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2497 2006 Beltwide Cotton Conferences, San Antonio, Texas - January 3 - 6, 2006

APPLICATIONS AND FUTURE OF NANOTECHNOLOGY IN TEXTILES Kumar Vikram Singh Louisiana State University Baton Rouge, LA Paul S. Sawhney and Nozar D. Sachinvala SRRC, ARS, USDA New Orleans, LA Guoqiang Li, and Su-Seng Pang Louisiana State University Baton Rouge, LA Brian Condon Southern Regional Research Center New Orleans, LA Radhakrishna Parachuru Georgia Institute of Technology Atlanta, GA

Abstract It is well known that cotton fabrics provide desirable properties such as absorbency, breathability and softness. But, their applications often are limited due to their inferior strength, durability, crease resistance, dirt resistance, and flame resistance. On the other hand, fabrics made with synthetic fibers generally are very strong, crease resistant and dirt resistant, but they lack the comfort properties of cotton fabrics. With recent advances in nanotechnology, it is possible to develop next-generation cotton-based fabrics that can complement the advantages of cotton and manmade fibers. Such advanced fabrics can be produced either by blending cotton with special man-made nano-fibers or by treating the yarns or fabrics with various design/material modifications at nano-scale. In this study, we have attempted to summarize the recent advances made in nano-technology and the latter's applications in cotton textiles, along with some ideas about the future research direction in this area. Introduction Nanotechnology deals with the science and technology at dimensions of roughly 1 to 100 nanometers (1 Billion Nanometers = 1 Meter), although 100 nanometers presently is the practically attainable dimension for textile products and applications. The technology can be used in engineering desired textile attributes, such as fabric softness, durability, and breathability and in developing advanced performance characteristics, namely, water repellency, fire retardancy, antimicrobial resistance, etc., in fibers, yarns and fabrics. Enhancement of textile materials by nanotechnology is expected to become a trillion dollar industry in the next decade, with tremendous technological, economic and ecologic benefits. It was estimated that for the year 2003, the worldwide government funding for the research and development in the area of nanotechnology had increased to $3 billion annually [Paul et. al., 2003], in addition to the millions of dollars invested by private industries. Although, textile industry is a small part of the global research in the emerging areas of nano-technology, the fibers and textiles industries in fact were the first to have successfully implemented these advances and demonstrated the applications of nano technology for consumer usage.

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Figure 1: Nano-technology in Fiber and Textile Manufacturing In this manuscript, we have summarized the recent advances made in nanotechnology and its applications to cotton textiles and fibers. We have classified our review in two main areas of interest: (a) applications of nanotechnology in fibers and yarn production and, (b) applications in fabric finishing (See Fig. 1). It is well known that the fabrics made of natural cotton fibers and those made of man-made synthetic fibers have their own advantages and limitations. For example, the cotton fabrics provide desirable comfort properties such as absorbency, breathability and softness. However, their applications often are limited due to their inferior strength, durability, crease resistance, dirt resistance, and flame resistance. Contrary to that, the fabrics made with synthetic fibers generally are very strong, crease resistant and dirt resistant, but they lack the comfort properties of cotton fabrics. The intention here is to demonstrate that the advancement of nanotechnology brings the possibility of developing next-generation cottonbased fabrics that could complement the advantages of cotton and man-made fibers. Applications of the nanotechnology in textile industries are also summarized in this paper with some novel ideas that can be utilized for the future research in this area. Advances in Nano-Fiber/Yarn Developments The discovery of Carbon Nano Tubes (CNT) by Iijima [1991], has led to the exploration of high strength and superior performance fibers. Recently, high-performance yarns were produced through super-aligned arrays of carbon nanotubes [Jiang et al., 2002]. Such yarns exhibit extraordinary mechanical properties, viz., the Young’s modulus in the TPa range, tensile strength of about 200 GPa, elastic strain up to 5 %, and breaking strain about 20 %. Such synthetic nano fibers that are being produced by electrospinning process can significantly enhance the strength and conductivity of the fabric after suitable heat treatment. Hence, these nano fibers and yarns can also be efficiently used as super capacitors in electronic textile components [Dalton et al., 2002, Schreuder et al., 2002, Dersch, et. al. 2003, Zarkoob, et. al., 2004, and Subbiah, et. al., 2005]. It is also shown that by simultaneous reduction of fiber diameter and increase in twist (1000 times), nano yarns can be spun comprising Multi-Walled Carbon Nano Tube (MWCNT) that consist several (7 to 20 usually) concentric cylinders of Single Walled CNT. Such yarns provide specific mechanical properties (such as strength, toughness, energy damping capability, etc.), which then can be deployed to produce electronic textiles for supporting multi-functionalities, such as capability for actuation, energy storage capacity, radio or microwave absorption, electrostatic discharge protection, textile heating, or wiring for electronic devices [Zhang et. al., 2004]. In a recent patented technology, it is shown that the combination of “nano-fibrils” and strengthening fibers can be used for producing nonwoven fabrics for tissue engineering [Scardino and Balonis, 2001]. By enforcing small

