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10 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Enthalpies of formation of CaAl4O7 and CaAl12O19 (hibonite) by high temperature, alkali borate solution calorimetry

Enthalpies of formation were determined for two calcium aluminate phases, CaAl4O7 and CaAl12O19, using high-temperature alkali borate solution calorimetry. The aluminates were synthesized by multiple-cycle heating and grinding stoichiometric mixtures of CaCO3 and Al2O3, and the products were characteized by X-ray diffraction and SEM microbeam analysis. The data on impurities (CaAl4O7 was found to be about 89.00 percent pure by weight and the CaAl12O19 samples about 91.48 percent pure) were used to correct the heat of solution values of the synthetic products. The enthalpies of formation, at 1063 K, from oxides, were found to be equal to -(25.6 + or - 4.7) kJ/g.f.w. for CaAl4O7 and -(33.0 + or - 9.7) kJ/g.f.w. for CaAl12O19; the respective standard enthalpies of formation from elements, at 298 K, were estimated to be -4007 + or - 5.2 kJ/g.f.w. and -10,722 + or - 12 kJ/g.f.w.

Geiger, C. A.↗
DOE OSTI2020

Materials Data on CaAl4O7 by Materials Project

CaAl4O7 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Ca2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Ca–O bond distances ranging from 2.36–2.45 Å. There are two inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four O2- atoms to form corner-sharing AlO4 tetrahedra. There are a spread of Al–O bond distances ranging from 1.74–1.82 Å. In the second Al3+ site, Al3+ is bonded to four O2- atoms to form corner-sharing AlO4 tetrahedra. There are a spread of Al–O bond distances ranging from 1.75–1.81 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to three Al3+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ca2+ and two Al3+ atoms. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+ and two equivalent Al3+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ca2+ and two equivalent Al3+ atoms.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Petrography, mineralogy, and Mg isotope composition of VICTA: A vigarano CaAl4O7-bearing type A inclusion

Thermodynamic calculations predict that Ca-dialuminate (CaAl4O7) condenses from a cooling gas of solar composition after hibonite and before melilite. Although Ca-dialuminate has now been recorded from Ca Al-rich inclusions (CAI's) in at least 9 meteorites, compared to hibonite it is a relatively rare phase. As pointed out by Michel-Levy et al., the absence of Ca-dialuminate from most hibonite-bearing inclusions poses a serious problem for the condensation model of CAI formation. Here we describe an inclusion which contains abundant CA-dialuminate partially altered to a hercynite-rich (FeAl2O4) assemblage. The evidence from VICTA indicates that compared to all other phases in type A inclusions, Ca-dialuminate is the most susceptible to secondary alteration; a feature which may explain its restricted occurrence. Unaltered Ca-dialuminate and melilite in VICTA display excess Mg-26 indicative of in situ decay of Al-26.

Greenwood, R. C.↗
NASA NTRS1988

The origin of type C inclusions from carbonaceous chondrites

The origin of type C inclusions found in carbonaceous chondrites and the relationship of the type C inclusions to other Ca- and Al-rich chondrules are discussed on the basis of major-element composition of these objects. The results on bulk composition analysis of primary phase assemblages in eight Allende-type inclusions and an Allende glass-spinel inclusion were found to be consistent with the following scenario: (1) the condensation of melilite + spinel + perovskite +/- hibonite +/- CaAl4O7; (2) the reaction of melilite + spinel with SiO2(g); (3) the removal of inclusions from further interaction with the reacting gas; (4) melting with little or no volatilization; (5) crystallization; (6) alteration; and (7) incorporation of inclusions into host meteorite. Type C inclusions are considered to be precursors to Al-rich chondrules in ordinary and enstatite chondrites, i.e., they are considered to be a spinel-rich class of type A that reacted with silica from a coexisting gas to produce anorthite plus diopside.

Beckett, John R.↗
NASA NTRS1993

The stability of hibonite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions

Phase fields in which hibonite (Hib) and silicate melt coexist with spinel (Sp), CaAl4O7 (CA2), gehlenitic melilite (Mel), anorthite (An), or corundum (Cor) in the system CaO-MgO-Al203-SiO2-TiO2 (CMAST) were determined and activity models developed for Mel and Hib solid solutions. Experimentally determined partition coefficients for Ti between Hib and coexisting melt, D sub t, vary from 0.8 to 2.1 and generally decrease with increasing TiO2 content in the liquid (L). Based on Ti partioning between Hib and melt, bulk inclusion compositions and Hib-saturated liquid use phase diagrams, the Hib in Fluffy Type A inclusions (FTA's) from Allende and at least some of the Hib from Hib-rich inclusions is relict; much of the Hib from Hib-glass spherules probably crystallized from a melt under nonequilibrium conditions. Bulk compositions for all of these Ca-Al-rich inclusions (CAI's) are consistent with an origin as Mel + Hib + Sp + perovskite (Pv) proto-inclusions in which Mel was partially altered. In some cases, the proto-inclusion was partially or completely melted with vaporization occurring over a period of time sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. If equilibration temperatures based on Hib-bearing CAI's reflect condensation in a cooling gas of solar composition, then Hib + Cor condensed at approximately 1260 C (referenced to 10 exp -3 atm) and Hib + Sp + Mel at approximately 1215 +/- 10 C. Simple thermochemical models for the substitution of trace elements into the Ca-site of meteoritic Hib suggest that virtually all Eu is divalent in early condensate Hibs but that Eu(2+)/Eu(3+) decreases by a factor of 20 or more during the course of condensation, primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic Hibs and CAI's may be influenced by this effect.

