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Powering the Next Frontier: Manufacturing Solar Cells in Space

In support of NASA's Artemis program with the goal of a sustained human-lunar presence, there is a need for very large (>100kW) and high-voltage-capable solar arrays, estimated to cost over $150M. Perovskite-based thin-film photovoltaics offer substantial advantages over state-of-the-art solar arrays from the perspective of manufacturing large arrays. Many of the challenges perovskite solar cells experience in terrestrial operations, e.g degradation caused by moisture and oxygen exposure, are not applicable in long-term space applications. The future of implementing perovskite photovoltaics in space is promising, further so is manufacturing these solar cells in space. Here we provide an overview of NASA Glenn Research Center's progress towards validating perovskite solar cells for operation in space and we illuminate innovation opportunities to which the greater community can contribute so that we may realize in-space manufacturing of perovskite photovoltaics.

Solar Cells↗

Terrestrial magma ocean and core segregation in the earth

According to the recent theories of formation of the earth, the outer layer of the proto-earth was molten and the terrestrial magma ocean was formed when its radius exceeded 3000 km. Core formation should have started in this magma ocean stage, since segregation of metallic iron occurs effectively by melting of the proto-earth. Therefore, interactions between magma, mantle minerals, and metallic iron in the magma ocean stage controlled the geochemistry of the mantle and core. We have studied the partitioning behaviors of elements into the silicate melt, high pressure minerals, and metallic iron under the deep upper mantle and lower mantle conditions. We employed the multi-anvil apparatus for preparing the equilibrating samples in the ranges from 16 to 27 GPa and 1700-2400 C. Both the electron probe microanalyzer (EPMA) and the Secondary Ion Mass spectrometer (SIMS) were used for analyzing the run products. We obtained the partition coefficients of various trace elements between majorite, Mg-perovskite, and liquid, and magnesiowustite, Mg-perovskite, and metallic iron. The examples of the partition coefficients of some key elements are summarized in figures, together with the previous data. We may be able to assess the origin of the mantle abundances of the elements such as transition metals by using the partitioning data obtained above. The mantle abundances of some transition metals expected by the core-mantle equilibrium under the lower mantle conditions cannot explain the observed abundance of some elements such as Mn and Ge in the mantle. Estimations of the densities of the ultrabasic magma Mg-perovskite at high pressure suggest existence of a density crossover in the deep lower mantle; flotation of Mg-perovskite occurs in the deep magma ocean under the lower mantle conditions. The observed depletion of some transition metals such as V, Cr, Mn, Fe, Co, and Ni in the mantle may be explained by the two stage process, the core-mantle equilibrium under the lower mantle conditions in the first stage, and subsequent downwards separation of the ultrabasic liquid (and magnesiowustite) and flotation of Mg-perovskite in the lower mantle.

Ohtani, Eiji↗

Electrically Variable or Programmable Nonvolatile Capacitors

Electrically variable or programmable capacitors based on the unique properties of thin perovskite films are undergoing development. These capacitors show promise of overcoming two important deficiencies of prior electrically programmable capacitors: Unlike in the case of varactors, it is not necessary to supply power continuously to make these capacitors retain their capacitance values. Hence, these capacitors may prove useful as components of nonvolatile analog and digital electronic memories. Unlike in the case of ferroelectric capacitors, it is possible to measure the capacitance values of these capacitors without changing the values. In other words, whereas readout of ferroelectric capacitors is destructive, readout of these capacitors can be nondestructive. A capacitor of this type is a simple two terminal device. It includes a thin film of a suitable perovskite as the dielectric layer, sandwiched between two metal or metal oxide electrodes (for example, see Figure 1). The utility of this device as a variable capacitor is based on a phenomenon, known as electrical-pulse-induced capacitance (EPIC), that is observed in thin perovskite films and especially in those thin perovskite films that exhibit the colossal magnetoresistive (CMR) effect. In EPIC, the application of one or more electrical pulses that exceed a threshold magnitude (typically somewhat less than 1 V) gives rise to a nonvolatile change in capacitance. The change in capacitance depends on the magnitude duration, polarity, and number of pulses. It is not necessary to apply a magnetic field or to cool the device below (or heat it above) room temperature to obtain EPIC. Examples of suitable CMR perovskites include Pr(1-x)Ca(x)MnO3, La(1-x)S-r(x)MnO3,and Nb(1-x)Ca(x)MnO3. Figure 2 is a block diagram showing an EPIC capacitor connected to a circuit that can vary the capacitance, measure the capacitance, and/or measure the resistance of the capacitor.

