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graphene nanocomposites
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Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites Mingwei Tian a,b,c,1, Xiaoning Tang a,b,1, Lijun Qu a,b,c,n, Shifeng Zhu a,b, Xiaoqing Guo a,b,c, Guangting Han b,c a
College of Textiles, Qingdao University, Qingdao, Shandong 266071, China Laboratory of New Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, Qingdao University, Qingdao, Shandong 266071, China c Collaborative Innovation Center for Marine Biomass Fibers, Materials and Textiles of Shandong Province, Qingdao University, Qingdao, Shandong 266071, China b
art ic l e i nf o
a b s t r a c t
Article history: Received 1 January 2015 Accepted 28 January 2015
To ameliorate the ultraviolet blocking performance of cotton fabric, novel chitosan/graphene (0.1–1 wt%) nanocomposites were prepared as functional UV blocker, and then deposited on the surface of fabric substrate via a pad-dry-cure approach. The as-obtained fabrics were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. The ultraviolet protection factor (UPF) of the fabric incorporating graphene 1 wt% could reach to 465.8, up to 60-fold higher than that of pristine cotton fabric (UPF 7.31), meaning that low graphene content (o1 wt%) could dramatically enhance the UV-blocking property of substrate with the aid of chitosan as dispersant. Furthermore, the treated cotton fabric also performed excellent washing durability after 10 times water laundering. Chitosan/graphene nanocomposites could be recommended as the remarkable efficient and durable UV-blocking additive for UV-blocking industrial applications. & 2015 Published by Elsevier B.V.
Keywords: Graphene Chitosan UV blocking fabric Nanocomposites Functional
1. Introduction Graphene, as the basic structural element of carbon allotropes, has dramatically attracted a great deal of interest in recent years [1]; its unique virtually single layer of carbon atoms two-dimensional structure endowed some exceptional properties and magical performance [2]. Recently, some researchers have been carried out to attempt to exploit the potential application of graphene in textile field [3–5]. For instance, Molina et al. [3] obtained conductive graphene coated fabric by readily dipping polyester fabric into graphene oxide (GO) dispersion. Shateri-Khalilabad and Yazdanshenas [4] fabricated the superhydrophobic and electroconductive fabric coating with reduced graphene oxide by chemical oxidation reduction. These previous research only deposited graphene on fabric surface by readily mechanical binding methods which could not effectively and durably graft the graphene on the fabric; furthermore, graphene had a pronounced tendency to irreversible aggregation during the preparation process, leading to significantly attenuate functional performance of graphene. Based on above analysis, combining reasonable dispersants with graphene could be
n Corresponding author at: College of Textiles, Qingdao University, Qingdao, Shandong 266071, China. E-mail address: [email protected] (L. Qu). 1 These authors equally contributed to this work.
viewed as the effective and facile route to improve the distribution conditions and durable period of graphene on the fabrics surface. Chitosan (CS), owing to excellent biodegradability and biocompatibility, has attracted significant attention in a broad range of applications [6]; meanwhile, chitosan based materials have also been investigated in the application of super-hydrophobic, antibacterial and electrical conductive textiles [7–9]. Here, in this paper, chitosan was employed as the dispersant and binding additive of graphene to form a homogenous nanocomposite system; therefore, graphene could uniformly and individually disperse in chitosan matrix; afterwards, the cotton fabrics were functionalized with the aid of chitosan/graphene nanocomposites and exhibited robust UV blocking performance.
2. Experimental Graphene nanosheet (GNS) with thickness (1–3 nm) and size (20–25 μm) was supplied by Ningbo Moxi Science and Technology, China; GNS was stably dispersed in aqueous solution with 20 mg/mL. Chitosan (degree of deacetylation 93%, average molecular weight (MW) 125,000 g/mol) was kindly donated by Qingdao JiFa Group, China; acetic acid (CH3COOH) was supplied by National Medicine Group, China. Commercial cotton fabric (plain woven, 160 g/m2) was used as the fabric substrate.
http://dx.doi.org/10.1016/j.matlet.2015.01.147 0167-577X/& 2015 Published by Elsevier B.V.
