Achieving clay dispersion and improving clay−polymer interactions are keys to producing superior nanocomposites. A supercritical CO2 (scCO2) processing method was utilized to prepare high molecular weight polystyrene (PS)/Cloisite 10A nanocomposites with significant dispersion and rheological enhancement. The effects of scCO2 processing, presence of cosolvent, and clay weight fraction on clay dispersion and polymer−clay interactions in nanocomposites were investigated. Rheology, WAXD, and TEM of the nanocomposites indicate that substantial improvements in the rheological properties of scCO2 nanocomposites are the result of increased dispersion and polymer−clay interactions. At low frequencies, the elastic plateau modulus of the scCO2-processing nanocomposites (5 wt % clay loading) is more than 40-fold higher than benchmark solution-blended samples. Our results suggest that the substantial contacting with scCO2, followed by rapid depressurization, produces a combination of disorder and dispersion of this “as-received” clay, and the presence of the cosolvent enables more intimate contact of the high molecular weight PS and clay.
Thermoplastic polyurethane is one of the most versatile thermoplastic materials being used in a myriad of industrial and commercial applications. Thermoplastic polyurethane foams are finding new applications in various industries including the furniture, automotive, sportswear, and packaging industries because of their easy processability and desirable customizable properties. In this study, three methods of manufacturing injection molded low density foams were investigated and compared: (1) using chemical blowing agents, (2) using microcellular injection molding with N2 as the blowing agent, and (3) using a combination of supercritical gas-laden pellets injection molding foaming technology and microcellular injection molding processes using co-blowing agents CO2 and N2. Thermal, rheological, microscopic imaging, and mechanical testing were carried out on the molded samples with increasing amounts of blowing agents. The results showed that the use of physical blowing agents yielded softer foams, while the use of CO2 and N2 as co-blowing agents helped to manufacture foams with lower bulk densities, better microstructures, and lower hysteresis loss ratios. Chemical blowing agent-foamed thermoplastic polyurethane showed an earlier onset of degradation. The average cell size decreased and the cell density increased with the use of co-blowing agents. A further increase in gas saturation levels showed a degradation of microstructure by cell coalescence.
Thermoplastic polyurethane is one of the most versatile thermoplastic materials being used in a myriad of industrial and commercial applications. Thermoplastic polyurethane foams are finding new applications in various industries including furniture, automotive, sportswear, and packaging because of their easy processability and desirable, customizable properties. Low bulk density and a good foam microstructure are important properties that affect the mechanical properties, economics, and performance of the final product. In this study, the effect of a cross-linking agent on the foamability of microcellular injection molded thermoplastic polyurethane was studied with an aim to reduce the bulk density while achieving a consistent microstructure. Gel permeation chromatography showed an increase in the weight average molecular weight by 5.0% with the addition of a cross-linking agent. Rheological studies on the materials showed that the addition of a cross-linking agent increased the storage modulus and viscosity, while reducing the tan δ value. Using microcellular injection molding, cross-linked thermoplastic polyurethane could be foamed to a minimum density of 0.159 g/cc at the higher end of the processing window, as compared with a minimum density of 0.193 g/cc for pure thermoplastic polyurethane foam. Scanning electron microscope analyses of the foamed parts showed a bimodal foam structure for thermoplastic polyurethane with a cross-linking agent and a more integral foam structure with less cell coalescence even at higher density reductions.
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