Microwave-assisted selective deoxygenation of layer- and chain-containing oxides

Very rapid (within 5 min), selective, single-step deoxygenation of layer- and chain-containing oxides, MoO3, CrO3, V2O5, alpha-VOPO4 . 2H(2)O and Ag6Mo10O33 has been accomplished using graphitic carbon in a microwave-assisted reaction. The products were found to be MoO2, Cr2O3, VO2, VPO4 and a mixture of (Ag + MoO2), respectively. Products were characterised by X-ray diffraction (XRD), differential scanning calorimetry (DSC), IR and electron paramagnetic resonance (EPR) spectroscopies. Although conventional methods of preparing these materials are tedious, the present method is simple, fast and yields very homogeneous products of good crystallinity. Our results reveal that while layer- and chain-containing oxides undergo rapid microwave-assisted carbothermal reduction, the non-layered materials do not. The high structural selectivity of these reactions is suggestive of the topochemical nature of the fast reduction process.

Structural and dielectric properties of Bi2NbxV1-xO5.5 ceramics

Bi2NbxV1-xO5.5 ceramics with x ranging from 0.01 to 0.5 have been prepared. The crystal system transforms from an orthorhombic to tetragonal at x greater than or equal to 0.1 and it persists until x = 0.5. Scanning electron microscopic (SEM) investigations carried out on thermally etched Bi2NbxV1-xO5.5 ceramics confirm that the grain size decreases markedly (18 mu m to 4 mu m) with increasing x. The shift in the Curie temperature (725 K) toward lower temperatures, with increasing x, is established by Differential Scanning Calorimetry (DSC). The dielectric constants as well as the loss tangent (tan delta) decrease with increasing x at room temperature.

Synthesis and characterization of poly(vinyl acetate peroxide)

Poly(vinyl acetate peroxide) (PVACP) was prepared from vinyl acetate by free-radical-initiated oxidative polymerization. The polyperoxide was isolated and characterized by different spectroscopic methods. The extreme instability of PVACP was demonstrated by FTIR spectroscopy. The H-1- and C-13-NMR studies show the irregularities in the polyperoxide chain due to the cleavage reactions of the propagating peroxide radical. Thermal degradation studies using differential scanning calorimetry revealed that PVACP degrades at a lower temperature and the heat of degradation is in the same range as reported for other vinyl polyperoxides. (C) 1996 John Wiley & Sons, Inc.

Synthesis and characterization of tetrapolymers of styrene, methyl methacrylate, alpha-methylstyrene, and oxygen

This paper presents the first report on a terpolyperoxide (TPPE) synthesized by the oxidative terpolymerization of styrene, methyl methacrylate, and a-methylstyrene. TPPEs of different compositions were synthesized by varying the vinyl monomers feed, and they were then characterized by spectroscopic and thermal studies. The conventional terpolymer equation has been used to predict the composition of TPPEs. The H-1 NMR chemical shift values of TPPEs were found to vary with the composition. The shape of the backbone methylene protons (4.00-4.50 ppm) was found to be sensitive to the sequence distribution of vinyl monomers in the polymer chain. Formaldehyde, benzaldehyde, acetophenone, and methyl pyruvate were identified as the primary degradation products. The overall thermal stability and the average enthalpy of degradation (Delta H-d), as obtained by thermogravimetric analysis and differential scanning calorimetry, respectively, do not vary much with the composition of TPPEs.

Synthesis of epoxy-terminated polymers by radical polymerization using alpha-(t-butylperoxymethyl)styrene as chain transfer agent

Epoxy-terminated polystyrene has been synthesized by radical polymerization using alpha-(t-butylperoxymethyl) styrene (TPMS) as the chain transfer agent. The chain transfer constants were found to be 0.66 and 0.80 at 60 and 70 degrees C, respectively. The presence of epoxy end groups was confirmed by functional group modification of epoxide to aldehyde by treatment with BF3.Et(2)O. Thermal stability of TPMS was followed by differential scanning calorimetry and iodimetry. Thermal decomposition of TPMS in toluene follows first order kinetics with an activation energy of 23 kcal/mol. (C) 1996 John Wiley & Sons, Inc.

Microstructural stability and nanoindentation of an electrodeposited nanocrystalline Ni-1.5wt.%P alloy

Microstructural stability of nanocrystalline Ni-1.5wt.%P alloy with an initial grain size of 3 nm processed by pulsed electrodeposition was studied using differential scanning calorimetry (DSC) and annealing. Microstructural characterization suggests that the observed exothermic peak during heating in DSC is related to both concurrent grain growth and Ni3P formation. Nanoindentation on samples with grain sizes from 3 to 50 nm revealed a breakdown in Hall-Petch strengthening in nano Ni-P alloy at grain sizes <= 10 nm, consistent with some previous observations. It is concluded that there is a grain boundary weakening regime for grain sizes < 10 nm, based on analysis which show that the data cannot be rationalized in terms of microstrain relaxation, variation in elastic modulus, texture evolution and duplex structure formation.

