Nanotechnology in Textiles

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Nanotechnology in Textiles
Article in ACS Nano · February 2016

DOI: 10.1021/acsnano.5b08176
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Journal: ACS Nano
Manuscript ID nn-2015-08176n
Manuscript Type: Review
Date Submitted by the Author: 28-Dec-2015
Complete List of Authors: Yetisen, Ali; Harvard Medical School, Massachusetts General Hospital
Qu, Hang; École Polytechnique de Montréal, Engineering Physics
Manbachi, Amir; Harvard Medical School
Butt, Haider; University of Cambridge,
Dokmeci, Mehmet; Brigham and Women's Hospital, Medicine
Hinestroza, Juan; Cornell University, Department of Fiber Science, College
of Human Ecology
Skorobogatiy, Maksim; Ecole polytechnique de Montreal, Department of
Engineering physics
Khademhosseini, Ali; Harvard Medical School, Brigham and Women's
Hospital
Yun, Seok Hyun; Harvard Medical School and Wellman Center for
Photomedicine, Massachusetts General Hospital
ACS Paragon Plus Environment

Page 1 of 86 ACS Nano
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Ali K. Yetisen†,*, Hang Qu,‡ Amir Manbachi §,∥ Haider Butt,⊥ Mehmet R. Dokmeci,§,∥ Juan P.
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15 Hinestroza,# Maksim Skorobogatiy,‡ Ali Khademhosseini,§,∥ and Seok Hyun Yun†,∥,*
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18 †
Harvard Medical School and Wellman Center for Photomedicine, Massachusetts General
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21 Hospital, 65 Landsdowne Street, Cambridge, Massachusetts 02139, USA
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24 Department of Engineering Physics, École Polytechnique de Montréal, Montréal, Québec,
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26 Canada
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29 Biomaterials Innovation Research Center, Division of Biomedical Engineering, Brigham and
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Women’s Hospital, Harvard Medical School, Cambridge, Massachusetts, 02139, USA; Wyss
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34 Institute for Biologically Inspired Engineering, Harvard University, Boston, Massachusetts
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36 02115, USA; Department of Physics, King Abdulaziz University, Jeddah, Saudi Arabia;
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Department of Bioindustrial Technologies, College of Animal Bioscience and Technology,
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41 Konkuk University, Hwayang-dong, Gwangjin-gu, Seoul 143-701, Republic of Korea
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44 ∥ Harvard-MIT Division of Health Sciences and Technology, Massachusetts Institute of
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46 Technology, Cambridge, Massachusetts 02139, USA
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49 ⊥ Nanotechnology Laboratory, School of Engineering Sciences, University of Birmingham,
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52 Birmingham B15 2TT, UK
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55 Department of Fiber Science, College of Human Ecology, Cornell University, Ithaca, New
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57 York, 14850, USA
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ACS Nano Page 2 of 86
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7 KEYWORDS: Nanotechnology; fashion; fabrics; fibers; nanoparticles; carbon nanotubes;
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9 graphene; energy storage; fiber optics; nanotoxicity
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VOCABULARY: Wearables - electronics, fiber optics, or nanomaterials embedded in clothing
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18 and accessories that offer improved mechanical, chemical, optical performance via sensing
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20 external stimuli and/or responding to the environment; Warp - to arrange threads in long lengths
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23 parallel to one another preparatory to further processing; Weft - threads widthways in a fabric as
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25 woven; Finishing - a process performed on yarn or fabric after weaving to improve the look,
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27 performance, or texture of the finished textile; Lotus effect - self-cleaning due to
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30 hydrophobicility induced by nano or microscale hierarchical structured surfaces;
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32 Supercapacitor - an electrochemical cell that allows storing electrical energy temporarily;
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34 Photonic bandgap material - a nano or microscale structure that controls the optical properties
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37 of incident light; Electromagnetic shielding - blocking the electromagnetic field by conductive
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39 or magnetic materials; Bragg fiber - fiber optics incorporating Bragg gratings to filter narrow-
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band light
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7 ABSTRACT
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11 Increasing customer demand for durable and functional apparels manufactured in a sustainable
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14 manner has created an opportunity for nanomaterials to be integrated into textile substrates.
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16 Nanomoieties can induce stain-repellence, wrinkle-freeness, static elimination, and electrical
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18 conductivity to fibers without compromising their comfort and flexibility. Nanomaterials also
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21 offer a wider application potential to create connected garments that can sense and respond to
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23 external stimuli via electrical, color, or physiological signals. This Review discusses electronic
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and photonic nonotechnologies that are integrated with textiles, and shows their applications in
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28 displays, sensing and drug release within the context of performance, durability, and
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30 connectivity. Risk factors including nanotoxicity, nanomaterial release during washing, and
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environmental impact of nanotextiles based on life cycle assessments have been evaluated. This
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35 Review also provides an analysis of nanotechnology consolidation in textiles market to evaluate
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37 global trends and patent coverage, supplemented by case studies of commercial products.
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40 Perceived limitations of nanotechnology in the textile industry and future directions are
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42 identified.
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6 The concept of clothing is undergoing a transformation through innovation in wearable
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8 technologies. Intelligent clothing has increasing presence in prominent fashion weeks in New
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York, London, and Paris. Fashion designers are creating functional materials and integrating
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13 emerging, communication devices, flexible electronics and nanomaterials to garments and
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15 designer clothes. For example, Philips designed a dress (Bubelle) that can tune its colors based
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18 on the wearer’s mood. Black Eyed Peas has also embraced technology at stage, for example, they
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20 used organic light-emitting diode (OLED) based clothing and adaptive materials in their
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22 performances. Fashion and technology company Studio XO has created "digital mermaid bra,"
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25 whose crystals sparkled in time to Azealia Banks' real-time rapping. Recently, TechHaus, the
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27 technical division of Haus of Gaga, has created a series of performance dresses for Lady Gaga's
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ARTPOP campaign (2013). Gaga’s featured artworks included a three-dimensional (3D)-printed
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32 bubble machine dress (Anemone), a Jeff Koons-inspired design called the Parametric Sculpture
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34 Dress, a piece with animated black mirrors (Cipher), and a flying drone-dress (Volantis).
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37 Singers, artists, designers, and fashion icons have directed their interest to new materials that can
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39 stand out in public events and media. The designers that have pioneered the use of technology in
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41 fashion include Ralph Lauren, Diane von Furstenberg, Hussein Chalayan, Zac Posen, Rebecca
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44 Minkoff, Richard Nicoll, and Iris van Herpen.
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46 Cotton is a widely used fiber type that exhibits high absorbency, softness, and breathability.
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48 However, the use of cotton in non-classical applications is limited since its fibers have relatively
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51 low strength, low durability, easy creasing and soiling, and flammability.2 Synthetic fibers can be
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53 antimicrobial, stain/crease-resistant, but generally lack comfort as compared to cotton. The
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development of new fiber types that combine the advantages of both natural and synthetic fibers,
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as well as offering novel functions has been desirable since the 1940s.3 Customer demand for
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6 improved appearance color, shape, texture, and functionality has also increased.4 Flexible
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8 electronics and optical devices can be integrated into textiles.2 The applications of the
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functionalized textiles include medical monitoring of body function and metabolism,5, 6
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13 rehabilitation,7 and electronic devices integrated into clothes.8 Furthermore, these technologies
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15 allow integrating sensors into textiles.9
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18 A new frontier in clothing technology is nanoengineered functional textiles.10-12 The
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20 advantage of nanomaterials concerns creating function without altering the comfort properties of
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22 the substrate.13 Textile is an universal interface and ideal substrate for the integration of
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25 nanomaterials, electronics, and optical devices. Such integrated materials and technologies offer
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27 a platform that responds to mechanical, chemical, electrical, thermal, optical, or magnetic
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stimuli. Such wearable devices may include sensors, data transmission, and processing units.
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32 These engineered materials should seamlessly integrate into garments, and be flexible and
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34 comfortable while having no allergic reaction to the body. Additionally, such materials need to
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37 satisfy weight, performance, and appearance properties (color). A significant challenge in the
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39 textile industry is that conventional approaches to functionalize fabrics do not lead to permanent
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41 effects. For example, laundering decreases imparted functional effects. Hence, nanotechnology
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44 can play a part to introduce new and permanent functions to fabrics. Textiles can be
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46 nanoengineered to have specific functions including hydrophobicity, antibacterial properties,
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48 conductivity, antiwrinkle properties, antistatic behavior, and light guidance and scattering
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51 (Figure 1). Using nanotechnology, these properties can be achieved without affecting
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53 breathability or texture. Such materials may be in the form of surface coatings, voided patterns,
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fillers, or foams.
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31 Figure 1. Applications of nanotechnology in textiles
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34 NANOENGINEERED TEXTILES
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37 Water and Oil Repellence. Water repellence can be imparted to textiles by forming
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39 nanowhiskers consisting of hydrocarbons that are three orders of magnitude smaller than a
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41 typical cotton fiber. Nanowhiskers are integrated within the fabric to create a peach fuzz effect.14
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44 Analogous to the Lotus effect, the spaces between individual whiskers are smaller than drop of
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46 water; however larger than water molecules, producing a high surface tension that allows the
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48 water to remain in the surface.15, 16 The whiskers maintain breathability as they permeate gases.
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51 Water repellence can also be induced through creation of 3D surface structures on the fabric by
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53 adding gel-forming additives, or coating the textile by nanoparticulate film.17 For example, audio
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frequency plasma of fluorocarbon derivatives can be applied to coat cotton fibers with
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nanoparticulates.18 By producing a roughness on the surface of the fabric, superhydrophobicity
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6 can be created without affecting abrasion resistance and softness of the fabric. Silica (SiO2)
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8 nanoparticles (NPs) in combination with water-repellent agents can also be utilized to impart
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hydrophobicity to textiles.19 SiO2 NPs (143-378 nm) were synthesized via sol-gel process.
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13 Cotton fabrics treated with both SiO2 NPs and water-repellent agent produced contact angles
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15 above 130°. SiO2 NPs could be coated over cotton in the presence of perfluorooctylated
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18 quaternary ammonium silane coupling agent (PQASCA) to produce hydrophobicity.20 While the
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20 SiO2 NPs create roughness on the surface of cotton fibers, PQASCA lowered the surface energy.
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22 The resulting textiles exhibited water repellence with a water contact angle of 145°. Oil
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25 repellency of the fabric also improved showing a 131° contact angle for a diiodomethane (CH2I2)
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27 droplet on the fabric surface. In another study, amphiphilic Janus micro/NPs were chemically
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immobilized on textile surfaces.21 While microparticles bound between fibers, NPs attached to
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32 fiber surface. Janus particle immobilized textiles showed water-repellence.
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34 Bioinspired design has also motivated the investigation of water-repellent materials. For
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37 example, duck feathers consist of multiscale structures having preening oil to repel water. The
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39 microstructure of duck feathers were simulated by coating cotton and polyester textiles with
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41 chitosan using a surface solution precipitation method followed by modification with a silicone
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44 compound to achieve a low surface energy.22 Figure 2a shows a scanning electron microscope
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46 (SEM) image of polyester and chitosan-treated polyester having nanosized roughness on the
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48 surface. Chitosan-treated polyester textiles provided flexibility and water repellence. Lotus leaf
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51 nanostructures also inspired biomimetic studies for application in textiles.23 Cotton fibers were
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53 coated with pristine and surface-modified carbon nanotubes (CNTs) to mimic the nanostructure
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of lotus leaves. The resulting cotton fabrics had contact angles greater than 150°. Another study
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that was inspired from lotus leaves involved the development of a nanocoating (20 nm) to create
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6 hydrophobic textiles.24 The nanocoating consisted of epoxy-containing poly(glycidyl
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8 methacrylate) (PGMA) and SiO2 NPs for the initial surface modification and generation of the
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primary reactive layer. Polymers with different functional groups (e.g., carboxy, anhydride,
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43 Figure 2. SEM images of nanoparticle functionalized fibers. (a) Water repellence: chitosan-
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45 treated polyester with nanoscale roughness on the surface. Scale bar = 10 µm. The inset shows
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48 the profile of a water droplet on the treated polyester fabric. Reprinted with permission from ref
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50 . Copyright 2008 IOP Publishing. (b) Antistatic properties: polyester fiber surfaces treated with
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52 NPs and fluorine. Scale bar = 20 µm. Reprinted with permission from ref 25
. Copyright 2010
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55 Sage Publications. (c) Wrinkle resistance: cotton fibers treated with 1,2,3,4-BCA and TiO2 NPs.