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amount of nano-fibers/particles in polymer matrix several nano-composites are being developed. By using melt spinning process polypropylene/nano-carbon fiber composites are spun that are capable of enhancing the modulus, compressive strength, and dispersion properties of the polymers significantly [Kumar et al., 2002]. Optimal crystallization and orientation of nanofibers yield excellent properties for micro-filtration applications in the medical field [Vijayaraaghavan and Karthik, 2004]. By suspending nano-antimony doped tin oxide particles during the fiber spinning process antistatic polyacrylonitrile fiber has been developed. [Wang et. al., 2004, Stegmaier et. al., 2004]. The desired functionality in the fibers can also be obtained by embossing the surface of synthetic fibers with nano structures [Halbeisen and Schift, 2004]. Moreover, integration of nano-sized antimicrobial particles into textile fibers can lead to the development of superior wound dressings. Advances in Fabric Finishes The recent advancement of fabric finishes is greatly contributed to the advancement in the area of Nano-technology. One of the leading companies to implement the nano-technology is Nano-TexTM. They have developed several fabric treatments such as (a) permanent anti-static treatment; (b) wrinkle free treatment using moisture-wicking technology; (c) stain resistance and oil repellent treatments; and (d) “nanobeads” to carry bioactive or anti-biological agents, drugs, pharmaceuticals, sun blocks, and even textile dyes by developing the novel nano-technologies (NanoCare, Nano-Pel, Nano-Touch and Nano-Press technology) [, Nanofinishing”, 2002, Parachuru and Sawheny, 2005]. These treatments onto textile substrates permanently alter properties of the textiles and are claimed to exhibit superior durability, softness, tear strength, abrasion resistance and capable of providing softness to durable press garments. For finishing purposes, another leading technology is chemical oxidative deposition technology, which deals with the deposition of Conducting Electroactive Polymers (CEP) onto different kinds of fibers and textiles, resulting composite materials with high tensile strength and good thermal stability [Li et. al., 1997]. Furthermore, Surface polymerization of CEP (Graft copolymerization) of polymer fibers has a potential to increase the conductivity almost 10 times by decreasing the electrical resistivity [Anbarasan et. al., 1999, Yin et. al., 1995, and Bhadani et. al. 1996]. Such coated polymeric composite materials can be used in microwave attenuation, EMI shielding, and dissipation of static electric charge. Hence, they can be useful for military applications, e.g., camouflage, stealth technology, etc., [Kuhn, 1995,1997]. \By combining the nano-particles with the organic and inorganic compounds, the surfaces of the fabrics treated with abrasion resistant, water repellent, ultraviolet (UV), electromagnetic and infrared protection finishes can be appreciably modified. Recently, the titanium-dioxide nanoparticles have been utilized for the UV protection [Beringer, 2004 and “The features…”, 2004]. Also by using nano-sized silicon dioxide, improvements in the strength and flame-resistance of textile fabrics can be achieved [De Meyere et al., 2004]. The usage of nanoengineered cross-link agents during finishing process enhances the wrinkle resistance of cotton fabrics [Yuen et. al., 2004]. The newly developed micro encapsulation technique is being used in textile industry for flame or fire retardant (FR) agents. Microcapsules containing silver nano-particles (Silver Cap) are also being investigated for providing anti-microbial effects [Erkan et al., 2004]. Applications in Textiles Due to the advancement of Nano-technology in the manufacturing of fibers/yarns as well as in the development of fabric finishes, the applications and scope of nano-technology in the area of textiles are widespread.

