Thermal stability analysis of organo-silicates, using solid phase microextraction techniques

An analysis of thermal degradation products evolved during the melt processing of organo-layered silicates (OLS) was carried out via the use of a solid phase microextraction (SPME) technique. Two commerical OLSs and one produced in-house were prepared for comparision. The solid phase microextraction technique proved to be a very effective technique for investigating the degradation of the OLS at a specific processing temperature. The results showed that most available OLSs will degrade under typical conditions required for the melt processing of many polymers, including thermoplastic polyurethanes. It is suggested that these degradation products may lead to changes in the structure and properties of the final polymer, particularly in thermoplastic polyurethanes, which seem significantly succeptable to the presence of these products. It is also suggested that many commercially available OLSs are produced in such a way that results in an excess of unbound organic modifier, giving rise to a greater quantity of degradation products. All OLSs where compared and characterised by TGA and GC-MS. (c) 2004 Elsevier B.V. All rights reserved.

Characteristics of low temperature PECVD silicon nitride for MEMS structural materials

Materials and mechanical characteristics of the low temperature PECVD silicon nitrides have been investigated using various analytical and testing techniques. TEM and SEM examinations reveal that there is no distinct microstructural difference existing between the films deposited under different conditions. However, their mechanical properties determined by nanoindentation indicate otherwise. The variations in mechanical properties with deposition conditions are found to be strongly correlated to the change in silicon-to-nitrogen ratio in the film.

The effects of temperature and salinity on Acacia harpophylla (brigalow) (Mimosaceae) germination

Acacia harpophylla F. Muell. (brigalow) used to naturally occur over a range of about 50 000 km(2) in Queensland and New South Wales, Australia. Large scale clearing for agriculture has reduced the area to less than 20 000 km(2) and it is estimated that 20-25% of vertebrate fauna living in brigalow communities will become locally extinct as a result of the current clearing induced loss of habitat. Some coal mining companies in central Queensland have become interested in providing habitat for the endangered bridle nail-tailed wallaby that lives in brigalow vegetation. However, there is little known about establishment techniques for brigalow on mine sites and other disturbed ground; an understanding of brigalow biology and ecology is required to assist in the conservation of this threatened vegetation community and for re-creation of bridled nail-tail wallaby habitat in the post mining landscape. Brigalow is an unusual species of Acacia because it is not hard-seeded and germinates readily without the need to break seed-coat imposed dormancy. Germination trials were undertaken to test the ability of brigalow seed to germinate with a range of temperatures and salinity levels similar to those experienced in coal mine spoil. Optimum germination was found to occur at temperatures from 15 to 38 degrees C and no germination was recorded at 45 degrees C. Brigalow was very tolerant of high salt levels and germinated at percentages greater than 50% up to the highest salinity tested, 30 dS/m. Germination of greater than 90% occurred up to an electrical conductivity of 20 dS/m. The results indicate brigalow seed can be sown in summer when rains are most likely to occur, however, shading of the seed with extra soil or mulch may ensure the ground surface does not become too hot for germination. Because of its ability to germinate at high salinity levels, brigalow may be suitable for use in saline mine wastes which are common on sites to be rehabilitated after mining.

Short-term electricity price forecasting using wavelet and SVM techniques

In deregulated electricity market, modeling and forecasting the spot price present a number of challenges. By applying wavelet and support vector machine techniques, a new time series model for short term electricity price forecasting has been developed in this paper. The model employs both historical price and other important information, such as load capacity and weather (temperature), to forecast the price of one or more time steps ahead. The developed model has been evaluated with the actual data from Australian National Electricity Market. The simulation results demonstrated that the forecast model is capable of forecasting the electricity price with a reasonable forecasting accuracy.

