Fibers and Polymers 2012, Vol.13, No.

2, 264-268 Communication

DOI 10.1007/s12221-012-0264-z

Synthesis and Characterization of Acrylic Fibers with Antibacterial Silver Nanoparticles

Azadeh Azadbakht* and Amir Reza Abbasi
Department of Chemistry, Faculty of Science, Islamic Azad University, Khorramabad Branch, Khorramabad, Iran (Received July 10, 2011; Revised August 26, 2011; Accepted September 1, 2011)
Abstract: The present investigation reports the novel synthesis of acrylic fibers containing Ag nanoparticles under ultrasound irradiation. The effect of temperature and power of ultrasound irradiation in growth of the Ag nanoparticles were studied. The physicochemical properties of the nanoparticles were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results show a decrease in the particles size as the power of ultrasound irradiation decreased. Particle sizes and morphology of nanoparticles depend on temperature. As a result, an increase in temperature led to increase of particle size. The textile containing nanoparticles were tested for their antibacterial efficacy against E. coli and S. aureus and were found to possess significant antibacterial activity. Keywords: Ultrasound, Acrylic, Nanoparticle, Silver, Antibacterial activity

Introduction
Metal nanoparticles have been of considerable interest by virtue of their unique physical and chemical properties. Transition metal nano-particles have a variety of applications ranging from pigments to electronics and in biological systems [1,2]. In electronics, these are potential candidates in the area of magnetic recording media and microelectronics. Silver metal has great significance in all industries, particularly in the electrical sector. Today silver is used in photography, medicine [1], electronic, magnetic, optical, catalytic properties [2]. Other application of silver nanoparticles deposited on various fabrics such as acrylic fiber is antibacterial effect [2,3]. Acrylic fiber is one of candidate materials for biomedical application, because it has good biocompatibility and minimal inflammatory reaction. The development of new clothing products based on the immobilization of nanophased materials on textile fibers has recently received growing interest from both academic and industrial sectors [3,4]. It is well known that acrylic fiber has excellent metalbinding capacities, such as chelating silver ions. It is accepted that the functional groups in the synthetic fibers are mainly responsible for the uptake of metal cations by a chelation mechanism. In general, positive ions are bound to functional groups and the electron pair on the functional groups is available for donation to silver ions. Silver nanoparticles have been synthesized through different methods such as thermal decomposition [5-8], metal salt reduction [9], microwave heating [10], radiation methods [11], microemulsion techniques [12], laser ablation [13], the polyol method, the solvothermal method [14], thermal and sonochemical reduction [15]. In this paper, we report the preparation of acrylic fiber containing Ag nanoparticles by using the ultrasound
*Corresponding author: azadeh_azadbakht@yahoo.com 264

technique. The sonochemical method has been used extensively to generate novel materials with unusual properties, since they form particles of a much smaller size and higher surface area than those reported by other methods [16-18]. The chemical effects of ultrasound arise from acoustic cavitation, that is, the formation, growth, and implosive collapse of bubbles in liquid. The implosive collapse of the bubble generates a localized hotspot through adiabatic compression or shock wave formation within the gas phase of the collapsing bubble [19-22].

Experimental
Materials The acrylic fibers were supplied by Amir Kabir University. All reagents and solvents were used as supplied by Merck chemical company and used without further purification. Methods The samples were characterized with different scanning electron microscope (SEM) equipments (Philips XL 30, S4160 and FE-SEM) with gold coating. The reactions were performed under ultrasound powers SONICA-2200 EP and TECNO-GAZ, Tecna 6. Powder X-ray diffraction (XRD) was carried out on a Philips diffractometer of Xpert Company with mono chromatized Cu K radiation. The contents of silver on the prepared acrylic yarn were measured by Inductive Coupled Plasma (ICP) and carried out on a VARIAN, VISTA-PRO and detector: CCD Simultaneous ICP-OES. We have employed a calorimetric measurement to determine the acoustic power. This method was used to calibrate the variable-frequency sonicator because of its simplicity and applicability. Each frequency was then calibrated for constant power by producing a number of heating curves at different input load powers and voltages [16].