Shangqing, Liu↗

Nuclear Microprobe using Elastic Recoil Detection (ERD) for Hydrogen Profiling in High Temperature Protonic Conductors

The interaction between hydrogen and various high temperature protonic conductors (HTPC) has not been clearly understood due to poor densification and unreacted secondary phases. the melt-processing technique is used in producing fully dense simple SrCe(0.9)Y (0.10) O(3-delta) and complex Sr3Ca(1+x)Nb(2+x)O(9-delta) perovskites that can not be achieved by solid-state sintering. the possibilities of ion beam analysis have been investigated to quantify hydrogen distribution in HTPC perovskites subjected to water heat treatment. Nuclear microprobe technique is based on the interactions of a focused ion beam of MeV light ions (H-1, H-2, He-3, He-4,.) with the sample to be analyzed to determine local elemental concentrations at the cubic micrometer scale, the elastic recoil detection analysis technique (ERDA) has been carried out using He-4(+) microbeams and detecting the resulting recoil protons. Mappings of longitudinal sections of water treated SrCeO3 and Sr(Ca(1/3)Nb(2/3))O3 perovskites have been achieved, the water treatment strongly alters the surface of simple SrCe(0.9)Y(0.10)O(3-delta) perovskite. From Rutherford Back Scattering measurements (RBS), both Ce depletion and surface re-deposition is evidenced. the ERDA investigations on water treated Sr3Ca(1+x)Nb(2+x)O(9-delta) perovskite did not exhibit any spatial difference for the hydrogen incorporation from the surface to the centre. the amount of hydrogen incorporation for Sr3Ca(1+x)Nb(2+x)O(9-delta) was low and required further development of two less conventional techniques, ERDA in forward geometry and forward elastic diffusion H-1(p,p) H-1 with coincidence detection.