2500 2006 Beltwide Cotton Conferences, San Antonio, Texas - January 3 - 6, 2006

Figure 2: Applications of Nano-technology in Textile Fabrics As discussed before, Nano-TexTM has already developed a process for fabric finishes to achieve wrinkle-resistant, stain-resistant, anti-static and sun-block or UV protection properties and are in the process of developing fabrics with these finishes. Recently, Scholler® has developed technology for dynamic climate control, known as “soft shells”, for clothings and gloves manufacturing that are extremely air-permeable, light, and water & wind resistant. [“Schoeller…”, 2004]. A new jacket has been developed by Bugatti with a Nanosphere finish, which has the moisture management features []. W.L.Gore's Airvantage system has claimed to manufacture the first personal thermal climate management system for clothing in the world. Gore-tex® and Windstopper® membrane systems have been developed for permanently airtight and breathable chambers in the clothing [“Adding…”, 2004]. Italy's Grado Zero Espace has developed a special suit based on a membrane employing shape memory polymers (SMP), which is capable of sensing and monitoring changes in the surrounding environment and even controlling the environment []. Germany's Franz-Ziener has introduced ski jackets for developing grime-resistant, windproof, waterproof, and breathable fabric [Lennox, 2003]. Otsuka Kagaku has developed new electro conductive fibers to be used for the protection from radiation emitted by electronics. For the purpose of de-odorizing, Traptek is developed odor-free clothing using activated carbon; J R Nanotech has developed socks containing nanoparticles of silver; Fuji Spinning's have developed "V-Up" functionalized fibers for de-odorising the undergraments; and Mitsubishi and Solutia have developed an

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antimicrobial and deodorant fiber made from seashells. Asahi Kasei has developed a stretchable raschel knitted fabric with elastomeric yarns to avoid yellowing in foundation garments. Moreover, Nano-filtration membranes are being used successfully for the treatment of dye effluents. These grafted membranes are capable of removing dyes so that the processed water can be recycled and reused [Van der Bruggen, 1999, Bowen, 1998, and Akbari et. al., 2002]. Strong graphite nanofibers have been developed, which can support large loads and high pressure at room temperature [Subramanian et. al., 2004]. A research group in Belgium is exploring the possibility of developing novel yarns by melt extruding a range of nano-additives [Everaert, 2003]. Recently, investigators at USDA have developed a technology by which the nanocomposites can be developed by using variety of types/sources of cellulose, such as grass, kenaf, cotton fiber, cotton plant material, etc with clays, which is used as the nanofiller material [White and Delhom, 2005]. Such composites improve the thermal stability of the cellulose and it could lead to the development of a flame retardant end-products such as nonwovens, papers, filament fibers, coatings, etc. Conclusions and Future Directions There is a significant potential for profitable applications of Nano-technology in cotton and other textiles. Several applications of Nano-technology can be extended to attain the performance enhancement of textile manufacturing machines & processes. In future, interdisciplinary research collaborations will lead to significant advancements in the desirable attributes of cotton and cotton blend textile applications. The textile industry has the biggest customer base in the world. Therefore, advances in the customer-oriented products should be the focus for the future nanotechnology applications. The future research should be targeted on developing improved dirt, crease and shrink resistance properties in fabrics, temperature adaptable clothing and odor-less undergarments. We envision that by combining the optical fibers, micro mirrors, functional coatings and electronic textiles customized fabrics can be developed which can change its color as per the desire of consumer’s taste. Several advances can also be made towards the development of strong fibers and fabrics for biomedical and military applications. Acknowledgment This study is supported by the specific cooperative research grant by the Southern Regional Research Center/Agriculture Research Service of United States Department of Agriculture (SRRC/ARS/USDA); towards the ongoing research collaboration between Louisiana State University and the Cotton Structure & Quality (CSQ) and the Cotton Chemistry and Utilization (CCU) Units of the SRRC/ARS/USDA. References “Adding function”, Textile Month, (3), 12-18, 2004. “Nanofinishing”, Advances in Textiles Technology, NOV, 4-5, 2002. “Schoeller Textil, Sevelen: High-tech from the land of Heidi”, Textile Network, 2(11): 48-49, 2004. “Schoeller: New concepts for sports' clothing”, TUT Textiles a Usages Techniques, (51), 42-5, 2004. “The features of nano fabric”, ATA Journal, 15(5), 40, 2004. Akbari A., Desclaux S., Remigy J. C., Aptel P., “Treatment of textile dye effluents using a new photografted nanofiltration membrane”, Desalination, 149(1-3): 101-107, 2002. Anbarasan R., Vasudevan T., Kalaignan G. P., and Gopalan A., “Chemical grafting of aniline and o-toluidine onto poly(ethylene terephthalate) fiber”, Journal of Applied Polymer Science, 73, 121-8, 1999. Beringer J. and Hofer D., “Nanotechnology and its application”, Melliand-International, 10(4), pp. 295-296, 2004. Bhadani S. N., Sen Gupta S. K., Sahu G. C., and Kumari M., “Electrochemical formation of some conducting fibers”, Journal of Applied Polymer Science, 61, 207-12, 1996.

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