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At least 523 records · Page 29

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

Interaction of Water with Carbon Fiber Reinforced Polymer Laminates under Dynamic Loading Conditions

With the aim of simulating the real conditions during the navigation, in this framework, impact tests were performed by loading CFRP laminates immersed in the water from the front side. The specimens, made by vinyl ester matrix because of the lower moisture absorption compared to the other epoxy systems, are in the presence of the water to accurately simulate the incidental impact on the hull of the vessel, immersed or partially immersed, during the navigation. It can be caused by the ice in the Arctic Ocean, by a projectile due to a terroristic attack or by debris from an explosion. The results are compared with the ones obtained by loading the laminates in pure traditional impact tests in the air. The influence of the clamping device has been tested too. The exciting results obtained on carbon fiber laminates in the air (pure traditional impact tests), water-backed (with water on the back side) and waterfront (water only on the front side) conditions at room temperature are here reported and compared. They highlighted the critical role played by the complex fluid–structure interaction.

36 MATERIALS SCIENCE↗

Extreme Temperature Cryptography Based On Nitrogen-Incorporated Ultrananocrystalline Diamond

Physical entropy sources that remain stable under extreme temperatures are essential for cryptography in emerging technological frontiers in deep space exploration, geothermal energy harvesting, and nuclear energy. However, conventional semiconductor platforms fail to generate stable and reliable cryptographic keys above 200 degrees C due to performance degradation. Here, we report a diamond-based cryptographic primitive that exploits the defect-rich sp 2 -bonded grain boundary network in nitrogen-incorporated ultrananocrystalline diamond (n-UNCD) film as a robust entropy source to generate cryptographic keys that remain operationally stable even after enduring extreme temperatures of 700 degrees C for 54 h while also surviving thermal cycling between room temperature and 700 degrees C for 48 h. The strength of the generated keys is assessed through several cryptographic metrics such as bit uniformity, entropy, hamming distances, and correlation coefficients, all of which are found to be near their respective ideal values. Moreover, the generated keys pass the NIST SP 800 and SP 800-90B tests and are also resilient to supply bias variations and a regression-based machine learning attack model based on the Fourier series. The robustness of the keys is attributed to the better thermal stability and chemical inertness of the n-UNCD film. This is supported by high-resolution energy-dispersive X-ray spectroscopy (EDS), which shows no significant lateral diffusion of metal atoms into the n-UNCD layer, and by Raman spectroscopy, which reveals no significant changes in the bonding configuration of the n-UNCD structure. Our findings highlight the remarkable potential of n-UNCD film for extreme environment cryptography by expanding the operational limits of conventional hardware security platforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Behaviors of Bilayer Oxygen Electrode for Reversible Solid Oxide Cells

Reducing the resistances of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) while retaining the stability of an oxygen electrode, even in the presence of air contaminants such as Cr, H2O and CO2, is of paramount importance to the current commercial development of intermediate-temperature reversible solid oxide cells (IT-RSOCs). In this presentation, a multifunctional, coarsening-resistant, air-contaminants-tolerant and yet ORR/OER-active oxygen electrode (OE) for IT-RSOCs is described. The testing results show that new bilayer OE exhibits a much better ORR/OER activity and stability than the single-layer benchmark LSCF-GDC OE. Remarkably, the new bilayer OE also demonstrates an exceptionally high resistance to Cr-attack, a critical issue to the development of commercial meal-interconnect loaded SOFC/SOEC stacks/systems. Theoretical analysis is also presented to understand the fundamental reasons for the improved ORR/OER activity and stability observed under real-world operating conditions.

