting of two bonded fabrics and being used as
artificial knee ligaments. The same material as used for the vascular prosthesis, namely,
biocompatible polyester can be used. In this case, the heald frame selection requires some
modification and also the yarn linear density and the density of reed have to be changed.
5. ANALYSIS OF MECHANICAL BEHAVIOR OF PROSTHESIS

Graft implantation is a common surgical procedure in the management of patients having
severe blood circulation difficulties. Textile technology has provided several solutions for
vascular surgery and a large number of textile vascular prostheses have been implanted in
patients to revascularize downstream from diseased or injured arteries. Since 1954, the date of
the first transplant on man, textile implants have saved millions of people, but they are not yet
perfect because of the complexity of arterial biology and textile mechanics. Biocompatibility
has been achieved but the problems of compliance and resistance to the blood flow remain. In
previous studies [16, 17], correlations between flow nature and pathologies in prostheses such
as progression of atherosclerosis, thrombosis and hyperplasia, have been established. The first
generation of cardiovascular textile prostheses made of hand-sewn woven structures
demonstrated some difficulties after implantation because of lack of compressionnal
resistance and a tendency to kink. Today, crimped textile implants made of polyester share
the market with those molded in one single piece of PTFE. In comparison with the flat shape
of molded grafts, the crimping of textile vascular prostheses showed several mechanical
advantages. In fact, crimping was achieved by fixation of an accordian pleat deformation
permitting the surgeon to control the longitudinal tension and improving the resistance to
kinking. Furthermore, knitted and woven structures showed better aptitude for sutures than
molded ones. For these reasons, textile implants are exclusively used in particular sites
472
needing long grafts with satisfactory bending properties such as femoral bypass at the knee
level. The mechanical behavior of vascular prostheses under steady and pulsatile flow has
been investigated. First, a theoretical model of the deformation based on elasticity hypotheses
has been established and a test system simulating blood flow conditions has been built. This
test system was linked to an image-processing device permitting the measurement of
prosthesis wall displacements. In the literature, the mechanical properties of biological
arteries have been widely investigated. Most studies [18-20] consider that arterial tissue is a
perfectly elastic material whereas studies concerning the mechanical behavior of textile
vascular prostheses appear to be extremely rare.
Under steady and pulsatile flow the prosthesis was bent and its axis remained in the same
vertical x-y plane of prosthesis deformation under flow pressure. The image processing
provided the coordinates of all points belonging to the graft boundaries and permitted the
determination of vertical displacement of the mid-point of the prosthesis lower boundary.
Vertical displacements in steady flow conditions, and the evolution of theoretical and
experimental values at different pressure levels, corresponding to a flow variation between 0
and 60 mL s-1, have been tested. The experimental results showed that vertical deformation
remained constant between p = 10 and p = 30 mm mercury and increased with pressure
elsewhere. The theoretical model predicted linear behavior for the vertical displacement.
The Dialine II prosthesis tested showed complex displacements of the boundaries under
pulsatile conditions. This deformation was essentially characterized by prosthesis bending
associated with a low horizontal deformation evolution of textile graft bending during a
cardiac pulse. The vertical displacement of the mid-point in the lower boundary of the
prosthesis under pressure and vertical displacements in pulsatile flow conditions have been
studied. These show a periodic deformation of the textile graft having the same frequency as
the pressure wave. The highest vertical displacements were obtained during the pressureincreasing period (systole). This deformation shows a sudden and rapid drop at the beginning
of the pressure-decreasing period (diastole).
The pressure variation obtained with the pulsatile flow system and measured with the
image processing device shows that the system correctly simulates the physiological flow.
The pressure curves obtained have the same shape as physiological pressure curves measured
for the human body and described by Westerhof et al. [19] and Womersly [20]. This flow
system made it possible to see that the textile vascular prosthesis bends under flow pressure.
This bending, which has never been observed with natural or molded grafts, is certainly due
to the crimping of the textile prosthesis.
The theoretical and experimental results show some divergences probably due to the
elasticity hypotheses considered as the developed theoretical model was based on describing
textile prosthesis bending under flow pressure on them. This elastic behavior was broadly
suggested by natural blood-vessel deformation, cited in the literature [17, 20, 21]. Several
studies concerning arterial mechanics showed that pressure inside natural grafts only induces
augmentation of the diameter of the elastic natural artery. The complex behavior of the textile
prosthesis seems to be linked to the viscoelastic character of the knitted fabric. An
investigation of the instantaneous elasticity and relaxation module recommended by Hofer et
al. [22] would lead to better results.
The experimental results show the influence of the pulsed character of unsteady flow on
the graft deformation. Indeed, in the case of steady flow, the vertical displacement evolves
almost proportionally to the flow and pressure inside the prosthesis. In the case of pulsatile
473
flow, the prosthesis bends in a periodic manner but not according to pressure evolution.
During the cardiac pulse, the graft bends almost permanently. It returns to its linear position
when pressure drops and bends again during that quarter of the cycle. Pulsatile flow evidently
generates a complex mechanical behavior of the knitted graft in which linearity between
pressure and deformation is not observed. This confirms the inadequacy of the elasticity
hypotheses selected in the case of steady flow. The prosthesis behavior seems to be viscoelastic at higher stresses and elastic at low stresses because of the crimped shape of the graft
walls.
6. WEAVING TECHNIQUE OF SMALL BLOOD VESSELS

For success in vascular surgery involving small-diameter (< 6 mm) vessels, a graft must
closely match the internal diameter of the host artery and have desired high elasticity,
porosity and transverse compliance. Thus although arterial grafts have gained acceptance in
larger-caliber (> 6 mm) applications, where the requirements are flexible, a vein from the
body continues to be preferred for small-vessel repair. An attempt has been made to develop
an understanding of the material and the construction factors that affect the values of a woven
tube's diameter, pore size, elastic recovery and transverse compliance [23-25]. This
information is largely absent in literature. By varying yarn size and fabric structure, seamless
tubes (1.57 mm diameter) were constructed. These were heat set for circular shapes and
characterized for size, geometry and radial elasticity. Propertystructure correlation models
have been presented. Grafts of desired size can be engineered and their properties predicted.
A number of factors are to be considered in the design of the blood vessels. These are
a)
b)
c)
d)
e)
Determination of the graft dimensions

Determination of the optimum heat setting conditions for the grafts
Determination of the pore size of the grafts
Determination of the compliance in grafts
Determination of the elastic recovery properties of grafts
The factors that affect the graft internal diameter are

a)
b)
c)
d)
e)
Denting order
Number of warps
Yarn size
Denting order x number of warps
Yarn size x denting order
The factors that affect the pore size of the graft are
a) Denting order
b) Pick density
c) Yarn size
474

d) Number of warp yarns
e) Yarn size x denting order
7. TEXTILE HEART VALVE PROSTHESIS

7.1. Manufacture and Performance Evaluation
Following the first attempt by Hufnagel [26] in 1952 to replace a faulty human valve with
a mechanical prosthesis, a large variety of artificial valves have been developed. There are
currently two types of prosthesis that fit the surgeons needs. Mechanical prostheses with
tilting disks (mono- or bileaflet) have shown good durability [27] but require long-term
anticoagulant medication for the patient because of the high risk of thrombo-embolism.
Biological valves (porcine valves or valves obtained from bovine pericardial tissue) respect
the haemodynamics of humans with a central opening, carrying less thrombo-embolic risk,
and in general do not require anticoagulation. Their durability (~10 years) is nevertheless
limited [28] due to tissue degeneration and accelerated calcification, especially in young
patients. The development of non-invasive surgical techniques [29, 30] (which are less
traumatic for the patient) requires flexible material that is less fragile than biological tissue to
prevent valve leaflets from rupturing when folded in a catheter. In this case, fabric seems to
be particularly adaptable because of both its resistance and flexibility. A fabric prosthesis has
been manufactured that is expected to respect haemodynamics, with a central opening, and
that is associated with good fatigue resistance for long-term durability. At the same time,
textile materials have very low bending stiffness due to the discontinuity of the fabric and
yarn structure (essential for good fatigue resistance and thereby durability of the valve leaflets
during the cyclic opening and closing phases), and good orthotropical traction stiffness
(essential for bearing the diastolic membrane stress under the closing pressure). At the same
time, the non-smooth surface of the material, when manufactured with controlled porosity,
should allow limited tissue in growth, making the prosthesis completely biocompatible. The
fabric material used is PET, which has been used extensively for vascular grafts and has been
demonstrated to be well tolerated in the bloodstream. The prosthesis is manufactured using a
forming process that will limit yarn deformation and optimize flow tightness through adapted
forming geometry.
7.1a. Testing and Analysis

To test the prototype in vitro, a sewing ring (also realized with fabric) is adapted to the
formed valve. In the closed position, the three cusps come together to ensure proper floodtightness. In the open position, flexibility of the cusps allows flow to push them aside with
low flow resistance. Free-edge curvature inverts easily during this process.
Static Regurgitation
As fabric has a more porous structure compared with biological material, leakage across
the textile prototype in the closed position is higher than in the bio-prosthesis. Compared with
a mechanical valve, the difference is not as relevant because the required functioning
tolerance on the mechanical valve also partly induces leakage of the device. Changing the
475
parameters of the fabric used (saturation index and yarn structure) could reduce porosity and
consequently leakage. However, from a biological point of view, tissue in growth on the
fabric scaffold can be expected once the valve is implanted in its biological environment.
Porosity of the material should therefore naturally decrease.
Dynamic Regurgitation
Dynamic regurgitation is higher for the fabric valve than for the reference valves used.
However, the closing volume (14%), corresponding indirectly to the time the valve needs to
close, is not far from that obtained with a biological valve (8%). It represents the largest part
of the whole dynamic regurgitation and it should be easy to reduce this value by using a
fabric with lower bending rigidity. The lower the material bending rigidity, the easier will be
the valve cusps movement from the closed to the open position. Valve closing time will
thereby be reduced. A plain weave fabric made up of microfilaments yarns and with a
reduced saturation index would be the best adapted material concerning this aspect. It should
be possible to reach at least the performances of the mechanical valve that do meet the
physiological requirements.
Pressure drop across the valve, when comparing the fabric prototype with a mechanical
valve, did not show significant difference, although the fabric valve is characterized with a
central opening geometry offering no flow resistance. This is due to the roughness of the
cusps fabric surface which induces a pressure drop at the flowmaterial interface. In contrast,
the smoothness of the biological tissue causes a reduced pressure drop with the biological
prosthesis. However, the tissue in growth that will occur on the fabric scaffold, once
implanted, should transform the initially rough surface into a smooth surface. Pressure drop
values will therefore decrease.
7.2. Fabric Construction and Durability

The rapid development and success of percutaneous vascular surgery over the last two
decades [31], with the now common stent graft implantation, make this non-invasive
technique attractive today even for heart valve replacement [32]. Research has been focused
to study the long term fatigue behavior of woven polyester fabrics of different yarn and
construction factors to find whether they are suitable for heart valve replacement.
A heart valve undergoes a combination of flexural and tensile stress during operation. A
fabric having lower flexural resistance can be expected to have a longer working life. Textiles
are unique materials in that they have low weight, high tensile strength, and high flexibility.
The latter is what makes them comfortable as apparel products. These properties in textiles
are primarily due to bonding between the chains in fibers and no direct bonding between
fibers in the yarn and between yarns in the fabric.
Fibers in yarns and yarns in a fabric can slip when flexed. Among the fibers available,
one that has been used most extensively in implants (arterial and stent grafts, for example) is
polyester. It is biocompatible and resistant to degradation when in contact with body fluids
[33, 34]. Polyester fabric has already been shown to be able to behave dynamically like a
valve in vitro [3537]. Tests were however only performed over a short period of time. When
an assembly is bent, the resistance to bending will be governed by the combined bending
rigidity of the individual elements and the frictional forces between the elements that resist
476
slippage between them [3839]. The role of friction or cohesion between the elements of an
assembly is not well detailed in the literature [41, 42]. For textile heart valve development, in
which extensive cyclic flexing must occur, inter-filament cohesion becomes a central issue.
At each valve cycle, the valve leaflets material undergoes flexure and tension stress. The
leaflet tension force, borne by the filaments, will generate radial yarn-to-yarn and filament-tofilament forces due to the cohesion of the fabric structure. At the contact zones, these radial
forces will generate friction forces. During the flexure of the leaflet, these friction forces will
consequently need to be overcome before the required flexing will occur. The energy
associated with that movement will be dissipated at the contact zone where the phenomenon
occurs. Cyclic flexing, therefore, leads to an increase in the energy that is dissipated, which
may cause damage to the surfaces in contact after a period of time. Even if the overall
(global) stiffness of fabrics is low, repeated cycling of textile heart valve prosthesis at heart
pulse rate may still lead to filament damage or rupture. A detailed assessment of these effects
will help to predict a materials durability when used as a heart valve. In order to find which
fabric construction factors will provide the suitable structure for the application, the effects of
yarn and fabric construction on the long term cyclic bending of fabrics, have been
investigated. Fabric strips of 5 mm width and of different yarn and fabric structures have been
subjected to combined flexure and tensile fatigue generated by cyclically pulsating water
flow. The test samples were taken out periodically from the dynamic tester and characterized
for change in their bending stiffness. As flexing of the specimen involved only small strains
which were well below a fibers elastic yield strain, the inherent elastic stiffness of specimen
was assumed to remain constant. Any change in bending stiffness was then assumed to be a
result of a change.
8. WEFT KNITS AS CARDIAC STENTS

Weft knits are used as stents in arterial implant. Stents have been used in treating
coronary arterial diseases. The stents could be implanted through a catheter to compress the
plaque and open the artery lumen for efficient flow of blood after the implant. The stent needs
to be flexible so as to enable it to be carried to the place in the artery where the injury is
located [42]. The stent should keep the artery open by allowing flow of blood and it should
also be elastic so that it may accompany contraction and expansion of the arteries as the heart
beats. The radial expansion force is the resistance of the stent to collapsing during expansion
[43]. This is a determining factor of the capacity of the stent to keep the adequate artery
geometry for the blood to flow. The structural design and the type of material determine the
radial elasticity and the flexibility of the stent.
Another important property of the stent is its fluoroscopic visibility, which enables its
exact detection on the harmed area of the artery. This is related to the material used to make
the stent and to its dimensions. Stainless steel has a low fluoroscopic visibility, while
tantalum has a good fluoroscopic visibility owing to its radio-opacity. If the stent is too small,
its fluoroscopic visibility is also poor. Yet another aspect to be considered is that the stent
should be able to be sterilized so as to avoid being contaminated by bacteria. A textile stent
should necessarily have lengthwise flexibility, high radial expansion force, high elastic
477
recovery after radial expansion, resistance to corrosion, good fluoroscopic visibility, and high
biocompatibility.
Invariably, biocompatibility becomes a necessary criterion for a stent for its effective use
[44, 45]. The performance of a stent will depend on its interaction with the human cells and
fluids. Recent developments have focused on developing a stent that minimizes the
occurrence of restenosis (blocking of artery). The problem is common with metallic stents
and could be improved by applying textile materials over the metallic stent or by the
application of special substances over the metallic structure. Polyester is generally used in
covering metallic stents. In other cases, the metallic stent is impregnated with anti blood
clotting substances. Researchers have proved that occurrence of restenosis may be reduced by
covering metallic stents with textile fibers, and this has paved way for the development of the
100% textile stent. Modern day stents are textile materials that could be designed with
improved properties over the metallic ones. Both knitted and braided textile stents could be
easily compressed, resulting in blocking of artery and thus lead to heart attack, or other
problems such as stent migration etc. [46]. The flexibility of a stent is one of the most
important characteristics, as without this property it may not be possible to reach the harmed
part of the artery. However, to obtain the ideal flexibility of the stent, the radial compression
force may be compromised. This latter property refers to the resistance to collapse when the
stent expands and is the stents capability to maintain the lumen geometry. Another critical
property of the stent is its biocompatibility which has to be very high to minimize the risk of
thrombosis or a neo-intimate proliferative response. Recent studies have focused on
development of 100%textile stents to replace commercially available metal and hybrid ones
[47].
Polypropylene fiber has been found to be suitable owing to its economical cost as well as
compatibility in physical properties. It is effective, readily available, versatile, and cheap. The
use of monofilament will enable a greater stiffness and better results when the stent is
subjected to compression, tensile, and bending forces as these will be directly borne by the
yarn.
MECHANICAL PROPERTIES
Studies on the radial compression tests for both knitted and braided fabrics have revealed
that the best results have been obtained for the braided fabrics with a marginal increase for
those heat-set at 140oC. It has been observed that as the fabric cover increases the resilience
of the structures also increases [48] Studies on bending tests at 90oC for both knitted and
braided samples have shown that the best results have been obtained for the braided fabrics
with the effect of the heat-setting temperature producing small and unclear differences. It has
been observed that resilience of the structures increases with the fabric cover. Studies on
tensile tests for the knitted fabrics have shown that the structures produced with the thicker
yarn have a greater stiffness. For the same yarn diameter, the shorter loop length resulted in
the stiffer structure. The braided structures produced with the thicker yarn have a greater
stiffness. For the same yarn diameter, the higher the braid angle the stiffer is the structure.
The braided structures were considerably stiffer than the knitted structures and therefore
performed better.
478
Overall, the braided structures had better mechanical properties, that is, higher stiffness,
than the knitted ones and this was due to their structure being made up of straight yarns rather
than loops. The tightness of the construction increased the stiffness in all cases as more fiber
per unit area is available to resist the loads. It has been observed that as the yarn diameter
increased, the thickness of the fabrics (stent wall) also increased. This may explain the
increase in the stiffness of the stents with yarn diameter due to an increase in the thickness of
the stent wall.
CONCLUSION
Polyester prosthesis used in vascular surgery has been crimped and analyzed for blood
flow. The effect of crimping on the blood flow has been measured. Experimental studies have
revealed that there are two zones of flow- one is the undisturbed central zone and the other is
the disturbed zone at the vascular wall caused due to crimping. A weaving technique has been
developed to manufacture bifurcated vascular prosthesis. Dacron polyester has been used
owing to its biocompatibility. Studies on the mechanical behavior of crimped polyester
prosthesis indicate that the behavior seems to be visco-elastic at higher stresses and elastic at
low stresses because of the crimped shape of the graft walls. Yarn size and fabric structure
have been varied to produce seamless tubes ranging between 1.5 7 mm in diameter. These
were heat set for circular shapes and characterized for size, geometry and radial elasticity.
Propertystructure correlation models have been presented. Grafts of desired size can be
engineered and their properties predicted. A fabric prosthesis has been manufactured that is
expected to respect haemodynamics, with a central opening, and that is associated with good
fatigue resistance for long-term durability.
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ISBN: 978-1-63117-262-5
Chapter 19
EFFECT OF CLOTHING MATERIALS ON

THERMOREGULATORY RESPONSES OF
THE HUMAN BODY
P. Kandha Vadivu*
Department of Fashion Technology, PSG College of Technology,
Coimbatore, India
ABSTRACT
The human body continuously generates heat by its metabolic processes. The heat is
lost from the surface of the body by convection, radiation, evaporation and perspiration.
In a steady-state situation, the heat produced by the body is balanced by the heat lost to
the environment by maintaining the body core temperature around a small range between
36 C and 38 C. Clothing is used outside the skin to extend the bodys range of
thermoregulatory control and reduce the metabolic heat by thermo regulation. Clothing
has a large part to play in the maintenance of heat balance, as it modifies the heat loss
from the skins surface and at the same time has the secondary effect of altering the
moisture loss from the skin. The properties of clothing materials critically influence the
comfort and performance of the wearer in different weather conditions. Heat transfer
through a textile assembly or a fabric system is a complex process, involving conduction,
radiation and convection across the fabric system, consisting of fabric and air layers. This
study discusses the thermoregulatory process of the human body, the thermal comfort
properties of fabrics and the effect of clothing material on the thermoregulatory process
of human body in different weather conditions.
1. INTRODUCTION
Comfort may be defined as a pleasant state of physiological, psychological and physical
harmony between a human being and the environment. Physiological comfort is related to the
*
Corresponding author: E-mail: vadivu67@yahoo.co.in.
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P. Kandha Vadivu
human bodys ability to maintain life, psychological comfort to the mind withstanding the
effect of the external environment on the body [1]. Thermo physiological comfort is defined
as the attainment of a comfortable thermal and wetness state; it involves transport of heat and
moisture through a fabric. For getting thermo physiological comfort the clothing should have
suitable thermal insulation properties as well as sufficient permeability to water vapour and /
or sufficient level of ventilation [2].
Comfort involves thermal and non-thermal components and it is related to wear situations
such as working, non-critical and critical conditions [3]. Comfort is related to complex
interactions between the fabric, climatic, physiological and psychological variables. A person
feels comfortable in a particular climatic condition if his energy production and energy
exchange with environment are evenly balanced so that heating or cooling of the body is
within tolerable limits. A core body temperature of approximately 37 C is required by an
individual for his well being. Hence, the body temperature is the most critical factor in
deciding comfort. Heat is gained by the body from the sun or intermediate source of energy,
by internal metabolism, by physical exercise or activity, or by involuntary contractions of
skeletal muscles in shivering [4].
The heat transport to the environment is achieved through a dry flux (conduction,
convection and radiation) and a latent flux produced by perspiration. The first flux depends
on the insulation property of clothing while the second one depends on its moisture transport
properties. The body vapour must have the opportunity to pass immediately from the skin to
the outer surface of the clothing. Heat loss by conduction, convection or radiation, depends
partly on the temperature gradient between the skin and the environment and this gradient is
modified by varying the skin temperature. Excessive heat may be dissipated rapidly by
vapourization of body water and the clothing system that hinders the free evaporation to any
appreciable extent will thus be uncomfortable. On the other hand, undesirable heat loss can be
prevented by increasing the thermal resistance of the barrier between the body and its
environment and a fabric with low resistance will again result in discomfort to the wearer [4].
So it is clear that clothing is a key to body comfort and it should essentially help the wearer in
his / her effort and not to give additional physical and heat stress.
2. MECHANISM OF THERMAL REGULATION OF HUMAN BODY

The metabolic heat generated by a human body differs based on the physical activity. A
base level of metabolism has been defined as the metabolism of a seated person resting
quietly and for a man of typical height and surface area, the metabolic rate is about 100W. To
normalize among people of different sizes, metabolism is typically expressed in per unit skin
surface area. A specialized unit, the met has been defined in terms of multiples of basal
metabolism: one met is equal to 58.15 w/m. A sleeping person has the rate of 0.7 met, and
reclining awake is 0.8 met. Office work (a mostly seated activity but one that involves
occasionally moving about) is 1.2 met: Walking slowly (0.9 m/s or 2 mph) is 2 met, moderate
walking (1.2 m/s or 2.7 mph) is 2.6 met, and fast walking is 3.8 met and jogging 8 to 12 met.
In terms of energy, a sleeping person has the rate of 40.71 w/m, and reclining awake is 46.52
w/m, Office work is 69.78 w/m [5].
Effect of Clothing Materials on Thermoregulatory Responses ...
485
The bodys heat loss is through radiation, convection, conduction, evaporation and
through respiration. In a neutral environment, where the body has no need to take thermo
regulatory action to preserve its balance, evaporation provides about 12% of total heat loss
and sensible heat loss provides 88%. In general, the heat transfer by conduction through the
soles of the feet or to a chair is small, around 3%. In normal indoor environments with still
air, the convective and radiation heat transfer are about equal. In the outdoors, wind strongly
affects convective heat loss or gain and radiation can also cause large losses and gains.
Sweating is important for heat regulation, and it is also a major source of water absolute
loss. There are two types of water loss: insensible perspiration and sweating. Insensible
perspiration loss from the skin cannot be eliminated. Daily loss is about 400 ml in an adult
and the respective heat loss is 238 kcal. The heat loss can be quite significant because there is
a loss of 0.58 kcal for every ml of water evaporated. The maximum rate of sweating is up to 5
ml/min or 2000 ml/hr in an acclimatized adult. This rate cannot be sustained, but losses up to
25% of total body water is possible under severe stress and could be fatal.
There is always a constant amount of trans-epidermal loss of water vapour directly
diffused through the skin resulting in heat loss by insensible evaporation. In addition the
breathing cycle involves humidifying exhaled air producing another evaporative heat loss.
The transversal moisture diffusion is about 100 to 150 ml per day per m of skin surface
representing a heat loss of 6% as great as the evaporation from a fully wetted surface. The
respiratory portion of the bodys total heat loss is estimated to be 12% depending on the
metabolic rate.
Clothing is used outside the skin to extend the bodys range of thermoregulatory control
and reduce the metabolic heat by thermo regulation. It reduces sensible heat transfer, while in
most cases, it permits evaporated moisture to escape. Bed clothes are a form of clothing used
for sleeping, because the metabolic rate during sleep is lower than the basal rate and the
bodys skin temperature tends to be higher during sleep, bed clothes typically have a higher
insulation value than clothing.
3. MECHANISM OF HEAT TRANSFER

To understand the thermal properties of the textile system, it is necessary to assess the
contributions of the various heat-transfer mechanisms that may be operative. These
mechanisms are conduction, convection and thermal radiation for dry heat transfer [6,7]
3.1. Conduction
Fibers and air intermingle together in any textile yarns and fabrics hence the fabrics are
neither homogeneous nor isotropic. However, with the preposition that the average heattransfer properties of fabrics are to be measured and calculated through the theoretical and
practical work, it is reasonable to assume that a fabric is a homogeneous and isotropic
material in heat transfer. In addition, since thickness of a fabric is substantially smaller than
the fabric width and length in normal clothing situations, it is also feasible to consider the
heat transfer through a fabric is a one-dimensional problem. Under such assumptions, the
486
P. Kandha Vadivu
transient heat-transfer process through the insulating material is described as in Equation (3.1)
[8].
T 2T
.
t cp x 2
Where,
T
t
c
x
(3.1)
temperature (K);
time (s);
conductivity (W m -1 K -1 );
mass density (kg m -1 );
specific heat (W S kg -1 K -1 ); and
direction of heat transfer.
3.2. Convection
As one of the basic heat-transfer mechanisms, convection involves the transport of
energy by means of the motion of the heat-transfer medium, in this case the air surrounding
the human body. When cold air moves past a warm body, it sweeps away warm air adjacent
to the body and replaces it with cold air. It has been found that there is no convection inside
clothing insulation even with a very low density [9]. In the finite element analysis, the
convective heat transfer will be set as a boundary condition. The heat flux due to convection
can be expressed as follows [10].
q h(Tr Tx )
(3.2)
heat flux (W m -2 );
h film coefficient (W m -2 K -1 );
T out surface temperature of the fabric (K); and
T temperature of the ambient atmosphere (K).
Where, q
3.3. Radiation
The heat loss carried out by radiation from a clad human body to the environment is a
situation where the clad human body as the heat source is enveloped by the environment. In
this case, the heat flux by radiation at the outer surface of the textile assembly is governed by
the following equations (3.3) and (3.4) [6].
q (Tr4 Tx4 )
Where, q
y
h( Tr Tx ) ( Tr4 Tx4 )
n
heat flux (W m -2 );
(3.3)
(3.4)
h
T
T
487
Stefan-Boltzmann constant which is 5.670310-8 W m-2 K-4

emissivity of the surface.
film coefficient (W m -2 K -1 );
out surface temperature of the fabric (K); and
temperature of the ambient atmosphere (K).
conductivity (W m -1 K -1 ).
4. MEASUREMENT OF CONDUCTIVE, CONVECTIVE, RADIATIVE AND

EVAPORATIVE HEAT TRANSFER OF HUMAN BODY
In order to clarify the heat transfer area involved in convective heat exchange for the
human body, which is required for calculating heat exchange between the human body and
the environment, Yoshihito Kurazumia et al. (2004) [11] calculated the total body surface
area of six healthy subjects and the non convective heat transfer area and floor and chair
contact areas for the various body positions. The effective thermal convection area factor for
nine common body positions such as standing, sitting in a chair, sitting in the seiza position,
sitting cross-legged, sitting sideways, sitting with both knees erect, sitting with a leg out, and
the lateral and supine positions are measured. The results showed that the effective thermal
convection area factor for the naked whole body in the standing position was 0.942, when
sitting in a chair 0.860, when sitting in a chair, excluding the chair contact area 0.918, in the
seiza sitting position 0.818, in the cross-legged sitting position 0.843, in the sideways sitting
position 0.855, in the both-knees-erect sitting position 0.887, in the leg-out sitting position
0.906, in the lateral position 0.877 and the supine position 0.844. For all body positions, the
effective thermal convection area factor was greater than the effective thermal radiation area
factor, but smaller than the total body surface area.
Kurazumia et al. (2008) [12] scrutinized the convective and radiative heat transfer
coefficients of the human body, while focusing on the convective heat transfer area of the
human body. Thermal sensors, directly measuring the total heat flux and radiative heat flux,
were employed. The mannequin was placed in seven postures. The regression equations for
the convective heat transfer coefficients (hc [W/ (m2 K)]) for natural convection, driven by the
difference between the mean skin temperatures corrected using the convective heat transfer
area and the air temperature, are given below:
Standing (exposed to atmosphere)
Standing (floor contact)
Chair Sitting (exposed to atmosphere)
Chair Sitting (contact with seat, chair back and floor)
Cross-Legged Sitting (floor contact)
Legs-out Sitting (floor contact)
Supine (floor contact)
hc = 1.007T 0:406
hc = 1.183T0:347
hc = 1.175T0:351
hc = 1.222T 0:299
hc = 1.271T 0:355
hc =1.002T 0:409
hc = 0:881T 0:368
where hc is the convective heat transfer coefficient [W/(m2 K)], and T the difference
between mean skin temperature corrected using convective heat transfer area and air
temperature [K].
488
P. Kandha Vadivu
Richard et al. (1997) [13] analyzed the convective and radiative heat transfer coefficients
for individual human body segments and found that the radiative heat transfer coefficient
measured for the whole-body was 4.5 W/(m2 K) for both the seated and standing cases,
closely matching the generally accepted whole-body value of 4.7 W/(m2 K). Similarly, the
whole-body natural convection coefficient for the manikin fell within the mid-range of
previously published values at 3.4 and 3.3 W/(m2 K) when standing and seated respectively.
In the forced convective regime, heat transfer coefficients were higher for hands, feet and
peripheral limbs compared to the central torso region. The ASHRAE Handbook of
Fundamentals (1993) has indicated a linearized radiative heat transfer coefficient hr=4.7
W/m2 per K which has been widely accepted as a reasonable whole-body estimate for general
purposes [14]. Jones (1998) [15] addressed the need to include the radiation non-uniformity
commonly found in indoor environments in body heat loss calculations.
Extensive research has been carried out to evaluate the sweating rate. In 1998, Toshio
Ohhashi et al. [16] reviewed the methods of human perspiration evaluation. In 1986, Kraning
and his co-operator [17] reported a new forced-evaporation-type skin capsule for measuring
local sweat gland activity in humans. Shamsuddiny and Togawa (1998) [18] reported a
method of continuous monitoring of sweating in which deion solution was perfused at a
constant flow rate through a chamber attached to the skin surface.
5. EFFECT OF CLOTHING ON THERMAL COMFORT

Clothing has a large part to play in the maintenance of heat balance as it modifies the heat
loss from the skin surface and at the same time has the secondary effect of altering the
moisture loss from the skin. However, no one clothing system is suitable for all occasions. A
clothing system which is suitable for one climate may not be suitable for another climate.
Good thermal insulation properties are needed in clothing and textiles used in cold
climates. The thermal insulation depends on a number of factors, viz, thickness and number
of layers, drape, fiber density, flexibility of layers and adequacy of closures. The thermal
insulation value of clothing when it is worn is not just dependent on the insulation value of
each individual garment but on the whole outfit as the air gaps between the layers of clothing
can add considerably to the total thermal insulation value. This assumes that the gaps are not
so large that air movement can take place within them, leading to heat loss by convection.
Because of this limitation the closeness of fit of a garment has a great influence on its
insulation value as well as the fabric from which it is constructed. The resistance that a fabric
offers to the movement of heat through it is of critical importance to its thermal comfort.
6. THERMAL COMFORT PROPERTIES OF FABRICS

Thermal properties of textile materials especially thermal conductivity have always been
the major concern when the comfort properties of clothing are concerned. The properties of
clothing materials critically influence the comfort and performance of the wearer. Clothing is
not just a passive cover for the skin. It interacts with and modifies the heat regulating function
of the skin and its effects are modified by the environment. Thermal conductivity and thermal
489
insulation or thermal resistances and thermal absorptivity are few measures of thermal
comfort.
6.1. Thermal Conductivity

