Browsing by Author "Hirschfeld, Deidre A."

Now showing 1 - 13 of 13
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    Alkali corrosion resistant coatings and ceramic foams having superfine open cell structure and method of processing
    (United States Patent and Trademark Office, 1993-12-07)
    Alkali corrosion resistant coatings and ceramic foams having superfine open cell structure are created using sol-gel processes. The processes have particular application in creating calcium magnesium zirconium phosphate, CMZP, coatings and foams.
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    Alkali/steam corrosion resistance of commercial SiC products coated with sol-gel deposited Mg-doped Al₂TiO₅ and CMZP
    Kang, Min (Virginia Tech, 1994-05-05)
    The corrosion resistance of two commercially available SiC filter materials coated with Mg-doped Al₂ TiO₅ and (Ca 0.6.6' Mg0.52) Zr₄P₆O₂₄ (CMZP) was investigated in high-temperature high pressure (HTHP) alkali-steam environments. Coated specimen properties, including cold and hot compressive strengths, bulk density, apparent porosity, permeability, and weight change, detected after exposure to 92% air-S% steam 10 ppm Na at 8OO°C and 1.8 MPs for 500 h were compared with those of uncoated specimens. Procedures for applying homogeneous coatings of Mg-doped Al₂ TiO₅ and CMZP to porous SiC filters were established and coating of the materials was successfully accomplished. Efforts to stabilize the Al₂ TiO₅ coating composition at elevated temperature were successful. Coatings show promise for providing improved corrosion resistance of the materials in pressurized fluidized bed combustion (PFBC) environments as evidenced by higher compressive strengths exhibited by coated SiC specimens than by uncoated SiC specimens following HTHP alkali-steam exposure.
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    Ceramic materials with low thermal conductivity and low coefficients of thermal expansion
    (United States Patent and Trademark Office, 1992-04-07)
    Compositions having the general formula (Ca.sub.x Mg.sub.1-x)Zr.sub.4 (PO.sub.4).sub.6 where x is between 0.5 and 0.99 are produced by solid state and sol-gel processes. In a preferred embodiment, when x is between 0.5 and 0.8, the MgCZP materials have near-zero coefficients of thermal expansion. The MgCZPs of the present invention also show unusually low thermal conductivities, and are stable at high temperatures. Macrostructures formed from MgCZP are useful in a wide variety of high-temperature applications. In a preferred process, calcium, magnesium, and zirconium nitrate solutions have their pH adjusted to between 7 and 9 either before or after the addition of ammonium dihydrogen phosphate. After dehydration to a gel, and calcination at temperatures in excess of 850.degree. C. for approximately 16 hours, single phase crystalline MgCZP powders with particle sizes ranging from approximately 20 nm to 50 nm result. The MgCZP powders are then sintered at temperatures ranging from 1200.degree. C. to 1350.degree. C. to form solid macrostructures with near-zero bulk coefficients of thermal expansion and low thermal conductivities. Porous macrostructures of the MgCZP powders of the present invention are also formed by combination with a polymeric powder and a binding agent, and sintering at high temperatures. The porosity of the resulting macrostructures can be adjusted by varying the particle size of the polymeric powder used.
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    Corrosion resistance of NZP and aluminum titanate
    Lu, Yangsheng (Virginia Tech, 1996-09-05)
    To determine the feasibility of using low thermal expansion ceramics and aluminum titanate in diesel engine applications, the mechanical and thermal properties and corrosion resistance were evaluated. NZP (Ba1.25Zr₄P5.5Si.0.50₂₄ and Ca0.5 SrO.5Zr₄P₆0₂₄) and aluminum titanate (AT) were exposed to a simulated diesel engine environment. The effects of thermal cycling from room temperature to 700°C, and a combination of alkali corrosion and thermal cycling on the mechanical and thermal properties of these ceramics were examined. It was found that NZP and AT materials demonstrated near zero bulk thermal expansion, good thermal up shock resistance and resistance to Na and V corrosion, because of their porous structure and low density. However, the AT materials exhibited lower flexural strength. This is a direct result of the inherent micro cracking across the AT grains upon cooling from the sintering temperature, which reduces the flexural strength and elastic modulus.