Berger, Pascal↗

Trace Elemental Abundances in Calcium-Aluminum-Rich Inclusions in CV Chondrites

Introduction: Calcium-aluminum-rich inclusions (CAIs), are the first formed solids that define the age of the Solar System [1,2]. CAIs are thought to have condensed from nebular gas [3,4] within the first <1 Ma of Solar System formation [5,6]. CAIs have experienced numerous early Solar System processes including condensation, evaporation, melting, recrystallization, and aqueous alteration [e.g., 7]. The chemical, mineralogical, and textural diversity among CAIs results from a range of chemical and physical processes recorded during nebular and parent body epoch. This study aims to explore the mineralogical, textural, and chemical compositions of CAIs including the trace elemental abundances in CAI phases to determine the early Solar System processes recorded in them. Samples and Analytical Methods: We analyzed one CAI each from CV3 chondrites Northwest Africa (NWA) 5508 designated as ‘Saguaro’, and Northwest Africa (NWA) 12772 designated as ‘Hoopoe’. Back-scatter electron (BSE) images were collected using a Phenom XL scanning electron microscope (SEM) at the Lunar and Planetary Institute (LPI) and the JEOL JXA-8530F electron probe microanalyzer (EPMA) at Johnson Space Center (JSC)-NASA. Additionally, energy dispersive X-ray spectrometry (EDS) elemental maps of select areas for these samples were collected using a 15.0kV beam energy and a 40µA emission current. Using the EPMA, wavelength-dispersive X-ray spectroscopy (WDS) quantitative data were collected. In-situ trace element measurements for both CAIs were determined at JSC-NASA using a Photon Machines 193nm laser ablation system and a Thermo-Scientific Element-XR inductively coupled plasma mass spectrometer (ICP-MS). Analyses consisted of 30s ablations at 10Hz, spot sizes of 20-25µm, and a fluence of 6.0 J/cm2 for anorthite and melilite, and a 3.5 J/cm2 fluence for all other phases. NIST612 was used to correct for instrument drift, while BHVO-2g was used as a primary calibration standard. BCR-2g and in-house mineral standards were regularly measured as unknowns to ensure accuracy. Results: Saguaro is a coarse-grained CAI, ~11 x 6 mm in dimensions. Saguaro contains spinel, Al-rich pyroxene, anorthite, Mg-rich melilite, and minor perovskite in its interior and is therefore classified as a Type B CAI. Individual melilite grains shows normal compositional zoning with an Ak content ranging from ~24 to 54 with no apparent trend from the core to the edge of the CAI. The spinel appears euhedral and occurs both as clusters and as spinel palisades [8]. Two rim sequences surround most of the sample: the inner rim being a Wark-Lovering (WL) rim (~10-35 µm) containing pyroxene, spinel, and melilite (or anorthite), and the outer rim is a finer-grained, thicker (~100 µm), accretionary rim (Fig. 1). The mineral phases in Saguaro record an overall flat REE pattern with an average negative Eu anomaly in pyroxene, and an average positive Eu anomaly in anorthite and melilite respectively. Anorthite, melilite, and pyroxene have a minor depletion in Tm (Fig. 2). The Hoopoe CAI is a compact, coarse-grained ~6 × 4 mm in size. The major mineralogy includes hibonite, spinel, melilite, anorthite, and perovskite. Therefore, it is classified as a compact transitional type A and B. (?)zoning was observed in some hibonites. Individual melilite grains show both reverse and normal zoning, where the Ak content ranges from ~6- to 28. Melilite shows two distinct textures. One texture consisted of smooth melilite that appeared homogenous, while the second appeared to consist of many fine fractures. The spinel also often appears clustered. The WL-rim sequence surrounding Hoopoe is ~25 µm thick and composed of spinel, perovskite, hibonite, and melilite/anorthite. It is then partially surrounded by an outer accretionary rim (~75µm). Like before, refractory metal nuggets appeared concentrated near the WL rims. Other metal assemblages rich in Fe and Ni were also observed. All major mineral phases in Hoopoe display relatively flat REE patterns, except for varying Eu and Tm between phases (Fig. 2). There is a prominent negative Eu anomaly in perovskite and an average positive Eu anomaly in spinel, anorthite, and hibonite respectively (Fig. 2, 3). The mixed phases along the rim of the CAI also display a negative Eu anomaly, and all phases the CAI were depleted in Pb. Discussion: The CV3 CAIs analyzed in this study were classified based on their mineralogy and textures into Type A versus Type B CAIs [10]. Hibonite appears to be pseudomorphically replacing the spinel, (i.e., is hibonite in composition, but appears in the shape of spinel). Spinel palisades. The presence of spinel palisades present in Saguaro are consistent with the melting and recrystallization experienced by this CAI. Trace elemental analyses. Saguaro and Hoopoe display similar trace element patterns to each other, with both appearing generally flat, with anomalies in Eu, and Tm. Melilite and anorthite display positive Eu anomalies in both CAIs, in addition to the hibonite in Hoopoe (Fig. 2). The phases that are depleted in Eu are pyroxene and perovskite in both Saguaro and Hoopoe, respectively (Fig. 3). Given that Eu is volatile in reducing environments [11], this could possibly indicate reducing conditions at the time anorthite and melilite crystallized, with the gas they formed from containing Eu. As these CAIs continued to form, this gas as a result would become depleted in Eu. This also could be supported by the propensity of anorthite and melilite to take up Eu from its surroundings and incorporate it into their structure [12]. In addition, analyzing the assemblage of the phases in the Saguaro, melilite and anorthite (Eu enriched) often surround the pyroxene (Eu depleted) as they are crystallized. This intergrowth of phases and the proximity of the phases would support that the Eu is being incorporated into some phases, preventing it from incorporating into other. Trace elemental analyses of the CAI rims will be evaluated in more detail, as they are complicated by the transient signal being composed of a mixture of mineral phases. Broadly, however, the patterns in the rims of both CAIs are comparable to each other, and for Hoopoe, to the mixed phase patterns in the core (Fig. 3). Other studies have found that CAI rims can be depleted in Ce and Yb [13], however we did not observe these anomalies in the two CAIs discussed here. Given their similarity, the trace elemental analyses of the mixed interior (i.e. core) and rim phases could be interpreted as forming from similar, if not the same, reservoirs. The REE abundance between the rim and core of Hoopoe are also similar, indicating they may have formed from a gas of the same or similar composition. Acknowledgments: We thank the ASU Center for Meteorite Studies for loaning the samples used in this work and Tabb Prissel for his assistance with the analysis. Mouti Al-Hashimi thanks Sam Crossley and Cyrena Goodrich for their help with the LPI SEM training. This work was supported by the LPI Summer Intern Program in Planetary Science and the LPI Cooperative Agreement. References: [1] Connelly J.N. (2012) Science, 338, 651-655. [2] MacPherson G. J. (2014) Treatise on Geochem., 2, 139-179. [3] Grossman L. (1972) GCA, 36, 597-619. [4] Ebel, D.S. (2006) Meteorites and the Early Solar System II (D. S. Lauretta & H. Y. McSween, Eds.) 253-277. [5] MacPherson G. J. (2012) Earth Planet. Sci. Lett., 331-332, 43-54. [6] MacPherson G.J. (2017) GCA, 201, 65-82. [7] Krot A.N. (1995) Meteoritics & Planet. Sci., 30, 748-775. [8] Wark and Lovering (1982) GCA, 46, 2595-2607. [9] Palme H. and Jones A. (2003) Treatise on Geochemistry (H. D. Holland and K. K. Turekian Eds.), 1, 41-61. [10] Grossman L. (1980) Ann. Rev. Earth Planet. Sci., 8, 559-608. [11] Floss C. et al. (1996) GCA, 60, 1975-1997. [12] Mason B. and Martin P. M. (1974) Earth Planet. Sci. Lett., 22, 141-144. [13] Wark B. and Boynton W. V. (2001) Meteoritics & Planet. Sci., 36, 1135-1166.

