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Ag Nanoparticles Growing onto Cotton Fabric Using Chitosan as a Template A. Abou-Okeil a
a
Textile Research Division, National Research Centre, Cairo, Egypt
Available online: 11 Jun 2012
To cite this article: A. Abou-Okeil (2012): Ag Nanoparticles Growing onto Cotton Fabric Using Chitosan as a Template, Journal of Natural Fibers, 9:2, 61-72 To link to this article: http://dx.doi.org/10.1080/15440478.2011.651841
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Journal of Natural Fibers, 9:61–72, 2012 Copyright © Taylor & Francis Group, LLC ISSN: 1544-0478 print/1544-046X online DOI: 10.1080/15440478.2011.651841
Ag Nanoparticles Growing onto Cotton Fabric Using Chitosan as a Template A. ABOU-OKEIL
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Textile Research Division, National Research Centre, Cairo, Egypt
Ag nanoparticles were grown on the surface of cotton fabric using chitosan as a template for preparing high uniform antibacterial cotton fabric. Chitosan was applied onto cotton fabric by pad-dry-cure method in presence of citric acid as crosslinking agent. Cotton fabric modified with chitosan was characterized by measuring nitrogen percentage (N%) and Fourier transform infrared spectroscopy (FTIR). Chitosan modified cotton fabric was used to grow Ag-nanoparticles on it. The fabrics with Ag nanoparticles were characterized by measuring X-Ray diffraction (XRD), Scanning Electron Microscope (SEM), Energy dispersive X-Ray (EDX), and tested for antibacterial properties against Staphylococcus aureus ( Staph. aureus, Gram-positive bacteria) and Escherichia coli ( E. coli, Gram-negative bacteria). The results obtained confirmed the presence of chitosan on the surface of cotton fabric that was confirmed by FTIR. The data obtained indicate also the presence of Ag nanoparticles on the surface of cotton fabric that was confirmed by XRD, SEM, EDX. Cotton fabric produced had antibacterial effect only against Staphylococcus aureus. KEYWORDS cotton fabric, antibacterial, Ag nanoparticles, uniform, chitosan, crosslinking
INTRODUCTION Cotton is a natural fiber that consists of cellulose with 1, 4-D-glucopyranose as a fundamental unit. Cotton textiles are highly popular because they are next to skin, sweat absorbing, and comfortable. However, cotton fabrics Address correspondence to A. Abou-Okeil, Textile Research Division, National Research Centre, El-Buhoth St., 12622 Cairo, Egypt. E-mail:
[email protected] 61
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provide an excellent environment for microorganisms to grow, owing to its ability to retain moisture (Lim and Hudson 2004; Son, Kim et al. 2006). Therefore, numerous chemicals have been used to improve the antimicrobial activity of cotton textiles (Lee et al. 2003; Lim and Hudson 2004; Son et al. 2004; Daoud et al. 2005; El-tahlawy et al. 2005; Son et al. 2006). The application of antimicrobial agents on textiles started very long time ago. The historical evidence showed that Egyptians used spices and herbs to preserve mummy wraps. In World War II, German soldiers’ uniforms were treated with quaternary ammonium compounds to prevent infection and odor (Sondi and Salopek-Sondi 2004). In the last few decades, there has been increased interest in antibacterial finishing on textiles materials. Several different classes of antimicrobial agents for textiles have been developed such as phenols, halogen, organometallics, and quaternary ammonium salt and metal salts (Nakashima et al. 2001; Chen et al. 2005). Silver has been widely used in many fields because it shows a strong biocidal effect on many pathogenic bacteria (Smith and Block 1982; Brady et al. 2003; Son and Sun 2003). The immobilization of silver nanoparticles on various fibers has recently attracted much attention (Yang et al. 2003; Lee et al. 2005; Xu et al. 2006; Hadad et al. 2007). Various modifications of cotton fibers with silver nanoparticles can increase both the price and purpose of these fibers (Yingjie et al. 1993; Dubas et al. 2006; Tarimala et al. 2006). Nanotechnology is concerned with materials whose structures exhibit significantly novel and improved physical, chemical, biological properties, and functionality due to their nano-scaled size (Wang 2000). Nanoparticles are defined as particulate dispersion or solid particles within the range of 1–100 nm. Metal nanoparticles have received attention in recent years because of their potential applications in microelectronics (Andres et al. 1996), photo catalysis (Kamat 2002), magnetic devices (Thomas 1988), and powder metallurgy (Perpenboom et al. 1981). The intrinsic properties of metal nanoparticles are mainly determined by size, composition, crystallinity, and morphology (Dickson and Lyon 2000). Ag nanoparticles possess many superior properties, such as increased electrical conductivity, antimicrobial activity (Loung et al. 2003; Li et al. 2006), catalytic effect, etc. (Hayward et al. 2000; Shipway et al. 2000; Kabashin et al. 2003). Many methods have been used to prepare Ag nanoparticles, such as chemical reduction (Zhang et al. 1996; Chou and Ren 2000; Cho and So 2006), photochemical, or radiation. Chemical reduction (Zhou et al. 1996), solo chemical method (Okista et al. 1996), and polyol method (Silvert et al. 1996) are applied to prepare Ag nanoparticles. Chemical reduction from aqueous solution is the most preferable method to prepare Ag nanoparticles. The aim of the present work is to grow Ag nanoparticles onto cotton fabric to prepare highly uniform antimicrobial cotton fabric using Ag nanoparticles.