Please cite this article as: Tian M, et al. Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites. Mater Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.01.147i
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Chitosan powder was first dispersed into distilled water containing 2% (v/v) acetic acid to prepare 2 wt% chitosan solution. Then, the required concentration (0.1, 0.3, 0.6 and 1 wt%) of GNS was added into the chitosan solution and vigorous stirred for 5 h. Afterwards, the cotton fabrics were impregnated in chitosan/graphene solution for 2 h, and then padded through two dips and two nips to reach an average wet pickup of 80%; the padded fabrics were then washed to remove the unreacted starting compound, and then dried at 70 1C for 10 min; the following curing was carried out at 110 1C for 10 min. The as-prepared fabrics were named as CS-Cotton, CS-G 0.1, CS-G 0.3, CS-G 0.6, CS-G 1. FTIR spectra of modified fabric were recorded with a Nicolet 5700 FT-IR Spectrometer (Thermo Nicolet Corporation, USA). The morphological structure was detected with scanning electron microscopy (SEM, JSM-5600LV). The ultraviolet blocking efficiency was recorded by a UV spectrophotometer (UV1000F, Labsphere, USA). Laundering durability of the treated fabric was measured according to AATCC Test Method 61-2006.
3. Results and discussion The FTIR spectra for chitosan/graphene nanocomposites modified cotton fabric are illustrated in Fig. 1. The control cotton fabric
Fig. 1. FTIR spectra of chitosan/graphene modified cotton fabrics.
depicted the absorption peaks at 3420, 2900, 1640, 1420 and 1070 cm 1 attributing to the OH stretching, CH stretching, OH of water absorbed from cellulose, CH2 symmetric bending and C–O stretching, respectively. After depositing chitosan on the surface of cotton fabric, two more characteristic peaks appeared at 1570 and 1170 cm 1 corresponding to the –NH bending and C–N stretch of chitosan [10]; however, the absorption peaks of –NH group-stretching vibration in chitosan around 3400 cm 1 were absent which might be caused by the intermolecular hydrogen bonds between cotton fabric and chitosan. In addition, in CS-G 1, the peak at 1570 cm 1 disappeared, implied that the hydrogen bonds occurred between chitosan and graphene. As shown in Fig. 2, the morphology of fabric with different chitosan/graphene nanocomposites can be obviously detected along with the control cotton fabric. Typical longitudinal fibril structure with some natural stripes could be detected on the control cotton fiber surface (Fig. 2a), after coating with chitosan, the CS-Cotton fiber tended to more smooth and the original natural stripes became faintly visible (Fig. 2b). Once graphene was incorporated into CS-G 0.1–CS-G 1 (Fig. 2c–f), some micro-wrinkled stripes appeared and protruded out from the fiber surface, and such micro-structure gradually increased indicating the increasing amount of graphene contents. More interestingly, it showed the well-dispersed status of graphene in the chitosan matrix without any aggregation, indicating chitosan acted as a reasonable dispersant for graphene. The ultraviolet transmittance spectra of CS-G fabrics are listed in Fig. 3a, the spectra tended to obvious attenuation along with increasing graphene content. Thus attenuation curves demonstrated that evenly deposited GNS acted as an effective component to shield UV-rays across fabric. In order to assess the degree of UV protection of each modified fabric, the ultraviolet protection factor (UPF) was employed and calculated according to the method described in the Australian/New Zealand Standard AS/NZS 4399:1996. In Fig. 3b, CScotton performed nearly the same UPF (9.02) as the control cotton (UPF¼7.31), but by adding only 0.1 wt% graphene in CS-G 0.1, its UPF fast ascended to 17.64, and the UPF value of CS-G 0.3 continued to rise to 35.76, CS-G 0.6–295.4 which has already far beyond the excellent protection UPF rating (50þ ). As expected, for the CS-G 1 fabric, the corresponding UPF value could reach to 465.8 which was up to more than 60-fold higher than that of pristine cotton fabric, meaning that the low graphene content (o1 wt%) could dramatically enhance the UV-blocking property of substrate with the aid of
Fig. 2. SEM images of (a) control cotton, (b) CS-Cotton, (c) CS-G 0.1, (d) CS-G 0.3, (e) CS-G 0.6, and (f) CS-G 1.
