Synthesis and characterization of SPE membrane based on sulfonated FEP‐g‐acrylic acid by radiation induced graft copolymerization for PEM fuel cell

A Novel solid polymer electrolyte (SPE) membrane containing both ? COOH and ? SO₃H group has been prepared by simultaneous method of radiation grafting of acrylic acid onto FEP followed by sulfonation. The presence of weakly acidic acrylic acid controls the swelling in water while ? SO₃H group provides conductivity due to its strongly ionic characteristic. FEP‐g‐acrylic acid and its sulfonated derivatives were characterized by their properties. While the mechanical properties decreased, other properties such as ion exchange capacity (IEC), water uptake and ionic conductivity increased with increase in graft content. These properties further changed on sulfonation. Acrylic acid being weakly acidic in nature, conductivity values of the grafted membrane were quite low. However, introduction of strong ? SO₃H group resulted in conductivity closer to Nafion 117. Few sulfonated membranes have been tested with respect to H₂/O₂ fuel cell performance. Short‐term fuel cell test for 100 hr gave a stable performance. These membranes are less expensive compared to Nafion. Copyright © 2004 John Wiley & Sons, Ltd.     

Langmuir-Blodgett films of 9-phenyl anthracene molecules incorporated into different matrices

This communication reports the surface pressure (pi) versus area per molecule (A) isotherm characteristics of the mixed films of 9-phenyl anthracene (PA) in stearic acid (SA) and polymethyl methacrylate (PMMA) matrices, at the air-water interface. The mixed Langmuir films at the air-water interface have been observed to be easily transferred onto solid substrates to form uniform Langmuir-Blodgett films. By changing various parameters, namely molefraction, surface pressure of lifting and number of layers, the mixed Langmuir-Blodgett (LB) films of various types have been fabricated successfully and their spectroscopic characteristics have been reported. From the isotherm characteristics and the area per molecule versus molefraction plot, it is evident that the PA molecules are successfully incorporated into mixed Langmuir-Blodgett films. UV-vis absorption spectroscopic study of the mixed LB films at various molefractions of PA in two different matrices reveal that formation of I-type aggregate in PMMA matrix whereas both I- and H-type aggregates are playing their dominant role in SA matrix. Moreover, fluorescence spectroscopic study reveals reabsorption effect. Molecular movement persists in the freshly prepared LB films, as is evident from the time dependent changes in both UV-vis absorption and fluorescence spectra of the mixed LB films in both matrices. From our observation it is evident that about 200 h is required to get the LB films in a stable condition. Dimers and higher order n-mers are formed at a higher surface pressure of 30 mNm(-1).     

Thermal noise in Hg0.795Cd0.205Te detectors for large biasing fields

Thermal noise in Hg_0.795Cd_0.205Te detectors is estimated for large biasing fields at a lattice temperature of 77 K, by computing the correlation functions of the velocity fluctuations with the Monte Carlo technique. The noise temperature for current components transverse to the field is almost independent of the field, but that corresponding to the parallel component increases by a factor of about 1.3 at 50 V/cm and by a factor of 3.0 at 300V/cm. The thermal noise voltage for a detector of 85 resistance increases from 0.6nV/Hz^1/2 at low biasing fields to about 3nV/Hz^1/2 at a field of 300 V/cm. The noise power is also found to remain constant up to about 75 GHz, and it decreases thereafter by a factor of 0.25 for doubling of the frequency.     

Immobilization of single-strand specific nuclease (S1 nuclease) fromAspergillus oryzae

S1 nuclease fromAspergillus oryzae (EC 3.1.30.1) was coupled to gelatin-alginate composite matrix using the residual free aldehyde groups on the surface of glutaraldehyde crosslinked matrix. The immobilized enzyme retained approximately 10% activity of the soluble enzyme. When partially purified enzyme was bound to the matrix, the immobilized preparation did not show any detectable enzyme activity. However, the activity could be restored when the coupling was carried out in the presence of a coprotein or substrate. The optimum pH of the immobilized S1 nuclease shifted to 3.8 from 4.3 for the soluble enzyme. Also, optimum temperature increased to 65°C after immobilization. Bound S1 nuclease showed increased pH and temperature stabilities. Immobilization brought about a twofold decrease in the Michaelis-Menton constant (K _m).     