Exploitation of fibre characteristics in temperature sensing and radio-over-fibre applications

The development of sensing devices is one of the instrumentation fields that has grown rapidly in the last decade. Corresponding to the swift advance in the development of microelectronic sensors, optical fibre sensors are widely investigated because of their advantageous properties over the electronics sensors such as their wavelength multiplexing capability and high sensitivity to temperature, pressure, strain, vibration and acoustic emission. Moreover, optical fibre sensors are more attractive than the electronics sensors as they can perform distributed sensing, in terms of covering a reasonably large area using a single piece of fibre. Apart from being a responsive element in the sensing field, optical fibre possesses good assets in generating, distributing, processing and transmitting signals in the future broadband information network. These assets include wide bandwidth, high capacity and low loss that grant mobility and flexibility for wireless access systems. Among these core technologies, the fibre optic signal processing and transmission of optical and radio frequency signals have been the subjects of study in this thesis. Based on the intrinsic properties of single-mode optical fibre, this thesis aims to exploit the fibre characteristics such as thermal sensitivity, birefringence, dispersion and nonlinearity, in the applications of temperature sensing and radio-over-fibre systems. By exploiting the fibre thermal sensitivity, a fully distributed temperature sensing system consisting of an apodised chirped fibre Bragg grating has been implemented. The proposed system has proven to be efficient in characterising grating and providing the information of temperature variation, location and width of the heat source applied in the area under test.To exploit the fibre birefringence, a fibre delay line filter using a single high-birefringence optical fibre structure has been presented. The proposed filter can be reconfigured and programmed by adjusting the input azimuth of launched light, as well as the strength and direction of the applied coupling, to meet the requirements of signal processing for different purposes in microwave photonic and optical filtering applications. To exploit the fibre dispersion and nonlinearity, experimental investigations have been carried out to study their joint effect in high power double-sideband and single-sideband modulated links with the presence of fibre loss. The experimental results have been theoretically verified based on the in-house implementation of the split-step Fourier method applied to the generalised nonlinear Schrödinger equation. Further simulation study on the inter-modulation distortion in two-tone signal transmission has also been presented so as to show the effect of nonlinearity of one channel on the other. In addition to the experimental work, numerical simulations have also been carried out in all the proposed systems, to ensure that all the aspects concerned are comprehensively investigated.

The temperature dependence of the electro-optic kerr effect in solutions

A novel Kerr cell of greater optical path length and temperature stability has been designed and built. The Kerr effect experimental has been substantially automated using an Apple IIe computer. Software has been written allowing the computer to partially control the Kerr effect equipment and to acquire and analyse the relevant data.The temperature dependent electro-optic Kerr effect of 2-methyl-4-nitroaniline, p-nitroaniline, nitrobenzene, aniline, and toluene as solutions in 1, 4-dioxane has been studied. The Kerr effect measurements combined with dipole moment, depolarisation ratio, dielectric, and electronic polarisation measurements have been used to calculate the first hyperpolarisability of the solute.Although first hyperpolarisabilities for the compounds studied have been measured in various physical states using a variety of experimental techniques, it is gratifying to find that the values presented in this thesis have a linear relationship with values reported by other workers.

Study of neutral Fe(III) complexes of pyridoxal-N-substituted thiosemicarbazone with desolvation induced spin-state transformation above room temperature

