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In this work, the deformation and strength of an oxide/oxide ceramic matrix composite system under stress-rupture conditions were studied both experimentally and analytically. A rupture model for unidirectional composites which incorporates fiber strength statistics, fiber degradation, and matrix damage was derived. The model is based on a micromechanical analysis of the stress state in a fiber near a matrix crack and includes the effects of fiber pullout and global load sharing from broken to unbroken fibers. The parameters required to produce the deformation and lifetime predictions can all be obtained independently of stress-rupture testing through quasi-static tension tests and tests on the individual composite constituents. Thus the model is truly predictive in nature. The predictions from the model were compared to the results of an extensive experimental program. The model captures the trends in steady-state creep and tertiary creep but the lifetime predictions are extremely conservative. The model was further extended to the behavior of cross-ply or woven materials through the use of numeric representations of the fiber stresses as the fibers bridge matrix cracks. Comparison to experiments on woven materials demonstrated the relationship between the behavior of the unidirectional and cross-ply geometries. Finally, an empirical method for predicting the durability of materials which exhibit multiple damage modes is examined and compared to results of accurate Monte Carlo simulations. Such an empirical method is necessary for the durability analysis of large structural members with varying stress and temperature fields over individual components. These analyses typically require the use of finite element methods, but the extensive computations required in micromechanical models render them impractical. The simple method examined in this work, however, is shown to have applicability only over a narrow range of material properties. / Ph. D.

A transmission electron microscopy study involving direct and replicating techniques is directed to a definition of the microstructure of radio frequency-sputtered, thin lead-dielectric cermet films. Once defined, this microstructure is used to obtain theoretical film refractive indices. The Maxwell Garnet theory provides a basis for the theoretical results. Measurements of film transmission and reflectivity are used to obtain rough experimental values for film refractive indices by the Tekucheva method. More exact values are obtained via ellipsometry. The rough Tekucheva values are used to determine the range over which computer calculations interpreting the ellipsometric results must be made. This technique yields accurate values for the film refractive indices. The films are radio-frequency-sputtered from lead glass targets with varying amounts of lead attached to their faces. Three different targets are used, resulting in three sets of films, each containing a different percentage of lead. The lead content of the films is measured by microprobe analysis as well as visual inspection of micrographs. The lower content lead films are seen to consist of tiny balls of lead embedded in the dielectric, as are the intermediate lead content films; but the higher lead content films form metallic networks throughout the dielectric. The lower and intermediate lead content films have indices which agree with the predictions of the Maxwell Garnett theory; but the higher lead content films, whose structure fails to conform to the Maxwell Garnett configuration, have indices whose values diverge from the Maxwell Garnett predictions. It is thus shown that the theory of Maxwell Garnett is valid for thin cermet films whose structure consists of tiny metal balls embedded in a dielectric medium. / Ph. D.

Increasing use of fiber reinforced ceramic matrix composites (CMC's) materials is needed, especially for hostile environments such as elevated temperatures. However, some fundamental issues regarding how these materials should be made for optimized performance are far from being settled. This study focuses on the modeling of the tensile behavior of unidirectional CMC using statistical methods and micro-mechanical analysis, based on laboratory observations. The model can be used to examine the effect of performance-influencing parameters on the strength of unidirectional CMC, thus shed light on how such material should be put together. The tensile strength model was then modified such that the behavior of unidirectioal CMC under cyclic tensile load can be studied. Results from the tensile strength model suggest that the Weibull modulus, <i>m</i>, of the strength of the reinforcing fibers and the fiber/matrix interfacial shear stress both have significant effect on the strength and toughness of the unidirectional composite: a higher <i>m</i> value and a lower interfacial shear stress result in a lower strength; a lower value of <i>m</i> and a higher interfacial shear stress results in a higher strength but lower toughness. Calculations from the tensile fatigue model suggest that a lower <i>m</i> value results in a longer fatigue life. / Ph. D.

A novel class of inorganic/ organic hybrid materials referred to as CERAMERs have been successfully prepared by a sol-gel process using a polymeric acid catalyst, poly(styrene sulfonic acid), to form a network from tetraethylorthosilicate (TEOS) and triethoxysilane end capped oligomers of poly( tetramethylene oxide) (PTMO). The structure-property relationships were determined for these hybrid networks from their dynamic mechanical behavior, mechanical properties, and SAXS behavior. Thermal gravimetric data coupled with FfIR analysis were used to obtain a qualitative measure of the extent of conversion of the metal alkoxides as a function of acid catalyst. Another new class of CERAMERs was successfully developed by the sol-gel processing of three different metal alkoxides in conjuction with the triethoxy silane end capped PTMO oligomers. The first novel hybrid is based upon complexes of aluminum tri-n-butoxide with ethyl acetoacetonate or titanium tetra-iso-propoxide with ethyl acetoacetate reacted with the triethoxysilane end capped PTMO. The hybrid networks were optically clear and could be easily formed as relatively large monoliths. A novel method of preparation of stable sols without the use of ethyl acetoacetate, developed by Dr. Bing Wang in this laboratory, led to more stable CERAMERS of titanium tetra-iso-propoxide (TiOPr) reacted with the functionalized P'TMO as well as a fourth inorganic/organic hybrid material based upon zirconium tetra-n-propoxide and PTMO. Indeed, the mechanical properties of the TiOPr/P'TMO CERAMERs and ZrOPr/P'TMO CERAMERs were significantly enhanced over the TEOS/PTMO CERAMERs in terms of both Young's modulus and stress at break. The structure-property relationships of these materials were adequately described by the morphological model originally developed for the CERAMERs based upon TEOS/PTMO. / Ph. D.