Antibacterial Acrylic Composites

Fibers and Polymers 2012, Vol.13, No.2 265

Figure 1. SEM image of the pristine acrylic fiber, the scale bar is 10 m.

Sample Preparation This work consisted of preparing acrylic fibers by coating its surface with Ag nanoparticles through the chemical reduction under ultrasound irradiation. In this system, ethylene glycol served as a reduction reagent and protecting silver nanoparticles from aggregation. We have also found that ethylene glycol not only acts as a polyol reduction agent, as in the preparation of silver-polymer composites, but also promotes the anchoring of silver nanoparticles to the surface of anchoring of silver nanoparticles to the surface of acrylic fiber by interaction with the surface functional groups. Figure 1 demonstrates the smooth texture of the pristine acrylic fiber. Several parameters were changed to obtain the best conditions for the coating of Ag nanoparticles on the acrylic fiber: the ultrasound power and temperature [2,23]. The optimal results representing a typical experiment were as follows. 1.0 gram of acrylic fiber was added to a 0.02 M AgNO3 solution of ethylene glycol and water (1: 10 v/v) in a 100 ml sonication flask. The reaction mixture was then purged under Ar for 40 min. to remove traces of O2/air and irradiated for 1 h under ultrasound irradiation under the flow of an Ar. A 25 wt % aqueous solution of ammonia [4] was added to the reaction slurry during the first 10 min of sonication. From the analytical results, it is clear that the presence of both ethylene glycol and ammonia is necessary to obtain a relatively high concentration of silver in the fiber [23]. The sonochemical reactions were carried in sonochemical bath as shown in Figure 2. The product was washed thoroughly water and methanol to remove the traces of ammonia and was dried in 65 oC. Seven experimental groups were used: (H-10 oC): reaction temperature=10oC, high power ultrasound irradiation (SONICA2200 EP, input: 50-60 Hz/305 W), (H-30 oC): reaction temperature=30oC, high power ultrasound irradiation, (H55 oC): reaction temperature=55 oC, high power ultrasound irradiation, (L-10 oC): reaction temperature=10 oC, low power ultrasound irradiation (TECNO-GAZ, S.p.A., Tecna 6, input: 50-60 Hz/138 W), (L-30 oC): reaction temperature=30oC, low power ultrasound irradiation, (L-55 oC): reaction temperature= 55 oC, low power ultrasound irradiation, Blank reaction:

Figure 2. Schematice of the experimental setup used for the sonochemical reactions: (a) double jacketed vessel, (b) ultrasound bath, (c) reaction cell, (d) silver nanoparticles@acrylic fibers, and (e) water circulation. Table 1. Experimental conditions of Ag nanoparticles@acrylic fibers Power of ultrasound ICPb irradiation L-10 oC 10 Low 1.8 Series L-30 oC 30 Low 103.3 Ld 55 Low 267.5 L-55oC H-10 oC 10 High 2.1 Series o H-30 C 30 High 25.3 Hd 55 High 200.9 H-55 oC Blank 30 0 a b c Reaction temperature, ICP measurement (ppm), average (nm), dH (high) and L (low power ultrasound irradiation). Samples T ( C)a
o

SEMc 74.9 160.1 223.4 120.4 166.1 317.8 330.1 diameter

reaction temperature=30 oC, a group that received without ultrasound (Table 1).

