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Polysiloxane Softener Coatings on Plasma-Treated Wool: Study of the Surface Interactions

Cristina Canal, Ricardo Molina, Enric Bertran, Pilar Erra*

Low temperature plasma (LTP) improves the shrink-resistance of wool fabrics but impairs their softness, so different polysiloxane coatings were applied. Modications in surface hydrophilicity and topography of fabrics and bres have been recorded through drop test, contact angle and SEM, respectively. LTP improves the deposition of the polysiloxanes which, depending on their functionalities alter the original hydrophilicity of the wool surface. Softness and shrink-resist results of the fabrics point out to a possible relationship between hydrophilicity of the wool bre surface and the shrinkage behaviour of the fabrics. A possible mechanism of interaction between the different polysiloxane groups and the surface of untreated (UT) and LTP-treated wool is proposed.

Introduction
Wool is a natural bre mainly constituted by keratins. Keratins contain high amounts of disulde bonds from cystine residues, crosslinking mainly adjacent protein chains and thus restricting their conformational rearrangements. Morphologically, the bres are formed by cortical and cuticular cells and cell membrane complex. Cuticular cells are located in the outermost part of the bre, surrounding the cortical cells. The cuticle consists of a layer

C. Canal, P. Erra Surfactant Technology Department, Institute of Chemical and Environmental Chemistry of Barcelona Consejo Superior de Investigaciones Cientcas, c. Jordi Girona 18-26, 08034 Barcelona, Spain Fax: (34) 93 204 5904; E-mail: pesqst@iiqab.csic.es R. Molina, E. Bertran Optical and Applied Physics Department, University of Barcelona, Avda. Diagonal 647, 08028 Barcelona, Spain
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of at scales of approximately 1 mm thickness overlapping one another like tiles on a roof, and forming a ratchet-like structure, which provokes a directional frictional effect[1] which has traditionally been considered the main reason for felting shrinkage of wool fabrics. Felting shrinkage is a process which comprises the compacting and entanglement of bres submitted to mechanical action, friction and pressure in the presence of heat and humidity and accounts for the undesirable and irreversible reduction of the area of the fabrics. From the chemical point of view, the outermost part of cuticle cells is of hydrophobic nature due to the presence of a fatty layer, a thin layer of 18-methyl eicosanoic acid (18-MEA) covalently bound via a thioester linkage to the protein layer of the cuticle.[2] It has recently been pointed out that the presence of this fatty layer on the surface could inuence the shrinkage behaviour of wool fabrics during aqueous washing.[3,4] Traditional shrink-resist treatments use chemicals that may produce a highly polluted waste water.[5] In addition, they may even damage the bulk of the bre. Low

