Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

Thermal decomposition of propargyl alcohol (C3H3OH), a molecule of interest in interstellar chemistry and combustion, was investigated using a single pulse shock tube in the temperature ranging from 953 to 1262 K. The products identified include acetylene, propyne, vinylacetylene, propynal, propenal, and benzene. The experimentally observed overall rate constant for thermal decomposition of propargyl alcohol was found to be k = 10((10.17 +/- 0.36)) exp(-39.70 +/- 1.83)/RT) s(-1) Ab initio theoretical calculations were carried out to understand the potential energy surfaces involved in the primary and secondary steps of propargyl alcohol thermal decomposition. Transition state theory was used to predict the rate constants, which were then used and refined in a kinetic simulation of the product profile. The first step in the decomposition is C-O bond dissociation, leading to the formation of two important radicals in combustion, OH and propargyl. This has been used to study the reverse OH propargyl radical reaction, about which there appears to be no prior work. Depending on the site of attack, this reaction leads to propargyl alcohol or propenal, one of the major products at temperatures below 1200 K. A detailed mechanism has been derived to explain all the observed products.

Impacts of modern transitions on thermal comfort in vernacular dwellings in warm-humid climate of Sugganahalli (India)

Sugganahalli, a rural vernacular community in a warm-humid region in South India, is under transition towards adopting modern construction practices. Vernacular local building elements like rubble walls and mud roofs are given way to burnt brick walls and reinforced cement concrete (RCC)/tin roofs. Over 60% of Indian population is rural, and implications of such transitions on thermal comfort and energy in buildings are crucial to understand. Vernacular architecture evolves adopting local resources in response to the local climate adopting passive solar designs. This paper investigates the effectiveness of passive solar elements on the indoor thermal comfort by adopting modern climate-responsive design strategies. Dynamic simulation models validated by measured data have also been adopted to determine the impact of the transition from vernacular to modern material-configurations. Age-old traditional design considerations were found to concur with modern understanding into bio-climatic response and climate-responsiveness. Modern transitions were found to increase the average indoor temperatures in excess of 7 degrees C. Such transformations tend to shift the indoor conditions to a psychrometric zone that is likely to require active air-conditioning. Also, the surveyed thermal sensation votes were found to lie outside the extended thermal comfort boundary for hot developing countries provided by Givoni in the bio-climatic chart.

TRANSIENT NATURAL CONVECTION FLOW IN A RECTANGULAR CAVITY FILLED WITH A POROUS MATERIAL WITH LOCALIZED HEATING FROM BELOW AND THERMAL STRATIFICATION

The transient natural convection flow with thermal stratification in a rectangular cavity filled with fluid saturated porous medium obeying Darcy's law has been studied. Prior to the time t* = 0, the flow in the cavity is assumed to be motionless and all four walls of the cavity are at the same constant temperature. At time t* = 0, the temperatures of the vertical walls are suddenly increased which vary linearly with the distance y and at the same time on the bottom wall an isothermal heat source is placed centrally. This sudden change in the wall temperatures gives rise to unsteadiness in the problem. The horizontal temperature difference induces and sustains a buoyancy driven flow in the cavity which is then controlled by the vertical temperature difference. The partial differential equations governing the transient natural convection flow have been solved numerically. The local and average Nusselt numbers decrease rapidly in a small time interval after the start of the impulsive change in the wall temperatures and the steady state is reached quickly. The time required to reach the steady state depends on the Rayleigh number and the thermal stratification parameter.

Solar thermal power system augmented with LHP

The present work reports the study of the bubble formation dynamics in the compensation chamber (CC) of the evaporator in Loop Heat Pipes. A series of experiments were conducted at different heat loads and bubbles in the CC were visualized. Bubbles diameter, frequency and velocity were measured and correlated against heat loads. Temperatures were measured at various locations and heat transfer coefficient was calculated. Performance of the LHP evaporator was evaluated at different heat loads. (C) 2013 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license

Effect of thermal annealing on dual photoluminescence emission characteristics of chemically synthesized uncapped Mn2+ doped ZnS quantum dots

