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Diffusion in the system K2O-SrO-SiO2. II - Cation self-diffusion coefficients.

The self-diffusion coefficients were measured by introducing a slab of glass previously irradiated in a reactor between two slabs of unirradiated glass. By heating the specimens, etching them sequentially and determining the radioactivity, self-diffusion coefficients for K and Sr were measured. It is pointed out that the results obtained in the investigations appear to support the proposal that the network of the base glass predominantly controls the activation energy for the diffusion of ions.

Varshneya, A. K.↗

CVD silicon carbide monofilament reinforced SrO-Al2O3-2SiO2 (SAS) glass-ceramic composites

Unidirectional CVD SiC fiber-reinforced SrO.Al2O3.2SiO2 (SAS) glass-ceramic matrix composites have been fabricated by hot pressing at various combinations of temperature, pressure and time. Both carbon-rich surface coated SCS-6 and uncoated SCS-0 fibers were used as reinforcements. Almost fully dense composites have been obtained. Monoclinic celsian, SrAl2Si2O8, was the only crystalline phase observed in the matrix from x-ray diffraction. During three point flexure testing of composites, a test span to thickness ratio of approximately 25 or greater was necessary to avoid sample delamination. Strong and tough SCS-6/SAS composites having a first matrix crack stress of approximately 300 MPa and an ultimate bend strength of approximately 825 MPa were fabricated. No chemical reaction between the SCS-6 fibers and the SAS matrix was observed after high temperature processing. The uncoated SCS-0 fiber-reinforced SAS composites showed only limited improvement in strength over SAS monolithic. The SCS-0/SAS composite having a fiber volume fraction of 0.24 and hot pressed at 1400 deg C exhibited a first matrix cracking stress of approximately 231 +/- 20 MPa and ultimate strength of 265 +/- 17 MPa. From fiber push-out tests, the fiber/matrix interfacial debonding strength (tau(sub debond)) and frictional sliding stress (tau(sub friction)) in the SCS-6/SAS system were evaluated to be approximately 6.7 +/- 2.3 MPa and 4.3 +/- 0.6 MPa, respectively, indicating a weak interface. However, for the SCS-0/SAS composite, much higher values of approximately 17.5 +/- 2.7 MPa for tau(sub debond) and 11.3 +/- 1.6 MPa for tau(sub friction) respectively, were observed; some of the fibers were so strongly bonded to the matrix that they could not be pushed out. Examination of fracture surfaces revealed limited short pull-out length of SCS-0 fibers. The applicability of various micromechanical models for predicting the values of first matrix cracking stress and ultimate strength of these composites were examined.

Bansal, Narottam P.↗

Short Range-Ordered Minerals: Insight into Aqueous Alteration Processes on Mars

Short range-ordered (SRO) aluminosilicates (e.g., allophane) and nanophase ferric oxides (npOx) are common SRO minerals derived during aqueous alteration of basaltic materials. NpOx refers to poorly crystalline or amorphous alteration products that can be any combination of superparamagnetic hematite and/or goethite, akaganeite, schwertmannite, ferrihydrite, iddingsite, and nanometer-sized ferric oxide particles that pigment palagonitic tephra. Nearly 30 years ago, SRO phases were suggested as alteration phases on Mars based on similar spectral properties for altered basaltic tephra on the slopes of Mauna Kea in Hawaii and Martian bright regions measured by Earth-based telescopes. Detailed characterization of altered basaltic tephra on Mauna Kea have identified a variety of alteration phases including allophane, npOx, hisingerite, jarosite, alunite, hematite, goethite, ferrihydrite, halloysite, kaolinite, smectite, and zeolites. The presence of npOx and other Fe-bearing minerals (jarosite, hematite, goethite) was confirmed by the M ssbauer Spectrometer onboard the Mars Exploration Rovers. Although the presence of allophane has not been definitely identified on Mars robotic missions, chemical analysis by the Spirit and Opportunity rovers and thermal infrared spectral orbital measurements suggest the presence of allophane or allophane-like phases on Mars. SRO phases form under a variety of environmental conditions on Earth ranging from cold and arid to warm and humid, including hydrothermal conditions. The formation of SRO aluminosilicates such as allophane (and crystalline halloysite) from basaltic material is controlled by several key factors including activity of water, extent of leaching, Si activity in solution, and available Al. Generally, a low leaching index (e.g., wet-dry cycles) and slightly acidic to alkaline conditions are necessary. NpOx generally form under aqueous oxidative weathering conditions, although thermal oxidative alteration may occasional be involved. The style of aqueous alteration (hydrolytic vs. acid sulfate) impacts which phases will form (e.g., oxides, oxysulfates, and oxyhydroxides). Knowledge on the formation processes of SRO phases in basaltic materials on Earth has allowed significant enhancement in our understanding of the aqueous processes at work on Mars. The 2011 Mars Science Laboratory (MSL) will provide an instrument suite that should improve our understanding of the mineralogical and chemical compositions of SRO phases. CheMin is an X-ray diffraction instrument that may provide broad X-ray diffraction peaks for SRO phases; e.g., broad peaks around 0.33 and 0.23 nm for allophane. Sample Analysis at Mars (SAM) heats samples and detects evolved gases of volatile-bearing phases including SRO phases (i.e., carbonates, sulfates, hydrated minerals). The Alpha Particle X-ray Spectrometer (APXS) and ChemCam element analyzers will provide chemical characterization of samples. The identification of SRO phases in surface materials on MSL will be challenging due to their nanocrystalline properties; their detection and identification will require utilizing the MSL instrument suite in concert. Ultimately, sample return missions will be required to definitively identify and fully characterize SRO minerals with state-of-the-art laboratory instrumentation back on Earth.