The preparation and characterization of two new neutral ferric complexes with desolvation-induced discontinuous spin-state transformation above room temperature are reported. The compounds, Fe(Hthpy)(thpy).CH3OH.3H2O (1) and Fe(Hmthpy)(mthpy).2H2O (2), are low-spin (LS) at room temperature and below, whereas their nonsolvated forms are high-spin (HS), exhibiting zero-field splitting. In these complexes, Hthpy, Hmthpy, and thpy, mthpy are the deprotonated forms of pyridoxal thiosemicarbazone and pyridoxal methylthiosemicarbazone, respectively; each is an O,N,S-tridentate ligand. The molecular structures have been determined at 100(1) K using single-crystal X-ray diffraction techniques and resulted in a triclinic system (space group P1) and monoclinic unit cell (space group P21/c) for 1 and 2, respectively. Structures were refined to the final error indices, where RF = 0.0560 for 1 and RF = 0.0522 for 2. The chemical inequivalence of the ligands was clearly established, for the "extra" hydrogen atom on the monodeprotonated ligands (Hthpy, Hmthpy) was found to be bound to the nitrogen of the pyridine ring. The ligands are all of the thiol form; the doubly deprotonated chelates (thpy, mthpy) have C-S bond lengths slightly longer than those of the singly deprotonated forms. There is a three-dimensional network of hydrogen bonds in both compounds. The discontinuous spin-state transformation is accompanied with liberation of solvate molecules. This is evidenced also from DSC analysis. Heat capacity data for the LS and HS phases are tabulated at selected temperatures, the values of the enthalpy and entropy changes connected with the change of spin state were reckoned at DeltaH = 12.5 0.3 kJ mol-1 and DeltaS = 33.3 0.8 J mol-1 K-1, respectively, for 1 and DeltaH = 6.5 0.3 kJ mol-1 and DeltaS = 17.6 0.8 J mol-1 K-1, respectively, for 2

Novel pH‐and temperature‐responsive methacrylamide microgels

A novel transition temperature in MeAM copolymer microgels is reported. Despite the fact that MeAM homopolymers do not show thermosensitive properties, a specific synthetic strategy leads to a thermo-responsive swelling behavior that could be potentially useful in medical and/or industrial applications. The pH and temperature-dependent swelling response of microgels of MeAM copolymerized with 2-aminomethylpyridine and ethylenediamine is reported. The changes in particle sizes, which depend on the nature of the surrounding environment, are recorded by QELS. The relation between copolymer structure and its novel behavior is analyzed by several techniques (1H NMR, TGA).

Ocular surface temperature:a review

Purpose. To review the evolution in ocular temperature measurement during the last century and examine the advantages and applications of the latest noncontact techniques. The characteristics and source of ocular surface temperature are also discussed. Methods. The literature was reviewed with regard to progress in human thermometry techniques, the parallel development in ocular temperature measurement, the current use of infrared imaging, and the applications of ocular thermography. Results. It is widely acknowledged that the ability to measure ocular temperature accurately will increase the understanding of ocular physiology. There is a characteristic thermal profile across the anterior eye, in which the central area appears coolest. Ocular surface temperature is affected by many factors, including inflammation. In thermometry of the human eye, contact techniques have largely been superseded by infrared imaging, providing a noninvasive and potentially more accurate method of temperature measurement. Ocular thermography requires high resolution and frame rate: features found in the latest generation of cameras. Applications have included dry eye, contact lens wear, corneal sensitivity, and refractive surgery. Conclusions. Interest in the temperature of the eye spans almost 130 years. It has been an area of research largely driven by prevailing technology. Current instrumentation offers the potential to measure ocular surface temperature with more accuracy, resolution, and speed than previously possible. The use of dynamic ocular thermography offers great opportunities for monitoring the temperature of the anterior eye. © 2005 Contact Lens Association of Ophthalmologists, Inc.

Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

Continuous property measurement techniques and physics based mathematical model for frost growth control

The development of a new set of frost property measurement techniques to be used in the control of frost growth and defrosting processes in refrigeration systems was investigated. Holographic interferometry and infrared thermometry were used to measure the temperature of the frost-air interface, while a beam element load sensor was used to obtain the weight of a deposited frost layer. The proposed measurement techniques were tested for the cases of natural and forced convection, and the characteristic charts were obtained for a set of operational conditions. ^ An improvement of existing frost growth mathematical models was also investigated. The early stage of frost nucleation was commonly not considered in these models and instead an initial value of layer thickness and porosity was regularly assumed. A nucleation model to obtain the droplet diameter and surface porosity at the end of the early frosting period was developed. The drop-wise early condensation in a cold flat plate under natural convection to a hot (room temperature) and humid air was modeled. A nucleation rate was found, and the relation of heat to mass transfer (Lewis number) was obtained. It was found that the Lewis number was much smaller than unity, which is the standard value usually assumed for most frosting numerical models. The nucleation model was validated against available experimental data for the early nucleation and full growth stages of the frosting process. ^ The combination of frost top temperature and weight variation signals can now be used to control the defrosting timing and the developed early nucleation model can now be used to simulate the entire process of frost growth in any surface material. ^

