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DOI 10.1007/s10570-009-9369-y
Received: 26 May 2009 / Accepted: 4 October 2009 / Published online: 22 November 2009
Springer Science+Business Media B.V. 2009
Abstract This paper focuses on the modification of OCO and OC=O) on the cotton fibres. The DC
cotton fabrics using a low pressure DC glow glow treatment has thus the potential to influence not
discharge obtained in air. The influence of different only the chemical but also the physical properties of
operating parameters such as treatment time, dis- cotton fabrics and this without the use of water or
charge power and operating pressure on the chemical chemicals.
and physical properties of the cotton fabrics is studied
in detail. Surface analysis and characterization of the Keywords Glow discharge Cotton Wicking
plasma-treated cotton fabrics is performed using X-ray photoelectron spectroscopy Process
vertical wicking experiments, X-ray photoelectron parameters
spectroscopy (XPS), scanning electron microscopy
(SEM) and weight loss measurements. The cotton
fabrics show a significant increase in wicking
behaviour; an effect which increases with increasing Introduction
treatment time, increasing discharge power and
increasing pressure. Results also show that low Cotton is the most important textile fibre in the world
pressure DC glow treatment leads to surface erosion despite the inroads made into its market by synthetic
of the cellulose fibres, accompanied by an incorpo- fibres (Johansson 2007). Cotton is mainly composed
ration of oxygen-containing groups (CO, C=O, of cellulose with some non-cellulosic components
including proteins, waxes, pectic substances, organic
acids, sugars, (Karahan and Ozdogan 2008). Cellu-
S. Inbakumar A. Anukaliani
lose has traditionally been modified through reactions
Department of Physics, Kongunadu Arts and Science
College, Coimbatore 641029, Tamilnadu, India of the various hydroxyl groups, leading to esterifica-
tion and etherification. In the last decades, non-thermal
R. Morent (&) N. De Geyter C. Leys (or cold) plasmas are gaining popularity as a cellulose
Research Unit Plasma Technology (RUPT), Department
modification technique since this technique varies
of Applied Physics, Faculty of Engineering, Ghent
University, Jozef Plateaustraat 22, 9000 Ghent, Belgium significantly from the traditional esterification and
e-mail: Rino.Morent@Ugent.be etherification routes (Johansson 2007). A non-thermal
plasma contains activated species, such as electrons,
T. Desmet P. Dubruel
ions, radicals, photons, which are able to abstract
Polymer Chemistry and Biomaterials Research Group,
Department of Organic Chemistry, Faculty of Sciences, hydrogen from either carbon or oxygen atoms present
Ghent University, Krijgslaan 281, 9000 Ghent, Belgium on the cotton surface. In this way, cellulose can be
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418 Cellulose (2010) 17:417426
oxidized, reduced and/or substituted in new, unique experiments. The untreated and plasma-treated cotton
ways (Johansson 2007). fabrics will also be characterized using X-ray photo-
In the last decades, the application of cold plasmas electron spectroscopy (XPS) in order to correlate the
to modify the surface properties of textile materials is hydrophilic properties with the chemical composition
experiencing rapid growth (Chen et al. 2008; De of the cotton surfaces. To gather information on the
Geyter et al. 2006; Morent et al. 2008; Samanta et al. plasma-induced physical changes, weight loss mea-
2009). Non-thermal plasmas are able to alter the surements and scanning electron microscopy (SEM)
physico-chemical properties of a polymer surface: the experiments will be carried out. The above-mentioned
main effects of interaction between active plasma experiments will be performed for selected plasma
species and polymeric surfaces is breaking polymer exposure times, operating pressures and discharge
molecular chains, inducing new functional groups powers in order to study the influence of these plasma
and altering morphological properties (Caiazzo et al. parameters on the hydrophilic behaviour of cotton
1996; Keil et al. 1998; Toufik et al. 2002). Some of fabrics.
the possible effects include improved hydrophilic
properties (De Geyter et al. 2006; Pandiyaraj and
Selvarajan 2008; Vesel et al. 2008), an improved Materials and methods
adhesion to coatings and to polymer matrices (Liston
1989; Liston et al. 1993; Dumitrascu and Borcia Materials
2006; Zhang et al. 2009), an improved dye ability
(Jocic et al. 2005; Ren et al. 2008), induced Commercially available woven grey cotton (warp
hydrophobic properties (Hodak et al. 2008; Leroux count = 29, weft count = 23), supplied by the South
et al. 2008), . Apart from creating interesting Indian Textile Research Association (Coimbatore
textile properties, plasma processing is a rapid and India) is used in this study. Before plasma treatment,
environmentally friendly technique producing virtu- the grey cotton samples were scoured by treating
ally no waste (Verschuren et al. 2007; Yip et al. them in a 2% aqueous NaOH (Nice Chemicals
2002). Moreover, plasma treatment only changes the India) solution for 2 h at 95 C followed by washing
uppermost layers of a material surface without in distilled water and drying in air. This pre-treatment
interfering with the bulk properties (Poll et al. 2001). is used to remove waxes, pectins and other impurities
Plasma modification of cotton fibres and textiles from the fabric surface (Chung et al. 2004).
