Sulphate ion dynamics in alpha-alums studied by esr at high pressures

The variation of zero-field splitting and linewidth of Cr3+ ion in KCr and KAI alums with hydrostatic pressure and with temperature is investigated. A model for the apparent phase transition is proposed on the basis of the reorientational motion of the SO2�4 groups.

Frequency and temperature-dependent mobility of a charged carrier on a randomly interrupted strand

A randomly interrupted strand model of a one-dimensional conductor is considered. An exact analytical expression is obtained for the temperature-dependent ac mobility for a finite segment drawn at random, taking into account the reflecting barriers at the two open ends. The real part of mobility shows a broad resonance as a function of both frequency and temperature, and vanishes quadratically in the dc limit. The frequency (temperature) maximum shifts to higher values for higher temperatures (frequencies).

Influence of the electric field on the low-temperature thermal decomposition of ammonium perchlorate/polystyrene propellant

An electric field (100 V/cm at 230°C and 150°C) has been applied to ammonium perchlorate (AP)/polystyrene (PS) propellant mixtures in order to understand the low temperature decomposition behavior of the propellant. The charge-carrying species is anionic in nature at 230°C, which could be ClO4−, but is cationic at 150°C, which could be either NH4+ or H+. These results are parallel to that observed for pure ammonium perchlorate (AP) pellets [1]. The burning rate (r' ) of the propellant was found to follow the same trend as that for the thermal decomposition of the propellant on application of an electric field. At 150°C Image was higher at the −ve electrode than at the +ve electrode, but at 230°C just the opposite was observed. Kinetic studies have confirmed that the decomposition of the orthorhombic AP follows two mechanism corresponding to E = 30 kcal mol−1 (180–230°C) and E = 15 kcal mol−1 (150–180°C).

Nucleosome core protein: Asymmetric dissociation of the octamer

The octameric nucleosomal core-histone complex, (H2A)2-(H2B)2-(H3)2-(H4)2, isolated from rat liver, undergoes dissociation during gel exclusion chromatography as a result of dilution occurring in the columns. The elution pattern at pH 7.0 and 4°C showed a sharp leading peak containing all four histones but predominantly H3 and H4, and a trailing peak containing equal amounts of histones H2A and H2B. As column length was increased the area under the leading peak decreased and that under the trailing peak increased. In addition the relative positions of the two peaks varied with column length. From an analysis of the data on increase in elution volume of the leading peak in relation to column length an apparent molecular weight of 86 000 was calculated for the undissociated molecule. Its apparent molecular weight, histone composition and pattern of further dissociation in relation to column length suggest that this species is the hexamer, (H2A-H2B)-(H3)2-(H4)2. At pH 7.0 and 4°C the dissociation of the core complex appears to be as follows: (H2A)2-(H2B)2-(H3)2-(H4)2 → (H2A-H2B) + (H2A-H2B)-(H3)2-(H4)2 → 2(H2A-H2B) + (H3)2-(H4)2 This dissociation was accelerated by an increase in temperature or decrease in pH and was accompanied by marked conformational changes as judged by circular dichroism measurements.

High temperature stability of oxysulfides containing Ce3+ and Y3+ ions

Standard Gibbs energies of formation of oxysulfides of cerium and yttrium from their respective oxedes were determined using solid oxide galvanic cells incorporating calcia-stabilized zirconia as the electrolyte in the temperature range 870–1120 K. The sulfur potential over the electrode containing the oxide and oxysulfide was fixed by a buffer mixture of Ag + Ag2S. A small amount of CaH2 was added to the buffer to generate an equilibrium ratio of H2S and H2 species in a closed system containing the buffer and the electrode. The sulfur potential is transmitted to the electrode via the gas phase. The results can be summarized by the equations 2left angle bracketCeO2right-pointing angle bracket+1/2(S2)→left angle bracketCe2O2Sright-pointing angle bracket+(O2) ΔG°=430600−109·7T(±400)J mol−1 left angle bracketY2O3right-pointing angle bracket+1/2(S2)→left angle bracketY2O2Sright-pointing angle bracket+1/2(O2) ΔG°=114780−1·45T(±200)J mol−1 The values are compared with data reported in the literature. The stability field diagram for the Ce---O---S system has been developed using the results of this study for Ce2O2S and data for other phases from the literature.

A study of the effect of N2 reservoir temperature on a 16 μm CO2-N2 downstream-mixing gasdynamic laser

A study of the effect of N2 reservoir temperature on the small-signal gain in a downstream-mixing 16 μm CO2-N2 GDL is presented. It is shown that the small-signal gain decreases with the increase of N2 reservoir temperature. The conditions for reversing this trend are discussed and the results are presented in the form of graphs.