Huang, Kevin↗

Interaction of gases with lunar materials

The surface chemistry of Apollo 17 lunar fines samples 74220 (the orange soil) and 74241 (the gray control soil) has been studied by measuring the adsorption of nitrogen, argon, and oxygen (all at 77 K) and also water vapor (at 20 or 22 C). In agreement with results for samples from other missions, both samples had low initial specific surface areas, consisted of nonporous particles, and were attacked by water vapor at high relative pressure to give an increased specific surface area and create a pore system which gave rise to a capillary condensation hysteresis loop in the adsorption isotherms. In contrast to previous samples, both of the Apollo 17 soils were partially hydrophobic in their initial interaction with water vapor (both samples were completely hydrophilic after the reaction with water). The results are consistent with formation at high temperatures without subsequent exposure to significant amounts of water.

Holmes, H. F.↗

Some surface properties of Apollo 17 soils

The surface chemistry of Apollo 17 lunar fines samples 74220 (the orange soil) and 74241 (the gray control soil) has been studied by measuring the adsorption of nitrogen, argon, and oxygen (all at -196 C) and also water vapor (at 20 C or 22 C). In agreement with results for samples from other missions, both samples had low initial specific surface areas, consisted of nonporous particles, and were attacked by water vapor at high relative pressures to give an increased specific surface area and create a pore system which gave rise to a capillary condensation hysteresis loop in the adsorption isotherms. In contrast to previous samples, both of the Apollo 17 soils were partially hydrophobic in their initial interaction with water vapor (both samples were completely hydrophilic after the reaction with water). The results are consistent with formation at high temperatures without subsequent exposure to significant amounts of water.

Holmes, H. F.↗

Single-Crystal NiAl-X Alloys Tested for Hot Corrosion

Single-crystal nickel aluminide (NiAl) has been investigated extensively throughout the last several years as a potential structural material in aero-gas turbine engines. The attractive features of NiAl in comparison to Ni-base superalloys include a higher melting point, lower density, higher thermal conductivity, and excellent oxidation resistance. However, NiAl suffers from a lack of ductility and fracture toughness at low temperatures and a low creep strength at high temperatures. Alloying additions of hafnium (Hf), gallium (Ga), titanium (Ti), and chromium (Cr) have each shown some benefit to the mechanical properties over that of the binary alloy. However, the collective effect of these alloying additions on the environmental resistance of NiAl-X was unclear. Hence, the present study was undertaken to examine the hot corrosion behavior of these alloys. A companion study examined the cyclic oxidation resistance of these alloys. Several single-crystal NiAl-X alloys (where X is Hf, Ti, Cr, or Ga) underwent hot corrosion testing in a Mach 0.3 burner rig at the NASA Lewis Research Center. Samples were tested for up to 300 1-hr cycles at a temperature of 900 C. It was found that increasing the Ti content from 1 to 5 at.% degraded the hot corrosion behavior. This decline in the behavior was reflected in high weight gains and large corrosion mound formation during testing (see the figures). However, the addition of 1 to 2 at.% Cr to alloys containing 4 to 5 at.% Ti appeared to greatly reduce the susceptibility of these alloys to hot corrosion attack and negated the deleterious effect of the increased Ti addition.

Nesbitt, James A.↗

Thermo-Hydro-Geochemical Evolution Influences on the Concrete Cask in Long-Term Storage Facility of Spent Fuel - 16171

Due to humid environment and weather condition in Taiwan's island, as well as the acid rain environment resulting from sulfur dioxide emissions, the concrete cask might be damaged or degraded under the effect of humid, salt, acid rain, and sulfate attack on cementitious materials. These degradation factors could influence the safety design of the long-term spent fuel storage facility. Due to the long-term decay heat of spent fuel and severe environments to be encountered, the thermo-hydro-geochemical evolution could play an important role in the safety assessment of concrete-cask storage facility. The effects of humid, salt, acid rain, and sulfate attack on the degradation of cementitious materials of concrete-cask facility in thermo-hydro-geochemical evolution under rain water quality conditions have been investigated. The results show that the main processes responsible for concrete degradation are species induced from hydrogen ion, sulfate and chloride. For most storage and disposal casks and conditions, the American Concrete Institute nuclear safety code requirements (ACI-349 Appendix A) specify a bulk-concrete shield temperature limit of 150 deg. F (65.5 deg. C). However, localized temperatures at the inner walls of the shielding casks could reach 200-300 deg. F (93-149 deg. C). Simulation of geochemical degradation reactions for 100 years of cask storage under two temperature scenarios was performed. The results indicate that the hydrogen ion, sulfate anion, and chloride do not result in the dissolution of portlandite, or formation of ettringite and Friedel's salt. Therefore, these results indicate the concrete cask may remain in a durable condition. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Formation of Leading-Edge Pinholes in the Space Shuttle Wings Investigated

