Studies of phosphazenes. Part 33. Thermal rearrangement of alkoxy(p-methylphenoxy)cyclophosphazenes: a synthetic route to oxocyclophosphazanes, phosphazadienes and phosphaz-1-enes

The aryloxy(alkoxy)cyclotriphosphazenes N3P3(OR)6�m(OC6H4Me-p)n(R = Me, n= 1�3; R = Et or CH2Ph, n= 3) rearrange on heating to give trioxocyclotriphosphazanes; the di- and mono-methoxy derivatives, N3P3(OMe)6�n(OC6H4Me-p)n(n= 4 or 5), yield dioxophosphaz-1-enes and an oxophosphazadiene respectively. The 1H, 13C and 31P NMR data for the starting materials and the products are presented. No evidence has been found for partially rearranged products. The geometrical disposition of the aryloxy groups in the starting material is retained in the rearranged products. Some aspects of the mechanism of the thermal rearrangement are discussed.

Control of transient thermal response during sequential open-die forging: A trajectory optimization approach

A trajectory optimization approach is applied to the design of a sequence of open-die forging operations in order to control the transient thermal response of a large titanium alloy billet. The amount of time tire billet is soaked in furnace prior to each successive forging operation is optimized to minimize the total process time while simultaneously satisfying constraints on the maximum and minimum values of the billet's temperature distribution to avoid microstructural defects during forging. The results indicate that a "differential" heating profile is the most effective at meeting these design goals.

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.

Molecular Dynamics Perspective on the Protein Thermal Stability: A Case Study Using SAICAR Synthetase

The enzyme SAICAR synthetase ligates aspartate with CAIR (5'-phosphoribosyl-4-carboxy-5-aminoimidazole) forming SAICAR (5-amino-4-imidazole-N-succinocarboxamide ribonucleotide) in the presence of ATP. In continuation with our previous study on the thermostability of this enzyme in hyper-/thermophiles based on the structural aspects, here, we present the dynamic aspects that differentiate the mesophilic (E. coli, E. chaffeensis), thermophilic (G. kaustophilus), and hyperthermophilic (M. jannaschii, P. horikoshii) SAICAR synthetases by carrying out a total of 11 simulations. The five functional dimers from the above organisms were simulated using molecular dynamics for a period of 50 ns each at 300 K, 363 K, and an additional simulation at 333 K for the thermophilic protein. The basic features like root-mean-square deviations, root-mean-square fluctuations, surface accessibility, and radius of gyration revealed the instability of mesophiles at 363 K. Mean square displacements establish the reduced flexibility of hyper-/thermophiles at all temperatures. At the simulations time scale considered here, the long-distance networks are considerably affected in mesophilic structures at 363 K. In mesophiles, a comparatively higher number of short-lived (having less percent existence time) C alpha, hydrogen bonds, hydrophobic interactions are formed, and long-lived (with higher percentage existence time) contacts are lost. The number of time-averaged salt-bridges is at least 2-fold higher in hyperthermophiles at 363 K. The change in surface accessibility of salt-bridges at 363 K from 300 K is nearly doubled in mesophilic protein compared to proteins from other temperature classes.

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.

On the thermal budget of Pahoehoe lava flows

In this thesis I investigate some aspects of the thermal budget of pahoehoe lava flows. This is done with a combination of general field observations, quantitative modeling, and specific field experiments. The results of this work apply to pahoehoe flows in general, even though the vast bulk of the work has been conducted on the lavas formed by the Pu'u 'O'o - Kupaianaha eruption of Kilauea Volcano on Hawai'i. The field observations rely heavily on discussions with the staff of the United States Geological Survey's Hawaiian Volcano Observatory (HVO), under whom I labored repeatedly in 1991-1993 for a period totaling about 10 months.

The quantitative models I have constructed are based on the physical processes observed by others and myself to be active on pahoehoe lava flows. By building up these models from the basic physical principles involved, this work avoids many of the pitfalls of earlier attempts to fit field observations with "intuitively appropriate" mathematical expressions. Unlike many earlier works, my model results can be analyzed in terms of the interactions between the different physical processes. I constructed models to: (1) describe the initial cooling of small pahoehoe flow lobes and (2) understand the thermal budget of lava tubes.

