Thermal Rearrangement of Azido Ketones into Oxazoles via Azirines: One-Pot, Metal-Free Heteroannulation to Functionalized 1,3-Oxazoles

alpha-Azidoacetophenones were converted into 2-aryl-1,3-oxazole-4-carbaldehydes through rearrangement of the carbon framework upon exposure to DMF/POCl3. The unprecedented rearrangement occurs via alkenyl azides and 2H-azirines. A mechanism for this unusual reaction was proposed and evidenced.

Proportional resonant controller based circulating power setup for thermal testing of multilevel inverter

A regenerative or circulating-power method is presented in this paper for heat run test on the legs of a three-level neutral point clamped (NPC) inverter. This test ensures that only losses are drawn from the dc supply, while rated power is circulated between the two legs, thus minimising wastage of energy. A proportional-resonant (PR) controller based current control scheme is proposed here for the circulating power test setup in NPC inverter. Simulation and experimental results are presented to validate the controller design at various operating conditions. Results of thermal test on the inverter legs are presented at two different operating conditions.

Experiments on thermal response of low aspect ratio packed beds at high Reynolds numbers with varying inflow temperature

An experimental study for transient temperature response of low aspect ratio packed beds at high Reynolds numbers for a free stream with varying inlet temperature is presented. The packed bed is used as a compact heat exchanger along with a solid propellant gas-generator, to generate room temperature gases for use in applications such as control actuation and air bottle pressurization. Packed beds of lengths similar to 200 mm and 300 mm were characterized for packing diameter based Reynolds numbers, Re-d ranging from 0.6 x 10(4) to 8.5 x 10(4). The solid packing used in the bed consisted of circle divide 9.5 mm and circle divide 5 mm steel spheres with suitable arrangements to eliminate flow entrance and exit effects. The ratios of packed bed diameter to packing diameter for 9.5 mm and 5 mm sphere packing were similar to 9.5 and 18 respectively, with the average packed bed porosities around 0.4. Gas temperatures were measured at the entry, exit and at three axial locations along centre-line in the packed beds. The solid packing temperature was measured at three axial locations in the packed bed. An average Nusselt number correlation of the form Nu(d) = 3.91Re(d)(05) for Re-d range of 10(4) is proposed. For engineering applications of packed beds such as pebble bed heaters, thermal storage systems, and compact heat exchangers a simple procedure is suggested for calculating unsteady gas temperature at packed bed exit for packing Biot number Bi-d < 0.1. (C) 2012 Elsevier Inc. All rights reserved.

Thermal vibration analysis of monolayer graphene embedded in elastic medium based on nonlocal continuum mechanics

This paper presents the thermal vibration analysis of single-layer graphene sheet embedded in polymer elastic medium, using the plate theory and nonlocal continuum mechanics for small scale effects. The graphene is modeled based on continuum plate theory and axial stress caused by the thermal effects is also considered. Nonlocal governing equation of motion for this graphene sheet system is derived from the principle of virtual displacements. The closed form solution for thermal-vibration frequencies of a simply supported rectangular nanoplate has been obtained by using the Navier's method of solution. Numerical results obtained by the present theory are compared with available solutions in the literature and the molecular dynamics results. The influences of the small scale coefficient, the room or low temperature, the high temperature, the half wave number and the aspect ratio of nanoplate on the natural frequencies are considered and discussed in detail. The thermal vibration analysis of single- and double-layer graphene sheets are considered for the analysis. The mode shapes of the respective graphene system are also captured in this work. The present analysis results can be used for the design of the next generation of nanodevices that make use of the thermal vibration properties of the graphene.

Study of thermal relaxation of Poly (HDDA-co-MMA) by temperature modulated DSC and dielectric spectroscopy

The thermal transitions in the copolymer of 1,6-hexanediol diacrylate (HDDA) and methyl methacrylate (MMA) was investigated to understand its use in microstereolithography. The glass transition temperature and the effect of interaction on this transition process was investigated by means of temperature modulated differential scanning calorimetry (TMDSC). The heat capacities were determined and PHDDA rich phases showed lower heat capacity than PMMA rich phases. The frequency dependence of glass transitions were studied by varying the modulation period of TMDSC and confirmed by dielectric relaxation spectroscopy. Vogel Fulcher Tammann Hesse (VFTH) parameters of homo and copolymers have also been reported.

Growth and characterization of micro and nanostructures of lead telluride (PbTe) by thermal evaporation method

Lead telluride micro and nanostructures have been grown on silicon and glass substrates by a simple thermal evaporation of PbTe in high vacuum of 3 x 10(-5) mbar. Growth was carried out for two different distances between the evaporation source and the substrates. Synthesized products consist of nanorods and micro towers for 2.4 cm and 3.4 cm of distance between the evaporation source and the substrates respectively. X-ray diffraction and transmission electron microscopy studies confirmed crystalline nature of the nanorods and micro towers. Nanorods were grown by vapor solid mechanism. Each micro tower consists of nano platelets and is capped with spherical catalyst particle at their end, suggesting that the growth proceeds via vapor-liquid-solid (VLS) mechanism. EDS spectrum recorded on the tip of the micro tower has shown the presence of Pb and Te confirming the self catalytic VLS growth of the micro towers. These results open up novel synthesis methods for PbTe nano and microstructures for various applications.

