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Refractory interplanetary dust particles

Criteria are described by which refractory interplanetary dust particles (IDPs) can be differentiated from the products of spacecraft debris. These criteria have been used to discover and characterize IDPs that are composed predominantly of refractory phases. Two of these particles contain hibonite, perovskite, spinel, refractory glass, and a melilite; only hibonite was identified within a third. The grain size for all particles ranges from 0.05 to 1 micrometer, so that they are much finer grained than the refractory calcium- and aluminum-rich inclusions in meteorites. The glass-containing refractory IDPs may be primitive nebular condensates that never completely crystallized and thus have been preserved extant.

Zolensky, Michael E.↗

Petrography and origin of refractory inclusions from the Murray and Murchison C2 chondrites

By freeze-thaw disaggregation, we have recovered a total of 47 refractory inclusions. New discoveries include the following: a hibonite-pyroxene spherule from Murray; a CaAl4O7-bearing spherule from Murchison; and a Sc-fassaite-bearing ultrarefractory inclusion from Murchison. Freeze-thaw disaggregation, combined with density separation and hand-picking as described is a proven method for recovering rare objects from carbonaceous chondrites. This method is especially effective on C2's due to their porosity and typically results in the discovery of new types of refractory inclusions. Because few refractory inclusions from Murray have been described, we studied this meteorite, although only a small amount of material (730 mg) was available for disaggregation. Many refractory inclusions from Murchison have been described, and we disaggregated a larger amount (approximately 18 g) of Murchison in an attempt to find new types of refractory inclusions, especially corundum-bearing ones.

Simon, S. B.↗

High temperature barrier coatings for refractory metals

Improvements in high temperature oxidation resistant metal coating technology will allow NASA and commercial entities to develop competitive civil space transport and communication systems. The success of investigations completed in this program will have a positive impact on broadening the technology base for high temperature materials. The work reported herein describes processes and procedures for successfully depositing coherent oxidation barrier coatings on refractory metals to prevent degradation under very severe operating environments. Application of the new technology developed is now being utilized in numerous Phase 3 applications through several prominent aerospace firms. Major achievements have included: (1) development of means to deposit thick platinum and rhodium coatings with lower stress and fewer microcracks than could be previously achieved; (2) development of processes to deposit thick adherent coatings of platinum group metals on refractory substrates that remain bonded through high temperature excursions and without need for intermediate coatings (bonding processes unique to specific refractory metals and alloys have been defined; (3) demonstration that useful alloys of refractory and platinum coatings can be made through thermal diffusion means; (4) demonstration that selected barrier coatings on refractory substrates can withstand severe oxidizing environments in the range of 1260 deg and 1760 deg C for long time periods essential to the life requirements of the hardware; and (5) successful application of the processes and procedures to prototype hardware. The results of these studies have been instrumental in improved thermal oxidation barrier coatings for the NASP propulsion system. Other Phase 3 applications currently being exploited include small uncooled thrusters for spacecraft and microsatellite maneuvering systems.

Malone, G. A.↗

Evaluation of Alternative Refractory Materials for the Main Flame Deflectors at KSC Launch Complexes

The deterioration of the refractory materials used to protect the KSC launch complex steel base structures from the high temperatures during launches results in frequent and costly repairs and safety hazards. KSC-SPEC-P-0012, Specification for Refractory Concrete, is ineffective in qualifying refractory materials. This study of the specification and of alternative refractory materials recommends a complete revision of the specification and further investigation of materials that were found to withstand the environment of the Solid Rocket Booster main flame deflector better than the refractory materials in current use in terms of compressive strength, tensile strength, modulus of rupture, shrinkage, and abrasion.

Calle, Luz Marina↗

Testing Requirements for Refractory Materials

Launch Pads 39A and 39B currently use refractory material (Fondu Fyre) in the flame trenches. This material was initially approved for the Saturn program. This material had a lifetime of 10 years according to the manufacturer, and it has been used for over 40 years. As a consequence, the Fondu Fyre at Launch Complex 39 requires repair subsequent to almost every launch. A review of the literature indicates that the gunned Fondu Fyre refractory product (WA-1G) was never tested prior to use. With the recent severe damage to the flame trenches, a new refractory material is sought to replace Fondu Fyre. In order to replace Fondu Fyre, a methodology to test and evaluate refractory products was developed. This paper outlines this methodology and discusses current testing requirements, as well as the laboratory testing that might be required. Furthermore, this report points out the necessity for subscale testing, the locations where this testing can be performed, and the parameters that will be necessary to qualify a product. The goal is to identify a more durable refractory material that has physical, chemical, and thermal properties suitable to withstand the harsh environment of the launch pads at KSC.

