1999 рік

Five different poly(amic dialkyl ester) precursors with various chain rigidities were synthesized and their powder and film samples were prepared in residual solvent free: poly(4,4⬘-oxydiphenylene biphenyltetracarboxamic diethyl ester); poly(p-phenylene biphenyltetracarboxamic diethyl ester); poly(p-phenylene biphenyltetracarboxamic dimethyl ester); poly(4,4⬘-oxydiphenylene pyromellitamic diethyl ester); and poly(p-phenylene pyromellitamic diethyl ester). Glass transition temperatures (T gs) of these precursors, which have never been reported so far, were successfully determined in the present study by the new oscillating differential scanning calorimetry (o.d.s.c.). In addition, their imidization behaviours and morphological structures were investigated by o.d.s.c. and X-ray diffraction, respectively. The measured T gs are in the range 179.2–235.4°C, depending upon the precursor backbone structure as well as the history of sample preparation: these T gs are very close to the imidization temperatures (T is), causing difficulties in the T g measurements. The measured T is are in the range 198.1–235.4°C, depending upon the precursor backbone structure as well as the history of sample preparation. The T gs are dependent on the chain rigidity and the morphological structure, whereas the T is are influenced by the chemical nature in addition to the chain rigidity and the morphological structure.

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Electrospinning is a straightforward method to produce polymer fibers from polymer solutions, with diameters in the range of 100 nm. Electrospun fibers often have beads in regular arrays. The viscoelasticity of the solution, charge density carried by the jet, and the surface tension of the solution are the key factors that influence the formation of the beaded fibers.

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A combined study of b 0 and a relaxations in poly(methyl methacrylate) (PMMA) by thermally stimulated depolarization currents and thermal step methods has been made. The use of null width polarization windows to form the electrets allows us to isolate the b 0 peak. The charge distribution profiles allow us to assign a polar orientational mechanism for the b 0 relaxation and in the case of the a peak a background polar mechanism over which a temperature-dependent injection and a conduction processes are overlapped. The charge distribution profiles observed by the thermal step method indicate that the increase of the conductivity observed in this material at temperatures just below the glass transition is mainly due to the positive carriers.

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We report on the dielectric normal mode relaxation of the isoprene block chains in dilute and semidilute solutions of butadiene–isoprene (BI) diblock copolymers and butadiene–isoprene–butadiene (BIB) triblock copolymers. The dielectric loss ε'' curves in dilute solutions with a concentration close to the overlapping concentration C* agreed approximately with those predicted by the bead–spring model. Above a concentration about three times higher than C*, the ε'' curves broadened with increasing concentration indicating the strong concentration dependence of the distribution of the normal modes. Two maxima of the ε'' curves were observed for BIB solutions. In semidilute solutions of BIB, the ε'' peak located in the high frequency side shifted little with concentration but the ε'' peak in the low frequency side shifted towards low frequency with increasing concentration. This suggests that the lower order normal modes are affected by entanglement effects but the higher order modes are not, for semidilute solutions. We have attempted to explain the distribution of the normal modes in terms of the blob model.

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Recently we reported on chitosan hydrogel systems having excellent laser damage resistance. The measured laser damage threshold (LDT) was better than BK7 glass and quartz, commonly used inorganic optical materials, and 20 to 35 times higher than commercial PMMA, a popular polymer optical material. In this study, we continue our investigation of the phase transition behavior of water within the hydrogels by means of oscillatory shear rheology. The crystallization and melting behavior of ice in these hydrogels is greatly affected by the internal structure of the network. Changes in this structure are probed by comparing differences in the rheological measurements at temperatures above and below freezing. Trends among the measured shear storage modulus (G 0 ), shear loss modulus (G 00 ) and shear loss tangent (tan d ) are shown to be related to the mobility of water within the gels. The activation energy associated with the melting of ice in a particular hydrogel was found to be significantly higher than the melting enthalpy of pure ice, suggesting imperfection in the ice crystals and/or a low degree of crystallinity in the hydrogel.

