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At least 19 records

Atomized BaF2-CaF7 for Better-Flowing Plasma-Spray Feedstock

Atomization of a molten mixture of BaF2 and CaF2 has been found to be superior to crushing of bulk solid BaF2- CaF2 as a means of producing eutectic BaF2-CaF2 powder for use as an ingredient of the powder feedstock of a high-temperature solid lubricant material known as PS304. Developed to reduce friction and wear in turbomachines that incorporate foil air bearings, PS304 is applied to metal substrates by plasma spraying. The constituents of PS304 are: a) An alloy of 80 weight percent Ni and 20 weight percent Cr, b) Cr2O3, c) Ag, and d) The BaF2-CaF2 eutectic, specifically, 62 weight percent BaF2 and 38 weight percent CaF2. The superiority of atomization as a means of producing the eutectic BaF2-CaF2 powder lies in (1) the shapes of the BaF2-CaF2 particles produced and (2) the resulting flow properties of the PS304 feedstock powder: The particles produced through crushing are angular, whereas those produced through atomization are more rounded. PS304 feedstock powder containing the more rounded BaF2-CaF2 particles flows more freely and more predictably, as is preferable for plasma spraying.

DellaCorte, Christopher↗

Hardness of CaF2 and BaF2 solid lubricants at 25 to 670 deg C

Plastic deformation is a prominent factor in determining the lubricating value of solid lubricants. Little information is available and its direct measurement is difficult so hardness, which is an indirect measure of this property was determined for fluoride solid lubricant compositions. The Vickers hardness of BaF2 and CaF2 single crystals was measured up to 670 C in a vacuum. The orientation of the BaF2 was near the (013) plane and the CaF2 was about 16 degrees from the degrees from the (1'11) plane. The BaF2 has a hardness of 83 kg/sq mm at the 25 C and 9 at the 600 C. The CaF2 is 170 at 25 C and 13 at 670 C. The decrease in hardness in the temperature range of 25 to 100 C is very rapid and amounts to 40% for both materials. Melts of BaF2 and CaF2 were made in a platinum crucible in ambient air with compositions of 50 to 100 wt% BaF2. The Vickers hardness of these polycrystalline binary compositions at 25 C increased with increasing CaF2 reaching a maximum of 150 kn/sq mm near the eutectic. The polycrystalline CaF2 was 14% softer than that of the single crystal surface and BsF2 was 30% harder than the single crystal surface. It is estimated that the brittle to ductile transition temperature for CaF2 and BaF2 is less than 100 C for the conditions present in the hardness tester.

Deadmore, Daniel L.↗

Microstructures and properties of superconducting Y-Er-BaCu-O thin films obtained from disordered Y-Er-BaF2-Cu films

Since the first reports on superconducting thin films obtained by evaporating BaF2, Cu and Y(sup 1), or Yb or Er(sup 2), several others have followed. All these reports describe thin films prepared by means of molecular beam cells or electron guns. Researchers show that films with similar properties can be obtained by radio frequency sputtering of a single mosaic target composed by Y-Er, BaF2 and Cu. Process steps are described.

Cikmach, P.↗

Vacuum ultraviolet thin films. I - Optical constants of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 thin films. II - Vacuum ultraviolet all-dielectric narrowband filters

An iteration process matching calculated and measured reflectance and transmittance values in the 120-230 nm VUV region is presently used to ascertain the optical constants of bulk MgF2, as well as films of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 deposited on MgF2 substrates. In the second part of this work, a design concept is demonstrated for two filters, employing rapidly changing extinction coefficients, centered at 135 nm for BaF2 and 141 nm for SiO2. These filters are shown to yield excellent narrowband spectral performance in combination with narrowband reflection filters.

Zukic, Muamer↗

Surface tension of ZrF4-BaF2-LaF3 glass

A solidified pendant drop technique is presently used in the measurement of surface tension of a 62 mol pct ZrF4, 33 mol pct BaF2, 5 mol pct LaF3 heavy metal-fluoride glass, in keeping with a requirement from a comparison experiment planned for microgravity conditions aboard the Space Shuttle. The surface tension at 550 C is 0.174 + or - 0.005 J/sq m.

