High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

Ultra-Low Temperature Partial Oxidation: Detailed Kinetics, Safety, and Environmental Issues

The innovation in several industrial sectors has been recently characterized by the need for reducing the operative temperature either for economic or environmental related aspects. Promising technological solutions require the acquisition of fundamental-based knowledge to produce safe and robust systems. In this sense, reactive systems often represent the bottleneck. For these reasons, this work was focused on the integration of chemical (i.e., detailed kinetic mechanism) and physical (i.e., computational fluid dynamics) models. A theoretical-based kinetic mechanism mimicking the behaviour of oxygenated fuels and their intermediates under oxidative conditions in a wide range of temperature and pressure was developed. Its validity was tested against experimental data collected in this work by using the heat flux burner, as well as measurements retrieved from the current literature. Besides, estimations deriving from existing models considered as the benchmark in the combustion field were compared with the newly generated mechanism. The latter was found to be the most accurate for the investigated conditions and fuels. Most influential species and reactions on the combustion of butyl acetate were identified. The corresponding thermodynamic parameter and rate coefficients were quantified through ab initio calculations. A reduced detailed kinetic mechanism was produced and implemented in an open-source computational fluid dynamics model to characterize pool fires caused by the accidental release of aviation fuel and liquefied natural gas, at first. Eventually, partial oxidation processes involving light alkenes were optimized following the quick, fair, and smoot (QFS) paradigm. The proposed procedure represents a comprehensive and multidisciplinary approach for the construction and validation of accurate models, allowing for the characterization of developing industrial sectors and techniques.

Voltage-composition profile and synchrotron X-ray structural analysis of low and high temperature LixCoO2 host material

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Molecular nitrogen in comet 67P/Churyumov-Gerasimenko indicates a low formation temperature

Molecular nitrogen (N2) is thought to have been the most abundant form of nitrogen in the protosolar nebula. It is the main N-bearing molecule in the atmospheres of Pluto and Triton and probably the main nitrogen reservoir from which the giant planets formed. Yet in comets, often considered the most primitive bodies in the solar system, N2 has not been detected. Here we report the direct in situ measurement of N2 in the Jupiter family comet 67P/Churyumov-Gerasimenko, made by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis mass spectrometer aboard the Rosetta spacecraft. A N2/CO ratio of Embedded Image (2σ standard deviation of the sampled mean) corresponds to depletion by a factor of ~25.4 ± 8.9 as compared to the protosolar value. This depletion suggests that cometary grains formed at low-temperature conditions below ~30 kelvin.

Design of a low power - high temperature heated ceramic sensor to detect halogen gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO 3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li 2SiO3 shows the best results, including a stable current and response to the gas. ^

Design of a Low Power – High Temperature Heated Ceramic Sensor to Detect Halogen Gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li2SiO3 shows the best results, including a stable current and response to the gas.

Modelling of ORC components and systems for low-medium temperature heat recovery applications with reduced environmental impact

Although its great potential as low to medium temperature waste heat recovery (WHR) solution, the ORC technology presents open challenges that still prevent its diffusion in the market, which are different depending on the application and the size at stake. Focusing on the micro range power size and low temperature heat sources, the ORC technology is still not mature due to the lack of appropriate machines and working fluids. Considering instead the medium to large size, the technology is already available but the investment is still risky. The intention of this thesis is to address some of the topical themes in the ORC field, paying special attention in the development of reliable models based on realistic data and accounting for the off-design performance of the ORC system and of each of its components. Concerning the “Micro-generation” application, this work: i) explores the modelling methodology, the performance and the optimal parameters of reciprocating piston expanders; ii) investigates the performance of such expander and of the whole micro-ORC system when using Hydrofluorocarbons as working fluid or their new low GWP alternatives and mixtures; iii) analyzes the innovative ORC reversible architecture (conceived for the energy storage), its optimal regulation strategy and its potential when inserted in typical small industrial frameworks. Regarding the “Industrial WHR” sector, this thesis examines the WHR opportunity of ORCs, with a focus on the natural gas compressor stations application. This work provides information about all the possible parameters that can influence the optimal sizing, the performance and thus the feasibility of installing an ORC system. New WHR configurations are explored: i) a first one, relying on the replacement of a compressor prime mover with an ORC; ii) a second one, which consists in the use of a supercritical CO2 cycle as heat recovery system.