has been extensively studied in numerous scientific
papers (Karahan and Ozdogan 2008; Pandiyaraj and Non-thermal plasma treatment
Selvarajan 2008; Samanta et al. 2009; Sun and Stylios
2004; Ward and Benerito 1982), however, there is a The plasma system used in this paper is schematically
lack of literature describing the effects of different shown in Fig. 1 and consists of a cylindrical plasma
process parameters such as discharge power, operat- chamber (length 0.5 m, diameter 0.25 m), a vacuum
ing pressure, exposure time, on the chemical and pumping system (VS-114D, Hindhivac India) and a
physical properties of cotton textiles. Therefore, in the DC power supply (Devi Electric Corporation
present work, the effect of different operating param- India). Inside the vacuum chamber, plasma is gener-
eters on cotton plasma modification will be studied in ated between two copper electrodes with a diameter
detail. Plasma treatment will be performed on cotton of 8 cm and a thickness of 1 mm. One electrode is
woven fabrics using a low pressure glow discharge permanently fixed, the other one is variable in height
operated in air in order to improve their hydrophilic- and the distance between both electrodes is set at
ity. This improved water wetting is essential for 3 cm. Before putting the fabric sample into the
effective processing (dyeing and finishing) and main- system, the chamber is first cleaned with distilled
tenance (cleaning) of cotton assemblies involving water and afterwards with acetone. After this clean-
aqueous media, because it facilitates the transport ing step, a cotton fabric sample is fixed in a sample
of active reagents between and into the fibres (Topal- holder and inserted into the plasma chamber by using
ovic et al. 2007). An evaluation of the hydrophilic an adjustable rod. For all experiments performed in
behaviour will be performed using wicking rate this paper, the cotton fabric is placed parallel with the
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Cellulose (2010) 17:417426 419
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420 Cellulose (2010) 17:417426
of the analyzed area is 250 lm 9 1,000 lm. The at 0.03 kPa and 4.2 W respectively, while the expo-
high-resolution spectra are collected in the constant sure time is varied between 1 and 10 min. Figure 2
analyzer energy mode and the value of 285.0 eV of shows the evolution of the average wicking height as
the C1s core level is used for calibration of the energy a function of wicking time for cotton fabrics which
scale. Curve fitting of the C1s peak is performed using were plasma-treated at different exposure times. The
CasaXPS software. wicking height of the untreated cotton fabric remains
the same (i.e. zero) as a function of the wicking time
Weight loss experiments and SEM measurements due to its poor wetting nature and is therefore not
presented in Fig. 2. This bad wicking behaviour of
Upon exposure to plasma, some degradation reactions the scoured untreated cotton fabrics can be explained
could potentially be initiated on the cotton surfaces by the significant amount of non-cellulosic compo-
due to ion and electron bombardment (Inagaki et al. nents present on the scoured cellulose fibres, as will
2004). As a result, weight loss of the cotton fabrics be explained in detail in XPS results. Figure 2
and morphological changes of the fibre surfaces can clearly shows that initially the wicking height
occur. In order to examine the etching effect of the increases fast with increasing wicking time for all
low pressure glow discharge on the cotton fabrics, plasma-treated samples before levelling off at a
weight loss experiments and SEM measurements are certain wicking time. For the upward wicking, it is
performed. To obtain the weight loss percentage of the obvious that if the distance travelled by the liquid
plasma-treated cotton fabrics, the weight of the becomes high enough, there will be a noticeable
samples is measured before and immediately after effect of gravity on the flow rate, leading to a
plasma exposure using a Shimadzu AUY220 analytic reduction of wicking height increase. As seen in
balance. The weight loss percentage is then calculated Fig. 2, increasing the plasma exposure time leads to a
according to the following equation: higher wicking rate. This observation suggests that
with increasing treatment time, the cellulose fibres
Wut Wpt
Wloss % 100 may become more hydrophilic since wettability is a
Wut
perquisite for wicking: a liquid that does not wet
where Wut and Wpt are the weight of the untreated and fibres cannot wick into a fabric. Moreover, due to
plasma-treated samples respectively. The weight plasma etching effects, the effective pore size present
measurements are repeated 10 times for each in the plasma-treated cotton fabrics may increase and
plasma-treated sample in order to obtain an average adversely reduce the capillary pressure, thus increas-
weight loss percentage. ing the wicking ability (Sun and Stylios 2004; Wong
In order to visualize the plasma-induced morpho- et al. 2001). Both of these aspects will be further
logical changes on the fibre surfaces, SEM measure- explored by performing weight loss, SEM and XPS
ments are performed using a Quanta 200F scanning measurements in order to determine the chemical and
electron microscope (FEI Japan). Prior to SEM
investigation, the cotton samples were coated with a
thin layer of gold since non-conducting specimens
(such as polymers) will charge under electron
bombardment.