The space shuttle wing leading edge and nose cap are composed of a carbon/carbon composite that is protected by silicon carbide. The coefficient of thermal expansion mismatch leads to cracks in the silicon carbide. The outer coating of the silicon carbide is a sodium-silicate-based glass that becomes fluid at the shuttles high reentry temperatures and fills these cracks. Small pinholes roughly 0.1 mm in diameter have been observed on these materials after 12 or more flights. These pinholes have been investigated by researchers at the NASA Johnson Space Center, Rockwell International, the Boeing Company, Lockheed Martin Corporation, and the NASA Glenn Research Center at Lewis Field to determine the possible sources and the extent of damage. A typical pinhole is illustrated in the photomicrographs. These pinholes are found primarily on the wing leading edges and not on the nose cap, which is covered when the orbiter is on the launch pad. The pinholes are generally associated with a bead of zincrich glass. Examination of the orbiter and launch structure indicates that weathering paint on the launch structure leads to deposits of zinc-containing paint flakes on the wing leading edge. These may become embedded in the crevices of the wing leading edge and form the observed zinc-rich glass. Laboratory experiments indicate that zinc oxide reacts vigorously with the glass coating on the silicon carbide. Thus, it is likely that this is the reaction that leads to pinhole formation (Christensen, S.V.: Reinforced Carbon/Carbon Pin Hole Formation Through Zinc Oxide Attack. Rockwell International Internal Letter, RDW 96 057, May 1996). Cross-sectional examination of pinholes suggests that they are enlarged thermal expansion mismatch cracks. This is illustrated in the photomicrographs. A careful microstructural analysis indicates that the pinhole walls consist of layers of zinc-containing glass. Thus, pinholes are likely formed by zinc oxide particles lodging in crevices and forming a corrosive zinc-rich glass that enlarges existing cracks. Having established the likely source of the pinholes, we next needed to model the damage. Our concern was that if a pinhole went through the silicon carbide to the carbon/carbon substrate, oxygen would have a clear path to oxidize the carbon at high temperatures. This possibility was examined with studies in a laboratory furnace. An ultrasonic drill was used to make artificial pinholes in a sample of protected carbon/carbon. After exposure, the specimens were weighed and cross-sectioned to quantify the extent of oxidation below the pinhole. The results at higher temperatures showed good agreement with a simple diffusion-control model. This model is based on the two-step oxidation of carbon to carbon monoxide and carbon dioxide. The fluxes are illustrated in the final figure. The model indicates a strong dependence on pinhole diameter. For smaller diameters and short times, the oxidation of carbon is very limited.

Jacobson, Nathan S.↗

NASA Common Research Model Test Envelope Extension With Active Sting Damping at NTF

The NASA Common Research Model (CRM) high Reynolds number transonic wind tunnel testing program was established to generate an experimental database for applied Computational Fluid Dynamics (CFD) validation studies. During transonic wind tunnel tests, the CRM encounters large sting vibrations when the angle of attack approaches the second pitching moment break, which can sometimes become divergent. CRM transonic test data analysis suggests that sting divergent oscillations are related to negative net sting damping episodes associated with flow separation instability. The National Transonic Facility (NTF) has been addressing remedies to extend polar testing up to and beyond the second pitching moment break point of the test articles using an active piezoceramic damper system for both ambient and cryogenic temperatures. This paper reviews CRM test results to gain understanding of sting dynamics with a simple model describing the mechanics of a sting-model system and presents the performance of the damper under cryogenic conditions.