Results and Discussion

Effect of Ultrasound Irradiation In order to investigate the role of power ultrasound irradiation on the nature of products, reactions were performed under different power ultrasound irradiation. Ultrasonic generator was carried out on a SONICA-2200 EP and TECNO-GAZ, S.P.A., Tecna 6. Reactions of Series L were performed by TECNO-GAZ S.p.A. Tecna 6 (input power and frequency of 138 W and 60 Hz) and the other reactions were prepared in an ultrasonic bath with an input power and frequency of 305 W and 60 Hz respectively (SONICA-2200 EP). These systems depicted a decrease in the particles size accompanying a decrease in the power of ultrasound irradiation as confirmed by the SEM images (Figure 3(a)-(f) and Table 1). As a result, particle sizes of series L (H-10 oC, H-30 oC, and H-55 oC) are smaller than particles size of series H (L-10 oC, L-30 oC, and L-55 oC). In this case, the ultrasonic waves promote the

266

Fibers and Polymers 2012, Vol.13, No.2

Azadeh Azadbakht and Amir Reza Abbasi

[18]. The reaction was explained as follows. The ultrasound resulted in decomposition of water into hydrogen and hydroxyl radicals. Hydrogen radicals would reduce silver ions into silver atoms, which subsequently nucleate and grow to silver nanoclusters. The sonochemical irradiation of a liquid causes two primary effects, namely, cavitations (bubble formation, growth, collapse) and heating. When the microscopic cavitations bubbles collapse near the surface of the solid substrate, they generate powerful shock waves and microjets that cause effective stirring/mixing of the adjusted layer of liquid. The after-effects of the cavitations are several hundred times greater in heterogeneous systems than in homogeneous systems [4,24]. In our case, the ultrasonic waves promote the fast migration of the newly-formed nanoparticles to the fabrics surface. There is reliable evidence that applying ultrasound not only induces nucleation, but also increases reproducibility. Another effect of ultrasound on nucleation is shortening the induction time between the establishment of supersaturation and the onset of nucleation and crystallization. The cavitation events allow the excitation energy barriers associated with nucleation to be surmounted, in which case it should be possible to correlate the number of cavitation and nucleation events in a quantitative way [24]. It has been suggested that nucleation caused by scratching the walls of a vessel containing a supersaturated solution with a glass rod spatula could be the result of cavitation [25]. Results show that in present of ultrasound radiation, particle sizes are in a very low range. This finding has already been observed in other studies on ultrasound-assisted synthesis of nanoparticles [19]. Effect of Temperature Particle sizes and morphology of nanoparticle are depending on temperature [16]. This finding has already been observed in other studies on ultrasound-assisted synthesis of nanoparticles [19]. An increased temperature results in an increased solubility, and thus a reduced supersaturation of growth species in the solution. As a result, nuclei with small sizes may become unstable and dissolve back into the solution; dissolved species will then deposit onto the surfaces of large particles [8]. Comparison between samples L-10 oC, L-30 oC, and L-55 oC shows that an increase in temperature led to increase of particle size. These facts are repeated for series H, respectively. Particle size distribution histograms of samples are summarized in supplementary material. The contents of Ag+ on the acrylic fiber were measured by Inductive Coupled Plasma (ICP). The results summarized in Table 1. With an increasing the temperature, growth toke place on more nuclei and Ag+ concentration on acrylic fiber will be increases. To determine the crystal phase of the silver nanoparticles@acrylic fibers, X-ray diffraction (XRD) measurements were carried out over the diffraction angle (2) 1080 o. Figure 4 shows the powder XRD of sample acrylic

Figure 3. SEM photographs of the samples; (a) L-10 C, (b) L30 oC, (c) L-55 oC, (d) H-10 oC, (e) H-30 oC, (f) H-55 oC, and (g) blank.

fast migration of the newly-formed nanoparticles to the fabrics surface, solubility increasing and probably nuclei with small sizes become unstable and dissolve back into the solution. Figures 3(a)-(f) and S1-7 shows SEM photographs and the corresponding particle size distribution histograms of products in various temperatures [23]. For the sake of investigating the role of sonicating, blank sample was performed without ultrasound irradiation (Figure 3(g)). The average particle size for blank sample is over 350 nm, while, the average particle size for ultrasound method in similar conditions is around 160 nm. In addition, in sonicating method, when a high concentration of AgNO3 was used, a large amount of metallic silver precipitated at the bottom of the sonication cell, and this required additional steps for separation [2]. The silver nanoparticles were prepared by sonochemical reduction of an aqueous silver nitrate solution in an atmosphere of argon and hydrogen

Antibacterial Acrylic Composites

Fibers and Polymers 2012, Vol.13, No.2 267

Figure 4. XRD pattern of the acrylic fiber containing Ag nanoparticles.

