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Opila, Elizabeth J.

Publications and source records attributed to Opila, Elizabeth J..

At least 19 records

Holistic comparison of environmental barrier coating material candidates through design of a figure of merit

The first figure of merit for environmental barrier coating (EBC) materials was designed through a ranking system for material properties pertaining to established EBC failure modes in service. Seven past, present, and novel EBC candidate materials were used in the figure of merit design: SiO 2 , Ba 0.75 Sr 0.25 Al 2 Si 2 O 8 (BSAS), HfSiO 4 , Yb 2 Si 2 O 7 , Yb 2 SiO 5 , Yb 2 O 3 , and YbPO 4 . Utilizing compiled data from the literature, the presented figure of merit verified Yb 2 Si 2 O 7 as the state-of-the-art candidate with optimal EBC properties and inferred that YbPO 4 should be considered as a potentially viable EBC material candidate. Further, the figure of merit allows for a holistic comparison of EBC candidates and informs experimental and computational search efforts for next-generation complex EBCs. Clear knowledge gaps found through this work include CaO–MgO–Al 2 O 3 –SiO 2 (CMAS)-resistant coatings, EBC lifetimes before delamination, and oxidant diffusion rates in relevant EBC microstructures. It was shown that while some materials show promise for solving a single key failure mode for EBCs (i.e., CMAS reactivity), a community-wide goal should be placed on materials development to achieve acceptable resistance against all major failure modes, which are interconnected. Novel compositionally complex EBC materials, in addition to layered EBC architectures, show promise for the optimization of material properties for long-lifetime EBCs in combustion environments.

36 MATERIALS SCIENCE↗

Phase stability and tensorial thermal expansion properties of single to high-entropy rare-earth disilicates

Temperature limitations in nickel-base superalloys have resulted in the emergence of SiC-based ceramic matrix composites as a viable replacement for gas turbine components in aviation applications. Higher operating temperatures allow for reduced fuel consumption but present a materials design challenge related to environmental degradation. Rare-earth disilicates (RE 2 Si 2 O 7 ) have been identified as coatings that can function as environmental barriers and minimize hot component degradation. In this work, single- and multiple-component rare-earth disilicate powders were synthesized via a sol-gel method with compositions selected to exist in the monoclinic C 2/m phase (β phase). Phase stability in multiple cation compositions was shown to follow a rule of mixtures and the C 2/m phase could be realized for compositions that contained up to 25% dysprosium, which typically only exists in a triclinic, P $\bar1$, phase. All compositions exhibited phase stability from room temperature to 1200°C as assessed by X-ray diffraction. The thermal expansion tensors for each composition were determined from high-temperature synchrotron X-ray diffraction and accompanying Rietveld refinements. It was observed that ytterbium-containing compositions had larger changes in the α 31 shear component with increasing temperature that led to a rotation of the principal axes. Principal axes rotation of up to 47° were observed for ytterbium disilicate. The results suggest that microstructure design and crystallographic texture may be essential future avenues of investigation to ensure thermo-mechanical robustness of rare-earth disilicate environmental barrier coatings.

36 MATERIALS SCIENCE↗

Observation of solid-state bidirectional thermal conductivity switching in antiferroelectric lead zirconate (PbZrO 3 )

Materials with tunable thermal properties enable on-demand control of temperature and heat flow, which is an integral component in the development of solid-state refrigeration, energy scavenging, and thermal circuits. Although gap-based and liquid-based thermal switches that work on the basis of mechanical movements have been an effective approach to control the flow of heat in the devices, their complex mechanisms impose considerable costs in latency, expense, and power consumption. As a consequence, materials that have multiple solid-state phases with distinct thermal properties are appealing for thermal management due to their simplicity, fast switching, and compactness. Thus, an ideal thermal switch should operate near or above room temperature, have a simple trigger mechanism, and offer a quick and large on/off switching ratio. In this study, we experimentally demonstrate that manipulating phonon scattering rates can switch the thermal conductivity of antiferroelectric PbZrO 3 bidirectionally by –10% and +25% upon applying electrical and thermal excitation, respectively. Our approach takes advantage of two separate phase transformations in PbZrO 3 that alter the phonon scattering rate in different manners. In this study, we demonstrate that PbZrO 3 can serve as a fast (<1 second), repeatable, simple trigger, and reliable thermal switch with a net switching ratio of nearly 38% from ~1.20 to ~1.65 W m –1 K –1 .