The field experiments were designed either to validate model results or to constrain key input parameters. In support of the cooling model for pahoehoe flow lobes, attempts were made to measure: (1) the cooling within the flow lobes, (2) the amount of heat transported away from the lava by wind, and (3) the growth of the crust on the lobes. Field data collected by Jones [1992], Hon et al. [1994b], and Denlinger [Keszthelyi and Denlinger, in prep.] were also particularly useful in constraining my cooling model for flow lobes. Most of the field observations I have used to constrain the thermal budget of lava tubes were collected by HVO (geological and geophysical monitoring) and the Jet Propulsion Laboratory (airborne infrared imagery [Realmuto et al., 1992]). I was able to assist HVO for part of their lava tube monitoring program and also to collect helicopterborne and ground-based IR video in collaboration with JPL [Keszthelyi et al., 1993].

The most significant results of this work are (1) the quantitative demonstration that the emplacement of pahoehoe and 'a'a flows are the fundamentally different, (2) confirmation that even the longest lava flows observed in our Solar System could have formed as low effusion rate, tube-fed pahoehoe flows, and (3) the recognition that the atmosphere plays a very important role throughout the cooling of history of pahoehoe lava flows. In addition to answering specific questions about the thermal budget of tube-fed pahoehoe lava flows, this thesis has led to some additional, more general, insights into the emplacement of these lava flows. This general understanding of the tube-fed pahoehoe lava flow as a system has suggested foci for future research in this part of physical volcanology.

Energy retrofits in social housing. Analysis of its thermal behaviour.

468 p.

Thermodynamic analysis of pumped thermal electricity storage

The increasing use of renewable energy technologies for electricity generation, many of which have an unpredictably intermittent nature, will inevitably lead to a greater need for electricity storage. Although there are many existing and emerging storage technologies, most have limitations in terms of geographical constraints, high capital cost or low cycle life, and few are of sufficient scale (in terms of both power and storage capacity) for integration at the transmission and distribution levels. This paper is concerned with a relatively new concept which will be referred to here as Pumped Thermal Electricity Storage (PTES), and which may be able to make a significant contribution towards future storage needs. During charge, PTES makes use of a high temperature-ratio heat pump to convert electrical energy into thermal energy which is stored as ‘sensible heat’ in two thermal reservoirs, one hot and one cold. When required, the thermal energy is then converted back to electricity by effectively running the heat pump backwards as a heat engine. The paper focuses on thermodynamic aspects of PTES, including energy and power density, and the various sources of irreversibility and their impact on round-trip efficiency.

Effect of rapid thermal annealing and hydrogen plasma treatment on the microstructure and light-emission of silicon-rich oxide film

Silicon-rich silicon oxide (SRSO) films are prepared by plasma-enhanced chemical vapor deposition method at the substrate temperature of 200degreesC. The effect of rapid thermal annealing and hydrogen plasma treatment on tire microstructure and light-emission of SRSO films are investigated in detail using micro-Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and photoluminescence (PL) spectra. It is found that the phase-separation degree of the films decreases with increasing annealing temperature from 300 to 600degreesC, while it increases with increasing annealing temperature from 600 to 900degreesC. The light-emission of the films are enhanced with increasing annealing temperature up to 500degreesC, while it is rapidly reduced when the annealing temperature exceeds 600degreesC. The peak position of the PL spectrum blueshifts by annealing at the temperature of 300degreesC, then it red-shifts with further raising annealing temperature. The following hydrogen plasma treatment results in a disproportionate increase of the PL intensity and a blueshift or redshift of the peak positions, depending on the pristine annealing temperature. It is thought that the size of amorphous silicon clusters, surface structure of the clusters and the distribution of hydrogen in the films can be changed during the annealing procedure. The results indicate that not only cluster size but also surface state of the clusters plays an important role in the determination of electronic structure of the amorphous silicon cluster and recombination process of light-generated carriers.

