Fibers and Polymers 2008, Vol.9, No.

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Study on the Influence of Scouring on the Wettability of Keratin Fibers before Plasma Treatment
C. Canal*, R. Molina1, E. Bertran1, and P. Erra
Institute of Chemical and Environmental Research of Barcelona, Consejo Superior de Investigaciones Cientficas, Barcelona 08034, Spain 1 Optical and Applied Physics Department, University of Barcelona, Barcelona 08034, Spain (Received December 19, 2007; Revised April 17, 2008; Accepted May 4, 2008)
Abstract: The present paper studies the wetting behavior and shrink-resistance of keratin fibers prepared by solvent extraction or by industrial-like surfactant washing as well as their response to plasma treatments. The results obtained reveal that keratin fibers can be prepared by surfactant washing instead of using solvents, which will allow carrying out research studies in closer conditions to the industrial reality, and indeed in a much economic and environmentally friendly way. Keywords: Low temperature plasma, Wettability, Keratin fiber, Wool fabric, Scouring, Shrink resistance

Introduction
Wettability of keratin fibers is studied either for cosmetic purposes or for textile studies. In the research of wool fabrics, several studies have used human hair fibers instead of wool fibers as a model for measuring the wetting properties of individual fibers according to the Wilhelmy balance method due to their experimental advantages [1]. Keratin fibers such as wool or human hair are, from the chemical point of view, mainly constituted of keratin, a protein, or protein complex characterized by the presence of a considerable quantity of the amino acid cystine. The three basic morphological components of wool or hair fibers from outside to inside are the cuticle, the cortex, and the medulla (although this last may not be present in all fibers). In the mature wool fiber the cuticle consists of a layer of flat scales of approximately 1 mm thickness which overlap one another, while human hair is composed of scales of 0.5 mm thickness which overlap one another in greater extent than wool, conferring the fiber greater structural rigidity [2]. Each cell of the fiber is covered by a thin membrane, the cytoplasmatic membrane. The cytoplasmatic membrane found on the outer part of the fiber is called epicuticle. The epicuticle, as usual in all biological membranes, is of protein nature (with a 12 % of cystine) and contains a certain lipid percentage [2]. The surface of cuticular cells is hydrophobic due to the presence of a fatty acids lipid monolayer, mainly constituted by 18-methyleicosanoic acid (65 %) [3]. This monolayer is called fatty-layer and is covalently bound to the protein matrix of the epicuticle by ester or thioester links, as shown in Figure 1. A number of investigations concerning the effect of lowtemperature plasma (LTP) treatment on the wool fiber have shown that the treatment can improve its processing and performance characteristics, such as reducing the tendency
*Corresponding author: ccbqst@iiqab.csic.es 444

to felting [4]. Previous studies have suggested a relationship between the shrink tendency and the amount of fatty acid present in the wool surface treated by LTP [5,6]. Up to now, the chemical, wettability, and topographic modifications of the wool surface as well as the shrink-resistance properties induced on the wool surface by an oxidative LTP discharge or by post-discharges have been studied [7-12]. According to Kamath [13] the study of their wetting behavior can be used as a measure of the superficial modifications undergone by keratin fibers. Previous studies [1,5,14] on the wetting properties of wool and keratin fibers treated by LTP used fibers and fabrics scoured with dichloromethane (CH2Cl2) using the Soxhlet extraction method to eliminate knitting oils

Figure 1. Scheme of the epicuticle of keratin fibers according to the model of Negri [3].