Bansal, N. P.↗

Crystallization of BaF2-ZnF2-YbF3-ThF4 glass

The phases and the rates of crystallization in a Ba-Zn-Yb-Th fluoride glass were studied using differential scanning calorimetry, XRD, and observational and chemical SEM analyses. The crystallizing phases that were identified included a BaYbTh fluoride, ZnF2, and YbF3. The BaYbTh fluoride crystallized first at about 450 C, and ZnF2, which was excluded from this phase, crystallized at its surfaces. At higher temperatures, the BaYbTh fluoride phase decomposed partially to BaThF6 and YbF3 phases.

Garcia, Roberto↗

Cryogenic Selective Surfaces

There are many challenges involved in deep-space exploration, but several of these can be mitigated, or even solved, by the development of a coating that reflects most of the Sun’s energy, yet still provides far-infrared heat emission. Such a coating would allow non-heat-generating objects in space to reach cryogenic temperatures without using an active cooling system. This would benefit deep-space sensors that require low temperatures, such as the James Webb Telescope focal plane array. It would also allow the use of superconductors in deep space, which could lead to magnetic energy storage rings, lossless power delivery, or perhaps a large-volume magnetic shield against galactic cosmic radiation. However, perhaps the most significant enablement achieved from such a coating would be the long-term, deep space storage of cryogenic liquids, such as liquid oxygen (LOX). In our Phase I NIAC study, we realized that a combination of scattering particles and a silver backing could yield a highly effective, very broadband, reflector that could potentially reflect more than 99.9% of the Sun’s irradiant power. We developed a sophisticated model of this reflector and theoretically showed that cryogenic temperatures could be achieved in deep space at one astronomical unit (1 AU) from the Sun. We showed how this new reflector could minimize heat conduction into the cryogenic tanks by coating the tank support struts. We then modelled a strawman architecture for a mission to Mars, using a coated LOX tank, coated struts, and infrared shields, to show that with our new coating it would be possible to maintain liquid oxygen passively. As a result of this work a patent application was generated and a paper published in Optics Letters. Our Phase II NIAC study had two primary goals, to develop a rigid version of the cryogenic selective surface proposed in Phase I and to test its performance in a simulated deep space environment. During the first year of the project the work concentrated on developing rigid tiles of BaF2, leading to tiles as large as 4 inches in diameter that transmitted very little visible light. In addition, during the first year a simulated deep space environment was created using a vacuum chamber and cryocooler. Using this facility, we showed that our BaF2 tiles absorbed less than ¼% of 375 nm radiation, a significant milestone for the work. During the second year of the project, we continued to develop the BaF2 tiles and we put significant effort into the construction of a deep space environment where we could project simulated solar radiation onto a sample. In the spring of 2018, we conducted our first solar simulator test with BaF2 and saw about 3.6% absorption. This is better than the state-of-the-art, but disappointing since predictions were for much lower absorption. We, erroneously, attributed this absorption to water retention by the BaF2, and decided to change materials. We considered several oxides and settled on yttrium oxide (Y2O3) for further development, because it is broadband, lightweight, has high index, and is hydrophobic. In July 2018 we conducted our first test of a rigid tile of Y2O3 in the simulated deep space environment and saw significant absorption again. We then realized that the issue was not water, but mid-wave radiation passing through the tile and being absorbed by the temperature sensor and the varnish used to hold it in place. We wrapped the sensor in silver foil, re-ran the test, and saw much lower absorption; only 1.1%. We then re-ran the BaF2 tile and saw 1.4% absorption. These values are almost adequate to maintain LOX in deep space, but we suspect that there are still issues in our test apparatus; we suspect thermocouple wires may be absorbing radiation. Further, post-NIAC, testing will better determine the performance of our new solar reflector. In order to restrict the size of this report, we will only briefly describe topics that we have previously published, allowing us to devote more time to new material. So minimal material will be devoted to modeling the material and deep space cryogenic storage, while longer sections will cover our material development, simulated deep space testing, and new applications. The Launch Service Program (LSP) requested that we explore ways to use this new coating to maintain LOX in low Earth Orbit and that work is described. In addition, the Nuclear Thermal Propulsion (NTP) Program asked us to explore ways to reduce the heat load for liquid hydrogen, resulting in the development of a spray-on version of the coating that should significantly improve in-space multi-layer insulation performance.