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temperature glow discharge plasmas (LTP) are considered as an emerging technique to obtain wool with shrinkresistant properties by environment friendly methods,[6] as they modify the wool bre surface to a depth of nanometers without altering the bulk properties of the bre. Plasma processes need only small amounts of selected chemicals and do not produce waste water or chemical efuents; so the plasma method is efcient, economical, and can reduce the environmental impact caused by the use of chemicals in the textile industry.[7] Plasma is a partially ionized gas generated by an electrical discharge, and consists of neutral particles (molecules, Figure 1. Chemical structure of the three modied polysiloxane softeners used in the present study RI, excited atoms, free radicals RA and RS. and metastable particles), charged particles (ions and effects of coating LTP-treated wool fabrics with polysiloxelectrons) and UV and Visible radiation.[810] LTP chemistry ane softener emulsions of different functionalities: one takes place while the gas remains at relatively low cationic (RI), its uncharged counterpart (RS) and an untemperatures, close to room temperature.[11] When the charged polysiloxane with amide group (RA) (Figure 1). plasma is generated by an oxidative gas, such as air, Different techniques have been used [drop test, contact oxygen or water vapour, the fatty layer on the wool bre angle, handle evaluation and scanning electron microsurface is oxidized progressively by forming C OH, C O, HOC O groups, and promoting an ablation effect.[1214] scopy (SEM)] to allow elucidation of the reasons for the shrinkage and handling variations of LTP-treated wool Also, the cystine residues are oxidized to cysteic acid fabrics and to explain the possible interactions between residues increasing the anionic groups on the wool bre the surface and the polysiloxane softeners. surface.[13,15] Due to these oxidative processes, the wetting properties of the surface are improved and therefore the adhesion properties.[16,17] Furthermore, tear strength and hygral expansion are reduced, and the bre-to-bre and Experimental Part interyarn friction are increased leading to improvement in Materials dimensional stability as well as the frictional coefcient [18] increase for an apparent harsher handling. Botany knitted merino wool fabric with a cover factor of 1.22 tex/mm was used throughout the work. Before treatments, the Preliminary studies of our group revealed that, while fabrics were washed with a nonionic surfactant, thoroughly LTP improves signicantly the shrink-resistance of wool rinsed with deionized water and dried at ambient temperature. fabrics, it produces, at the same time worsening of its Human hair bres were used as a model for the wool bre in the softness. To solve such a problem, conventional textile determination of contact angle thanks to their chemical and softeners are applied on LTP-treated wool fabrics; but morphological supercial similarities. In addition, the stiffness of although they confer better handling, it resulted in an hair bres allows their vertical introduction in the wetting liquid [19] increase in the shrinkage area to undesirable values. used for contact angle measurements producing reproducible Kim and Kang[20] also found that the hygral expansion of wetting force measurements.[21] Before treatments, hair bres LTP-treated wool fabrics increases with silicone postapunderwent the same washing process already described for plication, which they attribute to the effect of reduced yarn wool fabrics. Milli-Q water (pH 6.5), with a surface tension of 72.8 mN m1 was used as the wetting liquid. Decane (purum, interaction. The aim of this paper is to investigate the
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Fluka) with a surface tension of 23.8 mN m1 was employed as the zero contact angle liquid to determine the bre perimeter. Three softener polysiloxane microemulsions provided by Rudolf Chemie (Germany) were used, Rucon SIQ, Rucon GWA and Rucon GWS and will be identied as RI, RA and RS. They have the same basic polymeric silicone molecular structure and differ in some functional groups (Figure 1); RI possesses two quaternised amine groups which confer cationic character to the molecule at any pH, and a potentially reactive amine side chain. RA possesses an amide end group in the lateral chains and is consequently nonionic. RS possesses a potentially reactive amine end group in the side chain which can be protonated at acidic pH.

bres due to their experimental advantages, according to previous studies.[13,21] Hair bres had undergone the same treatments as wool fabrics. An average of eight or nine keratin bres were scanned over 1 mm at a speed of 0.5 mm min1 for both the advancing and receding modes using Milli-Q water as wetting liquid, at room temperature. The perimeter of the scanned bres was determined from the wetting force (Fw) measured in a completely wetting liquid, decane, where cos u was assumed to be unity. Calculations of the contact angle and perimeter were done as described elsewhere[24] applying the following equation:

Fw g L p cos u Treatments Low Temperature Plasma

A laboratory radiofrequency reactor operating at 13.56 MHz was employed using water vapour as plasma gas. The characteristics of this reactor are described elsewhere.[22] The distance between the electrodes was 8.5 cm, and the sample was hung equidistant between the electrodes. The samples were placed in the vacuum chamber, which was evacuated to a pressure of approximately 10 Pa before introducing the plasma gas. During treatments (120 and 300 s), pressure and incident power were kept constant at 100 Pa and 100 W, respectively. bre-liquid contact angle.

(1)

p being the bre perimeter, g L the liquid surface tension and u the

Determination of Shrink-Resistance
The shrink-resistance test was performed in accordance with Woolmark test method no. 31, 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.

Softness Evaluation
Softness evaluation was carried out with the aid of (n 1) nonexpert panelists, where n was the number of samples to evaluate. The panelists were required to assess the fabrics according to their softness.

Polysiloxane Softener Coatings

Polysiloxane softening coatings were carried out in the conditions suggested by the company which provided the polysiloxanes but always using the minimum concentration recommended. Treatments with RA and RI were carried out by exhaustion at 1% owf, pH 5.25 and a liquor to wool ratio of 20:1 at 40 8C for 20 min. Afterwards, the samples were squeezed in a padding mangle and dried at an ambient temperature. The samples treated with RS were padded at 1% owf and pH 5.25 to obtain a liquor pickup of 80% and further dried at 110 8C for 10 min.

Scanning Electron Microscopy

The topography of wool bre surface was studied by SEM using a JEOL JSM-5610 Scanning Electron Microscope for the observation of wool fabrics. All samples were AuPd coated with a BAL-TEC SCD Sputter Coater, prior to SEM observation.

