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).
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