Beckett, J. R.↗
NASA NTRS1993

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

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

Simon, S. B.↗
NASA NTRS1994

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Beckett, J. R.↗
NASA NTRSDate not supplied

A Record of Nebular and Parent Body Processes of Grossite-Bearing, Fine-Grained Refractory Inclusions from Reduced CV3 Chondrites

Grossite (CaAl4O7) is predicted to condense as the third major phase, after corundum and hibonite, from a cooling gas of solar composition and likely preserves an important record of physico-chemical conditions in the early Solar System. However, this mineral is relatively rare in CAIs from most carbonaceous chondrite groups, except for CH chondrites. In particular, from CV3 chondrites where CAIs are large and abundant, only six grossitebearing CAIs have been reported and studied, and most of them were coarse-grained Type A inclusions. Here, we report the occurrence of grossite-bearing, fine-grained inclusions (FGIs) from reduced CV3 chondrites. We present preliminary results of a FIB/TEM study of one grossite-bearing FGI that provide clues to constrain its formation and alteration history in the solar nebula and on the parent body and to address the overall rarity of grossite in CAIs.

J. Han↗
NASA NTRSDate not supplied

Mineralogical and Oxygen Isotopic Study of Grossite-Bearing Refractory Inclusions From Reduced CV Chondrites

Grossite (CaAl4O7) is predicted to condense as the third major phase, after corundum and hibonite, from a cooling gas of solar composition. Thus, this refractory phase likely preserves a crucial record of high-temperature conditions in the early solar nebula. However, grossite is relatively rare in CAIs from most carbonaceous chondrite groups, except for CH chondrites. Only six grossite-bearing CAIs were reported and studied from CV chondrites, and most of them were coarse-grained Type A inclusions. Our previous study reported the occurrence of six grossite-bearing, fine-grained Ca-Al-rich inclusions (FGIs) from reduced CV chondrites Efremovka, Thiel Mountains (TIL) 07003, and TIL 07007. Here we present oxygen isotopic data of grossite-bearing FGIs from reduced CV chondrites to determine if any oxygen isotopic heterogeneity occurs within and among these inclusions. This isotopic study was coordinated with a FIB/TEM study to examine the formation and alteration history of grossite-bearing FGIs in the early solar nebula and on the asteroidal parent body.

J. Han↗
NASA NTRS2019

Grossite-Rich Refractory Inclusions in Carbonaceous Chondrites: Evidence for Early Generation of Different O-Isotope Reservoirs in the Protoplanetary Disk and O-Isotope Exchange During Fluid-Rock Interaction

The oxygen isotopic composition of the Sun inferred from the measurements of the solar wind returned by the Genesis spacecraft is O-16-enriched (△O-17 = -28.4±3.6‰) relative to the whole-rock O-isotope compositions of chondrites and achondrites, and chondrule phenocrysts, which all plot close to the terrestrial fractionation line (△O-17 ∼ ±5‰). Vast majority of refractory inclusions (CAIs and AOAs) in carbonaceous chondrites of petrologic types 2-3.0 are iso-topically uniform and have solar-like △O-17. In contrast, CAIs and AOAs in metamorphosed CV and CO chondrites are isotopically heterogeneous with melilite, anorthite, perovskite, Zr- and Sc-rich oxides and silicates, and occasionally Al, Ti-diopside being O-16-depleted relative to hibonite, spinel, Al-diopside, and forsterite. The timing of generation of different O-isotope reservoirs and the nature of O-isotope heterogeneity in refractory inclusions in CO3 and CV3 chondrites are poorly known. Grossite (CaAl4O7) is one of the first minerals predicted to condense from a gas of solar composition and therefore it could have recorded isotopic compositions of reservoirs during the earliest stages of the Solar System evolution. Here we report on O-isotope compositions of grossite-rich CAIs in CH3 and CO3 chondrites measured in situ with the UH Cameca ims-1280. For analytical procedures see [9].

A N Krot↗