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57 Scale bar = 10 µm. Reprinted with permission from ref 26. Copyright 2010 Springer Publishing.
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(d) Strength enhancement: CNT coated cotton fibers. Scale bar = 10 µm. Reprinted with
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6 permission from ref . Copyright 2008 The Royal Society of Chemistry. The inset shows the
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8 magnified view of the fiber surface. Inset scale bar = 1 µm. (e) UV blocking: TiO2 treated cotton
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fiber. Scale bar = 1 µm. Reprinted with permission from ref . Copyright 2004 Sage
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13 Publications. (f) Antibacterial properties and odor control: cotton fibers treated with Ag NPs.
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15 Scale bar = 5 µm. The inset shows the magnified Ag NPs on the surface. Inset scale bar = 1 µm.
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18 Reprinted with permission from ref 29. Copyright 2012 Elsevier.
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21 Oil repellent textiles have been also produced. Polyester fabric could be coated with silicone
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23 nanofilaments and treated with plasma fluorination to impart superoleophobic properties.30 The
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26 produced fabric samples had oil repellency grade of 8, and repelled alkanes. Hydrophobic and
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28 oleophobic properties could be simultaneously imparted to textiles. For example, cotton fibers
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30 were impregnated with SiO2 particles to produce a dual-size surface roughness, followed by
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33 hydrophobization with poly(dimethylsiloxane) (PDMS), resulting in a static water contact angle
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35 of 155° for a droplet.31 To induce oleophobicity, the SiO2 particles on the fibers were treated
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37 with perfluoroalkyl chain, which was demonstrated by a static contact angle of 140° and a roll-
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40 off angle of 24° for oil droplets.
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42 Antistatic Properties. Synthetic fibers such as polyester and nylon have high static charge as
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they are not hydrophilic. On the other hand, cellulosic fibers limit the static charges due to their
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47 high moisture content. TiO2 NPs,32 ZnO whiskers,33 and antimony (Sb) doped tin oxide (SnO2)
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49 particles34 were utilized to impart antistatic properties to synthetic fibers. These materials are
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52 electrically conductive and dissipate the static charge accumulated on the textile. Additionally,
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54 silane nanosol enhances antistatic properties, as it absorbs moisture in the air through hydroxyl
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56 groups.35 In commercial products, poly(tetrafluoroethylene) (PTFE) (W.L. Gore) developed an
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antistatic membrane that consisted of electrically conductive NPs anchored in the fibrils of the
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6 membrane.36 This membrane limited the formation of isolated chargeable areas and voltage
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8 peaks. This approach is advantageous over other antistatic agents since it does not wash off
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during laundry. Sol-gel coatings could be applied as a surface treatment to impart antistatic
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13 properties combined with hydrophobic properties.37 Sol-gel composition consisted of
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15 hydrophobic compounds such as alkoxysilanes modified with alkyl chains and hydrophilic
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18 compounds including amino-functionalized alkoxysilanes. This combination allowed forming
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20 hydrophobic groups at the fiber-air interface while the deeper regions were hydrophilic. Sol-gel
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22 coated textiles had water repellence, but contained humidity in deeper regions of the coatings to
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25 produce antistatic properties. Antistatic charges with hydrophobicity could be achieved by
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27 treating polyester fabric with silver (Ag) NPs and fluorine water-repellent finish (Figure 2b).25
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After 10 washings, the polyester fabric had FTTS-FA-009 A grade antistatic property, and
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32 AATCC 22 spray rating 90 grade for its hydrophobic quality.
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34 ZnO NPs have been utilized to produce antistatic properties.38 ZnO NPs, prepared by direct
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37 precipitation using zinc chloride (ZnCl2), were immobilized both on polyester fabrics through
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39 pad-dry-cure process with antistatic finishing agent. The charge density of polyester fabrics
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41 reduced from 58 to 0.95 (units in ×10-7 C m-2). As the concentration of ZnO NPs increased in the
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44 finishing agent, the antistatic property of the fabric decreased due to reduced dispersion of NPs.
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46 Additionally, the addition of Ag NPs decreased the static voltage of polyester fabric by 60.4 %.39
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48 The combination of Ag, gold (Au) and Zn oxide particles decreased the static voltage by 77.7 %.
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51 In another study, Sb nanoparticle doped SnO2 particles were utilized to impart antistatic
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53 properties to polyacrylonitrile (PAN) fibers.40 These particles were dispersed in water using
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polyethyleneimine (PEIN), and this solution was added to the pre-heating bath during spinning
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of PAN fibers. The particles diffused into the fibers create electrically conductive channels,
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6 which produced antistatic properties.
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8 Wrinkle Resistance. Cellulose molecules in the cotton linearly organize themselves passing
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through the crystalline and amorphous sections of the fibers. Hydrogen bonds hold together
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13 cellulose molecules in their positions. Upon applying a force to the fibers, the cellulose chains
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15 displace from their original positions and hydrogen bonds reform at new locations. Nanocoatings
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18 that prevent crease while maintaining comfort is desirable in textile products. Traditionally,
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20 fabrics are impregnated with resin to impart wrinkle resistance to textiles. However, this
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22 approach decreases tensile strength of the fiber, abrasion resistance, and dyeability while
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25 inducing hydrophobicity. To impart wrinkle resistance, NPs have been applied to cotton and silk.
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27 TiO2 NPs with carboxylic acid as a catalyst were utilized to form crosslinks between cellulose
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molecules and the acidic groups.41, 42 The use of 1,2,3,4-butane tetracarboxylic acid (BCA) and
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32 succinic acid as crosslinking agents had the highest dry crease recovery angle and wet crease
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34 recover angles, respectively. Additionally, carboxylic acid treated fabrics with TiO2 NPs were
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37 softer as compared to untreated fabric.42 TiO2 through its catalytic property can be used as a co-
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39 catalyst with sodium hypophosphite (NaPO2H2) to treat cotton with 1,2,3,4-BCA.26, 43-45 Figure
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41 2c shows SEM images of cotton fibers treated with BTCA and TiO2 NPs. This increased the
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44 effectiveness of NaPO2H2, hence the wrinkle recovery of the cotton fabric. However, tear and
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46 tensile strength of the cotton fabric decreased due to the presence of TiO2 NPs. Bombyx mori silk
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48 was also treated with TiO2 NPs in chitosan by crosslinking reactions of citric acid and maleic
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51 anhydride.46 Dry and wet delay-wrinkle recovery angles of the treated silk were 267° and 250° as
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53 compared to untreated fabric of 235° and 178°, respectively. Additionally, SiO2 NPs and maleic
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anhydrate as a catalyst have been applied to silk to improve wrinkle resistance.47
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Strength Enhancement. CNT reinforced polymer composite fibers have been developed to
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6 improve strength, toughness, and decrease weight. These composite fibers could be produced
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8 through melt-spinning of polypropylene and carbon particles.48 Controlling the parameters in
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melt-spinning, the morphology, crystallinity and mechanical properties of nanostructured
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13 polycaprolactone non-woven mats were optimized.49 Melt extrusion also produced a wide range
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15 of nanoadditive yarns with improved mechanical properties and various textures.50
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18 Wet-dry spinning or jet melt spinning through spinnerets have been used to produce ordinary
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20 and fine denier textile fibers (1-100 µm in diameter). Nanoscale fibers require electrospinning, in
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22 which a solution is extruded though nanoscale spinnerets and the spun fibers are collected on a
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25 grounded plate. The fiber strength and conductivity can be increased by post-treatment
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27 approaches (e.g., heat). Synthetic nanofibers can also be produced through coagulation-based
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CNT electrospinning by controlling the fiber diameter and increasing twist. Such composite
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32 fibers can consist of multiwalled CNTs (5-20). Highly twisted yarns have high strength,
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34 toughness, and energy damping capability for application in electronic textiles including
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37 actuators, electrostatic discharge protection, energy storage, heating, and radio and microwave
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39 absorption. The integration of CNTs into fibers has been shown to improve the strength and
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41 performance. For example, super-aligned arrays of CNTs have Young’s modulus in the TPa
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44 scale, tensile strength of 200 GPa, breaking strain of 20 %, and elastic stain of 5 %.51
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46 Dipping and coating method was also utilized to immobilize CNTs on cotton.27 CNTs were
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48 modified with poly(butylacrylate) using surface grafting, and this composite was applied to
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51 cotton fabrics by dipping, drying, curing, and finishing. Figure 2d illustrates SEM images of
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53 CNT coated cotton fibers. The tensile strength of the CNT-coated cotton fabrics was improved
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along the weft and warp directions, showing enhancement in both the loading capability and
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flexibility (displacement). For example, the tensile strength of the CNT coated cotton was 0.5 kN
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6 at 13.5 cm displacement as compared to 0.25 kN for untreated fabrics.27
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8 UV Blocking. Inorganic UV blockers are non-toxic and chemically stable operating at high
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temperatures. Nanoscale semiconductor oxides such as TiO2 and ZnO efficiently absorb and
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13 scatter UV radiation.28, 52-54 Figure 2e shows a SEM image of a TiO2 (~100 nm) treated cotton
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15 fiber. At nanoscale, scattering depends on the wavelength and the size of the NP, where the
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18 scattering is inversely proportional to the wavelength of the fourth power of the wavelength. For
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20 example, to scatter UV light (200-400 nm), the optimum particle size is 20-40 nm.55 Sol-gel
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22 method can be used to form a thin layer of TiO2 on the surface of the treated cotton. The UV-
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25 protection effect may be maintained up to 50 launderings.56 Furthermore, ZnO nanorods (10-50
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27 nm) have been incorporated in cotton to induce scattering at a high UV protective factor rating.57
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Additionally, ZnO NPs synthesized through sedimentation and peptization were immobilized on
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32 dyed polyester/cotton fabrics.58, 59 The resulting fabric absorbed the light in the UV region.58
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34 Antibacterial Properties. Ag, TiO2 and ZnO NPs can be utilized to impart antibacterial and
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37 fungicidal properties to textiles.53, 55, 60-62
Ag NPs have large surface areas that increase their
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39 contact with bacteria and fungi. The antiseptic mechanism of Ag NPs is based on reacting with
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41 proteins in these organisms and adversely affecting their cellular function and inhibiting cell
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44 growth. They also reduce respiration, limiting the activity of the basal metabolism of the electron
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46 transfer system, and substrate transport into the cell membrane. When Ag NPs contact with
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48 moisture or bacteria, they adhere to the cell wall and membrane.63 While the Ag NPs in their
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51 metallic state are inert, they ionize in the presence of moisture. The Ag+ ions are reactive and
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53 they diffuse through the cell wall and membrane into cytoplasm. Ag+ ions bind to sulphur
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containing proteins on the cell membrane to structurally change the cell wall.64 These structural
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changes result in the release of the cellular components to extracellular fluid due to the changes
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6 in the osmotic pressure. Additionally, the Ag+ ions bind to phosphate containing proteins to
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8 condense DNA, leading to a reaction with thiol group proteins to cause cell death. They also
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suppress the function of enzymes and inhibit the cell to produce ATP.65 Ag NPs slow down the
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13 growth and multiplication of bacteria and fungi that are involved in odor creation and itchiness.
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15 Figure 2f shows cotton fibers treated with Ag NPs.29 For example, Ag NPs can be applied to
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18 socks to prevent the growth of bacteria and fungi.