The ability of a fabric to conduct heat through it is of critical importance to its thermal
comfort. Thermal conductivity is a property of materials used to describe the thermal transfer
behavior of the heat flow through a fabric due to a combination of conduction and radiation
where the convection within a fabric is negligible. The conduction loss can be determined by
the thickness of the fabric and its thermal conductivity. As defined by ASTM, thermal
conductivity is the time rate of unidirectional heat transfer per unit distance, per unit
difference of temperature of the planes. Another relevant concept is thermal conductance (C),
also defined by ASTM as the time rate of heat flux through a unit area of a body induced by
unit temperature difference between the body surfaces. Normally thermal conductivity can be
expressed in equation 6.1
Q/ A
T / L
(6.1)
Where Q is the amount of heat passing through a cross-section A, causing a temperature

difference T, over a distance of L. Q/A is therefore the heat flux which is causing the
thermal gradient. The measurement of thermal conductivity, therefore, always involves the
measurement of the heat flux and temperature difference. The difficulty of the measurement
is always associated with the heat flux measurement. Guarded hot plate, as described in ISO
8302, is a widely used and versatile method for measuring the thermal conductivity of
textiles. Another widely used simple method is directly using a heat flow meter as described
in ASTM C 518.
6.2. Thermal Insulation

Thermal insulation property of the fabric refers to the ability to resist the transmission of
heat by all modes. It can also be defined as effectiveness of a fabric in maintaining the normal
temperature of the body under equilibrium conditions. The most important thermal property
in most of the apparels is the insulation against heat flow, which is measured by thermal
resistance. It is defined as the ratio between temperature difference between the two faces and
heat flux.
The thermal resistance, R and thermal conductivity, K are related as follows,
R = d /K
(6.2)
Where d is the thickness of the material. Since K is roughly constant for different fabrics,
hence thermal resistance is approximately proportional to fabric thickness. Thermal insulation
value is higher in case of silk fabric compared to cotton fabric. It is due to openness of knit
490
P. Kandha Vadivu
structure of silk fabric. Silk fiber contains higher thermal insulation value as it has lower
thermal conductivity (50 mw/m/k) than cotton (71 mw/m/k).
In studying the thermal insulation properties of garments during wear, it is reported that
thermal resistance to transfer of heat from the body to the surrounding air is the sum of three
parameters: (i) the thermal resistance to transfer heat from the surface of the material, (ii) the
thermal resistance of the clothing material and (iii) the thermal resistance of the air interlayer.
It is obvious that heat transfer through a fabric is a complex phenomenon affected by many
factors. The three major factors in normal fabrics appear to be thickness, enclosed still air and
external air movement. Out of which, the entrapped air is the most significant factor in
determining thermal insulation. There are "microlayers" (those between contacting surfaces
of the materials) and "macrolayers" (between non-contacting surfaces) of air enclosed within
an assembly and an increase of either of these can increase thermal insulation. However, the
characteristics of fiber, yarns, fabrics and garment assemblies have also a major contribution
towards thermal comfort.
Most textile fibers are poor conductors of heat, but air conducts even less heat. If air is
confined in small spaces, then convection is also minimized, and the air is dead. The higher
the volume of dead air within a textile structure, the lower the thermal transmittance,
therefore, the better the insulation value of the textile material [19].
7. FACTORS AFFECTING CLOTHING COMFORT

Thermal wear comfort is mainly related to the sensations involving temperature and
moisture. This factor responds mainly with the thermal receptors in the skin and relates to the
transfer properties of clothing such as heat transfer, moisture transfer and air permeability.
Clothing protects cold or heat to maintain body thermal comfort throughout the full range of
human activity. Various types of tactile moisture and thermal interactions between the
clothing material and the human skin determine the comfort level of a person at a given
environmental condition while engaged in specific activity. The fabric type and its blend
composition, the tactile and thermal insulation behavior of the fabric assembly and the
moisture management capabilities of the clothing can affect the comfort [20].
A number of properties of fibers, yarns, fabrics and garments are significantly related to
comfort and must be taken into account in producing suitable apparel items. However,
suitable fabrics from the comfort point of view must be developed by textile technologists by
proper selection of fiber content, yarn and fabric construction techniques and finishing
treatments as they influence physiological comfort level through thermal retention or
transmission, moisture vapour permeability, water resistance, static charge build-up, UV
protection etc., Quality of fabrics for clothing depends to a great extent on aesthetic
performance, comfort related properties and wear related properties [21].
Of the various properties affecting comfort, fiber type, fineness, cross sectional shape,
crimp, length and surface properties are extremely important. Fabric structure includes yarn
linear densities, sett, weave, crimp levels and can influence such critical fabric properties as
cover, thickness, bulk density, mechanical and surface behavior which have direct relation
with fabric comfort. Finishes which affect the properties of the fabrics and appearance can
491
also significantly change the performance of a fabric in clothing. Fabric properties, together
with the garment design and size influences the various garment properties [21].
For getting thermo physiological comfort, the clothing should have suitable thermal
conducting properties as well as sufficient permeability to water vapour and / or sufficient
level of ventilation [2]. The textile structures can be developed to enhance the clothing
comfort by focusing principally on the thermal and mechanical properties [4]. There is
general agreement that the movement of heat and water vapour through clothing are probably
the most important factors in clothing comfort, and Rees [22] describes the temperature
regulation of the body in order to define the system in which comfort must be maintained.
Hollies (1977) [23] stresses the importance of contact comfort in dealing with a clothing
system.
8. HEAT TRANSFER THROUGH TEXTILES

In the case of clothing, the body temperature is nearly always higher than the temperature
of the surrounding environment, so the normal direction of heat transfer is from the warm
body to the outside environment. Of course, in particularly hot climates, the reverse is true.
When the surrounding environment is colder than the body, resistance to heat transfer
increases as the volume of dead air in the clothing increases, and more heat is kept near the
body. As long as the air within a fabric or fabric assembly is so called dead air, it provides
good resistance to heat transfer. However, as the volume of air space increases, the likelihood
of air movement, or convection, increases. When convection occurs, it is usually the
dominant mode of heat transfer, overpowering any effects of reduced conduction of heat [19].
Heat transfer through a textile assembly or a fabric system is a complex process,
involving conduction, radiation and convection. The combined heat transfer across the fabric
system, consisting of fabric and air layers, is not simply the sum of what each mechanism
would do in the absence of the others. The three heat transfer mechanisms work together to
determine the characteristics of the overall heat transfer process.
Heat transfer refers to the transfer of heat energy from one environment to another. Heat
transfer occurs whenever a temperature difference (T) exists between the two environments;
heat moves from the warmer surface or area to the cooler surface or area. Heat transfer will
continue until the two areas attain same temperature (at equilibrium). The rate at which heat is
transferred depends on T as well as any resistance imposed between the two environments.
For people, this means that if the ambient temperature is lower than the body temperature
(37 C), heat will flow from the body to the surrounding area. If the ambient temperature is
higher than the body, heat will flow the other way and the body will become warmer.
Clothing can provide resistance to heat transfer in either direction by serving as insulation
between the two environments [19].
For clothing textiles, heat transfer is a complicated transient process. Generated from the
body, heat transfers through the air gap between skin and fabric, then through the fabric
system, to the outer surface of the fabric system. During this process, conduction, convection
and radiation are all involved, may be to different extent, in determining the total heat loss.
492
P. Kandha Vadivu
8.1. Effect of Fiber Properties on Heat Transfer

Because various fibers differ little in thermal transmittance behavior, fiber physical
structure more than chemical make-up affects the overall insulation capacity of a fabric and
the thermal comfort of the user or wearer. Fibers have a high surface to volume ratio; thus
there are many small spaces for dead air within a fibrous structure. In those spaces, there is
little thermal transmittance because air is a very poor conductor of heat; and there is little
radiation because although air is transparent to radiation, fibers are not [19].
Some fibers have physical characteristics that enhance this effect of air insulation. For
example, wool is a good fiber for insulation because its natural crimp maintains a high
volume of dead air. Likewise, manufactured fibers are often given a degree of crimp or
surface irregularity that increases thermal resistance. In addition, hollow fibers that inherently
entrap air are produced specifically for end-uses in cold weather apparel. Finally, fiber size is
consideration in insulation effectiveness. Finer fabrics have more surface area, which results
in more dead air space between fibers. An example is the effective use of micro-fibers in
coats for use in cold climates [19].
8.2. Effect of Fabric Structure on Heat Transfer

Fabric construction also influences thermal insulation. Knitted fabrics generally have a
soft hand and higher heat-retaining properties compared with that of woven fabrics of a
specific thickness or weight. Knits usually will entrap more air than woven fabrics, although
the tightness of the weave or knit is a factor as well. In addition to the openness of the
structure, other fabric characteristics are influential in thermal insulation. Pile or napped
constructions are often good for cold weather because the yarns or fibers perpendicular to the
surface provide numerous spaces for dead air. This effect is maximized when such fabrics are
worn with the napped or pile surface next to the body, or when they are covered with another
layer. Otherwise, the protruding fibers in the nap structure may conduct heat away from the
body [19].
Fabric thickness is of primary importance and is usually considered to be the single more
important variable in determining thermal insulation and hence thermal comfort. A thicker
fabric provides more air space and, therefore, more resistance to heat transfer that a thin
fabric. However, there is a limit for the thickness of the fabric. It must also be lightweight
enough to be worn comfortably and, therefore, the ratio of thickness to weight is important
[19].
8.3. Heat Transfer through Multilayered Structures

Several textile properties affect the thermal resistance or insulation effectiveness of a
fabric or a layered assembly of fabrics. An important consideration is the amount of air space
contained within a textile structure. Air has low thermal transmittance and high thermal
resistance. Most textile fibers are poor conductors of heat, but air conducts even less heat. If
air is confined in small spaces, then convection is also minimized, and the air is dead. The
493
higher the volume of dead air within a textile structure, the lower the thermal transmittance,
therefore, the better the insulation value of the textile material [19].
Voinov and Karlina (1972) [24] suggested that in clothing assemblies that include air
layers, the thermal resistance of the air layer varies in a complex manner with the clothing
thickness; they used their results to postulate that better use of the insulating ability of air
layers could be made by suitable clothing structure design. Weiner and Shah (1969) [25]
however, made attempts to isolate the factors of thickness and weight, and found that for a
fixed weight, thermal insulation increases with thickness, whereas the property decreases with
increased weight if the thickness is maintained constant. Karlina, with various co-workers
(1971) [26] distinguishes microlayers (those between contacting surfaces of the materials)
and macrolayers (between non-contacting surfaces) of air enclosed within an assembly and
then shows that an increase in either of these can increase thermal insulation. Fonseca (1970)
[27] claims that the thermal characteristics of a clothing assembly are governed decisively by
the properties of outer layer and that any interior layers merely occupy a part of the still-air
layer; their presence therefore merely serves to prevent a decrease in the size of the still-air
layer by collapse of the outer garments onto the body. Kawabata and Akagi (1977) [28] found
a close correlation between the feeling of warmth on first touching a fabric and the maximum
absorption rate of heat flow as measured physically.
Markus Weder et al. [29] used Neutron radiography to study moisture transport in textiles
for the first time. Clothing systems composed of layers with differing water transport
properties were studied to demonstrate the feasibility of using the technique. The results were
compared to the weights of the individual layers and the results of the three measurement
approaches agree with respect to layer wise moisture distribution in the different textile
combinations, and the radiography data provide a lateral visualization of the distributions.
9. CONTROL OF HEAT TRANSFER IN TEXTILES

For effective use of textiles to enhance or control heat transfer, one must first identify the
primary mode of heat transfer and then select textiles that will modify or enhance that
particular mode. Textured, thick, bulky fabrics, and fabrics used in multiple layers reduce
conduction. Tightly woven fabrics and designs that restrict air movement control heat transfer
by convection. Finally, fabrics with smooth reflective surfaces influence heat transfer by
radiation [19].
Peirce and Rees (1946) [30] pointed out that at the outer surface of the clothing exposed
to the air; heat is lost by means of both convection and radiation. Farnworth (1983)
[31]presented a theoretical treatment of heat transfer through a bed of fibers considering
conduction and radiation and reported that no detectable convective heat transfer took place
inside the fiber bed. In a more recent study, Mohammade et al.(2003) [32] presented a
theoretical equation of the combined thermal conductive, convective, and radioactive heat
flow through heterogeneous multi-layer fibrous materials.
Dulnev and Muratova (1968) [33] discussed heat transfer processes in fibrous materials
and derived formulae from which effective thermal conductivity can be calculated from
thermal, geometrical, and volumetric parameters of the components. Mitu and Potoran (1971)
[34] used a formula derived by earlier workers for calculating the thermal resistance of
494
P. Kandha Vadivu
clothing to determine a series of values of this property that represent acceptable comfort
limits for the human body when engaged in lying, sitting, walking, running and other such
activities.
As long as the air within a fabric or fabric assembly is so called dead air, it provides
good resistance to heat transfer. However, as the volume of air space increases, the likelihood
of air movement, or convection, increases. When convection occurs, it is usually the
dominant mode of heat transfer, overpowering any effects of reduced conduction of heat [19].
Fibers have a high surface to volume ratio; thus there are many small spaces for dead air
within a fibrous structure. In those spaces, there is little thermal transmittance because air is a
very poor conductor of heat; and there is little radiation because although air is transparent to
radiation, fibers are not [19].
Heat transfer through a textile assembly consisting of fabric and air layers can be
calculated based on a theoretical model capable of dealing with conductive, convective and
radioactive heat transfer. The size of the air gaps has a significant influence on the heat
transfer. The balance heat flux drops by 40 per cent when the air gap increases from 2 to 10
mm. The influence of the air gap tends to become smaller as the air gap is further increased.
The number of fabric layers in the textile assembly has a noted influence; more so when the
ambient temperature is lower [35].
10. MEASUREMENT OF CLOTHING COMFORT USING

THERMAL MANIKIN
Since the first one segment copper thermal manikin in the world was made for the US
army in the early 1940s, more than 100 different thermal manikins have been employed for
research and product development worldwide. Holmer [36] reviewed thermal manikin
development history and summarized the milestones. Interest in using thermal manikins in
research and measurement standards is steadily growing and several international testing
standards have been developed in the field of the thermal comfort evaluation.
To date, thermal sweating manikins are widely used in large scale textiles and clothing
research laboratories all over the world for analyzing the thermal interface of the human body
and its environment. Normally, the thermal manikin is made from metal or fabric e.g., copper,
plastic or water / windproof fabric with an independent controllable heating/sweating
subsystem, data measurement and analyzing subsystems. With the development of computer
and computation technologies, visual realization models have become more and more
important and are now widely applied in the field of thermal comfort estimation. Li et al. [37]
developed a computer based model for studies of heat moisture transfer in clothing systems.
Buxton et al. in the UK are also developing a similar model that allows the use of human
body data from whole body scanners and motion patterns derived from real recordings.
495
11. MEASUREMENT OF CLOTHING COMFORT USING THERMAL /

SWEATING PLATE
The thermal/sweating plate has been used for years to determine the thermal and moisture
resistance properties of fabrics. The applications and description of sweating hot plates can be
found in Goldman [38] and Holmer et al. [39]. There are several types of skin model
employed in clothing comfort research. Firstly, Kawabata [28] reported the application of hot
plate technology for the measurement of fabric warm and cool feelings. The thermal lab is
only used to evaluate the warm or cool feeling produced upon touching a fabric. Thermal
conductivity is measured in the steady state. A damp paper was put on the hot plate to
stimulate human skin. A representative sweating hot plate is described in the Farnworths
paper [31]. This sweating hot plate is designed to maintain a constant surface temperature of
35C and consists of a circular shaped inner plate, a guard ring plate and a base plate. The
sides of the inner plate are separated from the guard ring plate by a 1 mm air gap and the
bottom of the inner plate is separated from the base plate by 50mm of foam insulation. The
guard ring plate and the base plate prevent heat flow away from the inner plate in the lateral
and downward directions, respectively. Electrical heaters, connected to DC power supplies,
are used to maintain the inner plate at a constant temperature of 35oC, which is determined by
a thermistor. All three plates are located inside a heated box to eliminate further heat flow
away from the inner plate in any direction other than that upward from the plate surface.
Typical structure and detailed description of a sweating hot plate can be found in ISO 119021993(E).
CONCLUSION
The properties of clothing materials critically influence the comfort and performance of
the wearer. Clothing is not just a passive cover for the skin, it interacts with and modifies the
heat regulating function of the skin and its effects are modified by the environment. The
combined effects of the properties of clothing materials and wind on the physiological
parameters of human wearers are the critical factors to be considered in designing functional
clothing and are going to be the niche area of research in future.
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[4]
Slater, K. (1977). Comfort Properties of Textiles. Textile progress, 9,

1-91.
Jeffries, R. (2005). Functional Aspects of High performance clothing. Book of
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Inc., New York, USA
Bhat, P. & Bhonde, H. U. (2006). Comfortable clothing for Defence Personnel. Asian
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Butera, F. M. (1998). Principles of thermal comfort. Renew. Sust. Ener. Rev., 2(1-2),
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Peirce, F. T. & Rees, W. H. (1946). The transmission of heat through textile fabrics,
Part II. J. Text. Inst., 37, 181-204.
Incropera, F. P. & DeWitt, D. P. (2002). Fundamentals of Heat Transfer, 5th ed. Wiley,
Somerset, NJ.
Kurazumi, Y., Tsuchikawa, T., Matsubara, N. & Horikoshi, T. (2004). Convective heat
transfer area of the human body. Eur. J. Appl. Physio., 93, 273-285.
Kurazumia, Y., Tsuchikawab, T., Ishiia, J., Fukagawaas, K., Yamatoc, Y. &
Matsubara, N. (2008). Radiative and convective heat transfer coefficients of the human
body in natural convection. Building and Environment, 43, 2142-2153.
Richard, J., Dear, D., Arens, E., Hui, Z. & Oguro, M. (1997). Convective and radiative
heat transfer coefficients for individual human body segments. Int. J. Biometeorol., 40,
141-156.
Fanger, P. O. (1977). Local Discomfort to the Human Body caused by Non-Uniform
Thermal Environments. Ann. Occup. Hyg., 20(3), 285-291.
Jones, B. W. (1998). Radiant heat transfer between the human body and its
surroundings. ASHRAE Transactions, 104(2), 1340-1350.
Ohhashi, T., Sakaguchi, M. & Tsuda, T. (1998). Human perspiration measurement.
Physiological Measurement, 19, 44.
Kraning K. K. & Gonzalez, R. R. (1991). Physiological consequences of intermittent
exercise during compensable and uncompensable heat stress. J. Appl. Physiol., 71(6),
2138-2145.
Shamsuddin A. K. M & Tatsuo, Togawa. (1998). Continuous monitoring of sweating
by electrical conductivity measurement. Physiological Measurement, 19(3), 375.
Collier, B. J. & Epps, H. H. (1999). Textile Testing and analysis. Prentice-Hall Inc.,
New Jersey, U.S.A.
Kothari, V. K. (2006). Thermophysiological comfort characteristics and blended yarn
woven fabrics. Indian J. of Fib.Text. Res., 31(1), 179-186.
Kothari, V. K. (2004). Fabric comfort. Proc. of the seminar on comfort in textiles, IIT
Delhi, New Delhi, India,
Rees, W. H. (1972). Materials and Clothing in Health and Disease-The Biophysics of
Clothing Material, Lewis Pub., London.
Hollies, N. R. S. & Goldman, R. F. (1977). Clothing comfort: Interaction of thermal,
Ventilation construction and Assessment Factors. Michigan, Ann Arbor Science
publishers Inc. ann harbor, USA.
Voinov, Y. F. & Karlina K. V. (1972). Assessment of the Thermal Resistance of
clothing. DRIC translation, 2920.
Weiner, L. I. &Shah, J. (1969). Insulating Characteristics of Battings. Text. Chem.
Color., 1, 301-306.
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[26] Karlina, E. V. & Tretyakova, L. I. (1971). Investigation of the Effect of Macro-Layers

of Air on the Thermal Insulation Properties of Clothing Assemblies. Teknolngiva,
Legrol Drom., 2, 98-102.
[27] Fonseca, C. F. &Breckenridge,J. R. (1965). Wind Penetration Through Fabric Systems,
Text. Res. J., 35, 95-103.
[28] Kawabata, S. & Akagi, Y. (1977). The Standardization and Analysis of Hand
Evaluation. Text. Mach. Soc. Japan, 3, T13.
[29] Weder, M., Brhwiler, P. A. & Herzig, U. (2004). Neutron Radiography Measurements
of Moisture Distribution in Multilayer Clothing Systems. Text. Res. J., 749s(8),695700.
[30] Peirce, F. T. & Rees, W. (1946). The transmission of heat through textile fabrics, Part
II. J. Text. Inst., 37, 181-204.
[31] Farnworth, B. (1983). Mechanisms of heat transfer through clothing insulation, Text.
Res. J., 53, 717-725.
[32] Mohammade, M. & Banks-Lee, P. (2003). Determining effective thermal conductivity
of multilayered nonwoven fabric. Text. Res. J., 73, 802-808.
[33] Dulnev, G. N. & Muratova. (1968). Thermal Conductivity of Fibrous Systems, J. Eng.
Phys. Thermo physics, 14(1), 15-18.
[34] Mitu, S. & Potoran, I., (1971). Fundamentals of Textile Clothing Technology. Bul. Inst.
polytech. Iasi, 17(1-4), 61.
[35] Sun, Y., Chen, X., Cheng, Z. & Feng, X. (2010). Study of heat transfer through layers
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[36] Holmer, I. (2004). Thermal manikin history and application. Eur. J. Appl. Physiol.,
92(6), 614-618.
[37] Li, Y. & Holcombe, B. V. (1998). Mathematical Simulation of Heat and Moisture
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[39] Holmr, I. & Elns, S. (1981). Physiological evaluation of resistance to evaporative
heat transfer by clothing. Ergonomics, 24, 6374.

ISBN: 978-1-63117-262-5
Chapter 20
DESIGNING OF JUTEBASED THERMAL INSULATING

MATERIALS AND THEIR PROPERTIES
Sanjoy Debnath
National Institute of Research on Jute and Allied Fibre Technology,
Indian Council of Agricultural Research, Kolkata, West Bengal, India
ABSTRACT
Among the different natural fibres, jute is less expensive, annually renewable and
commercially available fibre compared to other fibre crops. Jute is mostly cultivated in
India and Bangladesh. This fibre is being popularly used as packaging material, hessian
and carpet backing for over a century. After introduction of man-made fibres in the1950s,
the market of such traditional products made out of jute has been almost replaced by the
synthetic fibres due to their low cost and high production speed. As far as thermal
insulating material is concerned, wool-based material either from natural wool or
artificial fibres like acrylic is thought about but seldom jute/jute-blended materials.
However, in the present chapter, effort has been made on diversification of jute usage,
specifically, as thermal insulating material.
To upgrade its thermal insulation properties, the suitable modifications done to the
fibre/yarn structures, have been discussed here. Also, the structural design of weaving
using jute-based yarns and the design parameters involving in designing of suitable warm
garments from jute-based materials have been discussed. The measurement of thermal
insulating property and its factors affecting its insulating property have also been
covered. Besides, important area like nonwoven fabrics mostly used as industrial
material, its design towards development of jute-based thermal insulating material has
also been focused in this chapter.
Keywords: Blending of fibres, Chemical treatment, Jute fibre, Polyester fibre, Polypropylene
fibre, Thermal insulation, Warm fabrics
E-mail: sanjoydebnath@yahoo.com; sanjoydebnath@hotmail.com.
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Sanjoy Debnath
INTRODUCTION
Among the different fibre crops, jute is one of the oldest cultivated fibre crops in India.
India is the highest producer of jute in the world, and is mostly cultivated in the eastern part
of the country. It is the cheapest fibre crop available commercially in bulk quantities so jute
fibre is being technically used extensively over the centuries. For example it is used as,
packaging material, carpet backing, hessian as industrial applications. It is also used for
reinforcement of rural mud houses, thermal insulating material for domestic animals like
cattle, pet dogs etc. As far as the properties of jute fibre are concerned, it has both desirable
and undesirable ones. Basically, this fibre has mesh like structure which provides better
coverage, good tensile strength, toughness and durability. Due to its less extension at break, it
ensures dimensional stability. The natural colour of the fibre renders it an ethnic value, which
ensure its use as a material for various handicrafts and artefacts. Unlike any other fibres, the
drawbacks of jute fibre crop are high surface roughness and prickliness, low extension at
break and coarseness which restricts its use in textile garment. Keeping this in view warm
clothes has been designed and developed using jute-based fibres and yarns. Thermal
insulation is one of the essential properties for any warm fabrics [1]. Judicious modifications
of the fibre/yarn structure is one of the important aspect as far as its development as thermal
insulating material is concerned. The thermal insulation related properties mainly depends on
the availability of amount of air pores in the textile structure. Air trapped in fabric pores,
makes the fabrics act as thermal insulating media [2].
CLASSIFICATION OF WARM CLOTHS

Structurally, the warm fabrics can be classified into different categories viz., knitted,
woven, nonwoven and composite (more than one structure of fabric or combination of
structures). Also, as per the usage of the warm cloths, it can differentiated as wearable textile
and non-wearable textiles. Under the wearable textile the applications may be shawl, jacket,
blazer, muffler, sweater, pullover etc. on the other side the non-wearable textiles include
blanket, carpet, floor coverings, curtains, industrial insulation etc.
DESIGNING OF WARM FABRICS

The basic structures like woven and knitted, require yarn as prerequisite material for
designing of warm fabrics. However, in-case of nonwoven structures, instead of yarn, it may
be directly from fibre, where modifications in fibre or fabric stages are needed to achieve
desire properties for warm fabrics [3]. In case of woven and knitted structures modifications
during yarn forming or fabric manufacturing stages or modifications of both the stages are
essential to develop jute based warm fabrics. Bulking of yarn is prerequisite for designing of
warm fabrics either from weaving or knitted structures [4]. Following process describes about
the bulking methods used to achieve considerable bulk in the yarn structure of woven or
knitted fabric.
Designing of JuteBased Thermal Insulating Materials and Their Properties
501
WOOLLENISATION OF JUTE
As wool fibre is sourced from animal, fibre has limitation of production and also costly
compared to jute fibre. However, jute fibre does not have any crimp or scale as found in case
of wool fibre. Because of presence of these scales/crimps in wool fibre, the fibres do not
come close to each other in the fabric or yarn structure and as a result more void occurs in the
structure. The static air gets trapped in the void and acts as thermal insulating medium and
hence any material made out of wool seems to have higher thermal insulation. Woollenisation
is basically an alkaline treatment [5] and it is also called as chemical texturizing process of
jute. This process produces wool like crimp [6, 7, 8, 9] and thus increases available air space.
Breaking elongation increases after this treatment due to formation of crimp/lateral expansion
of the yarn. In this process, jute is treated with the NaOH solution and it is found that 18%
NaOH solution gives optimum result for the Woolenization [10]. Alkaline treatment removes
significant amount of the hemicellulose and small quantity of soluble lignin present in the jute
structure and as a result fall in strength of the jute has been observed. Several attempts were
also made to recover NaOH after this delignification process, from the spent liquor.
Woollenisation process introduces several changes in properties of the jute fibre.
Accordingly, yarn properties after woollenisation treatment also changes significantly
compared to un-treated yarn [11]. After this process, the surface of the yarn becomes rough,
and exaggerated further when bleached. Because of these reasons, fully woollenised jute yarn
is not solely appropriate for preparation of warm garments like shawl/wrappers, sweaters etc.
However to improve the surface feel and softness of the yarn, different chemical softeners
such as Velan PF and Sopamine OC, has been used. Further, to increase the water repellence
different silicone treatment is needed. The introduction of the silicone treatment gives a semipermanent water repellence property and it withstands laundering fairly well.
WOOLLENISED JUTE AND WOOL BLENDED YARN

Woollenised jute can be well mixed with natural wool at 50:50 ratio [1]. We can produce
coarse yarn in woollen/worsted systems. Other than the wool fibre, other natural or synthetic
fibres such as cotton or polypropylene (PP) can be blended with woollenised jute to produce
different unconventional high value products [5].
Bleaching of blended yarn produced from woollenised jute and wool can be done with
0.75 vol H2O2 solution for 2 hours at 80oC [5]. Twelve different shades were obtained by
dyeing of woollenised jute blended yarn; both bleached and unbleached woollenised jutes
were used and they were mixed with wool at the ratio of 35:65 [6, 12, 13].
WOOLLENISED JUTE AND POLYPROPYLENE BLENDED YARN

In several studies, different fibers were blended with the woollenised jute. One the fibres
that is often mixed with woollenised jute is Polypropylene (PP). The blend ratio of 80:20
(Jute: PP) is used to produce yarn and it is found that incorporation of PP to the blend gives a
higher bulk with stretch. It also facilitates the preferential migration to the surface of the yarn.
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Sanjoy Debnath
Woollenised jute and PP blended yarn have higher bulk in comparison to the yarn which is
produced from Indian Chokla wool. However, this wool yarn shows higher breaking
elongation and uniformity of diameter. The Tenacity of textured Jute:PP blended yarn is
higher than the wool yarn (Indian Chokla Wool), though at the time of woollenisation the
tenacity of the jute component drops significantly [1]. It is also found that wet/dry tenacity
ratio is higher in jute: PP blended textured yarns than the wool yarn [14, 15, 16].
WOOLLENISED JUTE-POLYESTER, JUTE-HOLLOW POLYESTER

AND JUTE-ACRYLIC BLENDED KNITTING YARN
Rotor spun short staple jute-polyester blended yarns were texturized and compared with
conventional apron draft jute spun texturized yarn by Ghosh and Samanta, 1997 [17]. It was
found that 70:30 of jute and polyester blended rotor spun yarn showed the optimum result.
Sinha and Basu, 2001 [18] used jute-shrinkable acrylic fibre to develop bulked knitted yarn.
They used a simple technique to develop bulk in the raw jute-acrylic blended yarn. The bulk
in the raw yarn can be developed by boiling the yarn in water for 15-30 min or steaming
treatment. Study was also conducted on effect of sodium hydroxide on jute-acrylic blended
yarn spun in DREF spinning system [19]. They studied the effect of treatment time,
concentration and blend proportion on yarn bulk, strength, extension and packing of juteacrylic blended DREF spun yarns. Jute and hollow polyester fibre (80:20) blended fine yarn
(130 tex) has been developed [20].
These yarns was further plied and made into 2-ply and 3-ply yarns. Woollenisation
treatment was done for 2-ply and 3-ply blended yarns. Further, bleaching and dyeing was also
conducted. The yarn shrinkage and weight loss properties have been studied at every stage
and compared with the untreated yarn. Also, other physical properties viz., tenacity, breaking
strain, diameter, coefficient of friction, specific work of rupture, bulk density have been
studied and compared with the similar woollen and acrylic commercial yarns.
This study (Debnath et al. 2007a) established that jute-hollow polyester blended yarn has
higher bulk over similar commercial yarns due to low yarn packing [20]. The 3-ply jutehollow polyester blended bulked yarn has better bulk, regularity (cv %), extensibility,
pliability and work of rupture than those of 2-ply yarn. The tenacity of 3-ply blended bulked
yarn deteriorates after 18% (w/w) NaOH chemical treatment while breaking extension
remarkably increases (Figure 1).
However the percentage coefficient of variation of both tenacity and breaking extension
decreases after bleaching and dyeing. This yarn shows almost similar tenacity with lower
extension compared to wool yarn (Figure 2). The lowest specific work of rupture is observed
in the 3-ply blended bulked yarn. This 3-ply blended bulked yarn also shows lower
coefficient of friction than wool yarn (Table 2). The specific flexural rigidity of jute-hollow
polyester blended yarns are lower than woollen yarn but comparatively higher than acrylic
yarns.
503
Table 1. Yarn shrinkage and weight loss behaviour of 80:20 jute-polyester (hollow)
blended bulked yarn [20]
Chemical
Processes
Bleaching
Dyeing
2-Ply blended yarn

Shrinkage (%)
Weight loss (%)
10
15.37
10
18.01
3-Ply blended yarn

Shrinkage (%)
Weight loss (%)
12.5
14.27
12.5
16.74
Table 2. Comparison of 80:20 jute-Polyester (hollow) bulk yarn with acrylic and wool
commercial yarns [20]
Properties
3-ply acrylic
Linear density (tex)
Diameter (mm)
Packing factor
Packing factor C.V.%
Bulk density (g/cm3)
Tenacity (cN/tex)
Tenacity C.V.%
Breaking strain (%)
Breaking strain C.V.%
Specific work of rupture
(mJ/tex-m)
Coefficient of friction of
yarn ()
Specific flexural rigidity
(mN-mm2/tex2 X 10-4)
Commercial yarns
4-ply acrylic
4-ply wool
3-Ply dyed jute-hollow

polyester yarn
170
1.19
0.128
15.46
0.153
7.44
7.01
37.35
9.83
290
1.71
0.106
11.56
0.126
9.10
6.55
45.42
11.57
300
1.35
0.161
11.61
0.210
4.00
10.12
18.01
16.73
370
1.85
0.094
16.14
0.138
3.84
9.09
8.6
7.83
16.85
14.00
4.47
1.27
0.81
0.80
0.90
0.84
9.57
5.20
23.20
11.98
Figure 1. Stress strain behaviour of jute-hollow polyester blended yarns [20].
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Sanjoy Debnath
Figure 2. Comparison of stress strain behaviour of jute-hollow polyester blended yarn with acrylic and
wool yarns [20].
BLANKET AND CARPET PRODUCTS FROM WOOLLENISED JUTE

