doi: 10.1111/j.1478-4408.2010.00273.

Colour and fastness of natural dyes: revival of traditional dyeing techniques

Maria Zarkogianni,a Eleni Mikropoulou,b Evangelia Varellab and Eforia Tsatsaronia*
a

Coloration Technology

Laboratory of Organic Chemical Technology, Department of Chemical Technology and Industrial Chemistry, School of Chemistry, Aristotle University, 54124 Thessaloniki, Greece Email: tsatsaro@chem.auth.gr Laboratory of Organic Chemistry, Department of Organic Chemistry and Biochemistry, School of Chemistry, Aristotle University, 54124 Thessaloniki, Greece Received: 16 June 2010; Accepted: 27 August 2010

Society of Dyers and Colourists

Cotton and wool fabrics were dyed with nine natural dyes obtained by aqueous extraction of the original plants insect in an attempt to reconstruct traditional textile dyeing recipes, to optimise the methodology at all stages, i.e. extraction, mordanting and dyeing, and to standardise it. Cochineal, madder, alkanna, henna, brazilwood, red sandalwood, safower, indigo and logwood were used for the dyeings, which were carried out directly and after mordanting of the textile material. A variety of mordants, namely, aluminium potassium sulphate, potassium dichromate, copper sulphate, zinc chloride, iron(III) chloride, iron(II) sulphate and tin chloride, is anticipated to meet both early and recent requirements and options. The dyeings were evaluated through colour measurements and standard wash, light and rub fastness tests. Generally, the mordanting process known for many centuries and connected with the textile dyeing resulted in an improvement in dye absorption and fastness properties mainly for the cotton samples, as is concluded from the tests and measurement assessments.

Introduction
The use of natural dyes has been ourishing in Europe for thousands of years and has been part of the cultural identity of the continent. In ancient times, dyed textiles were symbols of status and, because of their expense, were reserved only for the wealthiest. Early dye sources included plant, animal and mineral extracts. Madder, indigo and saffron were the three ancient dyes used in India since ca. 2500 years BC [13]. With the appearance of synthetic dyes, the use of natural dyes for textile dyeing almost disappeared. The wide range of colours available, with good fastness properties, at low to moderate costs, was the main reason for the replacement of natural dyes with their synthetic counterparts. However, in recent years, an upsurge in interest in natural dyes has been manifest by: reconstruction of ancient and traditional dyeing technology [46]; conservation and restoration of old textiles and museum textiles [718]; replacement of synthetic dyes by natural dyes for food, textiles, etc. The latter point is mainly because of environmental reasons. Nowadays, the dyestuff industry is suffering from the increase in costs of feedstock and energy for dye synthesis and is also under increasing pressure to minimise the damage to the environment caused by the production and application processes used and the efuent produced. Natural dyes exhibit better biodegradability and generally have higher compatibility with the environment compared with their synthetic counterparts [1930]. Traditionally, the use of natural dyes for textile dyeing is connected with the mordanting process, pre- or postmordanting. The process of mordanting has been known
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for many centuries and it is used to improve dye adsorption on the bre and its wash fastness because the mordant has a substantivity for both the colorant and the bre and, in bonding with the dye on the bre, forms an insoluble precipitate. The same dyestuff gives different hues or even different colour by using different mordants. Mordants are often polyvalent metallic ions which form a complex with the bre and the pigment. The most generally used mordant was alum (aluminum potassium sulphate). Other fairly common mordants were potassium dichromate (K2Cr2O7), tin chloride (SnCl2H2O), copper sulphate (CuSO45H2O), iron(II) sulphate or iron(III) chloride [5,6,18,31,32]. Nowadays, most of these mordants are unacceptable in accordance with environmental legislation, with potassium dichromate (K2Cr2O7) being a priority pollutant. Attempts were made to replace chromium (Cr) with iron (Fe) in the metal-complexed dyes [3335]. Alum and iron salts are today commonly used as mordants in textile dyeing with natural dyes. The general aim of this work was to combine both early and recent requirements and options of the textile dyeing with natural dyes, bearing in mind that, in recent years, there has been a growing interest in the revival of natural dyes in textile dyeing for environmental reasons and in the preservation of cultural heritage. In particular, this work focuses on the reconstruction of the old dyeing techniques, the formulation of regular protocols for dyeing with natural colorants, the optimisation of the application techniques according to new environmental requirements and new technological possibilities, and the standardisation of the whole procedure. The natural dyes used in this work are given in Figure 1. Having a number of traditional and contemporary recipes for dyeing on wool and cotton [31,32,36], and