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20 The antimicrobial efficacy of Ag additives depends on the concentration, surface area, and
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22 the release rate of the Ag+ ions.66-68 Ag-containing textiles can release dissolved and particulate
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25 Ag (20-30%) into washing liquid in the first cycle.69-71 In fabrics comprising Ag metal, oxidation
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27 from Ag(0) to Ag(I) is required for releasing Ag+ ions in solution.70 Ion release from Ag NPs is a
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cooperative oxidation process involving dissolved oxygen and protons to produce peroxide
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32 intermediates and complete reactive dissolution. The presence of oxygen is essential for the
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34 release of dissolved Ag through the surface oxidation of Ag NPs. The ion release rates increase
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37 as the temperature is increased and as the pH is decreased.72 For example, Ag NPs (2 mg L-1)
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39 released 0.3 mg L-1 dissolved Ag after 24 h incubation in air-saturated solution (9.1 mg L-1
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41 dissolved oxygen) at pH 5.68. The release of dissolved Ag was 0.6 and 0.1 mg L-1 at pH 4.0 and
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44 8.0 after 24 h incubation, respectively.72 Additionally, the change in ionic strength has negligible
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46 effect on the release kinetics.
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48 TiO2 NPs can also be utilized to impart textiles with antibacterial properties. Upon
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51 illumination with light with energy higher than its bandgap (3.2 eV), TiO2 as a photocatalyst has
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53 the ability to have its electrons jump from the valence band to the conduction band. The electron
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and electric hole pairs form on the surface of the photocatalyst, where the electrons and oxygen
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form O2¯ and the positive electric holes and water create hydroxyl radicals.52 The unstable
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6 substances on the surface of the photocatalyst are oxidized into CO2 and water. Through this
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8 mechanism, the photocatalyst decompose organic matters including odor molecules, bacteria,
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and viruses. The catalytic activity of TiO2 NPs has been utilized in textiles to provide
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13 antibacterial properties.56, 73
The photocatalytic activity might be improved by creating
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15 TiO2/SiO2 nanocomposites or Au-doped TiO2 nanocomposites in cotton fabrics with self-
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18 cleaning properties.74, 75
Furthermore, ZnO behaves similar to TiO2 to produce antibacterial
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20 properties.76 ZnO NPs (21-25 nm) have been synthesized in reverse micelle cores of polystyrene
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22 (PS) and polyacrylic acid.77 ZnO NPs coated onto textiles showed self-cleaning properties in the
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25 presence of gram-negative E. coli and aerobic gram-positive S. aureus. Additionally, SiO2 and
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27 Ag NPs with core-corona structure were electrostatically assembled onto cotton surfaces with
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high packing density to impart antibacterial properties to fabrics.78 The coronas of NPs can be
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32 loaded with antibacterial moieties such as quaternary ammonia salts as well as metal coatings on
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34 cotton fabrics.79 Discussions focusing on self-cleaning and antimicrobial nanomaterials in
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37 textiles can be found elsewhere.17, 80, 81
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41 ELECTRONICS IN TEXTILES
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44 Electrical Conductivity. Conducting polymers are attractive for creating textiles that enable
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46 the incorporation of sensors and actuators. For example, conducting polymers can change their
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48 resistivity and produce electrical signals in response to external stimuli. A range of dopants can
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51 be incorporated in these polymers. For example, polypyrrole (PPy) has high mechanical strength
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53 and is electroactive in organic and aqueous solutions. Another widely studied conductive
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polymer is polyaniline (PANI), which exist in three possible configurations: leucoemeraldine
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base (fully reduced), emeraldine base (partly oxidized), and pernigraniline base (fully oxidized).
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6 In its oxidized form, the conductivity of PANI increases about 10 orders of magnitude.
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8 Additionally, polythiophene (PTs) and its derivatives can be in p or n type forms for application
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in field-effect transistors in flexible logic circuits. The low production costs, light weight and
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13 flexibility allow these materials to be easily integrated in textiles.
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15 The surface structure of synthetic fibers can be modified to produce diverse functionalities.82
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18 SiO2 NPs can be incorporated in polyimidoamide fibers through spinning. Incorporation of
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20 nanoparticles in PAN fibers can create electrically conductive channels with enhanced
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22 mechanical and antistatic properties.40, 83 Fiber porosity, thermal and absorption characteristics
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25 can be controlled by chemically modifying the fibers. To improve thermal resistance and
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27 tenacity, the fibers can be coated with diamine (diaminodiphenyl methane), montmorillonite, and
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SiO2 NPs.84-86 Synthetic fibers can also be functionalized through chemical oxidative deposition,
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32 in which conducting electroactive polymers such as PANI, PPy, PTs are used to coat textiles for
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34 improving tensile strength and thermal stability.87, 88
Furthermore, surface deposition of
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37 electroactive polymers increases conductivity of the fibers one order of magnitude.89-91 Such
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39 composite fibers have application in the reduction of static electrical charge, microwave
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41 attenuation, and electromagnetic shielding.
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44 Finding the balance between electrical conductivity, flexibility and comfort of the textile is a
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46 challenge. Coatings have been developed to impart electrical conductivity to cotton. One
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48 approach involved polyelectrolyte-based coating with multiwalled carbon nanotubes
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51 (MWCNTs).92 Figure 3a shows SEM images of MWCNT-Nafion coated cotton threads. Charge
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53 transport through the network of nanotubes was 20 Ω cm-1. Another strategy used a combination
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of metal NPs conformally coated around the heterogeneous contour of cotton fibers.93 In-situ
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polymerization was utilized to create polymeric bridges between the NPs. These flexible bridges
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6 allowed for the creation of coatings that were durable and resilient to mechanical deformation for
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8 application in cotton-based transistors. Figure 3b shows a Transmission Electron Microscope
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(TEM) image of cross-section of the conductive cotton fibers, showing uniform coating with Au
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13 NPs and poly(3,4-ethylenedioxithiophene) (PEDOT).
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48 Figure 3. Conductive nanomaterials in textiles. (a) A SEM image of MWNT-Nafion coated
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thread. Scale bar = 10 µm. Reprinted with permission from ref . Copyright 2008 American
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53 Chemical Society. (b) A TEM image of cross-section of the conductive Au NP and PEDOT
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55 coated cotton fibers. Reprinted with permission from ref . Copyright 2011 Elsevier. (c)
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57 Fabrication of graphene woven fabric by CVD using copper (Cu) wire meshes as substrates.
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3 94
Reprinted with permission from ref . Copyright 2012 Nature Publishing Group. (d) Graphene
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6 woven fabric in PDMS. Scale bar = 5 mm. The top inset illustrates the twisted graphene fabric
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8 film. The bottom inset shows an SEM image of graphene fabric cross-section. Scale bar = 100
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µm. Reprinted with permission from ref 94. Copyright 2012 Nature Publishing Group.
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14 Graphene-based woven fabrics have been prepared by interlacing two sets of graphene
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16 microribbons.94 The resulting textile had dimensional stability in both the warp and the weft
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directions. The conductivity was optimized by tuning the ribbon packing density. Graphene
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21 woven fabrics were synthesized through atmospheric chemical vapor deposition (CVD) using Cu
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23 meshes consisting of wires with ~60 µm in diameter as substrates. The fabrication of the textiles
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26 involved growing graphene on the substrate, removing the Cu mesh wires, and subsequently
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28 collapsing the graphene to form double-layer microribbons (Figure 3c). Such polymers could be
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30 also embedded in PDMS or PET films (Figure 3d). The constructed fabric had a transparency of
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33 1000 Ω sq-1.94 Conductive textiles could also be produced by immobilizing graphene via
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35 reduction from graphene oxide on cotton fabric by using a conventional dip and dry method.95
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37 The electrical conductivity of the fabric enhanced three orders of magnitude as the number of
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40 coating cycles was increased from 1 to 20. The surface conductivity of the resulting graphene
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42 depended on the reducing agent type and concentration. The electrical resistivity of the graphene
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immobilized cotton ranged from 103 to 106 kΩ cm−1.95
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47 Power Sources. Flexible and lightweight fabric supercapacitor electrodes have been
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49 designed for energy storage.96 Activated carbon in poly(methyl methacrylate) (PMMA) and
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52 polyethylene glycol (PEG) were incorporated in woven cotton and polyester fabrics. The
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54 supercapacitor cells were assembled in a conventional symmetrical two electrode setup by screen
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56 printing on polyester microfibers. Electrodes coated with activated carbon had a gravimetric and
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areal capacitance of 85 F g-1 at 0.25 A g-1 on cotton lawn and polyester microfiber.96 Recently, a
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6 flexible supercapacitor textile consisting of CNTs/PANI composite fiber was developed.97 The
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8 supercapacitor was integrated with a photoelectric conversion function to create a self-powering
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energy textile that converted solar energy into electrical energy and stored it in a stacked
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13 multilayer structure. The CNT array was synthesized by CVD. Aligned CNT sheets were dry-
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15 drawn from the array and stacked into a thicker film along the length direction, and twisted into
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18 an aligned fiber, which was woven into textiles. The resulting textiles were electrodeposited with
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20 PANI to create an electrode, followed by coating with a layer of gel electrolyte to create a
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22 supercapacitor. The resulting material had a capacitance of 272 F g-1 with 96% maintenance after
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25 200 bending cycles.97 Another study that aimed to improve the performance of textile-based
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27 supercapacitors involved embedding a metal wire (monofilament) in the center a CNT yarn.98
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One-step continuous spinning allowed forming a core/sheath structured CNT yarn architecture to
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32 create linear supercapacitors. CNTs formed a layer around the conductive metal filament core.
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34 The filament core acted as a current collector to transport charges. Foldable nanopatterned
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37 wearable triboelectric nanogenerators were also reported.99 Figure 4a shows the device and its
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39 fabrication process using nanopatterned PDMS structure. Ag-coated textile and PDMS
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41 nanopatterns based on ZnO nanorod arrays were used as triboelectric materials. The
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44 nanopatterned structures produced 120 V (output) at 65 µA, and four-layered triboelectric
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46 nanogenerators produced 170 V (output) at 120 µA. No significant drift was observed after
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48 120,000 cycles.99 Another study reported the development of carbon-activated cotton threads on
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51 textile for energy generation.100 The device harvested electrostatic energy from the environment
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53 through contact and friction electrifications. It was fabricated by treating carbon black NPs and
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encapsulating them with a thin layer of PDMS for stability. By rubbing and tapping with a PTFE
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sheet, electrostatic charges were collected from the carbon-functionalized threads in textiles. The
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6 device had an open-circuit voltage of -60.9 V.100 Piezoelectrocity via electrostatic forces were
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8 also utilized in textiles to create a nanogenerator.101 ZnO nanowires and discharge films were
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incorporated into a textile to hybridize electrostatic and piezoelectric effects (Figure 4b). This
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13 nanogenerator had an output voltage of 8 V at 2.5 µA. The produced power source was utilized
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15 to power an OLED and a Liquid Crystal Displays (LCD) panel.101 Recently, pristine soft
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18 conductive yarns were produced via a twist-bundle-drawing technique (Figure 4c).102 Conductive
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20 yarns modified with reduced graphene oxide (rGO), MnO2 nanosheets, and PPy films were used
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22 to produce weavable supercapacitors. The yarns had specific capacitances of 31 mF cm-1 and 411
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25 mF cm-1 in solid-state two electrode cells with energy densities of 9.2 µWh cm-2 and 1.1 mWh
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27 cm-3.102
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40 Figure 4. Energy generation and storage in textiles. (a) Fabrication of nanopatterned wearable
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42 triboelectric nanogenerator showing SEM images of ZnO nanorod-templated PDMS
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nanopatterns. The inset shows a magnified image of surface morphology. Scale bar = 500 µm,
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46 99
47 inset scale bar = 1 µm. Reprinted with permission from ref . Copyright 2015 American
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49 Chemical Society. (b) SEM images of a textile electrostatic-piezoelectric hybrid nanogenerator
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containing ZnO nanowires. The inset shows magnified nanowires on the surface. Scale bar = 500
53 101
54 µm, inset scale bar = 1 µm. Reprinted with permission from ref . Copyright 2012 The Royal
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56 Society of Chemistry. (c) Twisted yarn fabrication and illustration of the yarn functionalized by
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rGO, MnO2, and PPy. (1) Hydrothermal treatment (2-3) Electrodeposition. Reprinted with
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6 permission from ref . Copyright 2015 American Chemical Society. (d) Fabrication and
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8 operation principle of magnetic-assisted, self-healable, yarn-based supercapacitors. Reprinted
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10 103
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with permission from ref . Copyright 2015 American Chemical Society. (e) A garment using
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13 cotton yarns coated with nanolayers of PEDOT-PSS. Copyright Abbey Liebman.