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    Corrosion resistant chemical vapor deposited coatings for SiC and Si3N4
    Graham, David W. (Virginia Tech, 1993-04-09)
    Silicon carbide and silicon nitride turbine engine components are susceptible to hot corrosion by molten sodium sulfate salts which are formed from impurities in the engine's fuel and air intake. Several oxide materials were identified which may be able to protect these components from corrosion and preserve their structural properties. Ta20, coatings were identified as one of the most promising candidates. Thermochemical calculations showed that the chemical vapor deposition(CVD) of tantalum oxide from O2 and TaCI5 precursors is thermodynamically feasible over a range of pressures, temperatures, and reactant concentrations. The deposition of Ta205, as a single phase is predicted in regions of excess oxygen, where the reaction is predicted to yield nearly 100% efficiency. CVD experiments were carried out to deposit tantalum oxide films onto SiC substrates. Depending on the deposition conditions, a variety of coating morphologies have been produced, and conditions have been identified which produce dense, continuous Ta205 deposits. Preliminary corrosion tests on these coatings showed no apparent degradation of the CVD deposited tantalum oxide coatings. The feasibility of depositing ZrTi04 as a coating material was also investigated based on thermochemical considerations. Since no data were available for this material, thermodynamic values were estimated. Thermochemical calculations indicated the chemical vapor deposition of zirconium titanate from O2, ZrCl4, and TiCl4 occurs over a range of temperatures in a very narrow region of the phase diagram. Deviations from the single phase region predicted the codeposition of either Zr02 or Ti02 with ZrTi04. These results suggested that the chemical vapor deposition of ZrTi04 may be difficult from a process handling perspective. Additionally, the process is predicted to be very inefficient, leaving substantial amounts of unreacted chlorides in the reactor exhaust.
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    Corrosion resistant CMZP and Mg-Al2TiO5coatings for SiC ceramics
    Yang, Shaokai (Virginia Tech, 1996)
    Thin film coatings of (Cao.6Mg0.4)Zr4(P04)6 (CMZP) and Mg stabilized AhTiOs ( Mg-Ah Ti05 ) on dense SiC substrates were investigated using sol-gel coating techniques. The thickness and quality of both CMZP and Mg-Ah Ti05 coatings were found to depend on the solution concentration and lift rate. Double coatings were applied to obtain homogeneous and crack-free coatings. The quality of double coatings was influenced by different first and second coating thickness. The CMZP coated samples were fired in controlled atmospheres to have the pure CMZP phase. Unhydrolyzed solution of Mg-AhTiOs was utilized instead of hydrolyzed solution to improve the quality of Mg-AhTiOs coatings. Aging process was found to improve the quality of CMZP and Mg-Ah TiOs coatings. SiC samples coated with CMZP and Mg-Ah TiOs exhibited good thermal shock resistance and greatly improved the high temperature alkali corrosion resistance.
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    Development of Low Expansion Glaze Coatings on As Fired Si₃N₄ to Enhance Room Temperature Flexural Strength
    Majumdar, Nandita N. (Virginia Tech, 1998-06-19)
    Silicon nitride (Si₃N₄) has the potential for use in various high-performance applications. However, surface defects such as voids/pits are commonly present on as processed Si₃N₄. When subjected to external forces, fracture originates at such flaws. To reduce or eliminate surface flaws, machining operations are required which constitute a major proportion of production costs. In order to offer an inexpensive alternative to machining and also to enhance the room temperature flexural strength of as fired Si₃N₄, low expansion glaze coatings of lithium aluminosilicate (LAS) and magnesium aluminosilicate (MAS) compositions were developed. Homogeneous and crack-free glaze coatings were successfully formed on as processed Si₃N₄. This ensured formation of compressive surface stresses on the as fired Si₃N₄ which, in turn, led to the reduction of the effects of surface flaws. When compared to the uncoated as fired Si₃N₄, both the glaze coatings helped achieve greater flexural strength. Analyses of the two glazes indicated better strength for the MAS coating compared to the LAS. Wear tests revealed that the MAS glaze exhibited higher wear resistance than the LAS glaze. These differences were attributed to the ability of the magnesium aluminosilicate glaze to achieve greater surface smoothness and better adherence to the substrate than the lithium aluminosilicate.
