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In analogy to 4-(para-substituted benzoyl)-N-methylpyridinium cations (1-X's), the title species (2-X's, -X = -OCH3, -CH3, -H, -Br, -COCH3, -NO2) undergo two reversible, well-separated (E(sub 1/2) greater than or equal to 650 mV) one-electron reductions. The effect of substitution on the reduction potentials of 2-X's is much weaker than the effect of the same substituents on 1-X's: the Hammett rho-values are 0.80 and 0.93 for the 1st- and 2nd-e reduction of 2-X's vs. 2.3 and 3.3 for the same reductions of 1-X's, respectively. Importantly, the nitro group of 2-NO2 undergoes reduction before the 2nd-e reduction of the 4-benzoylpyridinium system. These results suggest that the redox potentials of the 4-benzoylpyridinium system can be course-tuned via p-benzoyl substitution and fine-tuned via para-benzyl substitution. Introducing the recently derived substituent constant of the -NO2(sup)- group (sigma para-NO2(sup)- = -0.97) yields an excellent correlation for the 3rd-e reduction of 2- NO2 (corresponding to the reduction of the carbonyl group) with the 2nd-e reduction of the other 2-X's, and confirms the electron donating properties of -NO2(sup)-.

Bimorphous ceramics are a new class of materials that can be fabricated from the cellulose templates derived from natural biopolymers. These biopolymers are abundantly available in nature and are produced by the photosynthesis process. The wood cellulose derived carbon templates have three- dimensional interconnectivity. A wide variety of non-oxide and oxide based ceramics have been fabricated by template conversion using infiltration and reaction-based processes. The cellular anatomy of the cellulose templates plays a key role in determining the processing parameters (pyrolysis, infiltration conditions, etc.) and resulting ceramic materials. The processing approach, microstructure, and mechanical properties of the biomorphous cellular ceramics (silicon carbide and oxide based) have been discussed.

Surface segregation in Ni-Pd alloys has been studied using the BFS method for alloys. Not only does the method predict an oscillatory segregation profile but it also indicates that the number of Pd-enriched surface planes can vary as a function of orientation. The segregation profiles were computed as a function of temperature, crystal face, and composition. Pd enrichment of the first layer is observed in (111) and (100) surfaces, and enrichment of the top two layers occurs for (110) surfaces. In all cases, the segregation profile shows oscillations that are actually related to weak ordering tendencies in the bulk. An atom-by-atom analysis was performed to identify the competing mechanisms leading to the observed surface behaviors. Large-scale atomistic simulations were also performed to investigate the temperature dependence of the segregation profiles as well as for analysis of the bulk structures. Finally, the observed surface behaviors are discussed in relation to the bulk phase structure of Ni-Pd alloys, which exhibit a tendency to weakly order.

This paper, second in the series of three papers, develops a general, nonlinear, non-isothermal, compressible theory for finite rubber viscoelasticity and specifies it in a form convenient for solving problems important to the rubber, tire, automobile, and air-space industries, among others. Based on the quasi-linear approach of non-equilibrium thermodynamics, a general nonlinear theory of differential type has been developed for arbitrary non-isothermal deformations of viscoelastic solids. In this theory, the constitutive equations were presented as the sum of a rubber elastic (equilibrium) and a liquid type viscoelastic (non-equilibrium) terms. These equations have then been simplified using several modeling and simplicity arguments.

Atomistic modeling of RuAl and RuAlNi alloys, using the BFS (Bozzolo-Ferrante-Smith) method for alloys is performed. The lattice parameter and energy of formation of B2 RuAl as a function of stoichiometry and the lattice parameter of (Ru(sub 50-x)Ni(sub x)Al(sub 50)) alloys as a function of Ni concentration are computed. BFS based Monte Carlo simulations indicate that compositions close to Ru25Ni25Al50 are single phase with no obvious evidence of a miscibility gap and separation of the individual B2 phases.

The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

The NASA Strategic Plan identifies the long-term goal of providing safe and affordable space access, orbital transfer, and interplanetary transportation capabilities to enable scientific research, human, and robotic exploration, and the commercial development of space. Numerous scientific and engineering breakthroughs will be required to develop the technology required to achieve this goal. Critical technologies include advanced vehicle primary and secondary structure, radiation protection, propulsion and power systems, fuel storage, electronics and devices, sensors and science instruments, and medical diagnostics and treatment. Advanced materials with revolutionary new capabilities are an essential element of each of these technologies. A survey of emerging materials with applications to aerospace vehicle structures and propulsion systems was conducted to assist in long-term Agency mission planning. The comprehensive survey identified materials already under development that could be available in 5 to 10 years and those that are still in the early research phase and may not be available for another 20 to 30 years. The survey includes typical properties, a description of the material and processing methods, the current development status, and the critical issues that must be overcome to achieve commercial viability.