Synthesis, microstructure and thermal expansion studies on Ca0 center dot 5+x/2Sr0 center dot 5+x/2Zr4P6-2x Si-2x O-24 system prepared by co-precipitation method

We report on the synthesis, microstructure and thermal expansion studies on Ca0 center dot 5 + x/2Sr0 center dot 5 + x/2Zr4P6 -aEuro parts per thousand 2x Si-2x O-24 (x = 0 center dot 00 to 1 center dot 00) system which belongs to NZP family of low thermal expansion ceramics. The ceramics synthesized by co-precipitation method at lower calcination and the sintering temperatures were in pure NZP phase up to x = 0 center dot 37. For x a parts per thousand yen 0 center dot 5, in addition to NZP phase, ZrSiO4 and Ca2P2O7 form as secondary phases after sintering. The bulk thermal expansion behaviour of the members of this system was studied from 30 to 850 A degrees C. The thermal expansion coefficient increases from a negative value to a positive value with the silicon substitution in place of phosphorous and a near zero thermal expansion was observed at x = 0 center dot 75. The amount of hysteresis between heating and cooling curves increases progressively from x = 0 center dot 00 to 0 center dot 37 and then decreases for x > 0 center dot 37. The results were analysed on the basis of formation of the silicon based glassy phase and increase in thermal expansion anisotropy with silicon substitution.

Nanocomposites of crosslinked starch phthalate and silane modified nanoclay: Study of mechanical, thermal, morphological, and biodegradable characteristics

Biodegradable composites comprising of modified starch and modified nanoclay have been prepared. Starch has been modified by esterification and subsequently crosslinked. The thermal, mechanical, and biodegradation characteristics of the composites have been investigated. The compressive properties of the composites with the addition of nanoclay were twice that of crosslinked starch phthalate without addition of nanoclay. Predictive theories were used to analyze the obtained experimental results. SEM studies on fracture morphology indicated quasi-brittle fracture. Flexural properties showed considerable improvement due to nanoclay addition. The water uptake increased up to 6% nanoclay, beyond which the uptake decreased. Biodegradation studies showed an initial time lag prior to the onset of degradation.

Hardening and corrosion behaviour of copper added SUS 304H austenitic steels subjected to thermal cycling

This research was aimed at determining optimum Cu content for the alloy design of SUS 30411 austenitic steels having enhanced heat and corrosion resistance. Samples of the steel containing 1, 3, and 5 wt.% Cu were subjected to repeated heating and cooling to a temperature of 760 degrees C and to a maximum of 15 cycles. Hardness measurement and the corrosion behaviour in 1M NaCl solution were evaluated. The hardness increases with an increase in the number of heating cycles for the three compositions. The hardening response to the thermal cycles is however higher for the 1 wt.% Cu composition and decreases with an increase in the Cu wt.%. The SUS 30411 steel containing 3 wt.% Cu exhibited the least susceptibility to corrosion in the 1M NaCl solution irrespective of the number of heating cycles. The SUS 30411 steel containing 1 wt.% Cu was found to exhibit the highest susceptibility to corrosion for all heating cycles compared.

Effect of thermal and thermo-mechanical cycling on the microstructure of Ni-rich NiTi shape memory alloys

Microstructural changes of Ni-rich NiTi shape memory alloy during thermal and thermo-mechanical cycling have been investigated using Electron Back Scattered Diffraction. A strong dependence of the orientation of the prior austenite grain on the misorientation development has been observed during thermal cycling and thermo-mechanical cycling. This effect is more pronounced at the grain boundaries compared to grain interior. At a larger applied strain, the volume fraction of stabilized martensite phase increases with increase in the number of cycling. Deformation within the martensite leads to stabilization of martensitic phase even at temperatures slightly above the austenite finish temperature. Modulus variation with respect to temperature has been explained on the basis of martensitic transformation.

