Results for “Atmospheric sintering” — Page 7

NASA NTRS2012

Regolith Derived Heat Shield for Planetary Body Entry and Descent System with In Situ Fabrication

This NIAC project investigated an innovative approach to provide heat shield protection to spacecraft after launch and prior to each EDL thus potentially realizing significant launch mass savings. Heat shields fabricated in situ can provide a thermal-protection system for spacecraft that routinely enter a planetary atmosphere. By fabricating the heat shield with space resources from materials available on moons and asteroids, it is possible to avoid launching the heat-shield mass from Earth. Regolith has extremely good insulating properties and the silicates it contains can be used in the fabrication and molding of thermal-protection materials. Such in situ developed heat shields have been suggested before by Lewis. Prior research efforts have shown that regolith properties can be compatible with very-high temperature resistance. Our project team is highly experienced in regolith processing and thermal protection systems (TPS). Routine access to space and return from any planetary surface requires dealing with heat loads experienced by the spacecraft during reentry. Our team addresses some of the key issues with the EDL of human-scale missions through a highly innovative investigation of heat shields that can be fabricated in space by using local resources on asteroids and moons. Most space missions are one-way trips, dedicated to placing an asset in space for economical or scientific gain. However, for human missions, a very-reliable heat-shield system is necessary to protect the crew from the intense heat experienced at very high entry velocities of approximately 11 km/s at approximately Mach 33 (Apollo). For a human mission to Mars, the return problem is even more difficult, with predicted velocities of up to 14 km/s, at approximately Mach 42 at the Earth-atmosphere entry. In addition to human return, it is very likely that future space-travel architecture will include returning cargo to the Earth, either for scientific purposes or for commercial reasons. Platinum, titanium, helium 3, and other metals, elements and minerals are all high-value commodities in limited supply on Earth, and it may be profitable to mine these substances throughout the Solar System and return them to Earth, if an economical method can be found. To date, several private corporations have been launched to pursue these goals. Because the heat shield is the last element to be used in an Earth-return mission, a high penalty is paid in the propellant mass required to carry the heat shield to the destination and back. If the heat shield could be manufactured in space, and then outfitted on the spacecraft prior to the reentry at Earth, then significant propellant and mass savings could be achieved during launch and space operations. Preliminary mission architecture scenarios are described, which explain the potential benefits that may be derived from using an in-situ fabricated regolith heat shield. In order to prove that this is a feasible technology concept, this project successfully fabricated heat shield materials from mineral simulant materials of lunar and Martian regolith by two methods: 1) Sintering and 2) Binding the simulant with a "room-temperature vulcanizing" (RTV) silicone formulated to withstand high temperatures. Initially a third type of fabrication was planned using the hot waste stream from regolith ISRU processes. This fabrication method was discarded since the resulting samples would be too dense and brittle for heat shields. High temperature flame tests at KSC and subsequent arc jet tests at Ames Research Center (ARC) have proved promising. These coupon tests show favorable materials properties and have the potential to be a new way of fabricating heat shields for space entry into planetary atmospheres.

Hogue, Michael D.↗

NASA NTRS2013

Regolith Derived Heat Shield for Planetary Body Entry and Descent System with In Situ Fabrication