Please cite this article as: Tian M, et al. Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites. Mater Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.01.147i
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Fig. 3. The ultraviolet protection ability: (a) UV transmittance spectrum and (b) UPF values.
Table 1 UPF values of various UV protection fabric. No.
Fabric substrate
UV blocker
Treatment method
UPF
Ref.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Cotton Polyester Cotton Cotton Silk Wool Polyamide Cotton Cotton Polyester Cotton Cotton Cotton Cotton Polyester Cotton Cotton Cotton Cotton
Titania nanosols Silk sericin Polyurethane/zinc oxide nanocomposites Titania–silica nanosol FeSO4 CuSO4 ZnO–PMMA nanocomposites Nano-TiO2 Cupper acetate Nanostructured silver Needle-shaped ZnO nanorod PU/MWNT PU/nano-TiO2 Dumbbell-shaped ZnO crystallites Alginates and nano-TiO2 Chitosan/TiO2 FBAs/PDDA TiO2 nanoparticles Chitosan/graphene
Sol–gel process and pad-dry-cure Pad-dry-cure Electrospinning Dip-dry-cure Dyeing process Dyeing process Pad-dry-cure Ester-crosslinking and pad-dry-cure Pad-dry-cure Magnetron sputtering In-situ growth Pad-dry-cure Layer-by-layer deposition Low-temperature growth and hydrothermal method Dip-dry-cure Pad-dry-cure Layer-by-layer deposition Linking agent anchoring Pad-dry-cure
47.0 30.9 50 þ 50 þ 53.3 65.0 19.4 135.9 42.0 302.1 105.1 421.0 50þ 800 þ 119.8 50þ 50 þ 50 þ 465.8
[11] [12] [13] [14] [15] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [9] [25] [26] This study
chitosan as the dispersant. In addition, the washing durability of fabric was also investigated and the UV transmittance spectra and UPF value of each fabric marginally declined even after 10 times laundering. Here, our as-prepared fabric was compared with some other reported UV blocking fabric in Table 1. The UV protection efficiency of chitosan graphene modified cotton fabric possessed the highest UPF value (465.8) among all the UV protection fabrics excepting the dumbbell-shaped ZnO crystallites (UPF 800þ). However, the preparation process of chitosan/graphene nanocomposites was a pad-dry-cure method which was more facile and green than the low-temperature growth and hydrothermal method applied for the dumbbell-shaped ZnO crystallites fabric. Furthermore, considering the low graphene content (o1.0 wt%), cheap price of graphite and skin bio-friendly of chitosan, chitosan/graphene nanocomposites shined bright light in the application of UV protection textiles.
4. Conclusion Chitosan based nanocomposite with different low graphene contents (0.1–1 wt%) was prepared and acted as a novel UV blocker; the facile pad-dry-cure method was employed to deposit chitosan/graphene nanocomposites on the surface of cotton fabric. As expected, the extraordinary enhancement of UV protection efficiency of the modified fabric was obtained in this paper. The corresponding UPF of
the fabric with graphene 1 wt% could rated at 465.8, more than 60 times than pristine cotton fabric. The reasonable well dispersion condition of graphene with the aid of chitosan also contributed to such exceptional UV blocking. After comparing with the UV protection fabric in some previous studies, our treated cotton fabric can be recommended for durable UV protection clothing.