Figure 6. Antibacterial activity of acrylic fiber containing Ag nanoparticles against E. coli (top) and S. aureus (down).

Figure 5. Energy-dispersive X-ray spectroscopy (EDS) analysis of acrylic fiber containing Ag nanoparticles.

fibers-Ag nanoparticles and the characteristic peaks corresponding to the Ag crystal, which was identified as Chlrorargyrite [26,27]. The four major peaks found at 38.092, 44.214, 64.409, and 77.344 o on the 2 theta scale correspond respectively to the (111), (200), (220), and (311) crystal planes. The result indicated that Ag formed on the acrylic fiber and the crystalline phase of Ag is cubic, space groups Fm3m with the lattice parameters a=4.0862 , z=4, which are close to the reported values, (JCPDS cards number 04-0783). Estimated from the Sherrer formula, the size of the silver particles (sample L-10 oC) is about 56 nm, belonging to the nano-scale. The peaks at 14 to 32 o correspond to the acrylic fiber substrate. For further demonstration, the energy dispersive X-ray spectroscopy (EDS) analysis of the sample H-55 oC was performed. It indicated that the elements of Ag in the products were homogeneous distribution. The EDS spectrum shows the presence of Ag+ as the only element component [28]. The peaks of C, N and H from the fiber were observed at 0.1-1.0 KeV. Therefore, it is estimated that the entire nanoparticulate sample, generated by this method, was indeed Ag (Figure 5).

Bactericidal Tests The antimicrobial activity of the coated acrylic fiber was tested against Gram negative bacterial strain E. coli and Gram positive bacterial strain S. aureus using disk diffusion method according to previous works [29]. Antibacterial activity of fabric samples was determined in terms of inhibition zone formed on Mueller-Hintion Agar. The control samples (pristine fiber), which did not show any antibacterial activity. This result indicates that the pristine sample have no influence on the antibacterial activity. While the Ag+ is considered as an environmentally safe ion, a much more important and serious issue is the leaching of Ag nanoparticles. The Ag nanoparticles@fiber killed all the bacteria under and around them. We observed distinct zones of inhibition (clear areas with no bacterial growth) around the samples for both Escherichia and S. aureus (Figure 6). The observed zone of inhibition is a result of the leaching of active biocidal species Ag+ ion from the embedded Ag particles present in the fabric into the surrounding aqueous medium [2]. The presence of the inhibition zone clearly indicates that the mechanism of the biocidal action of the fabric is due to the leached Ag+ ion [30].

Conclusion
The silver nanoparticles@acrylic fibers were prepared under ultrasound irradiation. The sonicating effect and temperature of reaction were the parameters which were changed for reaching the optimized condition. XRD analyses indicated that the prepared Ag nanoparticles were crystalline in structure. An increase in temperature led to increase of particle size. Results show a decrease in the particles size as the power of ultrasound irradiation decreased. To investigate the role of sonicating on the nature of products one of the

268

Fibers and Polymers 2012, Vol.13, No.2

Azadeh Azadbakht and Amir Reza Abbasi

reactions was performed without ultrasound irradiation. The average particle size for blank sample is over 350 nm, while, the average particle size using ultrasound processing is around 160 nm. The fiber containing Ag nanoparticles were tested for their antibacterial efficacy against E. coli and S. aureus and were found to possess significant antibacterial activity.

Acknowledgements
Support of this investigation by Islamic Azad University, Khorramabad branch is gratefully acknowledged.

