Gas permeability and permselectivity of polyimides prepared from phenylenediamines with methyl substitution at the ortho position

Polyimides were prepared from diamines: 2,4,6-trimethyl-1,3-phenylenediamine (3MPDA) and 2,3,4,5-tetramethyl-1,4-phenylenediamine (4MPDA). 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3'-4,4'-diphenylsulphone tetracarboxylic dianhydride (SO(2)PDA), 3,3',4,4'-diphenylsulphide tetracarboxylic dianhydride (SPDA), pyromellitic dianhydride (PMDA), and 2,2'-bis(3,4-dicarboxyphenyl)hexa-fluoroisopropane dianhydride (6FDA) were used as dianhydride. The gas permeabilities of H-2, O-2 and N-2 through the polyimides were measured at temperatures from 30 degrees C to 90 degrees C. The results show that as methyl and trifluoromethyl substitution groups densities increase from 7.73 x 10(-3) molcm(-3) to 13.50 x 10(-3)molcm(-3), the peameability of H-2 increases 10-fold at 60% loss of permselectivity of H-2/N-2 however, the permeability of O-2 increases 20-fold at 20% loss of permselectivity of O-2/N-2. For O-2/N-2 separation, PMDA-3MPDA has similar performance to 6FDA-3MPDA and 6FDA-4MPDA; all have higher permeabilities for O-2 than normal polyimides, and the P(O-2)/alpha(O-2/N-2) trade-off relationships lie on the upper bound line for polymers. (C) 1999 Society of Chemical Industry.

Analysis of structural relaxation in a Li(2)O2SiO(2) glass using rate heating approach

The structural relaxation process of an inorganic glass (Li(2)O2SiO(2)) at different cooling rates has been studied by differential scanning calorimetry. A four-parameter model-Tool-Narayanaswamy-Moynihan (TNM) model was applied to simulate the normalized specific heat curve measured. Four parameters, Delta h*/R, beta, In A, and x were obtained and compared with the values obtained from the isothermal approach. (C) 1999 Kluwer Academic Publishers.

Microelectrode voltammetric measurement of heterogeneous electron transfer rate constants for reduction of 7,7,8 ',8 '-tetracyanoquinodimethane in polymer electrolytes

This paper presents a microelectrode voltammetric determination of heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of 7,7,8',8 '-tetracyanoquinodimethane (TCNQ) in polyelectrolytes. The diffusion coefficients are estimated using cyclic voltammetry under linear diffusion conditions, and the heterogeneous electron transfer rate constants are obtained under mixed linear and radial diffusion in the polyelectrolyte. k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction for reduction of TCNQ are obtained. On the other hand, the dependencies of D and k(s) of TCNQ on the size and charge of the counterion are compared in the polyelectrolyte. (C) 1998 Elsevier Science Ltd. All rights reserved.

Interparticle distance-temperature-strain rate equivalence for the brittle-tough transition in polymer blends

From the angle of energy transformation an equation was obtained for the brittle transition in polymer blends. The effects of interparticle distance, temperature and strain rate on the brittle-tough transition in polymer blends were characterized by this equation. The calculations show that, for this transition: (1) increasing temperature and decreasing interparticle distance are equivalent and the shift factor increases with increasing temperature; (2) decreasing strain rate and decreasing interparticle distance have equivalent effects on the transition; (3) the strain rate must be optimum in order to find the brittle-tough transition phenomena for a given temperature region. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Determination of the standard heterogeneous rate constant in polyelectrolyte using steady state microdisk voltammograms

The steady state voltammogram at a microdisk electrode is used to measure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtained is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by the relaxation rates of the ether dipole sites on the polymer chains, which are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.

An ultramicroelectrode study of ferrocene diffusion and heterogeneous electron transfer rate in polyelectrolyte

Steady-state voltammograms at a microdisk electrode are used to measure the diffusion coefficient (D) and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG.MClO(4). The diffusion coefficient and standard heterogeneous rate constant of ferrocene are both smaller in polymer solvents than in monomeric solvents. The D and k(s) of ferrocene have been estimated in PEG containing different concentrations and cations of supporting electrolytes, and the dependencies of D and k(s) on temperature have been observed. These results show that the D and k(s) of ferrocene increase with increasing temperature in polyelectrolyte, and with increasing cation radius of supporting electrolyte, eg D and k(s) increase in the order Bu(4)NClO(4) > NaClO4 > LiClO4. On the other hand, D and k(s) increase with decreasing concentration of supporting electrolyte. The dependence of the half-wave potential (E(1/2)) on the concentration of the supporting electrolyte is also observed. E(1/2) shifts in the negative direction as the concentration of supporting electrolyte increases. (C) 1997 Elsevier Science Ltd.