Results and Discussion

Methods
The methods used are the same as those described in ref.
[23]

Wettability According to Kamath,[25] wetting behaviour can be used as a measure of the supercial changes experienced by bres. In this work, we have used two techniques; drop test, which is commonly used for the quick evaluation of the wettability of fabrics, and the determination of contact angle on individual bres by the Wilhelmy balance method which provides quantitative data on surface hydrophilicity of bres and avoids the inuence of the capillary forces of the fabric. In Figure 2, drop test results reveal the important increase of wettability of wool fabrics conferred by the LTP treatment for 120 and 300 s. While the wetting time of untreated (UT) wool fabrics is above 3 h (and therefore considered a nonwetting fabric), the samples treated for both 120 and 300 s show immediate absorption (0 s) and

Wettability
Hydrophilicity of fabrics has been evaluated according to the AATCC Test Method 39-1980 by determining the wetting time in seconds using the drop test. The test schematically consists in depositing a droplet of water of constant volume, delivered by a burette, on the surface of the fabric and measuring the time required for its absorption. Results are the average of at least ve measurements.

Dynamic Contact Angle Measurements

The contact angles of individual bres were calculated from the dynamic wetting force (Fw) measurements carried out in an electrobalance KSV Sigma 70 contact angle meter by applying the Wilhelmy method. Human hair bres were used instead of wool
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opposition to the supercial chemical heterogeneity of UT bres as shown in previous results.[15,21] Application of softener polysiloxane microemulsions, RI, RA and RS on UT or LTP-treated wool reveals different behaviours. As expected, UT samples post-treated with polysiloxanes remain hydrophobic independently of the softener applied (Figure 2 and 3). LTP-treated samples post-treated with RI or RA polysiloxanes show an increase in wetting time (Figure 2) and in contact angle values (from around 508 to values slightly below 908) (Figure 3) (908 being considered the frontier between hydrophilic Figure 2. Wetting time (in seconds) of UT and LTP-treated fabrics (for 120 and 300 s) and below and hydrophobic above). subsequently treated with polysiloxanes. On the other hand, post-application of the polysiloxane RS confers hydrophobic character to the surface of LTP-treated bres, therefore reect hydrophilic fabric surfaces. Advancing producing contact angle values of 112.5 3.28 or 112.6 contact angle (Figure 3) shows that LTP modies the 1.28 on LTP-treated samples for 120 or 300 s, respectively. surface of wool bres turning them from hydrophobic Contact angle values being slightly higher in LTP-treated (102.8 1.68 in UT bres) to hydrophilic (50.7 2.78 after samples than in UT samples could indicate a greater 120 s of LTP and similar values after 300 s). By means of the deposition of the product on the bre due to the increase of contact angle measurements carried out on single bres, adhesion promoted by LTP or that RS polysiloxane the inuence of the capillary forces present in the wettability measurement on fabrics by drop test is molecules adopt a specic orientation on the plasmatreated wool surface. avoided. The increase in wettability is due to the generation of new hydrophilic groups ( COH, COO, C O, SO ) on 3 the surface of bres and to the total or partial elimination Shrink-Resistance of the fatty layer by LTP treatment.[21,26] This results in the An important reduction of the area shrinkage of fabrics chemical homogenization of the scale surface which is in treated only with LTP can be observed in Figure 4. According to previous studies, the shrink-resistance effect produced by LTP on wool fabrics is attributed to the various changes promoted in the surface of wool such as the formation of new hydrophilic groups as conrmed by XPS studies,[13,15] total or partial elimination of the fatty acids covalently linked to the epicuticle of wool bres and etching effect.[15,17] All these factors contribute to an increase of wettability and of interbre friction, and hence the bres have greater difculties to move relative to each other. However, it is important to take into account the inuence of the bre-medium interFigure 3. Advancing contact angle of UT and LTP-treated keratin bres (for 120 and 300 s) action; UT hydrophobic bres, in the presence of water during washing, and subsequently treated with polysiloxanes.
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Figure 4. Area shrinkage (%) after two washing cycles of wool fabrics UT and LTP treated and subsequently treated with polysiloxanes.

may tend to compact themselves to minimize contact with water, which will lead to bre--bre anchoring and irreversible felting shrinkage. In contrast, after LTP treatment, the bre surface interacts readily with water molecules of an aqueous medium and, therefore, the compacting process of bres is reduced and so is the natural tendency of wool for felting shrinkage. SEM pictures [Figure 6(b) and 6(c)] reveal that the LTP conditions used neither eliminate nor reduce the scale height (which was also conrmed by AFM analysis[27]), so the main effect responsible for the shrinkage reduction seems to be related with the hydrophilic nature of the outermost part of the bre surface after LTP.

