Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

T-300 carbon fibers and T-300 carbon fiber reinforced silicon carbide composites (C/SiC) were oxidized in flowing reduced oxygen partial pressure environments at a total pressure of one atmosphere (0.5 atm O2, 0.05 atm O2 and 0.005 atm O2, balance argon). Experiments were conducted at four temperatures (816deg, 1149deg, 1343deg, and 1538 C). The oxidation kinetics were monitored using thermogravimetric analysis. T-300 fibers were oxidized to completion for times between 0.6 and 90 h. Results indicated that fiber oxidation kinetics were gas phase diffusion controlled. Oxidation rates had an oxygen partial pressure dependence with a power law exponent close to one. In addition, oxidation rates were only weakly dependent on temperature. The C/SiC coupon oxidation kinetics showed some variability, attributed to differences in the number and width of cracks in the SiC seal coat. In general, weight losses were observed indicating oxidation of the carbon fibers dominated the oxidation behavior. Low temperatures and high oxygen pressures resulted in the most rapid consumption of the carbon fibers. At higher temperatures, the lower oxidation rates were primarily attributed to crack closure due to SiC thermal expansion, rather than oxidation of SiC since these reduced rates were observed even at the lowest oxygen partial pressures where SiC oxidation is minimal

Paralinear Oxidation of CVD SiC in Water Vapor

The oxidation kinetics of CVD SiC were monitored by thermogravimetric analysis (TGA) in a 50% H2O/50% O2 gas mixture flowing at 4.4 cm/s for temperatures between 1200 and 1400 C. Paralinear weight change kinetics were observed as the water vapor oxidized the SiC and simultaneously volatilized the silica scale. The long-term degradation rate of SiC is determined by the volatility of the silica scale. Rapid SiC surface recession rates were estimated from these data for actual aircraft engine combustor conditions

Stability of Materials in High Temperature Water Vapor: SOFC Applications

Solid oxide fuel cell material systems require long term stability in environments containing high-temperature water vapor. Many materials in fuel cell systems react with high-temperature water vapor to form volatile hydroxides which can degrade cell performance. In this paper, experimental methods to characterize these volatility reactions including the transpiration technique, thermogravimetric analysis, and high pressure mass spectrometry are reviewed. Experimentally determined data for chromia, silica, and alumina volatility are presented. In addition, data from the literature for the stability of other materials important in fuel cell systems are reviewed. Finally, methods for predicting material recession due to volatilization reactions are described

Oxidation of ZrB2 SiC TaSi2 Materials at Ultra High Temperatures

ZrB2 - 20v% SiC - 20v% TaSi2 was oxidized in stagnant air for ten minute cycles for times up to 100 minutes at 1627 C and 1927 C. The sample oxidized at 1627 C showed oxidation resistance better than that of the standard ZrB2 - 20v% SiC. The sample oxidized at 1927 C, however, showed evidence of liquid phase formation and complex oxidation products. The sample exposed at 1927 C was analyzed in detail by scanning electron microprobe and wavelength dispersive spectroscopy to understand the complex oxidation and melting reactions occurring during exposure. The as hot-pressed material shows the formation of a Zr(Ta)B2 phase in addition to the three phases in the nominal composition already noted. After oxidation, the TaSi2 in the matrix was completely reacted to form Ta(Zr)C. The layered oxidation products included SiO2, ZrO2, Ta2O5, and a complex oxide containing both Zr and Ta. Likely reactions are proposed based on thermodynamic phase stability and phase morphology

Characterizing novel transducers for high temperature thermal measurements using time domain thermoreflectance

Time domain thermoreflectance (TDTR) is an optical pump-probe technique used to measure thermal properties of material systems. Samples are typically coated with a thin metal transducer layer, such as aluminum or gold. At temperatures approaching 2,000°C, most transducers become limited by melting temperature, chemical reactions, or other phase transitions. Hafnium Nitride (HfN) is a conductive ceramic with a melting point exceeding 3300°C. It is estimated to have a constant reflectance of 17% and 64% at 400nm and 800nm, respectively. Iridium (Ir) has a melting temperature of 2,447°C. Our work characterizes the thermal properties of HfN and Ir, respectively, and investigates their viability as transducers for TDTR measurements at high temperatures to the point of thermodynamically-driven failure. Thermal conductivity is measured as a function of temperature for HfN and Ir, respectively, and thermoreflectance coefficients are measured and compared to that of typical transducers. Thermal conductivities for MgO, Al2O3, SiO2, and diamond substrates are measured using the aforementioned thin films as transducers to test material reliability. Results and implications for future high temperature TDTR measurements are discussed. This work is supported by the U.S. Office of Naval Research MURI program (grant No. N00014-15- 1-2863)

Phonon scattering mechanisms contributing to the low thermal conductivities of entropy stabilized oxides and high entropy carbides

