Clean coal technologies are now becoming popular because of their high efficiencies and minimal environmental impact. Higher operating pressures have been applied to clean coal technologies. The effect of pressure on coal pyrolysis and char combustion has been extensively studied but still remains to be further explored. The objective of this project was to characterize high pressure, high heating rate coal pyrolysis and char combustion, with emphasis on improving coal/char high pressure combustion models. A flat-flame burner was used in a high pressure laminar flow facility to conduct high temperature, high heating rate pyrolysis and combustion experiments for four coals. The high-heating-rate (10000 K/s), high-temperature atmosphere can better simulate industrial conditions than the conventional drop tube facility. Pressure and heating rate have a significant impact on the total volatiles, char physical structure including morphology, and char internal surface areas. The high heating rate decreases the swelling ratios of chars at pressures from 2.5 to 15 atm. TGA char oxidation reactivities were measured at the same total pressure as the char preparation pressure. The general trend was that the TGA reactivity on a gram per gram available basis decreased with increasing char formation pressure. When the reactivity was normalized by either the N2 or CO2 surface area, the normalized reactivity was found to be relatively constant with increasing pressure. Char burnout was measured at different pressures and O2 concentrations at high temperature in the pressurized flat flame burner facility. For a given pressure, the particle diameter ratio based on coal (d/dcoal,0) decreased with increasing O2 concentration. Two char kinetic models (CBK 8 and CBK/E) were used to fit the char burnout data, and the modeling results showed that the intrinsic char oxidation rate increased with increasing total pressure at constant oxygen partial pressure.

"The quench sensitivity of AA7136 has been experimentally investigated using Jominy end quench and test coupons of various heat treatments. It was found that this alloy is not quench sensitive. In addition, the effects of heating rate on both solution and aging treatments on AA7136 and AA7075 were determined using a newly developed reverse Jominy heating test. It was observed that hardness was reduced after rapid heating during aging and hardness increased slightly after rapid heating during solutionizing. These results are discussed in terms of microstructural developments. "

The effects of elevated pressure and high heating rates on coal pyrolysis and gasification were investigated. A high-pressure flat-flame burner (HPFFB) was designed and built to conduct these studies. The HPFFB was designed to provide an environment with laminar, dispersed entrained flow, with particle heating rates of ~10^5 K/s, pressures of up to 15 atm, and gas temperatures of up to 2000 K. Residence times were varied from 30 to 700 ms in this study. Pyrolysis experiments were conducted at particle heating rates of ~10^5 K/s and maximum gas temperatures of ~1700 K at pressures of 1 to 15 atm. A new coal swelling correlation was developed that predicts the effects of heating rate, pressure, and coal rank on the swelling ratio at heating rates above ~10^4 K/s. A coal swelling rank index system based on 13C-NMR chemical structural parameters was devised. The empirical swelling model requires user inputs of the coal ultimate and proximate analyses and the use of a transient particle energy balance to predict the maximum particle heating rate. The swelling model was used to explain differences in previously reported bituminous coal swelling ratios that were measured in facilities with different heating rates. Char gasification studies by CO2 were conducted on a subbituminous coal and 4 bituminous coals in the HPFFB. Pressures of 5, 10, and 15 atmospheres were used with gas compositions of 20, 40, and 90 mole % CO2. Gas conditions with peak temperatures of 1700 K to 2000 K were used, which resulted in char particle temperatures of 1000 K to 1800 K. Three gasification models were developed to fit and analyze the gasification data. A simple 1st-order model was used to show that the measured gasification rates were far below the film-diffusion limit. The other two models, designated CCK and CCKN, were based on three versions of the CBK models. CCKN used an nth-order kinetic mechanism and CCK used a semi-global Langmuir-Hinshelwood kinetic mechanism. The two CCK models fit the HPFFB gasification data better than the 1st-order model. The fits of the gasification data with CCK and CCKN were comparable to each other. The fit of the data in CCK suggests that Knudsen diffusion may have influenced the gasification rates in the HPFFB experiments. The gasification rate parameters in each of the three models were correlated with coal rank. 13C-NMR parameters were used to estimate a structural parameter of the coal char. Char-CO2 gasification rate coefficients correlated better with this NMR-based char structure index than it did with the carbon and oxygen content of the parent coal.