A 'C-coupon' was used to measure the interlaminar tensile behavior of five different composite materials: Sylramic/MI (melt infiltration SiC matrix), ZMl/MI, Sylramic/S300, and ZMI and Hi-Nicalon with an S200 matrix at room temperature, 816 C, and 1204 C. Fracture behavior was characterized by field emission scanning electron microscopy, and observed cracking compared with events measured by modal acoustic emission. Both radial and matrix hoop cracking along the inner radius arising from hoop stresses were observed for all material types. In those composites in which the radial cracks were sufficiently wide to view the composite interior, fracture was observed to occur at the fiber BN or BN matrix interface.

Oxidation kinetics of Cu-8Cr-4Nb was investigated by TGA (thermogravimetric) exposures between 500 and 900-C (at 25-50 C intervals) and the oxide scale morphologies examined by microscopy and micro-analysis. Because Cu-8Cr-4Nb is comprised of fine Cr2Nb precipitates in a Cu matrix, the results were interpreted by comparison with the behavior of copper (OFHC) and 'NARloy-Z' (a rival candidate material for thrust cell liner applications in advanced rocket engines) under the same conditions. While NARloy-Z and Cu exhibited identical oxidation behavior, Cu-8Cr-4Nb differed markedly in several respects: below approx. 700 C its oxidation rates were significantly lower than those of Cu; At higher temperatures its oxidation rates fell into two categories: an initial rate exceeding that of Cu, and a terminal rate comparable to that of Cu. Differences in oxide morphologies paralleled the kinetic differences at higher temperature: While NARloy-Z and Cu produced a uniform oxide scale of Cu2O inner layer and CuO outer layer, the inner (Cu2O) layer on Cu-8Cr-4Nb was stratified, with a highly porous/spongy inner stratum (responsible for the fast initial kinetics) and a dense/blocky outer stratum (corresponding to the slow terminal kinetics). Single and spinel oxides of Nb and Cr were found at the interface between the oxide scale and Cu-8Cr-4Nb substrate and it appears that these oxides were responsible for its suppressed oxidation rates at the intermediate temperatures. No difference was found between Cu-8Cr-4Nb oxidation in air and in oxygen at 1.0 atm.

Macrosegregation in metal casting can be caused by thermal and solutal melt convection, and the transport of unattached solid crystals. These free grains can be a result of, for example, nucleation in the bulk liquid or dendrite fragmentation. In an effort to develop a comprehensive numerical model for the casting of alloys, an experimental study has been conducted to generate benchmark data with which such a solidification model could be tested. The specific goal of the experiments was to examine equiaxed solidification in situations where sinking of grains is (and is not) expected. The objectives were: 1) experimentally study the effects of solid transport and thermosolutal convection on macrosegregation and grain size distribution patterns; and 2) provide a complete set of controlled thermal boundary conditions, temperature data, segregation data, and grain size data, to validate numerical codes. The alloys used were Al-1 wt. pct. Cu, and Al-10 wt. pct. Cu with various amounts of the grain refiner TiB2 added. Cylindrical samples were either cooled from the top, or the bottom. Several trends in the data stand out. In attempting to model these experiments, concentrating on experiments that show clear trends or differences is recommended.

Modal acoustic emission (AE) has proven to be an excellent technique to monitor damage accumulation in ceramic matrix composites. In this study, AE was used to monitor tensile load-unload-reload hysteresis tests for a variety of C fiber reinforced, SiC matrix composites. C/SiC composites were reinforced with T300 and IM7 fibers, had C, multilayer, or pseudo-porous C interphases, and had chemical vapor infiltrated SiC or melt-infiltrated SiC matrices. All of the composites exhibited considerable AE during testing. The extent and nature of the AE activity will be analyzed and discussed in light of matrix cracking and the variety of composite constituents. It is hoped that understanding the nature of stress dependent damage accumulation in these materials can be of use in life modeling for these types of composites.