X Mouti↗

Mineralogy of a refractory inclusion in the Allende (C3V) meteorite

A spherical 220-micrometer diameter, spinel-hibonite-perovskite inclusion from the Allende C3V meteorite contains a central hibonite cluster with an angular coundary. This central hibonite is enclosed within spinel that is zoned from Mg-rich at the hibonite boundary to more Fe-rich at the inclusion boundary. This spinel zone includes lath-shaped hibonites usually subradial to the central hibonites. Two textural types of perovskites are present as exsolution from the central hibonite and as equidimensional grains within both the central hibonite and spinel. These second perovskites have exsolution lamellae of Al2O3. Within the central hibonite and adjacent to some equidimensional perovskites, a fine porous phase interpreted as alteration has a composition of nearly pure Al2O3 with minor amounts of Na and Si. This is possibly either an intergrowth of corundum and nepheline or a modified Al2O3, Beta-alumina.

Steele, Ian M.↗

Metastable Phase Relations in the System Ca(sub O)-Al2(sub O)3-MgO-TiO(sub 2): Applications to Ca- And Al-Rich Inclusions

Introduction: High temperature phases such as corundum, hibonite, grossite, and perovskite are among the earliest phases that condensed in the early solar nebula. Recent work has shown that defect-structured phases occur in some ultrarefractory inclusions as metastable, possibly more kinetically-favored alternatives to the thermodynamically predicted stable phase assemblages [1-4]. For example, Han et al. have shown that non-stoichiometry in hibonite is accommodated by extra "spinel" blocks in the structure instead of the equilibrium assemblages hibonite+corundum or hibonite+spinel. To explore these relations, we have conducted a series of experiments in the system CaO-Al2O3- MgO-TiO2. Here we discuss the compositions and mineralogy of the experimental samples and how they relate to phases in refractory inclusions with a focus on perovskite and spinel. Methods: For the series of annealing studies, a CaO-Al2O3 eutectic melt is allowed to react with a pure alumina crucible at 1,530degC for either 4 hours or 5 days, followed by quenching in air. Later experiments were similar except that additions of 5 wt% MgO, and CaTiO(sub 3) were used to explore the effect of minor elements on the phase assemblages. The experimental conditions resulted in reaction zones approximately 100-300 m wide consisting of a hibonite layer immediately adjacent to the corundum, followed by a grossite layer, and finally krotite with residual quenched melt. For the experiments with Mg, spinel is distributed in all layers but is mainly concentrated in the krotite layer. In the Ti-bearing experiments, perovskite precipitated in association with the krotite and residual melt. In addition to the experiments, we also analyzed perovskite grains in the FUN inclusion SHAL [5] and a large compact type A CAI from Allende. The experiments and refractory inclusions were analyzed using a JEOL 7600F SEM and quantitative analyses were obtained using the JEOL 8530F field-emission electron microprobe.