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Stretchable PPy-based supercapacitors with cycling stability were also fabricated.104
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21 Electrochemical deposition of PPy on stretchable stainless steel meshes allowed producing solid
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23 state supercapacitors reaching 170 F g-1 at 0.5 A g-1. Under 20% strain, the capacitance can be
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26 enhanced up to 214 F g-1. These supercapacitors were operated at a scan rate of 10 V s-1, which is
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28 a magnitude higher than PPy electrodes in aqueous solutions. These solid-state supercapacitors
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30 under no-strain and 20% strain had capacitance retentions 98% and 87% at 10 A g-1 after 10,000
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33 cycles.104
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35 In conventional planar or structures, the reconnection of the broken yarn electrode and the
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37 restoration of the electrical conductivity are challenging.103 To improve the mechanical
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40 properties, yarns-based supercapacitors with self-healing properties have been developed. The
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42 electrodes fabricated by wrapping magnetic electrodes around a self-healing polymer shell
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(Figure 4d). The magnetic attraction reconnected broken fibers in the yarn electrodes to store
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47 electrical conductivity while polymer shell recovered mechanical strength and configuration
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49 integrity. The magnetic yarns allowed restoring the specific capacitance up to 71.8% after four
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52 breaking cycles by maintaining mechanical properties.103
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54 Conductive fabrics have been incorporated in garments. Figure 4e shows a garment using
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56 cotton yarns coated with nanolayers of PEDOT- poly(styrenesulphonate) (PSS) deposited over an
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array of Au NPs. These nanolayers allow the cotton yarns to become electrically conductive and
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6 transfer energy from solar cells attached to the exterior of the dress. A comprehensive discussion
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8 about energy storage technologies can be found elsewhere.10
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13 Fabrication of multifunctional composite fibers has received attention due to their
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15 applications in conductive structures and batteries in the textile industry. Here “fiber” refers to
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18 wire-like composite structures produced via drawing techniques used in the production of fiber
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20 optics. Composite fibers can be fabricated through preform heating and drawing. A
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22 geometrically complex fiber preforms at a length of tens of centimeters is assembled by stacking
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25 of tubes, rods, multilayered films, or functional components within a hollow structured rod that
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27 serve as cladding.105 The preform tip is then placed into the vertical furnace, where the
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temperature is increased above the softening or melting temperature of the preform materials. As
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32 a consequence, the preform tip melts, and then it is pulled downward, thus creating a slender rod
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34 that can be continuously pulled from the molten perform tip. Typically, a clamp tractor or a
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37 spooler is used to pull the fiber at a constant speed and tension. Geometry of the resultant fiber
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39 depends on parameters in the drawing process such as temperature distribution in a furnace, fiber
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41 drawing speed and preform feed velocity, pressurization of the preform, and electromagnetic
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44 fields.106 This process creates both non-optical fiber and optical fibers. Fibers drawn from the
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46 macroscopic preform would generally retain the preform structure; however, sizes of the
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48 constituent structures (e.g., layers, rods) will be reduced to micro- or nanoscale. Therefore, a
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51 geometrically complex, composite transverse structure could be realized within a fiber on a sub-
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53 micron scale by controlling the preform structure and optimizing the conditions of the fiber
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drawing process. This, generally, may not be accomplished by traditional yarn-spinning methods
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such as melt-spinning,107 wet-spinning,108 or electro-spinning,109, 110 which are typically utilized
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6 to produce fibers and yarns with simple structures in textile manufacturing. Moreover, materials
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8 including biofunctional polymers,111-113 low-melting-temperature metal alloys,114 optical
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plastics,114-123 conductive polymers,124-126 and electrochemical materials,127-130 could be
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13 integrated into a composite fiber during drawing.
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15 Flexible fiber or stripe batteries which can be directly weaved into a textile constitute a
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18 promising solution toward seamless integration with functional textiles. Flexible fiber batteries
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20 using both a simple inorganic chemistry127, 128
as well as Li-ion chemistry129, 130
have been
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22 proposed. The simplest fiber battery consisted of a microstructured low density polyethylene
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25 (LDPE) jacket with several intercommunicating channels running along the fiber. Aluminum
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27 (Al) and Cu wires were immobilized to produce a double stranded fiber as anode and cathode,
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respectively. The voids between these two channels were then filled with sodium hypochlorite
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32 (NaOCl) electrolyte. This fiber constituted a typical Al/air galvanic cell. To fabricate a fiber
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34 battery, the fiber jacket preform was prepared by drilling several interconnected channels
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37 throughout a LDPE rod. The two electrode wires (Al and Cu) were embedded into the two
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39 extreme channels of the fiber during production (i.e. drawing). Open cell voltage of a fiber
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41 battery was ~1.5 V with a linear capacity of 10−2–10−1 mAh cm-1. Flexible lithium (Li)-ion
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44 batteries could be built by from polyethylene oxide (PEO) as a thermoelastic polymer ionic
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46 electrolyte in all the electrodes and a separator layer. To assemble such a battery, solvent-casting
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48 method could be used to deposit an anode layer (Li4Ti5O12 + PEO), a separator layer (PEO+LiI),
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51 and a cathode layer (LiFePO4 + PEO) in sequence. The thermoelastic nature of PEO allows the
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53 production of such batteries in fiber drawing. This Li-ion battery could be cut into stripes that
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may be directly weaved into a textile.
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Two prototypes of textiles based on fiber and stripe batteries have been demonstrated. The
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6 first prototype was fabricated by weaving fiber batteries into a wool textile matrix.127 The
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8 maximum output power of a fiber battery textile could be achieved by optimizing series and
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parallel connections of the fiber batteries in the textile. Applications of this fiber battery
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13 integrated textile included lightning up a LED, driving a wireless mouse,127 and actuating a
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15 shape-memory alloy.127 The second prototype used flexible stripe Li-ion batteries.129 The Li-ion
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18 battery stripes were weaved into a textile. Each stripe had an open cell voltage of ~0.3V. A
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20 textile battery made of eight battery stripes woven with wool threads and connected in series
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22 using Cu and Al wires were used to light up a 3V LED. The flexible fiber or stripe batteries
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25 constitute a promising technique toward the realization of on-garment power supply. In fashion
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27 industry, LEDs or electroluminescent wires are used as light emitting elements; and shape-
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memory alloys may be weaved into garments to provide kinetic features. The fiber and stripe
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32 batteries could be used as an efficient power source for these electronics.
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34 Conductive fiber are widely used to interface with other electronic devices integrated into
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37 textiles. To fabricate conductive fiber, conductive fillers such as carbon black (CB)125 or
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39 CNTs131 are impregnated into plastic preform material. Fabrication of all-fiber electronic
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41 components is however a challenging task. The fabrication of a fiber electric capacitor using CB-
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44 impregnated LDPE films as compliant electrodes have been reported.124-126 The fiber preform
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46 was fabricated by consecutive stacking of two conductive and two isolating LDPE layers and
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48 then turning the multilayer into a Swiss-roll configuration featuring a large central hole. A
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51 tension-adjustable reel was installed on the top of the fiber drawing tower that hosted a spool of
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53 Cu wires. These wires were then passed through the preform core, pulled down and embedded
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into the fiber center during drawing by collapsing the plastic cladding. The as-drawn fiber
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capacitors featured one or two Cu wires as inner electrodes, and the outmost conductive LDPE
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6 layer constituted the outer electrode. The fiber capacitance was measured in the 60-100 nF m-1
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8 range. The fiber capacitors were also demonstrated to build touch sensitive textiles.
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Digital Components. OLEDs have been incorporated in soft fabrics.132 OLEDs fabricated by
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13 thermal evaporation were mechanically stable over 1000 cycle bending test with a bending
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15 radius of 5 mm, an emission angle of 70°, and a current efficiency of ~8 cd A-1.132 Schottky
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18 diodes were also fabricated on textiles.133 ZnO nanorods were grown on a Ag-coated textile
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20 fabric using a hydrothermal method, and Zn nitrate and hexamethylenetetramine were used to
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22 produce ZnO nanorods. The Schottky diode was prepared by applying photoresist and reactive
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25 plasma ion etching of the ZnO nanorods. A shadow mask was used to deposit Cu using thermal
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27 evaporation. The resulting diodes had performance comparable to glass-based diodes.133
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Schottky diode integrated textiles have potential applications in switched-mode power supplies,
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32 voltage clamping, and reverse current and discharge protection.
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34 Polymer yarns/fibers that are twisted/embedded with metal wires have been used for
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37 production of electromagnetic shield garments and fabrics. These metal wires could be
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39 embedded into polymer rods during a drawing process. The metal components in such rods
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41 generally have a melting temperature similar to that of polymers. A polycarbonate cable
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44 containing arrays of the bismuth-tin (Bi42Sn58, melting temperature ~140 °C) micro/nanowires
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46 has been fabricated using the stack-and-draw technique.114 For preform fabrication, molten
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48 Bi42Sn58 alloy was first filled into a polycarbonate tube to produce a preform that was
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51 subsequently drawn into cable. The resulting cable had a cross section featuring a metal core
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53 surrounded by a polycarbonate cladding. By stacking these cables within another polycarbonate
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tube, and by repeating the drawing process, metal wire arrays could be produced at smaller
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dimensions. After several drawings, nanowires separated into NPs. Recently, the fabrication of
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6 polymer/wire composites containing indium,134, 135 or tin-zinc136-144 has been demonstrated based
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8 on the same drawing technique. While such polymer/metal wire composites are mainly used for
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electromagnetic shielding, they also have a potential for producing metamaterials and optical
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13 components.
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18 PHOTONIC TECHNOLOGIES FOR TEXTILES
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20 Integration of optical technologies into garments and apparels is desirable in the fashion industry.
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22 Photonic materials and devices including films, nanoadditives or optical fibers have been
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25 adopted in the fabrication of textiles and garments to not only enhance the aesthetic performance
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27 but also endow the garments with additional functionalities. The most distinctive and basic
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application of optical technologies on fabrics or garments is perhaps tuning their appearance by
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32 controlling the intensity, color, and pattern of light. For example, optical films made of
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34 periodical dielectric multilayers could be directly coated on fabrics, thus offering highly
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37 reflective colorful appearance and enabling different color perceptions depending on the angle of
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39 observation. Holographic films may also achieve similar functions and even provide a more
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41 complex 3D visual effect.145, 146 Additionally, phosphorescent films can allow fabrics glow in the
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44 dark.147 Optical additives such as thermochromic and photochromic inks could be applied to
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46 yarns or textile, thus enabling the change of a textile color in response to ambient heat or
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48 illumination.148 Retro-reflective inks that could provide a high reflection directly toward a light
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51 source are widely used for security clothing.145 Moreover, electroluminescent wires or optical
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53 fibers serving as light emitting elements could be seamlessly weaved into a textile or garment.