Acknowledgment Financial support of this work was provided by National Natural Science Foundation of China via Grant no. 51273097 and 51306095, China Postdoctoral Science Foundation via Grant no. 2014M561887 and Taishan Scholars Construction Engineering of Shandong Province. References [1] Allen MJ, Tung VC, Kaner RB. Chem Rev 2010;110:132–45. [2] Kuila T, Bose S, Mishra AK, Khanra P, Kim NH, Lee JH. Prog Mater Sci 2012;57:1061–105. [3] Molina J, Fernández J, Inés JC, del Río AI, Bonastre J, Cases F. Electrochim Acta 2013;93:44–52. [4] Shateri-Khalilabad M, Yazdanshenas ME. Cellulose 2013;20:963–72. [5] Fugetsu B, Sano E, Yu H, Mori K, Tanaka T. Carbon 2010;48:3340–5. [6] Leceta I, Arana P, Guerrero P, de la Caba K. Mater Lett 2014;128:125–7. [7] Hebeish A, Sharaf S, Farouk A. Int J Biol Macromol 2013;60:10–7. [8] El.Shafei A, Abou-Okeil A. Carbohydr Polym 2011;83:920–5. [9] Gouda M, Keshk SMAS. Carbohydr Polym 2010;80:504–12.
Please cite this article as: Tian M, et al. Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites. Mater Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.01.147i
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[10] Lawrie G, Keen I, Drew B, Chandler-Temple A, Rintoul L, Fredericks P, et al. Biomacromolecules 2007;8:2533–41. [11] Abidi N, Cabrales L, Hequet E. ACS Appl Mater Interfaces 2009;1:2141–6. [12] Gulrajani ML, Brahma KP, Kumar PS, Purwar R. J Appl Polym Sci 2008;109:314–21. [13] Lee S. J Appl Polym Sci 2009;114:3652–8. [14] Abidi N, Hequet E, Tarimala S, Dai LL. J Appl Polym Sci 2007;104:111–7. [15] Mongkholrattanasit R, Krystufek J, Wiener J, Vikova M. Fibres Text East Eur 2011;19:94–9. [16] Sorna Gowri V, Almeida L, de Amorim MTP, Pacheco NC, Souto AP, Esteves MF, et al. J Mater Sci 2010;45:2427–35. [17] Ibrahim NA, Refaie R, Ahmed AF. J Ind Text 2010;40:65–83.
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Fahmy HM, Abdel-Halim ES. J Ind Text 2010;40:109–21. Jiang SX, Qin WF, Guo RH, Zhang L. Surf Coat Technol 2010;204:3662–7. Mao Z, Shi Q, Zhang L, Cao H. Thin Solid Films 2009;517:2681–6. Mondal S, Hu JL. J Appl Polym Sci 2007;103:3370–6. Uğur ŞS, Sarııšık M, Aktaş AH. Fiber Polym 2011;12:190–6. Wang RH, Xin JH, Tao XM. Inorg Chem 2005;44:3926–30. Mihailović D, Šaponjić Z, Radoičić M, Radetić T, Jovančić P, Nedeljković J, et al. Carbohydr Polym 2010;79:526–32. [25] Paul R, Bautista L, De la Varga M, Botet JM, Casals E, Puntes V, et al. Text Res J 2009;80:454–62. [26] Wang Q, Hauser PJ. Carbohydr Polym 2010;81:491–6.
Please cite this article as: Tian M, et al. Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites. Mater Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.01.147i
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Contents lists available at ScienceDirect
Materials Letters journal homepage: www.elsevier.com/locate/matlet
Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites Mingwei Tian a,b,c,1, Xiaoning Tang a,b,1, Lijun Qu a,b,c,n, Shifeng Zhu a,b, Xiaoqing Guo a,b,c, Guangting Han b,c a
College of Textiles, Qingdao University, Qingdao, Shandong 266071, China Laboratory of New Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, Qingdao University, Qingdao, Shandong 266071, China c Collaborative Innovation Center for Marine Biomass Fibers, Materials and Textiles of Shandong Province, Qingdao University, Qingdao, Shandong 266071, China b
art ic l e i nf o
a b s t r a c t
Article history: Received 1 January 2015 Accepted 28 January 2015
To ameliorate the ultraviolet blocking performance of cotton fabric, novel chitosan/graphene (0.1–1 wt%) nanocomposites were prepared as functional UV blocker, and then deposited on the surface of fabric substrate via a pad-dry-cure approach. The as-obtained fabrics were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. The ultraviolet protection factor (UPF) of the fabric incorporating graphene 1 wt% could reach to 465.8, up to 60-fold higher than that of pristine cotton fabric (UPF 7.31), meaning that low graphene content (o1 wt%) could dramatically enhance the UV-blocking property of substrate with the aid of chitosan as dispersant. Furthermore, the treated cotton fabric also performed excellent washing durability after 10 times water laundering. Chitosan/graphene nanocomposites could be recommended as the remarkable efficient and durable UV-blocking additive for UV-blocking industrial applications. & 2015 Published by Elsevier B.V.
