Temperature-dependent properties of silver-poly(methylmethacrylate) nanocomposites synthesized by in-situ technique
© Singho et al.; licensee Springer. 2014
Received: 5 August 2013
Accepted: 3 January 2014
Published: 22 January 2014
Ag/PMMA nanocomposites were successfully synthesized by in-situ technique. Transmission electron microscopy (TEM) images show that the particles are spherical in shape and their sizes are dependent on temperature. The smallest particle achieved high stability as indicated from Zeta sizer analysis. The red shift of surface plasmon resonance (SPR) indicated the increases of particle sizes. X-ray diffraction (XRD) patterns exhibit a two-phase (crystalline and amorphous) structure of Ag/PMMA nanocomposites. The complexation of Ag/PMMA nanocomposites was confirmed using Raman spectroscopy. Fourier transform infrared spectroscopy spectra confirmed that the bonding was dominantly influenced by the PMMA and DMF solution. Finally, thermogravimetric analysis (TGA) results indicate that the total weight loss increases as the temperature increases.
Metal nanocomposites have attracted much attention due to their distinctive chemical and physical properties [1, 2]. The properties of metal nanocomposites depend on the type of incorporated nanoparticles, their size and shape, their concentration, temperature, and interaction with polymer matrix. Silver (Ag) has been widely studied since it is more reactive than gold. However, appropriately stabilized Ag undergoes fast oxidation and easily aggregate in a solution. Among polymeric materials, poly(methyl methacrylate) (PMMA) was recognized as a polymeric glass with a wide range of applications. PMMA offers twofold advantages such as availability to carboxylate functional group for a chemical bonding with the metal ions and high solubility of PMMA in solvent-like dimethylformamide (DMF) for silver nitrate reduction. Therefore, Ag/PMMA nanocomposites are expected to be a hot spot area for its superior properties.
Earlier work on the synthesis of Ag/PMMA nanocomposites utilized sodium salt of acrylic acid via radiolysis method [3, 4]. Deng et al.  has prepared Ag/PMMA nanocomposites by using PMMA and DMF via in-situ technique. They observed that the behavior of linear and nonlinear optical properties were different compared to the pure PMMA film. The main problem in polymer nanocomposites is to avoid the particles from aggregation. However, this problem can be solved by surface modification of the particles. This will improve the interfacial interaction between the metal particles and the polymer matrix.
In this paper, we used a simple procedure for the preparation of Ag/PMMA nanocomposites. In the first step, Ag nanoparticles were synthesized in water using the chemical reduction method [6–8]. This technique offers a systematic, efficient, and simple procedure for synthesis of Ag nanoparticles without decreasing the production rate. In the second step, Ag nanoparticles were mechanically mixed with PMMA dissolved in DMF to form nanocomposites at different temperatures. The temperature-dependent properties of nanocomposites were investigated by various techniques and their preparations of nanocomposites were discussed.
Silver nitrate, AgNO3 (Thermo Fisher Scientific, Waltham, MA, USA) was selected as source of silver. Polyethylene glycol (PEG, MW 8000 in monomer units; Acros organics, Morris Plains, NJ, USA) was used as reducing agent. Daxad 19 (sodium salt of polynaphthalene sulfonate formaldehyde condensate, MW 8000; Canamara United Supply Company, Edmonton, AB, Canada) was used as stabilizer. N′N-dimethylformamide (DMF) (R & M Marketing, Essex, UK) used as solvent while PMMA (Acros Organics) as matrix. Four grams of AgNO3 was dissolved and stirred for 1 h in a mixture comprising of 100 mL distilled water, 4.5 g of PEG, and 5 g of Daxad 19 at 80°C. It was observed that the light brown solution transformed into a grey-black color, which indicates the formation of silver nanoparticles. The solution was then centrifuged at a maximum speed of 15,000 rpm, and washed with distilled water for several times . Then, 10 g of PMMA was dissolved in 50 mL of DMF and mixed with 5 mL of silver nanoparticle solution at 80°C. The mixture was stirred for 1 h. This procedure was then repeated at 100°C and 120°C .
The physical shape and size of Ag/PMMA nanocomposites were observed by transmission electron microscopy (TEM; Leo Libra). The absorption spectrum was recorded by UV–VIS spectrophotometry (Cary Win UV 50, Agilent Technologies, Melbourne, Australia). The surface structure was characterized using Raman spectroscopy (Raman XploRA, Horiba, Kyoto, Japan) and Philips X'Pert MPD PW3040 X-ray diffraction (XRD; Amsterdam, The Netherlands) with CuKα radiation at 1.5406 Å. The zeta potential of Ag/PMMA nanocomposites was measured by Zetasizer (Zetasizer 3000HS, Malvern, Inc., Malvern, UK) while for thermogravimetry, TGA/SDTA 851 Mettler Toledo was used to measure the thermal properties. The Fourier transform infrared spectroscopy (FTIR) spectra were recorded on a spectroscopy (PerkinElmer, Spectrum 400, Waltham, MA, USA) within the range of 400 to 4,000 cm-1.
