Molecular interpretation of the linear relationship between the entropy and the enthalpy of activation of charge transfer reactions in polar liquids

The well-known linear relationship (T?S# =??H# +?, where 1 >? > 0,? > 0) between the entropy (?S#) and the enthalpy (?H#) of activation for reactions in polar liquids is investigated by using a molecular theory. An explicit derivation of this linear relation from first principles is presented for an outersphere charge transfer reaction. The derivation offers microscopic interpretation for the quantities? and?. It has also been possible to make connection with and justify the arguments of Bell put forward many years ago.

Temperature-dependent photoluminescence of GaN grown on beta-Si3N4/Si (111) by plasma-assisted MBE

Photoluminescence (PL) of high quality GaN epitaxial layer grown on beta-Si3N4/Si (1 1 1) substrate using nitridation-annealing-nitridation method by plasma-assisted molecular beam epitaxy (PA-MBE) was investigated in the range of 5-300 K. Crystallinity of GaN epilayers was evaluated by high resolution X-ray diffraction (HRXRD) and surface morphology by Atomic Force Microscopy (AFM) and high resolution scanning electron microscopy (HRSEM). The temperature-dependent photoluminescence spectra showed an anomalous behaviour with an `S-like' shape of free exciton (FX) emission peaks. Distant shallow donor-acceptor pair (DAP) line peak at approximately 3.285 eV was also observed at 5 K, followed by LO replica sidebands separated by 91 meV. The activation energy of the free exciton for GaN epilayers was also evaluated to be similar to 27.8 +/- 0.7 meV from the temperature-dependent PL studies. Low carrier concentrations were observed similar to 4.5 +/- 2 x 10(17) Cm-3 by measurements and it indicates the silicon nitride layer, which not only acts as a growth buffer layer, but also effectively prevents Si diffusion from the substrate to GaN epilayers. The absence of yellow band emission at around 2.2 eV signifies the high quality of film. The tensile stress in GaN film calculated by the thermal stress model agrees very well with that derived from Raman spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Pillaring of smectites using an aluminium oligomer: A study of pillar density and thermal stability

Two smectite samples having different layer charges were pillared using hydroxy aluminium oligomers at a OH/Al ratio of 2.5 and at pH 4.3 to 4.6. Pillaring was carried out at different conditions such as ageing, temperature and base addition time of the pillaring solution, and also in the presence of nonionic surfactant polyoxyethylene sorbitanmonooleate (Tween-80). The primary objective of preparing at different conditions was to introduce varied quantities of aluminium oligomer between the layers and to study its effect on the properties of the pillared products. A simple method has been followed to estimate the amount of interlayer aluminium. A quantity called pillar density number (PDN) based on the ratio of interlayer Al adsorbed to CEC of the parent clay has been effectively used to evaluate the nature of the resulting pillared product. PDN, for a given clay, was found to correlate well with the sharpness of the d(001) peaks for the air dried samples. The calculated number of pillars, varied from 3.00 x 10(18) to 5.32 x 10(18) per meq charge. The present study shows that a higher value of PDN is indicative of better thermal stability. Pillar density number may be conveniently used as a measure of the thermal stability of pillared samples.

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.

Thermal Stability of Spherical Nanoporous Aggregates and Formation of Hollow Structures by Sintering-A Phase-Field Study

Nanoporous structures are widely used for many applications and hence it Is important to investigate their thermal stability. We study the stability of spherical nanoporous aggregates using phase-field simulations that explore systematically the effect of grain boundary diffusion, surface diffusion, and grain boundary mobility on the pathways for microstructural evolution. Our simulations for different combinations of surface and GB diffusivity and GB mobility show four distinct microstructural pathways en route to 100% density: multiple dosed pores, hollow shells, hollow shells with a core, and multiple interconnected pores. The microstructures from our simulations are consistent with experimental observations in several different systems. Our results have important implications for rational synthesis of hollow nanostructures or aggregates with open pores, and for controlling the stability of nanoporous aggregates that are widely used for many applications.

Thermal and electrical properties of AgI-based composites

AgI-based composites with a general formula AgI---MxOy (MxOy = ZrO2, CeO2, Fe2O3, Sm2O3, MoO3 and WO3) have been studied in detail. The enhancement in the conductivity of AgI and its unusual thermal stability and amorphization are explained assuming a chemical interaction at the oxide-AgI interface.

Thermal expansion of irradiated polyvinyl chloride from 10 K to 340 K

The coefficient of thermal expansion is measured for irradiated Polyvinyl Chloride (PVC) from 10K to 340K. The samples of PVC are irradiated, up to 500 Mrad in steps of 100 Mrad, in air at room temperature by using Co gamma rays with a dose rate of 0.3 Mrad/h. The PVC is an amorphous sample which is confirmed by X-ray diffraction. The coefficient of thermal expansion is found to decrease with radiation dose from 10K to 110K and it increaseswith radiation dose from 110K to 340K. The results are explained on the basis of radiation induced degradation of the sample.

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.

