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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1975

The effect of microstructure and strength on the fracture toughness of an 18 Ni, 300 grade maraging steel

A 300 grade maraging steel was chosen as a vehicle by which to understand the inverse relationship between strength and toughness in high strength alloys such as the 18 Ni maraging steels. The 18 Ni, 300 grade maraging material was a commercial grade consumable-electrode, vacuum arc remelted heat obtained in the form of forged and annealed plate. The matrix contained a population of second-phase impurity inclusions which was a product of the casting and hot working processes. These inclusions did not change with subsequent precipitation hardening. Changes in microstructure resulting in strength increases were brought about by variations in aging temperature and time. Maximum strength was attained in the 300 grade maraging steel by aging at 427 C (800 F) for 100 hours. Tensile, fatigue precracked Charpy impact, and plane-strain fracture toughness tests were performed at room temperature, 20 C (68 F). With increasing strength the fracture toughness decreases as smaller and smaller inclusions act as sites for void initiation.

Psioda, J. A.↗
NASA NTRS2009

Hypervelocity Impact Performance of Open Cell Foam Core Sandwich Panel Structures

Metallic foams are a relatively new class of materials with low density and novel physical, mechanical, thermal, electrical and acoustic properties. Although incompletely characterized, they offer comparable mechanical performance to traditional spacecraft structural materials (i.e. honeycomb sandwich panels) without detrimental through-thickness channeling cells. There are two competing types of metallic foams: open cell and closed cell. Open cell foams are considered the more promising technology due to their lower weight and higher degree of homogeneity. Leading micrometeoroid and orbital debris shields (MMOD) incorporate thin plates separated by a void space (i.e. Whipple shield). Inclusion of intermediate fabric layers, or multiple bumper plates have led to significant performance enhancements, yet these shields require additional non-ballistic mass for installation (fasteners, supports, etc.) that can consume up to 35% of the total shield weight [1]. Structural panels, such as open cell foam core sandwich panels, that are also capable of providing sufficient MMOD protection, represent a significant potential for increased efficiency in hypervelocity impact shielding from a systems perspective through a reduction in required non-ballistic mass. In this paper, the results of an extensive impact test program on aluminum foam core sandwich panels are reported. The effect of pore density, and core thickness on shielding performance have been evaluated over impact velocities ranging from 2.2 - 9.3 km/s at various angles. A number of additional tests on alternate sandwich panel configurations of comparable-weight have also been performed, including aluminum honeycomb sandwich panels (see Figure 1), Nomex honeycomb core sandwich panels, and 3D aluminum honeycomb sandwich panels. A total of 70 hypervelocity impact tests are reported, from which an empirical ballistic limit equation (BLE) has been derived. The BLE is in the standard form suitable for implementation in risk analysis software, and includes the effect of panel thickness, core density, and facesheet material properties. A comparison between the shielding performance of foam core sandwich panel structures and common MMOD shielding configurations is made for both conservative (additional 35% non-ballistic mass) and optimistic (additional mass equal to 30% of bumper mass) considerations. Suggestions to improve the shielding performance of foam core sandwich panels are made, including the use of outer mesh layers, intermediate fabric/composite layers, and varying pore density.

Ryan, Shannon↗
DOE OSTI2022

Novel method to control explosive shock sensitivity: A mesoscale study to understand the effect of thermally expandable microsphere (TEM) inclusions in high explosives (HE) microstructure

When the void content and/or void structure of a high explosive (HE) is altered by some means (i.e., bulk heating or mechanical damage), the shock initiation behavior of the material changes. The ability to precisely predict the change in shock sensitivity after an HE has undergone microstructural changes is a crucial capability in multi-scale reactive flow models. Here, we utilize thermally expandable microspheres (TEMs) as a dopant in a polymer bonded explosive (PBX) matrix to alter the shock initiation properties in a controlled fashion. Here, using a mesoscale modeling approach, we evaluated how a single TEM (before and after thermal expansion) behaves under shock compression, as well as how the matrix PBX in the direct vicinity of the TEM is affected. We first examined the effect of an unexpanded TEM in the explosive matrix and found that its presence does not significantly perturb the bulk flow and by extension will not affect bulk sensitivity. Next, we examined the effect of an expanded TEM and found that its presence significantly perturbs the flow via hydrodynamic jetting, which causes a secondary shock wave with a strength that exceeds that of the incident wave. Finally, we showed that this secondary shock interacts with the downstream porosity to ignite a larger fraction of the overall pore volume, commensurate with the secondary shock strength and the affected volume, increasing the global (bulk) shock sensitivity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1977

The effect of microstructure and strength on the fracture toughness of an 18 Ni, 300 grade maraging steel

Fractography and metallographic sectioning were used to investigate the influence of microstructure and strength on the fracture toughness (KIc) and fracture mechanism of an 18 Ni, 300 grade maraging steel. Increased yield strength from 1442 to 2070 MN/m squared through precipitation hardening results in a KIc loss from 143 to 55 MN/m superscript 3/2. Ti (C,N) Ti2S, and TiC inclusions in sizes from 1 to 8, 1 to 15, and 0.1 to 2 microns respectively serve as sites for void nucleation and lead to fracture by the dimpled rupture process in all strength levels considered. TiC nucleated dimples occupy more than half the fracture in all conditions. Void nucleation rate and resultant number of dimples per unit area of fracture increase with increasing yield strength. Average dimple size decreases with increasing strength and/or overaging which follows from the decreasing amount of stable void growth measured by sectioning tensile specimens. Void growth is assisted by crack branching along a path of TiC inclusions. Coalescence occurs in the highest strength materials by a combination of TiC void nucleation and premature separation at strengthening precipitates.