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Several series of copolymers were prepared from N-substituted acrylamides by free radical polymerization in solution. We have selected a group of monomers with varying degree of hydrophilicity including acrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-tert-butylacrylamide. The chemical composition in the final copolymers was found to be very close to the original monomer composition in the feed prior to polymerization. In an effort to elucidate the effect of the chemical composition on the phase separations of the aqueous solutions of the copolymers, the lower critical solution temperatures (LCST) of the copolymers in water were determined by differential scanning calorimetry and optical turbidimetry. In principal, the LCST of the copolymers can be adjusted within the freezing and boiling points of the solutions. The copolymers exhibit systematic changes in their LCSTs as a function of their comonomer composition, for which an empirical equation was established.

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The crystal structure of isotactic poly(2-vinylpyridine) (iP2VP) established in 1977 by Puterman et al. is shown to conform to a recently proposed frustrated packing scheme which involves three isochiral three-fold helices packed in a trigonal unit-cell, and observed in a number of polymers and biopolymers. Single crystals of iP2VP grown from thin films at high temperature (Tc = 200°C) display highly unusual morphologies with six (100) growth sectors but a three-fold overall symmetry apparent through different lame&r thicknesses in adjacent growth sectors, and oblique growth facets of three of the sectors. These features are morphological manifestations of the frustration of the helix packing, and support the P3 1or P32 space group of the unit-cell. The different lamellar thicknesses are mainly due to an isothermal thickening process, which has different impacts depending on the nature of the growth faces. Analysis of the growth features of frustrated structures can be of help when dealing with finer details of theories of polymer crystal growth

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A study has been made of the effect of an imposed tensile stress on the rate of hydrolysis of geotextile grade polyester in aqueous sodium hydroxide solution at room temperature. Weight losses of samples stressed with loads up to the yield point were virtually the same as for relaxed samples. For stresses which exceeded the yield point, significantly larger weight losses were obtained, particularly at longer reaction times. The mechanical properties of the filaments, particularly tenacity, breaking strain and work of rupture, were reduced as the imposed stress increased, and very severe losses in properties were observed when the stress exceeded the yield stress. Scanning electron microscopy revealed that, at the highest stresses studied, surface cracking occurred, which became progressively more severe as the time of treatment increased. An empirical equation was obtained which showed that the breaking load of the filaments decreased proportionally with time and with the square of the imposed stress.

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Small angle X-ray scattering measurements were performed on epoxies to determine their network structure. To provide the necessary scattering contrast the epoxy monomer used was a partially brominated diglycidyl ether of bisphenol A and the cross-linking agents were linear, low polydispersity, amine terminated poly(propylene oxide)s. Samples with both single and bimodal molecular weight distributions of cross-linking agent were prepared. A pronounced scattering maximum was observed in all networks and it can be interpreted in terms of correlation holes. Networks cured with a mixture of two cross-linking agents with different molecular weights, i.e. bimodal networks, exhibited scattering maxima at significantly lower scattering vector (q) than was observed for any single amine networks. In model bimodal epoxy graft copolymers with nearly identical chemical structure as the networks the shift to low q was barely perceptible. Experimental results from both epoxies and model graft copolymers are compared to a model calculation in order to establish a methodology to reduce molecular structure information from X-ray results.

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We present a new mechanistic model for the self-similar propagation of case II sorption fronts of diluents into glassy polymers. The model not only presents a clear differentiation between the chemical-potential-induced driving forces and the material misfit-induced pressures that develop in the Fickian precursor field that counteract the driving forces but also set up conditions for visco-plastic extrusion of the diluentenriched polymer out of the surface or into a zone of rubbery gel behind the case-II process front. The quantitative predictions of the model are capable of giving accurate comparisons with experimental measurements, particularly with those of Kramer and co-workers on the penetration of iodoalkanes into polystyrene.

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