• Volume 16, Issue 4

      August 1993,   pages  243-329

    • EXAFS: Determination of cation distribution in spinels

      G M Bhongale V B Sapre D K Kulkarni

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      In oxidic spinels containing transition metal ions, the tetrahedral and octahedral bond distances differ by less than 0·25 Å. Therefore, in the case of a cation occupying both the sites, the normalized EXAFS for first coordination shell gives the average bond distance and average coordination number respectively over all the bonds and the positions of the cation under investigation. EXAFS analysis of fourteen mixed lithium ferrite spinels was carried out to show how the average bond distance can fruitfully be used to obtain the exact cation distribution, in conformity with X-ray diffraction data.

    • Surface topographical studies of prism faces of barium copper oxalate single crystals

      Kasthuri V Bangera P Mohan Rao

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      The present paper reports observations made on microstructures of gel-grown barium copper oxalate crystals. Growth spirals, growth layers, liquid inclusions and growth of microcrystallites are described and discussed in relation to the mechanism and conditions of crystal growth.

    • Phase transitions in copper(II) orthovanadate

      N Suresh Rao O G Palanna

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      Data on the polymorphs of copper(II) orthovanadate are reported. The Cu3V2O8 phase synthesized in this laboratory exhibits phase transitions between 460° and 560°C. These phase transitions are identified through detailed DTA and high temperature XRD techniques; it is observed that these structural transitions are rapid and reversible. The crystal structure of Cu3V2O8 is similar to that of Mg3V2O8, Zn3V2O8, Co3V2O8 and Ni3V2O8.

    • Conduction mechanism in Sn4+ substituted copper ferrite

      B L Patil S R Sawant S S Suryavanshi S A Patil

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      Thermoelectric power (α) and electrical resistivity (ρ) are reported for the system Cu1+xSnxFe2−2xO4 (wherex=0·05, 0·1, 0·15, 0·2 and 0·3) from room temperature to 800 K. The compositions withx=0·05 and 0·2 exhibitn-type conduction while the compositions withx=0·1 and 0·15 showp- ton-type conduction change after 423 K. The conduction at low temperature (i.e. < 400 K) is due to impurities, while at higher temperature (i.e. > 400 K), it is due to polaron. Hopping conduction phenomenon for the present system has been explained on the basis of localized model of electrons. Additional localization may arise due to Sn4+ + Fe2+ stable pairs at B-site and Cu1+ + Fe3+ pair at A-site.

    • Electrical conductivity of modified poly(vinyl chloride)

      Meenakshi Maruthamuthu M Selvaraj S Annadurai

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      Chemical modification of poly(vinyl chloride) (PVC) by dehydrochlorination with ethanolic KOH is found to yield modified PVC with conjugated polyene sequence. The semiconducting nature of ethoxide-modified PVC is illustrated with temperature dependence of conductivity (σ). The relative ratios (r) of conductivity,σmodifiedpvc/σunmodifiedpvc, are greater than unity in the temperature range 50° to 180°C,r being maximum in the vicinity of glass-transition temperature (Tg).Tg inferred from conductivity-temperature profiles is found to be greater for modified PVC relative to unmodified PVC, which is explicable in terms of restricted free rotation limiting segmental motion. For comparison with the conductivity andTg of ethoxide-modified PVC, LiCl-modified PVC and (aniline + S2O82−)-modified PVC have also been studied.

    • Electrical conductivity and luminescence of 9-chloro-10,10′-bis-(dichloromethyleno)-(9′H)-10,10′-dihydro-9,9′-bianthryl (CDDB)

      A K Chattopadhyay S Basu S Das N B Palit S C Chakraborty

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      The absorption and fluorescenc of 9-chloro-10,10′-bis-(dichloromethyleno)-(9′H)-10,10′-dihydro-9,9′-bianthryl (CDDB) has been studied in polar and nonpolar solvents and also in microcrystal. In polar solvents CDDB emits from two molecular forms, the normal charge transfer form (locally excited, LE form) and the solvent-induced twisted intramolecular charge transfer (TICT) form. Electrically, CDDB possesses semiconducting property with conductivity approximately 10−9 S cm−1 and this conductivity further increases to 10−7 S cm−1 on photoexcitation. Intramolecular charge transfer by hopping mechanism is assumed to be the main process for controlling activation energy and electronic conduction.

    • Thermoelectric power of ferroelectric potassium vanadate, cesium vanadate, lithium vanadate and their solid solutions

      A J Kulkarni S P Rasal T S Magdum S H Chavan

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      The thermoelectric power of the vanadates of potassium, cesium and lithium and their solid solutions was measured in the temperature range covering their transition points. The thermoelectric power measurement was carried out by the two-electrode technique for pellets of polycrystalline ceramic samples. The thermoelectric power increased with temperature initially, then decreased attaining a zero value at the transition temperature. As the concentration of KVO3 increased the thermoelectric power decreased for the solid solutions (Kx − Cs1−x)VO3, whereas the thermoelectric power increased with increase in concentration of KVO3 for the solid solutions (Kx − Li1−x)VO3. Vanadates of potassium, cesium, and lithium and their solid solutions showedP type semiconductor behaviour in ferroelectric state andn type semiconductor behaviour in paraelectric region.

    • Development and characterization of a high dielectric constant paste based on BaTiO3 for use in thick-film capacitors

      A P Biur R U Khan

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      Results of measurements on a thick-film capacitor based on a paste of mixed ferroelectric phases made out of crystallization from a glassy phase are presented. This material can be used as a high dielectric constant paste for designing capacitors in hybrid circuits. The tanδ is observed to decrease with rise in temperature.

    • Nucleation and growth of CdC2O4·3H2O single crystals in silica gels

      M R Shedam A Venkateswara Rao

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      As part of our work on growth of cadmium oxalate single crystals in gels, we describe here variation of nucleation density and growth of these crystals as a function of concentration of feed solution, gel ageing, gel density, gel pH and intermediate neutral gel column. While high density and high pH gels have been found to produce opaque crystals, good quality transparent single crystals have been obtained in low density and low pH gels. It was observed that the intermediate neutral gel column and gel ageing considerably reduced the number of nucleation sites and increased the size of the crystals without affecting their quality. By concentration programming the size of the crystals increased.

    • Isothermalin situ reduction kinetic analysis of NiCl2-containing gel

      G C Das A Basumallick Kinjalkini Biswas (Sen) S Mukherjee

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      Isothermalin situ reduction kinetic study of NiCl2-containing gel was carried out. The detailed statistical as well as reduced time analysis show that contracting geometry and nucleation and growth type of mixed mechanisms are operative. The activation energy for reduction is in the range 158–193 kJ/mol. Thermal analysis on NiCl2-containing gel was carried out in the temperature range 800°C to 900°C.

    • Oxidation kinetics of reaction-sintered silicon carbide

      O P Chakrabarti J Mukerji

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      The oxidation kinetics of reaction-sintered silicon carbide has been studied over the temperature range 1200° to 1350°C. The material has a bulk density of 3·00 g/cm3 and the unreacted Si content is 22·5% (v/v). The activation energy for oxidation is 28·75 ± 2·61 kcal/mol. It is proposed that the diffusion of oxygen through the growing oxide film is the rate-controlling process.

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