High performance concrete applied to storage system buildings at low temperatures

According to some estimates, world's population growth is expected about 50% over the next 50 years. Thus, one of the greatest challenges faced by Engineering is to find effective options to food storage and conservation. Some researchers have investigated how to design durable buildings for storing and conserving food. Nowadays, developing concrete with mechanical resistance for room temperatures is a parameter that can be achieved easily. On the other hand, associating it to low temperature of approximately 35 °C negative requires less empiricism, being necessary a suitable dosage method and a careful selection of the material constituents. This ongoing study involves these parameters. The presented concrete was analyzed through non-destructive tests that examines the material properties periodically and verifies its physical integrity. Concrete with and without incorporated air were studied. The results demonstrated that both are resistant to freezing.

Influence of temperature and excitation procedure on the athermal behavior of Nd(3+)-doped phosphate glass: Thermal lens, interferometric, and calorimetric measurements

In this work, thermal and optical properties of the commercial Q-98 neodymium-doped phosphate glass have been measured at low temperature, from 50 to 300 K. The time-resolved thermal lens spectrometry together with the optical interferometry and the thermal relaxation calorimetry methods were used to investigate the glass athermal characteristics described by the temperature coefficient of the optical path length change, ds/dT. The thermal diffusivity was also determined, and the temperature coefficients of electronic polarizability, linear thermal expansion, and refractive index were calculated and used to explain ds/dT behavior. ds/dT measured via thermal lens method was found to be zero at 225 K. The results provided a complete characterization of the thermo-optical properties of the Q-98 glass, which may be useful for those using this material for diode-pumped solid-state lasers. (C) 2009 American Institute of Physics. [doi: 10.1063/1.3234396]

Conformational dynamics of thyroid hormones by variable temperature nuclear magnetic resonance: The role of side chain rotations and cisoid/transoid interconversions

H-1 NMR spectra of the thyroid hormone thyroxine recorded at low temperature and high field show splitting into two peaks of the resonance due to the H2,6 protons of the inner (tyrosyl) ring. A single resonance is observed in 600 MHz spectra at temperatures above 185 K. An analysis of the line shape as a function of temperature shows that the coalescence phenomenon is due to an exchange process with a barrier of 37 kJ mol(-1). This is identical to the barrier for coalescence of the H2',6' protons of the outer (phenolic) ring reported previously for the thyroid hormones and their analogues. It is proposed that the separate peaks at low temperature are due to resonances for H2,6 in cisoid and transoid conformers which are populated in approximately equal populations. These two peaks are averaged resonances for the individual H2 and H6 protons. Conversion of cisoid to transoid forms can occur via rotation of either the alanyl side chain or the outer ring, from one face of the inner ring to the other. It is proposed that the latter process is the one responsible for the observed coalescence phenomenon. The barrier to rotation of the alanyl side chain is greater than or equal to 37 kJ mol(-1), which is significantly larger than has previously been reported for Csp(2)-Csp(3) bonds in other Ph-CH2-X systems. The recent crystal structure of a hormone agonist bound to the ligand-binding domain of the rat thyroid hormone receptor (Wagner et al. Nature 1995, 378, 690-697) shows the transoid form to be the bound conformation. The significant energy barrier to cisoid/transoid interconversion determined in the current study combined with the tight fit of the hormone to its receptor suggests that interconversion between the forms cannot occur at the receptor site but that selection for the preferred bound form occurs from the 50% population of the transoid form in solution.

Time evolution in the unimolecular master equation at low temperatures: full spectral solution with scalable iterative methods and high precision

A new method is presented to determine an accurate eigendecomposition of difficult low temperature unimolecular master equation problems. Based on a generalisation of the Nesbet method, the new method is capable of achieving complete spectral resolution of the master equation matrix with relative accuracy in the eigenvectors. The method is applied to a test case of the decomposition of ethane at 300 K from a microcanonical initial population with energy transfer modelled by both Ergodic Collision Theory and the exponential-down model. The fact that quadruple precision (16-byte) arithmetic is required irrespective of the eigensolution method used is demonstrated. (C) 2001 Elsevier Science B.V. All rights reserved.

