Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

A physics-based flexural phonon-dependent thermal conductivity model for single layer graphene

In this paper, we address a physics-based closed-form analytical model of flexural phonon-dependent diffusive thermal conductivity (kappa) of suspended rectangular single layer graphene sheet. A quadratic dependence of the out-of-plane phonon frequency, generally called flexural phonons, on the phonon wave vector has been taken into account to analyze the behavior of kappa at lower temperatures. Such a dependence has further been used for the determination of second-order three-phonon Umklapp and isotopic scatterings. We find that these behaviors in our model are best explained through the upper limit of Debye cut-off frequency in the second-order three-phonon Umklapp scattering of the long phonon waves that actually remove the thermal conductivity singularity by contributing a constant scattering rate at low frequencies and note that the out-of-plane Gruneisen parameter for these modes need not be too high. Using this, we clearly demonstrate that. follows a T-1.5 and T-2 law at lower and higher temperatures in the absence of isotopes, respectively. However in their presence, the behavior of kappa sharply deviates from the T-2 law at higher temperatures. The present geometry-dependent model of kappa is found to possess an excellent match with various experimental data over a wide range of temperatures which can be put forward for efficient electro-thermal analyses of encased/supported graphene.

The irradiation of pure CH3OH and 1:1 mixture of NH3:CH3OH ices at 30 K using low energy electrons

The results of an experimental investigation of 1 keV electron irradiation of ices (deposited at 30 K) of (i) pure methanol and (ii) of a 1:1 mixture of NH3:CH3OH are reported. Molecular products formed within the ice were detected and monitored using FTIR spectroscopy. The products observed were methyl formate (H3COHCO), methane (CH4), hydroxymethyl (CH2OH), formamide (HCONH2), formic acid (HCOOH), formaldehyde (H2CO), formyl radical (HCO), cyanate ion (OCN-), isocyanic acid (HNCO), carbon monoxide (CO) and carbon dioxide (CO2). The consequences of these results for prebiotic chemistry in the interstellar medium and star forming regions are discussed. Crown Copyright (C) 2012 Published by Elsevier B. V. All rights reserved.

Thermal oxidation strategy for the synthesis of phase-controlled GeO2 and photoluminescence characterization

We report the synthesis of trigonal and tetragonal phase GeO2 films/microrods from a Ge wafer/powder by thermal oxidation. Both trigonal and tetragonal GeO2 exhibit excitation-dependent luminescence. Trigonal GeO2 exhibits strong green luminescence while tetragonal GeO2 exhibits strong blue luminescence when excited with ultra-violet light. Yellow-red luminescence is observed when both the phases are excited with green light. The emission wavelength varies almost linearly with the excitation wavelength both for trigonal and tetragonal GeO2. The variation is significant in the case of tetragonal GeO2, indicating a potential wavelength converter material.

Structure of SAICAR synthetase from Pyrococcus horikoshii OT3: Insights into thermal stability

The first native crystal structure of Phosphoribosylaminoimidazole-succinocarboxamide synthetase (SAICAR synthetase) from a hyperthermophilic organism Pyrococcus horikoshii OT3 was determined in two space groups H3 (Type-1: Resolution 2.35 angstrom) and in C222(1) (Type-2: Resolution 1.9 angstrom). Both are dimeric but Type-1 structure exhibited hexameric arrangement due to the presence of cadmium ions. A comparison has been made on the sequence and structures of all SAICAR synthetases to better understand the differences between mesophilic, thermophilic and hyperthermophilic SAICAR synthetases. These SAICAR synthetases are reasonably similar in sequence and three-dimensional structure; however, differences were visible only in the subtler details of percentage composition of the sequences, salt bridge interactions and non-polar contact areas. (c) 2012 Elsevier B.V. All rights reserved.

Optical properties change with the addition and diffusion of Bi to As2S3 in the Bi/As2S3 bilayer thin film

The role of Bi layer (thickness similar to 7 nm) on As2S3 film was extensively studied for different optical applications in which Bi (top layer) as active and diffusing layer and As2S3 as barrier (matrix) layer. Bilayer thin films of Bi/As2S3 were prepared from Bi and As2S3 by thermal evaporation technique under high vacuum. The decrease of optical band gap with the addition of Bi to As2S3 has been explained on the basis of density of states and the increase in disorder in the system. It was found that the efficient changes of optical parameters (transmission, optical band gap, refraction) could be realized due to the photo induced diffusion activated by the focused 532 nm laser irradiation and formation of different bonds. The diffusion of Bi into As2S3 matrix increases the optical band gap producing photo bleaching effect. The changes were characterised by different experimental techniques. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis, characterization and thermal degradation of dual temperature- and pH-sensitive RAFT-made copolymers of N,N-(dimethylamino)ethyl methacrylate and methyl methacrylate