Ming, Douglas W.↗

X-Ray Amorphous Phases in Antarctica Dry Valley Soils: Insight into Aqueous Alteration Processes on Mars?

The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 weight percentage) of X-ray amorphous materials in a windblown deposit (Rocknest) and in a sedimentary mudstone (Cumberland and John Klein) in Gale crater, Mars. On Earth, X-ray amorphous components are common in soils and sediments, but usually not as abundant as detected in Gale crater. One hypothesis for the abundant X-ray amorphous materials on Mars is limited interaction of liquid water with surface materials, kinetically inhibiting maturation to more crystalline phases. The objective of this study was to characterize the chemistry and mineralogy of soils formed in the Antarctica Dry Valleys, one of the driest locations on Earth. Two soils were characterized from different elevations, including a low elevation, coastal, subxerous soil in Taylor Valley and a high elevation, ultraxerous soil in University Valley. A variety of techniques were used to characterize materials from each soil horizon, including Rietveld analysis of X-ray diffraction data. For Taylor Valley soil, the X-ray amorphous component ranged from about 4 weight percentage in the upper horizon to as high as 15 weight percentage in the lowest horizon just above the permafrost layer. Transmission electron microscopy indicated that the presence of short-range ordered (SRO) smectite was the most likely candidate for the X-ray amorphous materials in the Taylor Valley soils. The SRO smectite is likely an aqueous alteration product of mica inherited from granitic materials during glaciation of Taylor Valley. The drier University Valley soils had lower X-ray amorphous contents of about 5 weight percentage in the lowest horizon. The X-ray amorphous materials in University Valley are attributed to nanoparticles of TiO2 and possibly amorphous SiO2. The high abundance of X-ray amorphous materials in Taylor Valley is surprising for one of the driest places on Earth. These materials may have been physically and chemical altered during soil formation, however, the limited interaction with water and low temperatures may result in the formation of "immature" X-ray amorphous or SRO materials. Perhaps, a similar process contributes to the formation of the high content of X-ray amorphous materials detected on Mars.