Rivers, Melissa B.↗

Mechanisms of atomic oxygen induced materials degradation

This paper includes discussions of mechanisms by which atomic oxygen may attack materials being flown in low earth orbit (LEO), suggestions for development of materials intrinsically resistant to the harsh LEO environment, and results of an Arrhenius fit to mass loss of Kapton under exposure to thermal atomic oxygen in a laboratory environment. Oxygen atoms are powerful oxidizing agents which can rapidly degrade many types of polymeric materials. The process details depend upon the specific material, its detailed bonding, the thermodynamic stability of potential products, temperature, and particle dynamics. With regard to spacecraft, many effects associated with atomic oxygen may be explained simply by ordinary thermal oxidation processes and by the fact that the oxygen has a preferred direction of impingement.

Pippin, H. G.↗

Interfacial chemistry of a perfluoropolyether lubricant studied by X-ray photoelectron spectroscopy and temperature desorption spectroscopy

The interfacial chemistry of Fomblin Z25, a commercial perfluoropolyether used as lubricant for space applications was studied with different metallic surfaces: 440C steel, gold, and aluminum. Thin layers of Fomblin Z25 were evaporated onto the oxide-free substrates, and the interfacial chemistry was studied using XPS and TDS. The reactions were induced by heating the substrate and by rubbing the substrate with a steel ball. Gold was found to be completely unreactive towards Fomblin at any temperature. Reaction at room temperature was observed only in the case of the aluminum substrate, the most reactive towards Fomblin Z25 of the substrates studied. It was necessary to heat the 440C steel substrate to 190 C to induce decomposition of the fluid. The degradation of the fluid was indicated by the formation of a debris layer at the interface. This debris layer, composed of inorganic and organic reaction products, when completely formed, passivated the surface from further attack to the Fromblin on top. The tribologically induced reactions on 440C steel formed a debris layer of similar chemical characteristics to the thermally induced layer. In all cases, the degradation reaction resulted in preferential consumption of the difluoroformyl carbon (-OCF2O-).

Herrera-Fierro, Pilar↗

X-33 Experimental Aeroheating at Mach 6 Using Phosphor Thermography

The goal of the NASA Reusable Launch Vehicle (RLV) technology program is to mature and demonstrate essential, cost effective technologies for next generation launch systems. The X-33 flight vehicle presently being developed by Lockheed Martin is an experimental Single Stage to Orbit (SSTO) demonstrator that seeks to validate critical technologies and insure applicability to a full scale RLV. As with the design of any hypersonic vehicle, the aeroheating environment is an important issue and one of the key technologies being demonstrated on X-33 is an advanced metallic Thermal Protection System (TPS). As part of the development of this TPS system, the X-33 aeroheating environment is being defined through conceptual analysis, ground based testing, and computational fluid dynamics. This report provides an overview of the hypersonic aeroheating wind tunnel program conducted at the NASA Langley Research Center in support of the ground based testing activities. Global surface heat transfer images, surface streamline patterns, and shock shapes were measured on 0.013 scale (10-in.) ceramic models of the proposed X-33 configuration in Mach 6 air. The test parametrics include angles of attack from -5 to 40 degs, unit Reynolds numbers from 1x106 to 8x106/ft, and body flap deflections of 0, 10, and 20 deg. Experimental and computational results indicate the presence of shock/shock interactions that produced localized heating on the deflected flaps and boundary layer transition on the canted fins. Comparisons of the experimental data to laminar and turbulent predictions were performed. Laminar windward heating data from the wind tunnel was extrapolated to flight surface temperatures and generally compared to within 50 deg F of flight prediction along the centerline. When coupled with the phosphor technique, this rapid extrapolation method would serve as an invaluable TPS design tool.

