Publications

Preliminary thermal decomposition experiments with Ablefoam and EF-AR20 foam (Ablefoam replacement) were done to determine the important chemical and associated physical phenomena that should be investigated to develop the foam decomposition chemistry sub-models that are required in numerical simulations of the fire-induced response of foam-filled engineered systems for nuclear safety applications. Although the two epoxy foams are physically and chemically similar, the thermal decomposition of each foam involves different chemical mechanisms, and the associated physical behavior of the foams, particularly ''foaming'' and ''liquefaction,'' have significant implications for modeling. A simplified decomposition chemistry sub-model is suggested that, subject to certain caveats, may be appropriate for ''scoping-type'' calculations.

The main goal of this research was to develop degradable systems either by developing weaklink-containing polymers or identifying commercial polymeric systems which are easily degraded. In both cases, the degradation method involves environmentally friendly chemistries. The weaklinks are easily degradable fragments which are introduced either randomly or regularly in the polymer backbone or as crosslinking sites to make high molecular weight systems via branching. The authors targeted three general application areas: (1) non-lethal deterrents, (2) removable encapsulants, and (3) readily recyclable/environmentally friendly polymers for structural and thin film applications.

The simultaneous formation of a filler phase and a polymer matrix via in situ sol-gel techniques provides silica-siloxane nanocomposite materials of high strength. This study concentrates on investigating the effects of temperature and relative humidity (RH) on a trimodal polymer system in an attempt to accelerate the reaction as well as evaluate subtle process-structure-property relationships. It was found that successful process acceleration is only viable for high humidity systems when using the tin(IV) catalyst dibutyltin dilaurate (DBTDL). Processes involving low humidity were found to be very temperature and time dependent. Bimodal systems were investigated and demonstrated that the presence of a short-chain component led to enhanced material strength. This part of the study also revealed a link between the particle size and population density and the optimization of material properties.

The effect of solvent addition on the phase separation, mechanical properties and thermal stability of silica/siloxane composite materials prepared by in situ reinforcement was examined. The addition of a solvent enhances the miscibility of the reinforcement precursor, a partial hydrolyzate of tetraethoxysilane (TEOS-PH), with the polydimethylsiloxane (PDMS) polymer. As a result, the phase separation at the micron level, termed the large-scale structure, diminished in size. This decrease in particle size resulting from the addition of moderate amounts of solvent was accompanied by an improvement in the mechanical properties. However, solvent addition in the excess of 50 weight percent led to a decrease in mechanical properties even though the large-scale structure continued to diminish in size. Small Angle X-Ray Scattering (SAXS) was used to examine the angstrom level or small-scale structure. This small-scale structure was only affected by the presence of solvent, not the amount. The silica/siloxane composite materials showed the same thermal transition temperatures as the original PDMS material.

Currently, the production of in situ reinforcement in polymeric systems by sol-gel methods is undergoing rapid development. However, understanding of synthesis/structure/property relationships is still lacking. In order to produce sol-gel derived composite materials with sufficient mechanical properties for commercial applications, this deficit of information must be addressed. We have completed a detailed investigation of in situ silica growth in polydimethylsiloxane (PDMS)/tetraethylorthosilicate (TEOS) systems. Factors which affect the domain growth, such as catalyst activity and silica loading, have been examined by solid state {sup 29}Si NMR, SEM, mechanical testing and small angle neutron scattering.