This NIAC project investigated an innovative approach to provide heat shield protection to spacecraft after launch and prior to each EDL thus potentially realizing significant launch mass savings. Heat shields fabricated in situ can provide a thermal-protection system for spacecraft that routinely enter a planetary atmosphere. By fabricating the heat shield with space resources from materials available on moons and asteroids, it is possible to avoid launching the heat-shield mass from Earth. Regolith has extremely good insulating properties and the silicates it contains can be used in the fabrication and molding of thermal-protection materials. Such in situ developed heat shields have been suggested before by Lewis. Prior research efforts have shown that regolith properties can be compatible with very-high temperature resistance. Our project team is highly experienced in regolith processing and thermal protection systems (TPS). Routine access to space and return from any planetary surface requires dealing with heat loads experienced by the spacecraft during reentry. Our team addresses some of the key issues with the EDL of human-scale missions through a highly innovative investigation of heat shields that can be fabricated in space by using local resources on asteroids and moons. Most space missions are one-way trips, dedicated to placing an asset in space for economical or scientific gain. However, for human missions, a very-reliable heat-shield system is necessary to protect the crew from the intense heat experienced at very high entry velocities of approximately 11 km/s at approximately Mach 33 (Apollo). For a human mission to Mars, the return problem is even more difficult, with predicted velocities of up to 14 km/s, at approximately Mach 42 at the Earth-atmosphere entry. In addition to human return, it is very likely that future space-travel architecture will include returning cargo to the Earth, either for scientific purposes or for commercial reasons. Platinum, titanium, helium 3, and other metals, elements and minerals are all high-value commodities in limited supply on Earth, and it may be profitable to mine these substances throughout the Solar System and return them to Earth, if an economical method can be found. To date, several private corporations have been launched to pursue these goals. Because the heat shield is the last element to be used in an Earth-return mission, a high penalty is paid in the propellant mass required to carry the heat shield to the destination and back. If the heat shield could be manufactured in space, and then outfitted on the spacecraft prior to the reentry at Earth, then significant propellant and mass savings could be achieved during launch and space operations. Preliminary mission architecture scenarios are described, which explain the potential benefits that may be derived from using an in-situ fabricated regolith heat shield. In order to prove that this is a feasible technology concept, this project successfully fabricated heat shield materials from mineral simulant materials of lunar and Martian regolith by two methods: 1) Sintering and 2) Binding the simulant with a "room-temperature vulcanizing" (RTV) silicone formulated to withstand high temperatures. Initially a third type of fabrication was planned using the hot waste stream from regolith ISRU processes. This fabrication method was discarded since the resulting samples would be too dense and brittle for heat shields. High temperature flame tests at KSC and subsequent arc jet tests at Ames Research Center (ARC) have proved promising. These coupon tests show favorable materials properties and have the potential to be a new way of fabricating heat shields for space entry into planetary atmospheres.

Hogue, Michael D.↗

NASA NTRS2011

Regolith-Derived Heat Shield for Planetary Body Entry and Descent System with In Situ Fabrication

In this paper we will discuss a new mass-efficient and innovative way of protecting high-mass spacecraft during planetary Entry, Descent & Landing (EDL). Heat shields fabricated in situ can provide a thermal-protection system (TPS) for spacecraft that routinely enter a planetary atmosphere. By fabricating the heat shield with space resources from regolith materials available on moons and asteroids, it is possible to avoid launching the heat-shield mass from Earth. Three regolith processing and manufacturing methods will be discussed: 1) oxygen & metal extraction ISRU processes produce glassy melts enriched in alumina and titania, processed to obtain variable density, high melting point and heat-resistance; 2) compression and sintering of the regolith yield low density materials; 3) in-situ derived high-temperature polymers are created to bind regolith particles together, with a lower energy budget.

Hogue, Michael D.↗

DOE OSTI2022

The effect of original and initial saturation on residual nonwetting phase capillary trapping efficiency

Injection of supercritical carbon dioxide (CO 2 ) into geological formations is a strategy for both atmospheric greenhouse gas reduction (climate change mitigation) and enhanced oil recovery. To understand CO 2 trapping efficiency, the capillary trapping behaviors that immobilize subsurface fluids were analyzed at the pore-scale using pairs of proxy fluids representing the range of in situ nonwetting and wetting fluid properties encountered in geologic storage reservoirs. The pairs of fluids were cycled through imbibition and drainage processes using a flow cell apparatus containing a sintered glass bead column. Computed x-ray microtomography (microCT) was used to identify immobilized nonwetting fluid after imbibition and drainage events. From microCT images, the trapped residual (post-secondary imbibition) nonwetting phase was spatially correlated to both the original (post-primary imbibition) and the initial (post-primary drainage) nonwetting phase; this relationship is referred to here as the original saturation dependence (SO-dependence) and initial saturation dependence (SI-dependence), respectively. Significant trends of decreasing SO- and SI-dependence with increasing wetting and nonwetting fluid phase viscosities were observed. This finding implies that the amount of CO 2 injected and ultimately trapped is dependent on the nonwetting phase (e.g. oil or gas) already present in the formation, as well as on the manner in which supercritical CO 2 is initially injected, which are factors not considered in current trapping models. To explore the potential effect that varying viscosity and interfacial tension (IFT) might have on this process, we report on a variety of fluid pairs with different viscosities and IFT.