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Textiles based on electroluminescent wires,149, 150
traditional single- or multi- mode optical
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fibers,151 fluorescent fibers152 and photonic bandgap fibers153 have been demonstrated. In
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6 addition to promoting aesthetics, multifunctional fibers could offer textiles with functionalities
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8 such as sensing of temperature,154, 155 humidity,156 strain,157 bending,158 and pressure,159 optical
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displays,160 data transfer and communication,161 lasing,162 and illumination.160, 163
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13 Color-Tunable Optical Fibers. Bragg fibers, a subset of photonic bandgap fibers, have a
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15 hollow- or solid- core surrounded by periodic dielectric nanolayers with high- and low-
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18 refractive indexes (Figure 5a).115-120 Recently, two methodologies have been reported for the
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20 fabrication of the all-polymer hollow-core Bragg fiber preforms.123 One approach utilized
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22 consecutive deposition of layers of two different polymers by solvent evaporation inside a
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25 rotating polymer cladding tube. The other approach adopted co-rolling of two different polymer
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27 films inside a plastic tube. Solid-core Bragg fiber preforms were fabricated by co-rolling the
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multilayer around a rod.155, 158, 159, 164
To fabricate Bragg reflectors, PMMA/PS or PVDF
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32 (polyvinylidene fluoride)/polycarbonate have been used. Solid-core Bragg fibers were
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34 manufactured by preform heating and drawing, while hollow-core fibers required core
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37 pressurization. Bragg fibers typically guide the light by the bandgap effect.165 Bandgaps of Bragg
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39 fibers are defined as spectral regions of high diffraction efficiency caused by the interference
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41 effects inside a periodic multilayer. Upon launching spectrally broadband light into a Bragg
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44 fiber, only the spectral components within the reflector bandgaps would be strongly confined and
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46 thus guided in the optical fiber core (Figure 5b). For the wavelengths outside the reflector
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48 bandgap, the light penetrated deeply into the multilayer region exhibits high propagation loss due
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51 to scattering from the imperfections inside the multilayer structure. Therefore, narrow-band
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53 colors were observed at the output end of a Bragg fiber (Figure 5b inset). Spectral position of the
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bandgap was affected by the core refractive index and multilayer geometry. Thus, bandgap
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guidance mechanism renders Bragg fibers suitable for application in spectral filtering,118, 119
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6 optical sensing,117, 119-121, 166 and photonic textiles.116, 122, 153
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25 Figure 5. Fiber optic and plasmonic technologies for textiles. (a) Cross section of a solid-core
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27 Bragg fiber and its multilayer structure. Scale bar = 50 µm. Inset scale bar = 10 µm. Reprinted
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30 with permission from Ref. . Copyright 2008 The Optical Society of America. (b) Light
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32 scattered from solid-core Bragg fibers. The inset shows Bragg fibers with different bandgaps.
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34 122
Scale bar = 200 µm. Reprinted with permission from Ref. . Copyright 2008 CTT Group. (c)
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37 PBG Bragg fibers woven into a black silk textile. The inset shows color of the fibers tuned by
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39 mixing the emitted guided color with the diffracted color from ambient illumination. Reprinted
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41 116
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with permission from ref . Copyright 2008 The Optical Society of America (d) The use of
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44 plasmonic NPs in a garment. The inset shows an SEM image of Au NPs on the surface of a
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46 167
cotton fiber. Scale bar = 500 nm. Reprinted with permission from ref . Copyright 2009 The
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49 American Chemical Society. Reprinted with permission from Olivia Ong.
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54 The key feature of bandgap guidance of a Bragg fiber is wavelength filtering. When
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57 launching broadband light into a Bragg fiber, only a specific color defined by the spectral
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position of the reflector bandgaps is guided. All the other colors are scattered out of the fiber
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6 after several centimeters of propagation. Moreover, due to the finite number of multilayers in the
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8 Bragg reflector, guided light partially leaks out from the fiber core. The leakage rate could be
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controlled by changing the number of multilayers. The spectral position of the reflector
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13 bandgaps, and hence the guided color, could be varied by changing the thicknesses of the
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15 reflector layers, with thicker layers shifting bandgaps to longer wavelengths. Layer thicknesses
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18 have been varied by drawing geometrically-similar preforms to optical fibers of different
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20 diameters.116, 122, 153
Furthermore, under ambient (external) illumination, the Bragg fibers are
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22 colored depending on their diffraction properties. Therefore, the fiber color under ambient
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25 illumination is typically different from the fiber color due to emission of the guided light. This
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27 offers an opportunity to tune the overall fiber color by controlling the relative intensities of the
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ambient and propagating light. A ribbon of Bragg fiber diffracted green under ambient
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32 illumination while an emission of guided light diffracted red. In the far field (defocused view),
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34 the resultant color of a fiber ribbon was yellow.116, 122
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37 Photonic Textiles Based on Bragg Fibers. A photonic textile based on solid-core Bragg
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39 fibers was hand woven on a Dobby loom.116 The photonic textile showed colors when externally
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41 illuminated (Figure 5c). The textile exhibited colored bands made of optical fibers with similar
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44 diameters and coloration. Upon launching broadband light, the textile sample showed a number
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46 of brightly lit bands of distinct colors. Figure 6c inset shows textile samples under the ambient
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48 illumination. The textile sample had different colors depending on whether the textile was lit or
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51 not. This opens the possibility of controlling the resultant textile color by balancing the
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53 intensities of the guided and ambient light. When used in fashion industry, Bragg fibers and
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photonic textiles based on these optical fibers could be conveniently weaved into garments.
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Compared to yarns or fabrics decorated by optical coatings or pigments, Bragg fiber-based
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6 textiles are resistant to mechanical abrasion and would not fade in color even under repeated
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8 washing.
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Plasmonic Textiles. Cotton fabrics were also colored using arrays of plasmonic Ag, Au and
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13 Ru NPs.167 The color in the fabrics originates from the closely packing of NPs, which were
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15 displayed on a garment (Figure 5d). TEM micrographs of the cotton fibers show the presence of
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18 conformal coatings of NPs assembled on the perimetries of the cotton fibers (Figure 5d inset).
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22 SENSING AND DRUG RELEASE IN TEXTILES
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25 Plasmonic bio/chemical optical fiber sensors can be fabricated via drawing techniques.
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27 Plasmonic sensors have been studied due to their high sensitivities for bio/chemical sensing.168-
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29 170
In a plasmonic fiber sensor, a lossy surface plasmon mode propagating along a
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32 metal/dielectric interface could be excited at its resonance by an optical fiber core-guided mode
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34 via evanescent-wave coupling when the phase matching condition between the two modes is
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37 satisfied at certain frequency. The presence of such a plasmonic mode manifests itself as a
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39 spectral dip in the fiber transmission spectrum with its spectral location corresponding to the
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41 phase-matching frequency. Variations in the refractive index of an analyte adjacent to the metal
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44 layer could significantly modify the phase-matching condition, thus displacing the spectral dip in
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46 the optical fiber transmission spectrum. This constitutes the general sensing principle of a
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48 plasmonic fiber sensor. In the fabrication of a plasmonic sensor using conventional single- or
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51 multi-mode optic fibers, a series of modifications such as cladding etching or polishing followed
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53 by a subsequent deposition of several tens of metal nanolayer are generally required, in addition
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to the interfacing with a microfluidic system in the proximity of the fiber sensing head.171-173
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These procedures bring challenges to the development of plasmonic fiber sensors. However, a
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6 complete plasmonic sensor fiber can be fabricated using stack-and-draw technique (Figure 6a). A
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8 fiber preform is first assembled at the microscale and it contains a plastic fiber core rod
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surrounded by the plastic tubes with one of them hosting a low melting temperature metal foil
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13 functionalized with a thermoplastic sensing layer. The inner channel of that tube is later used as a
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15 channel for analyte delivery. Next the preform assembly is drawn into fiber under pressure to
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18 keep the microfluidic channels in the fiber open. Finally, an additional wire can be passed
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20 through one of the tubes during drawing to be later used for active temperature control of the
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22 device. Additionally, high voltage supply can be connected to the wire and a foil to tune the
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25 distance between the fiber optic core and the plasmonic layer during drawing. Such fibers may
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27 contain multiscale features ranging from nano to macroscale, and consist of nano-additives for
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functionalization.
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39 Figure 6. Sensors and insecticide-releasing textiles. (a) Fabrication of multifunctional fiber
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composites for sensing applications. Reprinted with permission from Ref. . Copyright 2010
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44 The International Society of Optics and Photonics. (b) Woven touchpad sensor with a 1D array
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46 of capacitor fibers connected to the ADC board to monitor an image of a textile with a
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48 124
reconstructed touch position. Reprinted with permission from ref . Copyright 2012 IOP
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51 Publishing. (c) Die-coating system used in forming PEDOT:PSS and Cytop film on fibers.
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53 174
Reprinted with permission from ref . Copyright 2012 Elsevier. (d) Fabrication of electrodes
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via photolithography for sensing applications. Reprinted with permission from ref 175. Copyright
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2013 IEEE. (e) Temperature and humidity sensors woven in a tablecloth. Scale bar=1 cm.
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6 Reprinted with permission from ref . Copyright 2013 IEEE. (f) Permethrin-releasing textile
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8 net. Reprinted with permission from ref 176. Copyright 2012 Springer. Reprinted with permission
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from Matilda Ceesay.
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15 Using flexible fiber capacitors, touch sensor fabrics have been developed.124, 125 Flexible and
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18 elastic fiber capacitors are well suited for a conventional weaving process. A Dobby loom was
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20 used to weave the capacitor fibers into a 1D sensor array integrated into a wool textile matrix.
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22 The touch sensor fabric consisted of 15 capacitor fibers (Figure 6b). The inner electrodes of all
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25 the fibers (Cu wires) were connected to the voltage source integrated into an Analog-to-Digital
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27 Converter (ADC) card. One end of the outer plastic electrode of each fiber was grounded, while
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the other end was connected to the individual channels of the ADC card to measure the voltage
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32 at the fiber endpoint. The human body could be approximated by an equivalent electrical circuit
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34 comprising a resistor connected in series to a capacitor. Touching a capacitor fiber with finger
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37 modified the local current flow and voltage distribution, thus sensing the measured voltage to
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39 touch. Moreover, a 1 cm spatial resolution was achieved with a single fiber, thus allowing the
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41 fabrication of 2D touch sensitive textiles with a 1D array of capacitor fibers. The fiber capacitors
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44 may also interface with other fiber electronics such as conductive fibers or battery fibers to
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46 constitute a functional on-garment electric circuit. Potential application of such on-garments
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48 electronics may include fashion, safety clothes as well as programmable and computing textiles.