Electron-Beam-Induced Modifications in High-Density Polyethylene

Post-irradiation studies have been carried out to elucidate the effects of electron beam irradiation on the structural, optical, dielectric, and thermal properties of high-density polyethylene (HDPE) films. The experimental results showed that both the optical band gap and activation energy of HDPE films decreases with an increase in the doses of electron radiation. The electrical measurements showed that dielectric constant and the ac conductivity of HDPE increases with an increase in the dose of electron radiation. The thermal analysis carried out using DSC and TGA revealed that the melting temperature, degree of crystallinity, and thermal stability of the HDPE films increased, obviously, due to the predominant cross-linking reaction following high doses of electron irradiation.

Experimental results of an activated carbon-HFC 134a adsorption cooling system for thermal management of electronics

Results of performance measurement of a small cooling capacity laboratory model of an adsorption refrigeration system for thermal management of electronics are compiled. This adsorption cooler was built with activated carbon as the adsorbent and HFC 134a as the refrigerant to produce a cooling capacity under 5 W using waste heat up to 90 degrees C. The thermal compression process is obtained from an ensemble of four solid sorption compressors. Parametric study was conducted with cycle times of 16 and 20 min, heat source temperatures from 73 to 87 degrees C and cooling loads from 3 to 4.9W. Overall system performance is analyzed using two indicators, namely, cooling effectiveness and normalized exergetic efficiency. (C) 2011 Elsevier Ltd. All rights reserved.

Rapid thermal processed thin films of niobium pentoxide (Nb2 O5) deposited by reactive magnetron sputtering

Niobium pentoxide thin films have been deposited on silicon and platinum-coated silicon substrates by reactive magnetron sputtering. The as-deposited films were amorphous and showed good electrical properties in terms of a dielectric permittivity of about 30, and leakage current density of 10(-6) A cm(-2) al a field of 120 kV cm(-1). A rapid thermal annealing process at 800 degrees C further increased the dielectric constant to 90 and increased the leakage current density to 5 x 10(-6) A cm(-2). The current-voltage characteristics observed at low and high fields suggested a combination of phenomena at different regimes of applied electric field. The capacitance-voltage characteristics performed in the metal-insulator-semiconductor configuration indicated good electronic interfaces with a nominal trap density of 4.5 x 10(12) cm(-2) eV(-1), which is consistent with the behavior observed with conventional dielectrics such as SiO2 on silicon surfaces.

Rapid thermal processed thin films of reactively sputtered Ta2O5

Rapid thermal processed thin films of reactively sputtered tantalum pentoxide Ta2O5 thin films have been deposited on silicon and platinum coated silicon substrates by reactive magnetron sputtering. The as-deposited films were amorphous and showed good electrical properties in terms of a dielectric permittivity of about 24 and leakage current density of 9 x 10(-8) A cm(-2). A rapid thermal annealing process at temperatures above 700 degrees C crystallized the films, increased the dielectric relative permittivity, and decreased the leakage current. The dielectric constant for a film rapidly annealed at 850 degrees C increased to 45 and its leakage current density lowered to 2 x 10(-8) A cm(-2). The dielectric measurements in the MIS configuration showed that Ta2O5 might be used as a dielectric material instead of SiO2 or Si3N4 for integrated devices. The current voltage characteristics observed at low and high fields suggested different conduction mechanisms.

Surfactant lipids containing aromatic units produce vesicular membranes with high thermal stability

Six new vesicle-forming, cationic surfactant lipids are synthesized. Four of them contain 'flat' aromatic units at different locations of hydrophobic segments. In order to estimate the influence of aromatic units in the lipid monomer two other surfactant lipids of related structure with n-butyloxy units in the places of aromatic groups were also prepared. Transmission electron microscopy confirmed the vesicular membrane formation from these newly synthesized lipids. DSC or temperature-dependent keto-enol tautomerism of benzoylacetanilide-doped vesicles reveal a remarkable increase in the thermal stability of the membranes formed from aromatic surfactant lipids in contradistinction to their counterparts that contain n-butyloxy units. The enhanced thermal stability originates presumably as a consequence of inter-monomer stacking.

Thermal expansion studies of substituted CTP derivatives

Several new Na, Y and Zr substituted derivatives of Ca-0.5 Ti-2(PO4)(3) (CTP) have been synthesized. These derivatives retain the hexagonal structure of the parent (CTP) compound with minor changes in lattice parameters. Linear thermal expansion coefficients (alpha) have been obtained using a high sensitivity dilatometer.

Al2O3---ZrO2 composite coatings for thermal-barrier applications

Graded alternate layers of Al2O3 and 8% Y2O3-ZrO2 and their admixtures were plasma sprayed onto bond-coated mild steel. They were evaluated for thermal-shock resistance, thermal-barrier characteristics, hot corrosion resistance (molten NaCl corrodant) and depth of attack, adhesion strength and the presence of phases. Although front-back temperature drops of 423-623 K were observed, some of the coatings showed good adherence even after 100 thermal shack cycles. In the sequence of the graded layers, the oxide which is directly in contact with the bond coat appears to influence the properties especially in coatings of 150 and 300 mu m thickness. Molten NaCl readily attacks the films at high hot-face temperatures (1273 K for 1 h) and the adhesive strength falls significantly by 50-60%. Diffusion of alkaline elements is also found to depend on the chemical composition of the outer coating directly facing the molten corrodant. (C) 1997 Elsevier Science Limited.