- Open Access
Union dyeing of cotton/nylon blended fabric by plasma-nano chitosan treatment
© Kaliyamoorthi and Thangavelu. 2015
- Received: 18 April 2015
- Accepted: 9 June 2015
- Published: 27 June 2015
Current union dyeing processes rely on one or two dye baths with one or two dyes for cotton/nylon blend fabrics. For 50:50 cotton/nylon fabrics, cotton is dyed first under alkaline condition with reactive dyes and then the nylon is dyed with acid dyes under acidic condition. Atmospheric plasma- nano Chitosan treatment as an environmentally friendly method was employed to modify surface properties of cotton/nylon blend fabrics to develop union dyeing with acid dyes. Cellulose fibers when immersed in water produce a negative electro-kinetic potential. The negative charge on the fiber repels the anionic dye ions and consequently the exhaustion of the dye bath is limited. When the fabric is treated with chitosan, the primary hydroxyl groups of cellulose is partially modified into amide groups, which intern leads the cellulose to act like as polyamide fiber. Experimental work was carried out on finding the possibility of one bath dyeing of plasma- chitosan pretreated cotton/nylon fabric with acid dyes. Plasma treated cotton/nylon surface characteristics were evaluated using FTIR. The surface activation using air plasma introduces different functional groups in cotton/nylon blend fabric. The effect of plasma-nano chitosan pretreatment on dye ability, fastness, and few physicochemical properties has been investigated, and results are presented. The cotton/nylon sample treated with 0.3% of chitosan nanoparticles had higher K/S values, washing, and crocking fastness. New method of union dyeing showed good fastness properties and offers the option of eco-friendly.
- Acid dyes
- Colour strength
- Amino groups
Dyeing of fabric blends such as Cotton/Nylon (C/N) is presently dyed by two-bath or one-bath two-step dyeing. Good solidity of hue and depth is more critical in 50:50 blends and in union fabrics, such as nylon warp stretch fabrics, containing cotton or nylon/cotton wefts for swim wear and narrow fabrics, crimped nylon warp/viscose filament dress wear, or cotton warp/nylon weft constructions for uniforms, rain wear or work wear. Cotton/nylon is also used in socks. Nylon being a polyamide contains many amide groups in its structure. It also contains free amine groups at the ends of its polymeric chains, although the number of these free amine groups is less than the number of carboxylic groups, and the fiber possesses a negative charge unless in the appropriate pH region (Haji et al. 2014). These amine groups provide excellent electrostatic and hydrogen bonding sites and are the main factors contributing to the substantively of the dye molecules. Acid dyes have very little affinity for cotton, but cationic cotton can be dyed readily with acid dyes. The ammonium groups act as dye sites (Run-ling 2010).
Also, a variety of cationic agents with amino, ammonium, sulfonium, phosphonium and other groups has been employed to modify cellulose fabrics (Varma and Kulkarni 2002). However, some disadvantages, such as high cost, inadequate reactivity, fabric yellowing, excessive fabric tendering and toxicity, were observed with these substances, preventing their industrial application. Chitosan has the same backbone with cellulose except for its acetamide group instead of a hydroxyl group. Chitosan is naturally presenting ß-1, 4-linked linear polysaccharides, and most of its glucopyranose residues are 2, 2-deoxy-b-d-glucopyranos (Yang and Wang 2010). Chitosan can easily adsorb anionic dyes, such as direct, acid and reactive dyes, by electrostatic attraction due to its cationic nature in an acidic condition. The dye enhancement activity of Chitosan nanoparticles was seldom reported. Unique characters of nanoparticles for their small size and quantum size effect supposedly promised Chitosan nanoparticles to exhibit superior dye ability improvement (Rinaudo 2006).
Plasma treatment of textiles has been investigated as an alternative wet chemical fabric treatment and pre-treatment processes. It would result in desirable surface modification including but not limited to surface etching, activation, cross linking, chain scission, decrystallisation and oxidation (Kang and Sarmadi 2004; Vaananen et al. 2010; Voher et al. 1988). Glow discharge plasma of oxygen, nitrogen, ammonia etc. introduces functional groups like hydroxyl, peroxides, and amines on polymer surface. The technique of plasma treatment is an effective surface modification method to save processing costs and to avoid environmental pollution (Shahidi et al. 2007; Wakida et al. 1988). Atmospheric air plasma was used for oxidation of cotton/nylon fiber in the preparatory process with chitosan nanoparticles to produce aminised cotton/nylon fiber. The facility to attain high wet fastness standards on nylon/cellulosic blends by a one-bath technique at mildly acidic pH is a substantial advantage over the two-bath or two-stage. Meanwhile, this phenomenon gives a possibility to one-bath dyeing for blended fabrics, using aminised cotton and nylon fabric. The main objective of this research is to explore the possibilities of union dyeing of cotton/nylon fabric with acid dyes by introducing amino group in plasma treated cotton/nylon interwoven fabric using chitosan nano-particles.
