Mechanism and kinetics of thermal decomposition of precipitates of the zinc oxide-aluminium oxide system from non-isothermal tg curves

Kinetics of decomposition of the precipitates of the ZnO&2sbndAl₂O₃ system, prepared by coprecipitation and mechanical mixing of the individual precipitates, have been studied. The decomposition of zinc basic carbonate is a first order rate process with an activation energy of 34.5 kcal/mole (Coats and Redfern equation). The decomposition of aluminium hydroxide is also best described as a first order rate process with one break in the Coats and Redfern plot corresponding to activation energies of 29.4 and 8.3 kcal/mole respectively. The entire course of decomposition of coprecipitated as well as mechanically mixed samples cannot be described by any one of the many rate equations available. Consequently, the Coats and Redfern equation has been employed. The plots indicate one or two breaks and thus two to three values of activation energy are reported. From the results it is to be concluded that decomposition of these precipitates is a heterogeneous process. The first step is definitely the decomposition of zinc basic carbonate followed by decomposition of aluminium hydroxide and/or interaction of the two precipitates resulting in the formation of “precursor” to spinel. The results of our earlier investigation on the same system (especially the formation of precursors) are well supported by the results reported in this investigation. p]A new equation (a modified form of the Elovich equation) has been proposed for such heterogeneous decomposition processes. The proposed equation also appears to be the general form of the equations where diffusion is the rate controlling process.     

Interaction of chloroform with aniline, o-toluidine and N,N-dimethyl aniline

Heats of mixing aniline, o-toluidine, and N,N-dimethyl aniline with chloroform have been determined by an adiabatic calorimeter. The results have been examined for molecular interactions between them, and they indicate that aniline and o-toluidine are associated through hydrogen bonds. Enthalpy of bond formation in a 1:1 complex has also been determined.     

Carbazole substituted N-acylated linear polyethylenimines (PEI). synthesis and characterization of poly[N-(9-carbazolyl)acetylethylenimine] and poly[N-(2-(9-carbazolyl))propanoylethylenimine]

The synthesis of carbazola substituted N-acylated polyethylenimines, namely, poly[N-(9-carbazolyl)acetylethylenimine] 20 and poly[N-(2-(9-carbazolyl))propanoylethylenimine] 21 by a grafting reaction onto PEI and isomerization polymerization of the carbazole substituted 2-oxazolines is reported. A complete acylation of amino groups in PEI by the 9-carbazolylacetyl groups was achieved by the p-nitrophenyl active ester method but PEI was only partially N-acylated by the 2-(9-carbazolyl)propanoyl groups under similar reaction conditions. The carbazole substituted 2-oxazolines, namely, 2-(9-carbazolyl)methyl-2-oxazoline 18 and (R,S)-2-[1-(9-carbazolyl)]ethyl-2-oxazoline 19 , were prepared by a base induced cyclization of ß-chloroamides. The ring-opening isomerization polymerization of 18 and 19 in the molten state with a cationic initiator (dimethyl sulfate, methyl triflate, or ethylene glycol ditosylate) gave 20 and 21. Gel permeation chromatography of 20 and 21 obtained with different monomerto-initiator ratios gave evidence of a chain transfer reaction with the monomer. The polymers were characterized by elemental analyses, IR, and ¹H-NMR spectroscopy.     

Indentation deformation/fracture of normal and anomalous glasses

Vickers deformation/fracture indentations have been investigated in six silicate glasses. The characteristic damage patterns fall into two distinct groups, according to whether the glass shows “normal” or “anomalous” mechanical behaviour. Observations of the damage morphology during and after contact, of the scales of the deformation and fracture zones, and of the residual stress intensity about the impressions, all point to a basic difference in the local stress/strain micromechanics. This difference is discussed in relation to the factors which control the brittleness of glass.     

Optimization of facet coating for highly strained InGaAs quantum well lasers operating at 1200 nm

The optical output power of a laser diode can be enhanced by anti-reflection (AR) and high-reflection (HR) facet coatings, respectively, at the front and back facet. AR and HR coatings also serve the purpose of protection and passivation of laser diode facets. In this work, we have designed and optimized a single layer λ/4 thick Al₂O₃ film for the AR coating and a stack of λ/4 thick Al₂O₃/λ/4 thick Si bi-layers for the HR coating for highly strained InGaAs quantum-well edge emitting broad area (BA) laser diodes. Effect of the front and back facet reflectivities on output power of the laser diodes has been studied. The light output versus injected current (L–I characteristics) measurements were carried out on selected devices before and after the facet coatings. We have also carried out the numerical simulation and analysis of L–I characteristics for this particular diode structure. The experimental results have been compared and verified with the numerical simulation.     

Nano-graphitic clustering and break down of phonon selection rule in diamond-like carbon films

Diamond-like carbon films are deposited on silicon substrates at different substrate bias using ECR-CVD technique. Raman spectroscopic studies show the presence of broad G and D peaks. In contrast to the position of D peak, the G peak shows a systematic red-shift with increase in the bias voltage. From the analysis it is found that an increase in bias voltage decreases the sp² cluster diameter. Furthermore, two additional Raman peaks at around 690 and 880 cm^?1 are also observed. These peaks, forbidden in the first order Raman scattering, arise due to the breakdown of phonon selection rule in graphitic nanoclusters.     

High pressure behavior of ZrW2O8: Gruneisen parameter and thermal properties

High pressure Raman spectroscopic studies are carried out on negative thermal expansion material ZrW2O8. The system exhibits amorphization at 2.2+/-0.3 GPa via an intermediate orthorhombic phase. In the cubic phase most modes below 50 meV are found to have negative Gruneisen parameter. Using the reported phonon density of states thermal properties are calculated and compared with the reported results. In contrast to the earlier belief, the present results show that modes of energies much higher than 10 meV also contribute substantially to the negative thermal expansion.     

Study of precipitation in NaCl:Pb2+ by light scattering and ultramicroscopy

The formation and dissolution behaviour of precipitates in NaCl : Pb²⁺ single crystals is studied by light scattering and ultramicroscopy. Measurements of Rayleigh ratio together with ultramicroscopic observations during isochronal annealing indicate the presence of two types of precipitates in as-grown crystals. Isochronal annealing after suitable thermal and thermomechanical treatments shows that precipitates of first type (I) which form and dissolve at lower temperatures, are due to homogeneous nucleation. Precipitates of the second category (II) which form and dissolve at higher temperatures are aligned along crystallographic directions and have their origin in stress-assisted processes. Isothermal annealing has been used to study the dissolution kinetics of the precipitated fraction, and it is found that the kinetics is of first order. The enthalpy of solution is determined from a study of the temperature dependence of the kinetic rate constant, in conjunction with available information on the migration energy of Pb²⁺ in NaCl. The enthalpy so deduced is in good agreement with the value as usually obtained from the concentration dependence of the dissolution temperature.