Calle, Luz Marina↗

Testing Requirements for Refractory Materials

Launch Pads 39A and 39B currently use refractory material (Fondu Fyre) in the flame trenches. This material was initially approved for the Saturn program. This material had a lifetime of 10 years according to the manufacturer, and it has been used for over 40 years. As a consequence, the Fondu Fyre at Launch Complex 39 requires repair subsequent to almost every launch. A review of the literature indicates that the gunned Fondu Fyre refractory product (WA-1G) was never tested prior to use. With the recent severe damage to the flame trenches, a new refractory material is sought to replace Fondu Fyre. In order to replace Fondu Fyre, a methodology to test and evaluate refractory products was developed. This paper outlines this methodology and discusses current testing requirements, as well as the laboratory testing that might be required. Furthermore, this report points out the necessity for subscale testing, the locations where this testing can be performed, and the parameters that will be necessary to qualify a product. The goal is to identify a more durable refractory material that has physical, chemical, and thermal properties suitable to withstand the harsh environment of the launch pads at KSC.

Calle, Luz Marina↗

Testing Requirements for Refractory Materials

Launch Pads 39A and 39B currently use refractory material (Fondu Fyre) in the flame trenches. This material was initially approved for the Saturn program. This material had a lifetime of 10years according to the manufacturer, and it has been used for over 40 years. As a consequence, the Fondu Fyre at Launch Complex 39 requires repair subsequent to almost every launch. A review of the literature indicates that the gunned Fondu Fyre refractory product (WA-1 G) was never tested prior to use. With the recent severe damage to the flame trenches, a new refractory material is sought to replace Fondu Fyre. In order to replace Fondu Fyre, a methodology to test and evaluate refractory products was developed. This paper outlines this methodology and discusses current testing requirements, as well as the laboratory testing that might be required. Furthermore, this report points out the necessity for subscale testing, the locations where this testing can be performed, and the parameters that will be necessary to qualify a product. The goal is to identify a more durable refractory material that has physical, chemical, and thermal properties suitable to withstand the harsh environment of the launch pads at KSC.

Calle, Luz Marina↗

Commercial off-the-Shelf (COTS) Refractory Material Evaluation

Fondu Fyre (FF) is currently the only refractory material qualified for use in the flame trench at KSC's Shuttle Launch Pads 39A and 39B. However, the material is not used as it was qualified and has undergone increasingly frequent and severe degradation due to the launch blasts. This degradation is costly as well as dangerous for launch infrastructure, crew and vehicle. FF is applied at the pad via the gunnite process, where wetted refractory material is sprayed onto a steel grid mounted on a support structure. The water content in this process can be manually adjusted by operators, causing distinct visual and physical discrepancies among repair areas. Since the application process is unlikely to change for new refractory materials, it is important to understand the effects of water content on commercial off-the-shelf (COTS) refractory materials. The purpose of this study was to evaluate the performance of the FF with respect to various water contents as well as heat treatments, to simulate aging and exposure to the blast. Initial results indicated that different water contents and heat treatments result in distinct differences in crushing strength, apparent porosity and bulk density. However, water content became an insignificant factor in both crush strength and porosity when FF was cured to at least 1500 deg. Additionally, inspection of the material's surface microstructure by scanning electron microscopy indicated distinguishable characteristics for different heat treatment levels. Results from this study will help guide future studies on the development and identification of new refractory materials.