Keller, L. P.↗

Mineralogical Analysis of Calcium-Aluminum-Rich Inclusions Provides Insight Into Post-Formation Processes

Introduction: Calcium-aluminum inclusions (CAIs) are cm- to mm-sized intergrowths of refractory phases found in chondritic meteorites [1]. Their mineral compositions closely match the compositions of the solids thought to condense from an extremely hot (>1500K) gas with a bulk solar composition [2-4], suggesting that CAIs were the earliest solids within the Solar System [2-4]. These inclusions provide invaluable insights into the conditions and dynamics of the early Solar System. CAIs must be transported from their formation region near the protosun to the chondrite parent-body accretion region. The nature of their journey could affect how, when, and where the secondary processes recorded in these CAIs occurred [4]. Did these secondary processes occur in the solar nebula or during accretion with the parent body, or both? How were the CAIs affected by varying thermochemical processes? To better answer these questions, we have undertaken an in-depth, textural study of the secondary alteration of select CAI samples. Methods: We chose three CAIs that experienced a range of post-formation processing to gain better understanding of secondary alteration based on previous preliminary examination [5]. Representative CAIs were chosen from NWA 5508 (CV3), NWA 12772 (CV3), and Coolidge (CL4) carbonaceous chondrites. We used scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) techniques for detailed chemical, mineralogical, and textural analysis of the CAIs. Backscattered electron (BSE) images and X-ray elemental maps were taken of Coolidge and NWA 5508 using the Lunar and Planetary Institute (LPI) Phenom SEM. The JEOL 7900F SEM at NASA Johnson Space Center (JSC) was used to obtain energy dispersive spectroscopy (EDS) chemical maps of all samples. High resolution EBSD analysis identified the mineral phases and textures, providing key information on their nature. Based on the SEM and EBSD data, minerals of interest were selected for quantitative chemical electron probe micro-analysis (EPMA) using the JEOL JXA-8530F at NASA JSC. Results and Discussion: The EDS maps show that the NWA 5508 and NWA 12772 CAIs designated “Saguaro” and “Hoopoe” respectively [5] are enriched in calcium while the Coolidge CAI designated “Cottonwood” is aluminum and magnesium rich. Saguaro. A ~1.5cm diameter igneous Type B CAI with a rounded shape. The dominant phases are melilite, spinel, and Al-Ti pyroxene with minor anorthite. Spinel is subhedral and occurs in clusters. Some of these clusters have a circular geometry which encloses other minerals, known as a palisade structure [6] (Fig. 1). Some palisades form near perfect circles while others are more irregular in shape. Melilite in Saguaro ranges in size from coarse (>250m) to fine-grained (5-7m) and forms intergrown laths. A third of the melilite grains exhibit simple twinning about their <001> axis. The spinel palisades and twinned melilite in Saguaro suggest an igneous history, and the lack of secondary minerals suggests minimal aqueous alteration. At some point in time after the initial condensation of the minerals and formation of the inclusion, the sample was remelted and quickly solidified. The formation of the palisades is still heavily debated. One hypothesis is that the palisades are the rims of smaller CAIs that accreted early on, essentially acting as xenoliths within the larger CAIs [7]. Another hypothesis suggests an igneous origin for palisade structures [6-8] wherein the melt traps gas bubbles, and the spinel nucleates on the surface of this bubble. Based on the WDS spot analyses of 41 melilite grains using EPMA, the data suggest that the composition inside and outside the palisades is nearly identical. This finding indicates that these palisades are likely not exogenous but rather formed from melt-vapor reactions. Our results are consistent with studies by Simon and Grossman,1997 [6] and Zhang et al. (2019) [8]. Hoopoe. A ~0.5cm compact Type A CAI with an irregular shape. The dominant mineral phases are melilite, spinel, and hibonite with minor amounts of anorthite, augite, and perovskite. The melilite ranges in size from ~500 to 50µm. The larger melilite grains have simple twinning along the <001> axis like melilite in Saguaro. Melilite in Hoopoe exhibits crystal-plastic strain with misorientation dominantly about the <010> and <110> axes. Spinel shows subhedral to euhedral morphology and appears in clusters. Hibonite grains are similar to spinel in habit and size but show more plastic strain. The two minerals are often found together with one appearing to replace the other. Perovskite appears in fine grained recrystallized regions alongside fine augite and spinel. The abundant strain and deformation features in the melilite and hibonite suggest that Hoopoe experienced shock. This shock could have occurred in the nebula [9] or from an impact of another body on the parent body asteroid. The appearance of fine-grained (<10m) areas of augite, perovskite, and spinel in the dominantly coarse-grained inclusion suggest recrystallization, possibly due to the sudden increase in pressure and temperature. Cottonwood. This ~0.5cm CAI exhibits distinct mineralogy and textures suggesting a high degree of alteration. It is irregular in shape. The dominant mineral phases are spinel and anorthite with minor amounts of augite and rutile. The two main texture types can be seen in Fig. 2. The first type consists of coarse euhedral to subhedral spinel and anorthite. The second includes fine grained spinel, anorthite, rutile, and iron sulfides. Within these fine-grained regions, the anorthite grains are clustered into domains exhibiting the same crystallographic orientation. Rutile exclusively occurs with fine anorthite indicating a potential relationship between the two. Cottonwood has a clear and unbroken Wark-Lovering [10] rim (Fig. 2) on one side that consists of a sequence of spinel followed by anorthite and an outer layer of augite. The abundance of the fine-grained regions containing iron oxides and iron sulfides, secondary phases such as rutile, and oriented anorthite grains is evidence for recrystallization associated with a high degree of thermal metamorphism. The EPMA analyses on both coarse- and fine-grained spinel show that the fine spinel grains are more enriched in Cr (1-2 wt. %) than their coarse counterparts (0.1-0.5 wt. %). The data suggest thermal metamorphism drove chemical exchange of the previously refractory inclusion, introducing chromium and iron as well as sulfur, which is moderately volatile. Conclusions: The three CAIs analyzed record distinct secondary nebular and parent body processes. Saguaro melted in the nebula as seen by the twinned melilite and spinel palisades. Hoopoe experienced intense shock which deformed its melilite and recrystallized perovskite, augite, and spinel in fine-grained regions. Cottonwood shows evidence of recrystallization and chemical changes consistent with thermal metamorphism occurring after accretion into the parent-body.