AND POLYPROPYLENE BLENDED YARN
Different products have been developed out of woollenised jute and polypropylene fibre
blends, some of them are listed below:
CAPLON Blanket Main advantages of this blanket over wool blanket is higher
Strength, moth resistance, and good thermal insulation properties.
Carpet Different kinds of carpets that can be produced from the woollenised jute: PP
blended yarns are Chenile, hand knitted, tufted and woven carpets.
Chenile carpets These kind of carpets can be produced by doubling the woollenised
pile yarn and varying the length of pile. Main advantage of this kind of carpet is that, pile
yarns do not easily come out from the carpet body.
Hand knitted carpets This kind of carpets shows a similar tuft withdrawal force and
recovery from compression properties to wool carpets and its properties are superior than
carpets which are produced from the polypropylene.
Tufted carpets Tufted carpets have also been developed from woollenised-Jute/PP
blended yarn. They showed better performance because of high strength and uniformity of the
yarns.
Woven carpets Woven carpets are also known as Wilton and Tapestry carpets. Main
advantages of this kind of carpets are fly generation and fibre shredding are almost absent at
the time of production. The yarn breakage during production are also less. It gives a better
stretch property which enhance the formation of proper piles with less tension, and this piles
show better results to the seat and grip than jute pile yarns [16, 20].
505
Blanket from Woollenised Jute and Hollow Polyester Blended Fibre

Traditionally, one of the application of wool is well known to all of us for use in making
blanket. However, due to limited production of this natural fibre, nowadays synthetic fibres
like acrylic, polyester etc. are also being used in the area of blanket making. It is found that,
jute is still the most cheapest textile fibre available in some part of the world. Hence the
product made out of this cheap fibre will reduce the cost of production. The jute and hollow
polyester (PET) fibre were blended homogeneously in the ratio of 80:20 in first drawing
machine of jute spinning system [4].
The final blended yarns were spun in jute slip draft spinning machine to achieve the yarn
linear density of 276 tex (8 lbs/spy). These yarns are directly used in warp direction during
weaving. Further, these same yarns were plied into two ply and twisted to obtained linear
density of 552 tex (16 lbs/spy). This 2 ply is use as weft yarn during weaving of blanket. Both
these warp and weft yarns were chemically texturized separately using standard procedure
[10] and further dyed in dark shade (Figure 3). The yarns were finished as per standard
method to obtain melange effect. Jute-hollow polyester (80:20) blended yarns were used to
weave into fabric (2/2 twill) with 276 tex (8 lbs/spy) single yarn in weft direction (18-20
picks/inch). In warp direction, 276 tex (8 lbs/spy) 2-ply yarn (9-10 ends/inch) was used [22].
Normally, it is recommended that a reed width of more than 78 is essential for weaving of
blanket fabric, considering the loom stage shrinkage. It has been found from the literature that
80:20 jute-PET blended blanket and 100% woollen blanket are having thermal insulation
values (TIV) of 0.78 tog and 0.86 tog respectively [23]. Performance and cost wise jutehollow polyester (80:20) blended raised blanket and 90:10 raised blanket is lower (Rs.295/-)
compared to commercial woollen (Rs.450/-) and acrylic (Rs.825/-) blankets [23].
Figure 3. Blanket from chemically texturized jute-hollow polyester blended yarns.
SPINNING OF JUTE-BASED BLENDED FINE YARN FOR WARM CLOTHS

In case of apparels, wherein person has to wear it or wrap it around the body it is
essential to have the fabrics as light as possible. The final weight of the fabric for the
aforesaid purpose has to be reduced, so very fine yarn of 122 tex has been developed using
jute spinning system. The polyester (hollow) fibre of 6 denier, 110 mm is used to develop the
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Sanjoy Debnath
yarn for the warm cloth weaving. Jute-hollow fibre blended yarn has higher bulk density
compared to other blended yarns [24, 25]. The conventional jute spinning system is used to
produce blended yarn. The blended yarn of jute and polyester (hollow) fibre was successfully
spun from drawing stage of blending processes. The raw jute of TD-3 was used for
development of overall blended samples. The conventional jute batching oil was used before
piling for 48 hours. The blended yarn samples were produced both with 70:30 and 80:20
jute:polyester fibres [26]. These samples produced from spinning was of 122 tex with 6 t.p.i.
(twist per inch), Z twist. All these blended yarn samples were spun suitably in apron draft
spinning system over slip draft spinning system.
WEAVING OF SHAWL FABRIC FROM VERY FINE YARN

AND CHARACTERISATION
The jute-blended yarn was used as weft yarn and commercial cotton yarn of 5.9 tex (100s
Ne) as warp yarn for development of the shawl fabric. Handloom weaving machine [27] with
jacquard attachment (at least 100 hooks) and handloom preparatory machinery were used to
weave these fabrics. Plain and twill (3/1) are the two basic designs used to weave the fabrics.
For body and border of the shawl separate jacquard weaves were used. Ornamentation was
done with introduction of extra weft yarns [28] (commercial polyester-viscose of 14.7 tex or
40s Ne two ply) at the jacquard design areas on the fabric. Few samples were also developed
using localised dyeing in the warp yarn, giving a Kotkee look (tie-dye) to the fabric. Attempt
was also made to develop fabric with combination of plain and twill weave (Figure 4). The
developed shawl fabrics were characterised and compared with the commercial (khadi) cotton
and acrylic shawls. The fabric weight, fabric thickness, fabric cover factor, thermal insulation
value (tog) and flexural rigidity are the various properties that have been studied using
standard testing methods [29]. The thermal insulation value was studied using the instrument
developed by NIRJAFT [30, 31] where the test is non-destructive in nature.
Figure 4. Shawl from jute-polyester blended and cotton yarns.
507
The fabric weight increases with the increase in pick density for both the plain and twill
weaves [2]. The fabric weight is between 147 and 160 g/m2 for commercial fabrics under
consideration. However, the fabric weight of the developed fabric ranges between 169 and
263 g/m2. Both the thickness and thermal resistance values of the developed jute blended
fabric samples are closer to that of cotton/acrylic commercial shawl fabrics. The cloth cover
factor was also higher compared to commercial shawl fabrics (cotton/acrylic). The flexural
rigidity in warp direction of the developed fabrics is comparatively lower than the
cotton/acrylic fabrics due to use of very fine cotton yarn in warp direction (5.9 tex). Jute has
higher rigidity due to its coarseness, so when it is used in the weft direction of the jute
blended fabric, a tremendous increase in flexural rigidity in weft direction is observed in the
developed fabrics. It also increases with the increase in pick density of the fabric.
Few fabrics were developed where slit film were used alternately in weft direction along
with jute-polyester blended yarn. The fabric weight is between 147 and 160 g/m2 for
commercial fabrics under consideration. However, the fabric weight of the developed
lightweight shawl fabrics ranges between 136 and 162 g/m2. The thickness values of the
developed shawls are closer to cotton shawls but lower than acrylic shawls. Cover factor
values of the developed shawls are between 17 and 20 (which, is between the cover factor
values of commercial acrylic and cotton shawls). The thermal resistance values of the
developed jute blended fabric samples are 19% higher compared to acrylic and 66% higher
compared to cotton commercial shawl fabrics [32]. These developed shawl fabrics are moreor-less equally porous compared to commercial shawls under consideration as per as the
sectional air permeability is concerned.
The tenacity and breaking extension behaviour of the developed jute blended shawls and
compared with the commercial cotton and acrylic shawls both in warp and weft directions.
The tenacity values of the jute-blended shawls are closer to that of cotton shawls and lower
than acrylic shawls in warp direction. However, in weft direction, tenacity is little higher than
cotton and closer to acrylic shawls. Breaking extension values of the developed shawls are
much lesser than acrylic or cotton shawls both in warp and weft directions of the fabric
samples [31].
The effect of washing (after five-repeated detergent washing) on tensile and air
permeability property of jute-polyester and cotton blended shawls and compared with their
original values (before washing). This study reveals though there is little drop in tenacity after
wash in warp direction (cotton yarns) but no change have been found in weft direction (jutepolyester blended yarns). Little improvement in extension have been observed in weft
direction. There is a fall in flexural rigidity values in warp direction and an increase in trend
was found in weft direction after washing treatment. A significant drop in sectional air
permeability was observed after washing of the developed shawl samples [31].
Jacket from Jute-Based Yarn and Evaluation

Jackets have been developed using handloom to weave winter fabric. Three different
types of jute-polyester and cotton blended jacket fabrics have been developed. Handloom
jacquard has been used to introduce design in the fabric during weaving. The jute-blended
yarn and commercial cotton yarn were used alternately as weft and commercial cotton yarn of
5.9 tex (100s Ne) was used as warp for development of the jacket fabric of 136 g/m2. For
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Sanjoy Debnath
other two fabrics, in warp direction, cotton yarns were dyed in dark blue shade. In weft
direction alternate use of cotton and jute-blended yarn improves the fabric appearance and
other physical properties (Figure 5).
Figure 5. Jacket from jute-based jacket fabric.
The fabric weight and thermal insulation values were measured for the developed fabrics
and compared with the commercial (khadi) cotton and acrylic jacket fabrics. The developed
jacket fabric shows 30 % and 62 % higher thermal insulation value compared to commercial
acrylic and cotton jacket fabrics respectively. This developed fabric is also 8 % and 17 %
lighter in weight compared to commercial acrylic and cotton jacket fabrics respectively. The
fabric thickness of the developed jute based fabric is 47% and 19% lower compared to
commercial acrylic and cotton jacket fabrics respectively [32]. Alternate use of jute-polyester
and cotton yarn in weft direction has been used to improve the aesthetic and physical
properties of developed fabrics.
Other four different types of jackets have been tailored using these developed jacket
fabrics. Other than zip, buttons and sewing yarn, all these developed jackets comprise of three
basic materials: a) jacket fabric; b) lamination material and c) lining material. In one case the
lining material for developed jacket used as acrylic fabric and rest of the cases polyester
lining material have been used. Out of all these jackets, one reversible jacket has been
developed using developed jacket fabric.
Weight, thermal insulation and thickness properties of the developed jute-blended jackets
have been evaluated and compared with commercial jacket (Oswal make). It is found that
overall the thermal insulation of the developed jackets are higher than commercial jackets
(Anonymous, 2008). The thermal insulation of jackets can be lower or higher depending on
the constructional design of the jacket fabric and lining material of the jacket. The weight of
the jackets depend on the design of the jacket fabric and jacket type. Thickness values of all
developed jackets except those of reversible ones, are lower than commercial jacket (Oswal
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make). Apart from these no dimensional changes of jackets have been observed after one cold
water detergent wash.
Thermal Insulation Behaviour of Jute-Based Nonwoven Fabrics

Different types of parallel laid and random laid needle punched and adhesive bonded
nonwoven fabrics were prepared using blending of different fibre materials (polypropylene,
acrylic, jute, woollenised jute, jute caddis, cotton, wool, ramie, pineapple leaf fibres etc.).
Two types of blending methods were used such as sandwich and homogeneous. Sandwich
blending of polypropylene or acrylic with woollenised jute shows better thermal insulation
compare to homogeneous blended materials as found by Debnath et al., 1987 [3].
They also found that nonwoven prepared out of woollenised jute-wool (2:1), woollenised
jute-acrylic (2:1) and woollenised jute-pineapple leaf fibre (2:1) have better thermal
insulation property. Air permeability and thermal conductivity of jute needle-punched
nonwoven fabrics have been studied by Sengupta et al., 1985 [33] and found that jute needle
punched nonwoven has poor in heat transmission. Further, Box and Behnken factorial design
[34] was used to design and development of needle-punched nonwoven fabrics made from
jute and polypropylene blends to study the effect of fabric weight, needling density and blend
proportion on thickness, thermal resistance, specific thermal resistance, air permeability and
sectional air permeability. Polypropylene fibre of 0.44 tex fineness, 80 mm length and jute
fibres of Tossa-4 grade were used to develop the jute-polypropylene blended needle-punched
nonwoven [35]. Some of the important properties of these jute and polypropylene fibres are
presented in the Table 3.
Table 3. Properties of jute and polypropylene fibres [35]
Property
Fibre fineness, tex
Density, g/cm3
Moisture regain at 65% RH, %
Tensile strength, cN/tex
Breaking elongation, %
Jute
2.08
1.45
12.5
30.1
1.55
Polypropylene
0.44
0.92
0.05
34.5
54.13
PREPARATION OF JUTE-POLYPROPYLENE BLENDED THERMAL

INSULATION NONWOVEN FABRICS
The jute reeds were opened in a roller and clearer card, which produces almost mesh-free
stapled fibre. The woollenised jute and polypropylene fibres were hand opened separately and
then blended using three different blend proportions (Table 4). The proportion of woollenised
jute fibres taken is 2% higher than the blends showcased in Table 4 considering droppings of
jute component [35] in the card and subsequent processes to maintain target blend in the
output material. The blended materials were thoroughly opened by passing them through one
carding passage.
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Sanjoy Debnath
Table 4. Actual and coded values for three independent variables and the experimental
design [35]
Levels of variables
Fabric code
X1 level
Coded
Actual
Coded
Actual
Coded
Actual
250
150
60 : 40
250
350
60 : 40
450
150
60 : 40
450
350
60 : 40
250
250
40 : 60
250
250
80 : 20
450
250
40 : 60
450
250
80 : 20
350
150
40 : 60
10
350
150
80 : 20
11
350
350
40 : 60
12
350
350
80 : 20
13
350
250
60 : 40
14
350
250
60 : 40
15
350
250
60 : 40
X2 level
X3 level
X1 Fabric weight, g/m2; X2 Needling density, punches/cm2; and X3 Blend ratio (polypropylene:
woollenised jute).
The blended fibres were then fed to the lattice of the roller and clearer card at a uniform
and predetermined rate so that a web of 50 g/m2 can be achieved. The fibrous web coming out
from the card was fed to feed lattice of cross-lapper, and cross-laid webs were produced with
cross-lapping angle of 20. The web was then fed to the needling zone. The required needling
density was obtained by adjusting the throughput speed [36].
As per the fabric weight (g/m2) requirement, certain number of webs were taken and
passed through the needling zone of the machine for a number of times, depending upon the
punch density required. A punch density of 50 punches/cm2 was applied on each passage of
the webs reversing the face of the web alternatively [36]. The fabric samples were produced
as per the coded and actual levels of three variables (Table 4).
The depth of needle penetration was kept constant at 11 mm. For all webs, 15 18 36
R/SP, 3 9 needles were used.
Evaluation of Thermal Insulation and Resistance

The thermal insulation and resistance can be tested by using appropriate thermal
insulation and resistance tester. The conventional Marsh method and guarded two plate
511
method are more popular methods of measuring thermal insulation behaviour of textile
fabrics.
The thermal resistance (TRs) of jute-polypropylene blended needle-punched nonwoven
fabrics was measured using guarded two-plate thermal resistance instrument [30]. This
instrument [30,31,35] (Figure 6) is based on a microprocessor and provides automatic results
of thermal resistance value. The area of the test specimen used is 706.85 cm2 (diameter 30
cm). The test is non-destructive and process of preparation of sample is free from human
error. TRs of each fabric sample was measured randomly at five different places under a
pressure of 0.3352 kPa.
Average of five readings was considered and the coefficient of variation of readings was
2%. Specific thermal resistance (STRs) value was used to compare the thermal resistance of
different fabric samples. STRs values of all the samples were determined using the following
equation [35, 31]:
STRs
TRs
T0
(1)
where STRs is the specific thermal resistance in K m/W; TRs, the thermal resistance value of
fabric in K m2/W; and T0, the mean thickness in meter at 1.55 kPa pressure of the fabric
sample.
Figure 6. NIRJAFT thermal resistance instrument.
EFFECT OF FABRIC WEIGHT, NEEDLING DENSITY AND BLEND

PROPORTION OF JUTE-POLYPROPYLENE BLENDED
NEEDLE-PUNCHED NONWOVEN ON THERMAL RESISTANCE
It is found that the thermal resistance increases with the increase in fabric weight [35].
This can be supported by the existence of significant (p < 0.05000) positive correlation (r =
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Sanjoy Debnath
0.82) between fabric weight and thermal resistance, as observed from the correlation matrix
(Table 3). With the increase in fabric weight, thermal resistance increases more prominently
at lower needling density (150 punches/cm2), but its effect is negligible at higher needling
density (350 punches/cm2). However, at 40% and 60% jute content levels, the effect of fabric
weight on thermal resistance is almost similar at all needling densities between 150
punches/cm2 and 350 punches/cm2. The highest thermal resistance of 8.5 102 K m2/W has
been obtained at 430 g/m2 fabric weight and 150 punches/cm2 needling density for 40% jute
content level [34]. With the increase in fabric weight, the number of fibres per unit area of the
fabric increases. This causes increases in fabric thickness and also amount of pores in the
fabric structure, causing increase in thermal resistance. However, with the increase in
needling density, thermal resistance decreases because the fabric structure tends towards
higher degree of consolidation and hence reduces amount of pores in the structure. This can
also be supported by significant (p < 0.05000) negative correlation which exists between
needling density and thermal resistance (r = 0.67), as observed from the correlation matrix
(Table 5).
Thermal resistance = 4.0520833 0.0114167X1 0.0007917X2 +
0.0558333X3 0.0000079X12 0.0000104X22 0.0021979X32 +
0.0000250X1X2 0.0002125X1X3 0.0001X2X3 (R=0.9002; F9,5=15.04) ...
(2)
Table 5. Correlation matrix of variables

Variables
FW
J%
TRs
STRs
AP
SAP
FW
N
J%
T
TRs
1.00
0.00
0.00
0.05
0.51
1.00
0.00
0.49
*
0.67
0.00
0.00
1.00
0.39
0.26
0.50
0.49
0.39
1.00
0.82*
0.51
0.67*
0.26
0.82*
1.00
0.28
0.61*
0.02
0.29
0.78*
0.93*
0.11
0.19
0.36
0.37
0.75*
0.33
0.43
0.08
0.02
*
1.00
0.22
0.11
0.02
0.29
0.78*
0.61
*
*
AP
0.93
0.11
0.19
0.36
0.37
0.22
1.00
0.89
*
*
SAP
0.75
0.33
0.43
0.08
0.02
0.11
0.89
1.00
FW Fabric weight, g/m2; N Needling density, punches/cm2; J% Jute proportion, T0 Fabric
thickness, cm; TRs Thermal resistance 102, K m2/W; STRs Specific thermal resistance,
K m/W; AP Air permeability, cm3/cm2/s; SAP Sectional air permeability, cm3/s/cm.
*
Correlations are significant at p < 0.05000.
STRs
0.28
EFFECT OF FABRIC WEIGHT, NEEDLING DENSITY AND BLEND

PROPORTION OF JUTE-POLYPROPYLENE BLENDED
NEEDLE-PUNCHED NONWOVEN ON SPECIFIC THERMAL RESISTANCE
This study show the effect of fabric weight and needling density on specific thermal
resistance at the jute content levels of 20%, 40% and 60% respectively (Figure 7). It is found
that the specific thermal resistance decreases with the increase in needling density,
irrespective of the blend composition in jute-polypropylene blend [35]. Also, a significant (p
513
< 0.05000) negative correlation (r = 0.61) has been found between needling density and
specific thermal resistance, as observed from the correlation matrix (Table 5). This is due to
the formation of consolidated structure with the increase in needling density. The number of
fibres per unit area increases with the increase in fabric weight. This generates more air
pockets per unit thickness of the fabric apart from better entanglement, resulting in increase
of specific thermal resistance. The specific thermal resistance value initially increases up to
375 g/m2 fabric weight and thereafter it decreases, with the increase in fabric weight at 40%
jute content and higher needling density (350 punches/cm2) levels [35] as observed form
Figure 7a. The similar phenomenon has also been observed at higher jute content level (60%)
but the decrease in trend of specific thermal resistance occurs at lower fabric weight (325
g/m2) as obtained from Figure 7b.
Figure 7. Effect of fabric weight and needling density on specific thermal resistance at (a) 20% jute, (b)
40% jute and (c) 60% jute content levels [26].
Jute can easily form consolidated structure due to its poor resilience compared to
polypropylene fibre. Hence, at higher needling density and jute content levels, the fabric
consolidation initially improves and beyond certain fabric weight (325 g/m2) the bulkiness
increases. With the increase in fabric weight, more number of fibres will be available to the
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Sanjoy Debnath
needle barb during needling. Beyond certain level (325 g/m2) of fabric weight, the increasing
amount of fibres at the same needling density and needle barb is insufficient to form better
entanglement, resulting in poor consolidation. Hence, at higher jute content level (60%), the
fabric consolidation occurs at lower level of fabric weight (325 g/m2) as found from Figure
7c, compared to that at 40% jute content level [35, 36]. However, highest specific thermal
resistance of 20.6 K m/W is observed at 150 punches/cm2 needling density and 400-450 g/m2
fabric weight for 40% jute content in jute-polypropylene blended needle-punched nonwoven
(Figure 7a, 7b and 7c).
Specific thermal resistance= 2.3122917 + 0.0612292X1 0.0160917X2 +
0.5955833X3 0.0000490X12 + 0.0000452X22 0.0056073X32 0.0000365X1X2
0.0002725X1X3 0.0002163X2X3 (R=0.9327; F9,5=7.69) ...
(3)
MEASUREMENT OF THERMAL INSULATION VALUE AND

COMPARATIVE STUDY OF DIFFERENT JUTE BASED MATERIALS
Paul and Mukhopadhyay, 1977 used a simple method to measure the thermal insulation
value of different textile materials based on jute and cotton fibres [37]. The methods which
are commonly used for measurement of thermal insulation value are the disc method, the
constant temperature method and cooling method. Out of these three methods, cooling
method is the simplest compared to other two methods. In this method of measurement of
thermal insulation, a hot body is wrapped with the fabric and its rate of cooling is measured.
The outer side of the fabric is exposed to air. In this experiment, the time taken by a hot body
covered with the fabric sample (tc) and without the sample (tu) to cool through a particular
temperature range under identical atmospheric conditions.
To measure the thermal insulation with this method, a brass cylinder (45 cm length, 5 cm
external diameter and 2 mm thickness) closed at one end with a cork was filled with distilled
water heated to about 50C. The mouth of the cylinder was closed with a cork through which
a thermometer was inserted. To simulate the actual condition, a wire mesh has been wrapped
on the surface of the cylinder to obtain a clearance of 2 mm between fabric sample and brass
cylinder. A rectangular specimen of the fabric was used to cover the entire outer surface of
the brass tube. The length-wise edges of the specimen were made to touch each other closely
avoiding overlapping and kept in position by using cello-tape over the joint running parallel
to the length of the cylinder.
The experiment was started when the temperature of the water was exactly 48C. A stop
watch was used to find the time taken for the temperature fall at every 1C. A cooling curve
was drawn from these data and the time taken to cool from 48C to 38C was found. The
thermal insulation value (TIV) was calculated by Marsh method is as follows [37, 38]:
TIV = 1
tc
100
tu
(4)
515
where, (tc) is time taken by the covered body to cool through a certain temperature range and
(tu) is time taken by the uncovered body to cool through the same temperature range. They
found that thermal insulation value is related to the thickness of the fabric, the basis
weight(fabric weight) and the number of layers of the fabric [37]. The intra fabric air aspces
and inter space between fabric and body are also important. The thermal insulation value of
the fabric is greater when a non-conducting mesh (polythene) is present between the cylinder
and fabric instead of conducting metal mesh in the same position. Increase in any of these
factors increases the thermal insulation value significantly. There has been marginal effect on
thermal insulation value with varying fabric nature.
CONCLUSION
It is concluded that the thermal insulation of the warm fabric increases significantly after
chemical treatment. The blending with synthetic fibres like acrylic, polypropylene, polyester
improves the thermal insulation apart from appearance. With the change in structural design
of the garment/jacket, the thermal insulation varies widely. Overall, knitting yarn, warm
fabric, warm garments, blankets etc. can be developed from jute-based materials effectively.
These materials are comparable with commercially available similar material out of
synthetic/wool.
It has been established that the thermal insulation value is directly proportional to the
thickness of the fabric, the fabric weight and the number of layers of the fabric present
irrespective to the woven/nonwoven and raw material used to develop the fabric. The air
spaces within the fabric and between the body and fabric are also influence the thermal
insulation of the fabric. The thermal insulation value of the fabric is greater when a nonconducting mesh (polythene) is present between the cylinder and fabric, instead of conducting
metal mesh in the same position.
With regards to the nonwoven material, it has been observed that thermal resistance and
thickness increase but air permeability and sectional air permeability decrease significantly
with the increase in fabric weight at all levels of jute contents. The influence of fabric weight
on thickness is more prominent at 40% and 60% jute content levels than at 20% jute content
level. Both thermal resistance and specific thermal resistance decrease with the increase in
needling density as supported by significant (p < 0.05000) negative correlations r = 0.67
and r = 0.61 respectively. The highest values of thermal resistance and specific thermal
resistance of 8.5 102 K m2/W and 20.6 K m/W respectively are found at 150 punches/cm2
needling density and 430 g/m2 fabric weight for 40% jute content level. Cluster analysis
reveals that the thickness and thermal resistance form a cluster and specific thermal resistance
being sub-cluster depends on them. Thickness, thermal resistance and specific thermal
resistance as dependent variables together form a cluster influenced by jute percentage as an
independent variable. Sectional air permeability among the dependent variables are highly
influenced by fabric weight (Euclidean distance ~ 560) which is a different cluster identity.
This study is useful to develop thermal insulating material for industrial applications from
jute-polypropylene blended needle-punched nonwoven.
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Sanjoy Debnath
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518
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Institute 22(4), T245-273.

ISBN: 978-1-63117-262-5
Chapter 21
EFFECTS OF RING FLANGE TYPE,

TRAVELER WEIGHT AND COATING ON COTTON
YARN PROPERTIES
Muhammet Uzun1,2, and Ismail Usta2
1
Institute for Materials Research and Innovation, University of Bolton, Deane Road, UK
2
Goztepe, Istanbul, Turkey
ABSTRACT
Ring spinning is the most important and effective staple yarn production process. A
ring spinning machine consists of a variety of parts of which rings and travellers are the
dominant elements. This experimental study has highlighted that the ring flanges and the
ring travellers have an effect on the properties of 100% cotton yarn. The interaction
between the yarn quality and the spinning elements has been analysed. Ne 40/1 cotton
yarns were produced by using both flange 1 and flange 2 rings, half round (dr) and flat (f)
profile of ring travellers with four different traveller masses and five different traveller
coatings. 80 copses of yarn were produced by using different process combinations. The
yarn properties were tested in terms of yarn count, yarn twist, irregularity, yarn hairiness,
strength, elongation, spinning tension and balloon angle. As a result, yarn twist and count
decreased with increasing spinning tension. Spinning tension in Flange 1 was greater than
spinning tension in Flange 2. Increasing the spinning tension improved the following
yarn properties; yarn hairiness and yarn twist. The properties of the yarns produced with
Flange 2 show better properties than the yarns produced with Flange 1. Increase in ring
traveller weight also improved the yarn properties.
Keywords: Cotton yarn, Ring spinning, Flange, Traveller, Hairiness, Yarn irregularity
Email: m.uzun@marmara.edu.tr and muzun46@hotmail.com.
520
INTRODUCTION
The main advantages of spinning technology are high productivity, improved yarn
characteristics and special twist-imparting mechanism. In recent years, new yarn spinning
systems have been designed such as open-end rotor, friction, Sirospun, Vortex and compact
spinning. Despite the emergence of new spinning technologies, conventional ring spinning
still remains the most used. This process accounts for 80% of the total staple yarn production
due to its superior yarn properties and wide range of yarn productions. The ring spinning and
traveller system are illustrated in Figure 1 [1-5].
The spinning tension is one of the critical ring spinning parameters which depends
entirely on the ring and the traveller. Some studies aimed to determine the perfect balanced
spinning geometry yet there is still room for improvement to produce yarns with optimum
characteristics. During the production of yarn with ring spinning, the machine parameters
must be taken into consideration. These are traveller weight, traveller and ring geometry,
traveller and ring coating, ring position and traveller drive angle to the ring. An ideal
combination for production would be: higher traveller speed (which means higher
productivity), lower working temperature between ring flange and traveller, extended ring
and traveller usage time, better yarn quality (which means less hairiness), reduction of end
breaks which has negative effect on productivity, and also avoidance of yarn tension peaks
[6-11].
The main conclusion from the previous ring traveller studies show that yarn hairiness can
be reduced by using optimum traveller weights. It has also been observed that yarn hairiness
strongly depends on mean fibre position, with an inward shifting of the packing density
leading to low yarn hairiness [5]. The intervals of helix profiles decreased as the twist
increased, the yarn twist value can affect the mean fibre position and hairiness [12,13].
The main aim of this work is to utilise the ring flanges and travellers for the yarn quality
in terms of hairiness, twist, breaking strength and irregularity. For this purpose, 80 different
combinations were employed to produce yarns. The yarn characteristics were determined by
using standard test methods. The tests aimed to establish the impact of the machine parts on
the quality of cotton yarns. The results were conducted in an attempt to analyse the optimum
production parameters.
Figure 1. Ring and traveller system.
521
Effects of Ring Flange Type
MATERIALS AND METHODS

Materials
The cotton fibre specifications are shown in Table 1. The cotton roving was provided by
Marmaris Iplik Co., Kahramanmaras, Turkey. The roving count was 655tex (Ne0.91) and
irregularity values of 4.8 CV%.
Table 1. Cotton fibre specifications
Cotton fibre
Linear Density
(dtex)
1.7
Mean length
(mm)
28.1
Tenacity
(cN/tex)
17.5
Breaking
elongation (%)
4.9
The ring flanges and travellers were obtained from Temak Textile Machinery
Accessories Industry and Trade Co., Istanbul, Turkey. The ring flange 1 is 3.2mm wide and
flange 2 is 4.1mm wide. C type traveller with half round (dr) and flat (f) profiles with five
different coating types of blacknic (oxidized), bluenic (oxidized), micronic (nickel plated),
silvernic (silver plated) and superpolish (special polished) and four different traveller weights
of 35mg, 40mg, 45mg and 50mg were used in this study.
Methods
Yarn Production
The yarns were produced using a conventional laboratory-type ring spinning machine,
SUESSEN-Ringspinntester, the machine specifications are given in Table 2. The 15tex
(Ne40) yarns were produced with tex40 (e 4.2) twist level and spindle speed 10000rpm.
The yarn production was carried out in a conditioned laboratory at 65 % RH and 200C
atmosphere.
Table 2. Ring machine component specifications
Specifications
Size in mm
Machine size
65019601000
Drafting rollers
28
Front drafting zone
45
Main drafting zone
42
F1-Flange 1 and F2- Flange 2.
Specifications
Spindle length
Tube length
Ring diameter
Flange widths
Size in mm
210
260
50
(F1) 3.2 and (F2) 4.1
The Yarn Physical Properties

The produced yarn samples were tested individually and analysed to provide a
comprehensive understanding of their yarn count, yarn twist, irregularity, yarn hairiness,
strength, elongation, spinning tension and balloon angle. Whole yarn production and tests
were carried out under standard atmosphere condition (200C2 and 65%2 RH) [14].
522

a) Yarn counts: The yarn counts were determined in accordance with TS 244 EN ISO
2060: 1999. The yarn samples were prepared in 100m lengths for each yarn types
and their masses were weighed by using OHAUS balance and the results were
calculated in Ne.
b) Yarn twist: The twists were assessed in accordance with TS 247 EN ISO 2061: 1999,
by using James H. Heal twist counter equipment.
c) Yarn tensile properties: The breaking strength (cN) and elongation (%) properties of
yarns were determined using Instron 4411 with test parameters of 500 mm gauge
length, 10 cN pre-tension, 5 kg load cell with a test speed of 500mm/min [15,16].
d) Yarn irregularity: The irregularity of yarns were characterised by using Uster Tester
I equipment, in accordance with DIN 53817 [17]. The yarn properties obtained were
irregularity CV%, thin places (-50%), thick places (+50%) and neps (+200%) for one
km of yarn.
e) Yarn spinning tension: The aim of this test is to study the influence of the traveller
weight on yarn properties. The tension of yarn spinning was determined between the
end of the drafting system and yarn guide during the production process. The
measurement was performed by using Schmidt ZF2 [18,19].
f) Yarn hairiness: The yarn hairiness was determined by using Shirley Yarn Hairiness
Tester. This equipment can detect over 3mm hairs in the yarn surface over a chosen
period (5 to 40 seconds).
g) Balloon angle: The yarn ballooning angles were photographed during the yarn
production by using a Kodak digital camera. From these pictures the angle values
were calculated manually [19].
RESULTS AND DISCUSSION