Horvath, Thomas J.↗

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗

Multi-scale fission product release model with comparison to AGR data

TRistructural ISOtropic (TRISO) particle fuel is central to several advanced, high-temperature reactor designs. Each particle consists of a fuel kernel encapsulated by three layers of carbon and ceramics that prevent the release of fission products and ensure physical integrity. Despite outstanding retention properties, fission product release has been observed from intact particles. To better understand and quantify fission product release from TRISO particles, a multiscale, mechanistic model of fission product transport is being developed by the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program. Previous work focused on silver (Ag) transport and improved Ag release predictions. The work described in this report builds on this experience to better understand cesium (Cs) transport in silicon carbide (SiC), the main barrier to the release of fission products. Atomistic simulations provide bulk and grain boundary (GB) Cs diffusivities in SiC, which are used by phase field simulations in the mesoscale code Marmot to determine the temperature, microstructure, and irradiation-dependent Cs diffusivity at the mesoscale in SiC. This approach attributes the different temperature regimes experimentally observed for Cs diffusivities in SiC to a transition from bulk-dominated diffusivity at high temperatures to a GB-dominated regime at low temperatures, providing new insight. The multiscale, mechanistic effective diffusivity is then implemented in the fuel performance code BISON and further validated by comparing Cs release predictions from Advanced Gas Reactor (AGR)-1 and AGR-2 post-irradiation measurements. The new model improves BISON’s predictability. This document also reports improvements made on Ag transport modeling by accounting for different GB types having different diffusivities. Moreover, this report details preliminary efforts to model palladium (Pd) attack of the SiC at the mesoscale using a phase field approach. Pd attack and its impact on accelerated Ag transport remains a misunderstood phenomenon, and we use the model to demonstrate that the formation of lamellae that has been observed in experiments can be explained by the reaction of Pd with SiC to form alternating layers of graphite and Pd 2 Si. This effort aims to improve our understanding of the reaction and eventually provide a model for BISON to account for Pd penetration and its effects on fission product release.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Slow Strain Rate Testing of A537 Tank Wall Material

At Savannah River Site (SRS), High-Level Waste is stored in below-grade carbon steel tanks. This waste in part consists of sludge, salt cake, and/or supernate. Preparation of this waste for future processing involves dissolution of the salt cake layer. The salt dissolution process can create conditions that leave the carbon steel tanks susceptible to localized corrosion. The salt to be dissolved contains high concentrations of nitrate, that once released, create an environment that may be conducive to pitting corrosion and/or stress corrosion cracking (SCC) of carbon steel. The salt dissolution process also liberates interstitial liquid trapped between the salt crystals. This liquid is initially high in nitrite and hydroxide concentration. High pH and greater ratios of nitrite to nitrate act as inhibitors to minimize corrosion of carbon steel in high nitrate environments. However, as dissolution proceeds, the concentration of nitrate will increase, while the hydroxide and nitrite concentration of the interstitial liquid will deplete and become insufficient to prevent the onset of corrosion attack. Tank blending and the addition of inhibitors are used to ensure adequate concentrations of hydroxide and nitrite. However, this is not desirable during salt dissolution as it can reduce process efficiency and increase the amount of waste that needs processing. This testing program was designed to examine the risk of SCC associated with utilizing the pitting factor (PF) and nitrite/nitrate (NO 2 - /NO 3 - ) ratio limits for handling dissolved salt solutions at an elevated temperature in the carbon steel waste tanks. The previously identified limits are a PF of 1.2 and an NO 2 - /NO 3 - ratio of 0.15. The results indicate that as long as the NO 2 - /NO 3 - ratio exceeds 0.1 and the PF is above approximately 0.8, there is a discernible safety margin between the open circuit potential (OCP) and the critical cracking potential (CCP) observed during applied potential testing. However, this margin, defined by the difference between the OCP and CCP, is relatively narrow, ranging from 0.1 to 0.25 volts. This small margin raises concerns about potential shifts in OCP during waste retrieval operations, which could inadvertently increase the risk of SCC if the OCP approaches or exceeds the CCP. These results confirm that dissolved salt solutions provide a potent chemistry that, under certain conditions, makes carbon steel susceptible to SCC. The next question to consider is the influence these results have on decisions for storage and retrieval of waste from the tanks. For Type III/IIIA waste tanks, the risk of SCC remains very low. First, and most importantly, the post-weld stress relief of the tanks has reduced the residual stress near the welds. Thus, without the stress component, SCC risk is minimized. The material of construction (A537 Carbon steel) for the Type III/IIIA tanks is superior to the steel in its resistance to SCC than the steel that was utilized for the Type I, II, and IV tanks (A285 carbon steel). From a chemistry control standpoint for a Type III/IIIA tank directly involved with handling dissolved salt solutions, the PF and NO 2 - /NO 3 - ratio limits may be utilized wherein chemistry control provides an extra layer of defense against SCC. Chemistry control for a Type III/IIIA tank minimizes the risk for a tank that may receive the dissolved salt solution, particularly if that tank is a Type I, II, or IV waste tank. On the other hand, if the dissolved salt solution is handled by a Type I, II, or IV waste tank the risk of SCC is real. The potent chemistry, absence of stress relief, and inferior material result in a condition that is conducive to cracking. Efforts should be made to either avoid transferring waste that may not meet the PF and NO 2 - /NO 3 - ratio criteria to one of these tanks or if it is unavoidable, take measures to minimize the consequences of a leak. As shown by these tests, even if the PF and NO 2 - /NO 3 - ratio criteria are met, there is a risk that the tank potential may be disturbed in the positive direction and the risk of SCC increase.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Calculation of real-gas effects on airfoil aerodynamic characteristics

