Hydrogen Uptake Kinetics of 1,4-Bis(phenylethynyl)benzene (DEB) Rubberized Coating on Silicone Foam Substrate.

The hydrogen uptake kinetics of 1,4-bis(phenylethynyl)benzene, or DEB, mixed with palladium (Pd) on activated carbon in a rubber matrix coating on top of a porous silicone foam substrate are investigated. First, isothermal isobaric hydrogenation experiments were performed under different temperatures and H2 pressures to extract the uptake kinetics. The H2 uptake models based on the measured kinetic parameters were then employed to investigate/simulate the performance of the getter under dynamic application environments. The actual hydrogenation characteristics in this type of getter are multifaceted and involve actual H2 concentration in the getter matrix, micrometer-scale diffusion of atomic hydrogen away from Pd sites, precipitation of hydrogenated DEB crystals at the coating surfaces, and mobility of fresh DEB molecules. The kinetic analysis/modeling methodology described in this report can serve as a template for other gas-solid reactions as well. Besides possessing a good hydrogen capacity and excellent performance, this type of rubberized getter also offers some unique advantages over traditional solid getter: flexible structure and protection of the Pd catalyst from exposure to the environment.

The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers.

The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities-that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150°C for up to five hours or to 125°C for up to 24 hours if stabilized with 10,000 ppm BQ and could also be heated to 125°C for up to 5 hours if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization of radiation sensitizers, thereby facilitating further development of radiation crosslinkable thermoplastic SMPs.

Photothermal properties of shape memory polymer micro-actuators for treating stroke.

BACKGROUND AND OBJECTIVES: In this paper the photothermal engineering issues of novel shape memory polymer (SMP) microactuators for treating stroke are presented. The engineering issues for using lasers to heat and subsequently actuate these SMP devices are presented in order to provide design criteria and guidelines for intravascular, laser activated SMP devices. MATERIALS AND METHODS: A total of three devices will be presented: two interventional ischemic stroke devices (coil and umbrella) and one device for releasing embolic coils (microgripper). The optical properties of SMP, methods for coupling laser light into SMP, heating distributions in the SMP devices, and the impact of operating the thermally activated material in a blood vessel are presented. RESULTS: Actuating the devices requires device temperatures in the range of 65-85 degrees C. Attaining these temperatures under flow conditions requires critical engineering of the SMP optical properties, optical coupling into the SMP, and device geometries. CONCLUSION: Laser-activated SMP devices are a unique combination of laser-tissue and biomaterial technologies. Successful deployment of the microactuator requires well-engineered coupling of the light from the diffusing fiber through the blood into the SMP.