Ming, D. W.↗

Ternary and quaternary oxides of Bi, Sr, and Cu

Before the discovery of superconductivity in an oxide of Bi, Sr, and Cu, the system Bi-Sr-Cu-O had not been studied, although several solid phases had been identified in the two-component regions of the ternary system Bi2O3-SrO-CuO. The oxides Sr2CuO3, SrCu2O2, SrCuO2, and Bi2CuO4 were then well known and characterized, and the phase diagram of the binary system Bi2O3 -SrO had been established in the temperature range 620 to 1000 C. Besides nine solutions of compositions Bi(2-2x) Sr(x) O(3-2x) and different symmetries, this diagram includes three definite compounds of stoichiometries Bi(2)SrO4, Bi2Sr2O5, and Bi2Sr3O6 (x = 0.50, 0.67 and 0.75 respectively), only the second of which with known unit-cell of orthorhombic symmetry, dimensions (A) a = 14.293(2), b = 7.651(2), c = 6.172(1), and z = 4. The first superconducting oxide in the system Bi-Sr-Cu-O was initially formulated as Bi2Sr2Cu2O(7+x), with an orthorhombic unit-cell of parameters (A) a = 5.32, b = 26.6, c = 48.8. In a preliminary study the same oxide was formulated with half the copper content, Bi(2)Sr(2)CuO(6+x), and indexed its reflections assuming an orthorhombic unit-cell of dimensions (A) a = 5.390(2), b = 26.973(8), c = 24.69(4). Subsequent studies by diffraction techniques have confirmed the composition 2:2:1. A new family of oxygen-deficient perovskites, was characterized, after identifying by x ray diffraction the phases present in the products of thermal treatments of about 150 mixtures of analytical grade Bi2O3, Sr(OH)2-8H2O and CuO at different molar ratios. X ray diffraction data are presented for some other oxides of Bi and Sr, as well as for various quaternary oxides, among them an oxide of Bi, Sr, and Cu.

Casais, M. T.↗

Crystal chemical and quantum chemical studies of Ba(Sr)-Nb oxide compounds

The information available on the BaO(SrO)-NbO-NbO2 system with the niobium atom in the lower oxidation degree is very limited. Very few compounds have been found previously in this system. They are BaNbO3, SrxNbO3(0,7=x=1), Ba2Nb2O9, SrNb8O14; and some suggestions on the BaNb8O14 existence have been made also. At the same time Nb-based oxide compounds could be quite interesting in the search of new noncopper high T(sub c) superconductors Researchers studied Ba(Sr) NbxO2x-2 and Ba2(Sr2)-NbxO2x-1 compositions in the phase diagram of BaO(SrO)-NbO-NbO2 system. The synthesis of the materials was carried out in vacuum at the temperatures of 1000 to 1500 C. Barium carbonate and niobium pentoxide were used as initial components. X-ray analysis was carried out.

Zubkov, V. G.↗

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glasss transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder x ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structure transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Bansal, Narottam P.↗

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glass transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder X ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structural transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Bansal, Narottam P.↗

Direct Observations of Nucleation in a Nondilute Multicomponent Alloy

The chemical pathways leading to gamma'(L1(sub 2)) nucleation from nondilute Ni-5.2 Al-14.2 Cr at. %, gama(fcc), at 873 K are followed with radial distribution functions and isoconcentration surface analyses of direct-space atom-probe tomographic images. Although Cr atoms initially are randomly distributed, a distribution of congruent Ni3Al short-range-order domains (SRO), [R] approx. equals 0.6 nm, results from Al diffusion during quenching. Domain site occupancy develops as their number density increases leading to Al-rich phase separation by gamma'-nucleation, [R]=0.75 nm, after SRO occurs.

Sudbrack, Chantal K.↗

X-ray Amorphous Components of Antarctica Dry Valley Soils: Weathering Implications for Mars

The Antarctic Dry Valleys (ADV) comprise the largest ice-free region of Antarctica. Precipitation usually occurs as snow, relative humidity is frequently low, and mean annual temperatures are about -20°C [1]. Substantial work has focused on soil formation in the ADVs [2], however, little work has focused on the mineralogy of secondary alteration phases. The dominant weathering process in the ADV region is physical weathering, however, chemical weathering has been well documented [3]. The occurrence of chemical weathering processes are suggested by the presence of clay minerals and iron and titanium oxides in soil. Previously we have investigated soils from two sites in the ADV’s and have shown evidence of chemical weathering by the presence of clay minerals (vermiculite, smectite), short-range ordered (SRO) and/or X-ray amorphous materials, and Fe- and Tioxides as well as the presence of discrete calcite crystals [4, 5]. The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 wt. %) of X-ray amorphous materials in a windblown deposit or “soil” (Rocknest) and in a sedimentary rocks [6,7,8]. The occurrence of large amounts of X-ray amorphous materials in Mars sediments is surprising because these materials are usually present in small quantities in terrestrial environments. The objective of this study is to further characterize the chemistry and mineralogy, specifically the secondary alteration mineralogy and the presence of X-ray amorphous material, of soils from two sites we have previously studied, a subxerous soil in Taylor Valley, and an ultraxerous soil in University Valley. While the chemical alteration processes and mineralogy of the ADV has been documented previously, there has been limited discussion on the occurrence and formation of X-ray amorphous and SRO materials in Antarctica soils. The process of aqueous alteration in the ADVs may have implications for pedogenic processes on Mars, and may lead to a better understanding to the abundance of amorphous material found in sediments in Gale crater.