Poly{(N,N-(dimethylamino)ethyl methacrylate]-co-(methyl methacrylate)} copolymers of various compositions were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization at 70 degrees C in N,N-dimethylformamide. The polymer molecular weights and molecular weight distributions were obtained from size exclusion chromatography, and they indicated the controlled nature of the RAFT polymerizations; the polydispersity indices are in the range 1.11.3. The reactivity ratios of N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and methyl methacrylate (MMA) (rDMAEMA = 0.925 and rMMA = 0.854) were computed by the extended KelenTudos method at high conversions, using compositions obtained from 1H NMR. The pH- and temperature-sensitive behaviour were studied in aqueous solution to confirm dual responsiveness of these copolymers. The thermal properties of the copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The kinetics of thermal degradation were determined by Friedmann and Chang techniques to evaluate various parameters such as the activation energy, the order and the frequency factor. (c) 2012 Society of Chemical Industry

COMPARATIVE EVALUATION OF THERMAL CONDUCTIVITY OF ZIRCONIA SOLID AND HONEYCOMB STRUCTURES

Porous zirconia ceramic monoliths have been extensively used in thermo-structural applications due to their inherent low thermal conductivity in combination with their adaptability to form complicated shapes through advanced ceramic processing techniques. However, extruded cellular honeycomb structures made from these materials have been less explored for thermal management applications. There exist large potential applications due to their unique configurations, resulting in better heat-management mechanisms. Some of the studies carried out on zirconia honeycombs are safeguarded through patents due to its technical importance, or the information is not in the public domain. In the present study, for the sake of comparison, honeycomb specimens with varying wall thicknesses and unit cell lengths maintaining almost same bulk density of around 90% theoretical and relative density of 0.34-0.37 were prepared and subjected to thermal conductivity evaluation along with the solid samples with relative density of 1.0 using monotonic heating regime methodology. In addition, the effect of channel shape was also evaluated using square and triangular channeled honeycombs with the same relative densities. The results obtained from these specimens were correlated with their configurations to bring out the advantages accrued by using the honeycomb with these configurations. It was observed that a significant decrease in thermal conductivity was achieved in honeycombs, which can be attributed to the behavior of various heat transfer mechanisms that are operative at high temperatures in combination with the considerable reduction in thermal mass and the consequent conduction through the solids.

New metal-organic precursors for MOCVD applications: Synthesis, characterization, crystal structure and thermal properties of mixed-ligand Mg(II) complexes

In an effort to develop new MOCVD precursors, mixed-ligand metal-organic complexes, bis (acetylacetonato-k(2)O,O') (2,2'-bipyridine-k(2)N,N') magnesium(II), and his (acetylacetonato-k(2)O,O') (1,10-phenanthroline-k(2)N,N') magnesium(II) were synthesized. Spectroscopic characterization and crystal structures confirmed them to be monomeric and stable complexes. Crystal structure analysis suggests in each of the magnesium(II) complexes, the metal center has a distorted octahedral coordination geometry. Thermo-gravimetric analysis (TGA/DTA) suggests that these complexes are volatile and thermally stable. The thermal characteristics of newly designed complexes make them attractive precursors for MOCVD applications. (c) 2012 Elsevier B.V. All rights reserved.

Self catalytic growth of SnO2 branched nanowires by thermal evaporation

For the first time, Tin oxide (SnO2) multiple branched nanowires (NWs) have been synthesized by thermal evaporation of tin (Sn) in presence of oxygen without use of metal catalysts at low substrate temperature of 500 degrees C. Synthesized product consists of multiple branched nanowires and were single crystalline in nature. Each of the nanowire capped with catalyst particle at their ends. Energy dispersive X-ray analysis on the nanowires and capped nanoparticle confirms that Sn act as catalyst for SnO2 nanowires growth. A self catalytic vapor-liquid-solid (VLS) growth mechanism was proposed to describe the SnO2 nanowires growth. (C) 2012 Elsevier B.V. All rights reserved.

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.

Electron irradiation effects on TGA-capped CdTe quantum dots

8MeV electron irradiation effects on thioglycolic acid (TGA)-capped CdTe quantum dots (QD) are discussed in this study. CdTe QDs were characterized using x-ray diffraction (XRD), transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS). Steady-state and time-resolved emission spectroscopy and UV-visible absorption spectroscopy were performed before and after irradiation with 8MeV electrons. XRD and TEM confirm the growth of TGA-capped CdTe QDs. The photoemission wavelength, intensity and lifetimes were found to vary with electron dose. At lower doses, they were found to be increasing (red-shift of photoluminescence (PL) peak and intensity) while the intensity decreased at higher electron doses. The observed changes in PL property, XPS and XRD analysis suggest possible epitaxial growth of the CdS shell on the CdTe core. This work demonstrates electron beam induced formation of the CdS layer on the CdTe core, which is a key step towards growth of the water soluble CdTe/CdS core-shell structure for biomedical labelling applications.