QuynhGiao N. Nguyen

Oxidation of Ultrahigh Temperature Ceramics in Water Vapor

Ultra high temperature ceramics (UHTCs) including HfB2 + SiC (20% by volume), ZrB2 + SiC (20% by volume) and ZrB2 + SiC (14% by volume) + C (30% by volume) have historically been evaluated as reusable thermal protection systems for hypersonic vehicles. This study investigates UHTCs for use as potential combustion and aeropropulsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline comparison. Weight change measurements, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results will be compared with tests ran in static air at temperatures of 1327, 1627, and 1927 C. Oxidation comparisons will also be made to the study by Tripp. A small number of high pressure burner rig (HPBR) results at 1100 and 1300 C will also be discussed. Specific weight changes at all three temperatures along with the SIC results are shown. SiC weight change is negligible at such short duration times. HB2 + SiC (HS) performed the best out of all the tested UHTCS for all exposure temperatures. ZrB2 + Sic (ZS) results indicate a slightly lower oxidation rate than that of ZrBl + SiC + C (ZCS) at 1200 and 1400 C, but a clear distinction can not be made based on the limited number of tested samples. Scanning electron micrographs of the cross-sections of all the UHTCs were evaluated. A representative area for HS is presented at 1400 C for 26 hours which was the composition with the least amount of oxidation. A continuous SiO2 scale is present in the outer most edge of the surface. An image of ZCS is presented at 1400 C for 10 hours, which shows the most degradation of all the compositions studied. Here, the oxide surface is a mixture of ZrSiO4, ZrO2 and SO2.

A New Apparatus to Evaluate Lubricants for Space Applications: The Spiral Orbit Tribometer (SOT)

Lubricants used in space mechanisms must be thoroughly tested prior to their selection for critical applications. Traditionally, two types of tests have been used: accelerated and full-scale. Accelerated tests are rapid, economical, and provide useful information for gross screening of candidate lubricants. Although full-scale tests are more believable, because they mimic actual spacecraft conditions, they are expensive and time consuming. The spiral orbit tribometer compromises between the two extremes. It rapidly determines the rate of tribochemically induced lubricant consumption, which leads to finite test times, under realistic rolling/pivoting conditions that occur in angular contact bearings.

The Effect of Stress and TiC Coated Balls on Lifetime of a Perfluoropolyalkylether Using a Vacuum Rolling Contact Tribometer

A vacuum spiral orbit tribometer (SOT) was used to determine the relative lifetimes of a branched perfluoropolyalkylether (PFPAE) on 440C stainless steel. The effect of varying the mean Hertzian stress (0.75, 1.0, 1.5 and 2.0 GPa) and the use of TiC coated balls on lubricant lifetime was studied. Other conditions included: ∼100 rpm, ∼50 μg of lubricant, an initial vacuum level of < 1.3 × 10−6 Pa (< 1.0 × 10−8 Torr), and room temperature (∼23 °C). Increasing the mean Hertzian stress from 0.75 to 2.0 GPa results in an exponential decrease in lubricant lifetime for both material combinations. However, substituting a TiC ball for the 440C ball quadrupled lifetime at low stress levels (0.75 and 1.0 GPa) and doubled life at higher stresses (1.5 and 2.0 GPa). The reduced reactivity of the TiC surface with the PFPAE lubricant is considered to be the reason for this enhancement. Decreasing lifetime with increasing stress levels correlated well with energy dissipation calculations. Presented as a Society of Tribologists and Lubrication Engineers Paper at the ASME/STLE Tribology Conference in Seattle, Washington, October 1–4, 2000

Volatility and Wear Characteristics of a Variety of Liquid Lubricants for Space Applications

The vapor pressures and wear characteristics are critical properties for liquid lubricants to assure long-term reliability and performance in space applications. Vapor pressures, obtained using a Knudsen cell technique, and wear properties, obtained using a vacuum four-ball apparatus, were measured for a series of unformulated liquid lubricants. These included: two multiply alkylated cyclopentanes (MACs) (X-1000 and X-2000), two linear perfluoropolyalkylethers (PFPAEs) (Z-25 and 815Z), and four silahydrocarbons (a tri-, a tetra- and two pentas). Vapor pressures were measured at three elevated temperatures (423, 448 and 498K) and extrapolated to room temperature 298K. The lowest 298K vapor pressure of 5.7 × 10−10 Pa, was obtained with the PFPAE fluid (815Z) and the highest value with the low molecular weight MAC (X-1000) at 3.6 × 10−7 Pa. In addition, vacuum wear rates were determined for some of the lubricants. The lowest wear rates (approximately 3 × 10−11 mm3 lmm) were observed for three of the silahydrocarbons while the highest wear rates (approximately 2 × 10−9 mm3 lmm) were observed with the two PFPAE fluids (Z-25 and 815Z). The MAC (X-2000) yielded a wear rate of about 10−10 mm lmm. The results indicated that the silahydrocarbon class of liquid lubricants offers the better potential for space applications. Presented at the 55th Annual Meeting Nashville, Tennessee May 7–11, 2000

Computational and Experimental Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

Gaseous titanium hydroxide and oxyhydroxide species were studied with quantum chemical methods. The results are used in conjunction with an experimental transpiration study of titanium dioxide (TiO2) in water vapor-containing environments at elevated temperatures to provide a thermodynamic description of the Ti(OH)4(g) and TiO(OH)2(g) species. The geometry and harmonic vibrational frequencies of these species were computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. For the OH bending and rotation, the B3LYP density functional theory was used to compute corrections to the harmonic approximations. These results were combined to determine the enthalpy of formation. Experimentally, the transpiration method was used with water contents from 0 to 76 mol % in oxygen or argon carrier gases for 20-250 h exposure times at 1473-1673 K. Results indicate that oxygen is not a key contributor to volatilization, and the primary reaction for volatilization in this temperature range is TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods using the thermal functions derived from the theoretical calculations. The third law enthalpy of formation at 298.15 K for TiO(OH)2(g) at 298 K was -838.9 ± 6.5 kJ/mol, which compares favorably to the theoretical calculation of -838.7 ± 25 kJ/mol. We recommend the experimentally derived third law enthalpy of formation at 298.15 K for TiO(OH)2, the computed entropy of 320.67 J/mol·K, and the computed heat capacity [149.192 + (-0.02539)T + (8.28697 × 10-6)T2 + (-15614.05)/T + (-5.2182 × 10-11)/T2] J/mol-K, where T is the temperature in K.