Electron collision cross sections and rate coefficients for the Na-like Cu ion

Collision cross sections are calculated using the R-matrix method for excitations between the three lowest LS states for Na-like Cu ion. The complex resonance structures are investigated. The collision rate coefficients have been calculated assuming a Maxwellian distribution of electron-impact energies. The results of the collision cross sections are in good agreement with those of the other theory.

THE EFFECT ON PHYSICAL-PROPERTIES OF THE SUBSTITUTION OF CA OR BA FOR SR IN NDSRNIO4

A new solid solution series, NdSr(1-x)M(x)NiO(4) (M = Ca: 0.0 less than or equal to x less than or equal to 1.0; M = Ba: 0.0 less than or equal to x less than or equal to 0.6), was synthesized by solid state reaction, and the structures, magnetic and electrical properties and optical spectra of this series have been studied. All the samples crystalized in tetragonal systems, with the exception of NdCaNiO4, which crystallized in the orthohombic system. IR spectra of NdSr1-xCaxNiO4 indicated that the lengths of two Ni-O bonds decrease with increasing Ca content. The electrical conduction changed from metallic-type to semiconductive-type when x greater than or equal to 0.4 (M = Ca, Ba), and the room temperature resistivities of NdSr1-xCaxNiO4 increased with the increase of Ca content. Magnetic susceptibility measurements revealed that Ni+3 ions in all the samplies were in low-spin state over the temperature range 77-300 K.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

LANTHANIDE-INDUCED SHIFT AND RELAXATION RATE STUDIES OF THE AQUEOUS COMPLEXATION OF CITRATE

The aqueous complexation of lanthanide ions with citrate in pH 7.4 solution has been investigated with use of the lanthanide-induced shift and paramagnetic relaxation rate enhancement methods. The results show that citrate coordinates via hydroxyl and central carboxylate groups with lanthanide ions and forms 1:2 (Ln/cit) isostructural complexes through the lanthanide series. A new possible coordination geometry deduced from our experimental data is suggested and discussed.

TEMPERATURE AND STRAIN-RATE DEPENDENCE OF FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

A strong strain-rate and temperature dependence was observed for the fracture toughness of phenolphthalein polyether ketone (PEK-C). Two separate crack-blunting mechanisms have been proposed to account for the fracture-toughness data. The first mechanism involves thermal blunting due to adiabatic heating at the crack tip for the high temperatures studied. In the high-temperature range, thermal blunting increases the fracture toughness corresponding to an effectively higher test temperature. However, in the low-temperature range, the adiabatic temperature rise is insufficient to cause softening and Jic increases with increasing temperature owing to viscoelastic losses associated with the p-relaxation there. The second mechanism involves plastic blunting due to shear yield/flow processes at the crack tip and this takes place at slow strain testing of the single-edge notched bending (SENB) samples. The temperature and strain-rate dependence of the plastic zone size may also be responsible for the temperature and strain-rate dependence of fracture toughness.

INTRAANNULAR AND INTERANNULAR SUBSTITUENT MIGRATION AND INTRAMOLECULAR IPSO SUBSTITUTION OF BIPHENYL DERIVATIVES IN MASS-SPECTROMETRY

Biphenyl derivatives undergo extensive intraannular substituent migrations and subsequent intramolecular ipso substitutions giving rise to a fluorenyl cation and a biphenylene radical cation as common products in mass spectrometry. For biphenyls bearing an alkyl group, interannular substituent migration resulting in a substituted tropylium ion is also observed. Electron-withdrawing groups are found to be much more favourable to these reactions than the electron-donating ones.

INFLUENCE OF THE SUBSTITUTION OF Y BY IN ON THE STRUCTURE AND MAGNETIC PROPERTY OF Y2CU2O5

In2CuO5 is isostructural to Y2Cu2O5 both in its crystal and magnetic structure. In and Y can be substituted by each other in any ratio to make new compounds Y2-xInxCu2O5 (x = 0-2) which were identified by XRD and IR spectrum. The structural change in Y2-x

TEMPERATURE RATE DEPENDENCE OF YIELD AND FRACTURE-BEHAVIOR OF PHENOLPHTHALEIN POLY(ETHER KETONE)

The rate/temperature dependence of yield stress, tensile modulus and crack opening displacement of phenolphthalein poly(ether ketone) (PEK-C) has been investigated. The rate/temperature dependence of crack opening displacement and the correlation establis

INFLUENCE OF IONIC SUBSTITUTION ON THE MAGNETIC-BEHAVIOR OF Y2CU2O5

The influence of the substitution of Cu or O by various elements on the magnetic properties of Y2Cu2O5 has been studied. The substitution of Cu by metal ions with unpaired d electrons (M = Co2+, Ni2+) makes the superexchange in Cu2O8 chains stronger, but