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Zarkogianni et al. Colour and fastness of natural dyes

Madder O OH OH O OH H OH O Alizarin O OH COOH OH O OH O Munjistin O OH

OH H OH

O Xanthopurpurin O COOH OH

Purpurin O OH

CH3 OH O
Rubiantin

Pseudopurpurin

Cochineal CH2 O COOH HO O OH Kermesic acid Flavokermesic acid OH OH O CH2OH OH OH HO HO OH O OH HO O OH OH O CH3 COOH OH O CH3 COOH

Carminic acid

Alkanna OH O HO

Brazilwood O OH

HO

O OH

OH

OH HO O HO OH Brazilin

Alkannin
Figure 1 Structures of the main constituents of the dyes used

Brazilein

experimenting with the processes proposed, resulted in the adoption of most the appropriate methodologies. The large variety of mordants was used in order to meet both early and recent options. Optimisation attempts were made in all stages of the process, i.e. extraction, mordanting, dyeing. Quality control of the dyeings was made by standard fastness tests and colour measurements.

Experimental
Materials Commercially available cotton and wool fabrics (10 12 cm2, ca. 2 g) were used for the dyeings. Aqueous solutions (25 g l) of alum, potassium dichromate, hydrated copper sulphate, zinc chloride, iron(III) chloride, tin chloride (15 g l) and hydrated iron(II) sulphate (8 g l) were used as mordants. The mordants were purchased from Fluka GmbH (Switzerland) and were of commercial grade.Table 1 shows the natural pigments used with their origin and the main colorant constituents. The colouring agents used were purchased from Kremer Pigmente (Germany).

Apparatus A Zeltex Vistacolor dyeing machine (Zeltex Inc., USA) was used for the dyeing, the mordanting and the wash fastness tests of the cotton and wool samples. A Macbeth CE3000 Spectrophotometer [ultraviolet (UV) and specular component included, large area view, 25.4-mm diameter (Kollmorgen Instruments, USA)] was used for colour measurements. A Shimadzu UV-2101 Spectrophotometer (Shimadzu Europa GmbH, Germany) was used for obtaining the absorption spectra. A Q-Sun (Xe-1-B) Xenon test chamber (Q-LAB, USA) was used for the light fastness tests. An ASDL International Ltd (Shirley Developments Ltd, UK) apparatus was used for the rub fastness tests (wet and dry). A VeriVide D65 (Leslie Hubble Ltd, UK) colour assessment cabinet combined with an articial daylight (D65) lamp was used for the evaluation of colour change during the fastness tests. Extract preparation After repeated trials, the recommended extraction procedure was one which yielded high dye concentrations under realistic conditions of time and temperature.
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Zarkogianni et al. Colour and fastness of natural dyes

Safflower OH HO HO O HO O OH OH O OH OH OH

Red Sandalwood R HO OH O HO CH3 O OH Carthamin R=OH, Santalin A R=OCH3, Santalin B O OH O CH3

HO

HO

HO

HO O HO OH O

Henna O OH HO OH HO O OH O O OH O

OH OH O O

O OH Lawsone O

OH

HO OH Ellagic acid

Luteolin

Apigenin

Indigo O H HO N N H O N H O N O H

Logwood OH O CH 2 C C HO OH CH2 OH O CH 2 CH C OH CH2

HO Indigo
Figure 1 (Continued)

HO

OH

Indirubin

Heamatin

Heamatoxylin

Aqueous extracts were prepared by adding a certain amount (gram) of the original powdered plant insect material in 1 l distilled water. The mixture was kept at room temperature for a certain time (hour, Phase I), heated gradually under stirring at a certain temperature and then heated at the boil for a certain time (Phase II, Table 2). The mixture was allowed to stand in the dark for 24 h. Unltered aliquots of the clear supernatant liquor were used for the dyeings. Mordanting Mordanting was carried out using the pre-mordanting method. This was performed at 50 C for 45 min in a liquor ratio of 40:1. Samples were then squeezed and transferred into the dyebath (aqueous extract). Dyeing The mordanted samples were heated in a liquor ratio of 40:1 (80 ml of extract) at 100 C for 1 h. No adjustment of
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pH was made. The samples were then rinsed, squeezed and allowed to dry in open air [31]. The dyeing with indigo (15 g), a carbonyl vat dye, was completed in three steps: reduction of the water insoluble material (deep blue), with excess of sodium hydrosulphite 4 g g of textile material in the presence of sodium carbonate 2 g g of textile material; the mixture was added to 1 l water and the liquid was heated at 55 C. Reduction was carried out and the blue liquid turned to yellow (leucompound); immersion of the samples (pre-mordanted or not) in the yellow dyebath (80 ml per sample) for 5 min at 55 C; the samples (pale yellow) were removed from the dyebath and remained in the open air (gradual reoxidation and appearance of the blue hue depending on the mordant) (Tables 4 and 5) [36]; the pH of the indigo bath was adjusted by this sodium carbonate quantity.