Modal acoustic emission (AE) was used to monitor the acoustic activity during room temperature and elevated temperature c-coupon tests for a variety of SiC/SiC systems including composites containing Sylramic (trademark), ZMI (trademark), or Hi-Nicalon (trademark) fibers with melt-infiltrated or polymer-infiltrated SiC matrices. Modal AE proved excellent at monitoring matrix cracking in the curved portion of the C-coupon specimen with increasing load. This included the load at which the first AE event occurred and the location of AE events during the test that were, presumably, caused by the formation and growth of interlaminar cracks and, at higher loads, transverse cracks. Graphical techniques were employed to estimate the load for first AE. It was determined that for this test with these material systems, the first AE could be estimated within the load range bounded by the load at which initial deviation from linearity of the load-displacement curve occurs and the load where the 98% offset of the linear regression fit intercepted the load-displacement curve. The calculation of interlaminar tensile (ILT) stress from the load for first AE was determined for all the systems. Ultimate ILT strength usually corresponded to ILT stress determined from the ultimate load to failure of the C-coupon test, which was considerably higher than the first cracking stress.

A primarily silica-containing material with traces of organic compounds, as well as aluminum and calcium additions, was exposed to a Mach 0.3 burner rig at atmospheric pressure using jet fuel. The sample was exposed for 5 continuous hours at 1370 C. Post exposure x-ray diffraction analyses indicate formation of cristobalite, quartz, NiO and Spinel (Al(Ni)CR2O4). The rig hardware is composed of a nickel-based superalloy with traces of Fe. These elements are indicated in the energy dispersive spectroscopy (EDS) results. This material was studied as a candidate for high temperature applications under an engine technology program.

To increase performance and durability of high temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplied on most carbon fibers are not compatible with polyimides. This study was an extension of prior work characterizing the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) with typical fluorinated polyimide resins, such as PMR-II-50. A continuous desizing system which utilizes environmentally friendly chemical- mechanical processes was developed for tow level fiber and the processes were optimized based on weight loss behavior, surface elemental composition (XPS) and morphology (FE-SEM) analyses, and residual tow strength of the fiber, and the similar approaches have been applied on carbon fabrics. Both desized and further treated with a reactive finish were investigated for the composite reinforcement. The effects of desizing and/or subsequent surface retreatment on carbon fiber on composite properties and performance including fiber-matrix interfacial mechanical properties, thermal properties and blistering onset behavior will be discussed in this presentation.

Combustion tests on SiC/SiC CMC (Ceramic Matrix Composite) components were performed in an aircraft combustion environment using the Rich-burn, Quick-quench, Lean-burn (RQL) sector rig. SiC/SiC fasteners were used to attach several of these components to the metallic rig structure. The effect of combustion exposure on the fastener material was characterized via microstructural examination. Fasteners were also destructively tested, after combustion exposure, and the failure loads of fasteners exposed in the sector rig were compared to those of as-manufactured fasteners. Combustion exposure reduced the fastener failure load by 50% relative to the as-manufactured fasteners for exposure times ranging from 50 to 260 hours. The fasteners exposed in the combustion environment demonstrated failure loads that varied with failure mode. Fasteners that had the highest average failure load, failed in the same manner as the unexposed fasteners.

Current environmental barrier coatings (EBCs) for silicon-based ceramics consist of a bond coat and a top coat. Mullite bond coat modified by adding low CTE glass ceramics, such as BSAS (xBaO.1xSrO.Al2O3.2SiO2) or CAS (CaO.Al2O3.2SiO2), was developed in the NASA Enabling Propulsion Materials (EPM) Program. EBCs based on mullite+CAS bond coat were characterized using high steam thermal cycling test and high steam isothermal thermogravemitry (TGA) at 1225 C - 13,000 C. The Mullite+CAS bond coat showed far superior durability compared to mullite bond coat, due to enhanced crack resistance. A BSAS top coat provided further improved durability compared to EBCs with a yttria-stabilized zirconia (YSZ) top coat. Still further improvement in the durability was achieved by adding a silicon bond coat between the mullite and the substrate. However, the silicon/mullite+CAS/BSAS EBC showed inferior long-term durability compared to the current state-of-the art EBC (silicon/mullite+BSAS/BSAS EBC), presumably due to the higher CAS-silica chemical reactivity.