Calle, Luz Marina↗

The Diversity of Refractory Organic Material in Comets

Organic matter exists in comets (most notably in 81P/Wild 2 [Stardust], 67P/Churyomov- Gerasimenko (67P/C-G) [Rosetta], chondritic porous IDPS, and UCAMMs) and in primitive carbonaceous chondrites that likely retain some chemistry that reflects an origin in the prenatal cold molecular cloud (Alexander+2017). Heavy isotopic enrichments, 15N/14N and possibly D/H, signify preserved molecular cloud organics. In the cold outer disk, if grains are lofted above the disk mid-plane then organics likely experience significant UV processing (Ciesla+2012). In remote sensing of comet comae, organics in the dust are considered refractory or semirefractory. Semi-refractory organics have limited comae lifetimes and produce distributed sources of molecules (H2CO and CO). Rosetta's close passes of 67P/C-G's nucleus (10-15 km) reveals a distributed source of glycine, methyl amine and ethylamine (Altwegg+2016). Cometary samples and primitive meteorites have two types of organic matter: (1) acid-insoluble organic matter (IOM), which is a macromolecular polymer with a mixture of aromatic and aliphatic moieties, and (2) labile, soluble organics, which includes the amino acids, such as glycine (Stardust, Elsila+2009). Meteoritic IOM is robust, withstanding experimental temperatures of 1200 K (Dobrica+2011, Cody+2008). Nanoglobules are a type of IOM; they have a distinct physical structure, but often share the same chemistry as the other IOM from the same meteorite. Moderate-sized PAHs (20 C-atoms) are detected in Stardust samples (Clemett+2010). Refractory organic IOM is ubiquitous yet has a great diversity of abundances between cometary samples. IOM is in primitive chondrites, 67P/C-G (Rosetta), 81P/Wild 2 (Stardust), 1P/Halley, 26P/Grigg-Skjellerup, UCAMMs, anhydrous IDPs, and in chondritic porous IDPs (CP IDPs) and larger cluster IDPs (e.g., Fray+2016, Fomenkova+94, Busemann+ 09, Dobrica+2011, Dobrica+2012). 81P's refractory organic matter is of two types (De Gregorio+2011): nanoglobules of highly aromatic refractory organic matter and polyaromatic carbonyl-containing organic matter, which is similar to IOM in primitive meteorites and IDPs. Fray+2017 estimate that 50% of carbon in 67P/C-G is in IOM. 67P/C-G's organics appear to lack the soluble organic matter, aliphatic carbon, amino acids, and PAHs (Fray+2016). Other notable aspects of the diversity in IOM in cometary samples are the ranges of atomic ratios of N/C, O/C, and H/C, and the range of isotopic enrichments of 15N/14N and D/H. Aqueous and thermal processing on asteroids changes the balance of soluble to insoluble organics, and may be important for diversifying the range of OM delivered to Earth.

Wooden, Diane↗

Novel Ceramic Dispersion Strengthened Refractory Metals for Improved Printability and Properties

Refractory metals and alloys are of major interest for nuclear fusion systems, space nuclear power and propulsion, and hypersonic applications due to their desirable properties at elevated temperatures (>1500°C). Limitations of refractory materials include their low ductility, poor oxidation resistance, and high manufacture cost using traditional techniques. Additive manufacturing (AM) can reduce material waste associated with manufacture, but AM fabrication is impacted by the brittleness of these refractory metals, resulting in excessive cracking during printing. Cracking reduces the effectiveness of hot isostatic pressing (HIP) which is commonly used to improve density and mechanical properties of AM components. The goal of this work is to improve refractory metal printability without majorly affecting the material properties which are the main reason these materials are used. Ceramic nanoparticles have been shown to help improve material properties after heat treatment. Results will be shown that demonstrate the effectiveness of adding nanoparticles to refractory metals. Additionally, there will be discussion regarding how these nanoparticles change the effect of heat treatments such as HIP compared with the AM pure metal samples.

Carly J. Romnes↗

A Procedure to Quantify Interlaminar Damage in Refractory Composites by In-Situ Micro-X-Ray Computed Tomography

Refractory composites are relevant for hot-structure applications on re-entry vehicles. To develop optimized high-performance hot structures, accurate material property data is required. Material properties that often limit design in two-dimensional (2-D) composites are interlaminar strengths. A better understanding of the failure mechanisms for interlaminar shear (ILS), interlaminar tension (ILT), and curved-beam interlaminar tension (CB-ILT) tests can provide insight on improving the design and fabrication of refractory composites. In-situ tests were performed to capture the progressive failure in American Society for Testing and Materials (ASTM) sized ILS (ASTM D3846), ILT (ASTM D7291), and CB-ILT (ASTM D6415) specimens. Before measuring internal damage of refractory composites specimens, the methodology of the test setup warrants a complete and thorough discussion. Detail on the test procedure, test stand design, micro-x-ray computed tomography (CT) configuration, data processing, and CT system uncertainty is discussed. Through keeping the many parameters of the CT system consistent, the uncertainty of the CT system was minimized, optimizing the quality of measurements. The overall quality of a CT scan can be quantified by three metrics: voxel resolution, minimal voxel resolution feature detection, and directional variability. A better understanding of the progressive failure mechanisms of refractory composites is provided by the results of both the present discussion and the one found in the accompanying paper titled “Analysis of Interlaminar Damage in Refractory Composites by In-Situ Micro-X-Ray Computed Tomography”.

In-situ micro-x-ray CT↗

Refractory lithophile elements

The abundance and distributions of refractory lithophile elements in chondritic meteorites and calcium-aluminum inclusions (CAIs) are presently noted to indicate that protoplanetary material was heated to very high temperatures. Three subsequent elemental fractionations have since been resolved: (1) that within the CAIs, indicating temperatures high enough to evaporate much of the refractory element content; (2) that of the refractory lithophile elements; and (3) that of Mg and Si, which indicates that the high temperatures were prevalent throughout the chondrite-formation region. Attention is given to models that have been proposed to explain elemental and isotopic abundances of refractory lithophile elements in chondritic material.