A simple selenium source to synthesize CdSe via the two-phase thermal approach

A novel selenium source was developed to synthesize the size-controlled CdSe nanocrystals with relatively narrow size distribution successfully in a two-phase thermal approach. A highly reactive and aqueous soluble selenium source was provided by the reduction of selenite, and in this route the size of the nanocrystals can be adjusted by the reaction temperature and time. The size, crystalline structure and optical characteristics of these nanocrystals were investigated by transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, UV-vis spectroscopy, and photoluminescence spectroscopy. The influence factors for this approach were also discussed.

Super insulated aerogel windows: Impact on daylighting and thermal performance.

Window design plays an important role in achieving energy efficient buildings and in providing thermal comfort of building occupants. This paper investigates a newly developed aerogel window and the potential improvement on the comfort factors of an office in relation to daylighting. Improved comfort levels can impact on health and wellbeing of building occupants leading to knock on effects on absenteeism and productivity. A simulation tool was presently created that will easily enable comparison of different façade design and their impact on heat and light transmission and therefore enable optimisation. One of the most important aspects of the present work was comparing the performance of the newly developed aerogel window against the more traditional Argon-filled, coated double-glazing. Whereas the aerogel window provided an extremely low heat-loss index of 0.3 W/m2K, the latter usually offered a centre-glazing U-value of 1.4 W/m2K. On a like-with-like basis the daylight transmission of the aerogel window was significantly lower than double-glazing. However, in view of low thermal loss larger areas of the former can be deployed. This article presents the influence of three key parameters that may lead to an optimum design: daylight, thermal loss and solar gain.

Synthetic and mechanistic aspects of the reactions of α-diazosulfoxides

The research described in this thesis focuses, principally, on synthesis of stable α-diazosulfoxides and investigation of their reactivity under various reaction conditions (transition-metal catalysed, photochemical, thermal and microwave) with a particular emphasis on the reactive intermediates and mechanistic aspects of the reaction pathways involved. In agreement with previous studies carried out on these compounds, the key reaction pathway of α-diazosulfoxides was found to be hetero-Wolff rearrangement to give α-oxosulfine intermediates. However, a competing reaction pathway involving oxygen migration from sulfur to oxygen was also observed. Critically, isomerisation of α-oxosulfine stereoisomers was observed directly by 1H NMR spectroscopy in this work and this observation accounts for the stereochemical outcomes of the various cycloaddition reactions, whether carried out with in situ trapping or with preformed solutions of sulfines. Furthermore, matrix isolation experiments have shown that electrocyclisation of α-oxosulfines to oxathiiranes takes place and this verifies the proposed mechanisms for enol and disulfide formation. The introductory chapter includes a brief literature review of the synthesis and reactivity of α-diazosulfoxides prior to the commencement of research in this field by the Maguire group. The Wolff rearrangement is also discussed and the characteristic reactions of a number of reactive intermediates (sulfines, sulfenes and oxathiiranes) are outlined. The use of microwave-assisted organic synthesis is also examined, specifically, in the context of α-diazocarbonyl compounds as substrates. The second chapter describes the synthesis of stable monocyclic and bicyclic lactone derivatives of α-diazosulfoxides from sulfide precursors according to established experimental procedures. Approaches to precursors of ketone and sulfimide derivatives of α-diazosulfoxides are also described. The third chapter examines the reactivity of α-diazosulfoxides under thermal, microwave, rhodium(II)-catalysed and photochemical conditions. Comparison of the results obtained under thermal and microwave conditions indicates that there was no evidence for any effect, other than thermal, induced by microwave irradiation. The results of catalyst studies involving several rhodium(II) carboxylate and rhodium(II) carboxamidate catalysts are outlined. Under photochemical conditions, sulfur extrusion is a significant reaction pathway while under thermal or transition metal catalysed conditions, oxygen extrusion is observed. One of the most important observations in this work was the direct spectroscopic observation (by 1H NMR) of interconversion of the E and Z-oxosulfines. Trapping of the α-oxosulfine intermediates as cycloadducts by reaction with 2,3-dimethyl-1,3-butadiene proved useful both synthetically and mechanistically. As the stereochemistry of the α-oxosulfine is retained in the cycloadducts, this provided an ideal method for characterisation of this key feature. In the case of one α-oxosulfine, a novel [2+2] cycloaddition was observed. Preliminary experiments to investigate the reactivity of an α-diazosulfone under rhodium(II) catalysis and microwave irradiation are also described. The fourth chapter describes matrix isolation experiments which were carried out in Rühr Universität, Bochum in collaboration with Prof. Wolfram Sander. These experiments provide direct spectroscopic evidence of an α-oxosulfine intermediate formed by hetero-Wolff rearrangement of an α-diazosulfoxide and subsequent cyclisation of the sulfine to an oxathiirane was also observed. Furthermore, it was possible to identify which stereoisomer of the α-oxosulfine was present in the matrix. A preliminary laser flash photolysis experiment is also discussed. The experimental details, including all spectral and analytical data, are reported at the end of each chapter. The structural interpretation of 1H NMR spectra of the cycloadducts, described in Chapter 3, is discussed in Appendix I.