Thermally induced transformations in GexAsyTe100-x-y glasses

Chalcogenide glasses with compositions Ge7.5AsyTe92.5-y (y = 20, 40, 45, 47.5, 50, 52.5, 55) and Ge10AsyTe90-y (y = 15, 20, 22.5, 35, 40, 45, 50) have been prepared by the melt-quenching technique. The amorphous nature of these glasses has been confirmed by X-ray powder diffractometry. The thermal stability of these glasses has been studied using differential scanning calorimetry (DSC). The compositional dependence of the glass transition temperature, T(g), the crystallization temperatures, T(c1) and T(c2), and the melting temperature, T(m), are reported. The glass-forming tendency, K(gl), and the activation energy of crystallization, E, are calculated. The activation energy decreases with increasing tellurium content for both sets of glasses.

Threshold behaviour in the nonisothermal properties of Ge-Sb-Se glasses

Differential scanning calorimetry studies have been performed on GexSb5Se95-x (12.5≤x≤35) and GexSb10Se90-x (10≤x≤32.5) glasses. The observed dependence of the glass transition temperature on the mean coordination number up to =2.60 and the maxima in the glass transition temperature and the activation energy of crystallisation at =2.65 have been interpreted in terms of the mechanical and chemical thresholds occuring near these compositions.

Structural and electrical transport properties of Al-Cu-Cr quasicrystals

Transport properties of quasicrystals in rapidly solidified as well as heat-treated Al65CU20Cr15 alloys were studied over a wide temperature range as a function of structure and microstructure. The characterization was done using x-ray diffraction, transmission electron microscopy and differential scanning calorimetry. Particular attention was paid to primitive to face-centered quasicrystalline transformation which occurs on annealing and the effect of microstructures on the transport behavior. The temperature dependence of resistivity is found to depend crucially on the microstructure of the alloy. Further, ordering enhances the negative temperature coefficient of resistivity. The low-temperature (T less than or equal to 25 K) resistivity of Al65Cu20Cr15 has been compared with that of Al63.5Cu24.5Fe12 alloy. In this region p(T) can be well described by a root T contribution arising from electron-electron interaction. We discuss our results in view of current theories.

Synthesis and characterization of photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units

A series of new photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units have been studied. These units in the polymers function as mesogens as well as photoactive centres. Polyesters with three different bis(4-hydroxybenzylidene)cycloalkanones corresponding to three cycloalkanones, namely cyclopentanone, cyclohexanone and cycloheptanone, have been prepared. Three dicarboxylic acids with ether linkages, which were derived from oligoethylene oxides, namely triethylene glycol, tetraethylene glycol and pentaethylene glycol, have been used as spacers in these polymers. Polymerization was carried out by both solution and interfacial polycondensation; the latter method gave high-molecular-weight polymers. Structural characterizations were done by ultra-violet, infra-red and H-1 nuclear magnetic resonance spectroscopy. Liquid-crystalline properties were studied by differential scanning calorimetry and polarized-light optical microscopy. These polymers show a nematic mesophase. Liquid-crystalline transition temperatures were correlated with polymer structure. The decrease in transition temperature with increase in cycloalkanone ring size was explained in terms of the change in geometrical anisotropy of bis(benzylidene)cycloalkanone units. MNDO (modified neglect of differential overlap) calculations were performed on the model compounds, bis(4-acetyloxybenzylidene)cycloalkanone to elucidate the geometrical variation of the mesogenic units with cycloalkanone ring size. Studies of photolysis reveal the two kinds of photoreactions that proceed in these polymer systems, namely photoisomerization and photo-crosslinking. The former reaction disrupts the parallel stacking of the chromophores and is reflected as an increase in the ultra-violet spectral intensity. The favourability of these two reactions depends on the mobility of the polymer chains. When the photolysis was done below T-g, photo-crosslinking dominates over photoisomerization. Above T-g, photoisomerization is followed by photo-crosslinking. The photosensitivity of the polymers decreases with increase in size of the cycloalkanone ring.