Interaction of temperature and vegetative flush maturity influences shoot structure and development of lychee (Litchi chinensis Sonn.)

Potted lychee trees (cv. Tai so) of varying vegetative flush maturity were grown under a range of temperature regimes and monitored for subsequent shoot structure and development. A combination of low temperature (15/17 or 18/13 degreesC day/night) and high vegetative flush maturity was necessary for floral initiation to occur, Exposure to high temperatures (28/23 degreesC) invariably resulted in the production of vegetative shoots, irrespective of flush maturity. Strong floral initiation was marked by the emergence of terminal particles and accompanying axillary particles. A decrea,;e in vegetative flush maturity or increase in temperature (e.g. 23/18 degreesC) resulted in a decrease in axillary shoot formation and the production of several intermediate shoot structures. These included leafy particles, stunted particles, partially emerged buds and non-emergent swollen buds, often produced on the same tree. At 23/18 degreesC, closer synchronisation of initial flush maturity was required for the production of a consistent shoot-type. Trees with synchronised mature flushes (I-2) at 23/18 degreesC resulted in the production of swollen terminal buds. Healthy trees were maintained in this state for at least 11 months. These results indicate that both temperature and flush maturity can influence subsequent shoot structure of lychee. In the absence of either a strong floral temperature (18/13 degreesC) or strong vegetative temperature (28/23 degreesC), slight differences in initial flush maturity have gteater impact on the type of emerging shoot formed. (C) 2002 Elsevier Science B.V. All rights reserved.

Temperature dependence of the electrical conductivity of vapor grown carbon nanofiber/epoxy composites with different filler dispersion levels

The influence of the dispersion of vapor grown carbon nanofibers (VGCNF) on the electrical properties of VGCNF/epoxy composites has been studied. A homogeneous dispersion of the VGCNF does not imply better electrical properties. The presence of well distributed clusters appears to be a key factor for increasing composite conductivity. It is also shown that the main conduction mechanism has an ionic nature for concentrations below the percolation threshold, while above the percolation threshold it is dominated by hopping between the fillers. Finally, using the granular system theory it is possible to explain the origin of conduction at low temperatures.

Temperature-induced structural transitions in self-assembling magnetic nanocolloids

With the help of a unique combination of density functional theory and computer simulations, we discover two possible scenarios, depending on concentration, for the hierarchical self-assembly of magnetic nanoparticles on cooling. We show that typically considered low temperature clusters, i.e. defect-free chains and rings, merge into more complex branched structures through only three types of defects: four-way X junctions, three-way Y junctions and two-way Z junctions. Our accurate calculations reveal the predominance of weakly magnetically responsive rings cross-linked by X defects at the lowest temperatures. We thus provide a strategy to fine-tune magnetic and thermodynamic responses of magnetic nanocolloids to be used in medical and microfluidics applications.

Effect of temperature on different stages of Romanomermis iyengari, a mermithid nematode parasite of mosquitoes

The effect of temperature (20 degrees-35 degrees C) on different stages of Romanomermis iyengari was studied. In embryonic development, the single-cell stage eggs developed into mature eggs in 4.5-6.5 days at 25-35 degrees C but, required 9.5 days at 20 degrees C. Complete hatching occurred in 7 and 9 days after egg-laying at 35 and 30 degrees C, respectively. At 25 and 20 degrees C, 85-96 of the eggs did not hatch even by 30th day. Loss of infectivity and death of the preparasites occurred faster at higher temperatures. The 50 survival durations of preparasites at 20 and 35 degrees C were 105.8 and 10.6 hr respectively. They retained 50 infectivity up to 69.7 and 30.3 hr. The duration of the parasitic phase increased as temperature decreased. Low temperature favoured production of a higher proportion of females which were also larger in size. The maximum time taken for the juveniles to become adults was 14 days at 20 degrees C and the minimum was 9 days at 35 degrees C. Oviposition began earlier at higher temperature than at lower temperature. However, its fecundic period was shorter at 20 degrees C than at 35 degrees C indicating enhanced rate of oviposition at 20 degrees C. Fecundity was adversely affected at 20 degrees C and 35 degrees C. It is shown that the temperature range of 25 degrees-30 degrees C favours optimum development of R. iyengari.