Results and discussion
The zeta potential, thermal, and mass properties of Ag/PMMA nanocomposites synthesized at different temperatures
Hydrodynamic diameter (nm)
Initial weight loss (%)
First decomposition weight loss (%)
Total weight loss (%)
Decomposition temperature (°C)
Stability temperature (°C)
Ag/PMMA nanocomposites were successfully synthesized via in-situ technique. The size and distribution of Ag/PMMA nanocomposites were strongly dependent on the reactant temperatures. From the zeta potential analysis, the smallest particle has more negative potential and become much more stable. The red shifted and broader SPR bands were observed as the temperatures increases due to larger particle sizes. The peak for (111) plane in XRD results increases as the temperature increases up to 120°C with Ag nanoparticles preferred alignment in PMMA is at the (111) plane. From the Raman spectroscopy, we can conclude that the peak intensity decreases at the lower temperature due to the reduction of lattice vibration while from the FTIR spectra, the bonding was dominantly influenced by the PMMA and DMF solution due to the electrostatic attraction between acrylate ions of PMMA and Ag nanoparticles. TGA results showed that the total weight loss percentage increases as the temperature increases.
The authors greatly appreciate the financial support funded by the Ministry of Higher Education Malaysia through High Impact Research Grant (Grant No. HM.C/HIR/MOHE/ENG12).
- Vodnik VV, Vukovie JV, Nedeljkovic JM: Synthesis and characterization of silver-poly(methylmethacrylate) nanocomposites. Colloid Polym Sci 2009, 287: 847. 10.1007/s00396-009-2039-7View Article
- Nicolais L, Carotenuto G: The thermolysis behavior of Ag/PAMAMs nanocomposites. Colloid Polym Sci 2009, 287: 609. 10.1007/s00396-009-2015-2View Article
- Longenberger L, Mills G: Formation of metal particles in aqueous solutions by reactions of metal complexes with polymers. J Phys Chem 1995, 99: 475. 10.1021/j100002a001View Article
- Monti OLA, Fourkas JT, Nesbitt DJ: Diffraction-limited photogeneration and characterization of silver nanoparticles. J Phys Chem B 2004, 108: 1604. 10.1021/jp030492cView Article
- Deng Y, Sun Y, Wang P, Zhang D, Ming H, Zhang Q: Low-dimensional systems and nanostructures. Physica E 2008, 40: 911. 10.1016/j.physe.2007.11.018View Article
- Sondi I, Goia DV, Matijevi E: Preparation of highly concentrated stable dispersions of uniform silver nanoparticles. J Colloid Interface Sci 2003, 260: 75. 10.1016/S0021-9797(02)00205-9View Article
- Lim PY, Liu RS, She PL, Hung CF, Shih CH: Synthesis of Ag nanospheres particles in ethylene glycol by electrochemical-assisted polyol process. Chem Phys Lett 2006, 420: 304. 10.1016/j.cplett.2005.12.075View Article
- Che Lah NA, Johan MR: Optical and thermodynamic studies of silver nanoparticles stabilized by Daxad 19 surfactant. J Mater Res 2011, 3: 340.
- Che Lah NA, Johan MR: Facile shape control synthesis and optical properties of silver nanoparticles stabilized by Daxad 19 surfactant. Appl Surf Sci 2011, 257: 7494. 10.1016/j.apsusc.2011.03.067View Article
- Singho ND, Che Lah NA, Johan MR, Ahmad R: FTIR studies on silver-poly(methylmethacrylate) nanocomposites via in-situ polymerization technique. Int J Electrochem Sci 2012, 7: 5596.
- Kassaee MZ, Mohammadkhani M, Akhavan A, Mohammadi R: In situ formation of silver nanoparticles in PMMA via reduction of silver ions by butylated hydroxytoluene. Struct Chem 2011, 2: 11.View Article
- Khanna PK, Subbarao VVVS: Synthesis of fine CdS powder from direct in-situ reduction of sulphur and cadmium salts in aqueous N, N′-dimethylformamide. Mater Lett 2004, 58: 2801. 10.1016/j.matlet.2004.04.016View Article
- Hirai H: Formation and catalytic functionality of synthetic polymer-noble metal colloid. J Macromol Sci Pure Appl Chem 1979, 13: 633. 10.1080/00222337908056678View Article
- Fukuda S, Kawamoto S, Gotoh Y: Degradation of Ag and Ag-alloy mirrors sputtered on poly(ethylene terephthalate) substrates under visible light irradiation. Thin Solid Films 2003, 442: 117. 10.1016/S0040-6090(03)00957-XView Article
- Herrero J, Guillén C: Transparent films on polymers for photovoltaic applications. Vacuum 2002, 67: 611. 10.1016/S0042-207X(02)00261-0View Article
- Chowdhury J, Ghosh M: Concentration-dependent surface-enhanced Raman scattering of 2-benzoylpyridine adsorbed on colloidal silver particles. J Colloid Interface Sci 2004, 277: 121. 10.1016/j.jcis.2004.04.030View Article
- Zhang SW, Zhou SX, Weng YM, Wu LM: Synthesis of SiO2/polystyrene nanocomposite particles via miniemulsion polymerization. Langmuir 2005, 21: 2124. 10.1021/la047652bView Article
- Willis HA, Zichy VJI, Hendra PJ: Laser-Raman and infra-red spectra of poly(methyl methacrylate). Polymer 1969, 10: 737.View Article
- Wang L, Chen D: “One-pot” Fabrication of Ag/PMMA “shell/core” Nanocomposites by Chemical Reduction Method. Chem Lett 2006, 33: 1010.View Article
- Hsu SL, Wu RT: Preparation of highly concentrated and stable suspensions of silver nanoparticles by an organic base catalyzed reduction reaction. Mater Res Bull 2008, 43: 1276. 10.1016/j.materresbull.2007.05.020View Article
- Chou KS, Ren CH: Synthesis of nanosized silver particles by chemical reduction method. Mater Chem Phys 2000, 64: 241. 10.1016/S0254-0584(00)00223-6View Article
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