Dual photoluminescence (PL) emission characteristics of Mn2+ doped ZnS (ZnS:Mn) quantum dots (QDs) have drawn a lot of attention recently. However, here we report the effect of thermal annealing on the PL emission characteristics of uncapped ZnS:Mn QDs of average sizes similar to 2-3 nm, synthesized by simple chemical precipitation method by using de-ionized (DI) water at room temperature. As-synthesized samples show dual PL emissions, having one UV PL band centred at similar to 400 nm and the other in the visible region similar to 610 nm. But when the samples are isochronally annealed for 2 h at 100-600 degrees C temperature range in air, similar to 90% quenching of Mn2+ related visible PL emission intensity takes place at the annealing temperature of 600 degrees C. X-ray diffraction data show that the as-synthesized cubic ZnS has been converted to wurtzite ZnO at 600 degrees C annealing temperature. The nanostructural properties of the samples are also determined by transmission electron micrograph, electron probe micro-analyser and UV-vis spectrophotometry. The photocatalytic property of the annealed ZnS:Mn sample has been demonstrated and photo-degradation efficiency of the as-synthesized and 600 degrees C annealed ZnS:Mn sample has been found out to be similar to 35% and similar to 61%, respectively, for the degradation of methylene blue dye under visible light irradiation. The synthesized QDs may find significant applications in future optoelectronic devices. (C) 2014 Elsevier B.V. All rights reserved.

Cross-linked Chitosan/Thermoplastic Starch Reinforced with Multiwalled Carbon Nanotubes Using Maleate Esters as Coupling Agent: Mechanical, Tribological and Thermal Characteristics

Bio-nanocomposites have been developed using cross-linked chitosan and cross-linked thermoplastic starch along with acid functionalized multiwalled carbon nanotubes (f-MWCNT). The nanocomposites developed were characterized for mechanical, wear, and thermal properties. The results revealed that the nanocomposites exhibited enhanced mechanical properties. The composites containing 3% f-MWCNT showed maximum compression strength. Tribological studies revealed that, with the addition of small amount of f-MWCNTs the slide wear loss reduced up to 25%. SEM analysis of the nanocomposites showed predominantly brittle fractured surface. Thermal analysis showed that the incorporation of f-MWCNTs has improved the thermal stability for the nanocomposites.

Enhancement in threshold voltage with thickness in memory switch fabricated using GeSe1.5S0.5 thin films

Investigations on the electrical switching, structural, optical and photoacoustic analysis have been undertaken on chalcogenide GeSe1.5S0.5 thin films of various thicknesses prepared by vacuum evaporation technique. The decrease of band gap energy with increase in film thickness has been explained using the `density of states model'. The structural units of the films are characterized using Raman spectroscopy and the deconvoluted Raman peaks obtained from Gaussian fit around 188 cm(-1), 204 cm(-1) and 214 cm(-1) favors Ge-chalcogen tetrahedral units forming corner and edge sharing tetrahedra. All the thin films samples have been exhibited memory-type electrical switching behavior. An enhancement in the threshold voltages of GeSe1.5S0.5 thin films have been observed with increase in film thickness. The thickness dependence of switching voltages provide an insight into the switching mechanism and it is explained by the Joule heating effect. (C) 2014 Elsevier B.V. All rights reserved.

Impact of Stone-Wales and lattice vacancy defects on the electro-thermal transport of the free standing structure of metallic ZGNR

We report the effect of topological as well as lattice vacancy defects on the electro-thermal transport properties of the metallic zigzag graphene nano ribbons at their ballistic limit. We employ the density function theory-Non equilibrium green's function combination to calculate the transmission details. We then present an elaborated study considering the variation in the electrical current and the heat current transport with the change in temperature as well as the voltage gradient across the nano ribbons. The comparative analysis shows, that in the case of topological defects, such as the Stone-Wales defect, the electrical current transport is minimum. Besides, for the voltage gradient of 0.5 Volt and the temperature gradient of 300 K, the heat current transport reduces by similar to 62 % and similar to 50% for the cases of Stones-Wales defect and lattice vacancy defect respectively, compared to that of the perfect one.