A computer controlled, pulsed chemical vapor infiltration (CVI) system has been developed to deposit BN from a liquid borazine (B3N3H6) source, as well as silicon doped BN coatings using borazine and a silicon source, into 2-D woven ceramic fabric preforms. The coating process was evaluated as a function of deposition temperature, pressure, and precursor flow rate. Coatings were characterized by field emission scanning electron microscopy, electron dispersive spectroscopy and Auger spectroscopy. By controlling the reactant feed ratios, Si incorporation could be controlled over the range of 6-24 atomic percent.

Carbon fiber reinforced high temperature polymer matrix composites (PMC) have been extensively investigated as potential weight reduction replacements of various metallic components in next generation high performance propulsion rocket engines. The initial phase involves development of comprehensive composite material-process-structure-design-property in-service performance correlations and database, especially for a high stiffness facesheet of various sandwich structures. Overview of the program plan, technical approaches and current multi-team efforts will be presented. During composite fabrication, it was found that the two large volume commercial prepregging methods (hot-melt vs. solution) resulted in considerably different composite cure behavior. Details of the process-induced physical and chemical modifications in the prepregs, their effects on composite processing, and systematic cure cycle optimization studies will be discussed. The combined effects of prepregging method and cure cycle modification on composite properties and isothermal aging performance were also evaluated.

Environment conscious, biomorphic ceramics have been fabricated from pine and jelutong wood precursors. A carbonaceous preform is produced through wood pyrolysis and subsequent infiltration with oxides (ZrO2 sols) and liquid silicon to form ceramics. These biomorphic ceramics show a wide variety of microstructures, densities, and hardness behavior that are determined by the type of wood and infiltrants selected.

The infrared (IR) transmittance and reflectance of translucent thermal barrier coatings (TBCs) have important implications for both the performance of these coatings as radiation barriers and emitters as well as affecting measurements of TBC thermal conductivity, especially as TBCs are being pushed to higher temperatures. In this paper, the infrared spectral directional-hemispherical transmittance and reflectance of plasma-sprayed 8wt% yttria-stabilized zirconia (8YSZ) TBCs are reported. These measurements are compared to those for single crystal YSZ specimens to show the effects of the plasma-sprayed coating microstructure. It is shown that the coatings exhibit negligible absorption at wavelengths up to about 5 micrometers, and that internal scattering rather than surface reflections dominates the hemispherical reflectance. The translucent nature of the 8YSZ TBCs results in the absorptance/emittance and reflectance of TBC-coated substrates depending on the TBC thickness, microstructure, as well as the radiative properties of the underlying substrate. The effects of these properties on TBC measurements and performance are discussed.

Thermally sprayed coatings are being studied and developed as methods of enabling lightweight composites to be used more extensively as structural components in propulsion applications in order to reduce costs and improve efficiency through weight reductions. The primary goal of this work is the development of functionally graded material [FGM] polymer/metal matrix composite coatings to provide improved erosion/oxidation resistance to polyimide-based polymer matrix composite [PMC] substrates. The goal is to grade the coating composition from pure polyimide, similar to the PMC substrate matrix on one side, to 100 % WC-Co on the other. Both step-wise and continuous gradation of the loading of the WC-Co reinforcing phase are being investigated. Details of the coating parameter development will be presented, specifically the high velocity oxy-fuel [HVOF] combustion spraying of pure PMR-11 matrix material and layers of various composition PMR-II/WC-Co blends onto steel and PMR-15 composite substrates. Results of the HVOF process optimization, microstructural characterization, and analysis will be presented. The sprayed coatings were evaluated using standard metallographic techniques - optical and scanning electron microscopy [SEM]. An SEM + electron dispersive spectroscopy [EDS] technique has also been used to confirm retention of the PMR-II component. Results of peel/butt adhesion testing to determine adhesion will also be presented.

Three silicon nitride materials were exposed to dry oxygen flowing at 0.44 cm/s at temperatures between 1200 and 1400 C. Reaction kinetics were measured with a continuously recording microbalance. Parabolic kinetics were observed. When the same materials were exposed to a 50% H2O - 50% O2 gas mixture flowing at 4.4 cm/s, all three types exhibited paralinear kinetics. The material is oxidized by water vapor to form solid silica. The protective silica is in turn volatilized by water vapor to form primarily gaseous Si(OH)4. Nonlinear least squares analysis and a paralinear kinetic model were used to determine both parabolic and linear rate constants from the kinetic data. Volatilization of the protective silica scale can result in accelerated consumption of Si3N4. Recession rates under conditions more representative of actual combustors are compared to the furnace data.