Low-temperature preparation of fine-particle cobaltites

A novel solid-solution precursor method for the preparation of fine-particle cobaltites at low temperatures has been described. The precursors, hydrazinium metal hydrazine carboxylate hydrates, N2H5M1/3Co2/3(N2H3COO)3 · H2O, where M = Mg, Mn, Fe, Co, Ni, and Zn, decompose in air <250°C to yield corresponding metal cobaltites, MCo2O4. Formation of cobaltites has been confirmed by thermogravimetry (TG) weight loss, IR, and X-ray diffraction. Combustion of the precursor in air yields fine-particle cobaltites with surface areas in the range of 12–115 m2g−1 and particle sizes of 1–40 μm. Low decomposition temperatures of the precursors accompanied by the evolution of large amounts of gases appear to control the particle size of the cobaltites.

Small Polaron Hopping And High-Temperature Dc Conductivity Of Chalcogenide Glasses

D.C. conductivity behaviour of a variety of chalcogenide glasses have been analysed using ln σ vs Image plots as suggested in the multiphonon assisted polaron hopping model of Triberis and Friedman. The agreement with the model is very satisfactory and further analysis of the model using c.

Influence of electroslag refining on the hot ductility of AISI 4340 steel in torsion

Electroslag refining is a useful remelting process by which clean steels can be produced for sophisticated applications. In this investigation, AISI 4340 steel has been electroslag refined and the improvement in its hot ductility has been assessed using hot torsion tests; electroslag refining has improved the hot ductility considerably. The temperature at which peak ductility is obtained has also increased — from 1473 K in the unrefined steel to 1573 K in ESR steel. Results indicate that it should be possible to subject the ESR ingot to much higher strains per unit operation during industrial hot working processes such as forging, which would result in a considerable saving of power. The improvement in hot ductility in ESR steel has been attributed primarily to the removal of non-metallic inclusions and the reduction in sulphur content. From the apparent activation energy estimated from the hot torsion data, the dynamic recrystallization process is identified as the mechanism controlling the rate of hot deformation.

Low temperature Properties of glasses-unsolved problems

Glasses show very interesting behavior well below the glass transition temperature. Inspite of various experimental observations, even simple quantitative explanations relating these relaxation phenomena to structural properties are absent. In this paper we have tried to point out a phenomenological approach to this problem by identifying certain parameters which we think can be used to characterize these relaxations.

Temperature dependence of the surface conductivity of YBa2Cu3O7−δ accompanying the change in the concentration of dimerized oxygen holes

The intensity of inelastically scattered electrons measured by electron energy loss spectroscopy has been employed to monitor the surface conductivity of YBa2Cu3O6.9 as a function of temperature. The study shows a drastic change in surface conductivity precedes the superconducting transition at 90K. The increase in surface conductivity is accompanied by the formation of dimerized holes in the oxygen derived p-band. This phenomenon is not observed in the non-superconducting YBa2Cu3O6.2.

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

On the use of oxalates as starting materials for low-temperature preparation of bronzes and other reduced phases

A novel low-temperature method of preparing bronzes of tungsten and vanadium and other reduced phases is reported.

Mixed valency in the high-temperature phases of transition metal molybdates,AMoO4 (A=Fe, Co, Ni)

Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods shows that the phase transition is associated with a valence change of the typeA 2++Mo6+αA 3++Mo5+ in the cases of iron and cobalt molybdates.

Performance of an Al-Si-graphite particle composite piston in a diesel engine

Al-Si-graphite particle composite alloy pistons containing different percentages of about 80 μm uncoated graphite particles were successfully cast by foundry techniques. Tests with a 5 hp single-cylinder diesel engine show that Al-Si-graphite particle composite pistons can withstand an endurance test of 500 h without any apparent deterioration and do not seize during the running-in period. The use of the Al-Si-3% graphite particle composite piston also results in (a) up to 3% reduction in the specific fuel consumption, (b) considerable reduction in the wear of all four piston rings, (c) a reduction in piston wear, (d) a 9% reduction in the frictional horsepower losses of the engine as determined by the motoring test and (e) a slight increase in the exhaust gas temperature. These reductions (a)–(d) appear to be due to increased lubrication from the graphite particles which are smeared on the bearing surface, the higher damping capacity of the composite pistons and the reduced coefficient of thermal expansion of the composite pistons. Preliminary results indicate that aluminum-graphite particle composite alloy is a promising material for automotive pistons.