Made available in DSpace on 2014-12-17T14:07:22Z (GMT). No. of bitstreams: 1 RicardoPSD.pdf: 1922919 bytes, checksum: 54dfc0d5fe53e83de5babd021bd83da6 (MD5) Previous issue date: 2007-03-01 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Heating rate is one of the main variables that determine a fire cycle. In industrial processes that use high temperatures, greater fire great can reduce the cost of production and increase productivity. The use of faster and more efficient fire cycles has been little investigated by the structural ceramic industry in Brazil. However, one of the possibilities that aims at modernizing the sector is the use of roller kilns and the inclusion of natural gas as fuel. Thus, the purpose of this study is to investigate the effect of heating rate on the technological properties of structural ceramic products. Clay raw materials from the main ceramic industries in the state of Rio Grande do Norte were characterized. Some of the raw materials characterized were formulated to obtain the best physical and mechanical properties. Next, raw materials and formulations were selected to study the influence of heating rate on the final properties of the ceramic materials. The samples were shaped by pressing and extrusion and submitted to rates of 1 ?C/min, 10 ?C/min and 20 ?C/min, with final temperatures of 850 ?C, 950 ?C and 1050 ?C. Discontinuous cycles with rates of 10 ?C/min or 15 ?C/min up to 600 ?C and a rate of 20 ?C/min up to final temperature were also investigated. Technological properties were determined for all the samples and microstructural analysis was carried out under a number of fire conditions. Results indicate that faster and more efficient fire cycles than those currently in practice could be used, limiting only some clay doughs to certain fire conditions. The best results were obtained for the samples submitted to slow cycles up to 600 ?C and fast fire sinterization up to 950 ?C. This paper presents for the first time the use of a fast fire rate for raw materials and clay formulations and seeks to determine ideal dough and processing conditions for using shorter fire times, thus enabling the use of roller kilns and natural gas in structural ceramic industries / A taxa de aquecimento ? uma das principais vari?veis que determinam um ciclo de queima. Em processos industriais que utilizam elevadas temperaturas, uma maior velocidade de queima pode proporcionar uma diminui??o do custo de produ??o e aumento da produtividade. A ind?stria de cer?mica estrutural pouco tem investigado sobre a utiliza??o de ciclos de queima mais r?pidos e eficientes. Entretanto, uma das possibilidades que visam ? moderniza??o do setor ? a utiliza??o de fornos a rolos e a inclus?o do g?s natural como combust?vel. Neste contexto, o objetivo deste trabalho ? investigar o efeito da velocidade de aquecimento nas propriedades tecnol?gicas de produtos para cer?mica estrutural. Foram caracterizadas mat?riasprimas argilosas dos principais p?los cer?micos de Rio Grande do Norte. Algumas das mat?riasprimas caracterizadas foram formuladas visando obter as melhores propriedades f?sicas e mec?nicas. Em seguida, foram selecionadas mat?riasprimas e formula??es para o estudo da influ?ncia na taxa de aquecimento nas propriedades finais dos materiais cer?micos. As amostras foram conformadas por prensagem e extrus?o e submetidas ?s taxas de 1 ?C/min, 10 ?C/min e 20 ?C/min, com temperaturas finais de 850 ?C, 950 ?C e 1050 ?C. Tamb?m foram investigados os ciclos descont?nuos com taxas de 10 ?C/min ou 15 ?C/min at? 600 ?C e taxa de 20 ?C/min at? a temperatura final. Foram determinadas propriedades tecnol?gicas para todas as amostras e realizada a an?lise microestrutural em algumas condi??es de queima. Resultados indicam que ? poss?vel utilizar ciclos de queima mais r?pidos e eficientes que os atuais, limitando apenas algumas massas argilosas para certas condi??es de queima. Os melhores resultados foram obtidos para as amostras submetidas aos ciclos lentos at? 600 ?C e sinteriza??o com queima r?pida at? 950 ?C. Este trabalho apresenta como contribui??o original a utiliza??o de uma taxa de queima r?pida para mat?riasprimas e formula??es argilosas, procurando determinar as condi??es ideais de massas e de processamento para o uso de um menor tempo de queima, possibilitando assim, a utiliza??o de fornos a rolos e do g?s natural pelas ind?strias de cer?mica estrutural