The phase contents and morphology of a ZrO2 fiber coating deposited at 1050 C on Hi-Nicalon(Tm) by chemical vapor deposition were examined as a function of deposition time from 5 to 120 min. The morphological evolution in the ZrO2 coating was correlated to the development of delamination within the ZrO2 coating. The delamination appears to occur as a result of: (1) continuous formation of tetragonal ZrO2 nuclei on the deposition surface; (2) martensitic transformation of the tetragonal phase to a monoclinic phase upon reaching a critical grain size; and (3) development of significant compressive hoop stresses due to the volume dilation associated with the transformation. Our observations suggest that it will be of critical importance to further understand and eventually control the nucleation and grain growth behavior of CVD ZrO2 and its phase transformation behavior for its potential applications for composites.

Fiber reinforced ceramic matrix composites are under active consideration for use in a wide variety of high temperature applications within the aeronautics, energy, process, and nuclear industries. The engineering designs require fabrication and manufacturing of complex shaped parts. In many instances, it is more economical to build up complex shapes by Joining simple geometrical shapes. Thus, joining and attachment have been recognized as enabling technologies for successful utilization of ceramic components in various demanding applications. In this presentation, various challenges and opportunities in design, fabrication, and testing of high temperature joints in ceramic matrix composites will be presented. Various joint design philosophies and design issues in joining of composites will be discussed along with an affordable, robust ceramic joining technology (ARCJoinT). A wide variety of ceramic composites, in different shapes and sizes, have been joined using this technology. Microstructure and mechanical properties of joints will be reported. Current status of various ceramic joining technologies and future prospects for their applications will also be discussed.

In this paper we describe the Knudsen cell technique for measurement of thermodynamic activities in alloys. Numerous experimental details must be adhered to in order to obtain useful experimental data. These include introduction of an in-situ standard, precise temperature measurement, elimination of thermal gradients, and precise cell positioning. Our first design is discussed and some sample data on Ti-Al alloys is presented. The second modification and associated improvements are also discussed.

Fraction-order viscoelastic (FOV) material models have been proposed and studied in 1D since the 1930's, and were extended into three dimensions in the 1970's under the assumption of infinitesimal straining. It was not until 1997 that Drozdov introduced the first finite-strain FOV constitutive equations. In our presentation, we shall continue in this tradition by extending the standard, FOV, fluid and solid, material models introduced in 1971 by Caputo and Mainardi into 3D constitutive formula applicable for finite-strain analyses. To achieve this, we generalize both the convected and co-rotational derivatives of tensor fields to fractional order. This is accomplished by defining them first as body tensor fields and then mapping them into space as objective Cartesian tensor fields. Constitutive equations are constructed using both variants for fractional rate, and their responses are contrasted in simple shear. After five years of research and development, we now possess a basic suite of numerical tools necessary to study finite-strain FOV constitutive equations and their iterative refinement into a mature collection of material models. Numerical methods still need to be developed for efficiently solving fraction al-order integrals, derivatives, and differential equations in a finite element setting where such constitutive formulae would need to be solved at each Gauss point in each element of a finite model, which can number into the millions in today's analysis.

We discuss an Adams-type predictor-corrector method for the numerical solution of fractional differential equations. The method may be used both for linear and for nonlinear problems, and it may be extended to multi-term equations (involving more than one differential operator) too.

The behavior of acoustic waves produced by microfracture events and from pencil lead breaks was studied for two different silicon carbide fiber-reinforced silicon carbide matrix composites. The two composite systems both consisted of Hi-Nicalon (trademark) fibers and carbon interfaces but had different matrix compositions that led to considerable differences in damage accumulation and acoustic response. This behavior was primarily due to an order of magnitude difference in the interfacial shear stress for the two composite systems. Load/unload/reload tensile tests were performed and measurements were made over the entire stress range in order to determine the stress-dependence of acoustic activity for increasing damage states. It was found that using the extensional wave velocities from acoustic emission (AE) events produced from pencil lead breaks performed outside of the transducers enabled accurate measurements of the stiffness of the composite. The extensional wave velocities changed as a function of the damage state and the stress where the measurement was taken. Attenuation for AE waveforms from the pencil lead breaks occurred only for the composite possessing the lower interfacial shear stress and only at significantly high stresses. At zero stress after unloading from a peak stress, no attenuation occurred for this composite because of crack closure. For the high interfacial stress composite no attenuation was discernable at peak or zero stress over the entire stress-range of the composite. From these observations, it is believed that attenuation of AE waveforms is dependent on the magnitude of matrix crack opening.