The phonon thermal conductivity of solids is intimately related to any changes in atomic scale periodicity. As a classic example, the phonon thermal conductivity of alloys can be greatly reduced as compared to that of the corresponding non-alloy parent materials. However, the improved mechanical properties and environmental stability of alloyed materials makes these multi-atom solids ideal for a wide variety of applications. In this sense, entropy stabilized oxides and high entropy carbides are promising new materials that have potential to withstand extreme environments consisting of high temperatures and pressures. In these novel materials, thermal characterization is essential for understanding and predicting performance at elevated temperatures, as the presence of multi atomic species (5+ different atoms) in these solid solutions could lead to drastically modified phonon scattering rates and thermal conductivities. In this talk, we present recent measurements and molecular dynamics simulations on multiple atom alloys, including entropy stabilized oxides and high entropy diborides. We use time-domain thermoreflectance (TDTR), and optical pump-probe technique, to measure the thermal conductivity of these various systems. We also demonstrate the ability to extend TDTR measurements to temperatures above 1000 deg. C. The TDTR measurements show drastic reductions in the thermal conductivity of these crystalline solid solution materials, approaching values of the amorphous phases. These reductions in thermal conductivity can not be explained by phonon-mass scattering alone. Thus, to investigate the nature of the reduction in thermal conductivity of these multi-atom solid solutions, we turn to classical molecular dynamics simulations. In agreement with the Klemens’ perturbation theory, the thermal conductivity reduction due to mass scattering alone is found to reach a critical point, whereby adding more impurity atoms in the solid solution does not reduce the thermal conductivity. A further decrease in thermal conductivity requires a change in local strain-field, which together with mass defect scattering can lead to ultralow thermal conductivities in solid solutions, which surpasses the theoretical minimum limit of the corresponding amorphous phases. These simulations qualitatively agree well with our experimental measurements, and add insight into the nature of phonon scattering in entropy stabilized materials. This work is supported by the U.S. Office of Naval Research MURI program (grant No. N00014-15-1-2863

Movement Behavior of High-Heeled Walking: How Does the Nervous System Control the Ankle Joint during an Unstable Walking Condition?

The human locomotor system is flexible and enables humans to move without falling even under less than optimal conditions. Walking with high-heeled shoes constitutes an unstable condition and here we ask how the nervous system controls the ankle joint in this situation? We investigated the movement behavior of high-heeled and barefooted walking in eleven female subjects. The movement variability was quantified by calculation of approximate entropy (ApEn) in the ankle joint angle and the standard deviation (SD) of the stride time intervals. Electromyography (EMG) of the soleus (SO) and tibialis anterior (TA) muscles and the soleus Hoffmann (H-) reflex were measured at 4.0 km/h on a motor driven treadmill to reveal the underlying motor strategies in each walking condition. The ApEn of the ankle joint angle was significantly higher (p<0.01) during high-heeled (0.38±0.08) than during barefooted walking (0.28±0.07). During high-heeled walking, coactivation between the SO and TA muscles increased towards heel strike and the H-reflex was significantly increased in terminal swing by 40% (p<0.01). These observations show that high-heeled walking is characterized by a more complex and less predictable pattern than barefooted walking. Increased coactivation about the ankle joint together with increased excitability of the SO H-reflex in terminal swing phase indicates that the motor strategy was changed during high-heeled walking. Although, the participants were young, healthy and accustomed to high-heeled walking the results demonstrate that that walking on high-heels needs to be controlled differently from barefooted walking. We suggest that the higher variability reflects an adjusted neural strategy of the nervous system to control the ankle joint during high-heeled walking

Solubility of Rock in Steam Atmospheres of Planets

Extensive experimental studies show that all major rock-forming elements (e.g., Si, Mg, Fe, Ca, Al, Na, K) dissolve in steam to a greater or lesser extent. We use these results to compute chemical equilibrium abundances of rocky-element-bearing gases in steam atmospheres equilibrated with silicate magma oceans. Rocky elements partition into steam atmospheres as volatile hydroxide gases (e.g., Si(OH)4, Mg(OH)2, Fe(OH)2, Ni(OH)2, Al(OH)3, Ca(OH)2, NaOH, KOH) and via reaction with HF and HCl as volatile halide gases (e.g., NaCl, KCl, CaFOH, CaClOH, FAl(OH)2) in much larger amounts than expected from their vapor pressures over volatile-free solid or molten rock at high temperatures expected for steam atmospheres on the early Earth and hot rocky exoplanets. We quantitatively compute the extent of fractional vaporization by defining gas/magma distribution coefficients and show that Earth's subsolar Si/Mg ratio may be due to loss of a primordial steam atmosphere. We conclude that hot rocky exoplanets that are undergoing or have undergone escape of steam-bearing atmospheres may experience fractional vaporization and loss of Si, Mg, Fe, Ni, Al, Ca, Na, and K. This loss can modify their bulk composition, density, heat balance, and interior structure