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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.↗

Multicomponent, Rare-Earth-Doped Thermal-Barrier Coatings

Multicomponent, rare-earth-doped, perovskite-type thermal-barrier coating materials have been developed in an effort to obtain lower thermal conductivity, greater phase stability, and greater high-temperature capability, relative to those of the prior thermal-barrier coating material of choice, which is yttria-partially stabilized zirconia. As used here, "thermal-barrier coatings" (TBCs) denotes thin ceramic layers used to insulate air-cooled metallic components of heat engines (e.g., gas turbines) from hot gases. These layers are generally fabricated by plasma spraying or physical vapor deposition of the TBC materials onto the metal components. A TBC as deposited has some porosity, which is desirable in that it reduces the thermal conductivity below the intrinsic thermal conductivity of the fully dense form of the material. Undesirably, the thermal conductivity gradually increases because the porosity gradually decreases as a consequence of sintering during high-temperature service. Because of these and other considerations such as phase transformations, the maximum allowable service temperature for yttria-partially stabilized zirconia TBCs lies in the range of about 1,200 to 1,300 C. In contrast, the present multicomponent, rare-earth-doped, perovskite-type TBCs can withstand higher temperatures.

Miller, Robert A.↗

An experimental study of trace element partitioning between perovskite, hibonite and melt: Equilibrium values

The presence of perovskite (CATiO3) and hibonite (Ca Al12O19) within different regions of Calcium-, Aluminum-rich Inclusions (CAI) and the trace element concentrations of these minerals in each circumstance, constrain models of precursor formation, nebular condensation, the thermal history of inclusions with relict perovskite and hibonite, and the formation of the Wark-Lovering rim. At present mineral/melt partition coefficient data for hibonite are limited to a few elements in simple experimental systems, or to those derived from hibonite-glass pairs in hibonite/glass microspherules. Similarly, there is only limited data on perovskite D that are applicable to meteorite compositions. Apart from the importance of partitioning studies to meteorite research, D values also are invaluable in the development of thermodynamic models, especially when data is available for a large number of elements that have different ionic charge and radii. In addition, study of the effect of rapid cooling on partitioning is crucial to our understanding of meteorite inclusions. To expand our knowledge of mineral/melt D for perovskite and hibonite, a study was instituted where D values are obtained in both equilibrium and dynamic cooling experiments. As an initial phase of this study mineral/melt D was measured for major elements (Ca, Mg, Al, Ti, and Si), 15 rare earth elements (La-Lu) and 8 other elements (Ba, Sr, U, Th, Nb, Zr, Hf, and Ge) in perovskite and hibonite grown under equilibrium conditions, in bulk compositions that are respectively similar to Compact Type A (CTA) CAI and to a hibonite/glass microspherule. Experimental mixes were doped with REE at 20-50x chondritic (ch) abundances, Ba at 50 ppm, Sr, Hf, Nb, and Zr at 100 ppm and, U and Th at 200 ppm. Trace element abundances were measured with the PANURGE ion microprobe. Major element compositions were obtained by electron microprobe analysis.

Kennedy, A. K.↗

Electrical conductivity of (Mg,Fe)SiO3 Perovskite and a Perovskite-dominated assemblage at lower mantle conditions

Electrical conductivity measurements of Perovskite and a Perovskite-dominated assemblage synthesized from pyroxene and olivine demonstrate that these high-pressure phases are insulating to pressures of 82 GPa and temperatures of 4500 K. Assuming an anhydrous upper mantle composition, the result provides an upper bound of 0.01 S/m for the electrical conductivity of the lower mantle between depths of 700 and 1900 km. This is 2 to 4 orders of magnitude lower than previous estimates of lower-mantle conductivity derived from studies of geomagnetic secular variations.