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51 Pressure-sensitive fabrics were also developed.174 To fabricate the sensors, fibers were coated
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53 with organic conductive polymer poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate)
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and a dielectric film of perfluoropolymer using a die coating system (Figure 6c). The coated
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fibers were woven as wefts and warps, and the rest of the matrix was filled with pristine nylon
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6 fibers. Capacitors were formed at the nodes, where the fibers intersected. When a pressure of 4.9
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8 N cm-2 was applied on the fabric, capacitance increased from 0.22 to 0.63 pF with a sensitivity
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ranging from 0.98 to 9.80 N cm-2.174
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13 Temperature, humidity and pressure sensors have been incorporated in textiles.177 These
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15 studies have utilized photolithography and inkjet printing to create the sensors woven into
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18 textiles (Figure 6d). Capacitive humidity and resistive temperature sensors were developed on
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20 flexible polymer foils and integrated into textiles.175 To fabricate the sensors, metal films were
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22 deposited on polyimide sheets. In photolithography, a double metal layer of Cr/Au was electron
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25 beam evaporated under vacuum on polyimide sheets and patterned using a lift-off process. The
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27 sensing elements included an interdigitated thin-film capacitive transducer, and temperature
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29
sensitive thin-film meander-resistor. The inkjet printing of the sensors involved depositing Ag
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32 NP ink on the polyimide. Bus lines and interdigitated finger electrodes were printed in two
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34 separate printing steps (500-4000 dpi). The resulting line width and electrode gaps for resistors
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37 and capacitors were 80 µm, and the thickness of the printed layer was 400 nm. Sensing materials
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39 were encapsulated by laminating a photoresist film on the substrate. For the detection of
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41 humidity, cellulose acetate butyrate as the sensing medium was spray-coated on the capacitor
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44 through a stencil mask. In inkjet printing, the cellulose acetate butyrate in hexyl acetate was
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46 printed over the substrate to achieve a 5 µm film. The device was capped with a hydrophobic,
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48 gas permeable membrane. Subsequently, a commercial machine was used to weave the sensors
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51 into a textile band in weft direction with twill (1/8) pattern. Humidity and temperature sensors
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53 were inserted into the textile along the weft direction as replacement for weft yarn. Warp threads
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were replaced by conductive yarns to contact with the sensors inside the textile. The temperature
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sensors operated from 10 to 80 °C with a sensitivity of 5 °C. Humidity sensors had a detection
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6 range from 25 to 85 % with 10 % sensitivity.175 These textiles were combined with LEDs to give
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8 visual sensing information (Figure 6e).178
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Metal-Organic Frameworks (MOF) built with rare earth elements and/or quantum nanorods
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13 have been immobilized on cotton fabrics at high concentrations.179 These materials have shown
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15 the potential to be used as colorimetric sensors to detect the presence of toxic gases via the
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18 luminescence of the MOFs or the electrical conductivity of the nanorods.180 These chemical
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20 sensors can be incorporated into uniforms, apparels or any textile substrate. A dress designed by
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22 Matilda Ceesay using cotton mesh coated with a Cu benzene tricarboxylic acid MOF-199
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25 customized for capturing and controlled-release of permethrin (an insecticide) (Figure 6f). The
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27 designer aimed at functionalizing mosquito bed-nets commonly used as preventive measures in
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areas with high prevalence of malaria.176
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34 TOXICITY OF NANOMATERIALS IN TEXTILES
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37 The forms of NP released in washing liquid depend on the nanomaterial characteristics
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39 originally incorporated into the textile, the composition of the washing liquid, the washing
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41 procedure (e.g. rotation speed). Ag-containing textiles release significant amounts of dissolved
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44 and particulate Ag into washing liquid. The potential exposure to Ag NPs from a blanket has
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46 been evaluated. For a blanket containing 109.8±4.1 mg Ag kg-1, 4.8 ± 0.3 mg Ag kg-1 was
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48 released into sweat in 1 h.181 Commercial NP-impregnated socks (1360 µg-Ag g-1) leached up to
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51 650 µg of Ag in distilled water (500 mL) in 24 h.71 However, other commercial socks containing
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53 large amounts of Ag (2105 µg and 31242 µg) released small percentages (1 wt%) of total Ag into
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the ultrapure wash water while some brands released ~100 wt% of the Ag after four consecutive
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steps. These studies indicate that the manufacturing processes of these socks differ
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6 fundamentally. The socks released 155 µg and 15 µg of Ag into ultrapure water and tap water,
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8 respectively. Hence, tap water was less aggressive in stripping Ag from the textile than ultrapure
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water, which was attributed to differences in water corrosivity.15 Artificial sweat was also used to
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13 test the concentration of the Ag released from fabrics.182 The concentration of Ag released from
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15 Ag-impregnated fabrics was measured up to 322 mg kg-1 of fabric weight. The release rate
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18 depended on the concentration of the Ag in the fabric and pH of sweat. In another study, shirts
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20 and pants impregnated with TiO2 NPs ranging from 2.9-8.5 g Ti kg-1 textile.183 The release of
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22 TiO2 into sweat per gram of textile after 30 min incubation in 120 mL of sweat was evaluated.
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25 Substances released into acidic sweat were 63 ± 13 µg g-1L-1 (particulate size<450 nm) and 725 ±
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27 30 µg g-1 L-1 (particulate size >450 nm); whereas in alkaline sweat, the release amounts were 38
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± 13 µg g-1 L-1 (particulate size <450 nm) and 188 ± 213 µg g-1 L-1 (particulate size >450 nm).19
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32 External dermal exposure for TiO2 was as maximal 11.6 µg kg-1 body weight for total (mainly
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34 particulate) TiO2. When Ag was released from textiles, Ag-chloro complexes were the major
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37 dissolved species due to the presence of high chloride concentration in sweat. Figure 7 shows
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39 potential scenarios for Ag release from nanomatarial treated textiles.
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27 Figure 7. Scenarios for Ag release and subsequent transformation from nanomaterial-treated
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textiles. Blue shading indicate conventional materials or silver nitrate (AgNO3) that persists
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32 through the transformation process, and red shading indicate pristine nanomaterials. Green
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34 184
shading show a transformation product. Reprinted with permission from ref . Copyright 2014
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37 American Chemical Society.
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41 The release of NPs to the environment is a concern. Ag NPs are toxic to aquatic animals
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44 including fish, crayfish, and plankton.185-188 Furthermore, the antibacterial properties of Ag NPs
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46 might disrupt the bacterial habitat in sewage treatment plants.189 Nanowashing machines were
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shown to release Ag in effluent at a concentration of ~11 µg L-1.190 Recent life cycle assessments
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51 involved comparing environmental benefits and negative effects of nanoAg T-shirts with
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53 conventional textiles treated with triclosan (a biocide).191 Figure 8 shows lifecycle stages of one
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T-shirt (1.56 m2 textile, 130 g). The “cradle-to-gate” climate footprints of the manufacturing of
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nanoAg T-shirt were 2.70 kg of CO2-equiv for flame spray pyrolysis, and 7.67-166 kg of CO2-
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6 equiv for plasma polymerization with Ag co-sputtering. However, conventional T-shirts
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8 produced by triclosan had emissions of 2.55 kg of CO2-equiv. Additionally, the toxic releases
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from washing and disposal stages had minor relevance. However, the production phase holds
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13 importance due to toxic Ag emissions at mining sites. Overall, the use phase was the most
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15 important in terms of climate footprint in both nanoAg and triclosan cases. A limitation of these
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18 studies was that variation in Ag release rates was not taken into consideration. Also, current life
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20 cycle impact assessment methods do not distinguish colloidally bound phases of metals.192, 193
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22 Up to now, the life cycle assessments took into account only NP form. Considering other forms
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25 of nanomaterials such as ionic forms, agglomerated forms, and oxidized forms will provide
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27 improve life cycle assessments. While these assessments provide estimated effect of
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nanomaterials on the environment, public awareness holds importance in washing practices. For
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32 example, efficient washing procedures such as using tumblers less, and operating washing
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34 machine at lower temperatures with appropriate detergents may reduce the environmental
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37 impact. The increase in the awareness for recycling rate of NP embedded textiles may reduce the
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39 carbon footprint. Furthermore, exposure to NPs is a significant concern at workplace.194 For
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41 example, spraying methods may result in exposure to inhalation of NPs.195 The development of
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44 improved life cycle assessments will allow comparing nanoengineered textiles with conventional
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46 products in the market to prevent environmental consequences.
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24 Figure 8. Lifecycle stages of one nanoAg T-shirt showing system boundaries (dashed boxes).
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26 Reprinted with permission from ref 191. Copyright 2011 American Chemical Society.
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31 CONSOLIDATION OF NANOTECHNOLOGY IN TEXTILES MARKET
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33 Fashion and apparel industries were valued at $1.2 trillion globally in 2014, and the market
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35 size is expected to have a Compound Annual Growth Rate (CAGR) of 4.8% until 2025, mainly
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38 driven by emerging markets.196,197 In the United States, 1.9 million people are employed, and
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40 $250 million is spent in fashion industry annually.25 In 2014, the global smart textiles market
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was assessed as $795 million, which is anticipated to reach $4.72 billion by 2020 with a CAGR
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45 of 33%.198 Major drivers for the smart textiles market are wearable electronics, increasing
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47 demand for devices with advanced functions, miniaturization of electronics, and rapid growth of
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50 low-cost wireless sensor networks. Military and security sectors have the largest shares of the
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52 smart textiles, accounting for about 27% of the total market. The market shares for the sports and
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54 fitness segments are expected to increase at a CAGR of 40% until 2020.198 Americas was
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57 accounted for 41% of the global smart textiles market in 2014, followed by Europe (25%), and
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Asia-Pacific (21%) in 2014 (Figure 9). However, Asia-Pacific market is expected to have highest
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6 CAGR (44%) in the next five years. The United States market is projected to grow at a CAGR of
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8 31% until 2020.198 High growth rates may be attributed to trends outside conventional apparels.
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This is because in the traditional apparels, there is more demand for cost reduction, as oppose to
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13 performance enhancement. In the case of innovative and functional applications of wearables,
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15 the customer motivation is opposite.199 Furthermore, the market for nanofiber-based products is
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18 expected to reach over $1 billion by 2020.200 However, this market is not limited to textile and
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20 apparel industry.198, 201 With a demanding market for wearables and a growing trend for nano-
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22 fiber based products, the applications are diverse for the nanotextile products ranging from
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25 consumer apparels to medical wearables.202
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43 Figure 9. Smart textiles market. (a) Market shares and CAGRs by region in 2014198. (b) North
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45 America smart textiles market revenue by end-use, 2012–2020198
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A driving force for the smart textiles industry is sensing technologies with Internet
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51 connection. This capability can be used to communicate data such as location, as well as
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53 physiological parameters (e.g. heart rate), which are important in healthcare, sports, and fitness.
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Therefore, this trend is expected to affect the market globally. For example, the use of functional
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materials in textiles has led to electrophysical characteristics such as piezoresistive and
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6 conductivity. These technologies can aim to evaluate the patient's synoptic data. The process
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8 involves the development of smart textiles, communicating the data over the network, and using
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it to make informed decisions. One of the challenges facing the apparel industry in the use of
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13 such communication devices is ensuring simultaneous wearability, and functionality of efficient
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15 and portable power supplies.
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18 In general, fashionable functional products transcending the traditional functions of fabric are
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20 highly desirable. Growth in the fashion and entertainment industry is expected to contribute to
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22 overall market growth. Additionally, the demand from the sports and fitness sector has increased
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25 due to growing awareness about healthy lifestyles. End users participating in extreme sports,
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27 running, skiing, have also contributed to the demand for smart textiles. To increase the
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competitiveness with respect to Asia, European Union has created initiatives for promoting
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32 incentives.203 The European Commission has co-financed a number of projects such as Wealthy,
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34 MyHeart and Biotex. For example, Wealthy aims to create a wearable device for monitoring
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37 patient's vital signs.
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39 To meet a wide range of end user needs, it is vital to market smart wearables that offer
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41 various levels of performance and comfort to wide customer base. The necessity for various
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44 levels of performance stems from global customers who are willing to pay a premium price for
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46 smart functional garments. However, in another market segment, the target customer may
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48 demand affordable functional textiles. One possible reason for the interest in innovation in
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51 textiles is that porous materials, synthetic microfibers and membranes used commercially over
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53 the past 30 years have been commodified. This may be attributed to the accessibility of
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blockbuster technologies due to patent expirations. The commodification subsequently reduced
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profit margin and market share.200 As a result, companies in the textile industry need to offer
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6 competitive advantage through innovation by either enhancing performance or reducing the
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8 production cost.
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12 CASE STUDIES
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14 Gore-Tex is a lightweight, waterproof, breathable fabric membrane comprising of expanded
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polytetrafluoroethylene (ePTFE) for application in medical devices, fabrics, and electronics.44, 204
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19 W. L. Gore & Associates (Newark, DE) invented ePTFE in the 1970s. Gore-Tex was originally a
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21 microporous structure that could be stretched up to 800% of its original length.205 Gore-Tex is
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used in products manufactured by various enterprises including Patagonia, L.L. Bean, Oakley,
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26 Inc., Galvin Green, Marmot, Vasque, Arc'teryx, Haglöfs, and The North Face.206,207 W. L. Gore
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28 & Associates holds more than 71 issued patents related to Gore-Tex or the use of PTFE, in which
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31 18 patents are for use in garments. Although the basis for the Gore-Tex technology originated
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33 from microporous structures, the company has recently incorporated nanostructures into their
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35 products for the apparels market. For example, Nano and NanoPro jackets have been
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38 manufactured in conjunction with Marmot LLC.208 Other nanotechnology-based examples could
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40 be seen in the company’s patent portfolio. Examples include Nyagraph 351 (Nyacol Nano
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Technologies, Inc) for burn protective materials,209 nanoemulsions of functionalized PTFE,210
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45 prefiltration layers comprising of nanofibers,211 and NPs for improved insulated electrical
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47 conductors.212 These cases serve to illustrate the importance of nanotechnology to a well-
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50 established innovative company in the apparel industry.
