In this research, cubic zirconium tungstate (ZrW2O8) was used as a filler to reduce the CTE of polyimides (PI), and the effect of ZrW2O8 nanoparticles on the bulk polymer properties was studied. Polyimides are high performance polymers with exceptional thermal stability, and there is a need for PIs with low CTEs for high temperature applications. The nanofiller, cubic ZrW2O8, is well known for its isotropic negative thermal expansion (NTE) over a wide temperature range from -272.7 to 777°C.;The preparation of nanocomposites involved the synthesis of ZrW 2O8 nanofiller, engineering the polymer-filler interface using linker groups and optimization of processing strategies to prepare free-standing PI nanocomposite films. A hydrothermal method was used to synthesize ZrW 2O8 nanoparticles. Polyimide-ZrW2O8 interface interaction was enhanced by covalently bonding linker moieties to the surface of ZrW2O8 nanoparticles. Specifically, ZrW 2O8 nanoparticles were functionalized with two different linker groups: (1) a short aliphatic silane, and (2) low molecular weight PI. The surface functionalization was confirmed using X-ray photoelectron spectroscopy and thermal gravimetric analysis (TGA). Reprecipitation blending was used to prepare the freestanding PI-ZrW2O8 nanocomposite films with up to 15 volume% filler loading. SEM images showed the improvements in polymer-filler wetting behavior achieved using interface engineering. SEM images indicated that there was better filler dispersion in the PI matrix using reprecipitation blending, compared to the filler dispersion achieved in the nanocomposites prepared using conventional blending technique.;The structure-property relationships in PI-ZrW2O8 nanocomposites were investigated by studying the thermal degradation, glass transition, tensile and thermal expansion properties of the nanocomposites. The properties were studied as a function of filler loading and interface linker groups. Addition of ZrW2O8 nanoparticles did not alter the thermal degradation and glass transition temperatures of the base PI. The addition of ZrW2O8 nanoparticles increased the Young's modulus of the polymer, indicating the stiffening of polyimide matrix. The modulus showed a steady increase with increase in filler loading. The increase was higher for nanocomposites with engineered interface due to the efficient load transfer achieved through the presence of linker groups. The strain at yield and the tensile strength decreased with the addition of ZrW2O8. The experimental results for the moduli of nanocomposites were compared with moduli predicted using theoretical models. The results for the nanocomposites with unmodified ZrW2O8 followed Hashin-Shtrikman (H-S) lower bound, which showed the presence of mechanical interactions between the polymer and filler. The moduli for nanocomposites with engineered interface fell between the H-S bounds, demonstrating the stiffening of PI matrix through efficient load transfer.;The addition of ZrW2O8 reduced the in-plane CTE of the base PI at all loadings. The CTE of the nanocomposites decreased steadily with an increase in the filler loading. With the addition of 15 volume% APT-ZrW 2O8, the CTE of the base PI reduced from 64.3 +/- 1.3 ppm/°C to 51.9 +/- 0.9 ppm/°C. In other words, the CTE of the base PI was reduced by around 22% with the addition of ZrW2O 8 at 15 volume% loading. The CTE values were comparable for all samples at similar loadings irrespective of the interface groups. The experimental results for the CTEs of nanocomposites were compared with CTEs predicted using theoretical models. The data followed the Schapery upper bound, which was consistent with the results observed for the moduli data.;The effect of ZrW2O8 particle size on the bulk properties of the polyimide was also investigated. The CTE of composites with micron particles at 5 volume% was comparable to that obtained for nanocomposites at the same filler loading. But, there were significant differences in the mechanical strength of composites. PI composites with ZrW2O 8 micron particles were extremely brittle and readily crumbled at as low as 5 volume%, while composites with ZrW2O8 nanofiller had good mechanical strength up to 15 volume% filler loading.;The nanoparticles of ZrW2O8 exhibited autohydration under ambient conditions. Cubic ZrW2O8 nanoparticles continued to hydrate to the same extent even after incorporation into the polyimide matrix. Surface functionalization of ZrW2O8 with silane and PI oligomers did not alter the hydration behavior of ZrW 2O8. (Abstract shortened by UMI.)
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