Functionally Graded Alumina/Mullite Coatings for Protection of Silicon Carbide Ceramic Components from Corrosion

During the six months of this reporting period, we accomplished the following: Preparatory work was done on the development of the feed supply system (for mixtures of AlCl{sub 3}, SiCl{sub 4}, H{sub 2} and CO{sub 2}) and effluent treatment section for the CVD system we plan to employ for coating preparation. A comprehensive literature survey of past work done on the chemical vapor deposition of silica, alumina and aluminosilicates (mullite) was carried out, and work was initiated on the study of thermochemical equilibrium in the Al/Si/Cl/C/O/H system so as to identify the boundaries of the region of the space of operating parameters and conditions where preparation of functionally graded mullite/ alumina coatings through CVD from metal chloride, CO{sub 2}, and H{sub 2} is feasible. Since the alumina/mullite films that are proposed to be developed can also be applied to carbon matrix composites provided that a layer that bridges the gap that exists between the thermal expansion coefficient of carbon and that of mullite is employed, experiments were conducted on the preparation of compositionally graded carbon/silicon carbide coatings. Deposition from mixtures of ethylene and methyltrichlorosilane or tetrachlorosilane (silicon tetrachloride) in hydrogen was used for the preparation of SiC/C coatings, and our experiments focused on the study of the occurrence of multiple steady states in the deposition process and the effects of the type of chlorosilane on the deposition rate and the deposit composition and their variation along the length of the reactor. The results showed that when operation is carried out outside the multiplicity region, codeposition of SiC and C from ethylene and chlorosilanes is a feasible route for preparation of SiC/C graded coatings

The cosine law at the atomic scale: Toward realistic simulations of Knudsen diffusion

We propose to revisit the diffusion of atoms in the Knudsen regime in terms of a complex dynamical reflection process. By means of molecular dynamics simulation we emphasize the asymptotic nature of the cosine law of reflection at the atomic scale, and carefully analyze the resulting strong correlations in the reflection events. A dynamical interpretation of the accomodation coefficient associated to the slip at the wall interface is also proposed. Finally, we show that the first two moments of the stochastic process of reflection non uniformly depend on the incident angle

IMECE2002/HTD-33632 BIFURCATION ANALYSIS FOR HORIZONTAL LONGITUDINAL FINS UNDER MULTI- BOILING CONDITIONS

ABSTRACT A numerical bifurcation analysis is carried out in order to determine the solution structure of a fin subject to multi-boiling heat transfer mode. The thermal analysis can no longer performed independently of the working fluid since the heat transfer coefficient is temperature dependent and includes the nucleate, the transition and the film boiling regime where the boiling curve is obtained experimentally for a specific fluid. The heat transfer process is modeled using one-dimensional heat conduction with or without heat transfer from the fin tip. Furthermore, five fin profiles are considered: the constant thickness, the trapezoidal, the triangular, the convex parabolic and the parabolic. The multiplicity structure is obtained in order to determine the different types of bifurcation diagrams, which describe the dependence of a state variable of the system (for instance the fin temperature or the heat dissipation) on a design (CCP) or operation parameter (base TD). Specifically the effects of the base TD, of CCP and of the Biot number are analyzed and presented in several diagrams since it is important to know the behavioral features of the heat rejection mechanism such as the number of the possible steady states and the influence of a change in one or more operating variables to these states. Stability analysis is carried out using the "resonance integral" technique and the Sturm-liouville eigensystem analysis

Removal of H2S and SO2 by CaCO3-Based Sorbents at High Pressure

The theoretical and experimental investigation of the mechanism of SO2 and H2S removal by CaCO3 -based sorbents (limestones and dolomites) in pressurized uidized-bed coal combustors (PFBC) and high pressure gasi#12;ers, respectively, is the main objective of this study. It is planned to carry out reactivity evolution experiments under simulated high pressure conditions or in high pressure thermogravimetric and, if needed, uidized- bed reactor (high pressure) arrangements. The pore structure of fresh, heat-treated, and half-calcined solids (dolomites) will be analyzed using a variety of methods. Our work will focus on limestones and dolomites whose reaction with SO2 or H2S under atmospheric conditions has been studied by us or other research groups in past studies. Several theoret- ical tools will be employed to analyze the obtained experimental data including a variable di#11;usivity shrinking-core model and models for di#11;usion, reaction, and structure evolution in chemically reacting porous solids. During the six months of this reporting period, work was primarily done on the study of the behavior of the sul#12;dation of limestones under sequential calcination conditions in the presence of small amounts of oxygen and the development of a stochastic simulation code for determining the extent of pore volume trapping (formation of inaccessible pore space) in gas-solid reactions accompanied by pore volume reduction such as the sulfation and sul#12;dation of calcined limestones and dolomites. The incentive for carrying out sul#12;dation experiments in the presence of oxygen was provided by the observation that some sul#12;dation experiments that were conducted as oxygen was accidentally leaking into the feed mixture of the reactor showed completely di#11;erent behavior from that obtained in the absence of oxygen. Experiments were carried out in the thermogravimetric analysis system that we developed for studying gas-solid reactions at atmospheric or subambient pressures. The two CaCO3 solids (Greer limestone and Iceland spar) that we employed in our previous experiments were used in the sulfidation