Computational modeling of intermediate temperature proton exchange membrane (PEM) fuel cells

A two-phase three-dimensional computational model of an intermediate temperature (120--190°C) proton exchange membrane (PEM) fuel cell is presented. This represents the first attempt to model PEM fuel cells employing intermediate temperature membranes, in this case, phosphoric acid doped polybenzimidazole (PBI). To date, mathematical modeling of PEM fuel cells has been restricted to low temperature operation, especially to those employing Nafion ® membranes; while research on PBI as an intermediate temperature membrane has been solely at the experimental level. This work is an advancement in the state of the art of both these fields of research. With a growing trend toward higher temperature operation of PEM fuel cells, mathematical modeling of such systems is necessary to help hasten the development of the technology and highlight areas where research should be focused.^ This mathematical model accounted for all the major transport and polarization processes occurring inside the fuel cell, including the two phase phenomenon of gas dissolution in the polymer electrolyte. Results were presented for polarization performance, flux distributions, concentration variations in both the gaseous and aqueous phases, and temperature variations for various heat management strategies. The model predictions matched well with published experimental data, and were self-consistent.^ The major finding of this research was that, due to the transport limitations imposed by the use of phosphoric acid as a doping agent, namely low solubility and diffusivity of dissolved gases and anion adsorption onto catalyst sites, the catalyst utilization is very low (∼1--2%). Significant cost savings were predicted with the use of advanced catalyst deposition techniques that would greatly reduce the eventual thickness of the catalyst layer, and subsequently improve catalyst utilization. The model also predicted that an increase in power output in the order of 50% is expected if alternative doping agents to phosphoric acid can be found, which afford better transport properties of dissolved gases, reduced anion adsorption onto catalyst sites, and which maintain stability and conductive properties at elevated temperatures.^

Quantifying the effects of temperature and concentration on variable-density flow in numerical modeling of groundwater systems: Implications for predictive uncertainty and data collection

Groundwater systems of different densities are often mathematically modeled to understand and predict environmental behavior such as seawater intrusion or submarine groundwater discharge. Additional data collection may be justified if it will cost-effectively aid in reducing the uncertainty of a model's prediction. The collection of salinity, as well as, temperature data could aid in reducing predictive uncertainty in a variable-density model. However, before numerical models can be created, rigorous testing of the modeling code needs to be completed. This research documents the benchmark testing of a new modeling code, SEAWAT Version 4. The benchmark problems include various combinations of density-dependent flow resulting from variations in concentration and temperature. The verified code, SEAWAT, was then applied to two different hydrological analyses to explore the capacity of a variable-density model to guide data collection. ^ The first analysis tested a linear method to guide data collection by quantifying the contribution of different data types and locations toward reducing predictive uncertainty in a nonlinear variable-density flow and transport model. The relative contributions of temperature and concentration measurements, at different locations within a simulated carbonate platform, for predicting movement of the saltwater interface were assessed. Results from the method showed that concentration data had greater worth than temperature data in reducing predictive uncertainty in this case. Results also indicated that a linear method could be used to quantify data worth in a nonlinear model. ^ The second hydrological analysis utilized a model to identify the transient response of the salinity, temperature, age, and amount of submarine groundwater discharge to changes in tidal ocean stage, seasonal temperature variations, and different types of geology. The model was compared to multiple kinds of data to (1) calibrate and verify the model, and (2) explore the potential for the model to be used to guide the collection of data using techniques such as electromagnetic resistivity, thermal imagery, and seepage meters. Results indicated that the model can be used to give insight to submarine groundwater discharge and be used to guide data collection. ^