This is in accordance with the percentage area shrinkage results shown in Figure 4, and advancing contact angle results (Figure 3). Fabrics with lower shrinkage correspond to bres exhibiting low advancing contact angle values. For instance, UT fabrics with RI and RA-modied polysiloxanes are hydrophobic (uadv 99.3 4.78 and 104.6 1.48, respectively) and show area shrinkage values similar to UT fabric (70%). Meanwhile, LTP-treated fabrics with RI and RA polysiloxanes exhibit hydrophilic properties (advancing contact angles below 908) and area shrinkage values below 40%. Conversely, UT and LTPtreated fabrics, after the application of RS are highly hydrophobic, showing area shrinkage values even higher than UT wool (Figure 4). Such results suggest a correlation between hydrophilicity/hydrophobicity of the wool bre surface and the shrink-resistance properties of the fabrics. Indeed, if we take into account the results of Kan et al.[28] on D (density of felted balls), they recorded a reduction in felting of 70% with LTP and 43% with LTP Basolan MW (a cationic polysiloxane) with respect to UT wool. Our results of fabric felting shrinkage show a reduction of 82% with LTP and of 56% with LTP RI with respect to UT fabrics. Both results are comparable, which indicates that felting shrinkage variations obtained through the application of LTP and a cationic polysiloxane are comparable although the chemical formula and the product formulation might not be the same. This conrms the great relevance of hydrophilicity of the wool bre surface on the shrink-resistance of wool fabrics. Although shrinkage results obtained by the combined process of plasma RI or plasma RA are above the values by which they could be considered as machine washable, they have allowed achieving a 56 and 63% reduction of the area shrinkage in the second washing cycle with respect to UT wool fabrics.

Figure 5. Sensorial evaluation of the softness of fabrics submitted to different treatments.

Figure 6. Microphotographs of (a) UT, (b) LTP treated for 120 s, (c) LTP treated for 300 s wool bres.
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Figure 7. SEM pictures of wool (a) UT RI, (b) LTP 120 s RI, (c) LTP 300 s RI.

Softness Evaluation Softness evaluation by nonexpert panelists, shown in Figure 5 is the result of a consensus of 50% of the panelists who conrmed that fabrics treated with only LTP were found to be harsh and slightly unpleasant. In contrast, application of the modied polysiloxanes on UT and LTP-treated wool fabrics produced high acceptance of the fabrics, which were considered to have an agreeable handle. A previous work[29] found that the increased friction coefcients with plasma pretreatment are again reduced with the subsequent silicone application, which they explained by the surface coating effect of the silicone polymer, which acts as a lubricant between the bres.

Scanning Electron Microscopy From the SEM micrographs [Figure 6(a)] of the UT merino wool fabric, the diameter of the bres was measured to be around %1822 mm.[30] The cuticular cells (scales) of the surface can be clearly distinguished, the only roughness of the wool bre coming from the overlapping of the cuticle cells. Wool bres treated by LTP for 120 and 300 s [Figure 6(b) and 6(c)], apparently do not show morphological differences with respect to UT ones. However, an enlargement of Figure 6(c) reveals that, from 300 s of LTP treatment, etching effects due to the reactive species of plasma start to create microcraters on the wool surface.

Kim and Kang[20] found that the plasma pre-treatment of the cuticle surface of the wool bres increased the reactivity of the wool fabric towards silicone polymers, improved the dimensional stability, wrinkle resistance and performance properties of the wool. Figure 7 shows SEM micrographs of UT and 120 and 300 s water vapour LTP-treated fabrics with RI polysiloxane. While LTP-treated bres show a uniform adsorption of RI on the surface [Figure 7(b) and 7(c)], UT bres [Figure 7(a)] show irregular deposition of the polysiloxane RI, preferably adsorbed in the scale edges. That could be explained by taking into account that the cationic groups of the RI polysiloxane may preferably interact with the hydrophilic frontal area of the scales. That is in accordance with Kamaths research,[25] which suggests that the frontal of the scales is more hydrophilic than the dorsal as it is more exposed to mechanical damage, leaving bare part of the hydrophilic material under the epicuticle. However, after the hydrophilicity increase and homogenization of the bre surface through LTP, RI can interact with both the frontal and dorsal areas of the scales leading to a uniform deposition. Deposition of the polysiloxane RA (nonionic) is much more uniform in UT wool [Figure 8(a)] than RI, which can be explained by the fact that its nonionic character may impair the deposition on the hydrophilic scale edges. Figure 8(b) and 8(c) of LTP RA-treated wool also show a very uniform deposition. When RS is applied on UT wool [Figure 9(a)], an important deposition is observed on the surface as well as the presence of artefacts which we attribute to the

