We studied the hydrolysis kinetics of amorphous polylactide. It was found the hydrolysis rate had a slow-to-fast transition at a certain molecular weight (Mn). This transition was not correlated with the mass loss and water uptake of samples, nor the pH values of testing media. We speculated that this transition was due to the slow diffusion of polymer chain ends. The chain ends did not significantly promote the hydrolysis of samples until their concentrations (approximately 1/Mn) reached a critical value. The degradation tests were also conducted over a temperature range from 37 to 90 degrees C. A time-temperature equivalent relationship of degradation processes was established and a master curve spanning a time range equivalent to 3-5 years at 37 degrees C was constructed. This master curve can be used to predict polymer degradation processes based on accelerated tests. The functional time and disappearance time of degradable polymers were also discussed.

Segmented polyurethane multiblock polymers containing polydimethylsiloxane and polyether soft segments form tough and easily processed thermoplastic elastomers. Two commercially available examples, Elast-Eon E2A (denoted as E2A) and PurSil 35 (denoted as P35), were evaluated for molecular and mechanical stability after immersion in buffered water for up to 52 weeks at temperatures ranging from 37 to 85 °C. Dynamic mechanical spectroscopy experiments, performed in tension and shear, were used to characterize the linear viscoelastic properties of compression-molded (dry) specimens. Small-angle X-ray scattering measurements indicated a disorganized microphase-separated morphology for all test conditions. Upon aging in phosphate buffered saline, samples of E2A and P35 were analyzed by size exclusion chromatography (SEC) and tensile testing as a function of time and temperature. The absolute molar mass of each material prior to aging in water was determined by SEC using a multiangle light scattering detector. Aging at 85 °C and 52 weeks lead to a 67% and 50% reduction in molar mass from the original values for E2A and P35, respectively. We attribute the reduction in molar mass to hydrolysis of the polymer backbone and have evaluated the data using a pseudo-zero-order kinetics analysis. The temperature dependence of the extracted rate data is consistent with an activated (i.e., Arrhenius) process, and thus all the molar mass reduction data can be reduced to a single master curve. Concomitant with the reduction in molar mass, E2A and P35 transformed with aging from strain-hardening to strain-softening materials, characterized by substantially reduced tensile strength (stress at failure) and ultimate elongation (strain at failure) relative to the original properties.

Adding conductive fillers to nonconductive polymers is a common way to make soft conductive materials such as conductive adhesives. An important issue is how to achieve high volume conductivity with acceptable mechanical performance. Two questions pertaining to this issue were studied in this paper. One question was whether the maximum conductivity benefits from larger or smaller particle sizes. The second was what is the maximum achievable conductivity. One incentive for this work is the recent availability of nanomaterials that provide opportunities to make conductive composites using much smaller particles than in the past. We found that the conductivity of platinum, carbon black, and silver particles in their polyurethane composites did not vary greatly with particle size (from micrometer to nanometer range). What was unexpected was that in all the composite examples, the highest conductivity achieved was only on the order of 1% of that of the pure bulk conductive materials. Further experiments to emulate these conductive composites with platinum, carbon black, copper, and nickel particles without polymer matrix showed similar results, indicating the issue is not simply dispersion homogeneity, nano versus macro particles, particle connectivity/percolation, or the presence of the matrix materials. We interpret this to mean that the composite systems are intrinsically limited by the contact between filler particles.

New and improved properties can often be achieved by compounding two or more different but compatible materials. But, can failure possibility also be increased by such a compounding strategy? In this article, we compared the in vitro biostability of composites with that of the pure polymer. We tested three model composites in oxidative, acidic, basic, and neutral solutions. We found that oxidation degradation was much more profound in the composites than in the corresponding pure polymer. This degradation seemed to be an intrinsic property of composite materials. We also observed the well documented interfacial debonding between filler and matrix and its effects on the mechanical reinforcement of the hydrated composites. The improvements in acid and base resistance were also observed.

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