Microstructural and dielectric properties of KCl-added bismuth vanadate ceramics

The effect of KCI addition on the microstructural, structural and dielectric properties of bismuth vanadate, Bi2VO5.5 (BiV) has been examined. The average grain size of BN ceramics increases with increase in KCl content (from an average grain size of TO to 80 mu m) as a result of the increased liquid-phase formation of KCI, at the grain boundaries. Differential scanning calorimetry (DSC) carried out on the KCl-added samples indicates an upward shift in the transition temperature (T-c), from 723 K (for BN) to 734 K (for 5 mol% KCl-added BiV). On further increase in the KCI content, T-c shifts down to about 722 K for 10 mol%. This trend is consistent with that of the lattice strain data. The relative permittivity as well as the dielectric loss decrease by more than half of the original values upon the addition of KCI. The relative permittivities of the KCl-added ceramics are comparable with the values predicted by the logarithmic mixture rule. Impedance analyses suggest that the grain boundary resistance of the KCl-added BiV ceramics is higher by two orders of magnitude than that of BN ceramics. The KCl-added BN ceramics exhibit ferroelectric domains and the domain density decreases as the grain boundary region is approached.

Origin of carrier-type reversal in Pb-Ge-Se glasses: A detailed thermal, electrical, and structural study

A long-standing and important problem in glass science has been carrier-type reversal (CTR) in semiconducting glasses. This phenomenon is exhibited by Pb-Ge-Se glasses also. It has been addressed here by carrying out detailed electrical, thermal, and spectroscopic investigations. PbxGe42-xSe58 (x = 0-20) glasses were prepared by a two stage melt-quenching process and characterized using x-ray diffraction, high-resolution electron microscropy, and energy dispersive analysis of x-rays. Thermoelectric power and high-pressure electrical resistivity have been measured. IR, Raman, and X-ray adsorption near edge structure spectroscopies have been used for examining the glass structures as well as differential scanning calorimetry (DSC) for studying the thermal properties. A structural model based on the chemical nature of the constituents has been proposed to account for the observed properties of these glasses. Effect of Pb incorporation on local structures and qualitative consequences on the energy band structures of Ge-Se glasses has been considered. The p -->n transition has been attributed to the energetic disposition of the sp(3)d(2) band of Pb atoms, which is located closely above the lone pair band of selenium. This feature makes Pb unique in the context of p -->n transition of chalcogenide glasses. The model can be extended successfully to account for the CTR behavior observed in Bi containing chalcogenide glasses also.

Phase modification of ammonium nitrate by potassium salts

Modification of the room temperature phase (IV-III) of ammonium nitrate (AN) has been attempted using a variety of potassium salts namely, KF, KCl, KI, KNO3, K2CO3, K2SO4, KSCN and K2Cr2O7. No phase transition was observed when AN containing 1-2% by mass of these potassium salts is heated from room temperature (25 degrees C) onwards in DTA and DSC scans, but the linear expansion due to phase transition was still observable in TMA measurements. Complete arrest of the linear expansion occurs only when a higher concentration of the additive is used. Similarly, in thermal cycling experiments, complete phase modification in the temperature range -80 to 100 degrees C occurs only with a higher percentage of the potassium salt. The extent of modification, however, is found to be dependent both on the concentration, and the type of the anion. Potassium dichromate when used as an additive modifies the phase as well as the decomposition pattern of AN.

Thermal analysis of metalorganic complexes of copper for evaluation as CVD precursors

Metalorganic complexes of copper have been synthesized by modifying the ligand in the beta-diketonate class of compounds. Detailed thermal analysis of several beta-diketonate complexes of copper has been carried out to evaluate their suitability as precursors for chemical vapor deposition (CVD). A comparison of their relative volatilities has been made by determining their sublimation rates at different temperatures. Thermal analyses of these complexes reveal significant differences among their volatilities and decomposition patterns.

Thermal crystallization behaviour of Ge-Te-Se glasses

Ge10Te90-xSex (50 less than or equal to x less than or equal to 70) and Ge20Te80-xSex (x = 30, 50) glasses have been prepared by melt-quenching The thermal crystallization behaviour of these samples has been studied by Differential Scanning Calorimetry (DSC), in order to characterise these glasses for memory-threshold switching applications. It is found that Ge10Te90-xSex glasses have higher thermal stability and are more stable against devitrification. These samples may be suitable for threshold switching devices. Ge20Te80-xSex glasses, on the other hand, phase separate on heating and exhibit a double stage crystallization. Based on this, it can be expected that Ge20Te80-xSex samples will show memory behaviour. The activation energy for thermal crystallization of a representative Ge10Te40-xSe50 glass belonging to the Ge10Te90-xSex series has been found by the Kissinger's method to be 0.92 eV. The value of the activation energy obtained also indicates that Ge10Te90-xSex samples are less prone to devitrification and more suitable for threshold behaviour.