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and other possible contaminants. This has the disadvantage of being far from the industrial reality, where wool is washed with surfactants in aqueous media. The aim of the present paper is to determine the influence of using solvent extraction or surfactant aqueous washing on the wetting behavior of individual keratin fibers, and its influence on the results of a plasma treatment. Its effects on the shrinkage behavior of keratin fabrics (wool) are also evaluated.

to approx. 10 Pa before introducing the plasma gas. The treatments were carried out for different exposure times, keeping pressure and incident power constant at 100 Pa and 100 W, respectively. Contact Angle Wettability was determined from contact angle ( ) measurements on individual human hair fibers on the with-scale and the against-scale directions. Contact angles were calculated from adhesion tension (F/L) measurements carried out by the Wilhelmy method in an electrobalance (KSV Sigma 70). An average of 8-9 keratin fibers were scanned over 1 mm at a speed of 0.5 mm/min for both advancing and receding modes using Milli-Q water as wetting liquid. Calculations of the contact angle and perimeter were done as described elsewhere [5] by applying the following equation: Fw =LLcos (1) Fw being the wetting force, L the fiber perimeter, L the liquid surface tension, and the fiber-liquid contact angle. The perimeter of the scanned fibers was determined from the wetting force measured in a completely wetting liquid, decane, where cos was assumed to be unity. Determination of Shrink-resistance The shrink-resistance test was performed in accordance with Woolmark test method n31, in a Wascator washing machine model FOM 71 (Electrolux-Wascator AB, Ljungby, Sweden) with the ISO 6330 5A wash cycle program as a base to determine the total felting shrinkage of wool samples. Scanning Electron Microscopy Samples were gold coated with a Sputtering Polaron XC500 equipment previously to SEM observations, which were carried out in a HITACHI S-3500 scanning electron microscope in secondary electron detection mode.

Experimental
Materials Botany knitted Merino wool fabric with a cover factor of 1.22 tex1/2/mm was used for the area shrinkage determination. Caucasian human hair fibers were used as a model for the wool fiber on the determination of contact angle due to their chemical and morphological similarities, as described in detail previously. The higher stiffness of hair fibers with respect to wool Merino fibers allows their vertical immersion in the wetting liquid used for contact angle measurements, therefore producing reproducible wetting force measurements [14]. Milli-Q water (pH 6.5, =72.8 mN/m) was used as wetting liquid in the determination of contact angles. Decane (purum, Fluka) ( = 23.8 mN/m) was employed as the zero contact angle liquid to determine the fiber perimeter. Preparation Fibers and fabrics were either scoured by extraction with dichloromethane (CH2Cl2) or by washing with surfactant. CH2Cl2 Extraction Keratin samples were Soxhlet extracted with CH2Cl2 (Scharlau, Spain) for 2 h. The residual solvent present in keratin samples was removed by evaporation at room temperature, and then samples were further rinsed twice with 98 % ethanol (Panreac, Spain) for 10 min. Lastly, samples were thoroughly rinsed with deionized water and dried at room temperature. Aqueous Washing with Non-ionic Surfactant Samples were washed with 2 g/l of a non-ionic surfactant (Cadetram 9M, Cades, Spain) for 10 min at 25 C at a fabric to bath ratio of 1/30 and then rinsed with water for 3 min. A second scouring was carried out with a 1.5 g/l surfactant solution for 5 min at 25 C, with a 5 min rinsing with water at the same fabric to bath ratio of 1/30. Finally, samples were thoroughly rinsed with deionized water and dried at room temperature. Low Temperature Plasma A radio-frequency reactor (13.56 MHz) was employed [15] using water vapor as plasma gas. Samples were hung equidistant between the electrodes (which were separated 8.5 cm from one another). The vacuum chamber was evacuated

Results and Discussion

The adhesion tension hysteresis cycles of untreated keratin fibers Soxhlet extracted with CH2Cl2 (Figure 2(a)) or scoured in aqueous media with a non-ionic surfactant (Figure 2(b)) are equivalent in both cases disregard the scouring method applied to the fibers. Fibers have been measured in the withscale and in the against-scale directions. The untreated (UT) keratin fibers show the expected characteristic differences in the receding adhesion tension (F/L) as a function of scale direction during emersion in the water wetting liquid. In fact, the receding adhesion tension is higher in fibers measured in the against-scale direction. According to Kamath [13,16], this behavior can be attributed to the differences in hydrophilicity between the dorsal and the frontal of the scales. The frontal part of the scales undergoes more mechanical damage, which can leave bare the hydrophilic material below the hydrophobic