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Zarkogianni et al. Colour and fastness of natural dyes

Table 1 The natural dyes used with their origin and their main colorant constituents Natural pigments Cochineal CI Natural Red 4 Madder CI Natural Red 8 CI generic number 75470 Main colorant constituents Carminic acid Kermesic acid Flavokermesic acid Alizarin Puprurin Pseudopurpurin Rubiantin Munjistin Xanthopurpurin Alkanin Lawsone Luteolin Apigenin Ellagic acid Brazilein Brazilin Santalin A Santalin B Carthamin Indigo Indirubin Hematin Hematoxylin Botanical zoological name Porphyrophora polonica L. Porphyrophora hameli Brandt Dactylopius coccus Costa Rubia tinctorum L. Rubia peregrine L.

Alkanna CI Natural Red 20 Henna CI Natural Orange 6

75338 75410 75420 75350 75370 75340 75520, 75530 75480

Alkanna tinctoria Tausch. Lawsonia inermis L.

Brazilwood CI Natural Red 24 Red Sandalwood CI Natural Red 22 Safower CI Natural Red 26 Indigo CI Natural Blue 1 Logwood CI Natural Black 1&2

75280 75540 75140 75780 75790 75290

Caesalpinia trees Pterocarpus santalinus L. Carthamus tincorius L. Indigofera tinctoria Hematoxylon compechianum L.

Colour measurement This was carried out according to CIELAB 1976 and the modied CIELCH system (D65 10). Reproducibility was checked by taking four measurements and recording the variation in percentage reectance values over the range 400800 nm [37]. Fastness determination Wash, light and rub fastness tests were carried out according to BS 1006:1990 CO2 (test 2), BO2 and X12, respectively [38].

Results and Discussion

Colour Colour and colour yield values, CIE L*a*b*C*h* and K S, for cotton and wool fabrics dyed without mordant
Table 2 Dye extraction data Extraction Phase I Plant insect material Amount (g) 15 30 30 30 30 30 7.5 15 Phase II

Dye Madder Alkanna Henna Brazilwood Sandalwood Safower Cochineal Indigoa Logwood

Time (h) 12 24 24 16 72 72 12

Temperature (C) 7080 90 80 90 90 7080 7080 95

Time (h) 0.25 1 1 1 2 0.75 0.25 0.5

a The dyeing process of indigo: experimental, dyeing

(reference samples) are given in Table 3; corresponding values for dyeing in the presence of a mordant are shown in Tables 4 and 5 (cotton and wool samples, respectively). The h* values for the wool and cotton reference samples (Table 3) are in good agreement with the visual colour description for the dyes used. The variations in Dh* (Tables 4 and 5) indicate in almost all cases (wool and cotton samples) that the absolute h value of the sample [derived from the combination of the h value of the non-mordanted sample (Table 3) and the Dh value of the mordanted sample (Tables 4 and 5)] lies in the same h (hue) range in the colour circle with the non-mordanted sample (reference) (70110 yellow, 130200 green, 210 290 blue, 32040 red). Even in the case of brazilwood (mainly for the wool samples), with the highest Dh values, this is the rule, with minor exceptions. The DE values (total colour difference) are high in most cases, especially for the samples mordanted with iron(III) chloride and iron(II) sulphate. The high DE values were mainly attributable to high DC* and DL* values. This in turn was caused by the mordant effect, for example darkening in colour by iron sulphate or chloride results in high negative DL* values, but was also related to variations in dye uptake with different mordants. Given that DL* < 0 means that the sample is darker than the reference, Table 4 shows that mordanting results in darkening the colour for all the dyes and mordants on the cotton bre. In contrast, DL* has positive values on wool samples in many cases, meaning that mordanted wool samples are lighter than the reference sample. Mordanting with iron II and III salts again resulted in darkening in colour (DL* < 0) for all dyes (Table 5). The values of C* for the reference wool fabrics (dyed without mordant) were signicantly higher (double or
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Zarkogianni et al. Colour and fastness of natural dyes