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    Failure analysis of notched graphite-epoxy tubes
    Hirschfeld, Deidre A. (Virginia Tech, 1990-02-16)
    Notched unidirectional graphite/epoxy tubes with fiber orientations of 2.5°, 15°, 45°, and 87.5° were failed in tension, compression, torsion, and combined compression-torsion loading. The stress field around the slot-like notches, aligned with the tube axis, was determined using an infinite flat plate elasticity solution with an elliptical hole. The normal stress ratio theory was used to predict crack location, crack direction, and failure stress. The experimental failure modes of the tubes were determined using scanning electron microscopy and related to the stress field in the vicinity of the notch. The results showed that independent of loading the cracks usually initiated at the discontinuity of the notch where the semi-circular end intersects the straight sides and then grew along the fiber direction either at the fiber/matrix interface or within the matrix. The normal stress ratio theory correctly predicted the direction of crack growth but not the location of crack initiation since the model did not account for the notch discontinuity. The prediction of far-field failure stresses exhibited only limited agreement with the experimental results. When there was agreement, the predicted far-field failure stresses were dependent on the elliptical semi-axis ratio used to model the notch. The material principal stresses at the location of maximum normal stress ratio were correlated with the failure mode of the unidirectional tubes. Matrix failure tended to occur when the material principal shear stress and transverse stress (perpendicular to the fibers) were nearly equal in magnitude, while fiber/matrix interface failure was predominant when the stresses differed by a factor of 2.0 or more. In addition, several notched angle-ply ± 87.5° tubes were failed in torsion. The normal stress ratio theory was applied to these tubes and correctly predicted that fiber breakage would occur. The predicted crack initiation stress agreed poorly with experimental results and the location of the crack was influenced by the notch discontinuity not included in the model. The direction of crack growth and the failure morphology of the angle-ply tubes were dependent on the direction of torsion applied to the tubes.
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    Method of making in-situ whisker reinforced glass ceramic
    (United States Patent and Trademark Office, 1993-02-16)
    A heat processing procedure is used to create reinforcing whiskers of TiO.sub.2 in glass-ceramic materials in the LAS and MAS family. The heat processing procedure has particular application in creating TiO.sub.2 in-situ in a modified .beta.-eucryptite system.
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    The sintering effection of time, temperature, and ZnO additions on (Ca₀.₆,Mg₀.₄)Zr₄(PO₄)₆ [CMZP] ceramics
    Clarke, James R Jr. (Virginia Tech, 1996-07-05)
    The sintering of (Ca0.6,Mg0.4)Zr₄(PO₄)₆ powder (CMZP) synthesized via a new solid-state reaction method was investigated for application as a thermal barrier in next generation internal combustion engines. Specifically, CMZP is being considered as a potential material for the manufacture of exhaust port liners to increase the overall performance of diesel engines. The effects of firing time, firing temperature, and amount of ZnO sintering aid on modulus of rupture (MOR), bulk density, and coefficient of thermal expansion (CTE) were determined for both dry pressed and slip cast samples to optimize the physical properties for this application. For both processing methods, suppressing the formation of secondary interparticle phases (grain boundaries) was found to be the controlling factor for obtaining high strength and positive thermal expansion. For a given ZnO level, increases in firing time and/or temperature resulted in improved density but a degradation in microstructure (undesirable grain growth, formation of a liquid phase, and intra-/trans- granular microcracking), accompanied by a reduction in MOR and negative CTE values. Therefore, optimizing bulk density was determined to be counter-productive for improving strength when ZnO is used as a sintering aid.