Dynamics of intermittent force fluctuations in vesicular nanotubulation

Irregular force fluctuations are seen in most nanotubulation experiments. The dynamics behind their presence has, however, been neither commented upon nor modeled. A simple estimate of the mean energy dissipated in force drops turns out to be several times the thermal energy. This coupled with the rate dependent nature of the deformation reported in several experiments point to a dynamical origin of the serrations. We simplify the whole process of tether formation through a three-stage model of successive deformations of sphere to ellipsoid, neck-formation, and tubule birth and extension. Based on this, we envisage a rate-softening frictional force at the neck that must be overcome before a nanotube can be pulled out. Our minimal model includes elastic and visco-elastic deformation of the vesicle, and has built-in dependence on pull velocity, vesicle radius, and other material parameters, enabling us to capture various kinds of serrated force-extension curves for different parameter choices. Serrations are predicted in the nanotubulation region. Other features of force-extension plots reported in the literature such as a plateauing serrated region beyond a force drop, serrated flow region with a small positive slope, an increase in the elastic threshold with pull velocity, force-extension curves for vesicles with larger radius lying lower than those for smaller radius, are all also predicted by the model. A toy model is introduced to demonstrate that the role of the friction law is limited to inducing stick-slip oscillations in the force, and all other qualitative and quantitative features emerging from the model can only be attributed to other physical mechanisms included in the deformation dynamics of the vesicle. (C) 2014 AIP Publishing LLC.

Assessing impact of material transition and thermal comfort models on embodied and operational energy in vernacular dwellings (India)

Vernacular dwellings are well-suited climate-responsive designs that adopt local materials and skills to support comfortable indoor environments in response to local climatic conditions. These naturally-ventilated passive dwellings have enabled civilizations to sustain even in extreme climatic conditions. The design and physiological resilience of the inhabitants have coevolved to be attuned to local climatic and environmental conditions. Such adaptations have perplexed modern theories in human thermal-comfort that have evolved in the era of electricity and air-conditioned buildings. Vernacular local building elements like rubble walls and mud roofs are given way to burnt brick walls and reinforced cement concrete tin roofs. Over 60% of Indian population is rural, and implications of such transitions on thermal comfort and energy in buildings are crucial to understand. Types of energy use associated with a buildings life cycle include its embodied energy, operational and maintenance energy, demolition and disposal energy. Embodied Energy (EE) represents total energy consumption for construction of building, i.e., embodied energy of building materials, material transportation energy and building construction energy. Embodied energy of building materials forms major contribution to embodied energy in buildings. Operational energy (OE) in buildings mainly contributed by space conditioning and lighting requirements, depends on the climatic conditions of the region and comfort requirements of the building occupants. Less energy intensive natural materials are used for traditional buildings and the EE of traditional buildings is low. Transition in use of materials causes significant impact on embodied energy of vernacular dwellings. Use of manufactured, energy intensive materials like brick, cement, steel, glass etc. contributes to high embodied energy in these dwellings. This paper studies the increase in EE of the dwelling attributed to change in wall materials. Climatic location significantly influences operational energy in dwellings. Buildings located in regions experiencing extreme climatic conditions would require more operational energy to satisfy the heating and cooling energy demands throughout the year. Traditional buildings adopt passive techniques or non-mechanical methods for space conditioning to overcome the vagaries of extreme climatic variations and hence less operational energy. This study assesses operational energy in traditional dwelling with regard to change in wall material and climatic location. OE in the dwellings has been assessed for hot-dry, warm humid and moderate climatic zones. Choice of thermal comfort models is yet another factor which greatly influences operational energy assessment in buildings. The paper adopts two popular thermal-comfort models, viz., ASHRAE comfort standards and TSI by Sharma and Ali to investigate thermal comfort aspects and impact of these comfort models on OE assessment in traditional dwellings. A naturally ventilated vernacular dwelling in Sugganahalli, a village close to Bangalore (India), set in warm - humid climate is considered for present investigations on impact of transition in building materials, change in climatic location and choice of thermal comfort models on energy in buildings. The study includes a rigorous real time monitoring of the thermal performance of the dwelling. Dynamic simulation models validated by measured data have also been adopted to determine the impact of the transition from vernacular to modern material-configurations. Results of the study and appraisal for appropriate thermal comfort standards for computing operational energy has been presented and discussed in this paper. (c) 2014 K.I. Praseeda. Published by Elsevier Ltd.