The Yarn Physical Properties
a) Yarn Counts
The yarn counts in Ne are given in Figure 2. It can be observed that the counts are
affected by the weight of travellers. The yarns thinned when the travellers weights were 50
mg, for all the coatings.
The differences were less than Ne 0.5. It has been found that the yarns which were
produced by flange 1 were slightly thinner than those produced using flange 2. In general, the
yarn counts ranged from Ne 38.46 to Ne 41.12.
b) Yarn Twist
The number of twists per meter is affected by yarn production tension. The yarn twist
number produced with flange 1 was slightly higher than flange 2, but the differences were
insignificant (Figure 3). In this study, the highest twist number was found to be 1034.8 T/m,
which was produced by using flange 2 and 50 mg traveller weight.
The effect of profile of the travellers on yarn twist was analysed and it was observed that
the flange 2 yarns with dr profile traveller had more twists than flange 1 with dr and f profile
travellers, and also flange 2 with f profile traveller.
523
Yarn Count, Ne
F1-50
F1-45
F1-40
F1-35
F2-50
F2-45
F2-40
F2-35
Traveller profile and coating type

Figure 2. Yarn counts (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
F1-50
F1-45
F1-40
F1-35
Twist, T/m
F2-50
F2-45
F2-40
F2-35

Figure 3. Yarn twists (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
The lowest twist number was for the f type profile. The weight level of the travellers had
a significant effect on the yarn twist for flange 1. When the yarns were produced with heavier
travellers, the twist values increased. The traveller coatings effect on the yarn twist were not
statistically significant.
c) Yarn Breaking Strength and Elongation

The yarn breaking strength is directly dependent on the number of twists per meter in the
yarn. The strength will increase with increasing twist value. The flange 2 yarn breaking
strengths were higher than flange 1s breaking strength. Significant differences were
observed (50 cN) (Figure 4). The highest breaking strength value was demonstrated by flange
2 with 50 mg traveller mass. The traveller profile cross-section also affects the strength and f
profile had higher breaking strength than dr profile. The yarn which was produced by a
superpolish coating and f profile had superior breaking strength compared to other flangecoating-profile combinations. In general, increased traveller weights increases the yarn
strength.
524
Figure 4. Yarn breaking strength (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
Due to the difference in twist, elongation values of flange 2 were found to be higher than
flange 1. The elongations of the yarns were affected by the coating and weight in a variable
way. There was no constant interaction between the coatings and traveller weights. The
breaking elongation ranged from 3.5% to 5.5% (Figure 5). The traveller profiles did not have
a decisive influence on the breaking elongation of yarns. However, flange 2 dr profile did
have the highest elongation value which is about 5.5%.
d) Yarn Irregularity
In general, CV% values of the flange 2 had lower yarn unevenness than flange 1. Flange
1s unevenness was CV% 11 and flange 2s unevenness was CV% 8. The coatings were
found to be significantly important in terms of yarn unevenness (Figure 6). Blacnic and
micronic coatings had less unevenness compared to bluenic, silvernic and superpolish. Only
superpolish had less unevenness with flange 2 and f profile. Increased traveller weights
decreased the yarn unevenness. The minimum unevenness values were observed for flange 2
ring and dr profile traveller with black and micronic coatings.
Elongation, %
F150
F145
F140
F135

Figure 5. Yarn elongation (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
525
Irregularity, CV%
F150
F145
F140
F135

Figure 6. Yarn irregularity (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
The yarn neps decreased with increase in traveller mass. The number of neps in the yarn
varies between flanges. Another important finding of this assay was the effect of traveller
profile. f type traveller had significantly higher number of neps than dr type traveller. There
are no significant differences between the traveller coatings.
e) Yarn Spinning Tension

Yarn spinning tension is one of the important spinning parameters which can directly
affect the quality of yarn. Previous studies on the interaction between the traveller weights
and the spinning tension has confirmed that when the mass of traveller increase, the spinning
tension also increases [6, 18, and 19].
The results from this study confirm the hypothesis (Figure 7). The traveller with 50 mg
weights had the highest spinning tension for all the coating types. Flange 2 had slightly higher
spinning tension compared to flange 1 in some coatings. The spinning tension differences
between coatings are not significantly important.
Spinning tension, cN
F150
F145
F140
F135
F250

Figure 7. Spinning tension (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
f) Yarn Hairiness
In the case of yarn hairiness, the hairiness decreased when the traveller weights were
increased. It is observed that the yarns which were produced by using flange 2 had lower
hairiness value than those produced using flange 1. dr profile traveller caused less hairiness
when used with flange 1. The f profile traveller was effective when used in conjunction with
526
flange 2. The coating types did not affect the yarn hairiness significantly. The hairiness
ranged from 30 to 70 H/m (Figure 8).
Hairiness, H/m
F150
F145
F140
F135
F250
Balloo angle, degree
Figure 8. Yarn hairiness (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
F150
F145
F140
F135
Figure 9. Balloon angle (dr: Half round, f: Flat, F1: Flange 1, F2: Flange 2).
g) Balloon Angle
It was found from the statistical analyses that the balloon angle decreased with increased
traveller weight. Figure 9 shows the relationship between the traveller weight and the
spinning balloon angles. In this study, the angle of the spinning balloon decreases when the
travellers with an increase in weight was due to the increase in tension values. In general,
most types of coatings produced with flange 1 had higher balloon angle than flange 2.
Statistical Analysis
Variance analysis has been applied to check whether the results obtained are important
statistically.
The tests of significance were made at 95% and 99% confidence limits. Yarn properties
were investigated by two-way variance analysis depending on the traveller weight and coating
type. All the analysis results are given in Table 3.
527

Table 3. Variance analysis of yarn properties with
different traveller weight and coating
Properties
Yarn count
Variation
Sources
Traveller weight
Traveller coating
Flange 1
Traveller profile
dr
f
0.05
0.01
0.05
0.01
ns
ns
ns
ns
ns
ns
ns
ns
Traveller weight
ns
Traveller coating
ns
Yarn
Traveller weight
ns
strength
Traveller coating
s
Traveller weight
s
Elongation
Traveller coating
s
Traveller weight
s
Irregularity
Traveller coating
s
Spinning
Traveller weight
s
tension
Traveller coating
s
Traveller weight
ns
Hairiness
Traveller coating
s
Balloon
Traveller weight
s
angle
Traveller coating
s
s significant, and ns not significant.
Yarn Twist
ns
ns
ns
s
s
s
ns
ns
s
s
ns
s
s
s
ns
ns
ns
ns
ns
ns
ns
ns
s
s
ns
ns
s
s
ns
ns
ns
ns
ns
ns
ns
ns
s
s
ns
ns
s
s
Flange 2
Traveller profile
dr
f
0.05
0.01
0.05
0.01
ns
ns
ns
ns
ns
ns
s
s
ns
ns
ns
ns
ns
ns
ns
s
s
s
s
s
ns
s
ns
ns
ns
ns
ns
ns
ns
s
s
s
s
s
ns
ns
s
ns
ns
s
s
ns
ns
s
s
s
ns
ns
s
ns
s
ns
ns
ns
ns
ns
ns
s
s
s
ns
ns
s
ns
When Table 3 is examined, it can be clearly seen that traveller weight and coating have
an important effect on spinning tension in both significance levels. Balloon angle effect from
traveller weight and coating is important in flange 1 in both significance levels. Traveller
weight has not important effect on yarn count and yarn strength. Also traveller coating has not
important effect on yarn twist. Except flange 2 with f profile, traveller coating has not
important effect on yarn count. Except flange 2 with f profile, traveller weight has not
important effect on yarn twist. Traveller coating has an important effect in flange 1 with dr
profile. Yarn elongation effect from traveller weight and coating is important in flange 1 with
dr profile. Traveller coating has an important effect on yarn irregularity in flange 2 with dr
and f profiles. Yarn hairiness effect from traveller coating is important in dr profile with both
flange 1 and flange 2.
CONCLUSION
In order to define the relationship between the physical properties of the yarn and the
production process, it is considered that the usage of flange 2 has some advantages over
flange 1. In this study demonstrated that the traveller weight and yarn spinning tension are
important production parameters.
From the results and discussion of this study it can be concluded that the yarns produced
with flange 1 are slightly finer than flange 2, yet for most of the yarn this was not found to be
of a significant level. It was significant only for f profile travellers. Except flange 2 with f
profile, the traveller coatings did not have any important effect on the yarn counts.
528
The observed twist values of flange 1 and flange 2 were very similar. The highest twist
number(T/m) was found in the yarn that was manufactured by using flange 2 with a traveller
weight of 50 mg. Traveller profile had a variable effect on the yarn twist. Flange 2 with dr
profile traveller had higher twists in general. When the traveller weight was increased, the
twist value also increases.
In general, flange 2s breaking strengths were more than flange 1s breaking strength, and
the differences were of a significant level (50 cN). The highest breaking value was
demonstrated by flange 2 ring and 50 mg travellers. The yarn which was produced using the
superpolish coated f profile traveller had superior breaking strength compared to the other
combinations.
Yarn elongation was affected by the coating and weight in a variety of ways. The
traveller profiles did not have a decisive influence on the yarn elongation behaviour.
For most of the combinations, flange 2 had much lower yarn irregularity than flange 1.
Flange 1s irregularity was 11 CV% and flange 2s irregularity was 8 CV%. The coatings had
a considerable effect on the yarn irregularity.
The yarn spinning tension of this study was found to be similar to the previous studies.
When the traveller weight increased, the spinning tension increases. Flange 2 had slightly
higher spinning tension compared to flange 1. The coatings have important affect in the
spinning tension.
The yarn hairiness decreased with increased traveller weight and yarns produced using
flange 2 had less hairiness than those produced using flange 1.
The balloon angle changed with traveller weight changes, higher the traveller weight
lower the lower angle.
ACKNOWLEDGMENTS
The authors are thankful to Marmaris Iplik Co., Kahramanmaras, Turkey and Temak
Textile Machinery Accessories Industry and Trade Co., Istanbul, Turkey for their support
during this research.
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ASTM (D-1776-90), Standard Practice for Conditioning Textiles for Testing.
American Society for Testing and Materials, West Conshohocken, PA, 483-446.
Uzun, M., Patel, I. (2010). Mechanical properties of ultrasonic washed organic and
traditional cotton yarns. Journal of Achievements in Materials and Manufacturing
Engineering, 43/2, 608-612.
TS EN ISO 2062: 2010.
DIN 53817-1, (1981). Testing of Textiles; Determination of Unevenness of Slivers and
Yarns Deutsches Institut Fr Normung.
Demir, A., (1990). plik Gerginliinin nem ve lm, Blm 3: plik lmlerinin
Uygulamalar. Tekstil & Teknik, 94-99.
Usta, I. (2008). Effect of Balloon Angle on the Hairiness and other Yarn Properties of
Polyester Ring Spun Yarn. Fibres&Textiles in Eastenr Europe, 70, 40-47.

ISBN: 978-1-63117-262-5
Chapter 22
OPTICAL FIBER EXAMINATION BY

CONFOCAL LASER SCANNING MICROSCOPY
Andrea Ehrmann
Niederrhein University of Applied Sciences, Faculty of
Textile and Clothing Technology, Moenchengladbach, Germany
ABSTRACT
Confocal laser scanning microscopy (CLSM) is a microscopy technique which can
be used to obtain high-resolution optical pictures. By acquiring images from a series of
depth layers using a focused laser beam, a computer program can be used to reconstruct a
three-dimensional picture of a sample surface. This technique is on the one hand similar
to a scanning electron microscope (SEM); on the other hand, a CLSM needs no
introduction of samples into a vacuum chamber. The lateral resolution of a CLSM of
about 150 nm is most often sufficient to examine textile fibers, e.g., to distinguish
between different natural and man-made fibers as well as between different natural fibers.
This chapter will give an introduction into the technique of confocal laser scanning
microscopy and depict optical differences between several textile fibers, enabling a nondestructive examination of natural and chemical fibers.
INTRODUCTION
The resolution of optical microscopes is limited by the wavelengths of the visible light
spectrum, resulting in maximal resolutions of around 1 micron (i.e., 0.001 mm). Scanning
electron microscopes (SEM) can have resolutions in the order of 1 nm (0.001 micron);
however, they mostly require some sample preparation, such as sputtering a thin conductive
film on the surface, and samples are normally introduced into a vacuum chamber for
measurement.
Corresponding author: Andrea Ehrmann. Niederrhein University of Applied Sciences, Faculty of Textile and
Clothing Technology, Webschulstr. 31, 41065 Moenchengladbach, Germany. E-mail: andrea-ehrmann@gmx.
de.
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Andrea Ehrmann
For non-invasive examination of samples which require a higher resolution than possible
in optical microscopes, but should be measured without pretreatment (especially valid for
biological samples), a confocal laser scanning microscope can be the ideal solution.
The method of confocal laser scanning microscopy (CLSM) was patented by Marvin
Minsky, who needed to make real-time microscopic pictures of living systems, in 1961 [1]. It
tries to overcome the resolution limits of wide-field optical microscopy and additionally
enables seeing through semi-transparent sample parts into defined depths. After the first
confocal microscope built by Egger and Petran in the late 1960s, the development of CLSMs
was supported by advances in laser and computer technology, until in the late 1980s the first
commercial instruments became available [2].
The principle setup of confocal laser scanning microscopes is depicted in Figure 1. A
coherent laser beam is emitted through a pinhole and a lens onto a sample surface. The
reflected beams can only pass the second pinhole if both pinholes are in conjugate planes, i.e.,
confocal. This leads to elimination of out-of-focus signals (dotted line in Figure 1) as well as
of stray light. Refocusing of the microscopes objective results in a new plane of the sample
under examination being confocal with the pinhole planes and thus becoming visible in the
photo-detector.
In contrast, a sample examined by optical wide-field microscopy is evenly lit in all focal
planes, leading to a large unfocused background in the camera or photo-detector of a digital
microscope or in the users eye for an analog microscope, respectively.
While a usual optical microscopes lateral resolution can be calculated due to the
Rayleigh criterion as ropt = 0.6 / NA (with the light wavelength and the numerical aperture
of the objective lens NA), experimental investigations of CLSMs show that this value is
reduced to rCLSM = 0.4 / NA in confocal microscopes. With ultraviolet laser light (e.g., 408
nm wavelength [3]) and numerical apertures next to 1 (e.g., 0.95 for the highest-resolution
objectives [3]), resolutions of 170 nm are possible.
After [1], modified.

Figure 1. Principal sketch of a confocal microscope.
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While the confocal technique can significantly enhance the optical resolution by deleting
undesirable light from other focal planes, the elimination of large parts of the light by the
pinhole also results in longer measurement times. For each experiment, resolution and
exposure time have to be balanced according to the demands of the respective analysis.
Scanning the sample happens via the scan head which rasterizes the scans and collects the
signals from the sample in a CCD camera or a photomultiplier. The scan head contains inputs
from the laser sources by a fiber optic coupler, normally followed by a beam expander
leading to the laser beam filling the complete objective rear aperture, dichromatic mirrors, a
scanning system for x- and y-direction, variable pinhole apertures to generate the confocal
image, and a light detector [2].
Beam scanning can happen via two different techniques: Most CLSMs use single-beam
scanning, working with a pair of computer-controlled galvanometer mirrors which let the
laser beam scan the sample in a raster pattern. However, if faster scanning rates are desired
for real-time videos of living systems, a spinning Nipkow disk with an array of pinholes and
micro-lenses can be used instead.
In these multiple-beam systems, arc-discharge lamps can replace the laser to reduce
possible damage of the sample. Such microscopes can capture complete images with an array
detector, such as a CCD camera.
The aperture in front of the detector can contain pinholes of different diameters in a
rotating disk, allowing for adjustment of the focal plane thickness by the pinhole size. The
illumination spot on the sample, which is in the order of magnitude of 0.1 to 1 micron, is
defined by the numerical aperture of the objective [2].
Some CLSMs use a white light source additional to a short-wavelength (ultraviolet) laser.
While the laser light creates a high-resolution grayscale picture, as described above, the white
light produces a colored picture with lower resolution, showing the real colors of the observed
object. Superposing both pictures results in a high-resolution colored picture [3].
Other CLSMs allow for fluorescence pictures of biological samples. For this purpose,
multi-wavelength laser systems for ultraviolet, visible, and near-infrared spectral regions,
enhanced interference filters and sensitive low-noise wide-band detectors are of special
interest [2].
The software packages belonging to a commercial CLSM are normally able to generate
three-dimensional views of the sample under investigation, including the possibility of
measuring the depth of sample features or depicting the surface roughness by false color
representation.
EXPERIMENTAL
Several natural and chemical fibers used in the textile industry have been examined by
CLSM, giving rise to differences in the surface structure, allowing for differentiation between
natural and chemical fibers, on the one hand, but also between different kinds of wool etc.
Sometimes, the results of chemical or physical treatment are also visible, which is shown here
exemplarily by a chemical treatment of hemp and a laser-treated polyester fiber.
All microscopic images in this chapter have been taken with the microscope VK-9700 by
Keyence.
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Andrea Ehrmann
Figure 2. Overview on VK-9700 by Keyence (left panel); objectives with 20 x, 50 x, and 100 x
magnification (right panel).
Figure 2 (left panel) gives an overview on the CLSM system used for the microscopic
pictures in this chapter. The display on the left side shows the results of the measurements
performed with the laser head and the objective system on the right side. The objectives
(Figure 2, right panel) can be rotated to change the magnification and can be completely
exchanged.
Figure 3 shows the software front panel which is used to setup the CLSM. Firstly, the
software is switched to Camera to search the height area in which parts of the picture are
sharp. This area defines the measurement range, set by the values for the upper and lower
position of the motor stages. An auto gain allows for taking photographs which are neither
too dark nor too bright. The Z pitch defines the steps for the movement of the laser head
relative to the sample. The duration of taking one photograph can vary between a few seconds
(for rather flat samples, high Z pitch and low resolution) and ten or twenty minutes for rough
samples, low Z pitch and high resolution.
A special feature of the VK-9700 by Keyence is the possibility to superpose the laser
intensity with a color picture with lower resolution, which adds real colors to the sharp laser
intensity picture.
Most images in this chapter have been taken using an objective with 50 x magnification,
corresponding to a nominal magnification (on a 15 display) of 1000 x. That means each
microscopic picture (besides Figure 4) in this chapter shows an area of 202 m x 270 m.
These values can be extended to a magnification of 15 x / 3000 x by changing the
objective. Additionally, an optical zoom can add up to 6 x magnification, resulting in a
maximum nominal magnification of 18,000 x.
Opposite to a digital zoom, this optical zoom does not decrease the resolution, but can
really add more information. Since the optical zoom is not connected with a change of the
lenses, it can be very helpful, especially for investigations of fibers which may be touched
during a rotation of the objective system.
For comparison, Figure 4 depicts microscopic images of wool fibers with nominal
magnifications of 1000 x (left panel) and 3000 x (right panel). The typical scales on the fibers
are clearly visible in both pictures.
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Figure 3. The software used to control the CLSM allows for several adjustments, dependent on the
respective sample to be examined.
Figure 4. Wool fibers, microscopic images with nominal magnifications of 1000 x (left panel) and 3000
x (right panel).
Since the working distance for the objective with highest magnification is only ~ 0.2 mm,
fiber examinations can be performed more easily with a lower resolution. As Figure 4 shows,
it is often sufficient to work with a nominal magnification of 1000 x; otherwise, the optical
zoom can be used to enlarge the magnification.
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Andrea Ehrmann
Figure 5. Report with line measurement of the height of the wool scales.
Nevertheless, higher resolutions can be very helpful for more exact measurements, e.g.,
of the height of the scales on wool fibers. In Figure 5, a line measurement of this scale height
is depicted, performed on the microscopic image shown in Figure 4 (right panel). The
precision of measurements in lateral direction (i.e., in the sample plane) is defined by the
resolution of the microscopic image, while for measurements in z-direction (i.e.,
perpendicular to the sample plane) the Z pitch also influences the possible measurement
precision. Depending on the desired accuracy in distance measurements, it might be
supportive to enhance the magnification and / or the Z pitch, the latter resulting in more
images taken in different heights and correspondingly longer measurement times. After this
short introduction into the technique of CLSM, the next sub-chapters will give an overview of
different natural and man-made fibers and possibilities of differentiation between them.
ANIMAL FIBERS
Animal fibers, e.g., wool, silk, cashmere wool, mohair, angora, but also not commercially
used hair of dog, cat, wild pig etc. or feathers, consist mostly of proteins. In mass production,
sheep wool and silk are used most often, but alpaca or mohair are also quite common.
537
Figure 6. Undercoat (short hair lying underneath the longer outer hair) of dog (left panel) and guard hair
(hair on top) of wild pig (right panel). The magnification is identical for both pictures.
Differences in the fiber structure and surface (length, thickness, crimp, scale) define the
properties of the yarns and textiles produced from these fibers. Thus, microscopic pictures
can be a tool to distinguish between different animal fibers not only between, e.g., silk and
wool, but also between different sorts of sheep wool.
In Figure 6, undercoat of a dog and guard hair of a wild pig are shown. Compared with
the wool fibers in Figure 4 (left panel), both sorts of hair have a larger diameter. The scale
structure of the dog undercoat differs significantly from sheep wool, the latter having larger,
higher and more clearly defined scales. The wild pig guard hair, however, shows a
significantly larger diameter, with several well-defined scales positioned side by side on the
surface, opposite to sheep wool which mostly shows one or two scales on one circumference.
Apparently, distinguishing between different animals is possible with CLSM, if a reference
database is available. But can confocal microscopy also help in differentiating between, e.g.,
the wool of different sheep?
One of the properties which can often be used to distinguish between different fibers is
the fiber diameter. In Figure 7, microscopic images of the wool of a mountain sheep and a
Texel sheep are shown, both photographs taken with the same magnification. The difference
in the diameters of both sorts of wool is obvious.
Additionally, the forms and dimensions of the scales can support differentiation between
both types of wool. While the mountain sheep wool has irregular scales, partly forming
spikes and having similar heights and widths (left panel), the Texel sheep wool shows more
rounded scales which are mostly less high than wide (right panel). Moreover, the Texel sheep
wool shows several dot-like hills, additional to the scale structure (right panel), which is
significantly less pronounced in the picture of the mountain sheep wool. Such sub-structures,
however, must be treated carefully, since they might arise from contaminations with other
materials since the CLSM is not element-sensitive, only the color of such features can give
a hint about their nature. The final decision whether small structures are a basic part of a
certain sort of fiber, or if some impurities become visible in the CLSM pictures, is often up to
the experimentalists experience.
A simpler, but also more common question deals with fiber blends. Especially for
financial reasons, fiber blends may be declared incorrectly. Figure 8 shows microscopic
pictures of a fabric which has been declared to consist of 100 % finest wool.
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Andrea Ehrmann
Figure 7. Wool of mountain sheep (left panel) and Texel sheep (right panel), microscopic images both
taken at a nominal magnification of 1000 x.
Figure 8. Fine wool fibers (left panel) and unexpected addition of synthetic fibers (right panel).
While parts of the fabric do indeed consist of wool (left panel), additional synthetic fibers
can be found in the textile (right panel), which can clearly be identified by their flat surfaces
without any scale structures. In this way, microscopic images can even help to identify
possible imitations of fabrics made of valuable fibers, such as cashmere or pashmina, a
mixture of cashmere and silk [4].
PLANT FIBERS
Plant fibers can be bast fibers extracted from field crops, which are typically harvested
after one season of growing, opposite to trees which can be harvested continuously. Thus,
plant fibers often have to be stored for long times before they can be used in pulp mills.
Among the bast fibers, hemp, flax / linen, jute, nettles, ramie etc. can be found. Cotton,
bamboo, sisal and other fibers, however, are produced from leaf, fruit, and other fibers of
plants besides the stem-skin bast fibers. Plant fibers are based on cellulose which is often
bound by lignin, a material which can be found in the cell walls between cellulose,
hemicelluloses, and pectin. Some synthetic fibers are also based on cellulose fibers, such as
Lyocell, rayon or bamboo.
539
All bast fibers have a similar appearance, different from the typical scale structures of
animal fibers. Hemp fibers (Figure 9, left panel) are connected by pectin to form fiber
bundles. The single fibers become visible here due to biological and chemical treatment
which dissolves the pectin bonds. The transverse thickenings can be attributed to mechanical
load during growth or during digestion [5, 6]. Mechanical digestion separates the fibers from
the wooden parts.
Flax fibers (Figure 9, right panel) have been used for clothing production for tens of
thousands years until in the nineteenth century cotton became more popular. The fiber is quite
straight and smooth, soft and flexible, although less elastic than cotton. The chemical
procedure of retting the flax and the mechanical breaking, scotching, and heckling processes
separate the fibers from the inner wooden part of the stem and remove the straw from the
fibers. Figure 9 (right panel) shows a single fiber (smooth, shiny fiber in the middle of the
picture) between fiber bundles.
The optical appearance of both types of bast fibers, as can be seen in Figure 9, is thus
strongly dependent on the physical and chemical treatment prior to taking the CLSM pictures.
While the fibers can clearly be identified as types of bast fibers, optical differentiation
between them can be difficult, depending on the amount of digestion. Complete fiber bundles,
still containing the original amount of pectin and straw, can be hard to identify, as visible in
Figure 9, comparing the pectin-surrounded fiber bundles in both images. If the single fibers
are visible, then the irregularly formed hemp fibers can, e.g., be distinguished from the
polygonal flax fibers. Cotton fibers, consisting nearly completely of cellulose, grow in a
capsule around the seeds of cotton plants. Nowadays cotton is the most often used natural
fiber for clothing. Opposite to bast fibers (Figure 9), cotton fibers have a characteristic flatoval cross-section form which allows for differentiation from the triangular cross-section of
silk as well as from the smooth, even synthetic fibers.
CELLULOSE FIBERS
Synthetic fibers are normally produced by extrusion of the respective materials through
spinnerets into the air where the thread is formed. They can be subdivided into cellulose
fibers, polymer fibers, mineral, metallic and other fibers.
Figure 9. Microscopic images of hemp fibers (left panel) and flax fibers (right panel).
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Andrea Ehrmann
Figure 10. CLSM image of cotton fibers.
Figure 11. Lyocell (left panel) and alginate (right panel) fibers as examples for regenerated cellulose
fibers.
Manufactured cellulose fibers are extruded from a pulp of regenerated or pure cellulose.
Rayon (viscose), including modal and Lyocell fibers, are quite common. Other man-made
fibers from cellulose are, e.g., bamboo fibers or alginate, produced from seaweed.
Lyocell fibers (Figure 11, left panel) are, opposite to other viscose fibers, normally quite
smooth, with a roughly round cross-cut. The longitudinal grooves which are typical for
viscose fibers are not visible in Lyocell [7, 8]. The smooth, even alginate fibers (Figure 11,
right panel) are often used as wound dressing, since they swell during gelatinization due to
the moisture in the wound, thus completely filling even very deep wounds with nearly
inaccessible areas. Due to the spinning process from a pulp, synthetic cellulose fibers can
normally not be distinguished, although some cross-sections and surface structures can be
typical for certain materials.
POLYMER FIBERS
Opposite to synthetic cellulose fibers, polymer fibers are produced from synthetic
chemical materials.
541
Amongst them, materials like polyester, polyamide, polyolefin fibers or acrylic fibers can
be found as well as aromatic polyamides (aramids) or polyethylene with partly extremely
long chains, resulting in ultra-high-molecular-weight polyethylene (UHMWPE) fibers with
very special physical properties, such as very low elasticity and friction combined with very
high abrasion resistance.
Polyester (PES) (Figure 12) belongs to the polycondensation fibers which are based on
monomers reacting step-wise to dimers, trimers, and longer and longer oligomers, losing
small molecules as by-products. Polyester fibers normally have a round cross-section and a
flat, smooth surface; however, the structure can be influenced by the form of the spinneret
and chemical treatments.
Other polyconcensation fibers are polyamides or polyurethanes. Aliphatic polyamide 6
(PA 6) fibers are depicted in Figure 13 (left panel), aromatic polyamide (aramide) fibers are
shown in Figure 13 (right panel). Both look very similar to each other and to the PES fibers in
Figure 12.
Chain-growth polymerization fibers, e.g., polypropylene, polyethylene, or polyvinyl
chloride, are based on unsaturated monomer molecules adding on the active position of a
growing polymer chain without producing by-products with low molecular weight.
Figure 12. Microscopic image of polyester fibers.
Figure 13. CLSM pictures of polyamide 6 (left panel) and aramide fibers (right panel).
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Figure 14. Polyacrylonitrile (PAN) fibers (left panel) and UHMWPE fiber Dyneema produced by
DSM, Netherlands (right panel).
PAN (polyacrylonitrile) fibers (Figure 14, left panel) as well as the UHMWPE fiber
Dyneema (Figure 14, right panel) show structured surfaces, the PAN fibers additionally a not
round cross-section. However, these properties depend on the form of the spinnerets and thus
cannot be used for a differentiation between different types of fibers [8]. Nevertheless, the
fibril structure visible in the Dyneema fibers is a typical feature due to the special spinning
process. The loose fibril in Figure 14 (right panel) is the result of an improper rewinding
process.
METALLIC FIBERS
Pure metal fibers are mostly round, since they are drawn step-wise through smaller and
smaller spinnerets. Figure 15 shows stainless steel filaments from a pure stainless steel yarn.
Opposite to optical examinations by eye, the typical metallic brilliance is not visible here, due
to the auto gain function of the microscope which avoids too bright picture parts. On the
surface, fine longitudinal marks are visible, less pronounced than in the Dyneema fiber
(Figure 14, right panel), but also continuous, unlike the structure of the PAN fiber depicted in
Figure 14 (left panel). Although the surface structure of the metal filaments seems to be
unique, compared with the other figures in this chapter, care must be taken due to the possible
influences of the spinnerets and physical / chemical treatments of metal and other fibers.
PHYSICAL AND CHEMICAL TREATMENTS OF FIBERS

Opposite to pure metal fibers, partly metalized fibers can be recognized easily in CLSM
images. Figure 16 (left panel) shows fibers of a Shieldex yarn, consisting of pure PES and
silver coated fibers, the fine silver layer being partly destroyed by several washing cycles.
Here, the rougher surface structure, compared to pure polyester, and the metallic glittering on
the coated fibers clearly indicate a metallic coating on parts of the fibers.
Another way of physical treatment of PES fibers is exposition to a pulsed excimer laser.
The results are shown in Figure 16 (right panel).
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The lateral ripples are produced by the sudden heating and cooling due to the intense
laser pulses. In the middle of the image, several tipped-over ripples can be identified,
additional to a part of one fiber which has apparently been shaded from the laser light, thus
still presenting a flat surface without ripples. For the detection of such structures, a CLSM is
ideally suited, while a simple optical microscope can only give a rough idea of these laserproduced surface structures without more detailed information.
In some cases, the influence of chemical treatment of fibers is also visible in CLSM.
Figure 17 show hemp fibers treated by hammer mill, without (left panel) and with (right
panel) chemical after-treatment, i.e., digestion of the fibers by chemical retting in, e.g.,
sulfuric acid. Comparing both pictures, the vanishing of the pectin in the fiber bundle
apparently leads to dissolving of the fibers which become singularly visible.
It should be mentioned, however, that other chemical treatments, nano-coatings, etc., are
normally not visible in a confocal laser scanning microscope, since the resolution is not
sufficient to identify nano-scale features.
Figure 15. Stainless steel filaments, recorded by CLSM.
Figure 16. Shieldex yarn, produced by Statex, Bremen, Germany (left panel) and laser treated PES
fibers (right panel).
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Andrea Ehrmann
Figure 17. Hemp fibers treated by hammer mill only (left panel) and additionally treated chemically
(right panel).
Figure 18. Wool fibers with insufficient measurement range (left panel) and Lyocell fibers with only
one part of the possible measurement range (right panel).
CHANCES AND PROBLEMS

While especially natural fibers and physical treatments of fibers can often be identified
by CLSM, the technique possibilities are nevertheless limited. Especially the basic principle
of confocal laser scanning microscopy, i.e., scanning only in well-defined distances to the
objective, may be problematic.
Figure 18 depicts an image of wool fibers (left panel) for which an insufficient
measurement range has been chosen, leading to black areas inside the fibers where the surface
was not positioned between upper and lower limit of the measurement range.
While such a problem is evident and can thus be corrected in a new picture with extended
limits, it is also possible to completely miss some fibers. Comparing Figure 18 (right panel)
with Figure 11 (left panel), both pictures clearly show the same area of the same yarn;
however, in Figure 18 (right panel), some fibers are missing due to a wrong limit in the
measurement range. The shading effects, caused by higher fibers which are missed in this
way can nevertheless influence the appearance of the depicted fibers which might cause
additional interpretation problems.
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CONCLUSION
Similar to an SEM, a CLSM is not able to distinguish between all sorts of synthetic fibers
which often look identical, independent of their chemical composition. However, confocal
laser scanning microscopy is a powerful tool for optical examination of fibers, combining
some of the advantages of optical light microscopy and scanning electron microscopy. For
most fibers, the resolution of a CLSM is sufficient to analyze the surface structures which can
be used to identify the type of fiber.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Minsky, M. (1961). Microscopy Apparatus. US Pat. 3,013,467.