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epicuticle, and that results in lower receding contact angle values in the against-scale direction. Fibers with both kinds of scouring show receding contact angles following such trends (Table 1). Table 1 shows the contact angle values obtained for untreated keratin fibers during two wetting cycles, scoured either by Soxhlet extraction with CH2Cl2 or by an aqueous solution of non-ionic surfactant. All contact angle results shown in this work are the mean of at least 8-10 fiber measurements (with a significant level of 95 %). The advancing contact angle values in the first and second wetting cycles are above 90 , revealing hydrophobic surfaces of the fibers scoured differently. That is in good agreement

with the presence of the fatty layer on the epicuticle. The value obtained for fibers scoured by Soxhlet extraction (112 ) is slightly higher than that reported in a previous paper (103 ) [1] for keratin fibers scoured by the same method. Such difference could be attributed to the inherent variations associated with the natural origin of the fibers, coming from different individuals. On another hand, the contact angle of fibers scoured with surfactant (103 ) corresponds to that of ethylene groups (-CH2-CH2-), which is consistent with the model of the wool cuticle envelope proposed by Zahn et al. [17], in which the fatty acids of the fatty layer are folded towards the bulk of the fiber. The slight difference in hydrophilicity between extracted fibers and those scoured with surfactant could be attributed to the residual presence of traces of surfactant on the surface. The samples scoured by both methods show a decrease of around 3 in the advancing contact angle between the first

Figure 2. Adhesion tension hysteresis cycles of untreated keratin fibers in water. Fibers (a) soxhlet extracted with CH2Cl2 or (b) washed in an aqueous surfactant bath. Table 1. Advancing (adv) and receding (rec) contact angles of untreated keratin fibers scoured differently

adv () recwith-scale () recagainst-scale ()

1stcycle 2ndcycle CH2Cl2 extraction Surfactant scouring CH2Cl2 extraction Surfactant scouring 112.25.6 102.81.6 109.34.2 100.62.3 55.87.7 29.624.5 69.713.3 30.15.8 54.97.9 28.123.2 70.215.1 26.18.8 Figure 3. Adhesion tension hysteresis cycles of keratin fibers treated with H2O plasma. Fibers (a) soxhlet extracted with CH2Cl2 or (b) washed with an aqueous surfactant bath.

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and second wetting cycles (Table 1), which could be attributed to reorientation of hydrophilic groups and/or dissolution of hydrophilic material in the wetting liquid (water). The wetting hysteresis cycles of keratin fibers scoured by both methods and treated with LTP, using water vapor as plasma gas, are shown in Figure 3. The identical receding adhesion tension recorded in the measurements in water for both scale directions reveals that the differences in hydrophilicity between the dorsal and frontal part of the scales are no longer present. Therefore, as expected, plasma treatment produces a chemical homogenization on the surface of fibers which is independent of the scouring method used prior to the plasma treatment. Advancing contact angle values in the first cycle of fibers treated with water vapor plasma for different times are presented in Figure 4. Regardless of the scouring process carried on the fibers, water vapor LTP treatments (even at very short treatment times of 40 s) reduce significantly the contact angle, from 112 or 103 (UT fibers extracted or scoured, respectively) to around 54 . This hydrophilicity increase has been attributed to the total or partial oxidation of the fatty acid monolayer and the generation of superficial hydrophilic groups [12,14]. In recent papers [11,12] we demonstrated that the plasma species responsible for such modifications are the stable monoatomic species, which functionalize the surface and progressively etch the fatty layer. At short treatment times functionalization of the fatty acid monolayer prevails over its elimination [5]. In addition, an increase in treatment time with water vapor tends to reduce progressively the advancing contact angle, as observed for other plasma gases [14]. It is widely known [5,14,18-20] that hydrophilicity of polymer fibers treated by LTP decreases progressively with storage time in air atmosphere after treatment. Such contact angle increase was explained by rotation of chemical hydrophilic groups towards the bulk of the fiber and depends on the storage conditions [21], in a process known as ageing. However,

