Effects of leveling agent on the uptake of reactive dyes by untreated and plasma-treated wool

Atmospheric-pressure plasma treatment of wool fabric produced a significantly higher level of adsorbed fiber-reactive dye when applied at 50 °C (pH 3.0–6.0) in the absence of any organic leveling agent. In addition, color yields indicated that dye was more uniformly adsorbed by the plasma-treated fabric compared with the untreated material. When untreated fabric was dyed in the presence of a leveling agent (Albegal B), the extent and levelness of dye sorption were enhanced. These enhancements were, however, relatively small on the plasma-treated wool compared with those on untreated wool. A ‘surface’ mechanism, similar to that proposed when plasma-treated wool is dyed in the absence of leveling agent, can explain the leveling ability of Albegal B under adsorption conditions. Increasing the dyebath temperature to 90 °C resulted in dye penetration of the fibers. Under these conditions, any enhancements of dye uptake produced by the plasma treatment, as well as the use of Albegal B, were relatively small, in contrast to the behavior at 50 °C. Improvements in the uniformity of dye sorption observed at 50 °C were, however, maintained at the higher temperature. It is concluded that the inability of reactive dyes to migrate (and so promote leveling and uniformity) once they have reacted with the fiber, means that differences in the uniformity of dye sorbed at 50 °C are still apparent at equilibrium.

Ageing effect of plasma-treated wool

Atmospheric pressure plasma treatment of wool fabric, with a relatively short exposure time, effectively removed the covalently bonded lipid layer from the wool surface. The plasma-treated fabric showed increased wettability and the fibres showed greater roughness. X-ray photoelectron spectroscopy (XPS) analysis showed a much more hydrophilic surface with significant increases in oxygen and nitrogen concentrations and a decrease in carbon concentration. Adhesion, as measured by scanning probe microscopy (SPM) force volume analysis, also increased, consistent with the more hydrophilic surface leading to a greater meniscus force on the SPM probe. The ageing of fibres from the plasma-treated fabric was assessed over a period of 28 days. While no physical changes were observed, the chemical nature of the surface changed significantly. XPS showed a decrease in the hydrophilic nature of the surface with time, consistent with the measured decrease in wettability. This change is proposed to be due to the reorientation of proteolipid chains. SPM adhesion studies also showed the surface to be changing with time. After ageing for 28 days, the plasma-treated surface was relatively stable and still dramatically different from the untreated fibre, suggesting that the oxidation of the surface and modification or removal of the lipid layer were permanent.

Thermal and mechanical properties of ultrasonically treated wool

Wool fabrics, ultrasonically treated in various chemical conditions and for different time durations, were analysed for thermal properties by thermo-gravimetric analysis and differential scanning calorimeter, in comparison with the untreated fabric. Fabric mechanical properties, such as bending and tensile performance, and changes in fibre morphology were also evaluated before and after ultrasonic treatment.It is found that wool treated with ultrasonics at the appropriate time, has less mass loss and a higher thermal degradation temperature than that without ultrasonic treatment or with prolonged ultrasonic treatment. Resistance to thermal degradation is reduced when wool is ultrasonically treated in the presence of alkali. Differential scanning calorimeter analysis shows that while ultrasonic treatment has little effect on fibre crystallinity, an appropriate treatment can provide wool with increased water absorption. Ultrasonic treatment stiffens wool fabric to some extent when the treatment time is prolonged. The addition of detergent alone to the ultrasonic bath has little effect on fabric tensile behaviour, whereas a treatment with both detergent and alkali produces severe fibre damage and significant loss of fabric tensile strength.