Claxton, N. S., Fellers, T. J., Davidson, M. W. (2013). Laser scanning confocal
microscopy. Olympus website. 1-37. Available at: http://www.olympusfluoview.com/
theory/LSCMIntro.pdf.
Instruction book of VK9700K, Keyence.
Tillmanns, A., Korger, M., Weber, M. O. (2012). Konfokale LaserscanningMikroskopie Zerstrungsfreie Faseruntersuchung. forward textile technologies 4, 4647.
Thygesen, L. G., Hoffmeyer, P. (2005). Image analysis for the quantification of
dislocations in hemp fibres. Ind. Crop Prod. 21, 173-184.
Wang, H. M., Wang, X. (2005). Surface morphologies and internal fine structures of
bast fibers. Fiber Polym. 6(1), 6-12.
Abu-Rous, M., Ingolic, E., Schuster, K. C. (2006). Visualisation of the nano-structure
of Tencel (Lyocell) and other cellulosics as an approach to explaining functional and
wellness properties in textiles. Lenzinger Berichte 85, 31-37.
Kleinhansl, E., Mavely, J. (1986). Denkendorfer Fasertafel 1986; Textilpraxis Int.,
Leinfelden-Echterdingen, GE.
INDEX
#
20th century, 84, 201, 268, 319
21st century, 16
A
A(H1N1), 384
abatement, 311
abrasion, 23, 25, 41, 42, 43, 44, 48, 218, 343, 345,
375, 383, 386, 389, 541
abrasion resistance, 218, 375, 541
abrasion test, 383, 386
absorption spectra, 104, 177, 181, 183, 184, 185,
194, 200
absorption spectroscopy, 177, 321
abstraction, 176
access, 5, 195, 314, 356, 372
accessibility, 5, 129, 130, 140, 141, 148, 149, 268,
401, 411, 413, 419
accordion, 466
accounting, 113
acetic acid, 99, 123, 136, 137, 138, 140, 155, 179,
406
acetic acid content, 138, 140
acetone, 139, 140, 148, 149, 151, 179, 238
acetonitrile, 208
acetyl content, 138, 139, 140
acetylation, 136, 137, 139, 140, 141, 155, 404
acidic, 116, 177, 178, 179, 375, 412, 419
acidic functional groups, 412, 419
acidity, 217
acrylate, 155, 365
acrylic fibers, 165, 541
acrylic resin, 242, 321, 345
acrylics, 98, 100, 157, 159
acrylonitrile, 154, 217
activated carbon, 397, 430, 436, 444, 445
activation energy, 112

active site, 295, 420, 422
active smart textiles, 240
active thermal insulation effect, 242
active transport, 199
active type, 190
actuation, 244
actuators, 188, 189, 239, 241, 245, 250, 448
AD, 264, 266, 270, 276, 337
adaptation(s), 67, 68, 69, 82, 188, 400, 449
additives, 79, 82, 102, 109, 116, 208, 210, 220, 365
adhesion, 87, 101, 196, 249, 250, 256, 277, 283, 306,
313, 343, 362, 363
adhesion properties, 101, 196, 256
adhesives, 124, 344, 352
adjustment, 457, 533
adsorption, 115, 155, 280, 307, 351, 400, 412, 415,
419, 420, 421, 422, 436, 437, 438, 440, 441, 443,
444, 445
adsorption isotherms, 420
adsorption properties, 155, 400, 440
advancement(s), 188, 274, 415
adverse conditions, 320
adverse environmental effects, 294
aesthetic, 1, 21, 22, 24, 192, 244, 339, 490, 508
aesthetic finishing process, 21
aesthetic satisfaction, 192
aesthetics, 3, 191
AFM, 305, 306
Ag-agglomeration process, 301
agar, 296, 300
Ag-clusters, 277, 279, 282, 286, 306
Ag-disinfection performance, 289
age, 8, 9, 13, 322
aged textiles, 316, 336
aggregation, 113, 184, 292
Ag-hospital textiles, 289
Ag-nanoparticulate films, 278
Ag-nitrides, 278
548
Index
Ag-polyester fibers, 285

agriculture, 362
Ag-sputtered films, 277
Ag-textile surfaces, 278
air permeability, 384, 490, 507, 509, 512, 515, 517
air pollutants, 100
air temperature, 487
Akaike information criterion, 420, 421
alcohols, 98, 217, 328
aldehyde functionalities, 406
aldehydes, 370, 431
algae, 289
alginate, 350, 351, 383, 384, 385, 389, 395, 540
alginate chains, 384
alginate fibers, 540
algorithm, 61, 65
alkali-clearing property, 165
alkaline treatment, 324, 404, 407, 408, 412, 440, 501
alkyl methacrylates, 122
allergenic effect, 400, 403
allergic responses, 370
alters, 249
amine(s), 77, 154, 159, 165, 168, 173, 361, 372, 375
amine group, 361
amino, 23, 34, 43, 55, 78, 158, 164, 165, 166, 169,
170, 171, 172, 177, 179, 184, 185, 205, 236, 238,
373, 374, 375
amino acid(s), 23, 34, 43
amino groups, 158, 373, 374, 375
aminoazobenzene derivatives, 159
aminosilicone softener, 374, 375
ammonia, 99, 280
ammonium, 165, 167, 182, 218, 374
amorphous regions, 326, 329, 333, 401, 410, 413
amylase, 23
amylopectin, 23
anaerobic conditions, 271
anatase, 314
anatomy, 17
aneurysm, 467, 478
angioplasty, 480
angora, 536
anhydroglucose units, 405
aniline, 165, 172, 173, 176, 235, 236
ANOVA, 384, 387, 388, 391, 395
ANOVA analysis, 388
Anthraquinone, 159, 160
Anthraquinone derivatives, 159
Anthraquinone disperse dyes, 160
anthraquinone dyes, 159
anti-back staining agent, 28
antibacterial activity, 278, 301, 313, 314, 365
antibacterial surfaces, 278, 288
anticoagulant, 474
anticoagulation, 474
anti-counterfeit, vii, 81, 103, 118, 210
antimicrobial agents, 310, 365, 384
antimicrobial nanoparticulate films, 289
antimicrobial properties, 362, 403
antique, 2, 8
aorta, 467, 479
aortic stenosis, 479, 480
aortic valve, 480
apparel, 3, 8, 19, 20, 21, 22, 23, 24, 25, 26, 31, 34,
35, 36, 37, 38, 39, 40, 41, 42, 44, 46, 47, 48, 49,
136, 191, 211, 227, 243, 246, 367, 368, 390, 475,
490, 492
apparel industry(ies), 20, 21, 22, 23, 367
apparel manufacturers, 21, 22
apparel products, 475
apron draft spinning system, 506
aptitude, 471
aqueous solutions, 34, 177, 412, 413, 441, 443, 444
arabinofuranose units, 402
arc-discharge lamps, 533
archaeological excavations, 83
archaeological sites, 316
archaeological textiles, 274, 275, 276, 317, 336
archaeologists, 259, 260, 269, 270, 271, 272, 273,
274
archaeology, 269, 274, 276, 339
aromatic diazo compound, 163
aromatic polyamide, 541
aromatic rings, 207, 214
arteries, 471, 476
artery, 465, 467, 472, 473, 476, 477, 478, 479
artificial fibres, 278, 499
artificial textile prosthesis, 466
aryl azo pyridone dyes, 162, 185
aseptic, 400
aseptic properties, 400
Asia, 441, 442, 461
assessment, 31, 79, 181, 182, 227, 338, 476
atherosclerosis, 467, 471
atmosphere, 12, 278, 286, 290, 292, 301, 303, 306,
430, 432, 486, 487, 521
atmospheric pressure, 280, 441
atomic absorption spectroscopy, 321
atomic force, 305, 306
atoms, 108, 262, 263, 279, 283, 285, 286, 289, 297,
310, 375, 377, 432
ATP, 206
attachment, 77, 239, 254, 265, 506
attenuated total reflection FTIR spectroscopy, 321,
324
attractiveness, 5, 6
Index
attribution, 324
Austria, 264
authentication, 107, 117, 195, 209, 210
authenticity, 4, 9, 10, 11, 13
automation, 85
avoidance, 520
awareness, 5, 10, 12, 20, 22, 270, 271
azo colorants, 157, 159, 162, 163, 179
azo compounds, 157, 159, 166
azo coupling, 163
azo dyes, vii, 157, 159, 163, 164, 165, 167, 170, 175,
176, 177, 179, 180, 181, 182, 183, 184, 185
azo groups, 159, 179, 197
azo pigments, 167
azobenzene, 105, 159, 197, 208
azobenzothiazoles, 162
azo-hydrazone equilibrium, 158
Azo-hydrazone tautomerism, 157, 179
azopyrazolone, 162
azopyridones, 162
azothiophenes, 162
azulenes, 197, 203
B
backlash, 3
bacteria, 23, 165, 263, 277, 278, 279, 280, 283, 285,
289, 290, 291, 295, 296, 300, 305, 306, 310, 311,
313, 384, 395, 418, 460, 476
bacteria inactivation, 277, 297
bacteria respiratory enzyme, 278
bacterial cell wall membrane, 297
bacterial colonies, 296
bactericide surfaces, 290, 292
balloon angle, 519, 521, 526, 528
bamboo fibers, 540
ban, 400
band gap, 223
Bangladesh, viii, ix, xii, 19, 20, 26, 48, 49, 123, 124,
136, 153, 154, 499
baroque, 316
barriers, 22, 116, 314
base, 11, 13, 56, 61, 124, 129, 158, 168, 179, 185,
190, 212, 216, 227, 234, 241, 242, 251, 264, 363,
365, 369, 372, 406, 411, 425, 449, 461, 462, 484,
495, 499
basic dyes, 103, 165
bast fibers, 400, 441, 538, 539, 545
bath exhaustion, 343, 345
bathochromic effect, 176
baths, 76, 349
batteries, 210, 240, 252, 447, 448, 449, 450, 453,
454, 455, 460
549
beams, 166, 532

BED, 352
bedding, 243, 246
behaviors, 450, 455
Beijing, 496
Belgium, 121
bending, 19, 25, 31, 36, 51, 240, 247, 250, 253, 254,
328, 386, 390, 472, 474, 475, 477, 480
bending length, 19, 31, 36, 51, 386, 390
bending rigidity, 25, 475, 480
beneficial effect, 278
benefits, 5, 6, 16, 242, 253, 371
benzene, 176, 179, 235, 406, 419
benzene ring cleavage, 406, 419
benzodifurane, 159
beverages, 352
bias, 275
Bifurcated prosthesis, 466
bifurcated vascular prosthesis, 465, 469, 478, 479
bing, 351
biochemistry, 188
biocidal action, 263
biocidal properties, 263, 264
biocidal surfaces, 278, 384
biocompatibility, 278, 292, 299, 362, 465, 466, 471,
477, 478
biodegradability, 362, 403
biodegradable enzymes, 23
biodeterioration, 317, 320, 321, 337
biofinishing cotton, 47
biological samples, 532, 533
biological systems, 194
biomass, 399, 418, 430, 436, 441, 445
biomaterials, 54, 189, 480, 481
biomedical applications, 89, 90, 205, 292, 312, 351,
384
biomimetic systems, 219
biomimetics, 240
biomonitoring, 227
bioprocessing, 240
biosorbents, 399, 401, 418
biosorption capacities, 419
biostatic properties, 373, 381
biostoning denim, 47
biosynthesis, 50
biotechnology, 188, 240, 350, 455
biotic, 337
bisphenol, 217
blankets, 505, 515, 516
bleach wash, 20, 21
bleach washing process, 21
bleaching, 125, 353, 384, 406, 414, 502
bleeding, 59, 92
550
blends, 54, 164, 226, 249, 351, 442, 504, 509, 516,
518, 537
blood, 448, 465, 467, 468, 471, 472, 473, 476, 477,
478, 479
blood circulation, 468, 471
blood clot, 477
blood clotting substances, 477
blood constituents, 467
blood flow, 465, 467, 468, 471, 478
blood vessels, 465, 466, 468, 473, 479
bloodstream, 474
bluenic, 521, 524
body core temperature, 483
body fluid, 475
body temperature, 210, 211, 244, 384, 484, 491
Boltzmann constant, 487
bonding, 177, 230, 280, 329, 358, 404, 418, 475
bonds, 35, 268, 280, 289, 306, 317, 322, 323, 328,
329, 331, 332, 362, 368, 402, 430, 432, 539
bone(s), 246, 264
boric acid, 147, 217, 381
bounds, 414
boutique-style shops, 12
braided edge, 271
braided structure, 477, 478
braids, 136
brain, 241
branching, 401
brand image, 12, 13
brand name, 6, 9
brand protection, vii, 81, 107, 117, 118, 194, 209,
210
brass, 248, 514
breakdown, 159, 268, 317
breaking elongation, 56, 330, 334, 502, 524
breaking extension, 387, 388, 502, 507
breaking force, 30, 33, 51, 56
breaking strengths, 523, 528
breaking stress, 330, 334
breathing, 370, 455, 485
brilliant yellows, 161
Britain, 4
brittleness, 249, 333
brushing action, 24
bulk coloration, 171
bundle cross-section, 409
burial environment, 262, 264, 273, 274
buried contemporary materials, 318
burn, 310, 311
businesses, 7, 14, 55, 83
butadiene, 246
buttons, 11, 508
buyer(s), 20, 25
Index
by-products, 445, 541
C
Ca2+, 314
cables, 448, 455
CAD, 90
cadmium, 428, 429, 436, 444, 445
calamitic molecules, 215
calcification, 474
calcium, 94, 259, 321, 442
caliber, 473
calibration, 286
calorimetry, 361
camera, 55, 195, 522, 532, 533
candidates, 107, 224
cane sugar, 154
capillary, 408, 413, 414, 415, 416, 417, 419, 443
capsule, 488, 539
carbon, 152, 163, 201, 233, 234, 241, 248, 249, 262,
264, 294, 313, 377, 397, 399, 401, 404, 405, 407,
430, 432, 434, 436, 438, 440, 444, 445
carbon atoms, 377, 432
carbon dioxide, 263, 431
carbon materials, 399, 401, 430, 432, 434, 436, 438,
445
carbon monoxide, 431
carbon nanotubes, 233, 234, 249, 445
carbon precursor chemical structure, 432
carbon skeleton of the cellulose backbone, 405
carbonaceous materials, 430, 436
carbon-carbon bond cleavage, 405
carboncarbon linkages, 404, 407
carbonization, 399, 400, 430, 432, 433, 434, 436,
439, 440
carbonized hemp fibers, 400, 432, 433, 434, 437,
438, 439, 440, 441
carbonyl groups, 329, 358, 418
carboxyl, 280, 294, 384, 405, 411
carboxylic acid(s), 356, 357, 358, 360, 362, 365,
373, 375, 379, 381, 382, 402, 405
carboxylic groups, 371, 405, 434
carboxymethyl cellulose, 123, 124, 125, 153, 154,
155
carboxymethylation, 124, 125, 129, 130
carcinogenic amines, 159
cardiac care, viii, 465
cardiac pulse, 472, 473
cardiovascular surgeries, 465
cardiovascular textile prostheses, 471
carsolchromic, 246
case study(ies), 265, 266, 271, 272, 310
cashmere, 536, 538
Index
cashmere wool, 536
catalysis, 192, 231, 263, 313
catalyst, 27, 177, 263, 302, 357, 358, 362, 363, 364,
372, 375, 377, 378, 381
catalytic activity, 301
catalytic domain, 23
catalytic properties, 445
catheter, 474, 476, 479, 480
cation, 405
cationic agent printed cotton, 54
cattle, 500
CBD, 23
C-C, 150, 294, 406
cell development, 467
cell killing, 279, 311
cell phones, 250
cell surface, 361
cell wall components, 412
cellulase, 19, 20, 21, 23, 24, 25, 27, 33, 34, 35, 36,
37, 38, 39, 40, 41, 43, 44, 46, 47, 48, 49, 50, 51,
52, 340
cellulase enzyme, 19, 20, 21, 23, 27, 33, 36, 46, 47,
48, 49, 50
cellulose acetate, 123, 124, 136, 141, 153, 155, 157,
158, 159, 160
cellulose chains, 43, 323, 326, 329, 355, 367, 368,
369, 371, 372, 373, 375, 401
cellulose crystallinity, 323, 324
cellulose derivatives, vii
cellulose fibers, 355, 404, 442, 443, 445, 538, 539,
540
cellulose fibre, 211, 323, 397
cellulose I, 340, 404, 434, 442
cellulose II, 404, 434
cellulose macromolecules, 324, 330
cellulose microfibrils, 401, 403, 408
cellulose molecules, 360, 375, 403, 404
cellulose nitrate, 123, 124, 145, 152, 153, 155, 156
cellulose-binding domain, 23
cellulosic, 23, 24, 49, 51, 123, 124, 125, 136, 145,
153, 170, 263, 264, 266, 267, 273, 276, 318, 319,
321, 322, 326, 331, 336, 337, 340, 341, 355, 356,
360, 361, 363, 367, 371, 372, 377, 380, 381, 397,
401, 405, 430, 441
cellulosic derivatives, 123, 124
cellulosic textiles, 337, 367, 372
cellulosic wastes, 123, 153
cellumonas fimi, 23
cell-wall membrane, 300
Central Europe, 265
ceramic, 82, 93, 95, 245, 261
cesium, 199
CFI, 528
551
chain branching, 401

chain scission, 317
challenges, 11, 20, 55, 91, 92, 104, 276
changed appearance, 317
charge density, 418
charge transfer sites, 296
charity shops, 4
charm, 3
chemical characteristics, 76, 124, 133, 405, 416
chemical damage, 317
chemical fibers, viii, 400, 531, 533
chemical interaction, 99
chemical modification, 400, 407, 411, 432, 436, 440,
441, 443
chemical phenylpropane units, 402
chemical processing steps, 19
chemical properties, 104, 195, 340, 378
chemical reactions, 92, 377
chemical softeners, 501
chemical stability, 344
chemical structures, 335, 377
chemical texturizing process of jute, 501
chemical treatments, 31, 404, 405, 406, 411, 541,
542, 543
chemicals, vii, 20, 21, 22, 23, 25, 26, 28, 47, 48, 54,
55, 76, 78, 362, 365, 369, 371, 377, 384, 400,
441, 448, 461
CHF, 437
Chicago, 15, 17, 451
children, 188, 211, 460
China, 56
chiral molecules, 210
chirality, 207
chitin, 361
chitosan, 55, 78, 350, 351, 362, 365, 378, 443
Chitosan, 350, 361, 365
chlorine, 20, 24, 356, 406
chlorine bleach, 20, 24
chloroform, 179
cholesteric liquid crystal, 210
cholesterol, 210
Christianity, 320
chromatic adaptation-transformed values, 69
chromatography, 321, 438, 446
chromic materials, 193, 239, 240, 246, 247, 252
chromium, 167, 182
chromophore, 196, 215, 216
chromophoric azo group, 157, 159
circulation, 93, 468, 471
cities, 7, 264, 275
civilization, 83
clarity, 210
classes, vii, 86, 91, 92, 105, 107, 115, 158, 218, 438
552
Index
classification, 15, 85, 86, 158, 192, 193, 211, 220

cleaning, 21, 288, 310, 311, 312, 384, 406, 448
cleavage, 106, 107, 184, 405, 406, 419, 430, 432
climate(s), 244, 453, 488, 491, 492
clinical performance, 466
clinical trials, 250
Clostridium difficile, 384, 396
clothing materials, 400, 468, 483, 488, 495
clothing structure design, 493
clusters, 7, 277, 278, 279, 280, 282, 285, 306
CMC, 69, 79, 123, 124, 125, 126, 127, 128, 129,
130, 131, 132, 133, 134, 135, 136, 139, 144, 145,
147, 153, 154, 374, 375
CO2, 430, 431, 433, 434, 435, 436
coal, 400, 430
coatings, 122, 136, 154, 188, 220, 232, 248, 249,
256, 283, 289, 295, 313, 314, 519, 522, 524, 525,
526, 527, 528, 543
cobalt, 221, 234
coding, 87, 89, 90
coefficient of capillary diffusion, 416
coefficient of friction, 502
coefficient of variation, 409, 414, 502, 511
coffee, 444
collaboration, viii, 188, 259, 260, 269, 271, 272, 273,
274, 455
collagen, 466
colleges, vii
collisions, 280
colloidal suspension, 280
colonisation, 317
colonization, 279, 338
color constancy, 67, 68
color difference equations, 56
color fastness determinations, 286
color fields, 63
color filters, 157, 163, 179, 180, 182
color gamut, 55, 59, 62, 63, 64, 66, 67
color inconstancy index, 53, 54, 56, 67, 68, 69, 70,
76, 79
color management, vii, 53, 54, 55, 58, 59, 61, 65, 66,
79
color management application, vii, 53
color patches, 59, 60, 63, 65, 67
color patterns, 53, 55, 65, 74
color photography, 157, 159
color prints, 53, 54
color profiles, 53, 55, 56, 58, 61, 63, 65, 76
color stabilization, 58
color tone, 54
color transformations, 66
colorimetric matching, 65
colorimetrically transforms in-gamut colors, 67
colour change, 82, 99, 103, 104, 106, 108, 109, 113,
115, 117, 121, 190, 192, 193, 194, 195, 196, 197,
198, 199, 203, 209, 210, 211, 212, 213, 214, 216,
217, 218, 219, 220, 221, 222, 224, 229
Colour Index, 158, 159
combined effect, 495
comfortable garments, 367
comfortness, 36
commercial, 23, 49, 89, 90, 103, 106, 122, 159, 177,
188, 195, 245, 250, 289, 343, 345, 346, 400, 439,
440, 452, 502, 503, 505, 506, 507, 508, 532, 533
commercial colorants, 159
commercial fabrics, 507
communication, 6, 12, 13, 14, 84, 201, 229, 239,
250, 251, 252, 253, 260, 274, 447, 448, 449, 455
communication technologies, 252
community(ies), 12, 337, 338
compact spinning, 520
compaction, 471
comparative analysis, 311
compatibility, 98, 468, 477
compensation, 65
competition, 2, 5, 11, 84, 453, 462
competitive advantage, 5, 10, 17, 190
competitive conditions, 419
competitors, 5, 6
complex interactions, 484
complexity, 2, 71, 402, 419, 466, 471
compliance, 466, 468, 471, 473
composite materials, 145, 188, 399
composites, 189, 226, 240, 248, 249, 256, 303, 402,
441, 442, 481
composition, 19, 27, 91, 92, 97, 99, 100, 102, 145,
155, 181, 210, 222, 286, 295, 322, 325, 344, 345,
350, 382, 399, 401, 403, 404, 407, 409, 410, 411,
412, 414, 415, 416, 419, 440, 441, 490, 512, 545
compounds, 55, 78, 105, 107, 157, 158, 159, 161,
163, 166, 170, 171, 176, 183, 200, 205, 208, 211,
213, 214, 215, 216, 221, 230, 247, 249, 355, 361,
369, 370, 371, 372, 406, 430, 444
compressibility, 25
compression, 466, 477, 504, 517
compression resistance, 466
computation, 250, 494
computer, 55, 84, 188, 452, 467, 468, 478, 494, 531,
532, 533
computer program, 531
computer technology, 532
computer-aided design, 478
computer-controlled galvanometer mirrors, 533
computing, 188, 227
condensation, 167, 212
conditioning, 30, 33, 51, 255
Index
conductance, 489
conducting polymer composites, 256
conduction, 222, 223, 278, 282, 305, 483, 484, 485,
489, 491, 493, 494
conductive fibers, 239, 248, 249, 253, 447
conductive materials, 239, 240, 248, 254, 449
conductive smart textiles, 250
conductive textiles, 248, 249, 250, 257
conductive threads, 253, 254
conductivity, 92, 94, 98, 195, 219, 222, 233, 248,
249, 250, 254, 357, 383, 384, 386, 390, 391, 392,
394, 486, 487, 488, 489, 490, 493, 495, 496, 497,
509, 517
conductor(s), 211, 219, 247, 249, 254, 490, 492, 494
conference, 51, 255, 364, 447, 448, 453
confidence limits, 526
confocal laser scanning microscopy, 531, 532, 544,
545
confocal magnetron-sputtering systems, 292
conformity, 3
Congo, 236
Congress, 119, 364
conjugate planes, 532
conjugated double bond, 430
conjugated electrochromic polymers, 224
conjugation, 106, 193, 202, 212, 214, 215
consciousness, 190
conservation, 145, 259, 260, 268, 269, 270, 271, 272,
273, 274, 276, 316, 320, 325, 336, 338, 341
conservation process, 270
conserving, 260, 275, 276, 316
consolidation, 268, 273, 512, 513
constant ink composition, 100
constituent materials, 270
constituents, 2, 321, 402, 467
Constitution, 119
construction, 118, 242, 245, 270, 386, 455, 465, 473,
475, 476, 478, 490, 492, 496
consumers, 3, 4, 8, 9, 10, 11, 12, 13, 14, 21, 22, 25,
191
consumption, 2, 3, 14, 449, 450
contact time, 302, 309, 418, 419
contactless printing, 166
containers, 12, 266
contaminate historical textiles, 336
contamination, 289, 290, 315, 337, 339, 384, 396
contemporary costumes, 271
continuous inkjet printing technique, 85, 87, 94
continuous washing cycles, 349
controversial, 400
convection, 127, 483, 484, 485, 486, 487, 488, 489,
490, 491, 492, 493, 494, 496
conventional dyes, 82
553
conventional padmangle systems, 242

conventional ring spinning, 520
conventional textile materials, 384
convergence, 188, 239
COOH, 177, 411, 412
cooking, 352
cooling, 216, 241, 242, 244, 245, 289, 484, 514, 543
cooling process, 242
cooperation, 91
coordination, 211, 234
copolymer(s), 143, 150, 153, 235, 246, 255, 350,
365, 378
copolymerisation, 220
copolymerization, 154, 155
copper, 208, 231, 232, 248, 249, 259, 262, 263, 264,
266, 267, 268, 273, 276, 313, 383, 384, 385, 387,
388, 389, 390, 391, 393, 394, 395, 396, 444, 445,
494
copper alginate, 384, 389
copper sulphate, 383, 385, 395
copper volumes, 390
correlation(s), 71, 74, 176, 303, 409, 420, 437, 438,
467, 471, 473, 478, 479, 493, 512, 515
correlation coefficient, 420
correlation matrix, 512, 513
corrosion, 92, 94, 98, 99, 249, 262, 263, 264, 274,
275, 477
cortex, 332
cosmetic(s), 124, 157, 159, 195, 210, 344, 377, 455
cost, 76, 89, 101, 118, 123, 124, 136, 159, 221, 344,
356, 373, 399, 401, 430, 436, 440, 443, 477, 499,
505
cost effectiveness, 159
cotton and acrylic jacket fabrics, 508
cotton commercial shawl fabrics, 507
cotton fabrics, 24, 49, 50, 51, 54, 63, 129, 134, 136,
312, 347, 348, 352, 353, 356, 361, 362, 363, 364,
365, 367, 368, 370, 377, 378, 379, 380, 381
cotton fiber, 24, 55, 136, 144, 153, 154, 313, 346,
348, 349, 362, 365, 377, 539, 540
cotton linters, 124, 154
cotton textiles, 268, 282, 367, 370, 371, 375
cotton twill fabric, 21
cotton/acrylic commercial shawl fabrics, 507
cough, 370
country of origin, 6
coupling reaction, 163, 170, 179
covalent bond, 358
covalent chemical bond, 76
covering, 90, 322, 368, 387, 477
CPU, 252
crabs, 361
cracks, 44, 326, 413
554
Index
creatinine, 155
creativity, 3
creep, 518
crimped textile implants, 471
critical fabric properties, 490
critical ring spinning, 520
crop, 444, 500
crop residue, 444
crops, 438, 499, 500, 538
cross-contamination, 384, 396
crosslinking, 333, 355, 356, 357, 358, 360, 361, 362,
363, 364, 365, 367, 369, 370, 371, 372, 373, 374,
375, 377, 378, 379, 380, 381, 382
crown, 197, 199, 208, 230, 231
crystal structure, 434, 442
crystalline, 24, 155, 215, 232, 263, 268, 279, 323,
324, 329, 357, 368, 384, 401, 404, 412, 414, 442
crystalline structure, 279, 357, 384, 404
crystalline supermolecular structure, 401
crystallinity, 112, 268, 323, 324, 325, 328, 329, 330,
334, 336, 340, 408, 412, 414
crystallinity index, 324, 340, 414
crystallization, 241
crystallographic Ag-clusters, 285
crystals, 24, 193, 210, 215, 233, 247, 279, 285, 289,
449
Cuba, 351
cultivation, 268
cultural heritage, 316, 317, 337
cultural property, 260
culture, x, 2, 4, 8, 259, 260, 270, 272, 274, 295, 300,
351
cure, 85, 91, 100, 364, 372
curing process, 77, 102, 356, 379
currency, 20
current limit, 226
customer service, 6, 11, 14
customers, 8, 9, 10, 11, 12, 13, 14, 20, 22
cuticle, 332
CV, 521, 522, 524, 528
CVD, 289, 313
cyanamide, 362
cyanide, 205
cycles, 115, 196, 204, 230, 250, 289, 297, 305, 346,
348, 349, 363, 542
cycling, 22, 292, 476
cyclodextrins, 231, 377, 382
cyclohexanone, 179
cysteine, 333
cysteine residues, 333
cytotoxicity, 278, 292, 303, 305
Czech Republic, 386, 387, 397
D
dacron, 468, 471
damping, 245, 437, 480
damping coefficient, 437
danger, 251, 336
darker-grey metallic Ag-color, 292
data analysis, 7
data communication, 84
data processing, 251
data set, 387, 391
data transfer, 252, 253
database, 537
DC-magnetron sputtering, 277, 283, 286, 312
decay, 112, 315, 337, 341
decolouration, 112, 113, 114
decomposition, 92, 116, 176, 200, 268, 300, 305,
317, 340, 361, 365, 430, 431, 432, 434, 435, 445
decomposition temperature, 176
decontamination, 337
deconvolution, 290
decoration(s), 84, 90, 100, 210, 316, 447
decorative-protective applications, 455, 460
decoupling, 128
defects, 289
defence, 191, 397
deficiency, 249
deflate, 348
deformation, 89, 253, 329, 334, 368, 390, 466, 471,
472, 474
degradation, 24, 37, 43, 44, 116, 155, 177, 184, 196,
263, 264, 313, 317, 319, 320, 331, 337, 338, 339,
340, 341, 357, 372, 377, 405, 406, 407, 468, 475
degradation process, 320
degree of fiber swelling, 412
degree of lattice transformation, 404
degree of polymerisation, 329
degree of substitution, 123, 124, 126, 129, 136, 138,
139, 147, 148, 153
degree of swelling, 404, 412
Degussa, 177
dehydration, 211, 430
delignification process, 501
denim, vii, 8, 11, 19, 20, 21, 22, 23, 24, 25, 26, 27,
28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40,
41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 397
denim apparel, 19, 20, 21, 22, 23, 24, 25, 26, 29, 30,
31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,
44, 46, 47, 48
denim designs, 22, 23, 25
denim ready-made apparels, vii, 19, 20, 25, 47
denim trousers, 19, 28, 29
Denmark, 274
Index
dependent variable, 515
depolymerisation, 323, 326, 328, 329, 330, 333, 334,
336, 430
depolymerization, 404, 430
deposition, 82, 94, 136, 145, 153, 249, 253, 254,
279, 283, 286, 288, 289, 290, 292, 297, 298, 302,
311, 314, 345, 353, 428, 478
deposition rate, 286, 297, 298
deposits, 279, 286
depth, 31, 32, 90, 190, 389, 510, 531, 533
derivatives, vii, 23, 49, 123, 124, 136, 155, 159, 161,
164, 165, 168, 177, 181, 182, 183, 184, 185, 200,
202, 204, 205, 207, 208, 210, 216, 220, 230, 232,
234, 365, 372, 378, 381, 382, 402, 406, 432, 442
design, vii, 9, 20, 21, 22, 49, 50, 81, 82, 83, 92, 107,
117, 118, 119, 191, 194, 209, 210, 226, 227, 228,
239, 242, 247, 250, 251, 305, 381, 450, 455, 461,
462, 465, 467, 473, 476, 491, 493, 499, 506, 507,
508, 509, 510, 515
design and fashion apparel, 20
designers, 3, 4, 9, 15, 20, 21, 22, 25, 55, 78, 191
designing of warm fabrics, 500
desizing, 23, 28
desizing agent, 28
desorption, 377, 430, 434, 435, 436, 445
desorption of water, 430
destruction, 264, 271, 305, 397, 467
detectable, 104, 493
detection, 297, 455, 462, 476, 543
detection system, 462
detergent, 21, 28, 507, 509
detergents, 55, 63
detrimental effects, 262
developed countries, 344
developed fabrics, 507, 508
developed jacket fabric, 508
deviation, 421, 439
diabetic wound dressing, 289
diarylethenes, 107, 111, 115, 194, 197, 199, 201, 208
diastole, 472
diastolic membrane stress, 474
diazo compounds, 163
diazo printing, 157, 159
diazonium salts, 163, 164, 170, 177, 179
diazotization, 163, 170, 171
diazotized aromatic amines, 168
dichromatic mirrors, 533
dielectric constant, 105, 195
differential scanning, 361
differential scanning calorimetry, 361
diffraction, 155, 193, 285
555
diffusion, 158, 184, 221, 282, 295, 306, 386, 416,

