Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

640 × 512 pixel narrow-band, four-band, and broad-band quantum well infrared photodetector focal plane arrays

A 9 μm cutoff 640 × 512 pixel hand-held quantum well infrared photodetector (QWIP) camera has been demonstrated with excellent imagery. A noise equivalent differential temperature (NEDT) of 10.6 mK is expected at a 65 K operating temperature with f/2 optics at a 300 K background. This focal plane array has shown background limited performance at a 72 K operating temperature with the same optics and background conditions. In this paper, we discuss the development of this very sensitive long-wavelength infrared camera based on a GaAs/AlGaAs QWIP focal plane array and its performance in quantum efficiency, NEDT, uniformity, and operability. In the second section of this paper, we discuss the first demonstration of a monolithic spatially separated four-band 640 × 512 pixel QWIP focal plane array and its performance. The four spectral bands cover 4–5.5, 8.5–10, 10–12, and 13.5–15 μm spectral regions with 640 × 128 pixels in each band. In the last section, we discuss the array performance of a 640 × 512 pixel broad-band (10–16 μm full-width at half-maximum) QWIP focal plane.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007     

The synthesis,characterization, and weathering behavior of polycarbonates derived from bis(P-hydroxyphenyl) dimethylsilane (BPSI)

Polycarbonates and copolycarbonates based on BPSi and BPA were easily made using the standard interfacial technique. Molecular weight and NMR data indicate that up to 4 mol % of the BPSi decomposes during polymerization via a base-catalyzed rearrangement of BPSi to arylsiloxanes. Oxygen index studies show an increased flame resistance with increasing BPSi monomer content. DSC measurements show a decrease in glass transition with BPSi monomer concentration while TGA shows an increase in char residue with BPSi monomer content. In addition, TGA indicates no change in either thermal or thermooxidative stability with the relative BPSi/BPA concentrations. Outdoor weathering of BPSi PC and BPA PC films indicates that BPSi PC is ca. 5 times more weathering resistant than BPA PC. This latter result can be attributed to a combination of BPSi PC's lower UV absorptivity, higher water repellency, and lower likelihood for side chain photooxidation. © 1993 John Wiley & Sons, Inc.     

Wavelength dependence in photochemical vapor deposition of aluminum film using dimethylaluminum hydride

In photochemical vapor deposition of aluminum film on silicon using dimethylaluminum hydride, (CH₃)₂AlH, a surface reaction dominated below a (CH₃)₂AlH pressure of 0.3 m Torr at 200°C, which was induced only with the 160 nm band emitted from a deuterium lamp. A gas-phase reaction occurred above 0.3 mTorr at 200°C, which could be induced by both 160 nm and 240 nm emission bands from the lamp. To distinguish between surface ad gas-phase reactions, a thickness profile was used. At 240°C the surface reaction could be induced even by the 240 nm band, while the deposits formed under illumination of the two bands were thinner than those obtained with only the 240 nm band, indicating occurrence of vacuum ultraviolet (VUV)-enhanced desorption. The mechanism responsible for the observed wavelength dependence in unclear. The electrical resistivity of the films deposited at 200°C was 4.5 μΩ cm, which did not change with wavelength.     

Echo planar imaging of perfluorocarbons

Emulsions of perfluorotributylamine (FTBA) and perflubron were evaluated for their utility in ¹⁹F echo planar imaging. Fluorine images of the emulsions were obtained in a phantom and two mice that had been predosed. Both agents, but particularly perflubron, show potential for fluorine echo planar studies because of the long spin-spin relaxation times of the CF₃ resonances. High resolution thin slice images obtained in as little as 26.6 ms are presented.     

A facile synthesis of per (poly )fluoroalkyl substituted α-amino acid derivatives

Initiated by CrCl3/Fe redox couple, per(poly)fluoroalkyl iodides added to methyl a-acetylamino acrylate, giving B-per(poly)fluoroalkyl a-amino acid derivatives in good yields.