Robert C. Youngquist,↗

Particle Morphology Effects on Flow Characteristics of PS304 Plasma Spray Coating Feedstock Powder Blend

The effects of BaF2-CaF 2 particle morphology on PS304 feedstock powder flow ability have been investigated. BaF2-CaF2 eutectic powders were fabricated by comminution (angular) and by gas atomization (spherical). The fluoride powders were added incrementally to the other powder constituents of the PS304 feedstock: nichrome, chromia, and silver powders. A linear relationship between flow time and concentration of BaF2-CaF2 powder was found. Flow of the powder blend with spherical BaF2-CaF2 was better than the angular BaF2-CaF2. Flow ability of the powder blend with angular fluorides decreased linearly with increasing fluoride concentration. Flow of the powder blend with spherical fluorides was independent of fluoride concentration. Results suggest that for this material blend, particle morphology plays a significant role in powder blend flow behavior, offering potential methods to improve powder flow ability and enhance the commercial potential. These findings may have applicability to other difficult-to-flow powders such as cohesive ceramics.

Stanford, Malcolm K.↗

Particle Size Effects on Flow Properties of PS304 Plasma Spray Feedstock Powder Blend

The effects of BaF2-CaF2 particle size and size distribution on PS304 feedstock powder flowability have been investigated. Angular BaF2-CaF2 eutectic powders were produced by comminution and classified by screening to obtain 38 to 45 microns 45 to 106 microns, 63 to 106 microns, 45 to 53 microns, 63 to 75 microns, and 90 to 106 microns particle size distributions. The fluorides were added incrementally from 0 to 10 wt% to the other powder constituents of the PS304 feedstock: nichrome, chromia, and silver powders. The flow rate of the powder blends decreased linearly with increasing concentration of the fluorides. Flow was degraded with decreasing BaF2-CaF2 particle size and with increasing BaF2-CaF2 particle size distribution. A semiempirical relationship is offered to describe the PS304 powder blend flow behavior. The Hausner Ratio confirmed the funnel flow test results, but was slightly less sensitive to differences in BaF2-CaF2 particle size and size distribution. These findings may have applicability to other powders that do not flow easily, such as ceramic powders.

Stanford, Malcolm K.↗

Thermal Effects on a Low Cr Modification of PS304 Solid Lubricant Coating

PS304 is a high temperature composite solid lubricant coating composed of Ni-Cr, Cr2O3, BaF2-CaF2 and Ag. The effect of reducing chromium content on the formation of voids in the Ni-Cr particles after heat treatment in PS304 coating was investigated. Coatings were prepared with Ni-20Cr or Ni-10Cr powder and in various combinations with the other constituents of PS304 (i.e., chromia, silver and eutectic BaF2-CaF2 powders) and deposited on metal substrates by plasma spray. Specimens were exposed to 650 C for 24 hr or 1090 C for 15 hr and then examined for changes in thickness, coating microstructure and adhesion strength. Specimens with Ni-10Cr generally had less thickness increase than specimens with Ni-20Cr, but there was great variance in the data. Reduction of chromium concentration in Ni-Cr powder tended to reduce the appearance of voids in the Ni-Cr phase after heat exposure. The presence of BaF2-CaF2 resulted in a significant increase in coating adhesion strength after heat treatment, while coatings without BaF2-CaF2 had no significant change. Chemical composition analysis suggested that the void formation was due to oxidation of chromium in the Ni-Cr constituent.