Ag Nanoparticles Growing onto Cotton Fabric Using Chitosan as a Template
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EXPERIMENTAL Materials Desized, scoured, and bleached cotton fabric was used in this study. Chitosan (800,000 cps) is kindly supplied by Sigma (USA). Citric acid, acetic acid, sodium hypophosphite, silver nitrate, and sodium borohydride are of laboratory grade chemicals.
Methods
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IMMOBILIZATION
OF CHITOSAN ONTO THE SURFACE OF COTTON FABRIC
Cotton fabric was immersed in a solution containing 0.5% chitosan, 6% citric acid, and 3% sodium hypophosphite then padded to pick up 100%, dried at 100◦ C for 3 min and cured at 180◦ C for 1.5 min. Finally, the fabric was washed thoroughly with tap water and air dried.
PREPARATION
OF NANO -A G - LOADED COTTON FABRIC
Cotton fabric bearing chitosan was put into aqueous solution of AgNO3 prepared by dissolving 0.02 g AgNO3 into 30 mL distilled water for 24 h. Ag ions present onto the fabric were reduced by immersing the fabric into the solution containing 1 mmol of sodium borohydride in 30 mL distilled water and kept overnight at 25◦ C. The resulting dark brown fabric indicated the formation of Ag nanoparticles (Gupta et al. 2008). Then, the fabric was rinsed with distilled water and also distilled water containing 2% acetic acid, and finally the fabric was air dried at 40◦ C.
Characterization ●
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Nitrogen content (N%) was measured using micro Kjeldhal method (Vogel 1975). FTIR Spectroscopy was measured using FT-IR-FT-Raman, model: Nexus 670 (Nicolet-Madison-WI-USA). Cotton fabric was cut into very small pieces; these pieces were mixed with KBr. The spectral range was 400 to 4,000 cm−1 . Scanning Electron Microscope (SEM), the samples were examined by a JEOL–840X SEM, from Japan, magnification range 35–10.000, resolution 200 A◦ , and acceleration voltage 19 kV. All the samples were coated with gold before SEM testing. X-Ray Diffraction (XRD): X-ray diffractometer model Philips X’ Pert MPP with a type PW 3050/10 goniometer. The diffractometer was controlled and operated by a PC computer with the programs P Rofit and used a Mo Kα source with wavelength 0.70930 Ao, operating with Mo-tube radiation
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at 50 kV and 40 mA. The scan parameters ranged from 2◦ < 2θ < 50◦ with scanning step of 0.03 in the reflection geometry. Energy Dispersive X-Ray (EDX): The elemental ratio of prepared cotton fabric was characterized by SEM-EDS (electron dispersive spectroscopy) (JXA-840 an Electron Probe Microanalyzer-JOEL). Antibacterial, for antibacterial experiment, Staphylococcus aureus (S. aureus, Gram-positive bacteria), and Escherichia coli (E. coli, Gramnegative bacteria) were used. The antibacterial activity of prepared cotton samples was measured by the inhibition zone method (Qin et al. 2006).
RESULTS AND DISCUSSION
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Characterization of Cotton Fabric Bearing Chitosan Cotton fabric was characterized by measuring the nitrogen content (N%) and FTIR. The N% was found to be 0.2% indicating the presence of chitosan on the surface of the fabric. FTIR spectroscopy was also used to prove the presence of chitosan onto the fabric. Figures 1a and 1b shows FTIR spectra for cotton fabric and cotton fabric treated with chitosan. Figure 1a reveals the characteristic peaks of cotton fabric, i.e., a broad band corresponding to hydroxyl (OH) groups is observed in the range 3,600–3,200 cm−1 range, a peak of C–O is observed at 1,644 cm−1 and a peak of C–H at 2,903 cm−1 . Figure 1b shows the FTIR spectroscopy of cotton bearing chitosan. As shown by this Figure, the intrinsic amide band I is at 1,644, NH–OH is at the range 3,600–3,200 cm−1 ; also the C=O of ester of citric acid was also clear at 1,732 cm−1 that confirm the fixation of chitosan through this ester. The C–N and N–H band is also observed at 1,430 cm−1 .
