Laser light-scattering study of novel thermoplastics .1. Phenolphthalein poly(aryl ether ketone)

Five different molecular weight phenolphthalein poly(aryl ether ketone) (PEK-C) fractions in CHCl3 were studied by static and dynamic laser light scattering(LLS). The dynamic LLS revealed that the PEK-C samples contain some large polymer clusters. These large clusters can be removed by filtering the solution with a 0.1-mu m filter. We found that the persistence length of PEK-C in CHCl3 at 25 degrees C is similar to 2 nm and the Flory characteristic ratio, C-infinity is similar to 25. Our results showed that [R(g)(2)](1/2)(z) = (3.50+/-0.20) x 10(-2)M(w)(0.54+/-0.01) and [D] = (2.37+/-0.05) x 10(-4)M(w)(-0.55+/-0.01), with [R(g)(2)](1/2)(z), M(w), and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.20+/-0.10) x 10(-4)M(-0.555+/-0.015), where D and M correspond to monodisperse species. Using this calibration between D and M,we have determined molecular weight distributions of five PEK-C fractions from their corresponding translational diffusion coefficient distribution.

Enhanced glass fiber-reinforced phenolphthalein poly(ether ketone) composites by blending poly(phenylene sulfide)

The mechanical properties of glass fiber-reinforced phenolphthalein poly(ether ketone)/poly(phenylene sulfide) (PEK-C/PPS) composites have been studied. The morphologies of fracture surfaces were observed by scanning electron microscope. Blending a semicrystalline component, PPS, can improve markedly the mechanical properties of glass fiber-reinforced PEK-C composites. These results can be attributed to the improvement of fiber/matrix interfacial adhesion and higher fiber aspect ratio. (C) 1996 John Wiley & Sons, Inc.

MORPHOLOGY AND DYNAMIC-MECHANICAL PROPERTIES OF NYLON 66/POLY(ETHER IMIDE) BLENDS

The morphology and dynamic mechanical properties of blends of poly(ether imide) (PEI) and nylon 66 over the full composition range have been investigated. Torque changes during mixing were also measured. Lower torque values than those calculated by the log-additivity rule were obtained, resulting from the slip at the interface due to low interaction between the components. The particle size of the dispersed phase and morphology of the blends were examined by scanning electron microscopy. The composition of each phase was calculated. The blends of PEI and nylon 66 showed phase-separated structures with small spherical domains of 0.3 similar to 0.7 mu m. The glass transition temperatures (T(g)s) of the blends were shifted inward, compared with those of the homopolymers, which implied that the blends were partially miscible over a range of compositions. T-g1, corresponding to PEI-rich phase, was less affected by composition than T-g2, corresponding to nylon 66-rich phase. This indicated that the fraction of PEI mixed into nylon 66-rich phase increased with decreasing PEI content and that nylon 66 was rarely mixed into the PEI-rich phase. The effect of composition on the secondary relaxations was examined. Both T-beta, corresponding to the motion of amide groups in nylon 66, and T-gamma, corresponding to that of ether groups in PEI, were shifted to higher temperature, probably because of the formation of intermolecular interactions between the components.

THE COMPATIBILITY AND MORPHOLOGY OF CHITOSAN-POLY(ETHYLENE-OXIDE) BLENDS

Thermal behavior and morphology of blends prepared by solution casting of mixtures of chitosan and poly( ethylene oxide) were studied by means of differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The preliminary results indicate that both melting point and crystallinity depend on the composition of the blends, and that they exhibit minimum values when the blend contains 50% chitosan. From the prediction of melting point depression analysis, the compatibility of the blends shows a transition at this specific composition. This conclusion was further confirmed by observation of the morphology.

The electrochemical behaviours of soluble polyimides

The electrochemical behaviours of three kinds of soluble polyimides were investigated for the first time. It was observed that the cyclic voltammograms(CVS) of these polyimides in nonaqueous solutions are obviously different from that of the poly-imide films casted on surfaces of glass carbon electrode(GCEs) in aqueous solutions.

MEDIATORLESS HYDROGEN-PEROXIDE ELECTRODE BASED ON HORSERADISH-PEROXIDASE ENTRAPPED IN POLY(O-PHENYLENEDIAMINE)

A mediatorless H2O2 sensor based on coelectropolymerization of horse radish peroxidase (HRP) and o-phenylenediamine (o-PD) is described. The electrode responds to H2O2 in a few seconds and gives a current density of 73.3 nA 1 mu mol(-1) cm(-2) at -100 mV

SYNTHESIS AND PROPELLER PROPELLER TRANSITION OF OPTICALLY-ACTIVE POLY(DIPHENYL-O-METHOXYPHENYLMETHYL METHACRYLATE)

Diphenyl-o-methoxyphenylmethyl methacrylate was polymerized with several organolithium complexes of chiral ligand such as (-)-sparteine (Sp) and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB). (+)-DDB was effective in preparing a polymer of high optical rotation, whereas (-)-Sp only gave oligomers with low optical rotation for the repulsive hindrance between the bulky ester group and the rigid ligand. The optical rotation of the polymer decreased rapidly to a constant value due to the propeller-propeller transition, which has been demonstrated by H-1 n.m.r. and circular dichroic spectra.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

IMPEDANCE STUDY OF THE INTERFACES BETWEEN LITHIUM, POLYANILINE, LITHIUM-DOPED MNO2 AND MODIFIED POLY(ETHYLENE OXIDE) ELECTROLYTE

Impedance study was carried out for the interfaces between lithium, polyaniline (PAn), lithium-doped MnO2 and modified poly(ethylene oxide) (PEO) electrolyte under various' conditions. The interfacial charge-transfer resistances R(ct) on PEO/PAn, R(ct) on PEO/LiMn2O4 increase with depth-of-discharge and decrease after the charge of the cell containing modified PEO as electrolyte. The charge-transfer resistance R(ct) on PEO/PAn is higher than R(ct) on PEO/LiMn2O4 under the same condition, since inserted species and mechanism are different for both cases. In the case of PAn, an additional charge-transfer resistance might be related to the electronic conductivity change in discharge/charge potential range, as it was evident from a voltammetry curve. With increasing cycle numbers, the charge-transfer resistance increases gradually. The impedance results also have shown that at low frequency the diffusion control is dominant in the process of the charge and discharge of Li/PEO/PAn or Li/PEO/LiMn2O4 cell. The diffusion coefficients have been calculated from impedance data.