Stanford, Malcolm K.↗

Water Atomization of Barium Fluoride: Calcium Fluoride for Enhanced Flow Characteristics of PS304 Feedstock Powder Blend

PS304 is a plasma spray deposited solid lubricant coating with feedstock composed of NiCr, Cr2O3, Ag, and BaF2-CaF2 powders. The effects of rounded BaF2-CaF2 particles on the gravity-fed flow characteristics of PS304 feedstock have been investigated. The BaF2-CaF2 powder was fabricated by water atomization using four sets of process parameters. Each of these powders was then characterized by microscopy and classified by screening to obtain 45 to 106 micron particles and added incrementally from 0 to 10 wt% to the other constituents of the PS304 feedstock, namely nichrome, chromia, and silver powders. The relationship between feedstock flow rate, measured with the Hall flowmeter, and concentration of fluorides was found to be linear in each case. The slopes of the lines were between those of the linear relationships previously reported using angular and spherical fluorides and were closer to the relationship predicted using the rule of mixtures. The results offer a fluoride fabrication technique potentially more cost-effective than gas atomization processes or traditional comminution processes.

Stanford, Malcolm K.↗

Investigation of the Environmental Durability of a Powder Metallurgy Material

PM304 is a NASA-developed composite powder metallurgy material that is being developed for high temperature applications such as bushings in high temperature industrial furnace conveyor systems. My goal this summer was to analyze and evaluate the effects that heat exposure had on the PM304 material at 500 C and 650 C. The material is composed of Ni-Cr, Ag, Cr2O3, and eutectic BaF2-CaF2. PM304 is designed to eliminate the need for oil based lubricants in high temperature applications, while reducing friction and wear. However, further investigation was needed to thoroughly examine the properties of PM304. The effects of heat exposure on PM304 bushings were investigated. This investigation was necessary due to the high temperatures that the material would be exposed to in a typical application. Each bushing was cut into eight sections. The specimens were heated to 500 C or 650 C for time intervals from 1 hr to 5,000 hrs. Control specimens were kept at room temperature. Weight and thickness measurements were taken before and after the bushing sections were exposed to heat. Then the heat treated specimens were mounted and polished side by side with the control specimens. This enabled optical examination of the material's microstructure using a metallograph. The specimens were also examined with a scanning electron microscope (SEM). The microstructures were compared to observe the effects of the heat exposure. Chemical analysis was done to investigate the interactions between Ni-Cr and BaF2-CaF2 and between Cr2O3 and BaF2-CaF2 at high temperature. To observe this, the two compounds that were being analyzed were mixed in a crucible in varied weight percentages and heated to 1100 C in a furnace for approximately two hours. Then the product was allowed to cool and was then analyzed by X-ray diffraction. Interpretation of the results is in progress.

Ward, LaNita D.↗

Crystallization of heavy metal fluoride glasses

The kinetics of crystallization of a number of fluorozirconate glasses were studied using isothermal and dynamic differential scanning calorimetry and X-ray diffraction. The addition of the fluorides LiF, NaF, AlF3, LaF3 to a base glass composition of ZrF4-BaF2 reduced the tendency to crystallize, probably by modifying the viscosity-temperature relation. ZrF4-BaF2-LaF3-AlF3-NaF glass was the most stable against devitrification and perhaps is the best composition for optical fibers with low scattering loss. Some glasses first crystallize out into metastable beta-BaZr2F10 and beta-BaZrF6 phases, which transform into the most stable alpha-phases when heated to higher temperatures. The size of the crystallites was estimated to be about 600 A from X-ray diffraction.

Bansal, Narottam P.↗

Transmission and reflection studies of thin films in the vacuum ultraviolet

Both the transmittance and reflectance of 2 mm thick MgF2 substrates and of thin films of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 deposited on these substrates were measured for the wavelength range 120 nm to 230 nm. Results for BaF2, LaF2 and MgF2 show promise as being good materials from which interference filters can be made. The software and related hardware needed to take large amounts of data automatically in future measurements of the transmittance and reflectance was developed.

