Hybrids nanocomposites

The hybrid nanocomposite polymer-silica materials on the basis of oligomer alkoxysilane (polyethoxysilane (PES) obtained from tetraethoxysilane) with polycaproamide, polyacrylonitrile, chitosan and zirconyl oxychloride were investigated. 

Polymer-Inorganic Hybrid Nanocomposites through Sol-Gel Reaction.58... 

SCHEME 3.2 Preparation chart of mbber-m situ silica hybrid nanocomposites reported by Bandyopadhyay et al. (From Bandyopadhyay, A., Bhowmick, A.K., and De Sarkar, M., J. Appl. Polym. Sci., 93, 2579, 2004. Courtesy of Wiley InterScience.)... 

This process is highly suitable for rubbers with poor solubility. In this process, the rubber sheet is soaked in TEOS or quite often in TEOS-solvent mixture and the in situ sUica generation is conducted by either acid or base catalysis. The sol-gel reaction is normally carried out at room temperature. Kohjiya et al. [29-31] have reported various nonpolar mbber-silica hybrid nanocomposites based on this technique. The network density of the rubber influences the swelling behavior and hence controls the silica formation. It is very likely that there has been a graded silica concentration from surface to the bulk due to limited swelling of the rubber. This process has been predominantly used to prepare ionomer-inorganic hybrids by Siuzdak et al. [48-50]. 

The simultaneous polymerization and sol-gel reaction often brings complexity to the overall reaction. Moreover, it is difficult to control the molecular weight of the sample. Recently, Patel et al. [51] have synthesized the rubber grade acrylic copolymers and terpolymers-/n situ silica hybrid nanocomposites using this technique. 

EFFECT OF ALKOXYSILANE ON STRUCTURE AND PROPERTIES OF RUBBER-SILICA HYBRID NANOCOMPOSITES... 

FIGURE 3.3 (a) Transmission electron microscopic (TEM) image of acrylic rubber (ACM)-siUca hybrid nanocomposite synthesized from 10 wt% of tetraethoxysilane (TEOS). (From Bandyopadhyay, A., Bhowmick, A.K., and De Sarkar, M., J. Appl. Polym. Sci., 93, 2579, 2004. Courtesy of Wiley Interscience.) Transmission electron microscopic (TEM) photographs of acrylic rubber (ACM)-silica hybrid nanocomposites prepared from (b) 30 wt% and (c) 50 wt% tetraethoxysilane (TEOS) concentrations. (From Bandyopadhyay, A., Bhowmick, A.K., and De Sarkar, M., J. Appl. Polym. Sci., 93, 2579, 2004. Courtesy of Wiley InterScience.)... 

FIGURE 3.4 Scanning electron microscopic (SEM) images of acrylic copolymer-silica hybrid nanocomposites synthesized from (a) 10 wt% and (b) 50 wt% tetraethoxysilane (TEOS) concentrations. The first number in the legend indicates the wt% of ethyl acrylate (EA) (85) in the ethyl acrylate-butyl acrylate (EA-BA) copolymer, N stands for nanocomposite, and the last number (10, 50) is indicative of the tetraethoxysilane (TEOS) concentration. (From Patel, S., Bandyopadhyay, A., Vijayabaskar, V., and Bhowmick, A.K., J. Mater. Sci., 41, 926, 2006. Courtesy of Springer.)... 

Higher extent of silica generation with high TEOS concentration improves the mechanical properties severalfolds as illustrated by the tensile stress-strain plots on ACM-sdica hybrid nanocomposites on increasing TEOS concentrations in Figure 3.6. 

TEOS-Silica Interconversion in the Rubber-Silica Hybrid Nanocomposites... 

Dispersion of nanosilica within the mbber matrices usually generates optically transparent materials. All the ACM-silica and ENR-sihca hybrid composites are completely transparent up to 50 wt% of TEOS concentrations. EoUowing are the figures (Figure 3.9) which show the visual appearance of the representative hybrid nanocomposites. The logos over which the films (average film thickness 0.25 mm) are placed are clearly visible. 

FIGURE 3.9 Visual appearance of (a) ACM30 and (b) ENR30 hybrid nanocomposite films. The number indicates the wt% tetraethoxysilane (TEOS) concentration. (From Bandyopadhyay. A., Thesis submitted for PhD degree to Indian Institute of Technology, Kharagpur, India, August 2005.)... 

Different characteristics of solvents seriously affect the sol-gel reaction in solution. This in turn influences the physico-mechanical properties of the resultant rubber-silica hybrid composites. Bandyopadhyay et al. [34,35] have carried out extensive research on stmcture-property correlation in sol-gel-derived rubber-sihca hybrid nanocomposites in different solvents with both chemically interactive (ENR) and noninteractive (ACM) mbber matrices. Figure 3.12 demonstrates the morphology of representative ACM-sihca and ENR-sihca hybrid composites prepared from various solvents. In all the instances, the concentration of TEOS (45 wt%), TEOS/H2O mole ratio (1 2), pH (1.5), and the gelling temperature (ambient condition) were kept unchanged. 

Tian et al. [56] have studied poly(G-caprolactone)-silica and Sengupta et al. [57] have investigated nylon 66-silica hybrid systems and have observed that the phase separation started when Si/H20 mole ratio is increased above 2 and the resultant hybrid films become opaque. Gao [11] has reported similar observations on sol-gel-derived ionomeric polyethylene-silica system. A wide range of literatures is not available on this topic of mbber-silica hybrid nanocomposites, though Bandyopadhyay et al. [34,35] have reported the hybrid formation with different TEOS/H2O mole ratios from ACM and ENR and also demonstrated detailed structure-property correlation in these systems. The hybrids have been prepared with 1 1, 1 2, 1 4, 1 6, 1 8, and 1 10 TEOS/H2O mole ratios. Figure 3.14 shows the morphology of the ACM-silica hybrid composites prepared from different TEOS/H2O mole ratios. 

Adsorption of rubber over the nanosilica particles alters the viscoelastic responses. Analysis of dynamic mechanical properties therefore provides a direct clue of the mbber-silica interaction. Figure 3.22 shows the variation in storage modulus (log scale) and tan 8 against temperature for ACM-silica, ENR-silica, and in situ acrylic copolymer and terpolymer-silica hybrid nanocomposites. 

Presence of nanosilica and its interaction with the rubber matrices strongly affect the low and high temperature degradation behaviour of the hybrid nanocomposites. Figure 3.24 shows the post-aging swelling analysis of the cross-linked ACM-sihca and ENR-silica hybrid nanocomposites. The data points are collected after aging of the samples at 50°C, 70°C, and 90°C for 72 h. 

FIGURE 3.24 Plots of volume fraction of the filled rubber in the swollen gel (Vrf) against aging temperature for acrylic rubber (ACM)-silica and epoxidized natural rubber (ENR)-silica hybrid nanocomposites. (From Bandyopadhyay, A. and Bhowmick, A.K., Plastic Rubber Comp. Macromol. Eng., 35, 210, 2006. Courtesy of Money Publishers.)... 

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