Quinn, J. E.↗

Access to Space for NASA Small Sats: Current and Future Needs

Small spacecraft technology advancements have fundamentally shifted how NASA’s Science Mission Directorate (SMD) executes science investigations. To support this approach, the SMD Rideshare Office (SRO) was established in 2020 to lead the definition and implementation of a directorate-wide rideshare strategy. Serving as the central point of contact for coordinating compatible NASA payloads with launch opportunities, the SRO maximizes science, exploration, and technology return on investment by enabling rideshare or other access to space opportunities for small spacecraft on SMD primary mission launches, VADR commercial launch procurements, and other government agency launch opportunities. As NASA seeks to reduce costs and increase the rate of discovery, small satellites and multi manifest access to space have become integral to achieving the agency’s strategic vision. While NASA has created the above-mentioned mechanisms to expand access to space and achieve lower launch costs for its small satellites, many factors have limited full exploit of the opportunity these mechanisms can bring. NASA continues to evolve its mission cultures and technical requirements to adapt and take advantage of burgeoning commercial launch and rideshare advancements. To do so NASA requires collaboration with small satellite manufacturers, principal investigators, and commercial industry partners. Current needs include technical development and design of structurally robust spacecraft buses capable of withstanding varied launch loads, which will increase rideshare interchangeability and versatility. Further, instrument and spacecraft designs must also evolve to handle diverse launch environments and loads factors, while reducing reliance on complex purge and cleanliness constraints, sensitivities to silicones and hydrocarbons, and magnetic requirements. Continued maturation of small and medium launch providers in the near-term is also essential to drive down costs through competition. The current mission selection cadence often complicates the ability to synchronize multiple missions on a single launch. Future needs can include affordable space maneuverability options such as enhanced spacecraft propulsion systems and unique orbital maneuvering capabilities for our individual smallsats or constellations. These emerging capabilities offer a path to unique science orbits for NASA small satellites, but only under the condition that their cost remains affordable and competitive to accommodate inherently smaller mission budgets. Additionally, the projected surge of multiple SMD small satellites launching simultaneously and to unique deep space science orbits necessitates evaluation of expanding deep space communications capabilities. This presentation provides a comprehensive overview of NASA SMD’s access to space landscape and offers further unique insights and discussion, backed by NASA rideshare experiences and lessons learned, on the current and future developments required to unleash the full potential of rideshare opportunities.

Rideshare↗

Access to Space for NASA SmallSats: Current and Future Needs

Small spacecraft technology advancements have fundamentally shifted how NASA’s Science Mission Directorate (SMD) executes science investigations. To support this approach, the SMD Rideshare Office (SRO) was established in 2020 to lead the definition and implementation of a directorate-wide rideshare strategy. Serving as the central point of contact for coordinating compatible NASA payloads with launch opportunities, the SRO maximizes science, exploration, and technology return on investment by enabling rideshare or other access to space opportunities for small spacecraft on SMD primary mission launches, VADR commercial launch procurements, and other government agency launch opportunities. As NASA seeks to reduce costs and increase the rate of discovery, small satellites and multi manifest access to space have become integral to achieving the agency’s strategic vision. While NASA has created the above-mentioned mechanisms to expand access to space and achieve lower launch costs for its small satellites, many factors have limited full exploit of the opportunity these mechanisms can bring. NASA continues to evolve its mission cultures and technical requirements to adapt and take advantage of burgeoning commercial launch and rideshare advancements. To do so NASA requires collaboration with small satellite manufacturers, principal investigators, and commercial industry partners. Current needs include technical development and design of structurally robust spacecraft buses capable of withstanding varied launch loads, which will increase rideshare interchangeability and versatility. Further, instrument and spacecraft designs must also evolve to handle diverse launch environments and loads factors, while reducing reliance on complex purge and cleanliness constraints, sensitivities to silicones and hydrocarbons, and magnetic requirements. Continued maturation of small and medium launch providers in the near-term is also essential to drive down costs through competition. The current mission selection cadence often complicates the ability to synchronize multiple missions on a single launch. Future needs can include affordable space maneuverability options such as enhanced spacecraft propulsion systems and unique orbital maneuvering capabilities for our individual smallsats or constellations. These emerging capabilities offer a path to unique science orbits for NASA small satellites, but only under the condition that their cost remains affordable and competitive to accommodate inherently smaller mission budgets. Additionally, the projected surge of multiple SMD small satellites launching simultaneously and to unique deep space science orbits necessitates evaluation of expanding deep space communications capabilities. This presentation provides a comprehensive overview of NASA SMD’s access to space landscape and offers further unique insights and discussion, backed by NASA rideshare experiences and lessons learned, on the current and future developments required to unleash the full potential of rideshare opportunities.

