Styrene-block-butadiene-block-styrene (SBS) triblock copolymers epoxidized at several epoxidation degrees by hydrogen peroxide in water/dichloroethane biphasic system were blended with epoxy based on diglycidyl ether of bisphenol A (DGEBA) and DDM (4,4′-diaminodiphenyl methane) as curing agent. The incorporation of epoxidized block copolymers in epoxy resulted in the formation of nanostructured blends. The morphologies of the blended polymers were studied using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS) analysis. The key factor controlling the morphology is the mole percentage of epoxidised butadiene units in SBS. In fact, the morphologies changed from macroscopic phase separated domains in unmodified SBS to nanostructured domains in epoxidised SBS and the resulting morphologies were fixed by the cross-linking reaction. Nanostructured morphologies such as worm-like and spherical micelles (radius 8 nm) were generated due to reaction induced phase separation of PS phase followed by the self-assembly of PB sub chains. The mechanical properties such as fracture toughness (stress field intensity factor (K IC )), and impact strength of these blended systems were measured. It was established that nanostructured blends significantly improved fracture toughness and impact strength. Field emission scanning electron micrographs of fractured surfaces were examined to understand the toughening mechanism.
Styrene-block-butadiene-block-styrene (SBS) triblock copolymer epoxidized with 47 mol % degree of epoxidation (eSBS47) by hydrogen peroxide in a water/dichloroethane biphasic system was blended with epoxy based on diglycidyl ether of bisphenol A (DGEBA) and 4,4′-diaminodiphenylmethane (DDM) as a curing agent. The amounts of eSBS in the blends were 10 and 20 wt %. The evolution of the glass transition temperatures (T g) of the cured blends at different cure times was analyzed using differential scanning calorimetry (DSC) to understand the thermal behavior of epoxy system under dynamic conditions in the presence of eSBS. Transmission electron microscopy (TEM) analysis revealed core–shell nanodomains of eSBS dispersed in the epoxy matrix. The relationship between rheology and phase separation was carefully explored. Dynamic mechanical analysis (DMA) validated the nanophase-separated structure of the eSBS47-modified epoxy system. Upon addition of eSBS47 to the epoxy system, the fracture toughness of the nanostructured thermosets was improved, and the thermal stability was retained, but the dimensional stability was slightly decreased.
Nanocomposite membranes based on poly-(ethylene-co-vinyl acetate) copolymer (18% vinyl acetate content) and two different organomodified clays have been prepared by mechanical mixing using two roll mill method. The morphology of the nanocomposites was investigated using small angle X-ray scattering, scanning electron microscopy, and transmission electron microscopy. The mechanical and thermal studies were also performed using universal testing machine and differential scanning calorimeter, respectively. Samples with low filler content showed excellent dispersion of layered silicates resulting in a partially exfoliated structure. The diffusion and transport of organic solvents through the membranes have been investigated in detail as a function of clay content, nature of solvent and clay, and temperature in the temperature range of 28−70 °C. The influence of free volume on the transport properties of the membranes was studied using positron annihilation lifetime spectroscopy. The solvent uptake was minimum for composites with 3 wt % of filler, and it get increased with increasing filler content, which is presumably due to aggregation of clay filler at higher loading. The transport phenomenon was found to follow an anomalous mode. Activation parameters were estimated, and the molar mass between cross-links was calculated. Finally, the experimental transport data were compared with theoretical predictions.
The compatibility of styrene‐block‐butadiene‐block‐styrene (SBS) triblockcopolymer in epoxy resin is increased by the epoxidation of butadiene segment, using hydrogen peroxide in the presence of an in situ prepared catalyst in water/dichloroethane biphasic system. Highly epoxidized SBS (epoxy content SBS >26 mol%) give rise to nanostructured blends with epoxy resin. The cure kinetics of micro and nanostructured blends of epoxy resin [diglycidyl ether of bisphenol A; (DGEBA)]/amine curing agent [4,4′‐diaminodiphenylmethane (DDM)] with epoxidized styrene‐block‐butadiene‐block‐styrene (eSBS 47 mol%) triblock copolymer has been studied for the first time using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as kinetic constants and activation energy. The cure reaction rate is decreased with increasing the concentration of eSBS in the blends and also with the lowering of cure temperature. The compatibility of eSBS in epoxy resin is investigated in detailed by Fourier transform infrared spectroscopy, optical and transmition electron microscopic analysis. The experimental data of the cure behavior for the systems, epoxy/DDM and epoxy/eSBS(47 mol%)/DDM show an autocatalytic behavior regardless of the presence of eSBS in agreement with Kamal's model. The thermal stability of cured resins is also evaluated using thermogravimetry in nitrogen atmosphere. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers
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