Table 3 Colorimetric data (L*, a*, b*, C*, h*, K Skmax values) of non-mordanted dyed wool and cotton samples Dye Madder Alkanna Safower Henna Sandalwood Cochineal Brazilwood Logwood Indigo Fibre Wool Cotton Wool Cotton Wool Cotton Wool Cotton Wool Cotton Wool Cotton Wool Cotton Wool Cotton Wool Cotton L* 37.4 64.0 38.7 57.4 58.4 73.8 37.2 61.4 52.7 62.2 19.3 65.5 41.9 53.8 29.6 47.9 34.8 45.6 a* 25.4 16.0 6.2 0.6 8.9 0.7 14.8 4.8 19.2 14.7 16.1 11.8 22.2 16.5 14.1 7.3 )4.7 )5.8 b* 20.9 14.2 6.0 1.6 48.6 24.0 24.3 13.4 25.3 6.4 2.3 )2.0 29.7 22.0 12.6 3.6 )17.1 )13.3 C* 32.9 21.4 8.7 1.7 49.4 24.0 28.4 14.3 31.8 16.0 16.3 11.9 37.0 27.5 18.9 8.1 17.7 14.6 h* 39.5 41.6 44.1 111.1 79.7 88.3 58.6 70.2 52.8 23.5 8.1 350.3 53.2 53.2 41.8 26.3 254.7 246.4 KS 11.2 1.4 7.0 1.5 17.3 1.9 16.1 2.1 5.5 1.1 24.4 0.8 7.7 2.2 9.0 2.2 10.1 4.3

more) than that observed for the corresponding reference cotton fabrics (Table 3). This difference could be correlated with different dye uptake, which was also observed visually and conrmed with the signicantly different K S values. The K S value is proportional to the dye concentration on the bre according to the KubelkaMunk equation. This proportionality is the rule for concentrations C similar to those used (Eqn 1): K =S A C 1 R2 =2R f R 1

where K is the absorbance coefcient, S is the scattering coefcient, R is the reectance ratio, A is a constant and C is the dye concentration. Higher dye adsorption on the wool bre could be attributed to structural features of the bre. Electrostatic forces between the positively charged side chains of the protein bre and the dye molecule would be expected to play a dominant role in dye adsorption. In contrast, it is the weaker van der Waals and hydrogen bonding forces that are responsible for dye adsorption in cotton dyeing [39,40]. Mordanting results in a signicant increase of K S for all cotton samples, whereas K S values of the mordanted wool samples are higher, equal or even lower than the reference sample. Cochineal, a dye with animal (insect) origin does not dye cotton bres satisfactorily. Thus, pre-mordanting is necessary before cotton dyeing with cochineal. On the mordanted cotton bre, cochineal molecules act as ligands on the metal ion, which is also connected with the hydroxy groups of cellulose; thus, the dye adsorption on the mordanted cellulose increased dramatically (an increase of K S value from 0.8 to 1.7 20.5, depending on the mordant metal). In contrast, the side chains of the wool bre, hydroxy, carboxy, amine and thiol groups compete with the carboxy, carbonyl and hydroxy groups of the cochineal dye in its chelation with the mordant; thus, adsorption of cochineal on the mordanted wool is in most cases lower than that of the reference (K Sref = 24.4, K Smor = 2.527.7, depending on the mordantmetal).
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Fastness properties The fastness values to washing, articial light and rubbing of the cotton samples dyed with natural dyes 19 with or without mordanting are given in Table 6. In Table 7, the same values for the wool samples are given. A mordantmetal salt has a substantivity for both the colorant and the bre and, in bonding with the dye on the bre, forms an insoluble precipitate. Dyes that would not normally be fast to the bre can attach themselves to the mordant. Thus, mordanting improved wash fastness for those samples with low to medium wash fastness; for example: cochineal, reference sample: Colour Change 1; logwood (heamatoxylon compechianum), reference sample: Colour Change 1; safower, reference sample: Colour Change 3 (Table 6, cotton samples). In these cases, pre-mordanting results in a signicant improvement in wash fastness by 14 points of the greyscale (Table 6, cochineal, logwood). In contrast, samples dyed with madder, alkanna, sandalwood or indigo without mordant (reference samples) have very good to excellent wash fastness (45 to 5, Table 6). This could be correlated to the low K S values, which were signicantly improved by pre-mordanting the samples. Pre-mordanting results in an increase in dye adsorption on cotton, but this excess of dye adsorbed supercially could be removed by washing. Thus, wash fastness values were decreased. Fastness to washing of the wool samples was very good to excellent in all cases (Table 7). Fastness to articial light was low to medium in all cases, with the exception of wool samples dyed with cochineal, where pre-mordanting mainly with iron chloride and sulphate and copper sulphate resulted in excellent light fastness values (light fastness > 7) (Table 7). Iron (II) and iron(III) salts had the most marked effect on the light fastness of cotton samples, followed by copper sulphate (Table 6). Pre-mordanted wool samples presented as the same or 0.51.5 points of the greyscale higher light fastness values or even lower light fastness values (logwood) than the