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Table 2 O/C ratio of untreated and plasma-treated cellulose cellulose fibres, even after NaOH pre-treatment. This
fabrics (pressure = 0.03 kPa, discharge power = 4.2 W) result is in agreement with the results of Mitchell
Treatment time (min) O/C ratio (%) et al. (2005), who also observed the presence of non-
cellulosic components on scoured cotton fibres.
0 0.30 Table 2 also shows that with increasing plasma
2 0.38 exposure time, the O/C atomic ratio gradually
4 0.40 increases from 0.30 for an untreated sample to 0.46
6 0.42 for a sample plasma-treated for 10 min. This increase
8 0.43 suggests that new oxygen-containing groups are
10 0.46 formed on the cellulose fabrics after plasma treatment
in air. Since these oxygen groups have a polar
amount of carbon atoms without oxygen neighbours, character, one can conclude that plasma treatment
which should not be present in pure cellulose. increases the hydrophilicity of the cellulose fabrics,
However, it is well known (Topalovic et al. 2007; which can contribute to the increased wicking
Chung et al. 2004; Karahan and Ozdogan 2008) that behaviour observed in Effect of exposure time. It
laminar layers of waxes, proteins and pectin cover the is also important to mention that the plasma modi-
natural cotton fibres and since these layers mainly fication does not lead to a significant increase in N/C
consist of unoxidized carbon atoms, one can conclude atomic ratio. Therefore, no nitrogen-containing func-
that waxes, proteins, are still present on the tional groups are introduced on the cotton surfaces
Fig. 5 C1 s peak of a
untreated cotton fabric and
b cotton fabric plasma-
treated for 10 min
(operating
pressure = 0.03 kPa,
discharge power = 4.2 W)
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time equal to 4 min and (c) a SEM image of a loss percentage increases with increasing treatment
plasma-treated cotton fibre with an exposure time time up to approximately 4.5% at a treatment time of
equal to 10 min. The untreated cotton fabric consists 10 min. As a result, one can conclude with certainty
of cellulose fibres with a relatively smooth surface, that the discharge used in this paper etches the
however, some grooves and cracks are already surface of the cotton fabrics. It is however very
present. After plasma treatment, the surface of the difficult to know if the plasma removes the non-
cellulose fibres seems to become rougher with a cellulosic components from the cellulose fibres or if
significant amount of tiny grooves and cracks, as the plasma etches the cellulose fibres themselves.
illustrated in Fig. 6b, c. Based on these SEM images, Most likely, a combination of both effects will take
one may conclude that the applied plasma treatment place during plasma treatment.
etches the surface of the cotton fabrics. It should be This etching effect may be due to electron and ion
however highlighted that it is extremely difficult to bombardment in addition to the contribution of
make a sound and justified conclusion based on oxidative reactions with activated oxygen atoms to
SEM images alone. The SEM images provided in degradation reactions (Inagaki et al. 2004). Table 4
Fig. 6 show single fibres on local places of the also shows that the weight loss percentage increases
cotton fabric: other fibres in the untreated cotton with increasing discharge power and increasing
fabric seem to be as rough as the ones provided in operating pressure. This can be explained by the fact
Fig. 6c, while fibres in the plasma-treated fabrics are that more plasma species can interact with the fabric
as smooth as the ones shown for the untreated surface at higher discharge power and higher oper-
cellulose fabric. To confirm the etching behavior of ating pressure. Taking into account the above men-
the discharge used in this paper, weight loss tioned results, one can conclude that the low pressure
measurements are performed. Table 4 shows the DC glow discharge causes both chemical and phys-
average weight loss percentage for various plasma- ical modifications to the cellulose fibres, which both
treated samples together with the calculated standard attribute to the increased wicking behaviour after
deviations. Table 4 clearly shows that the weight plasma treatment.
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