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52 NanoSphere® marketed by Schoeller Textiles AG (Sevelen, Switzerland) is a finishing
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54 technology with hydrophobic surface properties that mimic the self-cleaning effect of lotus
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57 leafs.39 Schoeller claims that NanoSphere® has improved water/oil and dirt repelling properties,
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and washing performance as compared to traditional textile impregnation-based manufacturing.
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6 Furthermore, the protective function of NanoSphere® may be retained after frequent use and
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8 numerous washing cycles without affecting comfort, texture, and breathability. The textiles
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finished with NanoSphere® require less frequent washing at lower temperatures as compared to
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13 conventional textiles. Additionally, it has high abrasion resistance. The company’s other
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15 products address a variety of applications ranging from stretch fabrics, sun reflectors, and
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18 temperature resistance, and bionic climate conditioning.213 Their patent portfolio in
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20 nanotechnology includes PEIN NPs for antibacterial finishing of electrospinnable polymers,214
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22 NPs and CNTs for finishing of substrates,215 and nanofibers having microbicidal properties.216
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25 Aquapel, marketed by Nanotex LLC (Bloomfield Hills, MI), reproduces natural water-
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27 repellency of plant surfaces and animal coats.179 Aquapel technology involves permanent
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attachment of hydrophobic ’whiskers’ to individual fibers at the molecular level. Aquapel
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32 features a hydrocarbon polymer that is ecologically friendly and low-cost. Nanotex’s portfolio
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34 consists of 28 WO patent applications and addresses textile sectors including repellency/stain
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37 resistance, moisture management, odor control, static elimination, and wrinkle resistance. In
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39 2013, Nano-Tex products were on $280 million in branded products at retail.10 In the same year,
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41 Nanotex was acquired by soft-surface technology company Crypton Inc.217
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44 SmartSilver® is an antimicrobial yarn marked by NanoHorizons (Bellefonte, PA). It
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46 develops and manufactures Ag NP additives that provide antimicrobial characteristics to their
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48 products. The company markets Oeko-Tex® antimicrobial solution under the SmartSilver®
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51 brand.218,219
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53 Nanosan, marketed by SNS-Nano Fiber Technology (Hudson, OH) and Schill & Seilacher
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(Germany), consists of spun polymers for application in filters and adsorbent fabrics.220 SNS-
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59
60
44
1
2
3
Nano Fiber Technology integrates microscale particles into the nanofiber structure at high-
4
5
6 volume production. Nanosan fibers can be engineered to be function as high-strength, absorbent,
7
8 or flexible material. Its product line consists of nanofiber matrixes with different absorption
9
10
11
properties. The applications of Nanosan include filters, medical and military products and
12
13 personal care products such as cosmetics. Its patent portfolio includes debris and particle
14
15 absorbent materials.221,222,223,224 The company is currently exploring the use of nanofibers for
16
17
18 skin decontamination.
19
20 Wearable Motherboard™ (electronic shirt), marketed by Sarvint Technologies, Inc.
21
22 (Atlanta, GA), uses engineered fibers to sense body signs, such as heart rate, temperature, skin
23
24
25 conductivity, muscle exertion, blood pressure, and respiration rate.164 Its patent portfolio includes
26
27 the use of engineered fabric-based sensors (e.g. conductive fibers) for monitoring vital signs. Its
28
29
technology comprises microporous elastic Spandex fiber, a polyester-polyurethane copolymer
30
31
32 invented in 1958.225-227 Table 1 shows the companies involved in smart textiles and wearables
33
34 market.228 Some of these companies use microtechnology as opposed to nanotechnology in
35
36
37 apparels.
38
39
40
41
42 Table 1. Companies that have commercialized micro and nanotechnology-based apparels, their
43
44
45
major products and applications.
46
47
48 Number of
Area
49 Year Pending Technology &
Company (µ Applications Ref.
50 founded patents Products
/Nano)
51 /granted
52 Auxetic materials
Auxetic
53 (becomes thinner when Composite material, 229-231
Technologie 2004 3 µ/Nano
54 stretched, and thicker auxetic foams
s Ltd (UK)
55 when compressed)
56 Brandix Fabric and garment
2002 N/A Nano Functional clothing N/A
57 Lanka accessories
58
59
60
45
1
2
3 Limited (Sri
4 Lanka)
5 Comfortable
6 Clothing Heart rate sensing shirt biometric sensor
7 Plus Ltd 2001 2 µ (Combined textiles and electronics for 232, 233
8 (Finland) electronics) sports and medical
9 applications
10 1802 (sold
11 >100, out
its textiles Stretchable,
12 of which
DuPont business to Lycra (spandex), compression and 234-243
13 32 is µ/Nano
(US) Koch a stretch fiber shaped garments,
14 related to
Industries in home furnishings
15 garment
2004)
16 FabRoc™ and
17 Wireless heated
Exo2 (US) 2007 N/A Nano ThermoKnitt™ heating N/A
18 outdoor clothing
technology
19 FibeRio
20 Apparel, filtration,
Technology 2 244, 245
21 2009 µ/Nano Micro- and nanofibers healthcare, and
Corporation
22 electronics
(US)
23 Wearable
24 Fibretronic electronics and
25 limited smart fabrics
26 2004 N/A µ Textile electronics N/A
(Hong (sensors, heating
27 Kong) and cooling
28 elements)
29 Housewares and
30 Freudenberg
cleaning products, Nonwoven fabrics
31 Group 1849 N/A µ/Nano N/A
automobile parts, and and textile materials
32 (Germany)
textile
33 Thermoelectrically
34 Gentherm heated and cooled
35 Heating and cooling 246-255
Incorporated 1960 18 µ seat system
36 comfort
(US) (automotive,
37 medical, bedding)
38 1998,
39 Jacquard: a microfiber-
partnered Textile with digital
40 Google Inc. woven textile
with Levi N/A µ sensing microfibers N/A
41 (US)
Strauss &
42 Co.
43 Hollingswor Composite
44 Filtration and nonwoven 256-258
th and Vose 1843 3 µ/Nano materials, home
45 materials
(US) furnishings, apparel
46 HeiQ Dynamic cooling, water
47 Outdoor products, 1259-264
(Switzerland 2005 6 µ/Nano and oil repellency on
48 medical implants
) textiles
49 Functional textile
50 Interactive products: textile cable, Integrated textile
51 265, 266
Wear AG 2005 2 µ heating pads, interactive systems
52 (Germany) wearable solar energy
53 source
54 International Electronic textiles,
55 Electronically
Fashion which behave as an 267, 268
56 2002 2 µ controllable flexible
Machines, electronic circuit or
57 substrate
Inc. (US) device
58
59
60
46
1
2
3 Midé Piezo cooling, haptic
4 Technolog actuators, energy 269-279
5 1989 11 µ General wearables
Corporation harvesting, data
6 (US) logging)
7 Nanohorizo 218, 219
8 2002 2 Nano Ag NPs NanoAg textiles
ns (US)
9 Nanotex Nanoengineered Moisture resistance, 280-301
10 1998 22 Nano
(US) polymers odor management
11 Ohmatex Elastic textile cables,
12 Textiles combined
Aps 2004 N/A µ conductive textiles, N/A
13 with IT technology
(Denmark) textile-based sensors
14 Electroactive polymeric Force and touch
15 Peratech Ltd 302-313
1996 12 Nano material QTC (Quantum sensing within
16 (UK)
Tunnelling Composites) electronic circuits
17 Sarvint Garment with 226, 227,
18 Technologie 2014 6 µ/Nano Functional wearables intelligence 314-317
19 s, Inc. (US) capability
20 Schoeller Stretchable fabrics, 214-216,
21 Textiles AG 1967 9 µ/Nano protection fabrics, soft
NP-containing
318-323
22 fibers
(Germany) shells, protective fabrics
23 SensiumVitals®, a
24 Sensium lightweight patch
25 Wireless monitoring
Healthcare 2000 N/A µ reading of patients' N/A
26 of vital signs
(UK) heart rate, respiration
27 and temperature
28 Anklet and sensor
29 infused socks and
30 Sensoria Body -sensing wearable 324-326
2010 3 µ fitness bras and t-
31 Inc. (US) devices
shirts with heart rate
32 monitor
33 SNS Nano Debris and particle Textile composite 221-224
34 2007 4 Nano
(US) absorbent materials material
35 Semiconductors, Wearable displays,
36 Texas
microcontrollers Bluetooth wearable
37 Instruments 1951 >100 µ N/A
DLP Products & watch
38 (US)
MEMS
39 Textronics, NuMetrex, soft textile Health and fitness 327-332
40 2005 13 µ/Nano
Inc. (US) sensors monitoring
41 Heated fabric,
42 Thermosoft
conductive textile, 333-344
43 International 1996 6 µ Flexible electric heaters
heated bedding and
44 (US)
clothing
45 Body worn sensors:
46 Hexoskin (Sports Shirt),
47 Nonin (Wrist worn Continuous
48 Bluetooth pulse ambulatory
49 VivoMetrics 345-352
2009 8 µ oximeter), Onyx (Finger physiological
50 Inc (US)
clip Wireless pulse monitoring sensor
51 oximeter, LifeShirt systems
52 (garment with
53 embedded sensors)
54 Wearable Sports, fitness,
55 Information Smart fabrics and health prevention, 353
56 2007 1 µ
Technologie interactive textiles healthcare, and
57 s (Weartech) industrial safety
58
59
60
47
1
2
3 (Spain)
4 48 (Gore-
5 W. L. Gore Gore-Tex is a Widespread 205, 354-
Tex or
6 & 1958 µ/Nano waterproof, breathable products, including 372
PTFE): 13
7 Associates fabric membrane fashion and apparel
in garments
8
9
10
11
FUTURE DIRECTIONS
12
13 The integration of high-computing microprocessors and miniaturized computers can enable
14
15 the capability to collect information throughout a garment. For example, the physiology of the
16
17
18 body and posture data collection in garments could allow for correcting the unhealthy posture.
19
20 Wearing high heels shifts the center of gravity forward, and this causes disturbances in the
21
22 posture. This produces strains on the calf muscles and thigh muscles, and a forward tilt in the
23
24
25 pelvis. These changes have negative implications in the body including misalignment of hips and
26
27 spine and increase in the pressure on the forefoot, leading to degenerative arthritis in the knee.
28
29
New wearable technologies can be incorporated in garments and shoes to measure the pressure
30
31
32 and posture pattern and alert the user. Such technologies can be imparted to be active to loosen
33
34 or stiffen the dress, or shoe based on the motion to prevent pain or sag. Weight loss is another
35
36
37 potential area that can be explored with nanomaterials. For example, vibration motors can be
38
39 integrated in textiles to promote blood circulation and weight loss. These devices may also
40
41 achieve wireless powering of the internal or external electrical components. For example, self-
42
43
44 winding mechanisms developed in automatic watches can be utilized to generate energy from the
45
46 movement of the body. A significant area that nanotechnology-based energy sources can provide
47
48 a solution is cooling. Highly-dense fabric batteries or solar cells need to be developed to power
49
50
51 cooling without compromising comfort. Such powering mechanisms can be coupled with phase-
52
53 change materials to cool the body in hot environments, or cool the electronic components in the
54
55
56
textile.
57
58
59
60
48
1
2
3
Interactive garments in fashion will also evolve. Programmable visual components, LEDs
4
5
6 and fiber optics in garments will find increasing use in fashion and entertainment industries.