Leakage temperature dependency aware real-time scheduling for power and thermal optimization

Catering to society's demand for high performance computing, billions of transistors are now integrated on IC chips to deliver unprecedented performances. With increasing transistor density, the power consumption/density is growing exponentially. The increasing power consumption directly translates to the high chip temperature, which not only raises the packaging/cooling costs, but also degrades the performance/reliability and life span of the computing systems. Moreover, high chip temperature also greatly increases the leakage power consumption, which is becoming more and more significant with the continuous scaling of the transistor size. As the semiconductor industry continues to evolve, power and thermal challenges have become the most critical challenges in the design of new generations of computing systems. ^ In this dissertation, we addressed the power/thermal issues from the system-level perspective. Specifically, we sought to employ real-time scheduling methods to optimize the power/thermal efficiency of the real-time computing systems, with leakage/ temperature dependency taken into consideration. In our research, we first explored the fundamental principles on how to employ dynamic voltage scaling (DVS) techniques to reduce the peak operating temperature when running a real-time application on a single core platform. We further proposed a novel real-time scheduling method, “M-Oscillations” to reduce the peak temperature when scheduling a hard real-time periodic task set. We also developed three checking methods to guarantee the feasibility of a periodic real-time schedule under peak temperature constraint. We further extended our research from single core platform to multi-core platform. We investigated the energy estimation problem on the multi-core platforms and developed a light weight and accurate method to calculate the energy consumption for a given voltage schedule on a multi-core platform. Finally, we concluded the dissertation with elaborated discussions of future extensions of our research. ^

Noise in gallium nitride-based quantum well structures used for nanometer devices in the frequency range 1 Hz--3 Mhz and temperature range 77K--324K

Electronic noise has been investigated in AlxGa1−x N/GaN Modulation-Doped Field Effect Transistors (MODFETs) of submicron dimensions, grown for us by MBE (Molecular Beam Epitaxy) techniques at Virginia Commonwealth University by Dr. H. Morkoç and coworkers. Some 20 devices were grown on a GaN substrate, four of which have leads bonded to source (S), drain (D), and gate (G) pads, respectively. Conduction takes place in the quasi-2D layer of the junction (xy plane) which is perpendicular to the quantum well (z-direction) of average triangular width ∼3 nm. A non-doped intrinsic buffer layer of ∼5 nm separates the Si-doped donors in the AlxGa1−xN layer from the 2D-transistor plane, which affords a very high electron mobility, thus enabling high-speed devices. Since all contacts (S, D, and G) must reach through the AlxGa1−xN layer to connect internally to the 2D plane, parallel conduction through this layer is a feature of all modulation-doped devices. While the shunting effect may account for no more than a few percent of the current IDS, it is responsible for most excess noise, over and above thermal noise of the device. ^ The excess noise has been analyzed as a sum of Lorentzian spectra and 1/f noise. The Lorentzian noise has been ascribed to trapping of the carriers in the AlxGa1−xN layer. A detailed, multitrapping generation-recombination noise theory is presented, which shows that an exponential relationship exists for the time constants obtained from the spectral components as a function of 1/kT. The trap depths have been obtained from Arrhenius plots of log (τT2) vs. 1000/T. Comparison with previous noise results for GaAs devices shows that: (a) many more trapping levels are present in these nitride-based devices; (b) the traps are deeper (farther below the conduction band) than for GaAs. Furthermore, the magnitude of the noise is strongly dependent on the level of depletion of the AlxGa1−xN donor layer, which can be altered by a negative or positive gate bias VGS. ^ Altogether, these frontier nitride-based devices are promising for bluish light optoelectronic devices and lasers; however, the noise, though well understood, indicates that the purity of the constituent layers should be greatly improved for future technological applications. ^