References
1. W. Hu, S. Chen, X. Li, S. Shi, W. Shen, X. Zhang, and H. Wang, Mater. Sci. Eng. C, 29, 1216 (2009). 2. Y. Ma, T. Zhou, and C. Zhao, Carbohydr. Res., 343, 230 (2008). 3. C. Y. Chen and C. L. Chiang, Mater. Lett., 62, 3607 (2008). 4. I. Perelshtein, G. Applerot, N. Perkas, E. WehrschuetzSigl, A. Hasmann, G. Guebitz, and A. Gedanken, Surf. Coat. Technol., 204, 54 (2009). 5. Y. H. Kim, D. K. Lee, B. G. Jo, J. H. Jeong, and Y. S. Kang, Colloid Surf. A: Physicochem. Eng. Aspect, 364, 364 (2006). 6. A. G. Nasibulin, P. P. Ahonen, O. Richard, E. I. Kauppinen, and I. S. Altman, J. Nanoparticle Res., 3, 385 (2001). 7. L. Daroczi, M. T. Beck, D. L. Beke, M. Kis-Varga, L. Harasztosi, and N. Takacs, Mater. Sci. Forum., 269, 319 (1998). 8. A. R. Abbasi and A. Morsali, J. Inog. Organomet Polym., 20, 825 (2010). 9. H. Zhu, C. Zhang, and Y. Yin, Nanotechnology, 16, 3079 (2005). 10. S. S. Joshi, S. F. Patil, V. Iyer, and S. Mahumuni, Nanostruct. Mater., 10, 1135 (1998). 11. M. P. Pileni, B. W. Ninham, T. Gulik-Krzywicki, J. Tanori, I. Lisiecki, and A. Filankembo, Adv. Mater., 11, 1358

(1999). 12. M. M. Husein, E. Rodil, and J. H. Vera, J. Colloid Interface Sci., 288, 457 (2005). 13. B. K. Park, S. Jeong, D. Kim, J. Moon, S. Lim, and J. S. Kim, J. Colloid Interface Sci., 311, 417 (2007). 14. N. A. Dash, C. P. Raj, and A. Gedanken, Chem. Mater., 10, 1446 (1998). 15. A. R. Abbasi and A. Morsali, Ultrason. Sonochem., 17, 704 (2010). 16. A. R. Abbasi and A. Morsali, Ultrason. Sonochem. 17, 572 (2010). 17. Y. Liu, W. Huang, Y. Zhaoa, and T. Dou, React. Kinet. Catal. Lett., 96, 157 (2009). 18. R. A. Salkar, P. Jeevanandam, S. T. Aruna, Y. Koltypin, and A. Gedanken, J. Mater. Chem., 9, 1333 (1999). 19. N. Perkas, Y. Wang, Y. Koltypin, A. Gedanken, and S. Chandrasekaran, Chem. Commun., 988 (2001). 20. M. V. Landau, L. Vradman, M. Herskowitz, Y. Koltypin, and A. Gedanken, J. Catal., 201, 22 (2001). 21. K. S. Suslick, Science, 247, 1439 (1990). 22. K. H. Kim and K. B. Kim, Ultrason. Sonochem., 15, 1019 (2008). 23. A. R. Abbasi and A. Morsali, Ultrason. Sonochem., 18, 282 (2011). 24. M. D. Luque de Castro, and F. Priego-Capote, Ultrason. Sonochem., 14, 717 (2007). 25. J. W. Mullin, Crystallization, 4th ed., ButterworthHeinemann, Woburn, MA, 2001. 26. J. Yang, C. Lin, Z. Wang, and J. Lin, Inorg. Chem., 45, 8973 (2006). 27. A. Askarinejad and A. Morsali, Chem. Eng. J., 153, 183 (2009). 28. A. R. Abbasi and A. Morsali, Colloid Surf. A: Physicochem. Eng. Aspects, 371, 113 (2010). 29. M. Shateri Khalil-Abad, M. E. Yazdanshenas, and M. R. Nateghi, Cellulose, 16, 1147 (2009). 30. M. S. Khalil-Abad and M. E. Yazdanshenas, J. Colloid Interface Sci., 351, 293 (2010).