STUDY ON GAMMA-RADIATION INDUCED LAMELLAR DAMAGE MECHANISM OF POLY(VINYLIDENE FLUORIDE)

This paper studies gamma-radiation induced lamellar damage mechanism of poly(vinylidene fluoride), using wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), electronic paramagnetic resonance (EPR) and gel fraction determination. We believe that it is ''lamellae core damage'' rather than ''lamellae surface damage'' that results in the decrease of the crystallinity.

MISCIBILITY AND PHASE-BEHAVIOR IN BLENDS OF POLY(HYDROXYETHER OF BISPHENOL-A) WITH POLY(ETHYLENE OXIDE-CO-PROPYLENE OXIDE)

The miscibility of poly(hydroxyether of bisphenol A) (phenoxy) with a series of poly(ethylene oxide-co-propylene oxide) (EPO) has been studied. It was found that the critical copolymer composition for achieving miscibility with phenoxy around 60-degrees-C is about 22 mol % ethylene oxide (EO). Some blends undergo phase separation at elevated temperatures, but there is no maximum in the miscibility window. The mean-field approach has been used to describe this homopolymer/copolymer system. From the miscibility maps and the melting-point depression of the crystallizable component in the blends, the binary interaction energy densities, B(ij), have been calculated for all three pairs. The miscibility of phenoxy with EPO is considered to be caused mainly by the intermolecular hydrogen-bonding interactions between the hydroxyl groups of phenoxy and the ether oxygens of the EO units in the copolymers, while the intramolecular repulsion between EO and propylene oxide units in the copolymers contributes relatively little to the miscibility.

MISCIBILITY OF POLY(HYDROXYETHER OF PHENOLPHTHALEIN) WITH POLY(ETHER SULFONE)

Blends of poly(hydroxyether of phenolphthalein) (PHP) with poly(ether sulphone) (PES) were prepared by casting from a common solvent; they were found to be miscible and show a single, composition-dependent glass transition temperature. All the PHP/PES blends exhibited lower critical solution temperature behaviour, i.e. phase separation occurred at elevated temperatures. A F.T.-i.r. study revealed that a hydrogen-bonding interaction occurs between these polymers but it is weaker than in pure PHP. The observed miscibility is hence proposed to be the result of specific interactions between the polymers.

MAGNETIC-RESONANCE EXPERIMENTS ON UNDOPED AND DOPED POLY(PARA-PHENYLENE)

We investigated the electron paramagnetic resonance (EPR) spectra of undoped, FeCl3- and iodine-doped poly(para-phenylene) (PPP) prepared by the method of Kovacic. EPR measurements are used to characterize electronic states relevant for carrier transport in doped PPP. We found a novel dependence of room temperature linewidth (DELTAH(pp)) and spin density (N(spin)) on the dopant concentrations for iodine-doped PPP, namely, DELTAH(pp) first decreased and increased, and then decreased and increased again with increasing iodine concentration in the iodine-doped PPP. The corresponding value of N(spin) first increased and decreased, and then increased and decreased again with increasing iodine concentration in PPP. However, the changes in DELTAH(pp) and N(spin) with FeCl3 concentration in FeCl3-doped PPP differ from those of iodine-doped PPP. We explain the different EPR properties in FeCl3-doped and iodine-doped PPP.

DYNAMIC SCALING OF THE STRUCTURE-FUNCTION FOR SPINODAL DECOMPOSITION IN CRITICAL AND NONCRITICAL MIXTURES OF POLY(VINYL ACETATE) POLY(METHYL METHACRYLATE)

The dynamics of phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by using a time-resolved light-scattering technique. In the later stages of spinodal decomposition, a simple dynamic scaling law was found for the scattering function S(q, t)(S(q, t) approximately I(q, t)): S(q, t)q(m)-3 S approximately (q/q(m)). The scaling function determined experimentally was in good agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X8) for critical concentration, and approximately in agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X6) for non-critical mixtures. The light-scattering invariant shows that the later stages of the spinodal decomposition were undergoing domain ripening.

EPITAXIAL CRYSTALLIZATION OF TRANS-1,4-POLYBUTADIENE ON HIGHLY ORIENTED ISOTACTIC POLY(PROPYLENE) FILMS

Epitaxial crystallization of trans-1,4-polybutadiene (PBD) on highly oriented isotactic poly(propylene) (iPP) has been investigated at different crystallization temperatures and rates. From electron microscopy and electron diffraction, it is confirmed that epitactic growth of the low-temperature modification (monoclinic) with microcrystals of PBD on the iPP films takes place with their chain directions about +/- 50-degrees apart. No epitaxial relationship occurs between the high-temperature modification (hexagonal) of PBD and the iPP substrate. Thermal analyses of PBD-PP layered films indicate that the epitaxy has an important effect on the formation of the high-temperature modification of PBD.