FUNCTIONALLY GRADED ALUMINA/MULLITE COATINGS FOR PROTECTION OF SILICON CARBIDE CERAMIC COMPONENTS FROM CORROSION

The main objective of this research project was the formulation of processes that can be used to prepare compositionally graded alumina/mullite coatings for protection from corrosion of silicon carbide components (monolithic or composite) used or proposed to be used in coal utilization systems (e.g., combustion chamber liners, heat exchanger tubes, particulate removal filters, and turbine components) and other energy-related applications. Since alumina has excellent resistance to corrosion but coefficient than silicon carbide, the key idea of this project has been to develop graded coatings with composition varying smoothly along their thickness between an inner (base) layer of mullite in contact with the silicon carbide component and an outer layer of pure alumina, which would function as the actual protective coating of the component. (Mullite presents very good adhesion towards silicon carbide and has thermal expansion coefficient very close to that of the latter.

REMOVAL OF H2S AND SO2 BY CaCO3-BASED SORBENTS AT HIGH PRESSURES

The mechanism of the removal of SO{sub 2} and H{sub 2}S by CaCO{sub 3}-based sorbents in pressurized fluidized-bed coal combustors (PFBC) and high pressure gasifiers was investigated in this project. Reactivity evolution experiments were carried out in thermogravimetric apparatuses both under simulated high pressure conditions and at high pressures. Experiments at high pressure were conducted in a high pressure thermogravimetric arrangement that was set up and developed under this project. Two calcitic solids of high calcium carbonate content (over 97%) were employed in the experiments: a fine-grained distributed by Greer Limestone Co. (Greer Limestone) and a solid supplied in the form of large calcitic crystals (Iceland Spar). The decision to work with these solids was mainly based on the fact that they have been employed in several past studies of sulfation, sulfidation, and calcination in our laboratory, and therefore, a large volume of data on their performance under different conditions was available for comparison purposes. In addition to the experimental studies, work was also done on the development of rigorous mathematical models for the description of the occurrence of simultaneous processes (e.g., calcination and sulfation and carbonation and sulfation) in the interior of porous solids and for the simulation of the evolution of the pore structure of porous solids that undergo chemical transformation in their interior

FUNCTIONALY GRADED ALUMINA/MULLITE COATINGS FOR PROTECTION OF SILICON CARBIDE CERAMIC COMPONENTS FROM CORROSION

The main objective of this research project is the formulation of processes that can be used to prepare compositionally graded alumina/mullite coatings for protection from corrosion of silicon carbide components (monolithic or composite) used or proposed to be used in coal utilization systems (e.g., combustion chamber liners, heat exchanger tubes, particulate removal filters, and turbine components) and other energy-related applications. Mullite will be employed as the inner (base) layer and the composition of the film will be continuously changed to a layer of pure alumina, which will function as the actual protective coating of the component. Chemical vapor deposition reactions of silica, alumina, and aluminosilicates (mullite) through hydrolysis of aluminum and silicon chlorides in the presence of CO2 and H2 will be employed to deposit compositionally graded films of mullite and alumina. Our studies will include the kinetic investigation of the silica, alumina, and aluminosilicate deposition processes, characterization of the composition, microstructure, surface morphology, and mechanical behavior of the prepared films, and modeling of the various deposition processes. During this six-month reporting period, the experimental work on the investigation of the deposition of alumina, silica, and aluminosilicates from mixtures of methyltrichlorosilane (MTS), aluminum trichloride, carbon dioxide, and hydrogen was continued. Experiments were also conducted on the deposition processes of the simple oxides, alumina and silica, from mixtures containing only one chloride (AlCl3 and MTS, respectively). Deposition rate data were obtained in a relatively broad range of operating conditions: temperatures in the range 800-1000 o C, 100 Torr pressure, 0.006-0.015 AlCl3 feed mole fraction, 0.011- 0.027 CH3SiCl3 feed mole fraction, and 0.004-0.07 CO2 feed mole fraction, and various positions along the axis of the deposition reactor. Since the effect of temperature had been examined in detail in the previous reporting period, our efforts were mainly concentrated on the investigation of the effects of the other parameters on the three deposition processes. The results showed that the mole fraction of CO2 had a strong influence on all deposition rates, with the alumina deposition rate and the codeposition rate showing a tendency to increase significantly with increasing concentration of CO2 in the feed at low mole fraction values and reach a limiting value at high CO2/chloride ratios. The increase in the concentration of carbon dioxide had, in general, a negative effect on the rate of silica deposition. These effects were in agreement with the conclusions reached from the thermodynamic equilibrium analysis of the deposition processes in past studies. The increase in the mole fraction of AlCl3 had a positive effect on the rate of codeposition and the deposition of alumina. In the case of alumina deposition, the deposition rate leveled off in some cases as the AlCl3 concentration was increased, and this behavior was consistent with the results of past experimental studies. The deposition rate and the deposit stoichiometry were influenced strongly by the substrate position in the reactor, and the deposition rate could increase or decrease with increasing distance from the entrance of the reactor depending on the reaction temperature