Ready for dyeing 50/50 Cotton/Nylon blended fabric with the weights of 150 g/m2 was used. Chitosan (Degree of deacetylation 92.5%, MV 1,000 kD) and Acid Red 138 (CI 18073) were used respectively for pretreatment and dyeing. All other reagents are commonly used laboratory reagent grade.
Low temperature plasma treatment
The cotton fabric was treated with glow discharge plasma operated at a pressure of 0.5 mbar (Hydro pneo Vac). The distance between electrodes is 0.2 cm. The samples were placed between electrodes and treated on both sides, each side for 60 s (60 s × 2). In all treatments, a uniform glow discharge plasma system operating under atmospheric condition with air used as a processing gas. Due to interactions between air and activated surface, plasma treated fabric was conditioned for 24 h at standard atmospheric condition accordingly to ISO 139 test method.
Preparation of chitosan nanoparticles
Chitosan was dissolved in a dilute aqueous acetic acid solution of 0.5% (w/v) under microwave irradiation. Aqueous ammonia was then dropped into the chitosan solution to precipitate the chitosan. The obtained gel-like swollen chitosan was washed to neutral with DI water, and was then transferred into a 25 ml volumetric flask. The total volume of liquid was added to 25 ml with DI water. An ultrasound processor with a 6 mm probe was used and it was put into the volumetric flask. Ultrasound treatment was conducted under an ice-water bath. Finally, a milky nano-emulsion chitosan was obtained.
Pretreatment with nano-chitosan
Pre-washed cotton/nylon blend fabrics were soaked for 15 min at in chitosan nano-emulsion at five different concentrations separately 0.01, 0.05, 0.1, 0.3 and 0.5% (w/v). The padding processes were then completed with pick up weight of around 80%. All padded samples were dried at 100°C for 3 min, cured at 150°C for 3 min and finally rinsed with warm water (40°C) for 1 min. Finally fabric rinsed with running cold water and dried again.
Union dyeing with acid dyes
Dyeing of the pretreated blend fabrics were carried out in the laboratory dyeing machine by exhaust method. Fabrics were dyed with 3% (owf) Acid Red 138 in a bath containing 9% of Ammonium acetate, and 3% hydrochloric acid of 10%, with a liquor ratio of 1:20. Firstly, salt and acid were added to water and the dyeing bath was warmed at 60°C, then the samples were immersed in the dyeing bath and the dyeing continued for 15 min, followed by adding dye solution and the dyeing continued for 15 min., then the temperature was raised to 80°C through 20 min, the dyeing was continued at this temperature for 30 min, finally the dyeing was stopped and the dyeing bath was cooled. Dyed samples were thoroughly rinsed with running cold water, then washing with a solution containing 4 g/l ECE detergent and 1 g/l sodium carbonate at 40°C for 15 min. Washing carried out for three more times to ensure good washing fastness and finally rinsing with hot and cold water then air dried. A washed sample was kept in standard atmospheric conditioned for 1 h.
Evaluation of the dyed sample
Fourier transform-infrared analysis
Fourier Transform-infrared measurements carried out using a Nicolet 670 instrument (Thermo scientific). An average of 20 scans was recorded in the attenuated total reflection (ATR-Smart Endurance) mode.
Effect of plasma treatment on fabric properties
Characteristic of FTIR Transmission
Untreated fabric (% T)
Plasma treated (% T)
Morphology of treated sample
K/S Values of dyed sample
Chitosan concentration (%)
Acid Red 138
It has to be pointed out that several past researches showed that, in some cases, when chitosan interacts with non-activated cellulose, adsorption could also be irreversible (Cakara et al. 2009). That irreversible adsorption of chitosan onto weakly acidic cotton fabric is, under present conditions, predominately driven by a non-electrostatic attraction. Myllyte et al. (2009) evidenced a non-electrostatic interaction between chitosan and cellulose. This may be attributed to specific structural interaction between chitosan and cellulose (H-bonds and hydrophobic interactions). Under acidic condition, protonation of the carbonyl group oxygen atom of amide groups generates new cationic sites for dye adsorption. The higher amount of amino groups in plasma activated nano chitosan treated samples increased the probability that a protonated amino group met electrostatic bond with acid dye anions under acidic conditions. Once a dye anion with moderate substantively adsorbs onto an ammonium ion site in the cotton nylon, it is quite resistant to displacement. The dye–fiber interaction must involve forces other than the attraction of oppositely charged ions. Obviously, dipole–dipole and hydrophobic interactions between the dye and nylon molecules play an important role in determining the high substantively and good washing fastness of acid dyes.