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Zarkogianni et al. Colour and fastness of natural dyes

Table 4 Colorimetric data (DL*, Da*, Db*, DC*, Dh*, DE, K Skmax values) of dyed cotton samples after mordanting Dye Madder Mordant Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum DL* )13.7 )8.7 )12.2 )10.8 )18.4 )25.6 )24.6 )8.7 )2.2 )3.3 )9.5 )10.0 )20.7 )19.4 )11.1 )5.2 )8.3 )21.3 )13.9 )25.4 )23.7 )7.3 )4.6 )2.4 )17.6 )13.9 )28.1 )22.0 )3.4 )1.1 )2.5 )13.7 )13.5 )20.3 )14.2 )43.9 )25.2 )12.6 )32.5 )42.2 )44.2 )47.3 )18.6 )24.3 )23.9 )26.1 )14.4 )31.2 )31.9 )20.8 )29.2 )11.2 )22.8 )12.0 )21.1 )2.9 )2.0 )3.5 )0.5 )10.5 )7.0 Da* 10.5 10.4 )0.2 )6.4 6.8 )9.3 )9.9 1.1 3.2 )2.5 4.6 2.1 2.5 1.3 4.9 3.6 )2.2 4.5 3.8 6.0 2.1 1.1 1.3 )0.3 0.02 1.9 )3.1 )2.8 3.0 4.2 )5.2 )2.6 0.1 )8.1 )10.2 6.7 30.9 )5.9 )0.7 0.7 )10.4 )10.1 15.2 21.8 2.4 0.2 5.5 )10.7 )9.6 )5.2 )6.3 )6.0 )1.9 )8.3 )1.9 )12.2 )12.9 )9.4 )10.9 )10.6 )11.3 Db* )1.1 12.4 )5.5 )5.5 )5.4 )2.3 )9.8 9.2 12.1 4.7 11.8 8.4 10.7 4.1 20.0 18.5 9.7 5.3 12.4 2.6 )1.7 5.9 9.6 10.2 1.8 1.7 )6.5 )6.3 12.9 16.7 6.1 7.0 8.9 6.5 2.1 )6.1 13.5 3.8 )4.0 )7.0 2.3 0.9 )13.3 )12.6 )24.2 )21.5 )11.3 )23.9 )22.8 )4.2 1.1 )9.1 )6.1 )13.5 )10.0 )33.3 )32.2 )32.5 )32.1 )32.2 )33.5 DC* 8.2 16.1 )3.3 )8.4 3.1 )7.8 )13.9 9.1 12.2 5.3 12.2 8.4 10.7 4.0 20.3 18.7 9.8 5.8 12.7 3.4 )1.5 6.0 9.5 9.8 1.7 2.4 )7.2 )6.8 10.2 13.8 )0.3 2.0 5.2 )1.6 )6.4 8.2 32.3 )5.8 0.6 3.5 )10.5 )10.0 5.4 12.0 )8.5 )10.8 )3.1 )21.4 )20.5 )5.9 3.2 )2.5 )2.2 1.9 0.3 6.4 5.7 5.0 4.9 5.0 6.3 Dh* 6.7 1.8 4.4 0.2 8.1 5.6 1.4 1.8 2.7 0.3 3.2 2.2 2.4 1.5 3.2 2.3 2.1 3.9 2.8 5.6 2.3 0.9 1.6 2.9 0.6 1.2 0.9 0.6 8.5 10.3 8.1 7.2 7.2 10.2 8.3 3.8 9.8 3.9 4.0 6.2 1.5 2.0 19.5 22.2 22.8 18.6 12.2 15.2 13.9 3.1 0.3 10.6 6.0 15.8 10.2 1.8 0.9 3.9 2.5 2.7 2.6 DE 17.4 18.4 13.4 13.7 20.3 27.4 28.2 12.7 12.7 6.2 15.8 13.3 23.4 19.9 23.4 19.5 13.0 22.3 19.0 26.2 23.8 9.5 10.7 10.5 17.7 14.1 29.0 23.0 13.7 17.3 8.4 15.6 16.2 22.8 17.6 44.8 42.1 14.4 32.7 42.8 45.4 48.3 27.5 35.0 34.1 33.8 19.2 40.8 40.3 21.8 29.4 15.6 23.6 19.9 23.5 7.3 6.1 7.2 5.5 12.0 9.8 KS 2.8 3.4 2.7 2.2 3.3 8.8 4.9 5.2 4.7 2.5 5.1 5.1 12.5 7.3 11.8 6.7 5.3 9.7 10.2 10.6 7.9 4.8 5.5 3.6 6.6 5.4 9.7 6.2 2.3 3.2 2.1 4.0 3.9 7.9 3.8 20.5 9.2 1.7 7.1 15.5 14.4 19.1 10.6 20.8 9.5 11.9 6.1 14.2 15.5 8.8 20.2 46.9 11.1 5.0 10.0 7.2 6.6 5.8 5.2 10.1 9.1