A review of NASA GRCs Higher Operating Temperature Propulsion Components Project (HOTPC) on polymer matrix composites (PMCs) will be described. The summary includes research from NASA GRC in-house, university and industry's cooperative programs. Current research emphasis focuses on developing high temperature PMCs used in rapidly heated structures, erosion coatings for PMCs, nano-materials compatible with polyimide resins, and development of more durable high temperature PMCs.

A rocket engine's combustion chamber is lined with material that is highly conductive to heat in order to dissipate the huge thermal load (evident in a white-hot exhaust plume). Because of its thermal conductivity copper is the best choice of liner material. However, the mechanical properties of pure copper are inadequate to withstand the high stresses, hence, copper alloys are needed in this application. But copper and its alloys are prone to oxidation and related damage, especially "blanching" (an oxidation-reduction mode of degradation). The space shuttle main engine combustion chamber is lined with a Cu-Ag-Zr alloy, "NARloy-Z", which exhibits blanching. A superior liner is being sought for the next generation of RLVs (Reusable Launch Vehicles) It should have improved mechanical properties and higher resistance to oxidation and blanching, but without substantial penalty in thermal conductivity. GRCop84, a Cu-8Cr-4Nb alloy (Cr2Nb in Cu matrix), developed by NASA Glenn Research Center (GRC) and Case Western Reserve University, is a prime contender for RLV liner material. In this study, the oxidation resistance of GRCop-84 and other related/candidate copper alloys are investigated and compared

Room temperature debonding and sliding of La-Monazite coated fibers is assessed using a composite with a polycrystalline alumina matrix and fibers of several different single crystal (mullite, sapphire) and directionally solidified eutectic (Al2O3/Y3Al5O12 and Al2O3/Y-ZrO2) compositions. These fibers provide a range of residual stresses and interfacial roughnesses. Sliding occurred over a debond crack at the fiber-coating interface when the sliding displacement and surface roughness were relatively small. At large sliding displacements with relatively rough interfaces, the monazite coatings were deformed extensively by fracture, dislocations and occasional twinning, whereas the fibers were undamaged. Dense, fine-grained (10 nm) microstructures suggestive of dynamic recrystallization were also observed in the coatings. Frictional heating during sliding is assessed. The possibility of low temperature recrystallization is discussed in the light of the known resistance of monazite to radiation damage. The ability of La-Monazite to undergo plastic deformation relatively easily at low temperatures may be enabling for its use as a composite interface.

At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

Silicon carbide (SiC) and silicon nitride (Si3N4) are proposed for applications in high temperature combustion environments containing water vapor. Both SiC and Si3N4 react with water vapor to form a silica (SiO2) scale. It is therefore important to understand the durability of SiC, Si3N4 and SiO2 in water vapor. Thermogravimetric analyses, furnace exposures and burner rig results were obtained for these materials in water vapor at temperatures between 1100 and 1450 C and water vapor partial pressures ranging from 0.1 to 3.1 atm. First, the oxidation of SiC and Si3N4 in water vapor is considered. The parabolic kinetic rate law, rate dependence on water vapor partial pressure, and oxidation mechanism are discussed. Second, the volatilization of silica to form Si(OH)4(g) is examined. Mass spectrometric results, the linear kinetic rate law and a volatilization model based on diffusion through a gas boundary layer are discussed. Finally, the combined oxidation and volatilization reactions, which occur when SiC or Si3N4 are exposed in a water vapor-containing environment, are presented. Both experimental evidence and a model for the paralinear kinetic rate law are shown for these simultaneous oxidation and volatilization reactions.

Silicon carbide based, environment friendly, biomorphic ceramics have been fabricated by the pyrolysis and infiltration of natural wood (maple and mahogany) precursors. This technology provides an eco-friendly route to advanced ceramic materials. These biomorphic silicon carbide ceramics have tailorable properties and behave like silicon carbide based materials manufactured by conventional approaches. The elastic moduli and fracture toughness of biomorphic ceramics strongly depend on the properties of starting wood preforms and the degree of molten silicon infiltration. Mechanical properties of silicon carbide ceramics fabricated from maple wood precursors indicate the flexural strengths of 3441+/-58 MPa at room temperature and 230136 MPa at 1350C. Room temperature fracture toughness of the maple based material is 2.6 +/- 0.2 MPa(square root of)m while the mahogany precursor derived ceramics show a fracture toughness of 2.0 +/- 0.2 Mpa(square root of)m. The fracture toughness and the strength increase as the density of final material increases. Fractographic characterization indicates the failure origins to be pores and chipped pockets of silicon.