42 ENGINEERING↗

DOE OSTI2020

Microwave-assisted ammonia synthesis over Ru/MgO catalysts at ambient pressure

Here, in this work, a fixed frequency (2.45 GHz) microwave (MW) was used to synthesis ammonia over Ru/MgO catalysts under ambient atmospheric pressure at 320 °C. The loading of Ru catalyst over MgO was varied at 4% and 10 wt %. The metal support interaction was found to play an important role not only catalytically but also altering the microwave-catalyst interaction affecting the ammonia formation rate. The higher metal loading (10 wt%) produced the most activity, stability, and energy efficiency. It was found the Ru was better dispersed at higher loading which decreased the sintering of the catalyst due to lower microwave energy needed to maintain the reaction temperature. Additional effects from the microwave can include enhanced electron movement and/or electric fields formed between the metal sites of the catalyst. The microwave reactor offers a quick on/off catalyst recovery, within 11 min, compared to thermal convectional Haber Bosch (HB) technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1995

Absorption of water and lubricating oils into porous nylon

Oil and water absorption from air into sintered porous nylon can be described by infiltration into the pores of the material. This process can be modeled by a diffusion-like mechanism. For water absorption, we find a formal diffusion coefficient of 1.5 x 10(exp -4)sq cm/min when the nylon is initially dry. The diffusion coefficient is 4 x 10(exp -6)sq cm/min when the nylon is oil-impregnated prior to air exposure. In a 52% RH atmosphere, dry nylon absorbs 3% w/w water, and oil-impregnated nylon absorbs 0.6% w/w water. For oil absorption there are three steps: (1) surface absorption and infiltration into (2) larger and (3) smaller pores. Surface absorption is too fast to be measured in these experiments. The diffusion coefficient for the second step is 6 x 10(exp -4)sq cm/min for SRG-60 oil into dry nylon and 4 x 10(exp -4)sq cm/min for air-equilibrated nylon. The diffusion coefficient for the third step is about 1 x 10(exp -6)sq cm/min for both cases. The total amount of oil absorbed is 31% w/w. The interaction between water and nylon is not as strong as that between water and cotton-phenolic: oil can replace water, and only a small amount of water can enter previously oil-impregnated nylon.

Bertrand, P. A.↗

DOE OSTI2023

Testing of Helium Cooled Metal Molybdenum Disk Target System

NorthStar Medical Radioisotopes LLC is planning to produce the important medical radioisotope molybdenum-99 (Mo-99) through a photonuclear reaction on molybdenum-100 (Mo-100). In this approach, multiple thin disks of enriched molybdenum metal will be bombarded with a 40-MeV electron beam. Because enriched Mo-100 is expensive, we intend to use as much beam power as possible to achieve maximum production yield and minimize the size of the target. This requirement leads to very high beam power density (heat deposition in the target), which sets challenging requirements for cooling. Together with scientists at Los Alamos National Laboratory, a team at Argonne National Laboratory has developed and demonstrated a cooling approach using pressurized helium, which allows for efficient heat removal. One of the challenges in this approach is the management of the heat load on the target window. The target window separates the high-pressure helium atmosphere inside the target from the vacuum in the beamline, so it is constantly under stress from differential pressure. Also, the window is cooled only by the helium gas flow from one side, making the window design challenging. High heat deposition in the target disks also imposes a strict requirement on performance of the helium cooling system and thickness of the target disks. The target disks are produced from metal powder via a press-and-sinter process. The resulting disks do not possess as high a tensile strength as solid molybdenum and might not survive the vibration from the high-velocity helium coolant and the high thermal stress from beam heating.