Simulation of a collisionless planar electrostatic shock in a proton-electron plasma with a strong initial thermal pressure change

The localized deposition of the energy of a laser pulse, as it ablates a solid target, introduces high thermal pressure gradients in the plasma. The thermal expansion of this laser-heated plasma into the ambient medium (ionized residual gas) triggers the formation of non-linear structures in the collisionless plasma. Here an electron-proton plasma is modelled with a particle-in-cell simulation to reproduce aspects of this plasma expansion. A jump is introduced in the thermal pressure of the plasma, across which the otherwise spatially uniform temperature and density change by a factor of 100. The electrons from the hot plasma expand into the cold one and the charge imbalance drags a beam of cold electrons into the hot plasma. This double layer reduces the electron temperature gradient. The presence of the low-pressure plasma modifies the proton dynamics compared with the plasma expansion into a vacuum. The jump in the thermal pressure develops into a primary shock. The fast protons, which move from the hot into the cold plasma in the form of a beam, give rise to the formation of phase space holes in the electron and proton distributions. The proton phase space holes develop into a secondary shock that thermalizes the beam.

Estimating natural-ventilation potential considering both thermal comfort and IAQ issues

Natural-ventilation potential (NVP) value can provide the designers significant information to properly design and arrange natural ventilation strategy at the preliminary or conceptual stage of ventilation and building design. Based on the previous study by Yang et al. [Investigation potential of natural driving forces for ventilation in four major cities in China. Building and Environment 2005;40:739–46], we developed a revised model to estimate the potential for natural ventilation considering both thermal comfort and IAQ issues for buildings in China. It differs from the previous one by Yang et al. in two predominant aspects: (1) indoor air temperature varies synchronously with the outdoor air temperature rather than staying at a constant value as assumed by Yang et al. This would recover the real characteristic of natural ventilation, (2) thermal comfort evaluation index is integrated into the model and thus the NVP can be more reasonably predicted. By adopting the same input parameters, the NVP values are obtained and compared with the early work of Yang et al. for a single building in four representative cities which are located in different climates, i.e., Urumqi in severe cold regions, Beijing in cold regions, Shanghai in hot summer and cold winter regions and Guangzhou in hot summer and warm winter regions of China. Our outcome shows that Guangzhou has the highest and best yearly natural-ventilation potential, followed by Shanghai, Beijing and Urumqi, which is quite distinct from that of Yang et al. From the analysis, it is clear that our model evaluates the NVP values more consistently with the outdoor climate data and thus reveals the true value of NVP.

Thermo-optics parameters measurements in photorefractive sillenite Bi(12)SiO(20) crystals by thermal lens technique

The present work reports on the thermo-optical properties of photorefractive sillenite Bi(12)SiO(20) (BSO) crystals obtained by applying the Thermal Lens Spectrometry technique (TLS). This crystals presents one high photorefractive sensitivity in the region blue-green spectra, since the measurements were carried out at two pump beam wavelengths (514.5 nm and 750 nm) to study of the light-induced effects in this material (thermal and/or photorefractive). We determine thermo-optical parameters like thermal diffusivity (D), thermal conductivity (K) and temperature coefficient of the optical path length change (ds/dT) in sillenite crystals. These aspects, for what we know, not was studied in details up to now using the lens spectrometry technique and are very important against of the promising potentiality of applications these crystals in non linear optics, real time holography and optical processing data.