Figure 8. SEM pictures of wool (a) UT RA, (b) LTP treated 120 s RA, (c) LTP treated 300 s RA.
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Figure 9. SEM pictures of wool (a) UT RS, (b) LTP treated 120 s RS, and (c) LTP treated 300 s RS.

possible elimination of material from the softener layer due to tension effects and its low adhesion towards the scale surface. Nevertheless, the RS polysiloxane deposition on the LTP-treated fabrics is more even, which could be attributed to the better adhesion bre-polysiloxane. Whether deposition of the polysiloxanes on the surface is even or not, it does not seem to have any inuence on the shrink-resistance values, which seem to be much more dependent on the hydrophilic characteristics of the surface of bres. Figure 10 schematically shows a possible interpretation of the observed phenomena. After LTP, the dorsal of scales becomes hydrophilic and chemically homogeneous. This can promote the formation of ionic or covalent bonds between the functional groups of the polysiloxanes (RI, RS) and the anionic groups (COO, SO ) formed by the LTP 3 treatment throughout the wool bre surface. Therefore, the cationic group of RI could interact with the LTP-treated surface, leaving some quaternary ammonium groups and primary amine side groups oriented towards the outer part of the surface. That would justify the hydrophilic character observed in Figure 2 and 3. For the same reason, the amide side group of RA could interact with the hydrophilic groups created on the wool surface and leaving the hydrocarbon chains oriented towards the outside. In that case, a hydrophobic interaction between RA molecules forming a bilayer could take place, leaving the amide groups exposed to the outer surface, which would be in accordance with the contact angle results of Figure 3. Lastly, the uniform deposition of RS on LTP-treated fabrics [Figure 9(b) and 9(c)]

could be explained by the bond formation between the bre surface and the amine groups of the polysiloxane which would leave the hydrophobic chains of the molecule oriented towards the outer part of the molecule justifying its hydrophobicity (Figure 2 and 3). Similar results have recently been found by other authors[31] with a polysiloxane softener of a very similar chemical structure by using the AFM technique.

Conclusion
Low temperature plasma, generated from water vapour modies the wool surface, rendering it highly hydrophilic and increasing its shrink-resistance. The advancing contact angle determination on single bres evidenced that postapplication of the functional polysiloxane softeners on LTP-treated fabrics may increase hydrophobicity of the surface depending on the molecular structure of the softener applied. Combined application of LTP and RI (cationic polysiloxane with two quaternised amine groups and an amine side chain) or RA (nonionic polysiloxane with an amide end group) has allowed to obtain fabrics with an improved softness with respect to UT fabrics and a reduction of the area shrinkage of 56 and 63% respectively. Meanwhile, the application of RS (nonionic polysiloxane with an amine end group) on LTP-treated fabrics renders the surface highly hydrophobic and produces very high shrinkage values, as though dealing with UT wool fabrics. Surface modication of wool by LTP improves polysiloxane

Figure 10. Scheme of the proposed deposition of the polysiloxanes (a) RI, (b) RA, and (c) RS on LTP-treated wool bre surface.
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deposition in all cases. The handle of LTP-treated wool fabrics is largely improved with the application of any of the polysiloxane softeners studied. The results obtained have evidenced a relationship between increased surface hydrophilicity and reduced area shrinkage of the fabrics.

Acknowledgements: The authors are grateful to the MCYT (MAT2002-02613 project) for the nancial support, to FEMAN associated unit for the plasma treatments, to the quality group 2001SGR-00357, and would also like to acknowledge Mr. Oscar Batlle from Rudolf Iberica for providing the products, Mrs. Mun oz and Mrs. Dolcet for their help with the experimental work and Mrs. Escusa for her collaboration in SEM. Received: January 22, 2007; Revised: April 16, 2007; Accepted: May 4, 2007; DOI: 10.1002/mame.200700023 Keywords: chain; cold plasma; polysiloxane softeners; shrinkresistance; surface treatment; wool

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