Hyperthermia is usually used at a sub-lethal level in cancer treatment to potentiate the effects of chemotherapy. The purpose of this study is to investigate the role of heating rate in achieving synergistic cell killing by chemotherapy and hyperthermia. For this purpose, in vitro cell culture experiments with a uterine cancer cell line (MES-SA) and its multidrug resistant (MDR) variant MES-SA/Dx5 were conducted. The cytotoxicitiy, mode of cell death, induction of thermal tolerance and P-gp mediated MDR following the two different modes of heating were studied. Doxorubicin (DOX) was used as the chemotherapy drug. Indocyanine green (ICG), which absorbs near infrared light at 808nm (ideal for tissue penetration), was chosen for achieving rapid rate hyperthermia. A slow rate hyperthermia was provided by a cell culture incubator. The results show that the potentiating effect of hyperthermia to chemotherapy can be maximized by increasing the rate of heating as evident by the results from the cytotoxicity assay. When delivered at the same thermal dose, a rapid increase in temperature from 37 °C to 43 °C caused more cell membrane damage than gradually heating the cells from 37 °C to 43 °C and thus allowed for more intracellular accumulation of the chemotherapeutic agents. Different modes of cell death are observed by the two hyperthermia delivery methods. The rapid rate laser-ICG hyperthermia @ 43 °C caused cell necrosis whereas the slow rate incubator hyperthermia @ 43 °C induced very mild apoptosis. At 43 °C a positive correlation between thermal tolerance and the length of hyperthermia exposure is identified. This study shows that by increasing the rate of heating, less thermal dose is needed in order to overcome P-gp mediated MDR.

Gasification of black liquor is an alternative to the combustion of black liquor, which is currently the dominant form of chemical recovery in the paper industry. Gasification of black liquor offers the possibility of higher thermal efficiencies than combustion, reducing manufacturing costs and creating new revenue streams through a forest biorefinery. Pressurizing the gasification reactor further enhances the efficiency advantage of gasification over combustion. This study uses a pressurized entrained flow reactor (PEFR) to study black liquor gasification behavior under pressures, temperatures, and heating rates similar to those of next-generation high-temperature black liquor gasifiers. The effects of pressure on black liquor char morphology, gasification rates, pyrolysis carbon yields, and sulfur phase distribution were studied. These characteristics were investigated in three main groups of experiments at 900oC: pyrolysis (100% N2), gasification with constant partial pressure (0.25 bar H2O and 0.50 bar CO2), and gasification with constant mole fraction (10% CO2, 2% H2O, 1.7% CO, 0.3% H2), under five, ten, and fifteen bar total pressure. It was found that pressure had an impact on the char physical characteristics immediately after the char entered the reactor. Increasing pressure had the effect of decreasing the porosity of the chars. Pressure also affected particle destruction and reagglomeration mechanisms. Surface areas of gasification chars decreased with increasing pressures, but only at low carbon conversions. The rate of carbon conversion in gasification was shown to be a function of the gas composition near the particle, with higher levels of inhibiting gases slowing carbon conversion. The same phenomenon of product gas inhibition observed in gasification was used to explain carbon conversions in pyrolysis reactions. Sulfur distribution between condensed and gas phases was unaffected by increasing total pressure in the residence times investigated. Significant amounts of sulfur are lost during initial devolatilization. With water present this gas phase sulfur forms H2S and did not return to the condensed phase.