Vibrational spectroscopic studies of wool

Fourier transfonn (FT) Raman, Raman microspectroscopy and Fourier transform infrared (FTIR) spectroscopy have been used for the structural analysis and characterisation of untreated and chemically treated wool fibres. For FT -Raman spectroscopy novel methods of sample presentation have been developed and optimised for the analysis of wool. No significant fluorescence was observed and the spectra could be obtained routinely. The stability of wool keratin to the laser source was investigated and the visual and spectroscopic signs of sample damage were established. Wool keratin was found to be extremely robust with no signs of sample degradation observed for laser powers of up to 600 m W and for exposure times of up to seven and half hours. Due to improvements in band resolution and signal-to-noise ratio, several previously unobserved spectral features have become apparent. The assignment of the Raman active vibrational modes of wool have been reviewed and updated to include these features. The infrared spectroscopic techniques of attenuated total reflectance (ATR) and photoacoustic (P A) have been used to examine shrinkproofed and mothproofed wool samples. Shrinkproofing is an oxidative chemical treatment used to selectively modifY the surface of a wool fibre. Mothproofing is a chemical treatment applied to wool for the prevention of insect attack. The ability of PAS and A TR to vary the penetration depth by varying certain instrumental parameters was used to obtain spectra of the near surface regions of these chemically treated samples. These spectra were compared with those taken with a greater penetration depth, which therefore represent more of the bulk wool sample. The PA and ATR spectra demonstrated that oxidation was restricted to the near-surface layer of wool. Extensive curve fitting of ATR spectra of untreated wool indicated that cuticle was composed of a mixed protein conformation, but was predominately that of an a.-helix. The cortex was proposed to be a mixture of both a.helical and ~-pleated sheet protein conformations. These findings were supported by PAS depth profiling results. Raman microspectroscopy was used in an extensive investigation of the molecular structure of the wool fibre. This included determining the orientation of certain functional groups within the wool fibre and the symmetry of particular vibrations. The orientation ofbonds within the wool fibre was investigated by orientating the wool fibre axis parallel and then perpendicular to the plane of polarisation of the electric vector of the incident radiation. It was experimentally determined that the majority of C=O and N-H bonds of the peptide bond of wool lie parallel to the fibre axis. Additionally, a number of the important vibrations associated with the a-helix were also found to lie parallel to the fibre axis. Further investigation into the molecular structure of wool involved determining what effect stretching the wool fibre had on bond orientation. Raman spectra of stretched and unstretched wool fibres indicated that extension altered the orientation ofthe aromatic rings, the CH2 and CH3 groups of the amino acids. Curve fitting results revealed that extension resulted in significant destruction of the a-helix structure a substantial increase in the P-pleated sheet structure. Finally, depolarisation ratios were calculated for Raman spectra. The vibrations associated with the aromatic rings of amino acids had very low ratios which indicated that the vibrations were highly symmetrical.

Effects of atmospheric pressure plasma on dye uptake by the surface of wool

A woven pure wool fabric has been exposed to atmospheric pressure plasma for 30 seconds using a pilot-scale. commercial machine. X-ray photoelectron spectral data revealed large increases in oxygen and nitrogen. and a large reduction in carbon. on the surfaces of the plasma-treated fibres. A CIN ratio of 3.55 for plasma-treated wool was consistent with removal of the covalently-bound fatty acids from the surface of the cuticle cells. resulting in exposure of the proteinaceous epicuticle. Dye staining experiments revealed that the back of the fabric had received the same, uniform level of treatment as the face, despite the fact that only the face had been directly exposed to the plasma. Dyes (1 % oww) were applied to fabric at 50°C (liquor ratio =40: 1) and pH values from 3 to 6. The relatively low temperature of 50°C was selected in order to accentuate the effects of plasma on the rate of dye uptake. Under these conditions, dye was adsOibed onto the fibre surfaces, with very little penetration into the fibres. Effects of the plasma treatment on the rate of dyes adsorption were dyespecific. No significant effects of plasma on the rate of dye uptake were observed with relatively hydrophobic dyes, but hydrophilic dyes were adsorbed more rapidly by the plasmatreated fabric. It would appear that for more hydrophobic dyes, hydrophobic effects are more important for the adsorption of dyes by the plasma-treated fibres, even though these fibres were quite hydrophilic. On the other hand. it is concluded that for more hydrophilic dyes, electrostatic effects are more important for adsorption by the plasma-treated fibre.