Radiation chemistry of tris(acetylacetonato) cobalt(iii) in aqueous solutions

Abstract

On radiolysis tris(acetylacetonato) cobalt(III) in aqueous solutions is found to get reduced by reaction with (1) hydrated electrons, (2) H atoms, (3) OH radicals and (4) C₂H₂OH radicals. The bimolecular rate constants for the first three reactions, determined by competition kinetics are: 4 × 10¹⁰, 2.3 × 10⁹ and 4.7 × 10⁹ M^?1sec^?1 respectively. Absorption spectra of the irradiated solutions indicate the formation of bis(acetylacetonato) cobalt(II) from reaction (1), but not from (3). The total cobaltous yield in air-free solutions is given byG(Co⁺⁺) = 5.6 and 6.5 at pH 6.5 and 1 respectively. It appears that G_eaq- ∽ _H ⁺ G_oH ∽ 2.8 in neutral solutions. Considerations of material balance for the primary yields of radiolysis of water suggest the possibility that the so-called independent H-atoms in neutral solutions are probably excited water molecules or ion-pairs.     

E.S.R. and D.S.C. investigations of phase transitions in polymorphic 4-n-alkoxybenzylidene-4′-n-alkylanilines

Abstract

It is shown that the McMillan parameter M = T _SAN/T _N1 (where T _SAN and T _NI are respectively the temperatures of the smectic A to nematic (SAN) and the nematic to isotropic (NI) phase transitions) is useful in analysing the crossover between second and first order behaviour of the S_NN transition in the nO.m homologous liquid crystal series (the 4-n-alkoxybenzylidene-4′-n-alkylanilines). Using a phase diagram of orientational ordering versus M for this series, as obtained in this work (from E.S.R. and D.S.C), a symmetric tricritical point with mean field exponent β₂ = 1 is demonstrated. In a preliminary study of E.S.R. linewidth parameters B and C of nitroxide spin probes dissolved in members of the nO.m series exhibiting a first order S_AN transition, critical-type divergences are observed near this transition. In the case where M is closer to 0.959 (the value at the tricritical point), these divergences appear similar to those previously observed in related nO.m members with a second order S_AN transition; however, they are considerably enhanced for an M value closer to unity (i.e. more removed from the tricritical point). This indicates the importance of coupling between orientational and positional order parameters in the observed critical-type divergences.     

Phase behaviour of thermotropic banana-shaped compounds under pressure

The phase behaviour of two achiral bent core banana-shaped compounds, the hexyloxy (compound I) and decyloxy (compound II) members of the 1,3-phenylene bis[N-(2-hydroxy-4-n-alkoxybenzylidene)-4′-aminobenzoate] series was investigated under hydrostatic pressures up to 300?MPa using high pressure differential thermal analysis and light transmission methods. The reversible transition sequence crystal (Cr₁)–B₁ phase–isotropic liquid (I), observed at room pressure for compound I, remains in the pressure region up to c 70?MPa. At higher pressures a pressure-induced crystalline phase (Cr_i) appears between the Cr₁ and B₁ phases, its temperature region becoming wider with increasing pressure. The temperature vs. pressure phase diagram shows a triple point of 72.9?MPa and 160.3°C for the Cr₁, Cr_i and B₁ phases, indicating the lower limit of pressure for the Cr_i phase. In compound II the reversible transition sequence crystal (Cr₁)–B₂ phase–I is seen over the whole pressure region, and the temperature range of the B₂ phase remains unaltered. It is concluded that both the B₁ and B₂ banana phases are stable over the whole pressure region studied.