Li, Xiaoyuan↗

Microstructural Constraints on the Formation History of Hibonite in Refractory Inclusions

Hibonite is a primary refractory phase occurring in many Ca-Al-rich inclusions (CAIs), typically with spinel and perovskite [1]. Previous mi-crostructural studies of hibonite in CAIs revealed the presence of numerous stacking defects along the (001) plane and correlated non-stoichiometry in hibonite [2,3]. These features are interpreted as complex inter-growths of stoichiometric and Ca-deficient hibonites, as shown by experimental studies of reaction-sintered CaO-Al2O3 compounds [4]. Here, we extend our transmission electron microscope (TEM) studies to hibonite-bearing CAIs in CM chondrites that have been well characterized isotopically [5-7]. In addition, we have undertaken a series of anneal-ing experiments to explore the effect of minor elements (Mg and Ti) on the microstucure of hibonite [8,9,this study]. The results of these experiments are being applied to hibonite in CAIs in order to better understand its formation conditions.

Han, J.↗

A Coordinated Mineralogical and Oxygen Isotopic Study of Refractory Ca-Al-Rich Inclusions

Refractory Ca-Al-rich inclusions (CAIs) in primitive chondritic meteorites represent the oldest solids that formed in our Solar System. Coordinated analyses using multiple ion and electron-beam techniques are vital to fully understand complex nebular and asteroidal processes that CAIs may have experienced in the context of the formation and early evolution of our Solar System. We report the results of a coordinated mineralogical and oxygen isotopic study of unique grossite bearing CAIs from reduced CV (Vigarano type) carbonaceous chondrites using transmission electron microscopy and secondary ion mass spectrometry. Grossite (CaAl 4 O 7 ) occurs in cores of nodules in fine grained 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. This grossite alteration likely occurred via crystallographically controlled metasomatic reactions with Zn, Fe-rich aqueous fluids on the parent asteroid. The constituent phases of grossite bearing CAIs show heterogeneous oxygen isotopic compositions . That is, grossite and perovskite are 16 O poor and melilite is variably 16 O-depleted in contrast to solar like, 16 O-rich hibonite and spinel. The observed oxygen isotopic distribution is interpreted as a result of mineralogically controlled oxygen isotopic exchange with an 16 O-poor fluid on the parent asteroid. Collectively, we conclude that the presence of limited fluids played an important role in preferential alteration of grossite to hercynite and magnetite and various degrees of 16 O depletion in grossite, perovskite, and melilite during thermal metamorphism on the CV chondrite parent asteroid.

Jangmi Han↗

Mg-perovskite/silicate melt and magnesiowuestite/silicate melt partition coefficients for KLB-1 at 250 Kbars

The partitioning of elements amongst lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements was reported previously, and these results as well as interpretations based on them have generated controversy. Here we report what are to our knowledge only the second set of directly measured trace element partition coefficients for a natural system (KLB-1).

Drake, Michael J.↗

Perovskite Superlattices as Tunable Microwave Devices

Experiments have shown that superlattices that comprise alternating epitaxial layers of dissimilar paraelectric perovskites can exhibit large changes in permittivity with the application of electric fields. The superlattices are potentially useful as electrically tunable dielectric components of such microwave devices as filters and phase shifters. The present superlattice approach differs fundamentally from the prior use of homogeneous, isotropic mixtures of base materials and dopants. A superlattice can comprise layers of two or more perovskites in any suitable sequence (e.g., ABAB..., ABCDABCD..., ABACABACA...). Even though a single layer of one of the perovskites by itself is not tunable, the compositions and sequence of the layers can be chosen so that (1) the superlattice exhibits low microwave loss and (2) the interfacial interaction between at least two of the perovskites in the superlattice renders either the entire superlattice or else at least one of the perovskites tunable.

Christen, H. M.↗

The effects of Venusian mantle convection with multiple phase transitions

Recently there was a flurry of activities in studying the effects of phase transitions in the Earth's mantle. From petrological and geophysical considerations, phase-transitions would also play an important role in venusian dynamics. The basic differences between the two planets are the surface boundary conditions, both thermally and mechanically. In this vein we have studied time-dependent mantle convection with multiple phase transitions and depth-dependent thermal expansivity (alpha is approximately rho(exp -6)), based on high-pressure and temperature measurements. Both the olivine-spinel and spinel-perovskite transitions were simulated by introducing an effective thermal expansivity, as described. Used together with the extended Boussinesq Approximation this method serves as a powerful tool to examine the effects of phase transitions on convection at relatively low computational costs.