Cold, trapped atomic ions have enabled the investigation of fundamental physics and generated a rich field of applications. Foremost among these is quantum computation which has recently driven the development of the sophisticated, scalable surface-electrode trap. Despite the many advantages of surface-electrode traps, the typically smaller ion-electrode distance, d, in these traps results in an increased ion heating rate that is proportional to d^(-4) and a decreased trap well-depth that is proportional to d^(-2). These shortcomings can be simultaneously addressed by installing the trap into a cryogenic environment. With this in mind, a closed-cycle, cryogenic ion trapping apparatus that maintains excellent vacuum, is highly modular, has increased optical access, and uses a simple vibration isolation system has been developed. Single ions are trapped and used to characterize system properties such as the motion of the vibration isolation stage. In order to compare this system to a similar room temperature apparatus, the ion trapping lifetime and heating rate are determined. A single ion also serves as a sensitive electric field probe that is used to measure and compensate stray electric fields across the trap. Due to the long dark ion lifetimes in this system, it is well-suited to probing the stability of small, linear ion crystals. Linear ion crystals of arbitrary length are built in an automated fashion using transport waveforms and the scaling of dark lifetime with ion number for N <= 6 is investigated. These data are then used to consider the relevance of various loss channels.

Wildland fire, which includes both planned (prescribed fire) and unplanned (wildfire) fires, is an important component of many ecosystems. Prescribed burning (controlled burning) is used as an effective tool in managing a variety of ecosystems in the United States to reduce accumulation of hazardous fuels, manage wildlife habitats, mimic natural fire occurrence, manage traditional native foods, and provide other ecological and societal benefits. During wildland fires, both live and dead (biomass) plants undergo a two-step thermal degradation process (pyrolysis and combustion) when exposed to high temperatures. Pyrolysis is the thermal decomposition of organic material, which does not require the presence of oxygen. Pyrolysis products may later react with oxygen at high temperatures, and form flames in the presence of an ignition source. In order to improve prescribed fire application, accomplish desired fire effects, and limit potential runaway fires, an improved understanding of the fundamental processes related to the pyrolysis and ignition of heterogeneous fuel beds of live and dead plants is needed.In this research, fast pyrolysis of 14 plant species native to the forests of the southern United States has been studied using a flat-flame burner (FFB) apparatus. The results of fast pyrolysis experiments were then compared to the results of slow pyrolysis experiments. The plant species were selected, which represent a range of common plants in the region where the prescribed burning has been performed. The fast pyrolysis experiments were performed on both live and dead (biomass) plants using three heating modes: (1) convection-only, where the FFB apparatus was operated at a high heating rate of 180 °C s-1 (convective heat flux of 100 kW m-2) and a maximum fuel surface temperature of 750 °C; (2) radiation-only, where the plants were pyrolyzed under a moderate heating rate of 4 °C s-1 (radiative heat flux of 50 kW m-2), and (3) a combination of radiation and convection, where the plants were exposed to both convective and radiative heat transfer mechanisms. During the experiments, pyrolysis products were collected and analyzed using a gas chromatograph equipped with a mass spectrometer (GC-MS) for the analysis of tars and a gas chromatograph equipped with a thermal conductivity detector (GC-TCD) for the analysis of light gases.The results showed that pyrolysis temperature, heating rate, and fuel type, have significant impacts on the yields and the compositions of pyrolysis products. These experiments were part of a large project to determine heat release rates and model reactions that occur during slow and fast pyrolysis of live and dead vegetation. Understanding the reactions that occur during pyrolysis then can be used to develop more accurate models, improve the prediction of the conditions of prescribed burning, and improve the prediction of fire propagation.