Effects of plasma treatment of wool on the uptake of sulfonated dyes with different hydrophobic properties

A wool fabric has been subjected to an atmospheric-pressure treatment with a helium plasma for 30 seconds. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry confirmed removal of the covalently-bound fatty acid layer (F-layer) from the surface of the wool fibers, resulting in exposure of the underlying, hydrophilic protein material. Dye uptake experiments were carried out at 50 ºC to evaluate the effects of plasma on the rate of dye uptake by the fiber surface, as well as give an indication of the adsorption characteristics in the early stages of a typical dyeing cycle. The dyes used were typical, sulfonated wool dyes with a range of hydrophobic characteristics, as determined by their partitioning behavior between water and n-butanol. No significant effects of plasma on the rate of dye adsorption were observed with relatively hydrophobic dyes. In contrast, the relatively hydrophilic dyes were adsorbed more rapidly (and uniformly) by the plasma-treated fabric. It was concluded that adsorption of hydrophobic dyes on plasma-treated wool was influenced by hydrophobic interactions, whereas electrostatic effects predominated for dyes of more hydrophilic character. On heating the dyebath to 90 ºC in order to achieve fiber penetration, no significant effect of the plasma treatment on the extent of uptake or levelness of a relatively hydrophilic dye was observed as equilibrium conditions were approached.

An investigation into the ion-exchange properties of chemically modified wool for use in water treatment and chromatography

This study was undertaken to investigate the suitability of natural and chemically treated wool fibres for use in water treatment and in the separation of constituents for monitoring contaminants in water.

Experimental work was carried out to determine the ability of natural and treated wool fibres to remove these constituents from water,

This study provided information on the characteristics of the wool fibre as a medium in water treatment.

Effect of atmospheric plasma treatment on pad-dyeing of natural dyes on wool

Plasma treatment is an emerging surface modification technique that alters dye uptake of wool without using chemicals or water for pre-treatment. Padding is an established continuous dyeing technique known for its efficient use of water, time and energy. This study combined these two techniques for colouration of wool fabric using two natural dyes derived from the Acacia plant family. The investigation focused on the effects of plasma treatment and obtaining unique patterning effects. Helium (100%) and a mixture of helium and nitrogen (95%/5%) were used as the plasma gases under atmospheric conditions. Plasma treated wool fabric was padded with the above natural dyes. Copper sulphate and ferrous sulphate were applied on the dyed fabric as mordant yielding neutral shades of beige and grey respectively. Up to a 30% enhancement of dye adsorption on plasma treated wool substrate was observed as compared to untreated sample for both gases used. This higher adsorption indicates the hydrophilic character of the natural dyes used. Key performance parameters such as fastness to washing, rubbing and light were tested and found to be satisfactory. A single process tone-on-tone pattern was achieved by controlling the plasma exposure of treated area. This study concluded that a merger of natural dyes with modern plasma treatment and padding techniques for wool colouration was feasible.

Reducing the pilling propensity of wool knits with a three-step plasma treatment

A three-step plasma treatment, including surface activation with argon, surface functionalization with oxygen and then thin film deposition using a pulsed plasma polymerization of hexamethyldisiloxane (HMDSO), was used in low-pressure plasma to improve the pilling resistance of knitted wool fabric. The pilling propensity of the treated samples was investigated and compared with the pilling propensity of untreated, argon activated and oxygen functionized samples and argon and oxygen plasma-treated samples that were afterwards subject to continuous wave plasma polymerization of HMDSO. With the three-step treatment, a pilling grade of four was achieved for the treated wool fabric, while that of untreated and other plasma-treated was two and three, respectively. For the three-step plasma-treated sample, a uniform HMDSO polymer coating of 300 nm thickness was obtained; X-ray photoelectron spectroscopy (XPS) showed the presence of the silicone element, and Fourier transform infrared (FTIR) spectroscopy confirmed the chemical structure of the coating. No apparent differences were found in the whiteness index between the treated and untreated wool knits, but there was deterioration in the bursting strength and handle of the plasma-treated wool samples.

Reducing photoyellowing of wool fabrics with silica coated ZnO nanoparticles

Though ZnO nanoparticles (NPs) are an excellent UV absorber, their photocatalytic activity greatly limits the application areas of these particles. Under sunlight exposure, ZnO NPs used as a UV absorber can accelerate the wool yellowing process by generating free radicals. To reduce this photocatalysis effect, a physical barrier has been fabricated by coating the ZnO NPs with a silica layer (ZnO@SiO2), hence providing good UV-shielding with low photocatalytic activity. The structure and optical properties of ZnO and ZnO@SiO2 NPs were characterized by transmission electron microscope (TEM) and UV–Vis spectrum. The photocatalytic activity of ZnO and ZnO@SiO2 NPs was evaluated by photo-degradation of Rhodamine B. The ZnO and ZnO@SiO2 NPs were applied to knitted wool fabrics using the dip coating method. The treated wool fabrics were characterized by a scanning electron microscope (SEM) and the photoyellowing level of treated fabrics after exposure under simulated sunlight was evaluated by a Datacolor Spectraflash spectrophotometer. The ZnO@SiO2 NPs demonstrated excellent protection of wool against photoyellowing.