Steinbach, V.↗

Corrosion testing of candidates for the alkaline fuel cell cathode

It is desirable to employ a corrosion screening test for catalyst or support candidates for the fuel cell cathode before entering upon optimization of the candidate or of the catalytic electrode. To this end, corrosion test electrodes, intended for complete immersion and maximum wetting, have been made with 30 to 40 vol. pct Teflon; with perovskites this is about 10 to 15 pct. The candidates were synthesized by methods intended for single-phase product without special emphasis on high surface area, although the substances tested were no coarser than 2 m squared/g. A typical loading was 25 mg/cm sq of the pure substance, usually on gold screen, a few mm squared of which were left bare for contacting. Contact to the gold lead wire was made by welding with a micro-torch or a spot-welder. Corrosion testing consisted of obtaining current-voltage data under flowing inert gas in the potential region for reduction of O2. The electrode was immersed in 30 pct KOH. Observations were made at 20 C and 80 C, and the results compared with data from gold standards. Results with some perovskites, pyrochlores, spinels, and interstitial compounds will be discussed.

Singer, Joseph↗

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↗

Compositional Clues to the Origin of Refractory Metal Nuggets, Perovskite, and Zr-Rich Oxides in Hibonite from the Paris Cm Chondrite

Rare Ca-Al-rich inclusions (CAIs) in carbonaceous chondrites are dominated by Zr-, Sc-, Ti-,and/or Y-rich oxides and silicates, and often contain refractory metal nuggets (RMNs)[1-3]. These phases have ultra refractory (UR) rare earth element (REE)patterns that are complementary to Group II patterns[4]. Therefore, studies of such UR CAIs likely decipher a record of nebular conditions and processes at higher temperatures than other CAIs consisting mainly of spinel and melilite. Our previous TEM analyses reported a discovery of the assemblages of RMNs, perovskite, and Zr-rich oxides in hibonite from the Paris CM chondrite[5]. Here we present TEM results of a detailed chemical study of these UR phases to provide clues to their formation conditions in the early solar nebula.

J Han↗

Phase equilibria and trace element partitioning in a magma ocean to 260 kilobars

A magma ocean can solidify in a way that is intermediate between perfect equilibrium and perfect fractional crystallization. In order to model quantitatively any fractional crystallization scenario, it is necessary to understand the geochemical characteristics of the phases that crystallize from a magma ocean, and how they vary with pressure. The crystallizing phase is called the liquidus phase, and their identities were determined by numerous experiments utilizing the multianvil apparatus. For chondritic compositions the liquidus phases are as follows: olivine at 1 atmosphere to 100 kilobars; garnet from 100 to about 260 kilobars; silicate perovskite from 260 kilobars to possibly the core-mantle boundary in the Earth.

Herzberg, Claude↗

Hibonite, Ca2/Al, Ti/24O38, from the Leoville and Allende chondritic meteorites.

Hibonite was discovered in light-colored, Ca-Al-Ti-rich and Si-Fe-poor, achondritic inclusions of the Leoville and Allende HL-group chondrites. Two varieties of hibonite occur: one emits a bright red-orange luminescence under electron bombardment and has high amounts of Al2O3 (87.7; 87.9) and low amounts of MgO (0.65; 0.8) and TiO2 (0.68; 0.8). The other emits a bright blue luminescence and is low in Al2O3 (78.7; 79.2) and high in MgO (3.3; 3.7) and TiO2 (6.5; 7.9) (in wt. %). The oxide CaO is about the same in both varieties. It is suggested that the change in the color of the visible luminescence results from changes in composition. The origin of hibonite which occurs in complex mineral assemblages together with anorthite, gelhenite, wollastonite, aluminous diopside, andradite, Ca-pyroxene, perovskite, spinel, taenite, chromite, and pentlandite, and in close proximity to nodules containing calcite, whewellite, forsterite and many of the aforementioned phases, is discussed. The proposition that hibonite and associated phases originated by contact metamorphism and metasomatism of calcite-dolomite bearing assemblages cannot, at this time, be completely ruled out.