Keywords: Graphene Chitosan UV blocking fabric Nanocomposites Functional
1. Introduction Graphene, as the basic structural element of carbon allotropes, has dramatically attracted a great deal of interest in recent years [1]; its unique virtually single layer of carbon atoms two-dimensional structure endowed some exceptional properties and magical performance [2]. Recently, some researchers have been carried out to attempt to exploit the potential application of graphene in textile field [3–5]. For instance, Molina et al. [3] obtained conductive graphene coated fabric by readily dipping polyester fabric into graphene oxide (GO) dispersion. Shateri-Khalilabad and Yazdanshenas [4] fabricated the superhydrophobic and electroconductive fabric coating with reduced graphene oxide by chemical oxidation reduction. These previous research only deposited graphene on fabric surface by readily mechanical binding methods which could not effectively and durably graft the graphene on the fabric; furthermore, graphene had a pronounced tendency to irreversible aggregation during the preparation process, leading to significantly attenuate functional performance of graphene. Based on above analysis, combining reasonable dispersants with graphene could be
n Corresponding author at: College of Textiles, Qingdao University, Qingdao, Shandong 266071, China. E-mail address: [email protected] (L. Qu). 1 These authors equally contributed to this work.
viewed as the effective and facile route to improve the distribution conditions and durable period of graphene on the fabrics surface. Chitosan (CS), owing to excellent biodegradability and biocompatibility, has attracted significant attention in a broad range of applications [6]; meanwhile, chitosan based materials have also been investigated in the application of super-hydrophobic, antibacterial and electrical conductive textiles [7–9]. Here, in this paper, chitosan was employed as the dispersant and binding additive of graphene to form a homogenous nanocomposite system; therefore, graphene could uniformly and individually disperse in chitosan matrix; afterwards, the cotton fabrics were functionalized with the aid of chitosan/graphene nanocomposites and exhibited robust UV blocking performance.
2. Experimental Graphene nanosheet (GNS) with thickness (1–3 nm) and size (20–25 μm) was supplied by Ningbo Moxi Science and Technology, China; GNS was stably dispersed in aqueous solution with 20 mg/mL. Chitosan (degree of deacetylation 93%, average molecular weight (MW) 125,000 g/mol) was kindly donated by Qingdao JiFa Group, China; acetic acid (CH3COOH) was supplied by National Medicine Group, China. Commercial cotton fabric (plain woven, 160 g/m2) was used as the fabric substrate.
http://dx.doi.org/10.1016/j.matlet.2015.01.147 0167-577X/& 2015 Published by Elsevier B.V.
Please cite this article as: Tian M, et al. Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites. Mater Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.01.147i
67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96
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Chitosan powder was first dispersed into distilled water containing 2% (v/v) acetic acid to prepare 2 wt% chitosan solution. Then, the required concentration (0.1, 0.3, 0.6 and 1 wt%) of GNS was added into the chitosan solution and vigorous stirred for 5 h. Afterwards, the cotton fabrics were impregnated in chitosan/graphene solution for 2 h, and then padded through two dips and two nips to reach an average wet pickup of 80%; the padded fabrics were then washed to remove the unreacted starting compound, and then dried at 70 1C for 10 min; the following curing was carried out at 110 1C for 10 min. The as-prepared fabrics were named as CS-Cotton, CS-G 0.1, CS-G 0.3, CS-G 0.6, CS-G 1. FTIR spectra of modified fabric were recorded with a Nicolet 5700 FT-IR Spectrometer (Thermo Nicolet Corporation, USA). The morphological structure was detected with scanning electron microscopy (SEM, JSM-5600LV). The ultraviolet blocking efficiency was recorded by a UV spectrophotometer (UV1000F, Labsphere, USA). Laundering durability of the treated fabric was measured according to AATCC Test Method 61-2006.