V E Burnette↗

Pyroxenes and olivines: Structural implications of shock-wave data for high pressure phases

The nature of the shock-induced, high-pressure phases of olivine and pyroxene rocks is examined in the light of data for the densities of a new class of perovskite-related silicate structures. Also examined are some new Hugoniot and release adiabat data for bronzite. Reexamining available shock data for magnesian pyroxenes and olivines leads to the conclusion that they define a mixed phase (or disequilibrium) region to about the 100 GPa range, related to the kinetics of phase transformation in these silicates. By recognizing this point, certain discrepancies in previous interpretations of shock data can be explained. A set of theoretical Hugonoits for pyroxene and olivine stoichiometry, perovskite-bearing assemblages was constructed based on their properties deduced from high-pressure work, showing that the shock data is compatible with transformations to perovskites in the 45-7GPa region. Finally, the shock data indicate very similar properties for olivine and pyroxene at high pressures making them both equally likely candidates for the lower mantle.

Jeanloz, R.↗

Condensation and fractionation of rare earths in the solar nebula

The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

Davis, A. M.↗

Actinide chemistry in Allende Ca-Al-rich inclusions

Fission track radiography is used to investigate the U and Th microscale distribution in a set of Allende-meteorite Ca-Al-rich inclusions. In the Type B inclusions, the major phases melilite and fassaite are important actinide host phases, and on the rims of Type B inclusions and throughout all other inclusions studied, perovskite is the dominant actinide host phase. Results suggest that neither alteration nor loss or gain of an actinide-rich phase appears to have been an important Th/U fractionation mechanism, and that volatility differences may be the dominant factor. Th/U and rare earth element abundance patterns for the spinel and perovskite rim suggest rim formation by volatilization of interior material, and within the constraints of the brief time scale required for this heating, several mechanisms for spinel-perovskite rim formation are possible.