Keil, K.↗

Shock compression of a recrystallized anorthositic rock from Apollo 15

Hugoniot measurements on 15,418, a recrystallized and brecciated gabbroic anorthosite, yield a value of the Hugoniot elastic limit (HEL) varying from 45 to 70 kbar as the final shock pressure is varied from 70 to 280 kbar. Above the HEL and to 150 kbar, the pressure-density Hugoniot is closely described by a hydrostatic equation of state constructed from ultrasonic data for single-crystal plagioclase and pyroxene. Above 150 kbar, the Hugoniot states indicate that a series of one or more shock-induced phase changes are occurring in the plagioclase and pyroxene. From Hugoniot data for both the single-crystal minerals and the Frederick diabase, we infer that the shock-induced high-pressure phases in 15,418 probably consists of a 3.71 g/cu cm density, high-pressure structure for plagioclase and a 4.70 g/cu cm perovskite-type structure for pyroxene.

Ahrens, T. J.↗

High Temperature Ferroelectrics for Actuators: Recent Developments and Challenges

A variety of piezoelectric applications have been driving the research in development of new high temperature ferroelectrics; ranging from broader markets such as fuel and gas modulation and deep well oil drilling to very specific applications such as thermoacoustic engines and ultrasonic drilling on the surface of Venus. The focus has been mostly on increasing the Curie temperature. However, greater challenges for high temperature ferroelectrics limit the operating temperature to levels much below the Curie temperature. These include enhanced loss tangent and dc conductivity at high fields as well as depoling due to thermally activated domain rotation. The initial work by Eitel et al. [Jpn. J. Appl. Phys., 40 [10, Part 1] 59996002 (2001)] increased interest in investigation of Bismuth containing perovskites in solid solution with lead titanate. Issues that arise vary from solubility limits to increased tetragonality; the former one prohibits processing of morphotropic phase boundary, while the latter one impedes thorough poling of the polycrystalline ceramics. This talk will summarize recent advances in development of high temperature piezoelectrics and provide information about challenges encountered as well as the approaches taken to improve the high temperature behavior of ferroelectrics with a focus on applications that employ the converse piezoelectric effect.

Piezoelectric↗

Presolar isotopic and chemical signatures in hibonite-bearing refractory inclusions from the Murchison carbonaceous chondrite

The mineralogy and the major-element composition of phases within individual hibonite-bearing inclusions were determined, using SEM with EDAX analysis, for 37 hibonite-bearing inclusions which comprised 26 spinel-hibonite-perovskite inclusions, ten platy hibonite crystal fragments, and one blue hibonite aggregate. Results from all inclusions studied indicated the presence of correlations in hibonite isotopic systematics and chemistry. Namely, no inclusion had both a large Ti-50 anomaly and radiogenic Mg-26, and inclusions that were depleted in the ultrarefractory elements had radiogenic Mg-26 with the exception of those which a had a large Ti-50 anomaly. These features establish a relationship between chemical and isotopic characteristics of the inclusions which must predate their formation. It is suggested that depletions in ultrarefractory elements observed in these inclusions may be a memory of stellar condensation and are not necessarily related to a condensation event in the solar nebula.

Ireland, Trevor R.↗

Moessbauer spectroscopy of Mg(0.9)Fe(0.1)SiO3 perovskite

Ambient pressure Moessbauer spectra of Mg(0.9)Fe-57(0.1)SiO3 perovskite synthesized at pressure-temperature conditions of about 50 GPa and 1700 K show that the iron is entirely high-spin Fe(2+) and appears to be primarily located in the octahedral site within the crystal structure. We observe broad Moessbauer lines, suggesting a distribution of electric-field gradients caused by disorder associated with the Fe ions. Also, the perovskite exhibits magnetic ordering at temperatures lower than 5 K, implying that there is a magnetic contribution to the absolute ('third-law') entropy of this phase.

Jeanloz, Raymond↗