417, 421, 422, 423, 425, 426, 427, 428, 437, 444,
485
digestion, 539, 543
digital cameras, 250
digital dyeing, 82, 103
digital microscope, 532
digital printing, vii, 53, 54, 55, 61, 77, 79, 84, 100,
120, 250
digital technologies, 118
digital textile printing, 53, 54, 55, 58, 66, 78, 85
diketone keto esters, 167
dimensional stability, 20, 49, 54, 355, 500
dimensions, 8, 233, 263, 272, 285, 376, 386, 404,
450, 460, 473, 476, 537
dimethyl sulfoxide, 128, 139, 147, 155
dimethylformamide, 176, 178, 184
diodes, 189, 449, 453
diphenyldiazene, 159
dipoles, 306
direct mail, 90
dirndl skirts, 10
disabled patients, 188
disazo pyridone compound, 171
disazo reactive dyes, 183
discomfort, 252, 484
discontinuity, 474
discriminant analysis, 341
diseases, 460, 476
disinfectant, 279, 384
disinfectant reactivity, 279
disinfected properly, 384
disinfection, 278, 279, 288, 289, 303, 311, 314
disorientation of the fibrils, 409, 412, 417
disoriented fibrillar network, 409
disperse dyes, 84, 103, 116, 121, 122, 157, 158, 159,
160, 161, 162, 163, 164, 165, 179, 181, 182, 184,
229
dispersing metallic particles, 248
dispersion, 91, 94, 99, 158, 181
displacement, 89, 254, 472
dissociation, 5, 185, 195
distillation, 139
distilled water, 31, 123, 126, 128, 137, 146, 385, 514
distribution, 4, 5, 16, 52, 70, 112, 113, 155, 295, 345,
419, 420, 493
diverse core materials, 344
diversification, viii, 499
diversification of jute, viii, 499
diversity, 315, 336
DMF, 176
DNA, 54, 77, 234, 278, 305
DNA damage, 278, 305
556
Index
doctors, 447, 460

dogs, 500
DOI, 381
domestic animals, 500
domestic washing, 348, 349
donors, 217
doping, 222, 224, 296
doppler, 466, 467
dosing, 85
double bonds, 430
downstream shear stress, 467
draft, 53, 56, 58, 59, 502, 505, 506
draught, 453
drawing, 416, 451, 505, 506
dressings, 384
drop-on-demand inkjet printing technique, 86
DRS, 296, 303
drug carriers, 350
drug delivery, 192, 199, 209, 350
drug release, 188, 199, 205
drugs, 157, 159, 344
drying, 29, 30, 87, 90, 98, 100, 128, 343, 345, 346,
350, 351, 403
DSM, 352
durability, 21, 39, 54, 121, 191, 221, 250, 343, 344,
345, 346, 349, 353, 362, 363, 365, 370, 371, 465,
474, 476, 478, 500
durable fragrances, vii, 344
durable press, 355, 356, 362, 363, 364, 367, 368,
372, 377, 378, 379, 380
durable press finishing, 356, 362, 363, 367, 372, 377,
378, 379, 380
dye manufacturing companies, 158
dyeing, 34, 49, 51, 82, 84, 103, 122, 158, 160, 164,
165, 166, 170, 172, 174, 176, 179, 181, 182, 183,
184, 192, 195, 196, 200, 204, 218, 220, 242, 381,
384, 396, 414, 501, 502, 506
dyeing characteristics, 158, 183
E
Eastern Europe, 10, 256, 353, 397, 529
easy care finishing, 367, 377
easy-ironing clothes, 368
eco-fashion, 25
ecology, 450, 461
economic downturn, 4
economical cost, 477
economics, 162
eczema, 370
editors, 122, 154, 228, 229
education, 480
educational background, 269
egg, 396
Egypt, 83, 268, 337
Egyptian mummies, 338
elaboration, 252
elasticity, 95, 192, 245, 401, 403, 472, 473, 476, 478,
541
elasticity hypotheses, 472, 473
election, 469
electric charge, 410
electric current, 220
electric field, 87, 94, 244, 280
electrical conductivity, 248, 496
electrical properties, 249, 250, 256, 403
electricity, 82, 84, 119, 246, 401, 403, 447, 448, 449,
453
electrochemical reaction, 263
electrochromic dye, 103
electrochromic materials, 219, 220, 221, 224, 234
electrochromic switches, 187, 190, 194, 208
electrochromic textile production, 219, 224
electrodes, 201, 219, 227
electrolyte, 98, 220, 221, 235
electromagnetic, 192, 194, 280, 448, 460
electromagnetic influences, 448
electron diffraction, 155
electron microscopy, 44, 45, 285, 299, 303, 304, 316,
321, 322, 326, 327, 332, 341, 343, 345, 346, 545
electron-accepting group, 177, 179
electron-donating substituents, 177, 179, 229
electronic and photonic textiles, 190
electronic devices, 251, 254, 344
electronic materials, 54
electronic smart textile, 239, 252, 254
electronic structure, 195, 203
electronics, vii, viii, 54, 90, 96, 188, 189, 226, 227,
230, 240, 247, 249, 250, 256, 447, 448, 450, 452,
453, 455, 461
electrophotographic (, 55
electrospinning, 220
electrostatic properties, 400
elementary fibers, 408
elongation, 25, 30, 51, 56, 89, 132, 142, 150, 330,
334, 409, 501, 502, 509, 519, 521, 522, 524, 527,
528
e-marketing, 12
embedding microencapsulated phase change
materials, 455
embolism, 474
emergency, 64, 188
emerging markets, 10
emission, 193, 194, 195, 243, 295
empirical studies, 6
employees, 11
Index
employment, 273
emulsions, 351
encapsulate, 264
encapsulated nanoparticles, 344
encapsulation, 189, 344, 351
encouragement, viii
endangered, 320, 325
endorsements, 5
endothelial cells, 467
endothelium, 479
energy, 82, 92, 100, 112, 122, 158, 162, 190, 193,
198, 202, 214, 222, 223, 224, 230, 239, 241, 245,
251, 279, 280, 285, 301, 306, 308, 309, 383, 384,
385, 387, 388, 390, 392, 394, 395, 396, 444, 448,
449, 452, 453, 476, 484, 486, 491
energy constraint, 239
energy density, 241
energy supply, 251
energy transfer, 122, 193, 230, 241
enforcement, 250
engineering, 54, 77, 90, 188, 191, 210, 227, 239,
240, 245
England, 28, 29, 120, 124, 136, 145, 255, 276
entangled fibers, 399, 401, 418
entangled hemp fibers, 399, 401
entanglements, 245
entrapment, 98, 418
entrepreneurs, 7, 16
environmental change, 189, 245
environmental conditions, 103, 115, 117, 189, 190,
209, 271, 273, 278, 315, 320, 321
environmental effects, 294
environmental factors, 263
environmental impact, 441, 443
environmental influences, 368
environmental issues, 9
environmental pollution, 124
environmental protection, 240
environmental stimuli, 190, 192, 193, 214
environmental warning system, 117, 209
environmentally friendly clothes, 399
environments, vii, 83, 87, 109, 196, 240, 244, 260,
264, 268, 274, 321, 336, 449, 485, 488, 491
enzymatic action, 23
enzymatic degradation, 24, 377
enzymatic hydrolysis, 24, 41, 401
enzymatic process, 20, 24
enzyme(s), 19, 20, 21, 22, 23, 24, 26, 27, 28, 33, 34,
35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,
48, 49, 50, 51, 52, 117, 180, 192, 209, 278, 317,
338, 341, 403, 441
enzyme wash, 19, 20, 21, 22, 23, 26, 27, 28, 33, 34,
35, 37, 38, 39, 40, 41, 42, 44, 47, 48
557
enzyme washing process, 21, 22, 23

epidemic, 396
epidermis, 352
equilibrium, 158, 177, 178, 179, 212, 280, 414, 415,
416, 420, 421, 422, 423, 424, 426, 427, 436, 489,
491
equilibrium adsorption process, 422
equilibrium ion concentration, 423, 424, 426, 427
equipment, 24, 80, 100, 252, 522
ergonomics, 191
Escherichia coli, 384
estate sales, 4
ester, 30, 132, 134, 143, 150, 153, 163, 171, 173,
236, 356, 357, 358, 362, 363, 364, 365, 372, 379,
380
ester bonds, 362
etching, 254
e-textile applications, 462
e-textile fabric, 254
ethanol, 97, 98, 123, 124, 125, 129, 138, 145, 168,
178
etherification, 125, 129, 130, 131, 132, 154
ethers, 197, 217, 231, 434
ethical awareness, 10
ethical issues, 13
ethics, 276
ethyl alcohol, 124
ethylcellulose, 362, 365
ethylene, 164, 214, 246, 255, 350
ethylene glycol, 350
ethylene oxide, 255
EU, 226
Europe, 3, 10, 84, 180, 256, 265, 316, 353, 397, 529
evaporation, 92, 100, 295, 430, 483, 484, 485, 488
evaporative heat loss, 387, 395, 485
evenness, 401, 403
everyday life, 124, 136, 145, 260, 449
evidence, 7, 134, 143, 150, 260, 263, 270, 271, 272,
275, 283, 294
evolution, 2, 33, 42, 77, 260, 436, 472, 473
examinations, 535, 542
excavated textiles, 259, 260, 270, 271, 273, 274
excavation project, 270, 271
excavations, 83, 265, 271
excitation, 107, 116, 222, 224
execution, 66
exercise, 479, 484, 496
exertion, 244
expensive organic materials, 450
experimental condition, 426
experimental design, 510
expertise, 5, 9, 10, 12, 14, 113
558
Index
exposure, 74, 75, 76, 99, 104, 112, 113, 114, 115,
194, 196, 197, 205, 206, 218, 250, 322, 337, 340,
533
extension at break, 500
external compression, 466
external environment, 190, 484
external influences, 323
external surface adsorption, 422
extinction, 157, 159, 162, 280
extraction, 128, 247, 400, 438, 440, 441, 446
extrusion, 211, 218, 220, 241, 352, 539
F
fabric antibacterial kinetics, 280
fabric based circuits, 253
fabric construction factors, 476
fabric cover factor, 506
fabric deformation, 466
fabric dimensional properties, 385
fabric prosthesis, 465, 474, 478
fabric scaffold, 475
fabric thickness, 386, 391, 392, 489, 506, 508, 512
fabric weight, 19, 31, 34, 35, 36, 37, 39, 41, 345,
506, 507, 508, 509, 510, 511, 512, 513, 515
fabrication, 54, 77, 253
Fabrication, 119, 462
family members, 11
fashion, vii, x, xiii, xiv, xv, 1, 2, 3, 4, 7, 8, 9, 10, 12,
13, 15, 16, 18, 20, 21, 22, 23, 25, 49, 50, 63, 81,
85, 107, 117, 118, 119, 136, 187, 192, 209, 225,
234, 240, 247, 250, 367, 449, 450, 455, 457, 460,
465
fashion aspects, 367
fashion consumer, 1, 2, 7
fashion effects, 21
fashion industry, 2, 3, 4, 63
fashion trends, 3, 4, 8, 10, 20, 23, 450, 460
fastness properties, 104, 157, 163, 165, 168, 175
fat, 418
fatigue resistance, 106, 196, 200, 253, 465, 474, 478
fatty acids, 217
feelings, 495
fiber bundles, 409, 414, 415, 539
fiber content, 490
fiber crystalline phase, 414
fiber diameter, 406, 409, 414, 537
fiber movement, 449
fiber optic coupler, 533
fibre compositions, 319
fibre identification, 266
fibre position, 520
fibrillation, 331, 405, 406, 408, 411, 413, 417, 419,

432
fibrils, 24, 35, 44, 47, 332, 336, 402, 406, 408, 409,
412, 417
field crops, 538
filament, 249, 476
film thickness, 286
films, 101, 112, 123, 127, 128, 132, 136, 139, 145,
150, 155, 221, 224, 233, 234, 235, 253, 254, 277,
278, 283, 285, 286, 288, 289, 290, 292, 294, 297,
298, 301, 305, 306, 313, 314, 452
filters, 157, 163, 179, 180, 182, 195, 533
filtration, 94, 127
financial, 17, 180, 310, 537
financial support, 310
fineness, 24, 56, 401, 403, 407, 409, 490, 509
finishing, 19, 20, 21, 25, 48, 49, 58, 90, 344, 352,
353, 356, 361, 362, 363, 365, 367, 369, 371, 372,
373, 377, 378, 379, 380, 381, 382, 384, 386, 394,
462, 471, 490
finishing material, 386
finite element method, 467, 497
Finland, 256
fire fighting, 250
fire-retardant fabrics, 384
first aid, 240, 273
first generation, 240, 466, 471
fish, 351
fish oil, 351
fishing, 246
fitness, 250
fixation, 55, 78, 100, 377, 381, 466, 471
flame, 240, 356, 360, 361, 363, 364, 365
flame protection, 240
flammability, 243, 361, 373
flavor, 344
flavour, 351, 352, 353
flax, 266, 268, 320, 321, 322, 323, 324, 325, 337,
400, 410, 441, 443, 538, 539
flax fiber, 443, 539
flex, 460
flexibility, 19, 31, 55, 84, 191, 216, 240, 243, 248,
249, 253, 402, 409, 410, 474, 475, 476, 477, 488
flexible circuit boards, 253
flexible display techniques, 188
flexural rigidity, 51, 383, 384, 386, 390, 396, 502,
503, 506, 507
floating clothing, 448
floods, 453
flora, 339
flow field, 467, 468
flow properties, 94, 467
flowers, 218
559
Index
fluctuations, 241
fluid, 83, 85, 87, 90, 93, 94, 95, 96, 97, 98, 99, 118,
195, 414, 467, 478, 479
fluorescence, 19, 32, 33, 46, 47, 192, 202, 204, 205,
301, 533
fluorescence microscope, 19, 32, 33, 46
fluorescent brighteners, 64, 161
fluorescent lights, 67
fluorescent sensor, 204
fluorotriazine groups, 172
focal plane thickness, 533
food, 18, 54, 90, 124, 210, 344, 351, 362, 450, 455,
460
food decorating, 54
food products, 124
foods, 157, 159, 351
footwear, 104, 242, 243
force, 30, 33, 51, 56, 88, 96, 193, 305, 306, 308, 460,
476, 477, 504
forced-evaporation-type skin capsule, 488
formal suit, 8
formaldehyde, 345, 356, 362, 363, 364, 365, 369,
370, 371, 378, 379, 380
formaldehyde-based chemicals, 369
formaldehyde-free easy care agents, 370
formation, 82, 87, 88, 94, 98, 132, 141, 153, 155,
195, 213, 222, 239, 245, 254, 263, 276, 278, 279,
280, 285, 289, 290, 308, 333, 356, 357, 358, 361,
362, 368, 371, 372, 380, 404, 406, 408, 419, 432,
467, 472, 501, 504, 513, 516
formula, 32, 127, 395, 493
Fourier transform infrared spectroscopy, 316, 340
fragmentary painted clay-covered basketry, 270
fragments, 261, 264, 265, 272, 275
fragrance microcapsule, 344, 345
France, 10, 51, 479
free radicals, 233, 357, 375
free volume, 112, 113
free world, 450
freedom, 108, 390
freezing, 102, 244, 272, 351
friction, 25, 35, 245, 283, 346, 476, 502, 503, 520,
541
frictional washing, 347
fruits, 446
FTIR, 123, 128, 132, 133, 134, 139, 142, 143, 145,
147, 150, 151, 153, 274, 321, 322, 323, 324, 326,
328, 329, 330, 332, 333, 334, 337, 339, 340, 341,
357, 358, 363, 364, 380, 397
FTIR spectroscopy, 321, 323, 324, 326, 339, 341,
380
fulgides, 107, 194, 197, 199, 201, 202, 230
fulgimides, 107, 197, 202
functional dyes, 81, 82, 103, 104, 118

functional inkjet ink, 98, 103
functionalized smart textiles, 239
fundamental weave, 385
funding, 153
fungal colonisation, 317
fungal contaminations, 316
fungal growth, 92, 283, 316, 320, 321, 322, 323, 330
fungal infection(s), 320, 321, 322, 324, 325, 336
fungal proteolytic activities, 333
fungal species, 315, 317, 325, 326, 331, 332, 333,
334, 336
fungal spores, 320
fungi, 23, 50, 289, 315, 316, 317, 318, 320, 321, 323,
326, 329, 330, 331, 332, 334, 336, 338, 340, 341
fungus, 326, 340
furan, 202
furnishings, vii, 316
fusion, 191, 242, 276
fusion technology, 191
G
galactoglucomannans, 402
Galaxy, 451
garage sales, 4
garment industries, 20, 124
gasification, 435
gasification process, 435
gel, 91, 122, 128, 132, 139, 142, 147, 150, 235, 277,
278, 362, 375, 384
gel content, 132, 139, 142, 147, 150
gelation, 350
genus, 320
geometry, 58, 116, 208, 211, 297, 473, 474, 475,
476, 477, 478, 520
Georgia, 319
Germany, ix, xi, xiv, 28, 99, 124, 227, 228, 255, 256,
257, 295, 310, 313, 346, 367, 387, 453, 531, 543
germination, 317
gland, 488
glass transition, 245
glass transition temperature, 245
glass transition temperature polymers, 245
glasses, 195, 232
global awareness, 22
global brands, 2
Global Positioning System, 241
glucose, 20, 23, 199, 328, 329, 377
glucoside, 401
glue, 242
glycerol, 98, 441
glycol, 98, 350
560
Index
glycoside, 322, 323, 328, 329

glycosidic bonds, 402
glycosidic linkages, 401
GPS, 241, 250
grades, 123, 124, 153
graduate students, viii
graft implantation, 475
graft polymerization, 139, 147
grafting, 124, 127, 132, 134, 141, 143, 149, 150,
362, 382
grafting efficiency, 127, 141, 149
grafts radial resistance, 466
grain size, 306
graphite, 432
grass, 85
gravimetric analysis, 360, 361
gravity, 92, 414, 416
gravure printing, 242
Great Britain, 4
Greece, v, x, xii, xiv, 259, 260, 261, 262, 265, 266,
268, 269, 273, 274, 276
green chemistry, 22
growing polymer chain, 541
growth, 2, 18, 84, 92, 99, 264, 272, 278, 281, 283,
285, 295, 296, 316, 317, 320, 321, 322, 323, 326,
330, 331, 336, 361, 400, 402, 415, 440, 474, 475,
539, 541
guidance, 270, 272
guidelines, 320
H
haemodynamics, 467, 474, 478
haemolysis phenomenon, 467
hair, 339, 341, 536, 537
hairiness, viii, 519, 520, 521, 522, 525, 526, 527, 528
hallucinogenic properties, 400
halochromic, 218
halogenation, 184
hand sewn woven structures, 466
handloom preparatory machinery, 506
hardwoods, 402
harmony, 483
harvesting, 103, 452
hazardous substances, 448
hazards, 101, 370
HCC, 323, 329
headache, 370
healing, 310
health, 92, 101, 187, 188, 190, 199, 225, 227, 240,
250, 252, 253, 278, 279, 356, 448, 449, 481
health care, 187, 199, 225, 250, 252, 278, 448, 481
health information, 240
health status, 240, 252

heart attack, 477
heart rate, 240, 455
heart valve application, 466
heart valve replacement, 465, 475
heat loss, 246, 384, 387, 395, 483, 484, 485, 486,
488, 491
heat release, 242
heat resistance, 158, 163, 171, 180, 289
heat resistance surfaces, 289
heat transfer, 158, 393, 485, 486, 487, 488, 489, 490,
491, 492, 493, 494, 496, 497
heat transfer coefficients, 487, 488, 496
heat transfer printing, 158
heating rate, 432
heat-retaining properties, 492
heat-setting temperature, 477
heat-storage capacity, 242
heat-transfer mechanisms, 485, 486
heavier travellers, 523
heavy metal biosorbents, 399, 401
heavy metal ions biosorption, 399, 440
heavy metal ions solution, 418
heavy metals, 400, 420, 422, 430, 436, 437, 440, 443
height, 324, 414, 415, 416, 484, 534, 536
helix profiles, 520
hemicellulose(s), 321, 323, 329, 399, 401, 402, 403,
404, 405, 407, 408, 409, 410, 411, 412, 413, 414,
415, 416, 417, 418, 419, 430, 432, 441, 442, 443,
501, 538
hemp fiber chemical composition, 399, 417, 440
hemp fiber surface, 411, 413, 417, 419
heterocyclic components, 159, 162, 184
heterogeneity, 56, 112
heterogenous chemical composition, 399, 401
hexane, 176, 197
high energy disperse dyes, 158
high fat, 200
high performance fabrics and garments, 241
high performance photo-responsive surfaces, 88
high strength, 34, 40, 43, 48, 504
high value-added products, 384
high-density imperfections, 289
higher molar mass dyes, 158
high-pressure liquid chromatography, 321
high-resolution optical pictures, 531
high-tech dresses, 450
high-technology applications, 81, 103, 118
historical and archaeological textile objects, 318
historical overview, 85
historical textiles, 317, 318, 320, 321, 322, 325, 335,
336, 337, 339
561
Index
history, 9, 10, 13, 83, 210, 233, 270, 272, 315, 321,
322, 335, 462, 494, 497
homeland security, 250
homogeneity, 113, 419
Hong Kong, 28
hormones, 344
host, 192, 199, 271, 473
hot-melt inks, 157, 173, 179, 183
House, 255, 312
HPLC analysis, 266
hub, 187
hue, 59, 65
human, viii, 21, 67, 71, 191, 209, 226, 243, 251, 260,
278, 279, 292, 310, 316, 339, 356, 368, 377, 387,
472, 474, 477, 479, 480, 483, 484, 486, 487, 488,
490, 494, 495, 496, 511
human activity, 490
human body, viii, 191, 243, 368, 472, 483, 484, 486,
487, 488, 494, 496
human health, 356
human perspiration, 488
human skin, 209, 377, 387, 490, 495
human visual system, 71
Humicola insolens, 23
humid wound-pads, 279
humidity, 54, 74, 104, 112, 118, 219, 244, 250, 283,
285, 315, 317, 320, 324, 326, 336, 377, 384, 403,
410, 411
humidity sensor, 54
Hunter, 182, 442
hunting, 12
hybrid, 77, 113, 118, 122, 234, 255, 452, 455, 461,
477
hybrid film/fiber, 452
hydazone tautomers, 179
hydrazone, 157, 177, 178, 179, 185
hydrocarbons, 217
hydrochromic, 247
hydro-extractor, 28
hydrogels, 205, 206, 219, 351
hydrogen, 22, 124, 125, 136, 163, 169, 170, 172,
176, 177, 178, 212, 218, 230, 232, 306, 323, 329,
358, 368, 375, 401, 404, 414, 418
hydrogen abstraction, 176
hydrogen bonds, 306, 323, 368
hydrogen peroxide, 22, 124, 125, 136
hydrogen peroxides, 22
hydrolysis, 24, 33, 34, 35, 38, 39, 41, 43, 44, 48, 51,
123, 139, 140, 263, 317, 323, 329, 338, 375, 401
hydrolytic degradation, 319, 340
hydrophilic gel, 384
hydrophilicity, 311
hydrophobic fibers, 157, 158, 164, 165, 181
hydrophobic lignin network, 403

hydrophobic synthetic fibers, 164
hydrophobicity, 95, 307, 308
hydroxide, 123, 124, 125, 126, 400, 404, 406, 410,
417, 434, 436, 440, 445, 502, 516
hydroxyl, 129, 130, 134, 141, 148, 152, 158, 172,
179, 355, 356, 357, 358, 362, 368, 371, 372, 373,
375, 377, 401, 402, 404, 405, 406, 430
hydroxyl groups, 130, 134, 141, 149, 152, 355, 358,
362, 368, 371, 372, 373, 377, 401, 405, 406, 430
hygiene, 396
hygroscopicity, 400
hyperplasia, 467, 471, 479
hyphae, 317, 318, 322, 329
hyphal penetration, 317
hypochlorite bleaches, 22
hypothermia, 244
hypothesis, 525
hypsochromic shifts, 176
hysteresis, 480
I
ICC, 54, 55, 58, 59, 61, 63, 64
ideal, 109, 240, 241, 397, 477, 520, 532
identification, 147, 189, 211, 266, 268, 283, 341, 457
identity, 5, 316, 515
illumination, 56, 65, 67, 69, 75, 76, 533
image analysis, 462
image generation software, 90
image makers, 3
imagination, 457
imitation, 5
immersion, 31, 33, 52, 128, 147
immobilization, 145, 442
implantable materials, 468
implants, 188, 279, 313, 465, 466, 471, 475, 480,
481
impregnation, 263, 283, 343, 345, 346
improvements, vii, 101, 103, 250
impurities, 99, 136, 289, 401, 403, 406, 537
in vitro, 350, 474, 475, 480
in vivo, 279
incandescent light, 67, 69
incidence, 285, 313
income, 1
incompatibility, 98
increased competition, 2
incubation, 316, 326, 327, 328, 329, 331, 333, 334,
336
incubation period, 316
incubation time, 329, 334, 336
independent variable, 510, 515
562
Index
India, x, xiii, xiv, xv, 28, 124, 136, 145, 268, 396,
465, 483, 496, 499, 500, 516, 517
indigo dye, 23, 25, 27, 35, 49
individuality, 2
individuals, 10
inducible enzyme, 23
induction, 50, 246
inductively coupled plasma mass spectrometry, 321
industrial environments, 87
industrial wastes, 430
industries, 20, 22, 23, 24, 47, 54, 83, 123, 124, 136,
153, 455
industry, vii, 1, 2, 3, 4, 20, 21, 22, 23, 24, 47, 49, 50,
55, 63, 65, 81, 82, 84, 102, 120, 124, 136, 145,
154, 188, 190, 210, 246, 343, 344, 352, 353, 356,
361, 367, 399, 401, 440, 455, 517, 533
infants, 250, 455
infection, 320, 324, 325, 331, 336, 460
information technology, 188, 240
infrared spectroscopy, 316, 340, 341, 379
ingredients, 94, 99
inhibition, 121, 281, 338, 367
inhibitor, 97, 99
inhomogeneity, 71, 74, 76
inhumation burials, 259, 261, 265, 266, 268, 273
initial state, 109
injury, 240, 476
ink droplet, 82, 88, 89, 92, 95, 98
ink formulations, 92, 95, 97, 98, 99, 106, 108, 109,
112, 116
inkjet disposing fluids, 97
inkjet inks, 64, 81, 84, 86, 88, 91, 92, 94, 98, 99,
100, 101, 102, 103, 104, 105, 109, 111, 115, 117,
118, 121
inkjet inks formulations humectants, 98
inkjet nozzles, 94
inkjet printed image, 81, 103, 118
Inkjet printed photo-responsive textiles, 197, 229
inkjet printed substrates, 82, 104, 111, 113, 115, 116,
117
inkjet printing, 54, 55, 61, 64, 71, 76, 77, 78, 81, 82,
84, 85, 86, 87, 88, 90, 91, 94, 95, 98, 100, 101,
103, 104, 105, 108, 111, 115, 118, 119, 120, 166,
192, 195, 220
inkjet printing technology, 54, 82, 86, 95, 103, 104,
120
inoculation, 316, 326, 330, 331, 334
insect repellents, 344
insertion, 190, 247, 457
inspections, 316
institutions, 316, 317, 320, 321, 322, 324, 335, 336,
337
Instron, 386, 522
insulating material, 486, 499, 500, 515

insulation, 242, 243, 246, 251, 254, 386, 397, 484,
485, 486, 488, 489, 490, 491, 492, 493, 495, 497,
499, 500, 501, 504, 505, 506, 508, 509, 510, 514,
515, 516, 517, 518
insulin, 443
integration, 90, 100, 104, 118, 188, 190, 210, 226,
228, 234, 248, 350, 447, 448, 455
intelligent coating/membranes, 240
intense laser pulses, 543
interactive textiles, 249, 449
interface, 247, 251, 253, 283, 424, 475, 494
interfacial capillary forces, 414
interfacial charge transfer, 278, 297, 301, 305, 306,
308, 309, 314
interfacial charge transfer mechanism, 297
interference, 193, 533
interfibrillar regions, 412
interfibrillar spaces, 427
inter-filament cohesion, 476
interlacing, 247, 455
intermolecular interactions, 113, 334
international competition, 453
interventive action, 271
intramolecular bonding, 329
intraparticle diffusion model, 421
intrinsic ink characteristics, 92
intrinsic viscosity, 126, 127, 130, 131
invertebrates, 264, 275
investment, 4, 289
inward diffusion, 295
iodine, 351, 413, 414
iodine sorption, 413, 414
iodine sorption values, 413
ion exchange mechanism, 384
ion transport, 422, 427, 437, 438
ion-exchange, 443
ion-fiber interactions, 427
ionic crosslinking, 374, 377, 381
ionization, 283, 404, 410, 418
ionochromic dye, 103
IPO, 440
IR spectra, 177
IR spectroscopy, 341, 380
Iran, ix, 239
iridium, 220, 221
iron, 262, 264, 267, 268, 273, 313, 351
irradiation, 103, 105, 106, 107, 108, 109, 110, 111,
114, 115, 117, 167, 180, 194, 196, 197, 199, 200,
206, 207, 278, 280, 288, 289, 292, 293, 294, 295,
300, 301, 305, 306, 309, 313, 317, 337, 357, 364,
376, 381
IR-spectra, 128
563
Index
Islam, viii, 154
isomerization, 105, 208
isomers, 112, 113, 194
isotherms, 420
isotope, 185
issues, 7, 9, 10, 13, 81, 90, 98, 101, 104, 195, 225,
239, 251, 260, 288
Italy, 256
J
jacket fabric, 507, 508
jacquard weaves, 506
Japan, 32, 44, 46, 49, 56, 121, 127, 128, 129, 226,
228, 280, 311, 481, 497
jettable inks, 81, 118
Jordan, 270, 276
jute fibre, 500, 501, 509, 516
jute spinning system, 505
jute-acrylic blended yarn, 502
jute-based materials, viii, 499, 515
jute-blended yarn, 506, 507
jute-hollow polyester blended yarns, 502, 503, 505
jute-polyester blended yarns, 502, 507
jute-polypropylene blended needle-punched
nonwoven fabrics, 511
jute-shrinkable acrylic fibre, 502
juxtaposition of vintage, 3
K
K+, 221, 296, 297, 300, 314
KBr, 128, 132
keratin, 333, 341
keratin oxidation, 333
ketones, 217
kidney, 346, 348, 349
kill, 165
kinetic model, 112, 420, 421, 444
kinetic parameters, 421
kinetics, 24, 112, 113, 114, 176, 184, 263, 277, 278,
279, 280, 283, 284, 287, 290, 292, 295, 297, 301,
303, 305, 306, 341, 415, 444, 479
knees, 487
knitted fabrics, 397, 468, 477
knitted rag, 124, 125, 126, 128, 129, 130, 132, 133,
136, 137, 138, 139, 141, 143, 145, 146, 148, 149,
150, 153
knitted structure, 468, 477, 500
knitting machines, 254, 468
knitting yarn, 515
KOH, 404, 435, 436, 444, 445
Korea, 257
Kubelka-Munk function, 108
L
lactose, 50
lamella, 408, 409, 413, 417, 419
laminar, 82, 444
lamination, 101, 242, 508
Langmuir and Freundlich adsorption isotherms, 420
laptop, 452
laser and computer technology, 532
laser beam, 166, 531, 532, 533
laser-produced surface structures, 543
lasers, 193
laser-treated polyester fiber, 533
lattice transformation, 404
law enforcement, 250
leaching, 278, 289, 294
leadership, 5
leakage, 297, 300, 361, 474
Leather, 11, 119, 121, 122, 229
LED, 64, 101, 118, 447, 448, 450, 451, 453, 454,
455, 457, 459, 460
LED light, microcontroller, 448
leisure, 226, 247
lending, 248
lens, 246, 532
leuco dyes, 210
leuco-derivative, 204, 205
leveling properties, 158
liberation, 407, 408, 411
ligand, 211
light conditions, 56, 109, 457
light- induced colour changes, 194
Light irradiation photo-activates, 300
light transmission, 115
light-emitting diodes, 189
light-emitting polymers, 189
lightfastness, 53, 54, 56, 76, 78, 184, 217, 218
lightweight optical fibers, 253
lightweight shawl fabrics, 507
lignin, 399, 401, 402, 403, 404, 405, 406, 407, 408,
409, 410, 411, 412, 413, 414, 415, 416, 417, 418,
419, 430, 432, 440, 441, 442, 443, 501, 538
lignocellulosic fibers, 404, 405
lignolytic white rot fungi, 326
limestone, 264
linear cellulose chains, 401
linen, 51, 54, 58, 315, 339, 443, 538
lipids, 24
liposomes, 351
liquid chromatography, 321, 438, 446
564
Index
liquid chromatographytandem mass spectrometry

