Chapter two Review of nanomaterials 2.1. Synthesis of nanomaterials Materials Scientists are conducting research to develop novel materials with better properties, more functionality and fower cost than the existing ones. Several physical, chemical and biological synthesis methods have been developed to enhance the performance of nanomaterials displaying improved properties with the aim to have a better control over the particle size, distribution and morphology [1-3]. Synthesis of nanoparticles to have a better control over particles size, distribution, morphology, purity, quantity and quality, by employing environment friendly economical processes has always been a challenge for the researchers [4]. Synthesis methods and properties of nanomaterials studied in this research work are reviewed below. ‘The present work is focused at synthesis of nanoparticles and nanocomposites by Sol-gel and inert gas condensation methods, Basic infrastructure for these synthesis methods was ayailable in the labs of Department of Chemical and Materials Engineering (DCME), Pakistan Institute of Engineering and Applied Sciences (PIEAS). Sol-gel is considered a low temperature synthesis method that gives pure, homogeneous nanoparticles with good size distribution. Chemical reactions can be tailored at the molecular level to have a better control over the process and hence the properties of product particles. Spherical, pure nanoparticles having better size distribution are synthesized by inert gas condensation method. It is possible to produce nanoparticles of metal oxides and multi-components by using this method. The synthesized nanoparticles can be dispersed and embedded in polymer matrix with ease, Both these synthesis methods are easy to handle, economical and environmentally benign.2.2. Nanocomposites synthesized of by Sol-gel Sol-gel synthesis method has been used for the production of metal, metal oxide and ceramic nanoparticles with high purity and good homogeneity. Silica gels were synthesized in the year 1846, whereas alumina gels in 1870, since then, aerogels of zirconia, silazane, borate and other ccramics are being synthesized using Sol-gel method. This process involves the evolution of inorganic networks through formation of a colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase (gel). Three reactions generally describe the Sol-gel process: hydrolysis, alcohol condensation and water condensation. The characteristics and properties of a Sol-gel inorganic network have been related to a number of critical process parameters such as pH, temperature and time of reaction, reagent concentrations, catalyst nature and concentration, H2O/St molar ratio, aging temperature and time, and drying. These factors significantly affect the rate of hydrolysis and condensation reactions. The precursors for synthesizing colloids consist of a metal or metalloid element surrounded by various reactive ligands, The most widely used metal alkoxides are the alkoxysilanes, such as tetracthoxysilane (TEOS) and tetramethoxysilane (TMOS) however, other alkoxides such as aluminates, titanates and borates have also been used in the Sol-gel process, often mixed with TEOS [5-7]. 2.1.1. Silver-silica nanocomposite system Silver nanoparticles embedded in the silica matrix have been studied for a wide range of applications such as in optoelectronics, optical switches, optical waveguides, catalysts, antibacterial, surface-enhanced Raman scattering substrates [8-9]. Sol-gel is considered a promising low temperature method for preparation of metallic nanoparticles in temperature stable oxide matrices such as SiOz. 2.2.1.1. Optical studies on silver-silica nanocomposite Extensive work has been performed to investigate and tailor optical properties of silver nanocomposites for novel applications. Shibata ef al [10] have used a modified Stober method [11], and a silica film formation method, both Sol-gel based processes, to produce silica spheres containing silver nanoparticles. Surface smoothness, film thickness and particles mean size have been studied by SEM and TEM. In these samples, Surface PlasmonResonance (SPR) absorption peak has been observed at wavelength 420 nanometers (nm), attributed to formation of silver nanoparticles of mean size 2-6 nm. These silver-doped-silica spheres provide optical cavities that have been found useful to optical confinement and optical bi-stability, An annealing induced reversible change in optical absorption behavior of silver-silica nanocomposite has been reported by Bi ef a/ [2]. In this study, silver nanoparticles of mean size 10 nm have been found dispersed within pores of monolithic mesoporous silica. It has been demonstrated that heat treatment of samples in hydrogen or nitrogen environment has induced a strong