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    A study of the promolecule radius of nitrides, oxides and sulfides and of the bond critical point properties of the electron density distribution in nitrides
    Feth, Shari (Virginia Tech, 1996-12-05)
    "We cannot afford the luxury any longer of ignoring the nature of the bonding in these interesting compounds .... " P.E.D. Morgan, (1974). An understanding of bonding is paramount to furthering our understanding of materials (Morgan, 1974). The properties of materials are governed by the interactions between atoms. These interactions are governed by the nature of the bonds. In this study, two methods are explored which provide insight into chemical interactions. First, promolecule radii, calculated for nitride, oxide, and sulfide coordinated polyhedra with bond lengths fixed at the sums of effective ionic and crystal radii, are analyzed. Radii calculated for transition and non-transition cations for the first four rows of the periodic table are highly correlated with crystal radii derived for oxide and sulfide crystals and with ionic radii derived for nitride crystals. Promolecule radii calculated for the coordination polyhedra match experimentally determined bonded radii to within ~0.02Å, on average. Calculated radii anions tend to match ionic radii when bonded to highly electropositive cations and atomic radii when bonded to highly electronegative cations. In the second study, molecular orbital calculations were completed on a series of small molecules containing the nitride anion. Bond type can be characterized by studying the systematics of parameters derived from the bond critical point properties of the electron density distributions. A set of criteria is established to suggest how covalent or ionic a bond is. This criteria is based on bond critical point properties such as the Laplacian of the electron density distribution evaluated at the bond critical point, the electron density distribution at the critical point, the local energy density at the critical point, the relative electronegativity of the cation, the curvatures of the electron density distribution, and the distance from the nucleus of the nitride anion to the bond critical point, (the bonded radius of the nitrogen atom). Parameters computed for promolecule data indicate that these easily obtained results offer a method of calculating bond critical properties which are close in value to the more extensive results derived from molecular orbital calculations.
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    Tensile behavior of unidirectional and cross-ply ceramic matrix composites
    Herrmann, Rebecca K. (Virginia Tech, 1996-02-15)
    The tensile behavior of two ceramic matrix composites (CMC's) was observed. The materials of interest in this study were a glass-ceramic matrix composite (GCMC) reinforced with Nicalon fibers and a Blackglas™ composite also reinforced with Nicalon fibers. Both had a symmetric cross-ply layup. Initial observations of the composites showed significant porosity and some cracking in the Blackglas™ samples. The GCMC samples showed considerably less damage. From the observed tensile behavior of the cross-ply composites, a 'back-out' factor for determining the 0° ply data of the composite was calculated using Classical Lamination Theory (CLT). The predicted behavior of the 0° ply was then compared to actual data supplied by McDonnell Douglas Corporation. While the Blackglas™ material showed good correlation, the GCMC did not. Analysis indicates that the applicability of this technique is strongly influenced by the initial microstructure of the composite, i.e., porosity, cracking. Fracture mirror measurements were also observed to determine the in-situ strength of the Nicalon fibers. Resulting characteristic strength and Weibull modulus values combined with measured fiber pullout lengths were then used to determine material parameters such as the ultimate tensile strength, strain to failure, work of pullout, sliding distance at the characteristic strength, and interfacial shear stress. Comparisons of measured and calculated ultimate tensile strengths and strains to failure showed good agreement. This research was sponsored by the Naval Surface Warfare Center (NSWC) in Dahlgren VA.
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    Transformation induced plasticity in ceramics
    Focht, Eric M. (Virginia Tech, 1992-04-15)
    Transformation induced plasticity was investigated in a model ceramic. The effect upon toughness of the martensitic transformation from the cubic (paraelectric) to the tetragonal ( ferroelectric) phase in BaTiO3 was determined. The K1C fracture toughness, as measured by the hardness indentation technique, exhibits a maximum within a temperature range approximately 50°C above the stress-free transformation temperature. Unlike the martensitic transformation associated with partially stabilized zirconia, there is no volume change during the cubic-to-tetragonal phase change in BaTi03. In addition, no evidence of microcracking was observed. The enhanced toughness in the vicinity of the transition temperature was attributed to limited plasticity at crack tips provided by the transformation shear strains. The effective strains at the crack tips required to produce the observed fracture toughness values are consistent with transformation strains calculated using the phenomenological theory of martensite.