25 ENERGY STORAGE↗

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

The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. 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 to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.

equilibrium↗

In-Situ Growth of Yb2O3 Layer for Sublimation Suppression for Yb14MnSb11 Thermoelectric Material for Space Power Applications

The compound Yb14MnSb11 is a p-type thermoelectric material of interest to the National Aeronautics and Space Administration (NASA) as a candidate replacement for the state-of-the-art Si-Ge used in current radioisotope thermoelectric generators (RTGs). Ideally, the hot end of this leg would operate at 1000 C in the vacuum of space. Although Yb14MnSb11 shows the potential to double the value of the thermoelectric figure of merit (zT) over that of Si-Ge at 1000 C, it suffers from a high sublimation rate at elevated temperatures and would require a coating in order to survive the required RTG lifetime of 14 years. The purpose of the present work is to measure the sublimation rate of Yb14MnSb11 and to investigate sublimation suppression for this material. This paper reports on the sublimation rate of Yb14MnSb11 at 1000 C (approximately 3 x 10(exp -3) grams per square centimeter hour) and efforts to reduce the sublimation rate with an in situ grown Yb2O3 layer. Despite the success in forming thin, dense, continuous, and adherent oxide scales on Yb14MnSb11, the scales did not prove to be sublimation barriers.

Nesbitt, James A.↗

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Opila, Elizabeth J.↗

Oxidation of TaSi2-Containing ZrB2-SiC Ultra-High Temperature Materials

Hot pressed coupons of composition ZrB2-20 v% SiC-5 v% TaSi2 and ZrB2-20 v% SiC-20 v% TaSi2 were oxidized in stagnant air at temperatures of 1627 and 1927C for one, five and ten 10-minute cycles. The oxidation reactions were characterized by weight change kinetics, x-ray diffraction, and SEM/EDS. Detailed WDS/microprobe quantitative analyses of the oxidation products were conducted for the ZrB2-20 v% SiC-20 v% TaSi2 sample oxidized for five 10-minute cycles at 1927C. Oxidation kinetics and product formation were compared to ZrB2-20 v% SiC with no TaSi2 additions. It was found that the 20 v% TaSi2 composition exhibited improved oxidation resistance relative to the material with no TaSi2 additions at 1627C. However, for exposures at 1927C less oxidation resistance and extensive liquid phase formation were observed compared to the material with no TaSi2 additions. Attempts to limit the liquid phase formation by reducing the TaSi2 content to 5 v% were unsuccessful. In addition, the enhanced oxidation resistance at 1627C due to 20 v% TaSi2 additions was not achieved at the 5 v% addition level. The observed oxidation product evolution is discussed in terms of thermodynamics and phase equilibria for the TaSi2-containing ZrB2-SiC material system. TaSi2-additions to ZrB2-SiC at any level are not recommended for ultra-high temperature (>1900C) applications due to excessive liquid phase formation.

Opila, Elizabeth J.↗

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

Carbon-fiber reinforced SiC (C/SiC) composites are proposed for leading edge applications of hypersonic vehicles due to the superior strength of carbon fibers at high temperatures (greater than 1500 C). However, the vulnerability of the carbon fibers in C/SiC to oxidation over a wide range of temperatures remains a problem. Previous oxidation studies of C/SiC have mainly been conducted in air or oxygen, so that the oxidation behavior of C/SiC at reduced oxygen partial pressures of the hypersonic flight regime are less well understood. In this study, both carbon fibers and C/SiC composites were oxidized over a wide range of temperatures and oxygen partial pressures to facilitate the understanding and modeling of C/SiC oxidation kinetics for hypersonic flight conditions.

Opila, Elizabeth J.↗

Followup to Columbia Investigation: Reinforced Carbon/Carbon From the Breach Location in the Wing Leading Edge Studied

Initial estimates on the temperature and conditions of the breach in the Space Shuttle Columbia's wing focused on analyses of the slag deposits. These deposits are complex mixtures of the reinforced carbon/carbon (RCC) constituents, insulation material, and wing structural materials. Identification of melted/solidified Cerachrome insulation (Thermal Ceramics, Inc., Augusta, GA) indicated that the temperatures at the breach had exceeded 1760 C.

Jacobson, Nathan S.↗

Thermodynamics of Volatile Species in the Silicon-Oxygen-Hydrogen System Studied

The volatilization of silica (SiO2) to silicon hydroxides and oxyhydroxides because of reaction with water vapor is important in a variety of high-temperature corrosion processes. For example, the lifetimes of silicon carbide (SiC) and silicon nitride (Si3N4) - based components in combustion environments are limited by silica volatility. To understand and model this process, it is essential to have accurate thermodynamic data for the formation of volatile silicon hydroxides and oxyhydroxides.