3. Results and discussion The FTIR spectra for chitosan/graphene nanocomposites modified cotton fabric are illustrated in Fig. 1. The control cotton fabric
Fig. 1. FTIR spectra of chitosan/graphene modified cotton fabrics.
depicted the absorption peaks at 3420, 2900, 1640, 1420 and 1070 cm 1 attributing to the OH stretching, CH stretching, OH of water absorbed from cellulose, CH2 symmetric bending and C–O stretching, respectively. After depositing chitosan on the surface of cotton fabric, two more characteristic peaks appeared at 1570 and 1170 cm 1 corresponding to the –NH bending and C–N stretch of chitosan [10]; however, the absorption peaks of –NH group-stretching vibration in chitosan around 3400 cm 1 were absent which might be caused by the intermolecular hydrogen bonds between cotton fabric and chitosan. In addition, in CS-G 1, the peak at 1570 cm 1 disappeared, implied that the hydrogen bonds occurred between chitosan and graphene. As shown in Fig. 2, the morphology of fabric with different chitosan/graphene nanocomposites can be obviously detected along with the control cotton fabric. Typical longitudinal fibril structure with some natural stripes could be detected on the control cotton fiber surface (Fig. 2a), after coating with chitosan, the CS-Cotton fiber tended to more smooth and the original natural stripes became faintly visible (Fig. 2b). Once graphene was incorporated into CS-G 0.1–CS-G 1 (Fig. 2c–f), some micro-wrinkled stripes appeared and protruded out from the fiber surface, and such micro-structure gradually increased indicating the increasing amount of graphene contents. More interestingly, it showed the well-dispersed status of graphene in the chitosan matrix without any aggregation, indicating chitosan acted as a reasonable dispersant for graphene. The ultraviolet transmittance spectra of CS-G fabrics are listed in Fig. 3a, the spectra tended to obvious attenuation along with increasing graphene content. Thus attenuation curves demonstrated that evenly deposited GNS acted as an effective component to shield UV-rays across fabric. In order to assess the degree of UV protection of each modified fabric, the ultraviolet protection factor (UPF) was employed and calculated according to the method described in the Australian/New Zealand Standard AS/NZS 4399:1996. In Fig. 3b, CScotton performed nearly the same UPF (9.02) as the control cotton (UPF¼7.31), but by adding only 0.1 wt% graphene in CS-G 0.1, its UPF fast ascended to 17.64, and the UPF value of CS-G 0.3 continued to rise to 35.76, CS-G 0.6–295.4 which has already far beyond the excellent protection UPF rating (50þ ). As expected, for the CS-G 1 fabric, the corresponding UPF value could reach to 465.8 which was up to more than 60-fold higher than that of pristine cotton fabric, meaning that the low graphene content (o1 wt%) could dramatically enhance the UV-blocking property of substrate with the aid of
Fig. 2. SEM images of (a) control cotton, (b) CS-Cotton, (c) CS-G 0.1, (d) CS-G 0.3, (e) CS-G 0.6, and (f) CS-G 1.
Please cite this article as: Tian M, et al. Robust ultraviolet blocking cotton fabric modified with chitosan/graphene nanocomposites. Mater Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.01.147i
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Fig. 3. The ultraviolet protection ability: (a) UV transmittance spectrum and (b) UPF values.
Table 1 UPF values of various UV protection fabric. No.