7
8 Incorporation of new approaches including structural colors, luminescence, plasmonics,
9
10
11
metamaterials, holography, photonic crystals (PCs) and LED displays in textiles can create
12
13 mesmerizing effects on garments. These dresses can be combined with pressure or motion
14
15 sensors that can change the color of the dress based on touch, movement, temperature, light,
16
17
18 electric field, or other external stimuli. The material may also include bioinspired patterns and
19
20 chemical reactions with the environment.
21
22 In addition to serving as light emitting elements to enable the shinning and colorful
23
24
25 appearance for fashion apparels, optical fibers offer more capabilities. For example, an array of
26
27 fibers can be weaved into a garment to constitute a programmable fiber-optic display that is able
28
29
to show dynamic graphics. Optical fibers can also be used as sensing components in
30
31
32 multifunctional garments for sports and fashion. Recently, Cambridge Consultants has developed
33
34 Xelflex fabric that was equipped with optical fiber sensors for tracking movements of human
35
36
37 body.373 Xelflex could be used in fitness and sports coaching as well as part of physiotherapy.
38
39 Additionally, fiber sensor-based gloves and garments that can recognize postures of human hand
40
41 and body have been demonstrated.374 Physical or biological measurements may be detected by
42
43
44 on-garment fiber sensors such as strain, pressure, temperature, humidity, and metabolites.375
45
46 Thus, in the near future a fully functionalized sportswear based on fiber-optics sensors will be
47
48 produced for monitoring of physiological conditions of human body including heart beating rate,
49
50
51 blood pressure, sweating, body motions, temperature, and even potential disease risks. Such
52
53 garments can also be used for increasing the interaction and connectivity of user with gaming
54
55
56
consoles and virtual reality platforms.
57
58
59
60
49
1
2
3
Integration of optical displays into textiles or garments is desirable for many applications.
4
5
6 Current textile displays are mostly based on LEDs. Although LEDs are low cost, small, and
7
8 available in an array of different colors, they are not truly compatible with textiles due to their
9
10
11
rigidity. Additionally, the resolution of the LED textile displays is typically low (LED pitch: 1-
12
13 100 mm).376 The LCDs that are commonly used in current smartphones, tablets and computers
14
15 are usually inflexible.377 Considering the flexibility and light weight required for textile displays,
16
17
18 OLEDs composed of thin films of organic molecules constitute a potential candidate.378 Another
19
20 promising technology for the fabrication of textile displays is quantum-dot light emitting diode
21
22 (QLED), which is similar to OLED in structure but have an additional active layer consisting of
23
24
25 quantum dots.379, 380
In textile displays, QLEDs could offer higher luminance efficiency and
26
27 consume less energy than OLEDs. These technologies maybe combined with optical components
28
29
such as diffraction gratings, diffusers, lenses, or microcavities.381-384
30
31
32 Photonic crystals are nanostructures in which the dielectric constant has a periodic variation
33
34 in one, two or in all three orthogonal directions.385-387 In such structures, one observes formation
35
36
37 of the spectral photonic bandgaps, which are the spectral regions where photons are unable to
38
39 propagate in the bulk of the periodic structure. Therefore, narrow-band colors could be seen in
40
41 the light diffracted or transmited by PCs. They can be incorporated into flexible thin films that
42
43
44 may be conveniently attached to a fabric or garment.388, 389 These PC films may have their color
45
46 changed when stimulated by external stimuli such as current, compression, stretch, or
47
48 temperature and humidity. The structural parameters of PCs or the effective refractive index of
49
50
51 PCs are modified by these stimuli, thus shifting the PC spectral bandgaps.390, 391
This color-
52
53 tuning property may be utilized for garments to not only promote the aesthetic performance, but
54
55
56
also enable the garments for sensing applications.392
57
58
59
60
50
1
2
3
Combining holograms with garments and wearable devices is another potential research
4
5
6 direction.393, 394 A hologram is first produced by encoding interference information of an object
7
8 on a recording medium. A 3D image of the recorded object could be reconstructed by
9
10
11
illuminating the holographic film with a broadband light.395, 396 To date, a variety of holographic
12
13 films have been used as decorative coatings that are able to provide garments with iridescent
14
15 appearances and 3D graphics.145 Holograms may also be used in other wearable gadgets such as
16
17
18 helmets and glasses for virtual-reality applications. In Hololens (Microsoft), holographic gears
19
20 are equipped on a headset.397 Thus, wearers of Hololens may appreciate a virtual life experience
21
22 by visualizing and interacting with the environment on demand. Moreover, holographic sensors
23
24
25 that are fabricated into thin films could also be integrated into garments for detecting metabolic
26
27 function.398-403
28
29
Metamaterials are artificial structured substances made by assembling composite materials
30
31
32 such as metals and plastics in periodic patterns at scales that are smaller than the wavelength of
33
34 interest.404 Metamaterials due to their extraordinary structures exhibit complex behavior to
35
36
37 electromagnetic waves (e.g. negative refractive index). Many intriguing features could be offered
38
39 by metamaterials when used in textiles and garments. For example, metamaterials have potential
40
41 for the development of cloaking devices that are used to make a defined region invisibly isolated
42
43
44 from the passing electromagnetic waves. While some progress on metamaterial-based cloaking
45
46 devices was made at microwave405 and THz frequencies,406, 407 truly invisible garments may be
47
48 realized in the visible spectral region. Moreover, many thin-film metamaterial sensors have been
49
50
51 demonstrated.408 These sensors could be potentially integrated into textiles and garments for
52
53 monitoring physiological biomarkers.
54
55
56
57
58
59
60
51
1
2
3
Nanotextiles can be functionalized with molecular dyes and analyte-sensitive compounds.
4
5
6 For example, microfluidics can be incorporated in thread-based channels for application in point-
7
8 of-care diagnostics.409-417 In the future, we expect many functional components being seamlessly
9
10
11
integrated into textile architecture. Accordingly, production processes will also evolve to
12
13 combine electronics, biomaterials, and optics into textile weaving. Applications in fashion and
14
15 arts will also be realized.418, 419
These sensing and display technologies may be controlled by
16
17
18 smartphones.420-422
19
20 Another potential research area is to create green chemistries and fabrication approaches to
21
22 synthesize nanomaterials that stay intact after laundering. For example, development of new
23
24
25 covalent binding mechanics to attach nanomaterials to cotton or synthetic fibers is desirable.
26
27 These nanomaterials may also require new surface finishing processes to ensure their
28
29
immobilization in textiles and maintenance any environmental condition. Additionally,
30
31
32 agglomeration of deposited nanomaterials is a major challenge and this requires the development
33
34 of new nanoadditives and stabilizers in formulations and finishing treatments. These approaches
35
36
37 may require functional surface-activated polymer or cotton composites to immobilize
38
39 nanomaterials on textile without comprising their chemical, optical, and electrical properties.
40
41 Furthermore, recycling of clothing is generally carried out by creating landfills. A significant
42
43
44 concern about the nanomaterials is potential contamination of water or soil.184 Hence, life cycle
45
46 assessments should also focus on identifying risk factors for laundering, recycling and particle
47
48 release after degradation while accounting different forms of nanoparticles and release rates.
49
50
51 Effects of uncontrolled release of nanomaterials to the environment, and toxicity to humans,
52
53 marine life needs to be evaluated before the introduction of nanoproducts to the market. Since
54
55
56
these nanomaterial-based textiles are likely to be produced in the emerging economies, the safety
57
58
59
60
52
1
2
3
of the workers and exposure to nanomaterials warrant nanotoxicity analyses. The
4
5
6 commercialization of nanotechnology-based textiles may be limited due to government
7
8 regulations. For example, Biocidal textiles containing nanoAg are registered by the Environment
9
10
11
Protection Agency (EPA) in the United States.193 ISO catalogue enlists a number of standards for
12
13 formulating and testing nanoproducts.423
14
15
16
17
18 CONCLUSIONS
19
20 The customer demand in improved appearance, functionality, and connectivity in fashion has
21
22 motivated the development of nanotechnology-based textiles. Over the last two decades,
23
24
25 numerous nanostructures and nanomaterials including NPs, CNTs, Bragg diffraction gratings,
26
27 and nano-electronic components have been deposited or woven into textiles. The development of
28
29
these nanomaterials also created new fabrication methods involving particle impregnation, spray
30
31
32 coating, multifunctional composite fiber drawing, and direct weaving at industrial scale. The
33
34 application of nanomaterials in the form of surface modifications, electronics and optics offers
35
36
37 functionality as well as the potential of improved appearance. Realized nanotechnology
38
39 applications in textiles include antibacterial properties, odor control, UV protection, water
40
41 repellence, wrinkle resistance, antistatic properties, and strength enhancements. Advanced
42
43
44 technologies included incorporation of moisture, temperature, pressure sensors, drug release, and
45
46 fiber optics powered by textile-based batteries. With the emergence of nanomaterials, these
47
48 technologies are transitioning from rigid to seamlessly integrated flexible substrates while
49
50
51 offering light weight.
52
53 In parallel to the development of nanotextiles, life cycle assessments and toxicity of released
54
55
56
nanomaterials from textiles are being critically evaluated. Nanotechnology-based products will
57
58
59
60
53
1
2
3
continue to emerge with new applications; however, manufacturers and regulatory agencies must
4
5
6 ensure that these technologies will not have a negative effect on human health and the planet
7
8 during their manufacture and life cycle. The textile industry is under scrutiny due its impact on
9
10
11
climate change.424 Today textiles and apparels account for ~10% of the total carbon emissions.425
12
13 17-20% of industrial water pollution originates from dyeing and finishing agents in textile
14
15 industry, negatively affecting people inhabiting regions around textile production plants,
16
17
18 particularly in the developing world.426 The use of dyes and fixing agents (e.g., chromium) in
19
20 textile manufacturers and tanneries are major pollutants, particularly in Southeast Asia.427 Hence,
21
22 the effect of nanoproducts on the production dynamics and pollution remains questionable.
23
24
25 Growing concerns among customers has begun forcing the manufacturers to reduce the
26
27 environmental impact of their production methods, which will also involve the use of
28
29
nanomaterials.428, 429
Social awareness among customers has probed companies to invest in
30
31
32 corporate social responsibility to offer environmentally sustainable products with reduced carbon
33
34 footprints.430-432 These trends in customer behavior and climate change will involve the use of
35
36
37 nanotextiles, which need to be climate neutral and recyclable aimed at reducing greenhouse
38
39 emissions. Nanotechnology will undoubtedly evolve textiles transcending style changes to shape
40
41 the next big concept: the connected couture.
42
43
44
45
46 AUTHOR INFORMATION
47
48
49 Corresponding Author
50
51
52
* e-mail: ayetisen@mgh.harvard.edu, syun@mgh.harvard.edu
53
54
55 Author Contributions
56
57
58
59
60
54
1
2
3
A.K.Y. designed the project. A.K.Y. and H.Q. wrote the article. A.M. contributed to Market and
4
5
6 Case Studies sections. S.H.Y., A.K., H.B., J.H., and M.S. made intellectual contributions and
7
8 edited the manuscript.
9
10
11 Notes
12
13
14 The authors declare no competing financial interests.
15
16
17 ACKNOWLEDGMENT
18
19
We thank Huseyin Avci for discussions.
20
21
22
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26 Scenarios for Ag release and subsequent transformation from nanomaterial-treated textiles
27 147x82mm (150 x 150 DPI)
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32 Lifecycle stages of one nanoAg T-shirt showing system boundaries
33 457x214mm (95 x 150 DPI)
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21 Smart textiles market
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Nanotechnology in Textiles

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Article in ACS Nano · February 2016

Amir Manbachi Haider Butt

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Mehmet R Dokmeci Juan P Hinestroza

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Journal: ACS Nano

Manuscript Type: Review

Date Submitted by the Author: 28-Dec-2015

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