Rideshare↗

Advanced thermionic converter development

Recent progress at Thermo Electron in developing advanced thermionic converters is summarized with particular attention paid to the development of electrodes, diodes, and triodes. It is found that one class of materials (ZnO, BaO and SrO) provides interesting cesiated work functions (1.3-1.4 eV) without additional oxygen. The second class of materials studied (rare earth oxides and hexaborides) gives cesiated/oxygenated work functions of less than 1.2 eV. Five techniques of oxygen addition to thermionic converters are discussed. Vapor deposited tungsten oxide collector diodes and the reflux converter are considered.

Huffman, F. N.↗

Rapid Solidification of Magnetic Oxides

The enhanced control over microstructural evolution inherent in rapid solidification processing techniques are exploited to create novel ceramic magnetic materials. The great sensitivity of magnetic properties to local structure provides a powerful probe both for the study of structure and of microscopic solidification mechanisms. The first system studied is the SrO-Fe2O3 binary, which contains the commercially important hard magnetic compound strontium hexaferrite. The products were analyzed by transmission electron microscopy, Mossbauer spectroscopy, magnetic measurements, and differential thermal analysis. As-quenched ribbons contain high concentrations of super-paramagnetic particles, 80 to 250 Angstroms in diameter, in a glassy matrix. This suggests the possibility of crystallizing monodomain strontium hexaferrite during subsequent heat treatment, with a resulting increase in coercivity over conventionally processed ferrite magnets. That magnetic properties can be controlled in solidification processing by varying the quench rate is demonstrated.

Kalonji, G.↗

Thermodynamic properties of some metal oxide-zirconia systems

Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

Jacobson, Nathan S.↗

Ternary and quaternary oxides of Bi, Sr and Cu

Before the discovery of superconductivity in an oxide of Bi, Sr, and Cu, the system Bi-Sr-Cu-O had not been studied, although several solid phases had been identified in the two-component regions of the ternary system Bi2O3-Si-O-CuO. The oxides Sr2CuO3, SrCu2O2, SrCuO2, and Bi2CuO4 were then well known and characterized, and the phase diagram of the binary system Bi2O3-SrO had been established in the temperature range 620 to 1000 C. Besides nine solutions of compositions Bi(2-2x) Sr(x) O(3-2x) and different symmetries, this diagram includes three definite compounds of stoichiometries Bi(2)BrO4. Bi2Sr2O5, and Bi2Sr3O6 (x - 0.50, 0.67 and 0.75 respectively), only the second of which with known unit-cell of orthorhombic symmetry, dimensions (A) a = 14.293(2), b = 7.651(2), c = 6.172(1), and z = 4. The first superconducting oxide in the system Bi-Sr-Cu-O was initially formulated as Bi2Sr2Cu2O(7+x), with an orthorhombic unit-cell of parameters (A) a = 5.32, b = 26.6, c = 48.8. In a preliminary study the same oxide was formulated with half the copper content, Bi(2)Sr(2)CuO(6+x), and index its reflections assuming an orthorhombic unit-cell of dimensions (A) a = 5.390(2), b = 26.973(8), c = 24.69(4). Subsequent studies by diffraction techniques have confirmed the composition 2:2:1. A new family of oxygen-deficient perovskites, was characterized, after identifying by x ray diffraction the phases present in the products of thermal treatments of about 150 mixtures of analytical grade Bi2O3, Sr(OH)2-8H2O and CuO at different molar ratios. X ray diffraction data are presented for some other oxides of Bi and Sr, as well as for various quaternary oxides, among them an oxide of Bi, Sr, and Cu.

Casais, M. T.↗