Murrell, M. T.↗

Sintering of BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) with/without SrTiO3 Dopant

The perovskite composition, BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta), displays excellent protonic conduction at high temperatures making it a desirable candidate for hydrogen separation membranes. This paper reports on the sintering behavior of BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) powders doped with SrTiO3. Two methods were used to synthesize BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) powders: (1) solid state reaction and (2) wet chemical co-precipitation. Co-precipitated powder crystallized into the perovskite phase at 1000 C for 4 hrs. Complete reaction and crystallization of the perovskite phase by solid state was achieved by calcining at 1200 C for 24 hrs. Solid state synthesis produced a coarser powder with an average particle size of 1.3 microns and surface area of 0.74 sq m/g. Co-precipitation produced a finer powder with a average particle size of 65 nm and surface area of 14.9 sq m/g. Powders were doped with 1, 2, 5, and 10 mole % SrTiO3. Samples were sintered at 1450 C, 1550 C and 1650 C. SrTiO3 enhances sintering, optimal dopant level is different for powders synthesized by solid state and co-precipitation. Both powders exhibit similar grain growth behavior. Dopant levels of 5 and 10 mole % SrTiO3 significantly enhances the grain size.

Dynys, F.↗

A-site- and/or B-site-modified PbZrTiO3 materials and (Pb, Sr, Ca, Ba, Mg) (Zr, Ti, Nb, Ta)O3 films having utility in ferroelectric random access memories and high performance thin film microactuators

A modified PbZrTiO.sub.3 perovskite crystal material thin film, wherein the PbZrTiO.sub.3 perovskite crystal material includes crystal lattice A-sites and B-sites at least one of which is modified by the presence of a substituent selected from the group consisting of (i) A-site substituents consisting of Sr, Ca, Ba and Mg, and (ii) B-site substituents selected from the group consisting of Nb and Ta. The perovskite crystal thin film material may be formed by liquid delivery MOCVD from metalorganic precursors of the metal components of the thin film, to form PZT and PSZT, and other piezoelectric and ferroelectric thin film materials. The thin films of the invention have utility in non-volatile ferroelectric memory devices (NV-FeRAMs), and in microelectromechanical systems (MEMS) as sensor and/or actuator elements, e.g., high speed digital system actuators requiring low input power levels.

Roeder, Jeffrey F.↗

A-SITE-AND/OR B-SITE-MODIFIED PBZRTIO3 MATERIALS AND (PB, SR, CA, BA, MG) (ZR, TI,NB, TA)O3 FILMS HAVING UTILITY IN FERROELECTRIC RANDOM ACCESS MEMORIES AND HIGH PERFORMANCE THIN FILM MICROACTUATORS

A modified PbZrTiO.sub.3 perovskite crystal material thin film, wherein the PbZrTiO.sub.3 perovskite crystal material includes crystal lattice A-sites and B-sites at least one of which is modified by the presence of a substituent selected from the group consisting of (i) A-site substituents consisting of Sr, Ca, Ba and Mg, and (ii) B-site substituents selected from the group consisting of Nb and Ta. The perovskite crystal thin film material may be formed by liquid delivery MOCVD from metalorganic precursors of the metal components of the thin film, to form PZT and PSZT, and other piezoelectric and ferroelectric thin film materials. The thin films of the invention have utility in non-volatile ferroelectric memory devices (NV-FeRAMs), and in microelectromechanical systems (MEMS) as sensor and/or actuator elements, e.g., high speed digital system actuators requiring low input power levels.

Roeder, Jeffrey F.↗

NWA10758: A New CV3 Chondrite Bearing a Giant CAI with Hibonite-Rich Wark-Lovering Rim

Northwest Africa (NWA) 10758 is a newly identified carbonaceous chondrite that is a Bali-like oxidized CV3. The large Ca-Al rich inclusion (CAI) in this sample is approx. 2.4 x 1.4 cm. The CAI is transitional in composition between type A and type B, with interior mineralogy dominated by melilite, plus less abundant spinel and Al-Ti rich diopside, and only very minor anorthite (Fig. 1A). This CAI is largely free of secondary alteration in the exposed section we examined, with almost no nepheline, sodalite or Ca-Fe silicates. The Wark-Lovering (WL) rim on this CAI is dominated by hibonite, with lower abundances of spinel and perovskite, and with hibonite locally overlain by melilite plus perovskite (as in Fig. 1B). Note that the example shown in 1B is exceptional. Around most of the CAI, hibonite + spinel + perovskite form the WL rim, without overlying melilite. The WL rim can be unusually thick, ranging from approx. 20 microns up to approx. 150 microns. A well-developed, stratified accretionary rim infills embayments of the CAI, and thins over protuberances in the convoluted CAI surface.