Sunlight-Induced Covalent Marriage of Two Triply Interlocked Pd-6 Cages and Their Facile Thermal Separation

A template-free triply interlocked Pd-6 cage (2) was synthesized by two-component self-assembly of cis-blocked 90 degrees acceptor cis-(tmen)Pd(NO3)(2) (M) and 1,3,5-tris((E)-2-(pyridin-3-yl)vinyl)benzene (L). Assembly 2 was characterized by H-1 NMR and ESI-MS, and the structure was confirmed by X-ray crystallography, which revealed a parallel conformation of the olefin double bonds belonging to the adjacent cages in the solid state at a distance of 3.656 angstrom, thereby indicating the feasibility of 2+2] photochemical reaction. Two adjacent interlocked cages were covalently married together by intermolecular 2+2] cycloaddition in a single crystal-to-single crystal fashion upon exposure to sunlight/UV irradiation. Most surprisingly, the covalently married pair was easily separated thermally in aqueous medium under mild reaction conditions.

Structural transition and enhanced phase transition properties of Se doped Ge2Sb2Te5 alloys

Amorphous Ge2Sb2Te5 (GST) alloy, upon heating crystallize to a metastable NaCl structure around 150 degrees C and then to a stable hexagonal structure at high temperatures (>= 250 degrees C). It has been generally understood that the phase change takes place between amorphous and the metastable NaCl structure and not between the amorphous and the stable hexagonal phase. In the present work, it is observed that the thermally evaporated (GST)(1-x)Se-x thin films (0 <= x <= 0.50) crystallize directly to the stable hexagonal structure for x >= 0.10, when annealed at temperatures >= 150 degrees C. The intermediate NaCl structure has been observed only for x, 0.10. Chemically ordered network of GST is largely modified for x >= 0.10. Resistance, thermal stability and threshold voltage of the films are found to increase with the increase of Se. The contrast in electrical resistivity between the amorphous and crystalline phases is about 6 orders of magnitude. The increase in Se shifts the absorption edge to lower wavelength and the band gap widens from 0.63 to 1.05 eV. Higher resistance ratio, higher crystallization temperature, direct transition to the stable phase indicate that (GST)(1-x)Se-x films are better candidates for phase change memory applications.

Structural, thermal and quantum chemical studies of p-coumaric and caffeic acids

Two hydroxycinnamic acids viz., p-coumaric, and caffeic acids have been extracted and purified from Parthenium hysterophorus, subsequently characterized by elemental analysis, FT-IR, NMR, single crystal X-ray crystallography. The optimized structures of these acids were calculated in terms of density functional theory by Gaussian 09. The validation of experimental and theoretically obtained data for structural parameters such as bond lengths and bond angles has have been carried out to analyze the statistical significance by curve fitting analysis and the values of correlation coefficient found to be 0.985, 0.992, and 0.984, 0.975 in p-coumaric, and caffeic acids, respectively. The calculated HOMO and LUMO energies show the eventual charge transfer interaction within the molecule. Thermal studies were also carried out by thermogravimetry (TG), differential thermogravimetric analysis (DTA), and derivative thermogravimetry (DTG). (C) 2014 Elsevier B.V. All rights reserved.

Novel triethylamine mediated thermal reactions of 3-aryl-2-cyanoprop-2-enoic acid derivatives-demethylation, reduction and vinylogation

3-Aryl-2-propenoic acid derivatives undergo interesting reactions with hot triethylamine. Substrates like 6 having a methoxyl with a nitro in the ortho and cyanoacrylic derivatives in the para positions give O-demethylated products, for example, entacapone 7. On the other hand compounds like 16 having the NO2 in the para and cyanoacrylic in the ortho position undergo reduction and vinylogation. The latter phenomenon is observed in the absence of the NO2 group also. (C) 2015 Elsevier Ltd. All rights reserved.

Electron transfer statistics and thermal fluctuations in molecular junctions

We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects. (C) 2015 AIP Publishing LLC.