The effects of high temperature thermochemical phenomena on the aerodynamic characteristics at hypersonic speeds are calculated for two-dimensional airfoils in air. The calculations are performed on an airfoil similar to that used for the Space Shuttle Orbiter, and ellipses of thickness ratios varying between 5 and 15 percent. For the airfoil, one flight condition is considered. For the ellipses, the calculations are carried out over a range of chord lengths, flight velocities, flight altitudes, and angles of attack. It is shown that the lift and drag coefficients are consistently reduced by the thermochemical phenomena, and that the behavior can be represented by a specific heat ratio value less than 1.4. The center of pressure shifts forward due to the thermochemical phenomena, but its extent is sensitively affected by the geometry and angle of attack and cannot be represented by a fixed specific heat ratio. The calculated results are in qualitative agreement with the data obtained during the entry flights of the Space Shuttle vehicle.

Park, Chul↗

Interfacial chemistry of a perfluoropolyether lubricant studied by XPS and TDS

The interfacial chemistry of Fomblin Z25, a commercial perfluoropolyether used as lubricant for space applications, with different metallic surfaces: 440C steel, gold and aluminum was studied. Thin layers of Fomblin Z25 were evaporated onto the oxide-free substrates and the interfacial chemistry studied using XPS and TDS. The reactions were induced by heating the substrate and by rubbing the substrate with a steel ball. Gold was found to be completely unreactive towards Fomblin at any temperature. Reaction at room temperature was observed only in the case of the aluminum substrate, the most reactive towards Fomblin Z25 of the substrates studied. It was necessary to heat the 440C steel substrate to 190 degree C to induce decomposition of the fluid. The degradation of the fluid was indicated by the formation of a debris layer at the interface. This debris layer, composed of inorganic and organic reaction products, when completely formed, passivated the surface from further attack to the Fromblin on top. The tribologically induced reactions on 440C steel formed a debris layer of similar chemical characteristics to the thermally induced layer. In all cases, the degradation reaction resulted in preferential consumption of the difluoroformyl carbon (-OCF2O-).

Herrera-Fierro, Pilar C.↗