Alkanna

Safower

Henna

Sandalwood

Cochineal

Brazilwood

Logwood

Indigo

reference sample, with the exception of cochineal (Table 7), while the improvement of the light fastness values was higher for cotton samples (0.52.5 points of the greyscale). Fastness to rubbing, wet and dry, was in most cases lower for the pre-mordanting samples of both cotton and wool than the reference samples (Tables 6 and 7),

attributable again to the supercially adsorbed excess of pigment which could be more easily removed in the test conditions.

Conclusions
The aim of this work was the reconstruction of the old dyeing techniques, the formulation of regular protocols
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Zarkogianni et al. Colour and fastness of natural dyes

Table 5 Colorimetric data (DL*, Da*, Db*, DC*, Dh*, DE, K Skmax values) of dyed wool samples after mordanting Dye Madder Mordant Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum DL* 1.1 5.9 )5.9 3.6 )4.2 )9.3 )11.0 4.5 2.3 5.7 1.1 2.0 )7.4 )5.1 )0.7 1.0 )4.5 )9.5 )0.8 )24.8 )8.7 )2.1 0.6 3.0 )8.1 )4.1 )12.9 )10.5 8.5 9.0 )9.6 )10.2 )7.5 )23.2 )20.9 4.0 11.2 26.1 )1.4 )2.8 )2.2 )4.3 )10.6 )4.6 )18.0 )21.1 )8.4 )3.1 )23.8 )10.4 )14.8 )1.3 12.5 13.6 )10.2 )4.4 6.9 6.8 5.8 12.5 )8.0 Da* 7.2 12.4 )8.8 )10.9 3.9 )14.7 )14.5 0.6 0.3 )9.2 )2.0 )0.8 )1.4 )3.5 4.4 5.1 )7.0 )1.7 2.9 )3.6 )4.7 )0.6 2.1 )3.8 )3.1 )0.4 )7.5 )7.5 )1.9 )1.5 )14.2 )8.9 8.2 )1.5 )1.3 9.2 22.4 )13.6 )4.8 )3.1 )12.7 )14.1 12.8 17.0 )12.7 )5.0 )0.3 )6.0 )18.3 )13.0 )6.1 )14.0 )8.2 )11.6 )11.7 )8.4 )11.4 )11.8 )10.6 )11.8 )6.9 Db* 3.7 13.8 )8.8 )1.7 )4.9 )9.7 )14.1 5.8 12.8 2.7 8.8 3.6 1.6 )1.7 3.4 3.0 )21.1 )11.4 )1.0 )23.1 )11.2 0.2 3.0 )0.2 )6.5 )2.0 )12.3 )11.2 2.4 9.0 )6.3 )5.9 )3.0 )19.2 )20.9 0.2 8.9 8.5 )3.7 )3.3 )2.3 )5.3 )13.5 )17.6 )26.8 )22.9 )10.2 1.3 )29.8 )10.9 )16.4 )9.9 )10.8 )8.4 )10.0 )32.9 )27.2 )18.5 )31.6 )27.7 )33.1 DC* 7.9 18.4 )12.4 )8.8 0.5 )17.4 )20.1 5.0 11.3 0.5 6.8 2.4 0.4 )3.5 4.2 4.1 )21.8 )11.5 )0.4 )23.3 )11.8 )0.1 3.7 )2.0 )7.1 )1.9 )14.4 )13.4 0.9 6.8 )12.1 )9.8 3.6 )13.0 )13.3 9.2 23.8 )5.2 )4.9 )3.3 )12.9 )12.7 1.5 4.0 )27.1 )18.6 )7.8 )2.1 )33.1 )16.9 )10.1 )16.2 )12.7 )14.0 )15.4 )1.5 )5.6 )10.4 )2.0 )5.0 )1.6 Dh* 1.6 2.2 1.5 6.6 6.2 2.7 2.6 3.0 6.1 9.6 6.0 2.8 2.0 1.7 3.6 4.3 4.2 0.5 3.0 0.9 3.0 0.7 0.3 3.3 0.8 0.8 0.03 0.8 2.9 6.0 9.7 4.2 8.0 14.2 16.1 0.9 3.6 15.2 3.6 3.1 1.1 8.2 18.5 24.1 11.9 14.3 6.7 5.8 11.2 1.8 14.4 5.6 4.6 2.8 0.8 0.6 4.7 11.9 2.0 4.8 2.2 DE 8.2 19.5 13.8 11.6 7.6 19.9 23.0 7.4 13.0 11.1 9.1 4.19 7.7 6.4 5.6 6.0 22.7 14.9 3.2 34.1 14.9 2.2 3.7 4.8 10.8 4.6 19.4 17.1 9.1 12.7 18.2 14.8 11.5 30.2 29.6 10.1 26.5 30.6 6.2 5.3 13.1 15.7 21.4 24.9 34.7 31.5 13.3 6.8 42.3 19.9 22.9 17.2 18.4 19.7 18.4 4.7 10.0 17.2 6.5 14.3 8.4 KS 12.4 12.1 14.4 9.0 12.0 15.8 14.4 7.5 16.0 6.5 10.9 7.8 12.6 9.2 20.1 16.0 8.5 19.6 20.1 26.4 18.3 19.5 17.6 12.6 20.5 18.3 22.4 20.5 3.9 6.7 12.7 10.1 5.7 9.1 7.2 21.9 17.5 2.5 23.7 27.7 22.9 26.0 16.3 11.9 13.7 22.3 9.7 6.8 20.0 16.7 29.6 8.3 22.1 22.5 16.7 12.5 5.5 4.0 6.5 4.0 13.6