Larimer, John W.↗

Chemical compositions of refractory inclusions from the Vigarano and Leoville carbonaceous chondrites

The contents of the major and the trace elements of three refractory inclusions from Leoville and two hibonite-rich refractory inclusions and a dark clast from Vigarano were investigated using INAA technique, and the results were compared with results reported for an Allende inclusion. It was found that two out of the three refractory inclusions from Leoville and both inclusions from Vigarano have lower Na and Au contents than the coarse-grained inclusion from Allende. It is shown that the concentrations of all volatile elements in refractory inclusions in the Leoville and Vigarano meteorites tend to be either below or at the low end of their concentration ranges in Allende coarse-grained inclusions. This is considered to be due to the fact that the former were altered in parts of the solar nebula where grain-bias separation processes removed the inclusions from chemical communication with the gas at a higher temperature or after a shorter time than for the inclusions from Allende.

Mao, Xue-Ying↗

Isotopic and trace element characteristics of an unusual refractory inclusion from Essebi

The isotopic and chemical properties of Ca-Al-rich inclusions (CAI) provide important clues to the early solar nebula environment. While the abundances of refractory major and trace elements are similar to those expected for high temperature condensates, the variety of textural, chemical, and isotopic signatures indicate most CAI experienced complex, multi-stage histories involving repeated episodes of condensation, evaporation, and metamorphism. Evidence of multiple processes is especially apparent in an unusual refractory inclusion from Essebi (URIE) described by El Goresy et al. The melilite (mel)-rich core of URIE contains polygonal framboids of spinel (sp) and hibonite (hb) or sp and fassaite (fas) and is surrounded by a rim sequence consisting of five layers. In contrast to rims on Allende, the mineralogy of the URIE rim layers becomes increasingly refractory from the core outwards, ending in a layer of spinel-Al2O3 solid solution + Sc-rich fassaite. The chemical and mineralogical features of URIE are inconsistent with crystallization from a homogeneous melt, and El Goresy et al. proposed a multi-step history involving condensation of sp + hb and aggregation into framboids, capture of framboids by a refractory silicate melt droplet, condensation of rim layers, and alteration of mel to calcite and feldspathoid. The PANURGE ion probe was used to investigate the isotopic and trace element characteristics of URIE to develop a more complete picture of the multiple processes leading to formation and metamorphism.

Deloule, E.↗

Nucleation, Growth, Annealing, and Coagulation of Refractory Oxides and Metals: Recent Experimental Progress and Applications to Astrophysical Systems

Starting with cooling, refractory vapors diluted in significant quantities of H and He there are four processes that most natural systems will undergo: nucleation, growth, annealing, and coagulation. Nucleation is the processes by which the first stable refractory nuclei form in the vapor. These are the seeds onto which the remaining vapors will condense during the growth stage. Solids of any composition will try to arrange themselves into the least energetic configuration, provided that there is sufficient energy available to support such processes as diffusion and the breaking of chemical bonds. There is a significant activation energy associated with the annealing process in refractory solids due to the relatively high energy of the chemical bonds in solids. The grains formed in most cosmochemical systems are extremely small and often tightly coupled to the gas. Because of their small physical cross sections coagulation may be a very slow process unless there is another driving force involved in addition to normal Brownian motion. In what follows we will briefly cover each of these four stages for refractory oxide and metal grains, although in inverse order.

Nuth, J. A.↗

Performance Assessment of Refractory Concrete Used on the Space Shuttle's Launch Pad

The John F. Kennedy Space Center (KSC) maintains several facilities for launching space vehicles. During recent launches it has been observed that the refractory concrete materials that protect the steel-framed flame duct are breaking away from this base structure and are being projected at high velocities. There is significant concern that these projected pieces can strike the launch complex or space vehicle during the launch, jeopardizing the safety of the mission. A qualification program is in place to evaluate the performance of different refractory concretes and data from these tests have been used to assess the performance of the refractory concretes. However, there is significant variation in the test results, possibly making the existing qualification test program unreliable. This paper will evaluate data from past qualification tests, identify potential key performance indicators for the launch complex, and will recommend a new qualification test program that can be used to better qualify refractory concrete.

Trejo, David↗

Properties of Refractory Concrete in Tension and Compression

Refractory concrete on the LC-39A Flame Deflector has been damaged during multiple Space Shuttle launches (e.g. STS-124, STS-126, STS-119, and STS-125, STS-127). These events have prompted a better understanding of the system via an analytical model of the Flame Deflector assembly to include the Fondu Fyre refractory concrete. This model requires test data inputs of the refractory concrete's mechanical properties, which include stress versus strain curves in tension and compression, modulus of elasticity, and Poisson's ratio. Sections of Fondu Fyre refractory concrete removed from the LC-39A Flame Deflector were provided for this testing.

Sampson, Jeffrey↗