Colour fastness properties
Colour fastness properties
Chitosan concentration (%)
Wet crocking fastness
Staining on cotton
Staining on nylon
Acid Red 138
Physical Properties of dyed samples
Chitosan concentration (%)
Tensile strength-warp (N)
Vertical wicking (cm in 5 min)
Air permeability (l/m2/s)
Acid Red 138
This paper described the ability to dye cotton/nylon blend fabric in one step, one dyeing bath with shortened time. It was found that the treatment of cotton/nylon fabrics with plasma-nano chitosan enhanced the dye uptake of cotton/nylon fabrics compared with untreated fabric. The improved dye ability of cotton to acid dye is postulated due to the presence of amine groups available from the chitosan. Based on the depth of shade values, it was found that by increasing chitosan nanoparticles concentration up to 0.3% (w/v), there was significant improvement of color strength. Moreover, colorfastness properties to washing and wet crocking of the treated samples were improved at higher chitosan concentration. Union dyeing of cotton/nylon fabrics with acid dyes using biodegradable modification agent such as chitosan is an environmental friendly approach in textile dyeing industry.
KK and RT conceived and designed the experiments. KK performed the experiments, analyzed the data in consultation with RT. All authors read and approved the final manuscript.
Compliance with ethical guidelines
Competing interests The authors declare that they have no competing interests.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
- Cakara, D., Fras Zemljic, L., Bracic, M., & Stana-Kleinschek, K. (2009). Protonation behavior of cotton fabric with irreversibly adsorbed chitosan: a potentiometric titration study. Carbohydrate Polymers, 78(1), 36–40.View ArticleGoogle Scholar
- Haji, A., Shoushtari, A. M., & Mirafshar, M. (2014). Natural dyeing and antibacterial activity of atmospheric-plasma-treated nylon 6 fabric. Coloration Technology, 130(1), 37–42.View ArticleGoogle Scholar
- Kang, J., & Sarmadi, M. (2004). Plasma treatment of textile- synthetic polymer-based textile. American Association of Textile Chemists and Colorists Review, 4(11), 29–33.Google Scholar
- Myllyte, P., Salmi, J., & Laine, J. (2009). The influence of pH on the adsorption and interaction of chitosan with cellulose. Bio Resources, 4(4), 1674.Google Scholar
- Rinaudo, M. (2006). Chitin and chitosan: properties and applications. Progress in Polymer Science, 31, 603–632.View ArticleGoogle Scholar
- Run-ling, S. (2010). One-bath dyeing of cotton-nylon mixture with reactive and acid dyes. Dyeing and Finishing, 16, 2101–2116.Google Scholar
- Shahidi, S., Ghoranneviss, M., Moazzenchi, B., Rashidi, A., & Dorranianl, D. (2007). Effect of using cold plasma on dyeing properties of polypropylene fabrics. Fibers and Polymers, 8(1), 123–129.View ArticleGoogle Scholar
- Vaananen, R., Heikkila, P., Tuominen, M., Kuusipalo, J., & Harlin, A. (2010). Fast and efficient surface treatment for nonwoven materials by atmospheric pressure plasma. AUTEX Research Journal, 10(1), 8–13.Google Scholar
- Varma, A. J., & Kulkarni, M. P. (2002). Oxidation of cellulose under controlled conditions. Polymer Degradation and Stability, 77, 25–27.View ArticleGoogle Scholar
- Voher, U., Muller, M., & Andoehr, C. (1988). Glow- discharge treatment for the modification of textile. Surface and Coating Technology, 98, 1128–1131.View ArticleGoogle Scholar
- Wakida, T., Cho, S., Choi, S., Tokino, S., & Lee, M. (1988). Effect of low temperature plasma treatment on color of wool and nylon 6 fabrics dyed with natural dyes. Textile Research Journal, 68(1998), 848–853.Google Scholar
- Yang, H. C., & Wang, W. H. (2010). Preparation and application of nano chitosan to finishing treatment with anti-microbial and anti-shrinking properties. Carbohydrate Polymers, 79, 176–179.View ArticleGoogle Scholar