Alkanna

Safower

Henna

Sandalwood

Cochineal

Brazilwood

Logwood

Indigo

for dyeing with natural colorants, the optimisation of the application techniques according to new environmental requirements and new technological possibilities, and the standardisation of the whole procedure. Aqueous extracts of dyes 19 were used for dyeing cotton and wool bres, with and without pre-mordanting, with the mordants of potassium dichromate, copper
24

sulphate, zinc chloride and tin chloride, as well as alum and iron(II) and iron(III) salts. These mordants were used as representatives commonly used in textile applications in the past. Alum and iron salts are still used as mordants necessary for dyeing with natural dyes. Mordanting resulted in a signicant improvement of the dye adsorption on the cotton fabrics and an increase

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Zarkogianni et al. Colour and fastness of natural dyes

Table 6 Wash, light and rub fastness values of dyed cotton samples
Wash fastness Dye Madder Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alkanna Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Safower Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Henna Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Sandalwood Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Cochineal Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Brazilwood Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Logwood FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum Indigo FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum a CC, colour change b CS, colour staining c w, wool; c, cotton; n, nylon d (g), greener; (b), bluer Mordant CCa 45 45 4 5 3 3 4 5 45 4 45 5 45 4 45 45 3 3 4 5 2 12 5 5 4 23 3 5 d 2 3 (g) 12 45 45 5 4 4 5 45 4 5 5 1 3 3 5 2 2 4 4 3 3 45 5 4 3 45 45 1 4d (b) 4 45 (b) 1 4 4 45 45 45 45 45 45 45 CSb,c w: 4 5, n: 4 5, c: 4 5 w: 3 4, n: 4, c: 4 w: 3 4, n: 4, c: 4 5 all n: 4 5, c: 4 5 w: 4, n: 4, w: 4, n: 4 5, c: 4 5 w: 4 5, c: 4 5 n: 3 n: 3 n: 3 n: 4 55 n: 4 5 n: 3 n: 3 4 n: 4 5 all 5 all 5 all 5 all 5 all 5 all 5 all 5 all 5 5 5 5 c: 3 4 5 5 5 5 all 5 all 5 all 5 all 5 all n: 4 5, c: 4 5 5 all 5 all 5 all c: 4 5 c: 4 5 5 all c: 4 5 w: 4 5, c: 4 5 5 all 5 all w: 4 5, c: 4 5 w: 3 4, c: 4 5 w: 4 5, c: 3 5 all w: 4 5, c: 1 2 w: 4 5, c: 4 5 w: 4 5, c: 4 5 w: 4 5, c: 4 5 w: 3 4, c: 4 w: 4 5, c: 4 w: 2, c: 2 w: 4, c: 4 w: 2, c: 3 4 w: 4, c: 3 4 w: 3, c: 3 4 w: 4 5, c: 4 5 w: 4 5, c: 4 5 w: 4 5, c: 4 5 w: 4 5, c: 4 5 w: 4 5, c: 4 5 w: 4, c: 4 w: 5, c: 4 5
c