Peterson, Lennart R.↗

The effect of temperature cycling typical of low earth orbit satellites on thin films of YBa2Cu3O(7-x)

The refrigeration of superconductors in space poses a challenging problem. The problem could be less severe if superconducting materials would not have to be cooled when not in use. Thin films of the YBa2Cu3O(7-x) (YBCO) superconductor were subjected to thermal cycling, which was carried out to simulate a large number of eclipses of a low earth orbit satellite. Electrical measurements were performed to find the effect of the temperature cycling. Thin films of YBCO were formed by coevaporation of Y, BaF2, and Cu and postannealing in wet oxygen at 850 C for 3.5 h. The substrates used were (100) SrTiO3, polycrystalline alumina, and oxidized silicon; the last two have an evaporated zirconia layer. Processing and microstructure studies of these types of films have been published. THe zero resistance transition temperatures of the samples used in this study were 91, 82, and 86 K, respectively. The samples were characterized by four point probe electrical measurements as a function of temperature. The parameters measured were: the zero resistance transition temperature, the 10 to 90 percent transition width, and the room temperature resistance, normalized to that measured before temperature cycling. The results for two samples are presented. Each sample had a cumulative exposure. Cycling in atmospheric pressure nitrogen was performed at a rate of about 60 cycles per day, whereas in vacuum the rate was only about 10 cycles per day. The results indicate only little or no changes in the parameters measured. Degradation of superconducting thin films of YBCO has been reported due to storage in nitrogen. It is believed that the relatively good performance of films after temperature cycling is related to the fact that BaF2 was used as an evaporation source. The latest result on extended temperature cycling indicates significant degradation. Further tests of extended cycling will be carried out to provide additional data and to clarify this preliminary finding.

Mogro-Campero, A.↗

Radiation Damage Effects in Far Ultraviolet Filters and Substrates

New advances in VUV thin film filter technology have been made using filter designs with multilayers of materials such as Al2O3, BaF2, CaF2, HfO2, LaF3, MgF2, and SiO2. Our immediate application for these filters will be in an imaging system to be flown on a satellite where a 2 X 9 R(sub E) orbit will expose the instrument to approximately 275 krads of radiation. In view of the fact that no previous studies have been made on potential radiation damage of these materials in the thin film format, we report on such an assessment here. Transmittances and reflectances of BaF2, CaF2, HfO2, LaF3, MgF2, and SiO2 thin films on MgF2 substrates, Al2O3 thin films on fused silica substrates, uncoated fused silica and MgF2, and four multilayer filters made from these materials were measured from 120 nm to 180 nm before and after irradiation by 250 krads from a Co-60 gamma radiation source. No radiation-induced losses in transmittance or reflectance occurred in this wavelength range. Additional postradiation measurements from 160 nm to 300 nm indicated a 3 - 5% radiation-induced absorption near 260 nm in some of the samples with MgF2 substrates. From these measurements it is concluded that far ultraviolet filters made from the materials tested should experience less that 5% change from exposure to up to 250 krads of high energy radiation in space applications.

Keffer, Charles E.↗

Continued Development of a Highly Reflective Solar Coating for Cryogenic Liquid Storage in Space

State-of-the-art solar reflectors absorb 6-8 % of the sun's irradiant power, which is adequate for spacecraft thermal control; but not for storage of cryogens in tanks exposed to the Sun. A solar reflector must absorb less than 0.4% of the Sun's power, while radiating effectively in the far IR, to allow LOX storage. Hibbard realized this in 1960's, at about the same time that nearly perfect optical reflectors were developed based on particle scattering. In 2015, under funding from the NASA Innovative Advanced Concepts Program (NIAC), these breakthroughs were rediscovered. Theoretical analysis showed that a tank coated with a thick (1 cm) layer of 150 nm particles, composed of a broadband material, could allow the tank to chill to cryogenic temperatures, even in the presence of 1 AU solar irradiance. Subsequent work lead to the demonstration and testing of BaF2 based rigid coupons. Placing one of these in a cryocooler-based simulated deep space environment and irradiating with simulated sunlight has shown about 1% absorption. This is better than the state-of-the-art but not yet sufficient for LOX storage.This paper will review the background material presented above but will concentrate on work performed over the last year, including the design and build-up of the testing apparatus. Since our last publication, we have changed materials from BaF2 to Y2O3. Y2O3 has slightly higher solar absorptance, but is hydrophobic and higher index.

Swanger, Adam↗