The hydrolytic stability of high-temperature deposited Si-doped BN has been shown in the past to be superior in comparison to "pure" BN processed at similar or even higher temperatures. This type of material would be very desirable as a SiC/SiC composite interphase that is formed by chemical infiltration into multi-ply woven preform. However, due to rapid deposition on the preform outer surface at the high processing temperature, this has proven very difficult. To overcome this issue, single plies of woven fabric were infiltrated with Si-doped BN. Three composite panels of different SiC fiber types were fabricated with Si-doped BN interphases including Sylramic, Hi-Nicalon Type S and Sylramic-iBN fiber-types. The latter fiber-type possesses a thin in-situ grown BN layer on the fiber surface. High Si contents (approx. 7 to 10 a/o) and low oxygen contents (less than 1 a/o) were achieved. All three composite systems demonstrated reasonable debonding and sliding properties. The coated Sylramic fabric and composites were weak due to fiber degradation apparently caused during interphase processing by the formation of TiN crystals on the fiber surface. The Hi-Nicalon Type S composites with Si-doped BN interphase were only slightly weaker than Hi-Nicalon Type S composites with conventional BN when the strength on the load-bearing fibers at failure was compared. On the other hand, the Sylramic-iBN fabric and composites with Si-doped BN showed excellent composite and intermediate temperature stress-rupture properties. Most impressive was the lack of any significant interphase oxidation on the fracture surface of stress-ruptured specimens tested well above matrix cracking at 815C.

In recent years, NASA has embarked on several new and exciting efforts in the exploration and use of space. The successful accomplishment of many planned missions and projects is dependent upon the development and deployment of previously unproven propulsion systems. Key to many of the propulsion systems is the use of structural ceramics and ceramic matrix composites. In spite of their promise, a number of programmatic and technical hurdles remain before the potential of ceramic materials can be realized. A programmatic environment which focuses on relatively short term hardware demonstration programs precludes traditional longer term material's development efforts. The challenge oftentimes becomes one of engineering ceramics into proposed missions. This is dependent upon a fundamental understanding of processing, degradation and design issues unique to space vehicle design and operations. A review of the general missions and benefits of utilizing ceramics and ceramic matrix composites will be presented. The design parameters and operating conditions will be presented for both specific missions/vehicles and classes of components. Key technical challenges and opportunities are identified along with suggested paths for addressing them.

Montmorillonite clay was organically modified by co-exchange of an aromatic diamine and a primary alkyl amine. The clay was dispersed into a PMR (Polymerization of Monomer Reactants)-15 matrix and the glass transition temperature and thermal oxidative stability of the resulting nanocomposites were evaluated. PMR-15/ silicate nanocomposites were also investigated as a matrix material for carbon fabric reinforced composites. Dispersion of the organically modified silicate into the PMR-15 matrix enhanced the thermal oxidative stability, the flexural strength, flexural modulus, and interlaminar shear strength of the polymer matrix composite.

Ceramic Matrix Composites (CMCs) are attractive candidate aerospace materials due to their high specific strength, low density and high temperature capabilities. The National Aeronautics and Space Administration (NASA) is pursuing the use of CMC components in advanced Reusable Launch Vehicle (RLV) propulsion applications. Carbon fiber-reinforced silicon carbide (C/SiC) is the primary material of interest for a variety of RLV propulsion applications. These composites consist of high-strength carbon fibers and a high modulus, oxidation resistant matrix. For RLV propulsion applications, environmental durability will be critical. Two types of carbon fibers were processed with both standard (pyrolytic carbon) and novel (multilayer and pseudoporous) types of interface coatings as part of a study investigating various combinations of constituents. The benefit of protecting the composites with a surface sealant was also investigated. The strengths, durability in oxidizing environments, and microstructures of these developmental composite materials are presented. The novel interface coatings and the surface sealant show promise for protecting the carbon fibers from the oxidizing environment.

The paper develops a general theory for finite rubber viscoelasticity, and specifies it in the form, convenient for solving problems important for rubber, tire and space industries. Based on the quasi-linear approach of non-equilibrium thermodynamics, a general nonlinear theory has been developed for arbitrary nonisothermal deformations of viscoelastic solids. In this theory, the constitutive equations are presented as the sum of known equilibrium (rubber elastic) and non-equilibrium (liquid polymer viscoelastic) terms. These equations are then simplified using several modeling arguments. Stability constraints for the proposed constitutive equations are also discussed. It is shown that only strong ellipticity criteria are applicable for assessing stability of the equations governing viscoelastic solids.