Characterization of Ag-loaded Cotton Fabric FTIR Figure 2 shows the FTIR spectrum of Ag-loaded cotton fabric. As seen in Figure 2, the broad band at 3,600–3,200 cm−1 (NH–OH) became weaker due to the binding of Ag to the N and O moieties of their functional groups. The characteristic peak of ester (1,732 cm−1 ) is almost disappeared that give the possibility of binding of Ag to the O of the ester and/or carboxylic of citric acid. Amide I and II are also shifted to 1,586 cm−1 and 1,642 cm−1 that indicates the binding of Ag to the amide. SEM SEM photographs of cotton fabric and Ag-loaded cotton fabric were shown in Figures 3a and 3b. The dark texture of the ultra fine fabrics is caused by the presence of Ag nanoparticles with high electron density. The almost
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(a)
(b) FIGURE 1 (a) FTIR spectrum of cotton fabric, (b) FTIR spectrum of chitosan treated cotton fabric.
high uniformity of Ag can be attributed to (a) ion exchange between H+ and Ag+ (b) the affinity of Ag ions to bind to the electron rich N and O atoms present in the chitosan and cotton. This leads to the uniform localization of Ag ions that when reduced will give Ag nanoparticles distributed with high uniformity on the surface of cotton fabric as shown by Figure 3b. EDX The incorporation of Ag nanoparticles in the cotton fabric was verified by EDX (Figure 4). As observed in Figure 4, the EDX of Ag-loaded cotton fabric
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FIGURE 2 FTIR spectroscopy of Ag-loaded cotton fabric.
confirms the presence of zero-valent silver on the surface of cotton fabric. The Ag content on cotton structure was 1.57% with respect to the mass of Ag-loaded cotton fabric as shown by Table 1.
XRD The crystalline characteristics of Ag nanoparticles on cotton fabric are confirmed by the XRD. Figure 5 shows the four distinct XRD peaks are clearly observed at 2θ values 38.2◦ , 44.3◦ , 64.4◦ , and 77.3◦ . The presence of these peaks confirms the formation of Ag nanoparticles on the surface of cotton fabric.
ANTIBACTERIAL Figure 6 shows the results of the antibacterial action of nano-Ag-loaded cotton fabric on the growth of S. aureus. It is clear from Figure 6 that the growth of the staph. Aureus around the cotton samples is inhibited that is not present in the control sample (untreated cotton fabric and also chitosan treated cotton fabric). This means that the presence of Ag nanoparticles is the responsible for this inhibition. This is not the case in the nano-Ag-loaded cotton fabric with respect to E. coli (Gram negative), that is no inhibition zone observed with respect to all samples that can be explained by the low concentration of nano-Ag (1.57%).
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(a)
(b) FIGURE 3 (a) SEM of cotton fabric, (b) SEM of Ag-loaded cotton fabric.
CONCLUSION Ag nanoparticles were grown on the surface of cotton fabric after treatment of cotton fabric with chitosan using pad-dry-cure method with pick up 100% and cured at 180◦ C for 1.5 minutes after drying at 100◦ C. From the results obtained, we can conclude that chitosan was fixed onto the surface of cotton fabric using citric acid as crosslinker, which was confirmed by N% and FTIR Spectroscopy. From the results obtained, it can be concluded
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FIGURE 4 EDX of nano-Ag-loaded cotton fabric.
FIGURE 5 XRD of nano-Ag-loaded cotton fabric.
that treatment of cotton fabric with chitosan leads to a uniform layer of Ag nanoparticles, which was confirmed by the SEM. The high uniformity of Ag can be attributed to (a) ion exchange between H+ and Ag+ (b) the affinity of Ag ions to bind to the electron rich N and O atoms present in the chitosan and cotton. This leads to the uniform localization of Ag ions, which, when reduced, will give Ag nanoparticles distributed with high uniformity on the surface of cotton fabric The presence of Ag nanoparticles was confirmed
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TABLE 1 Elemental analysis of EDX Element
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CK OK Ag L Totals
Weight%
Atomic%
52.10 46.34 1.57 100.00
59.84 39.96 0.20
FIGURE 6 Antibacterial of untreated and nano-Ag-loaded cotton fabric against S. aureus (a) untreated cotton fabric, (b) nano-Ag-loaded cotton fabric.
by XRD, which showed the characteristic peaks of Ag nanoparticles. Also EDX showed the presence of zero valent Ag on the surface of cotton fabric. The antibacterial of cotton fabric was measured using the inhibition zone method on Staphylococcus aureus (S. aureus, Gram-positive bacteria) and Escherichia coli (E. coli, Gram-negative bacteria). From the results obtained we can conclude that the cotton fabric produced has antibacterial effect only against Staphylococcus aureus (staph. aureus, Gram-positive bacteria) that can be attributed to the lower concentration of Ag.
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