42 ENGINEERING↗

DOE OSTI2025

Microwave-Assisted Reactive CO 2 Capture with the SrCO 3 -Graphite System

This study details the initial development of a microwave heat-driven reactive CO 2 capture (RCC) process using the SrO/SrCO 3 cycle and graphitic carbon to absorb ppm-levels of CO 2 from humidified room temperature air and selectively convert it into CO. By combining first-principles density functional theory (DFT) simulations with thermogravimetric analysis (TGA) and X-ray diffraction (XRD) verification, it is demonstrated that SrO spontaneously absorbs moisture to generate Sr(OH) 2 followed by Sr(OH) 2 *1H 2 O, which then can spontaneously react with atmospheric levels of CO 2 to form SrCO 3 . The resulting SrCO 3 can then react with solid carbon at elevated temperatures to selectively produce CO and regenerate SrO. Graphitic carbon is an excellent microwave absorber that can quickly generate temperatures approaching 1000 °C and then cool to room temperature within minutes, potentially allowing for integration with intermittent electricity. It is shown that using microwaves to selectively heat a mixture of graphitic carbon and SrCO 3 produced CO with 85 ± 3% selectivity and stable performance over ten cycles. The rapid heating for release and room temperature CO 2 uptake processes appeared to prevent performance loss from particle sintering typically observed with traditional thermal systems. In conclusion, these results demonstrate a new RCC approach that adds to the growing number of potential technologies available for converting CO 2 to useful chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2018

Method of Manufacturing a Humidity Sensing Material

A method is provided for manufacturing a humidity sensing material. Particles of a trivalent rare earth hydroxide or oxide (such as lanthanum hydroxide) are mixed with particles of barium oxide and titanium dioxide in specified proportions. The particle mixture is heated to generate a sintered mixture that is milled. The resulting milled particles are mixed with glass particles, an organic surfactant, a solvent, an organic vehicle, and an alkali hydroxide. The resulting liquid mixture is deposited as a layer thereof onto a substrate. The substrate and layer thereon are processed to remove liquid portions of the liquid mixture. Such liquid removal processing includes at least one cycle of heating the layer followed by a corresponding cycle of cooling the layer in a nitrogen atmosphere containing less than 25 parts per million of oxygen.

Rolin, Terry D.↗

DOE OSTI2024

Facile Interfacial Reduction Suppresses Redox Chemical Expansion and Promotes the Polaronic to Ionic Transition in Mixed Conducting (Pr,Ce)O 2−δ Nanoparticles

Mixed ionic/electronic conductors (MIECs) are essential components of solid-state electrochemical devices, such as solid oxide fuel/electrolysis cells. For efficient performance, MIECs are typically nanostructured, to enhance the reaction kinetics. However, the effect of nanostructuring on MIEC chemo-mechanical coupling and transport properties, which also impact cell durability and efficiency, has not yet been well understood. Here, in this work, Pr 0.2 Ce 0.8 O 2−δ (PCO20) nanopowders were prepared by coprecipitation, then sintered in a modified dilatometer at three different temperatures (600, 725, and 850 °C) for microstructure evolution, resulting in three samples with different average particle sizes (23, 30, and 53 nm). The chemical strain and electronic/ionic conductivity were then measured simultaneously on stable nanostructures in four isotherms from 550 to 400 °C with steps in pO 2 (1 to 10 –4 atm O 2 ). A microcrystalline bar was prepared and measured for comparison. Particle size reduction led to a monotonically decreasing isothermal redox chemical strain, confirmed by in situ high-temperature, controlled-atmosphere XRD measurements. The corresponding conductivity measurements provided defect chemical insight into the particle size-dependent chemical expansion behavior. The significant weakening of the pO 2 dependence and decreased activation energy for electrical conduction with decreasing particle size indicated a decrease in the reduction enthalpy of PCO, shifting the transition from (Pr) polaronic to ionic behavior to higher pO 2 . STEM-EELS measurements confirmed the majority of Pr was reduced to 3+ in the nanoparticles, while Ce remained 4+. These results demonstrate suppression of deleterious chemical expansion and tailoring of the dominant charge carrier simply through controlling the particle size, providing insights for MIEC microstructural design.

ceria↗

NASA NTRS1994

Preparation and Dielectric Measurements of the Rare Earth Green Phases R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb)