High-temperature slow-crack growth of single crystal 10 wt% Cr2O3 - Al2O3 (nominal composition) fibers has been studied by tensile rupture experiments at 1400 C, under different stressing rates (0.5 to 41.5 MPa/s). Slow-crack growth (SCG) is less pronounced with increasing Cr2O3. Rupture stresses increased with the stressing rate from 397 MPa to 515 MPa, resulting in a SCG exponent, N=19. The Cr2O3 composition was analyzed by Energy Dispersed X-Ray Spectra (EDS) and fracture surfaces were studied by scanning electron microscopy (SEM). Results are compared with previous studies on 100-300 ppm Cr3(+) doped sapphire fibers and on commercial sapphire fibers.

Biomorphic SiC ceramics have been fabricated using different wood precursors. The evolution of volume, density and microstructure of the woods, carbon performs, and final SiC products are systematically studied in order to establish experimental guidelines that allow materials selection. The wood density is a critical characteristic, which results in a particular final SiC density, and the level of anisotropy in mechanical properties in directions parallel (axial) and perpendicular (radial) to the growth of the wood. The purpose of this work is to explore experimental laws that can help choose a type of wood as precursor for a final SiC product, with a given microstructure, density and level of anisotropy. Preliminary studies of physical properties suggest that not only mechanical properties are strongly anisotropic, but also electrical conductivity and gas permeability, which have great technological importance.

GRCop-84 is a high strength-high conductivity copper-based alloy developed at NASA Glenn Research Center for combustion chamber liners of regeneratively cooled rocket engines. It also has promise for other high heat flux applications operating at temperatures up to 700 C (1292 F) and potentially higher. The alloy must be made by powder metallurgy techniques such as gas atomization. Slower cooling rates such as those experienced during casting do not develop a proper microstructure. Once made into powder, the alloy exhibits excellent processability using conventional consolidation and forming techniques, e.g., extrusion and rolling. GRCop-84 is strengthened by a combination of dispersion and precipitation strengthening by fine (50-500 nanometer (2-20 microinch)) Cr2Nb particles and Hall-Petch strengthening from a fine copper grain size. The presence of a high volume fraction of particles prevents grain boundary sliding at high temperatures and contributes to the alloy's overall good high temperature mechanical properties. Maximum thermal conductivity is obtained by using two alloying elements (Cr, Nb) with limited solubility in solid Cu that form a high temperature intermetallic compound with an even lower solid solubility. The resulting matrix of the alloy is nearly pure copper. The limited solubility also minimizes Cr2Nb particle coarsening at elevated temperatures and enhances microstructural and mechanical property stability. Further enhancement of the microstructural stability is obtained by using a high volume fraction (approx. 14 vol.%) of Cr2Nb particles that effectively pin grain growth.

The Advanced High-Temperature Engine Materials Technology Program is described in terms of its research initiatives and its goal of developing propulsion systems for civil aeronautics with low levels of noise, pollution, and fuel consumption. The program emphasizes the analysis and implementation of structural materials such as polymer-matrix composites in fans, casings, and engine-control systems. Also investigated in the program are intermetallic- and metal-matrix composites for uses in compressors and turbine disks as well as ceramic-matrix composites for extremely high-temperature applications such as turbine vanes.

NASA's 'HITEMP' program has been charged with development of propulsion systems technologies for next-generation civil and military aircraft, stressing high-temperature/low-density composites. These encompass polymer-matrix composites for fans, ducts, and compressor cases, and intermetallic and metallic alloy matrix composites for applications in turbine disks, blades, and vanes, and ceramic matrix composites for combustors and turbines. An overview is presented of program concerns and achievements to date.

An evaluation is made of the state-of-the-art and foreseeable development prospects in high temperature engineering materials applicable to advanced heat engines and other aerothermodynamically affected structures. Attention is given to monocrystal- and microcrystal-producing metal solidification processes, soft oxide and chemically stable fluoride high temperature solid lubricants, polyimide and other high temperature polymers for propulsion system applications, high strength/toughness ceramics for heat engine structural components, thermal barrier coatings, and metal-matrix composites employing refractory matrices as well as reinforcing fibers.