Investigating thermal stability of structural defects and its effect on d(0) ferromagnetism in undoped SnO2

The effect of annealing on structural defects and d(0) ferromagnetism in SnO2 nanoparticles prepared by solution combustion method is investigated. The as-synthesized SnO2 nanoparticles were annealed at 400-800 degrees C for 2 h, in ambient conditions. The crystallinity, size, and morphology of the samples were studied using x-ray diffraction and transmission electron microscopy studies. The annealing results in grain growth due to coarsening as well as reduction in oxygen vacancies as confirmed by Raman spectroscopy, photoluminescence spectroscopy, and x-ray photoelectron spectroscopy. All the as synthesized and annealed samples exhibit room temperature ferromagnetism (RTFM) with distinct hysteresis loops and the saturation magnetization as high as similar to 0.02 emu/g in as-synthesized samples. However, the saturation magnetization is drastically reduced with increasing annealing temperature. Further the presence of singly charged oxygen vacancies (V-o(-) signal at g-value 1.99) is confirmed by electron paramagnetic resonance studies, which also diminish with increasing annealing temperature. The observed diminishing RTFM and simultaneous evidences of diminishing O vacancies clearly indicate that RTFM is driven by defects in oxide lattice and confirms primary role of oxygen vacancies in inducing ferromagnetic ordering in metal oxide semiconductors. The study also provides improved fundamental understanding regarding the ambiguity in the origin of intrinsic RTFM in semiconducting metal oxides and projects their technological application in the field of spintronics. (C) 2013 AIP Publishing LLC.

A new 3D cadmium(II) coordination polymer having mu(4)-oxalato, mu-aquo and mu-chlorido bridges: crystal structure, solid state fluorescence and thermal behavior

A new 3D cadmium(II) coordination polymer, Cd(C2O4)(0.5)Cl(H2O)](n) (1) has been synthesized from a mixture of CdCl2. H2O and (NH4)(2)C2O4 in a slightly acidic pH. Its molecular structure was determined by single crystal X-ray diffraction which reveals that the new polymeric structure consists of simultaneous mu(4)-oxalato, mu-aquo, and mu-chlorido bridges between the metal centers, embedded in distorted pentagonal bipyramidal geometries. On thermal analysis compound exhibits high thermal stability up to 330 degrees C. Compound 1 also exhibits strong fluorescent emission. (c) 2013 Elsevier B.V. All rights reserved.

A model of coupled thermal, mechanical, and electrostatic field effects in III-N thin film heterostructures

A one-dimensional coupled multi-physics based model has been developed to accurately compute the effects of electrostatic, mechanical, and thermal field interactions on the electronic energy band structure in group III-nitrides thin film heterostructures. Earlier models reported in published literature assumes electro-mechanical field with uniform temperature thus neglecting self-heating. Also, the effects of diffused interface on the energy band structure were not studied. We include these effects in a self-consistent manner wherein the transport equation is introduced along with the electro-mechanical models, and the lattice structural variation as observed in experiments are introduced at the interface. Due to these effects, the electrostatic potential distribution in the heterostructure is altered. The electron and hole ground state energies decrease by 5% and 9%, respectively, at a relative temperature of 700 K, when compared with the results obtained from the previously reported electro-mechanical model assuming constant and uniform temperature distribution. A diffused interface decreases the ground state energy of electrons and holes by about 11% and 9%, respectively, at a relative temperature of 700 K when compared with the predictions based on uniform temperature based electro-mechanical model. (C) 2013 AIP Publishing LLC.

Photo-thermal modifications in ultrafast laser inscribed chalcogenide glass waveguides

We report here, a finite difference thermal diffusion (FDTD) model for controlling the cross-section and the guiding nature of the buried channel waveguides fabricated on GeGaS bulk glasses using the direct laser writing technique. Optimization of the laser parameters for guiding at wavelength 1550 nm is done experimentally and compared with the theoretical values estimated by FDTD model. The mode field diameter (MFD) between 5.294 mu m and 24.706 mu m were attained by suitable selection of writing speed (1mm/s to 4 mm/s) and pulse energy (623 nJ to 806 nJ) of the laser at a fixed repletion rate of 100 kHz. Transition from single-mode to multi-mode waveguide is observed at pulse energy 806nJ as a consequence of heat accumulation. The thermal diffusion model fits well for single-mode waveguides with the exception of multi-mode waveguides.

Information content of molecular graph and prediction of gas phase thermal entropy of organic compounds

Entropy is a fundamental thermodynamic property that has attracted a wide attention across domains, including chemistry. Inference of entropy of chemical compounds using various approaches has been a widely studied topic. However, many aspects of entropy in chemical compounds remain unexplained. In the present work, we propose two new information-theoretical molecular descriptors for the prediction of gas phase thermal entropy of organic compounds. The descriptors reflect the bulk and size of the compounds as well as the gross topological symmetry in their structures, all of which are believed to determine entropy. A high correlation () between the entropy values and our information-theoretical indices have been found and the predicted entropy values, obtained from the corresponding statistically significant regression model, have been found to be within acceptable approximation. We provide additional mathematical result in the form of a theorem and proof that might further help in assessing changes in gas phase thermal entropy values with the changes in molecular structures. The proposed information-theoretical molecular descriptors, regression model and the mathematical result are expected to augment predictions of gas phase thermal entropy for a large number of chemical compounds.