Rubbing Light fastness 23 3 2 34 5 4 5 4 2 23 2 23 4 34 4 4 2 23 2 3 3 23 3 3 2 2 2 23 3 23 3 3 12 2 2 23 34 23 4 34 3 4 2 3 45 56 56 56 2 2 2 23 3 2 34 34 12 4 2 23 23 4 34 5 5 5 56 5 5 4 Dry 45 34 3 4 34 23 3 4 5 34 4 4 4 3 3 34 45 3 34 45 3 3 3 4 4 4 4 45 34 34 34 45 45 34 23 45 34 34 23 4 45 2 3 45 34 23 23 3 45 3 2 34 3 4 3 3 Wet 4 3 3 4 23 3 3 34 5 34 4 45 34 4 34 34 45 34 4 45 3 34 3 4 45 45 34 4 34 34 34 4 45 34 3 45 34 3 34 34 45 2 3 45 12 23 3 3 3 23 2 34 2 23 2 2

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Zarkogianni et al. Colour and fastness of natural dyes

in K S values. The adsorption improvement for the wool samples was lower because dye adsorption on wool, even without mordant, was signicantly higher than that of the cotton without mordant. Thus, the K S improvement of the mordanted cotton samples was more impressive than that of the mordanted wool samples. The wash fastness of some dyed cotton fabrics without mordant was low to medium and was improved in almost all cases when the samples were dyed after mordanting.
Table 7 Light, rub and wash fastness values of dyed wool samples Rubbing Dye Madder Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Alkanna Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Safower Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Henna Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Sandalwood Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Cochineal Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Brazilwood Alum SnCl2 K2Cr2O7 CuSO4 ZnCl2 FeCl3 FeSO4 Mordant Light fastness 3 34 45 45 45 34 45 45 34 34 4 45 45 34 4 34 34 34 34 45 45 3 45 4 34 34 34 4 4 34 4 4 3 3 3 4 4 3 34 34 34 45 45 5 >7 6 >7 >7 34 34 4 4 34 34 34 4 Dry 45 34 3 4 23 34 4 45 45 4 3 45 4 3 34 4 45 4 3 45 4 45 34 45 45 45 4 45 5 5 5 5 45 4 3 4 4 3 12 2 45 12 2 4 34 34 4 4 4 2 2 2 3 34 3 23 Wet 45 34 34 45 23 4 4 45 45 4 3 45 34 34 3 4 4 34 34 45 4 34 34 4 5 45 4 45 45 45 45 45 45 4 34 4 34 3 3 23 45 12 23 4 2 23 45 4 4 3 3 23 34 4 34 4

Table 7 continued Wash fastnessa

b

CS Wool 23 3 23 3 3 3 23 5 34 4 4 4 4 3 Light fastness 12 6 23 3 12 6 3 5 6 6 6 6 5 6

Dye Logwood

Mordant

CCb 45 5 4 45 5c (b) 5 5 45 4 4 4 4 45 4

Cotton 3 3 3 4 23 12 2 45 3 4 4 4 4 23

FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum Indigo FeCl3 SnCl2 K2Cr2O7 ZnCl2 CuSO4 Alum

a Wash fastness very good to excellent in all cases above b CC, colour change, CS, colour staining c (g), greener; (b), bluer

Fastness to washing of the wool samples was very good to excellent in all cases (Table 7). Light fastness was also improved, mainly for the cotton samples, whereas a decrease or no improvement was observed for the wool samples. Iron(II) and iron(III) salts as mordants proved to be the most advantageous in K S increase and fastness improvement, albeit darkening the colour of the samples. In contrast, rub fastness values were in most cases slightly decreased or remained the same compared with the directly dyed cotton and wool samples.

Acknowledgement
The work is part of a Specic Targeted Research Project FP6-2003 Group B 2.1 (MED-COLOUR-TECH).

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