Ross, D. K.↗

Northwest Africa 10758: A New CV3 Chondrite Bearing a Giant CAI with Hibonite-Rich Wark-Lovering Rim

Northwest Africa (NWA) 10758 is a newly identified carbonaceous chondrite that is a Bali-like oxidized CV3. The large Ca-Al rich inclusion (CAI) in this sample is approx. 2.4 x 1.4 cm. The CAI is transitional in composition between type A and type B, with interior mineralogy dominated by melilite, plus less abundant spinel and Al-Ti rich diopside, and only very minor anorthite (Fig. 1A). This CAI is largely free of secondary alteration in the exposed section we examined, with almost no nepheline, sodalite or Ca-Fe silicates. The Wark-Lovering (WL) rim on this CAI is dominated by hibonite, with lower abundances of spinel and perovskite, and with hibonite locally overlain by melilite plus perovskite (as in Fig. 1B). Note that the example shown in 1B is exceptional. Around most of the CAI, hibonite + spinel + perovskite form the WL rim, without overlying melilite. The WL rim can be unusually thick, ranging from approx.20 microns up to approx. 150 microns. A well-developed, stratified accretionary rim infills embayments of the CAI, and thins over protuberances in the convoluted CAI surface.

Ross, D. K.↗

Grossite-Bearing Refractory Inclusions from Reduced CV Chondrites: Mineralogical and Oxygen Isotopic Constraints on the Parent Body Alteration History

We report the results of coordinated mineralogical, microstructural, and oxygen isotopic analyses of grossite-bearing refractory inclusions from reduced CV (Vigarano type) chondrites to obtain a more complete picture of secondary parent body alteration processes and conditions. Grossite (CaAl 4 O 7 ) occurs in cores of nodules in fine-grained Ca,Al-rich inclusions (CAIs) that likely represent aggregates of nebular condensates. In many occurrences, grossite has been partially replaced by hercynite [(Fe,Mg,Zn)Al 2 O 4 ], which displays complex microstructures and compositions, and magnetite nanoparticles. The alteration of grossite was a crystallographically-controlled, fluid-driven process that occurred via partial dissolution of grossite and subsequent precipitation of hercynite and magnetite during short-lived and low-temperature metasomatic alteration on the CV chondrite parent body. The constituent phases of grossite-bearing CAIs show heterogeneous oxygen isotopic compositions, with grossite and perovskite displaying systematically 16O-depleted compositions (Δ 17 O = −12‰ to −1‰) relative to uniformly 16 O-rich hibonite and spinel (Δ 17 O = −25‰ to −21‰). Melilite is variably 16 O-depleted (Δ 17 O = −25‰ to −2‰). The observed oxygen isotopic distribution is interpreted as a result of mineralogically controlled oxygen isotopic exchange with an 16 O-poor fluid on the CV chondrite parent body. Collectively, the presence of limited fluids played an important role in preferential alteration of grossite to hercynite and magnetite and various degrees of 16O depletion in grossite, perovskite, and melilite during thermal metamorphism. We conclude that, among refractory phases in the inclusions, grossite was the most susceptible to metasomatic reactions with Fe-rich fluids and the second most susceptible, after perovskite, to oxygen isotopic exchange with an 16 O-poor fluid during the thermal history of the CV chondrite parent asteroid.

Calcium-aluminum-rich inclusions↗

Amoeboid olivine aggregates in the Allende meteorite

Greyish-brown irregularly-shaped aggregates composed predominantly of olivine make up nearly 2% of the Allende meteorite by volume. Many of the aggregates are constructed of subspherical lumps of micron-sized crystals of olivine, pyroxene, nepheline and sodalite surrounded by coarser-grained olivine. Rarely, anorthite, spinel and perovskite are also present. The olivine ranges in composition from Fo64 to Fo99. Pyroxenes range from aluminous diopside to hedenbergite to very Al-rich and Ti-Al-rich varieties. The nepheline contains 1.6-2.4% K2O and 1.6-5.2% CaO but the sodalite is significantly poorer in these elements. The spinel contains 2.1-13.4% FeO. Textural information and oxygen isotopic data suggest that the aggregates are composed of primary, solid condensates from the solar nebula. The perovskite, spinel and Ti-Al-rich pyroxenes are the remains of high-temperature condensates, but the olivine compositions and the presence of feldspathoids indicate that some of the grains continued to react with the solar nebular vapor in the temperature range 500-900 K.

Grossman, L.↗