technique, 438
liquid crystals, 193, 210, 215, 233, 247
liquid phase, 127, 244
liquid-crystal display panels, 157, 182
liquids, 414, 415, 441
Listeria monocytogenes, 384, 396
lithium, 98
lithography, 233
livestock, 250
living organism, 23, 418
longevity, 21
long-term preservation, 270, 272
long-term storage, 317
low temperatures, 202, 320
lower breaking strain, 330
lubricants, 414
luggage, 457
lumen, 476, 477
luminescence, 230, 322
Luo, 79, 80, 226, 255
luxury vintage gowns, 3
lying, 494, 537
M
machinery, 84, 506
macromolecular chains, 113, 430
macromolecular systems, 212, 214
macromolecule orientation, 329
macromolecules, 214, 317, 324, 330, 333, 334
magazines, 9
magnesium, 94
magnetic field, 244, 245
magnetic resonance, 156, 467
magnetic resonance imaging, 467
magnetic shape memory alloys, 245
magnitude, 67, 277, 421, 426, 533
majority, 8, 12, 25, 102, 105, 158, 247, 252, 259,
265, 266, 273, 308
man, 158, 211, 397, 400, 471, 484, 499, 531, 536,
540
management, vii, 4, 6, 16, 18, 53, 54, 55, 58, 59, 61,
65, 66, 78, 79, 93, 191, 227, 246, 455, 471, 490
manganese, 221
manipulation, 193, 210
man-made fibres, 499
manufacturing, 22, 28, 89, 90, 93, 118, 124, 136,
158, 159, 241, 397, 457, 466, 500
manufacturing companies, 158
mapping, 210
market position, 6, 17
market segment, 227
market share, 101

marketing, 4, 5, 6, 12, 15, 17, 397
marketing literature, 4, 6
marketing strategies, 17
marketing strategy, 6
marketplace, 6
masking, 268
mass, 3, 4, 9, 32, 51, 56, 82, 158, 286, 296, 297, 300,
305, 321, 390, 422, 423, 430, 438, 446, 455, 486,
523, 525, 536
mass loss, 430
mass spectrometry, 286, 296, 297, 300, 305, 321,
438, 446
material surface, 255, 434
matrix, 107, 112, 113, 115, 116, 117, 193, 194, 242,
247, 249, 306, 350, 401, 402, 408, 443, 512, 513
matrixes, 122
matter, 190, 263, 368, 372
maxi dresses, 10, 11
maximum sorption, 418, 419
meat, 351
mechanical abrasion, 23, 25, 41
mechanical properties, 19, 29, 30, 36, 51, 248, 249,
315, 322, 329, 334, 336, 372, 386, 403, 442, 466,
472, 478, 480, 491
mechanical resistance, 240
mechanical responsive materials, 240
media, 2, 3, 4, 12, 13, 55, 63, 65, 66, 67, 92, 112,
113, 177, 190, 200, 220, 230, 292, 405, 462, 500
medical, vii, 85, 188, 210, 240, 244, 245, 247, 250,
257, 278, 344, 395, 449, 455, 460, 465, 468, 479
medical and health care applications, 278
medical textiles, vii, 85, 188, 244, 247, 449, 465, 479
medication, 474
medicinal applications, 447
medicine, 227, 240, 255, 344, 362
Mediterranean, 276
MEG, 16
MEK, 98
melamine-formaldehyde, 369
melt, 102, 157, 165, 173, 179, 183, 220
melting, 210, 216, 241, 357
melts, 241
membranes, 240, 300, 370
memory, 188, 189, 206, 210, 226, 239, 240, 244,
245, 246, 255, 432
MEMS, 77, 84, 88, 103, 118, 189, 449
mercerization, 404, 442
merchandise, 6, 10, 12, 13, 14, 15
merchandise strategy, 6
merchandising, 4, 7
mercury, 263, 280, 472
mesh-free stapled fibre, 509
Index
messages, 252
metabolic processes, 483
metabolism, 484
metabolites, 317
metal corrosion products, 262, 263, 264, 275
metal fibers, 248, 542
metal ion(s), 199, 208, 218, 221, 230, 231, 262, 263,
389, 399, 412, 418, 419, 420, 422, 423, 424, 425,
426, 427, 428, 429, 436, 437, 438, 440, 441, 443,
445, 446
metal nanoparticles, 279, 285
metal oxides, 220, 221, 248, 249
metal salts, 94, 248, 249
metallic brilliance, 542
metallic glittering, 542
metals, 189, 193, 211, 219, 221, 223, 248, 249, 250,
262, 263, 264, 267, 273, 289, 400, 418, 420, 422,
430, 436, 437, 440, 443
meter, 31, 56, 489, 511, 522, 523
methacrylates, 122
methanol, 123, 127, 145, 146
methicillin-resistant, 384, 396
methodology, 76, 184
methyl methacrylate, 123, 124, 127
micro encapsulation, 189
microbial attack, 283, 317
microbial communities, 337
microbial community, 338
microbial degradation, 320, 339
microcapsules, 195, 216, 241, 242, 243, 255, 343,
344, 345, 346, 347, 348, 349, 350, 351, 352, 353,
362, 365, 455, 462
microcapsules stability, 343, 348, 349
microclimate, 243, 244
micro-disposal technique, 83, 85, 87, 90
micro-electromechanical machines, 240
micro-electronic mechanical systems, 189
microelectronics, 240
microemulsion, 77
micro-engineering industries, 54
microfibril, 401
micro-lens, 533
microorganism(s), 50, 317, 339, 377, 384
micro-organisms inhibitors, 263
microporous structure, 436
microscope, 19, 32, 33, 44, 46, 57, 58, 266, 323, 358,
531, 532, 533, 542, 543
microscopic images, 533, 534, 535, 537, 538
microscopy, viii, 44, 45, 46, 47, 284, 285, 299, 303,
304, 305, 306, 308, 310, 316, 321, 322, 326, 327,
332, 339, 341, 343, 345, 346, 531, 532, 537, 544,
545
Microsoft, 7, 462
565
Microsoft Word, 7
microspheres, 350
microstructure, 277, 286, 303, 305, 306, 307, 351,
401
microtome, 282
microwave irradiation, 167, 180
middle class, 3
middle lamella, 408, 409, 413, 417, 419
migration, 120, 158, 171, 263, 477, 501
migration resistance, 171
military, 194, 240, 244
military applications of smart textiles, 240
mineralised fibres, 263
mineralization, 177, 274
mini dresses, 11
Ministry of Education, 153, 180
mixing, 248
MMA, 123, 124, 127, 128, 131, 132, 133, 134, 139,
141, 142, 143, 149, 150, 151, 152
mobile phone, 190, 241, 450, 460
mobile phone technology, 241
mobile telecommunication, 239
modelling, 121, 274
models, 10, 78, 80, 101, 112, 113, 311, 420, 421,
450, 473, 478, 494
modifications, 216, 254, 499, 500
modified hemp fibers, 399, 405, 407, 409, 410, 411,
412, 413, 414, 415, 416, 417, 418, 419, 420, 421,
440
modules, 190, 251
modulus, 330, 334
mohair, 536
moisture, 123, 132, 139, 142, 147, 150, 154, 191,
242, 246, 250, 265, 283, 367, 368, 397, 410, 414,
415, 483, 484, 485, 488, 490, 493, 494, 495, 540
moisture content, 123, 132, 139, 142, 147, 150, 410,
415
moisture sorption, 154, 415
molar extinction coefficient, 157, 162
moldings, 136
mole, 172, 280
molecular chains, 262, 368
molecular motors, 201, 206, 207, 229
molecular orientation, 214, 418
molecular sensors, 230
molecular stoichiometry, 430
molecular structure, 107, 134, 143, 153, 193, 203,
211, 248, 360, 364
molecular weight, 98, 123, 124, 126, 127, 130, 131,
139, 141, 147, 149, 153, 245, 372, 379, 402, 405,
541
molecules, 34, 54, 107, 108, 109, 112, 113, 115, 116,
158, 164, 176, 193, 199, 203, 206, 210, 211, 212,
566
Index
213, 215, 220, 290, 333, 360, 367, 372, 375, 377,
402, 403, 404, 410, 413, 414, 435, 541
momentum, 82
monoazo, 158, 159, 163, 164, 165, 175, 176, 181,
184
monoazo pyridone dyes, 163, 164, 175, 176
monoclinic crystalline lattice, 404
monolayer, 286
monomer molecules, 541
monomers, 102, 154, 155, 248, 384, 541
monosaccharide, 401, 432
morphological changes, 326, 331, 336
morphology, 129, 268, 316, 326, 358, 400, 402, 406,
408, 409, 432, 436, 437, 440
motivation, 13, 25
mountain climbers, 240
mountain sheep wool, 537
mucous membrane(s), 370
multi-colour printing, 101
multidimensional, 409
multi-functional switches, 203, 207
multifunctional textiles, 240
multimillion pound industry, 1
multiples, 484
multiplication, 467
multi-wavelength laser systems, 533
murals, 101
muscles, 484
museum collections, 337
museums, vii, 259, 260, 315, 316, 317, 320, 321,
322, 324, 335, 337
music, 8, 12
mycelium, 319, 322
mycology, 316
N
Na+, 221, 297, 300, 314
Nacellulose I lattice, 404
NaCl, 127, 131, 237, 295
nano-coatings, 543
nanoimprint, 233
nanomaterials, 240
nanometer, 357, 375
nanoparticle(s), 235, 249, 278, 279, 285, 286, 289,
303, 305, 309, 310, 311, 312, 313, 344, 356, 362,
375, 376
nanotechnologies, 239
nanotechnology, 188, 240, 279, 312, 375
naphthalimide, 159, 161
naphthopyrans, 105, 122, 194, 197, 201
native cellulose, 155, 402, 430, 442
natural blood-vessel deformation, 472
natural colour, 115, 500

natural crystalline structure, 404
natural fibers, 158, 400, 404, 531, 544
natural textiles fibers, 278
needling density, 509, 510, 512, 513, 515
negative casts, 263, 264
negativity, 307
neighbourhood feel, 12
nematic liquid crystals, 210
Netherlands, 542
nettles, 538
neurobiology, 233
neutral, 23, 27, 32, 34, 35, 36, 37, 38, 39, 40, 43, 48,
99, 178, 179, 234, 313, 485
neutral cellulose, 34, 36
new spinning technologies, 520
Newtonian fluids, 94
next generation, 118
NH2, 167
nickel, 220, 248, 263, 521
NIR, 296, 341
nitrates, 156
nitration, 145, 146, 148, 149, 152
nitrides, 278, 307
nitrodiphenylamine, 159
nitrogen, 105, 147, 148, 202, 214, 217, 306, 314,
361, 365, 370, 375, 432
nitrogen content, 147, 148
N-methylol compounds, 369, 370
NMR, 123, 128, 134, 139, 143, 147, 151, 152, 155,
177, 185, 340, 341
no dimension, 509
nominal magnification, 534, 535, 538
noncellulosic components, 400, 403, 405
nonconductive threads, 253, 254
non-destructive examination, viii, 531
non-heat resistant surfaces, 279
non-invasive examination, 532
non-ionic compounds, 158
non-linear least-squares regression, 426
non-linear optics, 296
non-porous media, 92
non-radiative transition, 107
non-wearable textile, 500
North America, 259, 339
nostalgia, 9, 13
nouveau vintage, 3
novel technique, 384
nozzle density, 88
nozzle spray technique, 242
nuclear magnetic resonance, 156
nucleus, 159
numerical analysis, 467
567
Index
numerical aperture, 532, 533
nutrient, 283, 295
nutrition, 317
nylon, 81, 112, 113, 115, 117, 118, 121, 157, 158,
162, 163, 164, 174, 204, 229, 246, 468
O
objective rear aperture, 533
obstacles, 455
obstruction, 428
occlusion, 480
odor intensity, 349
odor measurements, 344
OFS, 256
OH, 125, 130, 141, 143, 148, 149, 157, 167, 168,
177, 285, 294, 301, 323, 329, 362, 402, 404, 406
OH-groups, 404
oil, 102, 338, 351, 352, 353, 400, 414, 415, 417, 441,
506
old clothes, 4
older customers, 9
oligomers, 102, 231, 361, 541
opacity, 476
open-end rotor, 520
openness, 490, 492
operations, 196
opportunities, 2, 10
optic sensors, 227
optical brightener, 53, 55, 63, 65
optical brightening agents, 55
optical density, 113
optical differences, viii, 531
optical examinations, 542
optical fiber, 239, 240, 247, 253, 257, 462
optical fibers, 239, 247, 253
optical light microscopy, 545
optical microscopes, 531, 532
optical microscopy, 321, 532
optical properties, 220, 247, 314
optical wide-field microscopy, 532
optimal performance, 48
optimization, 177, 297, 399, 429, 438, 440
ores, 500
organ(s), 77, 211, 241
organic chemicals, 400
organic chemicals resources, 400
organic compounds, 100, 317
organic fibres, 262, 263
organic matter, 263
organic polymers, 113, 317, 449
organic solvents, 167
organism, 23, 263
original garment, 9
originality, 2, 9
orthotropical traction stiffness, 474
Ostwald viscometer, 126
outdoor clothing, 246, 251
out-of-focus signals, 532
ownership, 3
ox, 430
oxidation, 105, 195, 196, 208, 220, 221, 248, 256,
279, 283, 285, 290, 292, 294, 297, 303, 317, 329,
333, 351, 353, 405, 406, 408, 409, 419, 434, 442
oxidative agents, 405
oxidative reaction, 341
oxidative stress, 341
oxidizing agents, 405
oxygen, 214, 261, 262, 264, 266, 273, 277, 279, 280,
290, 306, 310, 312, 314, 317, 400, 433, 434, 436,
440, 445
P
padding, 343, 345
pagers, 250
pain, 449
paints, 157, 159, 211
palladium, 346
PAN, 442, 542
paper, 53, 55, 56, 58, 65, 66, 67, 69, 71, 74, 76, 80,
82, 83, 85, 101, 119, 124, 128, 154, 157, 159,
166, 256, 260, 317, 318, 337, 340, 341, 355, 448,
461, 495
paper sludge, 124, 154
parallel, 44, 301, 401, 509, 514
parentage, 5
participants, 7, 8, 9, 10, 11, 12
passive smart textiles, 240
passive thermal insulation effect, 242
pathogenic bacteria, 278, 289
pathogenic biofilms, 278
pathogens, 310, 311, 313
pathological effects, 467
pathology, 467
patients wear clothing, 449
PCA, 357, 363
PCBs, 77
PCM, 239, 241, 242, 243, 244, 255, 449
PCT, 119
peace, 450, 460
peat, 418
pectin, 399, 401, 403, 405, 418, 441, 538, 539, 543
pectin-surrounded fiber bundles, 539
pedal, 8
pendant side groups, 401
568
Index
pentose sugars, 401

peptide, 332
percolation, 249
permeability, 36, 190, 297, 361, 383, 384, 387, 395,
396, 397, 484, 490, 491, 507, 509, 512, 515, 517
permit, 123, 409, 414, 449
peroxide, 124, 125, 136, 314, 345, 406
personal communication, 260
personal contact, 5
personality, 6, 12, 13, 14
perspiration, 168, 176, 218, 251, 368, 483, 484, 485,
488, 496
perspiration resistance, 218
PES, 56, 312, 397, 541, 542, 543
pesticide(s), 352, 400, 430, 438, 439, 440, 441, 444,
445, 446
pesticide analysis, 400, 438, 440
PET, 246, 466, 474, 505
pH, 19, 27, 90, 92, 93, 94, 97, 99, 103, 158, 164,
178, 185, 192, 193, 194, 203, 210, 215, 216, 218,
219, 230, 235, 236, 237, 238, 244, 300, 301, 313,
360, 372, 380, 405, 411, 418, 455, 462
pharmaceutical(s), 54, 124, 350, 351, 362, 377, 455
phase change materials, 189, 239, 240, 241, 242,
243, 244, 344, 352, 455, 462
phase transitions, 195, 211
phase-transfer catalysis, 231
phenol, 217, 218, 402
phenolic compounds, 216, 444
phosphate, 372
phosphorescence, 193
phosphorus, 145, 361, 365, 372, 380
photocatalysis, 305, 311, 314
photocatalysts, 312, 314
photocatalytic efficiency, 288
photochromic azulene, 203, 204, 205
photochromic colorants, 109
photochromic disperse dye, 204
photochromic dyes, 81, 99, 103, 104, 105, 108, 111,
113, 115, 116, 117, 118, 121, 122, 194, 195, 228,
229
photochromic fluorescent fabrics, 203
Photochromic napthopyrans, 106
photochromic reaction, 105, 106, 107, 195, 208
photochromic smart textiles, 209
photochromic spirooxazine, 109, 111, 114, 116, 196
photochromic textiles, 112, 196, 202, 219
photodegradation, 176, 177, 184
photo-detector, 532
photoelectron spectroscopy, 291
photo-excited organic molecules, 107
photofading kinetics, 176
photographs, 32, 332, 408, 433, 534, 537
photo-induced charge transfer, 297

photoisomerization reactions, 107
photoluminescence, 189
photomultiplier, 533
photonic fibers, 240
photonics, vii, 226, 227, 240, 249
photons, 109, 194
photo-responsive, vii, 81, 82, 88, 104, 108, 109, 110,
111, 113, 116, 117, 118, 195, 197, 199, 200, 204,
205, 206, 209, 229
photo-responsive fluorescence, 204, 205
photo-responsive inkjet printed textiles, 82
photostability, 107, 176, 184, 196
photoswitching, 108, 202
photovoltaic cells, 447, 448, 449, 452, 453, 454, 460
photovoltaic fibers, 449, 452
photovoltaic-piezoelectric device, 452, 461
physical activity, 484
physical and mechanical properties, 29, 30
physical characteristics, 71, 123, 190, 492
physical environment, 215
physical exercise, 484
physical features, 384
physical properties, 132, 142, 150, 193, 194, 200,
242, 249, 364, 383, 389, 407, 440, 477, 502, 508,
517, 527, 541
physical structure, 368, 492
physical treatments, 544
physicochemical properties, 92, 116
physics, 239, 240, 497
Physiological, 386, 483, 496, 497
physiological comfort, 397, 484, 490, 491
physiological measurement sensors, 251
physiological pressure curves, 472
physiological properties, 383, 384, 401
Pie chart, 261, 262, 265, 266, 269
piezo crystals, 449
piezochromic, 246
piezoelectric drop-on demand ceramic print heads,
95
piezoelectric element, 89
piezoelectric inkjet print head, 83, 88
piezoelectric materials, 240
piezoelectric resistance, 189
pigmentation, 317
pigmented binder-less inkjet inks, 84
pigments, 82, 91, 102, 103, 163, 167, 182, 193, 195,
210, 216
pinhole size, 533
pitch, 90, 210, 534, 536
plain fabric, 343, 345, 349
plain weave, 56, 286, 385, 475
plain woven woollen fabrics resistance, 389
Index
plants, 10, 218, 264, 418, 538, 539
plaque, 476
plasma chamber, 290
plasma deposition, 286
plasma particle deposition, 286
plastic shielded wires, 253
plastics, 63, 101, 157, 159, 167, 171, 313
platelets, 467
platform, 8
playing, 84, 248
plethora of guides, 2
point defects, 289
Poiseuille flow, 467
polar, 178, 213, 277, 279, 307
polar groups, 277, 279
polar solvents, 178, 213
polarity, 105, 112, 113, 158, 177, 306, 402, 414
police, 240
pollutants, 100, 430
pollution, 123, 124, 153
pollution problems, 153
poly(ethylene terephthalate), 164
polyacetylene, 248
polyacrylonitrile, 164, 165, 542
polyacrylonitrile fast yellow shades, 165
polyacrylonitrile fiber, 164
polyamide(s), 64, 121, 157, 159, 165, 170, 172, 176,
182, 229, 278, 541
polyamide fiber, 165, 170, 182
polyaniline, 220, 223, 234, 235, 248, 250
polycarbonate, 101, 247
polycarboxylic acid, 355, 356, 357, 361, 362, 363,
364, 365, 371, 372, 373, 375, 379, 380, 381
polyconcensation fibers, 541
polycondensation, 541
polyester fibre, 502, 506, 516
polyester vascular prosthesis, 465, 479
polyesters, 157, 159, 179
polyethylene, 98, 246, 278, 286, 289, 541
polyethylene-terephthalate, 286
polyglucuronic acids, 405
polyhydric alcohol, 98, 405
polymer chain(s), 33, 245, 248, 541
polymer composites, 226, 248, 256
polymer fibers, 539, 540
polymer films, 233, 278, 289
polymer matrix, 112, 113, 194
polymer media, 112
polymer melts, 241
polymer photovoltaic solar cells, 453, 454
polymer solutions, 241
polymer structure, 389
polymer-chain scission, 317
569
polymerization, 127, 139, 147, 154, 364, 375, 379,

401, 432, 462, 541
polymethylmethacrylate, 247
polymorphic transformation, 434
polymorphism, 155
polyolefin fibers, 541
polyolefins, 157, 159
polypeptide, 333
polypeptide chains, 333
polypropylene, 98, 101, 278, 481, 501, 504, 509,
510, 511, 512, 513, 515, 516, 517, 518, 541
polypropylene fibre, 504, 509, 513
polypyrrole, 220, 223, 233, 248, 250, 256
polysaccharide(s), 23, 24, 136, 155, 377, 396, 401,
402, 418, 442
polystyrene, 220, 246, 248
polythene, 272, 515
polythiophene, 220, 223, 234, 248
polyurethane, 77, 242, 245, 250, 255, 278
polyurethane foam, 242
polyurethane foam matrix, 242
polyurethanes, 344, 541
polyvinyl chloride, 541
population, 7, 400
porosity, 81, 115, 118, 190, 263, 307, 415, 437, 473,
474, 475
porous fiber matrices, 399, 422, 429, 440
porous media, 92
porous membrane, 387
positioning statement, 6
positive correlation, 511
potassium, 98, 124, 400, 405, 406, 434, 440, 445
potassium bromide, 124, 405
potassium permanganate, 406
poverty, 3
precipitation, 92, 125, 263, 418
pregnancy, 188
preparation, 11, 53, 55, 64, 66, 88, 125, 126, 138,
146, 148, 154, 155, 163, 164, 171, 181, 182, 183,
199, 219, 248, 278, 279, 283, 305, 313, 430, 438,
444, 445, 501, 511, 531
preservation, vii, 259, 261, 262, 263, 264, 265, 266,
267, 268, 270, 271, 272, 273, 274, 275, 276, 315,
317
prestige, 6
prevention, 240, 336
preventive conservation, 273
primary fibrils, 403
primary structural network, 403
primary wall, 24, 35, 402
principles, 4, 50, 71, 76, 83, 415
570
Index
print head, 71, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91,
92, 93, 94, 95, 96, 97, 99, 100, 103, 104, 108,
118, 120, 121
print head nozzle, 94, 95, 96
print head technologies, 88, 93, 97
print media, 92
print mottle, 71, 80
print simulation, 53, 54, 55, 65, 67, 76
printed circuit boards, 54, 253, 254, 448, 450, 455
printed dress, 452
printed-textile, 82
printer color profiles, 53, 65
print-head clogging, 100
printing colors, 53, 55
printing electronic materials, 54
printing industry, 81, 84, 120
printing inks, 157, 159, 163, 167, 179, 195, 232, 250
printing technology, 54, 81, 82, 86, 88, 90, 95, 103,
104, 118, 120
procurement, 11
producers, 22
product design, 49, 210
product performance, 5
production technology, 400
professionals, 3, 260, 269, 270, 272, 273, 274
profilometer, 286
prognosis, 16
programming, 448, 450, 457, 461
project, viii, 49, 90, 153, 180, 270, 271, 274, 338,
396
propagation, 89
propane, 406
proposition, 6
proprietors, 12, 13, 14
prostheses, 466, 467, 468, 471, 474, 480
prosthesis, 465, 466, 467, 468, 469, 470, 471, 472,
474, 475, 476, 478, 479, 480
prosthesis flow properties, 467
prosthesis to kinking, 466
prosthesis wall displacements, 472
protection, vii, 81, 107, 117, 118, 194, 209, 210, 240,
320, 337, 395, 400, 403, 440, 447, 448, 449, 490
protective clothing, 243, 246, 250, 397, 447
protective coating, 133
proteinaceous fibres, 266, 267, 268, 273, 317, 318,
323, 336
proteinaceous material, 264, 316, 322, 325
proteins, 24, 145, 268, 321, 332, 341, 536
proton-accepting solvents, 178
proton-donating solvents, 179
protons, 279
prototype(s), 256, 452, 455, 469, 474, 475, 480
pseudomorph, 263
pseudo-vintage, 10
psychological variables, 484
PTFE, 471
PTT, 164, 165
public safety, 250
pulp, 125, 154, 538, 540
pulsatile flow conditions, 472, 478
pulse plasma power magnetron sputtering, 277
pulsed direct magnetron sputtering, 277
pumice stone, 19, 20, 21, 24, 25, 27, 41, 42, 43, 44,
47, 48
pumice stone-enzyme, 19, 41, 42, 47
purification, 136, 145, 400, 401, 430, 440
purity, 92, 153
PVC, 100
pyridinium group, 165
pyrolysis, 360, 430, 432, 444, 445
pyrolysis of celluloses, 430
Q
quality control, 53
quantification, 545
quantum size nanoparticles, 309
quaternary ammonium, 165, 182
quaternary ammonium salt, 165, 182
Queensland, 341
questionnaire, 259, 260
quinoline derivatives, 159
quinones, 434
R
radial distance, 426
radiation, 64, 65, 119, 194, 203, 205, 229, 256, 280,
375, 403, 448, 460, 483, 484, 485, 486, 487, 488,
489, 491, 492, 493, 494
radicals, 233, 279, 285, 290, 301, 357, 375
radio, 189, 280, 476
radiography, 493
radius, 415, 416, 423, 424, 427
Raman spectra, 185, 322, 323, 327, 328, 329
Raman spectroscopy, 185, 316, 321, 322, 326, 329,
332, 339, 340, 341, 357
ramie, 51, 442, 509, 538
rate of change, 425, 427
raw materials, 155, 321, 400
rayon, 51, 157, 159, 538
reactant, 356
reactants, 377, 380
reaction mechanism, 105, 106, 107, 111
reaction time, 107, 167, 294
571
Index
reactions, 27, 92, 105, 107, 109, 170, 183, 200, 230,
279, 301, 357, 358, 375, 377, 405, 419, 430
reactive azo dyes, 170, 182, 183
reactive group(s), 375, 377
reactive oxygen, 278, 312
reactive polymers, 344
reactivity, 116, 132, 142, 150, 279, 289, 360, 364,
404, 405, 407, 436
reagents, 356, 362, 378
realism, 468
reality, 188, 226, 256, 311, 312
receptors, 117, 209, 490
recognition, 2, 192, 231
recombination, 301, 306, 309
recovery, 139, 244, 245, 255, 270, 283, 351, 356,
360, 367, 372, 375, 377, 381, 386, 393, 473, 477,
504
recycling, 4, 9, 10, 13, 124, 293, 297, 399, 401, 430
recycling plants, 10
red cell destruction, 467
red shift, 303
reflectance spectra, 296, 303, 304
refractive index, 105, 194, 195
refractive indices, 194
regenerated cellulose, 540
regeneration, 166
regression, 420, 426, 487
regression analysis, 420
regression equation, 487
rehabilitation, 188, 240, 252
reinforcement, 441, 500
relative humidity, 74, 315, 317, 320, 326, 410, 411
relaxation, 111, 112, 472
relaxation model, 112
relaxation process, 111
reliability, 5, 6, 54, 93, 98, 221, 250
remote sensing, 187, 225
renaissance, 400
repair, 473
reparation, 444
repeating unit, 401
repellent, 363, 365
repression, 50
reproduction, 55, 63, 71, 84
repulsion, 206
reputation, 5
requirements, 5, 54, 61, 88, 90, 91, 92, 93, 97, 100,
104, 109, 118, 191, 196, 227, 228, 239, 243, 251,
252, 253, 292, 473, 475
researchers, 23, 24, 55, 124, 191, 260, 272, 324, 363,
372, 384, 455, 467
residuals, 421, 426
residues, 34, 43, 154, 182, 307, 333, 361, 402, 444
resilience, 477, 513

resins, 321, 344, 367, 369, 378
resolution, 87, 297, 531, 532, 533, 534, 535, 536,
543, 545
resources, 6, 16, 120, 400
respiration, 240, 455, 485
response, 6, 111, 115, 184, 192, 200, 210, 219, 220,
221, 231, 244, 246, 250, 341, 350, 360, 368, 477
response time, 200, 221
restenosis, 477, 480
restoration, 337, 338
restrictions, 272
retail, 2, 3, 4, 6, 7, 13, 15, 16, 17, 18, 79, 250
retail guru, 4
retail marketing literature, 6
retail premises, 7
retailing planning context, 6
retro subculture, 3
RF-plasma pretreatment, 280
RH, 30, 31, 261, 509, 521
Rhizopus, 319
rice husk, 445
rights, 10
ring flanges, viii, 519, 520, 521
ring spinning, viii, 519, 520, 521
ring spinning machine, 519, 521
ring travellers, 519
rings, 198, 207, 208, 214, 323, 328, 329, 399, 401,
404, 436, 519
risk(s), 100, 101, 252, 316, 317, 384, 395, 474, 477
risk factors, 317
room temperature, 158, 197, 198, 208, 211, 213, 214,
222, 244, 285, 320, 386, 404
root, 306
roughness, 306, 404, 408, 413, 417, 419, 475, 500,
533
routes, 279
Royal Society, 50, 119, 228, 232, 339
rubber, 31, 157, 159, 242, 245
rubbing fastness, 165
Russia, 10
ruthenium, 221
S
saccharin, 217
safety, 5, 92, 145, 187, 191, 192, 227, 250, 447, 448,
449, 453, 457, 460
salts, 94, 163, 164, 167, 170, 177, 179, 241, 248,
249, 259, 261, 263, 264, 267, 268, 273, 279, 321,
372
sample surface, 300, 306, 531, 532
SAP, 512
572
Index
satisfactory whiteness, 372