SPR absorption peak around 400 nm. Subsequent annealing of these samples in air environment resulted into disappearance of SPR peak, which is attributed to formation of silver oxides particles. Thermodynamic analysis has revealed that a critical particle size existed for the oxidation of silver nanoparticles. Alternate annealing of samples in air and hydrogen or nitrogen environment has shown to induce an interchanging redox process of silver nanoparticles, demonstrating a reversible change in optical absorption. Li ef af [13] have described changes in optical and physical properties of silver nanoparticles of mean size 5-7 nm, embedded in silica thin films on the soda lime glass substrate, as a function of heating temperature, A blue shift in the SPR absorption peak has been observed in the samples when heat treatment temperature was increased from 373K to 473K, which is attributed to a decrease in particles size. Intensity of the silver SPR absorption peak reduced with the increasing heating temperature, which has been considered due to oxidation of silver nanoparticles. Silver concentration has been found to influence the viscosity and gelation process. Sodium from the glass substrate has diffused into the silver above 373K and enhanced the stability of silver oxide particles. Kiran er al [14] have investigated nonlinear optical behavior and the role of SPR on optical limiting (OL) properties of Ag-Cu nanoparticles, codoped in SiO; matrix at three wavelengths by shining Nd:YAG laser. These samples have shown self-defocusing nonlinearities in both nanosecond and picosecond laser pulses but a good nonlinear absorption leading to the OL behavior has been observed in the nanosecond excitation, The major contribution toward OL has been suggested due to the interband absorption and from a possible energy transfer within the higher anoccupied states of Cu and Ag, OL devices keep the laser energies below the damage threshold and are required to protect sensors and human eyes. Nonlinear optical properties of silver-silica nanocomposite thin films as a function of silver nanoparticles density have beenstudied by Scalisi et al [15]. At lower nanoparticles density, an optical limiting effect has becn observed, while at higher density values the nonlinear absorption coefficient changed its sign due to a saturable absorption process. A quantitative analysis of the nonlinear optical activity in these samples has shown a strong dependence of optical absorption on the nanoparticles size and concentration. Garcia et af [16] have synthesized silver-doped-silica thin coatings on pure silica and soda- lime substrates and subjected to different annealing processes. As reported by them, Ag” ions have been found diffused into pure silica matrix during annealing processes that reduced to ‘Ag’ and subsequently transformed to silver nanoparticles, even in oxidizing atmospheres. The diffusion kinetics of silver ions in glassy matrices, the interaction between these ions and their environment and optical response of the system have been discussed in this study, It has been demonstrated that due to presence of a large amount of nonbridging oxygen in the amorphous matrix, silver ions bonded to the oxygen remained stable and gave rise to their characteristic photoluminescence (PL) emission. Ameen ef al [17] have carried out physico- optical characterization of silver nanoparticles of mean size range 6-80 nm, well-dispersed in the silica matrix. SPR absorption has been analyzed as a function of nanoparticles size in the samples annealed at 573K and 773K. Silver oligomers have been found quite stable at 773K. It has been reported that in the samples containing silver nanoparticles of mean size range 6- 8 nm, porosity at the metal-matrix interface and the chemisorption occurring at the particle surface, were believed to dictate the position of optical absorption peak. Whereas for silver nanoparticles of relatively larger size 25-80 nm, diffused electron cloud outside the potential well has been observed and caused a red shift in the SPR absorption peak. 2.2.1.2. Effect of process parameters on the evolution of silver-silica nanocomposite Optimization of process parameters of synthesis methods has always been an interesting research area for the scientific community to improve the quality of processes. The effect of process variables such as annealing environment, temperature, duration and precursor concentration, etc. on the evolution of silver-silica nanocomposites synthesized by Sol-gel method has been reviewed in this section. Mitrikas ef al [18] have investigated the spin lattice relaxation (SLR) times by pulsed electron paramagnetic resonance (EPR) spectroscopy in a temperature range of 4-300K on silver nanoparticles of mean size 1-10 nm,