Prescribed (i.e., controlled) burning is a common practice used in many vegetation types in the world to accomplish a wide range of land management objectives including wildfire risk reduction, wildlife habitat improvement, forest regeneration, and land clearing. To properly apply controlled fire and reduce unwanted fire behavior, an improved understanding of fundamental processes related to combustion of live and dead vegetation is needed. Since the combustion process starts with pyrolysis, there is a need for more data and better models of pyrolysis of live and dead fuels. In this study, slow pyrolysis experiments were carried out in a pyrolyzer apparatus and a Thermogravimetric analyzer (TGA) under oxygen free environment in three groups of experiments. In the first group, the effects of temperature (400–800 °C), a slow heating rate (H.R.) (5–30 °C min−1), and carrier gas flow rate (50–350 ml min−1) on yields of tar and light gas obtained from pyrolysis of dead longleaf pine litter in the pyrolyzer apparatus were investigated to find the optimum condition which results in the maximum tar yield. In the second group of experiments, 14 plant species (live and dead) native to forests in the southern United States, were heated in the pyrolyzer apparatus at the optimum condition. A gas chromatograph equipped with a mass spectrometer (GC–MS) and a gas chromatograph equipped with a thermal conductivity detector (GC-TCD) were used to study the speciation of tar and light gases, respectively. In the third group of experiments, the slow pyrolysis experiments for all plant species (live and dead) were carried out in the TGA at 5 different heating rates ranged from 10 to 30 ℃ min-1 to study the kinetics of pyrolysis. The results showed that the highest tar yield was obtained at a temperature of 500 °C, heating rate of 30 °C min−1, and sweep gas flow rate of 100 ml min−1. In addition, the tar composition is dominated by oxygenated aromatic compounds consisting mainly of phenols. The light gas analysis showed that CO and CO2 were the dominant light gas species for all plant samples on a dry wt% basis, followed by CH4 and H2. The kinetics of pyrolysis was studied using one model-free method and three model-fitting methods. First, the model-free method of Kissinger-Akahira-Sunose (KAS) was used to calculate the rates of pyrolysis as a function of the extent of conversion. The results showed that different plant species had different rates at different conversions. Then, three model fitting methods were used to find the kinetic parameters to potentially provide a single rate for each plant species. The results showed that the simple one-step model did not fit the one-peak pyrolysis data as well as the distributed activation energy model (DAEM) model. The multiple-reaction DAEM model provided very good fits to the experimental data where multiple peaks were observed, even at different heating rates.

The formation of liquid films is a widely known problem in aluminium heat exchanger materials. The phenomenon results in decreased brazeability along with severely deteriorated mechanical properties which might cause assembly collapse. In addition, low-melting-point elements like tin, bismuth and lead are thought to promote grain boundary sliding which is the main deformation mechanism during brazing. Their melting characteristics are not adequately reported in literature. It is therefore of great importance to examine the behaviour of these elements.The main objectives with this work is melting range determination of fin heat exchanger materials, melting detection of low-melting-point elements and calculation of tin, bismuth and lead solid-solubility in aluminium. This work does also involve distribution analysis of such elements in aluminium matrix after heat treatment.These investigations require development of a differential scanning calorimetry (DSC) technique that is applicable for analysis of aluminium fin heat exchanger material containing low-melting-point elements on ppm level. Optimization of the technique includes parameter control; like heating rate, sample mass, reproducibility and choice of crucible material. Laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) is additionally used in order to analyse solid solubility and distribution of low-melting-point elements in aluminium after heat treatment.The developed DSC technique shows a sensitivity limit in the range of 260-600 ppm. It means that it is not possible to detect melting of phases within and below that range. Solid solubility of tin was calculated for the three heat treatment temperatures, 400°C, 500°C and 625°C. Same procedure was applied on bismuth and lead. However, calculated values did not agree with Thermo-Calc. The distribution analysis indicate an exudation of trace elements i.e. diffusion toward surface during heat treatment.In conclusion, more knowledge regarding liquid films in aluminium fin heat exchanger material was obtained. Future work should be to further optimize the DSC technique for trace element analysis for concentrations below 100 ppm. The LA-ICP-MS technique is likely to improve experimentally unverified binary phase diagrams like Al-Bi, Al-Pb and Al-Sn phase diagrams. It can also be used to study exudation behaviour of liquid films.