saturation, 296, 475
saturation index, 475
scaling, 478
scaling law, 478
scanning calorimetry, 361
scanning electron microscopy, 316, 321, 322, 326,
327, 341, 346, 545
scanning electronic microscope, 32
scarcity, 11
scattering, 108, 303, 341
scent, 346
school, 13, 278, 289
science, vii, 260, 269, 270, 288, 316, 336, 362, 377,
397
scope, 74, 82, 84, 190, 193, 260
screen-printing, 242
seafood, 361
second hand clothing stores, 10
second hand stock, 11
Second World, 84, 400
secondary cell, 24, 403
secondary hydroxyl groups, 130, 141, 149
secretion, 317, 319, 331
security, vii, 5, 81, 103, 107, 117, 118, 187, 194,
195, 209, 225, 250, 253, 448
sedimentation, 96
selectivity, 52, 312, 419
self-expression, 1
self-indicating alert systems, 81, 118
SEM micrographs, 346, 347, 348
semiconductor(s), 211, 222, 277, 278, 279, 289, 308,
309, 311, 314, 453
semiconductor TiO2, 279
sensation(s), 393, 490
senses, 241
sensing, 118, 187, 190, 192, 194, 209, 225, 227, 240,
244, 247, 252, 460
sensing applications, 247
sensitivity, 176, 271, 290
sensors, vii, 188, 189, 208, 226, 227, 230, 239, 240,
245, 247, 250, 251, 252, 257, 447, 448, 449, 450,
455, 460, 461, 462, 487
Serbia, ix, x, xii, xiii, 162, 163, 166, 167, 168, 169,
170, 171, 172, 173, 174, 175, 319, 399
serine, 338
services, 17, 252, 253, 259, 260, 271
severe stress, 485
shade, 31, 34, 35, 36, 37, 39, 40, 41, 42, 43, 65, 164,
505, 508
shape, 107, 127, 188, 189, 190, 194, 206, 208, 226,
239, 240, 244, 245, 246, 247, 253, 255, 262, 265,
296, 346, 348, 349, 450, 471, 472, 473, 478, 490
shape memory alloys and polymers, 189, 244

shape memory materials, 226, 239
shape memory polymers, 206, 240, 245, 246
shape-memory, 245
shawl fabric, 506, 507
shear, 25, 51, 86, 93, 94, 95, 253, 467, 478
shear rates, 467, 478
shear rigidity, 25
sheep, 536, 537, 538
sheep wool, 536, 537
short-chain polysaccharides, 23
showing, 104, 182, 200, 261, 262, 265, 266, 269,
283, 291, 296, 299, 313, 314, 322, 327, 332, 533
side chain, 402
signals, 84, 134, 152, 240, 294, 448, 455, 532, 533
significance level, 527
signs, 64, 101, 227, 250, 252, 256, 329, 457, 462
silane, 404
silica, 127, 155, 362
silicon, 449
silicone treatment, 501
silicones, 375
silk, 54, 55, 78, 81, 112, 113, 115, 117, 118, 157,
158, 159, 168, 266, 268, 315, 317, 321, 325, 337,
339, 375, 400, 490, 536, 537, 538, 539
silk screen printed polyester, 168
silver, 165, 182, 246, 249, 262, 264, 267, 268, 273,
278, 280, 283, 286, 289, 294, 310, 311, 312, 313,
314, 384, 389, 397, 521, 542
silver biocidal surfaces, 278
silver treated wound dressings, 384
silvernic, 521, 524
simulation, 53, 54, 55, 56, 65, 66, 67, 71, 76, 115,
444, 467, 468, 479
simulations, 65, 467, 468, 478
Singapore, 381
SiO2, 27, 288, 362
SIP, 90
sisal, 538
skeletal muscle, 484
skeleton, 405
skin, vii, 209, 244, 250, 251, 264, 344, 370, 377,
387, 393, 460, 483, 484, 485, 487, 488, 490, 491,
495, 538
skin softeners, vii, 344
skin temperatures, 487
slip draft spinning system, 506
slow fashion, 3
sludge, 124, 154
small business sector, 4
small businesses, 55
small diameter blood vessels, 465, 466
small-scale retailers, 12
Index
smart clothing, viii, 191, 192, 226, 251, 252, 253,
447, 448, 452
smart clothing design, 191
smart clothing system, 191, 192
smart materials, 189, 190, 227
smart medical textiles, 188
smart or intelligent textiles, 188
smart products, 384
smart structures, 247, 255
smart textile, vii, 187, 188, 189, 190, 191, 192, 194,
195, 196, 197, 199, 200, 201, 203, 204, 206, 207,
209, 211, 218, 219, 225, 226, 227, 239, 240, 242,
243, 244, 246, 248, 250, 251, 252, 254, 255, 344,
449, 450, 461, 462
smart wound-care materials, 188
smoothness, 475
social judgment, 3
social order, 15
societal acceptance, 1
sodium, 123, 124, 125, 126, 145, 147, 154, 155, 167,
172, 237, 241, 356, 361, 363, 364, 365, 372, 373,
375, 380, 383, 384, 385, 395, 404, 405, 406, 407,
408, 410, 417, 419, 502, 516
sodium alginate, 383, 384, 385, 395
sodium carbonate, 124, 372
sodium chlorite, 406, 407, 408, 410, 419
sodium chlorite modification, 406
sodium hydroxide, 123, 124, 125, 126, 404, 406,
410, 417, 502, 516
sodium hypochlorite, 405
Sodium periodate oxidation, 406
sodium salts, 372
softener, 374, 375
softness, 19, 36, 40, 49, 242, 501
software, 58, 59, 61, 65, 76, 79, 90, 290, 457, 533,
534, 535
softwoods, 402
solar cells, 189, 226, 449, 453, 454, 462
solar simulator, 294, 295, 297
soldier and weapons camouflage, 247
sol-gel, 277, 278, 375
sol-gel films, 277
sol-gel processes, 375
solid matrix, 107
solid phase, 244, 438
solid state, 109, 158, 232
solidification, 102
solubility, 92, 94, 98, 124, 129, 136, 140, 148, 157,
158, 159, 195, 279, 289, 418
solvatechromic, 246
solvation, 176, 427, 428
solvatochromism, 213
solvent molecules, 211
573
solvents, 87, 97, 98, 99, 100, 102, 121, 157, 167,
176, 177, 178, 179, 184, 185, 213, 216, 217, 229,
401, 402
sorption, 154, 399, 400, 403, 405, 406, 408, 413,
414, 415, 418, 419, 420, 423, 424, 428, 429, 436,
437, 440, 442, 443, 444
sorption process, 418, 419, 436, 437
sorption properties, 400, 403, 405, 406, 408, 415,
418, 440
SP, 510
Spain, x, xi, xii, xiii, 343, 345, 346, 353, 355
specialists, 271, 346
species, 112, 194, 195, 197, 208, 218, 230, 241, 278,
279, 280, 289, 290, 292, 294, 306, 312, 313, 315,
317, 318, 319, 320, 321, 325, 326, 328, 329, 331,
332, 333, 334, 336, 411, 427, 445
specific computer code, 467, 468
specific flexural rigidity, 502
specific gravity, 92
specific heat, 394, 486
specific properties, 400
specific structure, 399, 401
specific surface, 399, 402, 411, 432, 434, 435, 436,
440
specific surface area, 399, 411, 432, 434, 435, 436,
440
specific surface morphology, 402
specific thermal resistance, 509, 511, 512, 513, 514,
515
specific work of rupture, 502
specifications, 7, 20, 26, 367, 521
spectroscopy, 134, 155, 177, 185, 224, 290, 296,
312, 313, 316, 321, 322, 323, 324, 326, 329, 332,
339, 340, 341, 357, 364, 365, 379, 380
spherical shape, 346, 348, 349
spin, 289
spindle, 521
spindle speed, 521
spinnerets, 539, 542
spinning balloon angles, 526
spinning off primary fibrils, 403
spinning tension, 519, 520, 521, 522, 525, 527, 528
spirooxazines, 105, 107, 110, 115, 194, 197, 201,
213
spiropyrans, 105, 107, 194, 197, 201, 213, 216
sports clothing, 455
sports garments, 243, 247
sportsmen, 240
sportswear, 246, 457
Spring, 17
sputtering, 249, 277, 278, 283, 285, 286, 288, 289,
290, 292, 295, 296, 297, 301, 302, 303, 305, 306,
307, 312, 531
574
Index
Sri Lanka, 27
stability, 20, 27, 49, 54, 74, 92, 94, 104, 105, 107,
160, 166, 182, 198, 200, 208, 221, 243, 248, 249,
256, 288, 312, 343, 344, 345, 348, 349, 351, 355,
466, 500
stabilization, 58, 146, 198, 436
stable states, 192
stainless steel filaments, 542
stainless steel yarn, 542
standard deviation, 421, 439
standard Martindale abrasion test method, 386
standard plastic optical fiber, 247
standard relative humidity, 410
standard test method, 383, 520
standard washing procedure, 28
Staphylococcus, 279, 313, 384, 396
Staphylococcus aureus, 279, 313, 384, 396
staple yarn production process, viii, 519
starch, 23, 36, 351, 377
static electricity charges, 401, 403
statistical analysis, 55, 259, 261, 296, 394
statistical significance, 296, 384
steady and pulsatile regimes, 467
steel, 95, 248, 254, 396, 468, 476, 542, 543
stenosis, 467, 478, 479, 480
stent, 465, 475, 476, 477, 478, 480
stereoisomeric forms, 214
stereomicroscope, 57
steric obstruction for sorption, 428
sterile, 295, 319
stiffness tester, 31, 386
stigma, 3
stimuli-responsive materials, 190, 226
stimuli-responsive smart textiles, 187, 225
stimulus, 103, 116, 190, 193, 194, 200, 208, 218,
220, 226, 244, 246
STM, 30
stock, 10, 11
stoichiometry, 430
Stokes-Einsteind diffusion coefficient, 423
stone wash, 20, 21, 24, 41, 51
stone-wash effect, 25
storage, 92, 103, 104, 182, 194, 195, 210, 220, 239,
241, 242, 260, 269, 271, 272, 274, 315, 317, 320,
322, 335, 336, 337, 370, 449
storage and exhibition rooms of museums, 320
storage conditions, 320, 322, 335
store image, 12, 13
store interior, 12, 14
strategic management, 18
strategic position, 6
street style, 4
stress, 6, 241, 244, 245, 329, 330, 334, 341, 357,

409, 466, 467, 474, 475, 476, 484, 485, 496, 504
stress-strain curves, 330, 329, 330, 331, 334
stretching, 132, 134, 143, 150, 330
STRs, 511, 512
structural changes, 112, 321, 322, 323, 326, 330,
336, 339, 417
structural characteristics, 317
structural design of weaving, 499
structural formation, 213
structuring, 402
style, 2, 3, 4, 8, 9, 10, 11, 12, 13, 14, 243
stylists, 3, 9
styrene, 98
sublimation fastness, 158, 165, 176
sublimation ink, 84
sublimation transfer printing techniques, 84
substitutes, 466, 480
substitution, 106, 123, 124, 126, 129, 130, 131, 136,
138, 139, 140, 141, 147, 148, 149, 153, 341, 400
substitution reaction, 129, 131, 141, 148, 149
succession, 469
succinic acid, 319, 326, 331, 357, 360, 361, 364,
371, 375, 376, 381
sugar beet, 154
sugar industry, 154
sulfadiazine-Ag salt, 279
sulfate, 167, 169, 170
sulfuric acid, 136, 145, 543
Sun, 365, 396, 443, 446, 497
super-hydrophilic, 279
supermolecular structure, 316, 321, 322, 332, 401,
442
superpolish, 521, 523, 524, 528
supply chain, 4, 90
surface area, 279, 295, 400, 411, 412, 430, 432, 433,
434, 435, 436, 440, 484, 487, 492
surface characteristics, 20, 432
surface deformation, 390
surface energy, 92, 279, 306, 308
surface functional groups, 412, 432, 436
surface layer, 249, 326
surface modification, 382
surface plasmon resonance, 303
surface pore structure, 408
surface properties, 324, 415, 440, 490
surface reactions, 279
surface structure, 67, 384, 533, 540, 542, 543, 545
surface tension, 92, 94, 99, 416
surfactants, 99, 350
surgical technique, 474
surplus, 243
surrogates, 5
Index
survival, 260, 268, 281, 282, 293, 396
sustainability, 13, 20, 22, 25, 49, 50, 118
sustainable denim, 20, 21, 22, 23, 25, 26
sustainable development, 353
suture, 468, 479
sweat, 377, 455, 488
Sweden, 83, 244
swelling, 92, 125, 404, 409, 412, 413, 415, 417, 423,
516
swelling and shrinkage of ultimate cells, 412, 417
swelling process, 423
Switzerland, x, xi, xiv, 51, 128, 136, 277
synergistic effect, 208
synthesis, v, vii, 107, 123, 124, 129, 136, 139, 140,
145, 146, 148, 157, 163, 167, 168, 170, 171, 173,
175, 179, 180, 181, 182, 183, 185, 191, 215, 216,
231, 234, 352
synthetic antibiotics, 278, 289
synthetic chemical materials, 540
synthetic fiber, 157, 163, 164, 184, 288, 400, 410,
538, 539, 545
synthetic fibers, 157, 163, 164, 184, 288, 400, 410,
538, 539, 545
synthetic organic colorants, 157, 159
synthetic textiles, 165, 317
T
tailor-made eco-smart clothes, 450
tantalum, 476
tapestries, 316
target, 5, 6, 189, 283, 286, 292, 298, 438, 509
taste-makers, 3
tear resistance, 253
technical applications, 465
technical textiles, vii, 85, 189, 243, 344, 399
techniques, vii, 6, 20, 81, 82, 84, 85, 90, 92, 93, 94,
95, 103, 108, 116, 117, 118, 119, 124, 188, 189,
192, 195, 196, 199, 204, 209, 216, 220, 278, 326,
338, 340, 344, 351, 355, 356, 462, 474, 480, 490,
533
technological advancement, 274
technological advances, vii, 465
technology(ies), 5, 21, 49, 54, 55, 77, 78, 80, 81, 82,
83, 84, 85, 86, 87, 88, 90, 92, 95, 100, 101, 103,
104, 118, 120, 188, 189, 190, 191, 227, 228, 234,
240, 241, 250, 252, 253, 260, 272, 275, 344, 350,
351, 377, 400, 447, 449, 450, 452, 455, 460, 461,
466, 471, 495, 520, 532, 545
teflon, 468
telecommunications, 240
TEM, 282, 285, 303
temperature-programmed desorption, 434, 445
575
TEMPO oxidation process, 405

temporarily prevent active fungal growth, 320
tenacity, 242, 403, 409, 410, 502, 507
tensile properties, 329, 330, 334, 336, 383, 384, 387,
388, 389, 409, 442, 522
tensile strength, 19, 20, 25, 30, 33, 34, 36, 37, 39, 41,
42, 128, 132, 139, 142, 147, 150, 321, 326, 357,
360, 371, 372, 373, 381, 383, 387, 388, 389, 396,
409, 468, 475, 500
tension, 92, 93, 94, 99, 416, 466, 471, 476, 504, 519,
520, 521, 522, 525, 526, 527, 528
TEOS, 375, 381
territory, 191
test prints, 65
testing, 5, 6, 7, 51, 53, 56, 74, 76, 154, 305, 313,
326, 351, 386, 397, 480, 494, 506
tetrachloroethylene, 164
tetraethoxysilane, 375
textile artificial vessels, 467
textile conservator, 271, 272, 273
textile fabrics, 51, 78, 101, 219, 240, 281, 386, 393,
397, 496, 497, 511
textile fibers, viii, 50, 248, 345, 449, 455, 477, 490,
492, 531
textile finishing process, 384, 394
textile fragments, 264, 275
textile heart valve, 466, 476
textile heart valve prosthesis, 476
textile historians, 259, 269, 273
textile implants, 471
textile industry, vii, 20, 23, 24, 47, 49, 50, 55, 63,
124, 136, 343, 344, 353, 356, 399, 401, 440, 533
textile materials, vii, 225, 239, 257, 312, 316, 322,
339, 362, 367, 377, 378, 384, 400, 440, 443, 465,
474, 477, 480, 488, 514
textile polymer surface, 280
textile preservation, 262, 273
textile printing, 53, 54, 55, 58, 66, 77, 78, 81, 83, 84,
85, 89, 90, 100, 120
textile prostheses, 466, 467, 471
textile reinforced synthetic material, 241
textile researchers, 260, 272
textile scaffolds, 241
textile sciences, 316
textile sensors, 188, 226, 250
textile substrates, vii, 53, 56, 59, 61, 76, 99, 108,
112, 114, 115, 117, 248, 249, 253, 345, 453
textile surface structure, 384
textile synthetic substrates, 56
textile vascular prosthesis, 472, 478
textile-based drug release systems, 188
textiles excavated, 260, 261, 262, 265, 266, 269, 272,
273
576
Index
texture, 80, 115, 247, 317, 351

TGA, 360, 361
theatre, 9
therapy, 118, 189, 209, 252, 310, 460
thermal (bubble) inkjet printers, 54
thermal absorbtivity, 383, 384, 386, 391, 393, 394,
396
thermal absorbtivity values, 383, 394, 396
thermal analysis, 360, 361, 380
thermal comfort, viii, 383, 384, 395, 397, 483, 488,
489, 490, 492, 494, 496
thermal comfort properties, viii, 383, 384, 395, 483
thermal conductivity, 384, 386, 391, 392, 394, 488,
489, 490, 493, 497, 509, 517
thermal decolouration, 112, 114
thermal decomposition, 361, 365, 430, 431, 432, 445
thermal degradation, 116, 155
thermal diffusion, 386
thermal energy, 190, 241
thermal feeling, 387
thermal history, 210
thermal inkjet print heads, 86
thermal insulating applications, viii
thermal insulating material, 499, 500, 515
thermal insulation, 242, 246, 397, 484, 488, 489,
490, 492, 493, 499, 500, 501, 504, 505, 506, 508,
509, 510, 514, 515, 518
thermal insulation properties, 397, 484, 488, 490,
499, 504, 518
thermal management system, 93
thermal properties, 384, 391, 485
thermal resistance, 383, 384, 386, 391, 392, 396,
484, 489, 490, 492, 493, 507, 509, 511, 512, 513,
514, 515
thermal stability, 105, 198, 208
thermal storage materials, 241
thermal transmittance, 490, 492, 494
thermal treatment, 404, 444
thermal-transfer recording, 165, 181
thermo physiological properties, 383, 384
thermochromic dye, 210
thermochromic materials, 189, 211, 214, 247
thermochromic molecular switches, 211
thermochromic pigments, 210, 216
thermodynamics, 184, 444
thermofixation, 158
thermo-regulating effect, 242, 243
thermoregulatory process of human body, viii, 483
thickness, 56, 242, 243, 286, 287, 288, 295, 306,
323, 384, 386, 391, 392, 427, 455, 478, 485, 488,
489, 490, 492, 493, 506, 507, 508, 509, 511, 512,
513, 514, 515, 533, 537
thin films, 101, 155, 224, 283, 292, 314
thinning, 94
thrombo-embolism, 474
thrombosis, 467, 471, 477
time periods, 2, 279
time use, 450
TiN-Ag nanoparticulate films, 292
tinctorial strength, 159, 171
TIR, 323
tissue, 77, 90, 128, 188, 240, 466, 472, 474, 475
tissue degeneration, 474
tissue engineering, 77, 90, 188, 240
titanate, 89
titania, 313
titanium, 220, 248, 311, 357, 364, 375, 376, 381
titanium dioxide (TiO2) nanoparticles, 375
TLC analysis, 266
tobacco, 377
tobacco smoke, 377
toluene, 128
tones, 62
torus, 377
toxic metals, 219
toxicity, 263, 289, 352, 362
toys, 195, 210, 245
trade, 7, 10, 12
traditional vintage retailers, 2
training, 101
transcripts, 7
transformation(s), 66, 73, 104, 105, 116, 194, 201,
213, 289, 313, 404, 430, 434
transition metal, 193, 211, 220, 221
transition temperature, 244, 245
translation, 87, 496
transmission, 84, 108, 115, 195, 240, 251, 297, 323,
341, 449, 479, 489, 490, 496, 497, 509
transparency, 248
transplant, 471
transport, 90, 199, 249, 260, 271, 353, 395, 399, 415,
422, 423, 427, 428, 429, 437, 438, 440, 446, 484,
486, 493
transport phenomena within the fibers, 429
transportation, 85, 447
transverse thickenings, 539
traveller coating, 519, 523, 525, 527
traveller coatings effect, 523
traveller drive angle, 520
traveller profile cross-section, 523
traveller profiles, 524, 528
traveller weight, 519, 520, 521, 522, 523, 524, 525,
526, 527, 528
treatment methods, 384
triangular cross-section, 539
tricarboxylic acid, 379
577
Index
Trichoderma ressei, 23
trickle down, 4
trisazo pyridone colorants, 173
trypsin, 442
tungsten, 64, 220, 221
Turkey, xi, xiii, 27, 383, 519, 521, 528
twill fabric, 21
twist, viii, 329, 384, 506, 517, 519, 520, 521, 522,
523, 524, 527, 528
U
United Kingdom (UK), xi, xiii, xiv, 1, 3, 10, 14, 15,
18, 30, 50, 81, 84, 119, 121, 153, 187, 190, 229,
255, 259, 286, 289, 290, 292, 339, 383, 385, 386,
494, 519
ultra-high local temperature, 88
ultra-high-molecular-weight polyethylene, 541
ultra-microtome, 282
ultrasonic anemometry, 467
ultrasonic application, 385, 393, 394
ultrasonic bath, 385
ultrasonic energy, 383, 384, 387, 388, 390, 392, 394,
395, 396
ultrasonic energy application, 383, 385, 387, 390,
396
ultrasound, 396
underclothes, 251
unethical practices, 2, 3
unevenness, 524
uniform, 72, 92, 99, 112, 113, 249, 254, 279, 280,
283, 289, 305, 306, 314, 510
unique features, 124, 197
uniqueness, 1, 3, 4, 9, 13
universities, vii, 247
unpleasant mouldy odour, 317
unsaturated monomer molecules, 541
upholstery, 85, 517
urea, 54, 237, 356, 369, 370
urea-formaldehyde, 369
uronic acid monomers, 384
United States (USA), 56, 58, 59, 72, 74, 83, 99, 119,
120, 121, 190, 227, 228, 229, 235, 255, 257, 275,
345, 346, 378, 386, 495, 496
7, 364, 375, 376, 381, 400, 403, 447, 460, 490
UV absorption spectra, 184
UV irradiation, 103, 105, 106, 107, 108, 109, 110,
111, 114, 115, 117, 196, 197, 206, 317, 357, 364,
376, 381
UV light, 82, 100, 101, 102, 103, 104, 105, 107, 108,
109, 110, 111, 113, 115, 116, 117, 194, 196, 197,
200, 201, 203, 205, 206, 207, 244, 357, 460
UV protection properties, 400
UV radiation, 64, 65, 375, 403

UV-curable inkjet inks, 100, 101
UV-vis reflectance, 303
V
vacancies, 296
vacuum, 88, 125, 128, 280, 281, 286, 289, 531
valence, 222, 223, 375
Valencia, 351
validation, 16, 26
valuation, 80, 480, 488, 494, 497
valve, 89, 465, 466, 474, 475, 479, 480
van der Waals forces, 306
vanadium, 220
vapor, 36, 155, 245, 290, 308, 401
variables, 154, 345, 424, 484, 510, 512, 515, 517
variance analysis, 526
variations, 66, 71, 79, 108, 157, 159, 221, 222, 242,
388, 409
varieties, 47, 199
varnishes, 157, 159, 167
vascular prostheses, 466, 471
vascular surgery, 466, 471, 473, 475, 478
vascular wall, 467, 478
VDF, 452
vegetables, 218
vehicles, 64, 352
vein, 473
velocity, 87, 88, 90, 92, 93, 96, 466, 467, 479
ventilation, 336, 484, 491
versatility, 84, 216
vessels, 266, 465, 466, 467, 468, 473, 479
vibration, 134, 330
videos, 533
vintage, vii, 1, 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14
vintage clothing, 1, 2, 3, 4, 8, 10
vintage concept, 12, 13
vintage connoisseur, 3
vintage consumer, 3, 4, 8
vintage definitions, 2
vintage era, 10
vintage fashion, vii, 1, 2, 3, 4, 7, 8, 9, 12, 13
vintage fashion clothing, vii, 1
vintage fashion community, 12
vintage fashion consumer, 1, 2, 7
vintage fashion retailers, 1, 2, 7, 13
vintage retail store, 7
vintage retailing literature, 7
vintage trend, 2, 4, 8, 10
vinyl monomers, 154
viscoelastic character, 472
578
Index
viscose, 51, 112, 113, 115, 117, 157, 159, 340, 410,
506, 517, 540
viscose rayon, 51, 157, 159
viscosity, 54, 90, 92, 93, 95, 98, 126, 127, 130, 131,
139, 141, 149, 195, 385, 414, 416, 467
viscosity control agent, 98
visible light spectrum, 531
vision, 191, 227, 455
visual impression, 67
visual system, 71
visualization, 195, 493
vitamin A, 351
vitamins, 210, 344
volatile organic compounds, 100, 317
volatile solvent, 87, 100
volatility, 98
volume electric resistance, 410, 411
W
walking, 449, 450, 484, 494
wall crimping, 467
war, 84
wardrobe designers, 9
warehouse, 8
warm body, 486, 491
warm cloth weaving, 506
warm fabrics, 500
warm garments, 499, 501, 515
warning systems, 104, 240
warp directions, 386, 387
warp-knitted fabrics, 468
wash fastness, 104, 115, 165, 176, 182, 396
washing effects, vii, 20, 21, 23, 24, 33, 41, 48, 345
washing industries, 20, 24, 47
washing process, 21, 22, 23, 24, 35, 48, 55, 348, 349
washing techniques, 20
washing/finishing treatment, 20
Washington, 50, 79, 120, 314, 336, 339, 340
waste, 22, 100, 101, 153, 338, 399, 401, 418, 430,
436, 440, 441, 443, 444, 445, 450, 455
waste disposal, 399, 401, 430
waste management, 455
wastewater, 440, 443
watches, 11
water absorption, 19, 25, 31, 33, 35, 36, 38, 39, 40,
42, 43, 48, 52, 132, 139, 142, 147, 150
water holding capacity, 413
water purification, 399, 401, 430
water repellence property, 501
water retention value, 412, 413
water sorption, 414
water vapor, 36, 245, 308
water vapour permeability, 383, 384, 395, 396

waterproof elements, 457
waterproof fabrics, 384
wavelengths, 64, 107, 116, 192, 194, 200, 210, 295,
531
WAXS, 340, 442
wealth, 190
weapons, 247, 252
wear, 10, 11, 14, 20, 21, 22, 211, 239, 242, 243, 255,
367, 386, 389, 449, 484, 490, 505
wear performance, 21, 22
wearable computers, 226, 227, 240
wearable electronics, 188, 249, 250, 447, 448, 450,
455
wearable textiles, 188, 500
wearing apparel, 136
weather conditions, viii, 74, 246, 251, 252, 253, 447,
483
weaving technique, 466, 478
web, 120, 510
websites, 7, 12
wedding dress, 8
weft directions, 30, 34, 35, 37, 38, 39, 40, 41, 42,
386, 507
weft-knitted structures, 468
weight changes, 528
weight loss, 30, 31, 34, 35, 37, 39, 40, 41, 42, 43, 48,
407, 430, 502, 503
welfare, 270, 272
wellness, 545
wet-spinning process, 241
wettability, 51, 192, 415, 416, 417
wettability relationships, 416
wetting, 92, 94, 95, 99, 249, 393, 414, 415, 417
white light source, 533
White Paper, 461
wide band-gap semiconductors, 278, 314
wide-field optical microscopy, 532
windows, 244
wires, 189, 200, 240, 248, 253, 447, 452, 462
Wisconsin, 340
withdrawal, 504
wood, 101, 124, 154, 155, 166, 264, 317, 326, 338,
339, 340, 341, 430, 441
wood residue, 124, 154
wool fabric, 325, 382, 383, 384, 385, 387, 389, 390,
391, 395
wool fibre, 266, 331, 332, 334, 336, 340, 383, 501
wool proteins, 268
wool-based material, 499
woollen blanket, 505
woollenisation, 501, 502
woollenised jute, 501, 504, 509, 510
579
Index
woollenised jute yarn, 501
workers, 101, 244, 289, 316, 360, 409, 449, 493
workflow, 53
working conditions, 239
workload, 251
worldwide, 262, 400, 494
wound dressing, 289, 384, 540
wound infection, 310
woven and knitted grafts, 468
woven bifurcated prosthesis, 471
woven carpets, 504
woven fabrics, 136, 386, 390, 392, 393, 394, 480,
492, 493, 496
woven polyester fabrics, 465, 475
wrinkle resistant cotton, 367
wrinkle resistant textiles, 371
wrinkle-resistant effect, 371
wrinkling, 240, 355, 367, 368
X
xerophilic species, 318
xerotolerant fungi, 320
XML, 180
X-ray photoelectron spectroscopy (XPS), 280, 282,
283, 290, 291, 292, 294, 313, 353
X-ray diffraction (XRD), 285
Y
yarn breaking strength, 523
yarn characteristics, 520
yarn count, 519, 521, 522, 527
yarn elongation, 528
yarn hairiness, 519, 520, 521, 522, 525, 528
yarn irregularity, 527, 528
yarn production tension, 522
yarn properties, 329, 384, 501, 519, 520, 522, 527
yarn spinning, 242, 520, 522, 527, 528
yarn spinning systems, 520
yarn spinning tension, 527, 528
yarn structure, 474, 475, 499, 500, 501
yarn twist, 519, 520, 521, 522, 523, 527, 528
yarn twist number, 522
yarn twist value, 520
yield, 109, 127, 129, 130, 131, 132, 140, 141, 148,
149, 150, 168, 172, 208, 272, 361, 400, 430, 476
young people, 3
young professionals, 3
Z
zeitgeist, 8
zero-test length, 409
zinc, 420, 421, 422, 428, 429, 436, 444, 445
ZnO, 211

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CHEMISTRY RESEARCH AND APPLICATIONS

CHEMISTRY RESEARCH AND APPLICATIONS

Additional e-books in this series can be found on Novas website

CHEMISTRY RESEARCH AND APPLICATIONS

MD. IBRAHIM H. MONDAL

Copyright 2014 by Nova Science Publishers, Inc.

Library of Congress Cataloging-in-Publication Data

Published by Nova Science Publishers, Inc. New York

Contributor Contact Details

An Exploration of Vintage Fashion Retailing

Developing Sustainable Design on Denim Ready-Made Apparels

Digital Textile Printing Using Color Management

Inkjet Printed Photo-Responsive Textiles for Conventional

Synthesis and Grafting of Cellulose Derivatives from

History, Synthesis and Properties of Azo Pyridone Dyes

Smart Textiles and the Effective Uses of Photochromic,

Overview of Textiles Excavated in Greece

Fungal Deterioration of Aged Textiles

Durability of Functionalized Textiles by Microcapsules

New Approaches and Applications on Cellulosic

Wrinkle Resistant and Comfort Finishing of Cotton Textiles

Evaluation of Physical and Thermal Comfort Properties of

Hemp Fibers: Old Fibers - New Applications

Textiles Using Electronic Applications

Textiles for Cardiac Care

Effect of Clothing Materials on Thermoregulatory Responses

Designing of JuteBased Thermal Insulating Materials

Effects of Ring Flange Type, Traveler Weight and Coating on

Optical Fiber Examination by Confocal Laser Scanning Microscopy

Md. Ibrahim H. Mondal

Department of Applied Chemistry & Chemical Engineering,

CONTRIBUTOR CONTACT DETAILS

Ali Akbar Merati

Md. Ibrahim H. Mondal

Contributor Contact Details

Md. Ibrahim H. Mondal

Mashiur Rahman Khan

Md. Ibrahim H. Mondal

Contributor Contact Details

Md. Ibrahim H. Mondal

Shah M. Reduwan Billah

Contributor Contact Details

In: Textiles: History, Properties and Performance

AN EXPLORATION OF VINTAGE FASHION RETAILING

Department of Business Management, Glasgow

Keywords: Vintage, fashion, definition, customer characteristics, positioning

Julie McColl, Catherine Canning, Louise McBride et al.

An Exploration of Vintage Fashion Retailing

Characteristics of the Vintage Consumer

History and Key Drivers

Julie McColl, Catherine Canning, Louise McBride et al.

An additional driver acknowledged by Tungate [8] is customer defiance of expensive,

Market Structure and Vintage Retail Formats

An Exploration of Vintage Fashion Retailing

Aaker and Shansby [59];

Ries and Trout [66]

Easingwood and Mahajan

Arnott [61, 58]

Kalafatis, et al. [72]

Positioning constructs i.e., concepts

Source: Adapted from Blankson and Kalafatis [64].

Blankson and Kalafatis [64], however, consider existing studies to be descriptive,

Julie McColl, Catherine Canning, Louise McBride et al.