the ageing process depends on the surface characteristics of the material and it may therefore be influenced by the preparation of the fiber surface. The following results (Figure 5(b)) reveal a slight contact angle increase of fibers washed with surfactant and treated with water vapor plasma as a function of time elapsed after treatment (samples were stored in air atmosphere at 21 C and 65 % R.H.). Previous papers [5] reported the same tendency for soxhlet-extracted water vapor plasma-treated keratin fibers, as shown in Figure 5(a). For instance, they observed a contact angle increase of 5 after 14 days for fibers soxhlet extracted and treated with water-vapor LTP for 120 s, which corresponds very well with the present results, in which the fibers washed with surfactant and treated with LTP for 120 s also show a 5 contact angle increase after 9 storage days. It has to be remarked that while samples treated with plasma for shorter times tend to show fastest aging (although

Figure 4. Advancing contact angle values of fibers treated for different times with water vapor plasma previously extracted with CH2Cl2 or scoured with aqueous surfactant solution.

Figure 5. Advancing contact angle of the (a) CH2Cl2 extracted adapted from [5] and (b) aqueous surfactant scoured keratin fibers as a function of the time elapsed after treatment.

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Figure 6. Scheme representing the action of LTP on the fatty-layer (found on the epicuticle of keratin fibers) as well as the reorientation of hydrophilic groups towards the inside of the fiber in contact with air.

remaining always at values below the 103 -112 of the untreated fiber), those treated for 300 s conserve the advancing contact angle practically stable with time. This may be illustrated by the picture of Figure 6. The progressive reduction of the fatty-layer length with treatment time, as mentioned previously, is explained [12] by a combined effect of etching of the lipid layer and of generation of oxidized groups on the surface which may produce volatile compounds (such as CO2). Such chain length reduction may reduce the mobility of the chains, which contain hydrophilic groups also generated by LTP. With lower mobility, the orientation of the hydrophilic groups towards the inside of the fiber is impaired. This results in that the longer the plasma treatment time, the more stable the wetting properties. Additionally, the ageing undergone by the fibers could also be affected by other causes, such as reactions of the less stable groups in contact with air after LTP treatment. Nevertheless, as reflected in Figure 5, the ageing of the LTP treated keratin fibers is independent of the kind of scouring to which fibers have been subjected. It is widely known [4,22] that LTP treatments are effective in reducing felting shrinkage of wool fabrics. It has also been shown that there is a linear relationship between the hydrocarbon chain length on the surface of wool (and therefore the surface contact angle) and the area shrinkage of LTP treated fabrics [6]. Figure 7 shows the reduction in area shrinkage from 70 % in UT wool fabrics (in the second washing cycle) to 10 % in LTP treated fabrics after 40 s and even less after 120 s. Very little differences are observed in area shrinkage values of the UT or LTP treated fabrics depending on the kind of scouring carried out, which confirms the independence of the kind of scouring on the properties of wool. Surface topography analysis by SEM of the fibers extracted and scoured reveals no differences amongst them (Figure 8). The results presented in this work show that it is possible to use fabrics prepared by surfactant washing for plasma studies and applications, and therefore, in a much easier,

Figure 7. Area shrinkage of untreated and 120 s LTP treated wool fabrics, previously scoured either by solvent extraction or aqueous washing as a function of the 5A washing cycle in Wascator.

Figure 8. Scanning electron micrographs of (a) untreated wool fibers scoured with CH2Cl2 or (b) washed with aqueous surfactant bath.

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economical and environmentally friendly way.

Conclusion
In this study, it has been demonstrated that the surface of untreated keratin fibers, their surface modifications after LTP treatment, and the ageing process follow the same trend regardless of scouring methods (Soxhlet extraction with organic solvent or aqueous washing with a non-ionic surfactant). The surface topography and shrink-resistance of the fabrics are also independent of the scouring method used. Therefore, future studies using keratin fibers may avoid cleaning with solvents and use more ecological aqueous washing methods, which in addition are closer to industrial reality.

Acknowledgements
This research has been carried out within the FEMAN partner unit.

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