Fabric substrate
UV blocker
Treatment method
UPF
Ref.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Cotton Polyester Cotton Cotton Silk Wool Polyamide Cotton Cotton Polyester Cotton Cotton Cotton Cotton Polyester Cotton Cotton Cotton Cotton
Titania nanosols Silk sericin Polyurethane/zinc oxide nanocomposites Titania–silica nanosol FeSO4 CuSO4 ZnO–PMMA nanocomposites Nano-TiO2 Cupper acetate Nanostructured silver Needle-shaped ZnO nanorod PU/MWNT PU/nano-TiO2 Dumbbell-shaped ZnO crystallites Alginates and nano-TiO2 Chitosan/TiO2 FBAs/PDDA TiO2 nanoparticles Chitosan/graphene
Sol–gel process and pad-dry-cure Pad-dry-cure Electrospinning Dip-dry-cure Dyeing process Dyeing process Pad-dry-cure Ester-crosslinking and pad-dry-cure Pad-dry-cure Magnetron sputtering In-situ growth Pad-dry-cure Layer-by-layer deposition Low-temperature growth and hydrothermal method Dip-dry-cure Pad-dry-cure Layer-by-layer deposition Linking agent anchoring Pad-dry-cure
47.0 30.9 50 þ 50 þ 53.3 65.0 19.4 135.9 42.0 302.1 105.1 421.0 50þ 800 þ 119.8 50þ 50 þ 50 þ 465.8
[11] [12] [13] [14] [15] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [9] [25] [26] This study
chitosan as the dispersant. In addition, the washing durability of fabric was also investigated and the UV transmittance spectra and UPF value of each fabric marginally declined even after 10 times laundering. Here, our as-prepared fabric was compared with some other reported UV blocking fabric in Table 1. The UV protection efficiency of chitosan graphene modified cotton fabric possessed the highest UPF value (465.8) among all the UV protection fabrics excepting the dumbbell-shaped ZnO crystallites (UPF 800þ). However, the preparation process of chitosan/graphene nanocomposites was a pad-dry-cure method which was more facile and green than the low-temperature growth and hydrothermal method applied for the dumbbell-shaped ZnO crystallites fabric. Furthermore, considering the low graphene content (o1.0 wt%), cheap price of graphite and skin bio-friendly of chitosan, chitosan/graphene nanocomposites shined bright light in the application of UV protection textiles.
4. Conclusion Chitosan based nanocomposite with different low graphene contents (0.1–1 wt%) was prepared and acted as a novel UV blocker; the facile pad-dry-cure method was employed to deposit chitosan/graphene nanocomposites on the surface of cotton fabric. As expected, the extraordinary enhancement of UV protection efficiency of the modified fabric was obtained in this paper. The corresponding UPF of
the fabric with graphene 1 wt% could rated at 465.8, more than 60 times than pristine cotton fabric. The reasonable well dispersion condition of graphene with the aid of chitosan also contributed to such exceptional UV blocking. After comparing with the UV protection fabric in some previous studies, our treated cotton fabric can be recommended for durable UV protection clothing.
Acknowledgment Financial support of this work was provided by National Natural Science Foundation of China via Grant no. 51273097 and 51306095, China Postdoctoral Science Foundation via Grant no. 2014M561887 and Taishan Scholars Construction Engineering of Shandong Province. References [1] Allen MJ, Tung VC, Kaner RB. Chem Rev 2010;110:132–45. [2] Kuila T, Bose S, Mishra AK, Khanra P, Kim NH, Lee JH. Prog Mater Sci 2012;57:1061–105. [3] Molina J, Fernández J, Inés JC, del Río AI, Bonastre J, Cases F. Electrochim Acta 2013;93:44–52. [4] Shateri-Khalilabad M, Yazdanshenas ME. Cellulose 2013;20:963–72. [5] Fugetsu B, Sano E, Yu H, Mori K, Tanaka T. Carbon 2010;48:3340–5. [6] Leceta I, Arana P, Guerrero P, de la Caba K. Mater Lett 2014;128:125–7. [7] Hebeish A, Sharaf S, Farouk A. Int J Biol Macromol 2013;60:10–7. [8] El.Shafei A, Abou-Okeil A. Carbohydr Polym 2011;83:920–5. [9] Gouda M, Keshk SMAS. Carbohydr Polym 2010;80:504–12.
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