It has been demonstrated that R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb) does not undergo significant densification unless the sintering temperatures are near the incongruent melting point or the sintering times are long. Good quality powders of Y2BaCuO(5-x) have been synthesized by using oxide raw materials or precursors such as acetates and nitrates. The acetates- and the nitrates-derived yttrium green phase resulted in finer particle sizes, acceptable dielectric properties and lower melting temperatures than those processed via oxide raw materials. The hot pressing technique has been employed to produce a dense R2BaCuO(5-x) (R=Y,Gd) substrate with satisfactory dielectric properties. Reactivity to reducing conditions, i.e. graphite die, limited the optimization of the properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO,.,,. Oxygen treatment at 950 OC has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO(5-x). Oxygen treatment at 950 C has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. The dielectric constants of the rare earth green phases R2BaCuO(5-x) were found to be low. Relaxation peaks were detected at low temperatures (T less than 150 K) and at high temperatures (150 less than T greater than 420 K). The dielectric losses and conductivities at 77 K were measured to be in the range of 10(exp -4) and 10(exp -12) (Omega-cm)(exp -1), respectively. Many parameters were found to exhibit dependencies on the rare earth cation sizes.

Gonzalez-Titman, Carlos↗

NASA NTRS2008

Conductometric Sensors for Detection of Elemental Mercury Vapor

Several organic and inorganic materials have been tested for possible incorporation into a sensing array in order to add elemental mercury vapor to the suite of chemical species detected. Materials have included gold films, treated gold films, polymer-carbon composite films, gold-polymer-carbon composite films and palladium chloride sintered films. The toxicity of mercury and its adverse effect on human and animal health has made environmental monitoring of mercury in gas and liquid phases important (1,2). As consumer products which contain elemental mercury, such as fluorescent lighting, become more widespread, the need to monitor environments for the presence of vapor phase elemental mercury will increase. Sensors in use today to detect mercury in gaseous streams are generally based on amalgam formation with gold or other metals, including noble metals and aluminum. Recently, NASA has recognized a need to detect elemental mercury vapor in the breathing atmosphere of the crew cabin in spacecraft and has requested that such a capability be incorporated into the JPL Electronic Nose (3). The detection concentration target for this application is 10 parts-per-billion (ppb), or 0.08 mg/m3. In order to respond to the request to incorporate mercury sensing into the JPL Electronic Nose (ENose) platform, it was necessary to consider only conductometric methods of sensing, as any other transduction method would have required redesign of the platform. Any mercury detection technique which could not be incorporated into the existing platform, such as an electrochemical technique, could not be considered.

mercury sensor↗

DOE OSTI2023

Investigation of oxygen ion mobility through Zr x Ta 2 O 2x+5 (ZTOx) and Hf 6 Ta 2 O 17 (HTO) at elevated temperatures

Thermal Protection Systems (TPS) allow for technology to withstand high heat, which is especially critical for aerospace applications. As technology advances, better TPS are required to keep up with more extreme operating temperatures. Ultra-High Temperature Ceramics (UHTCs) are of interest because of their high melting points above 3000°C, but they suffer from oxidation when exposed to the atmosphere. A standard remedy to prevent oxidation is the use an oxide coating to shield from oxygen in the atmosphere while still allowing high operating temperatures and thermal cycling. However, standard oxide coatings such as yttria stabilized zirconia (YSZ) have limited operating temperatures before they allow oxygen to diffuse into the substrate material. A recently proposed alternative material has the formula A 6 B 2 O 17 (A: Zr or Hf) (B: Ta or Nb). In this study, determination of the oxygen protection ability of Hf 6 Ta 2 O 17 (HTO), Zr 6 Ta 2 O 17 (ZTO6), and various Zr x Ta 2 O 2x+5 (ZTOx) was determined using Electrochemical Impedance Spectroscopy (EIS). Optimal synthesis and sintering conditions were determined for ZTO6 and several of its ZTO variations. Activation energy for oxygen mobility was also determined. The importance of ball milling was found to be crucial to achieve high sintering density with these ceramics. The sintering study revealed that the ideal temperature of the ZTO variations increased with increased Zr/Ta ratio in the formulation. It was determined that both HTO and the ZTO variations conduct oxygen ions less than current ceramic coatings such as YSZ, with HTO conducting the least, with results confirming the validity of both HTO and ZTO materials as candidates for TPS coatings based on their low oxygen ion conductivity.