Transglutaminase mediated grafting of silk proteins onto wool fabrics leading to improved physical and mechanical properties

Transglutaminases have the ability to incorporate primary amines and to graft peptides (containing glutamine or lysine residues) into proteins. These properties enable transglutaminases to be used in the grafting of a range of compounds including peptides and/or proteins onto wool fibres, altering their functionality. In this paper we investigated the transglutaminase mediated grafting of silk proteins into wool and its effect on wool properties. A commercial hydrolysed silk preparation was compared with silk sericin. The silk sericin protein was labelled with a fluorescent probe which was used to demonstrate the efficiency of the TGase grafting of such proteins into wool fibres. The TGase mediated grafting of these proteins led to a significant effect on the properties of wool yarn and fabric, resulting in increased bursting strength, as well as reduced levels of felting shrinkage and improved fabric softness. Also observed was an accumulation of deposits on the surface of the treated wool fibres when monitored by SEM and alterations in the thermal behaviour of the modified fibres, in particular for mTGase/sericin treated fibres which, with the confocal studies, corroborate the physical changes observed on the treated wool fabric. © 2006 Elsevier Inc. All rights reserved.

Electrical conductivity of single walled and multiwalled carbon nanotube containing wool fibers

The main purpose of this study was producing conductive wool fabric applying carbon nanotubes. Raw and oxidized wool samples were treated with carbon nanotubes in the impregnating bath in the presence of citric acid as a crosslinking agent and sodium hypophosphite as a catalyst while sonicating them in the ultrasonic bath. Electrical resistance, washing durability, and color variation of treated samples were assessed. Through SEM images, the surface morphology of treated samples was studied confirming the surface coating through carbon nanotubes. According to the results, the electrical resistance of treated wool with carbon nanotubes reduced substantially. However, the single-walled carbon nanotubes are more useful to increase the conductivity. In addition, the wool color changed into gray after the treatment.

Photo induced silver on nano titanium dioxide as an enhanced antimicrobial agent for wool

In this study an effective nanocomposite antimicrobial agent for wool fabric was introduced. The silver loaded nano TiO(2) as a nanocomposite was prepared through UV irradiation in an ultrasonic bath. The nanocomposite was stabilized on the wool fabric surface by using citric acid as a friendly cross-linking agent. The treated wool fabrics indicated an antimicrobial activity against both Staphylococcus aureus and Escherichia coli bacteria. Increasing the concentration of Ag/TiO(2) nanocomposite led to an improvement in antibacterial activities of the treated fabrics. Also increasing the amount of citric acid improved the adsorption of Ag/TiO(2) on the wool fabric surface leading to enhance antibacterial activity. The EDS spectrum, SEM images, and XRD patterns was studied to confirm the presence of existence of nanocomposite on the fabric surface. The role of both cross-linking agent and nanocomposite concentrations on the results was investigated using response surface methodology (RSM).

Diameter variations of irregular fibers under different tensions

The cross-section area of animal fibers varies along the fiber length, and this geometrical irregularity has a major impact on the mechanical properties of those fibers. In practice fibers are often subjected to tensile stresses during processing and application, which may change fiber cross-section area. It is thus necessary to examine geometrical irregularity of fibers under tension. In this study, scoured animal fibers were subjected to different tensile loading using a Single Fiber Analyzer (SIFAN) instrument. The 3D images of the fiber specimens were first constructed, and then along-fiber diameter irregularities of the specimens were analyzed for different levels of tensile loading. The changes in effective fineness of the fiber specimens were also discussed. The results indicate that for the wool fibers examined, there is considerable discrepancy in the fiber diameter results obtained from the commonly used single scan along fiber length and that from multiple scans at different rotational angles, and that the diameter variation along fiber length increases as fiber tension increases. The results also show that when diameter reduction treatments are applied to wool by stretching, the reduced average fiber diameter is associated with an increase in both within-fiber and between-fiber diameter variations. So in terms of effective fineness, the change is much smaller than the difference between the average diameters of the parent and treated wool. These results have significant implications for improving the accuracy of fiber diameter measurement and evaluation.