Jacobson, Nathan S.↗

Volatility of Common Protective Oxides in High-Temperature Water Vapor: Current Understanding and Unanswered Questions

Many structural materials rely on the formation of chromia, silica or alumina as a protective layer when exposed in high temperature oxidizing environments. The presence of these oxide layers provides a protective diffusion barrier which slows down further oxidation. In atmospheres containing water vapor, however, reactions to form volatile hydroxide species occur which remove the surface oxide, thus, lowering the protective capability of the oxide scale. This paper summarizes the current understanding of volatility of chromia, silica and alumina in water vapor containing combustion environments. In addition unanswered questions in each system are discussed. Th current paper represents an update on the considerable information learned in the past five years for these systems.

Opila, Elizabeth J.↗

Characterization of an Ultra-High Temperature Ceramic Composite

Ultra-high temperature ceramics (UHTC) are of interest for hypersonic vehicle leading edge applications. Monolithic UHTCs are of concern because of their low fracture toughness and brittle behavior. UHTC composites (UHTCC) are being investigated as a possible approach to overcome these deficiencies. In this study a small sample of a UHTCC was evaluated by limited mechanical property tests, furnace oxidation exposures, and oxidation exposures in a flowing environment generated by an oxy-acetylene torch. The composite was prepared from a carbon fiber perform using ceramic particulates and a pre-cerns about microcracking due to thermal expansion mismatch between the matrix and the carbon fiber reinforcements, and about the oxidation resistance of the HfB2-SiC coating layer and the composite constituents. However, positive performance in the torch test warrants further study of this concept.

Levine, Stanley R.↗

Oxidation of Ultra High Temperature Ceramics in Water Vapor

Ultra High Temperature Ceramics (UHTCs) including HfB2 + 20v/0 SiC (HS), ZrB2 + 20v/0 SiC (ZS), and ZrB2 + 30v/0 C + 14v/0 SiC (ZCS) have been investigated for use as potential aeropropulsion engine materials. These materials were oxidized in water vapor (90 percent) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 h at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline for comparison. Weight change, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results are compared with tests ran in a stagnant air furnace at temperatures of 1327 C for 100 min, and with high pressure burner rig (HPBR) results at 1100 and 1300 C at 6 atm for 50 h. Low velocity water vapor does not make a significant contribution to the oxidation rates of UHTCs when compared to stagnant air. The parabolic rate constants at 1300 C, range from 0.29 to 16.0 mg(sup 2)cm(sup 4)/h for HS and ZCS, respectively, with ZS results between these two values. Comparison of results for UHTCs tested in the furnace in 90 percent water vapor with HPBR results was difficult due to significant sample loss caused by spallation in the increased velocity of the HPBR. Total recession measurements are also reported for the two test environments.

Nguyen, QuynhGiao N.↗

Oxidation of Ultra-High Temperature Ceramics in Water Vapor

Ultra High Temperature Ceramics (UHTCs) including HfB2 + 20% SiC (HS), and ZrB2 + 20% SiC (ZC), and ZrB2 + 30% C + 14% SiC (ZCS) have been investigated for use as potential aeropropolsion 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 temperature of 1200, 1300, and 1400 C. CVD SiC was also evaluate as a baseline for comparison. Weight change, X-ray diffraction analysis, surface and cross-sectional SEM and EDS were performed. These results are compared with tests conducted in a stagnant air furnace at temperatures of 1327 C for 100 minutes, and with high pressure burner rig (HPBR) results at 1100 and 1300 C at 6 atm for 50 h. Total recession measurements are also reported for the two tests environments.

Nguyen, QuynGiao N.↗

Ultra-high Temperature Ceramic Composites for Leading Edges, 2004

Ultrahigh temperature ceramics (UHTC) have performed unreliably due to material flaws and attachment design. These deficiencies are brought to the fore by the low fracture toughness and thermal shock resistance of the UHTC. If these deficiencies are overcome, we are still faced with poor oxidation resistance as a limitation on UHTC applicability to reusable launch vehicles. We have been addressing the deficiencies of UHTC for the past two years via a small task at GRC that is in the Airframe part of the Next Generation Launch Technology Program. Our focus is on composite constructions and functional grading to address the mechanical issues and on composition modification to address the oxidation issue. The progress on approaches to improving oxidation resistance by alloying and functional grading will be reported.

Levine, Stanley R.↗

UHTC Composites for Leading Edges

Ultrahigh temperature ceramics (UHTC) have performed unreliably due to material flaws and attachment design. These deficiencies are brought tot he fore by the low fracture tougness and thermal shock resistance of UHTC. In addition, poor oxidation resistance is a limitation on UHTC applicability to reusable launch vehicles. We have been addressing these deficiencies for the past two years via a small task at GRC that is in the Airframe part of the Next Generation Launch Technology Program. Our focus is on UHTC composite (UHTCC) constructions and functional grading to address the mechanical issues and on composition modification to address the oxidation issue. Processing, mechanical property, and oxidation resutls will be reported.

Levine, Stanley R.↗