36 MATERIALS SCIENCE↗

NASA NTRS2003

A Microphysically-based Approach to Inferring Porosity, Grain Size, and Dust Abundance in the Seasonal Caps from Atmospherically-corrected TES Spectra

One of the highlights of the TES observations in the polar regions has been the identification of a "cryptic" region in the south where CO2 appears to be in the form of a solid slab rather than a fluffy frost. While the exact mechanism(s) by which the cryptic region is formed are still subject of some debate, it appears certain that a type of rapid metamorphism related to the high volatility of CO2 ice is involved. The high volatility of CO2 ice under martian conditions has several Solar System analogs (N2 on Triton and Pluto, SO2 on Io), thus making the martian cryptic region somewhat less cryptic and certainly non-unique among planetary objects. In an endmember scenario, both the formation and the spectral properties of the cryptic region (and of other areas in the seasonal caps) can be quantitatively modeled by considering sintering of an ensemble of quasi-spherical CO2 grains. This model includes the special case of instanteneous slab formation, which occurs when the grains are sufficiently small (in the submicron range) so that their sintering timescale is short relative to the deposition timescale (a situation analogous to the "sintering" of water droplets falling into a pond).

Eluszkiewicz, J.↗

NASA NTRS1993

High temperature sensor/microphone development for active noise control

The industrial and scientific communities have shown genuine interest in electronic systems which can operate at high temperatures, among which are sensors to monitor noise, vibration, and acoustic emissions. Acoustic sensing can be accomplished by a wide variety of commercially available devices, including: simple piezoelectric sensors, accelerometers, strain gauges, proximity sensors, and fiber optics. Of the several sensing mechanisms investigated, piezoelectrics were found to be the most prevalent, because of their simplicity of design and application and, because of their high sensitivity over broad ranges of frequencies and temperature. Numerous piezoelectric materials are used in acoustic sensors today; but maximum use temperatures are imposed by their transition temperatures (T(sub c)) and by their resistivity. Lithium niobate, in single crystal form, has the highest operating temperature of any commercially available material, 650 C; but that is not high enough for future requirements. Only two piezoelectric materials show potential for use at 1000 C; AlN thin film reported to be piezoactive at 1150 C, and perovskite layer structure (PLS) materials, which possess among the highest T(sub c) (greater than 1500 C) reported for ferroelectrics. A ceramic PLS composition was chosen. The solid solution composition, 80% strontium niobate (SN) and 20% strontium tantalate (STa), with a T(sub c) approximately 1160 C, was hot forged, a process which concurrently sinters and renders the plate-like grains into a highly oriented configuration to enhance piezo properties. Poled samples of this composition showed coupling (k33) approximately 6 and piezoelectric strain constant (d33) approximately 3. Piezoactivity was seen at 1125 C, the highest temperature measurement reported for a ferroelectric ceramic. The high temperature piezoelectric responses of this, and similar PLS materials, opens the possibility of their use in electronic devices operating at temperatures up to 1000 C. Concurrent with the materials study was an effort to define issues involved in the development of a microphone capable of operation at temperatures up to 1000 C; important since microphones capable of operation above 260 C are not generally available. The distinguishing feature of a microphone is its diaphragm which receives sound from the atmosphere: whereas, most other acoustic sensors receive sound through the solid structure on which they are installed. In order to gain an understanding of the potential problems involved in designing and testing a high temperature microphone, a prototype was constructed using a commercially available lithium niobate piezoelectric element in a stainless steel structure. The prototype showed excellent frequency response at room temperature, and responded to acoustic stimulation at 670 C, above which temperature the voltage output rapidly diminished because of decreased resistivity in the element. Samples of the PLS material were also evaluated in a simulated microphone configuration, but their voltage output was found to be a few mV compared to the 10 output of the prototype.

Shrout, Thomas R.↗

DOE OSTI2023

Biphasic Janus Particles Explain Self-Healing in Pt–Pd Diesel Oxidation Catalysts

The addition of Pd to Pt-based diesel oxidation catalysts is known to enhance performance and restrict the anomalous growth of Pt nanoparticles when subjected to aging at high temperatures in oxidative environments. To gain a mechanistic understanding, we studied the transport of the mobile Pt and Pd species to the vapor phase, since vapor phase transport is the primary route for sintering in these catalysts. The results are surprising: there is a 30-fold drop in the effective vapor pressure of Pt in the Pt-Pd catalysts compared to monometallic Pt. At the same time, there is a significant enhancement in the vapor pressure of Pd, compared to PdO, which otherwise has a negligible vapor pressure at the aging temperature. Such behavior cannot be explained simply by alloying Pt and Pd in the metallic phase, or a core-shell morphology where a PdO shell covers a Pt core. Transmission electron microscopic examination of catalysts aged up to 50 h in air at 800 °C shows that the particles exhibit a biphasic “Janus”-like structure. The metal and oxide phases are conjoined, exposing a metal and an oxide face to the gas phase. The high mobility of the Pt and Pd allows them to be partitioned into the metal and oxide phases, in apparent thermodynamic equilibrium. The PdO helps to trap mobile PtO2 and as a result contains high concentrations of Pt oxide, consistent with its role in mitigating the transport of Pt to the vapor phase and preventing the growth of anomalously large particles. In turn, Pt allows Pd to remain metallic, allowing the catalyst to retain both metal and oxide functionality for catalysis. The regeneration of deactivated catalysts typically requires an external input, such as a change in the working environment from reducing to oxidizing or vice-versa. Here, we show that the mobile species, which are primary contributors to catalyst sintering are effectively returned to the active site, hence our use of the term “selfhealing”. The detailed insights into the inner workings of the Pt-Pd diesel oxidation catalysts can help provide clues to the design of robust and durable heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1997

MS212--A Homogeneous Sputtered Solid Lubricant Coating for Use to 800 C

Composite coatings containing chromium carbide, stable fluorides and silver were prepared by magnetron sputtering. The microstructure of the coatings is very homogeneous compared to that of plasma sprayed and sintered versions of the same chemical composition. Friction and wear of MS212-coated and baseline uncoated aluminum and Inconel X-750 are compared. At room temperature, the friction and wear of coated aluminum is dramatically better compared to the baseline. The acceptable load is limited by deformation of the soft aluminum substrate. In the case of the nickel alloy, lower friction is observed for the coated alloy at all temperatures up to the maximum test temperature of 800 C. Pin wear factors for sliding against the coated alloy are lower than the baseline at room temperature and 350 C, and comparable to baseline wear at higher test temperatures. Low baseline wear at high temperatures is due to the lubricious nature of the natural oxides formed on nickel-chromium alloys in a hot, oxidizing atmosphere. No load limit was found for coated Inconel X-750 at loads up to five times the load limit for coated aluminum.

Sliney, Harold E.↗

NASA NTRS1960

Lubricating Properties of Some Bonded Fluoride and Oxide Coatings for Temperature to 1500 F

The lubricating properties of some experimental ceramic coatings, diffusion-bonded fluoride coatings, and ceramic-bonded fluoride coatings were determined. The experiments were conducted in an air atmosphere at a sliding velocity of 430 feet per minute and at temperatures from 75 to 1500 F. Several ceramic coatings provided substantial reductions in friction coefficient and rider wear (compared with the unlubricated metals). For example, a cobaltous oxide (CoO) base coating gave friction coefficients of 0.24 to 0.36 within the temperature range of 75 to 1400 F; serious galling and welding of the metal surfaces were prevented. The friction coefficients were higher than the arbitrary maximum (0.2) usually considered for effective boundary lubrication. However, when a moderately high friction coefficient can be tolerated, this type of coating may be a useful antiwear composition. Diffusion-bonded calcium fluoride (CaF2) on Haynes Stellite 21 and on Inconel X gave friction coefficients of 0.1 to 0.2 at 1500 F. Endurance life was dependent on the thermal history of the coating; life improved with increased exposure time at elevated temperatures prior to running. Promising results were obtained with ceramic-bonded CaF2 on Inconel X. Effective lubrication and good adherence were obtained with a 3 to 1 ratio of CaF2 to ceramic. A very thin sintered and burnished film of CaF2 applied to the surface of this coating further improved lubrication, particularly above 1350 F. The friction coefficient was 0.2 at 500 F and decreased with increasing temperature to 0.06-at 1500 F. It was 0.25 at 75 F and 0.22 at 250 F.

Sliney, Harold E.↗