Psioda, J. A.↗
DOE OSTI2025

Non-solvents as physical blowing agents in printable silicone foams

Silicone foams were produced by dispersing an incompatible liquid phase (i.e. a non-solvent) into an uncured, liquid silicone. The formulation and processing parameters were varied to see the effect on porosity and pore morphology. Specifically, two fluorosilanes were added to stabilize the inclusion of fluorinated solvents as blowing agents. As the floruosilane content increased, the void content increased up to about 44 vol. % when the fluorosilane comprised 18 wt. % of the initial formulation. Fumed silica that was treated with a fluorinated silane was also used to try to stabilize the dispersed liquid. While the fumed silica content did not have a strong effect on the total void content, the morphology changed when silica content changed. Various fluorinated solvents with distinct chemical structures were used as the non-solvent and then removed after curing of the silicone. The interaction of the internal non-solvent phase and the silicone phase was expected to influence the porosity. These insights highlight how the manipulation of formulation and processing parameters, focusing on the inclusion of fluorosilanes and fluorinated solvents, contributes to the understanding of how incompatible liquid phases interact with silicone matrices to control porosity and pore morphology. Additionally, these interactions also influenced processability, leading to formulations that could be printed. Higher content of non-solvent inclusions could increase the yield stress and storage modulus of an uncured formulation, leading to the ability to tune intrastrand porosity while a 3D printed architecture could be modified to introduce porosity between the strands. Furthermore, in addition to fluorinated solvents, we also considered non-fluorinated solvents since these may be more industrially relevant in the future. Overall, this approach provides an alternative route to producing porous foams that can be 3D printed, which could be useful for applications like cushioning and protective gear.

physical blowing agent↗
DOE OSTI2021

Thermal History of Matrix Forsterite Grains from Murchison Based on High-resolution Tomography

Protoplanetary disks are dust- and gas-rich structures surrounding protostars. Depending on the distance from the protostar, this dust is thermally processed to different degrees and accreted to form bodies of varying chemical compositions. The primordial accretion processes occurring in the early protoplanetary disk such as chondrule formation and metal segregation are not well understood. One way to constrain them is to study the morphology and composition of forsteritic grains from the matrix of carbonaceous chondrites. Here, we present high-resolution ptychographic X-ray nanotomography and multimodal chemical microtomography (X-ray diffraction and X-ray fluorescence) to reveal the early history of forsteritic grains extracted from the matrix of the Murchison CM2.5 chondrite. Here,. the 3D electron density maps revealed, at unprecedented resolution (64 nm), spherical inclusions containing Fe–Ni, very little silica-rich glass and void caps (i.e., volumes where the electron density is consistent with conditions close to vacuum) trapped in forsterite. The presence of the voids along with the overall composition, petrological textures, and shrinkage calculations is consistent with the grains experiencing one or more heating events with peak temperatures close to the melting point of forsterite (~2100 K), and subsequently cooled and contracted, in agreement with chondrule-forming conditions.

58 GEOSCIENCES↗
NASA NTRS1984

Influence of soft inclusions on the strength of wrought materials

The three dimensional soft particles (such as sulfides, silicates and voids) present in most materials are modelled by circular voids in sheet metal. Relationships are sought between the shape and orientation of a hole after rolling and testing in tension. Then, the effect of hole shape and size on mechanical properties is considered experimentally. The presence of voids has a negligible influence on the ultimate tensile stress of ductile materials based on the unperforated area because plastic flow neutralizes the stress intensification present in the elastic region. However, the shape and orientation of the defects are found to play an important role relative to strain at fracture. In certain engineering applications the strain at fracture is more important than the stress at fracture and in this sense the presence of voids are considered to influence the strength of a ductile material.

Pai, D. M.↗
NASA NTRS1974

Shock-induced melting in anorthositic rock 60015 and a fragment of anorthositic breccia from the 'picking pot' /70052/

Microscopic and chemical evidence are presented to support the contention that shock-generated incipient grain-boundary melting of plagioclase occurred in an anorthositic lunar rock and that shock-generated plagioclase liquid was present along grain boundaries during post-shock adiabatic expansion in a fragment of anorthositic breccia. The first contention is supported by microtextural relationships in the rock, the composition of its metal particles (most iron with some cobalt and less nickel), and glass inclusions with vapor bubbles. The second contention is supported by angular irregular voids in the fragment as well as the occurrence of oriented glass filaments in some of the voids. It is shown that shock-generation of 'cataclastic anorthosite' and high-temperature plagioclase liquids can explain the exceptionally young lead and argon ages of the anorthositic rock. The results of the breccia study indicate that shock lithification of plagioclase-rich particulate material from the highland regolith is due to grain-boundary melting of plagioclase.

Sclar, C. B.↗
NASA NTRS2006

Non-nebular Origin of Dark Mantles Around Chondrules and Inclusions in CM Chondrites

Our examination of nine CM chondrites that span the aqueous alteration sequence leads us to conclude that compact dark fine mantles surrounding chondrules and inclusions in CM chondrites are not discrete fine-grained rims acquired in the solar nebula as modeled by Metzler et al. [Accretionary dust mantles in CM chondrites: evidence for solar nebula processes. Geochim. Cosmochim. Acta 56, 1992, 2873-28971. Nebular processes that lead to agglomeration produce materials with porosities far higher than those in the dark mantles. We infer that the mantles were produced from porous nebular materials on the CM parent asteroid by impact-compaction (a process that produces the lowest porosity adjacent to chondrules and inclusions). Compaction was followed by aqueous alteration that formed tochilinite, serpentine, Ni-bearing sulfide, and other secondary products in voids in the interchondrule regions. Metzler et al. reported a correlation between mantle thickness and the radius of the enclosed object. In Yamato 791 198 we find no correlation when all sizes of central objects and dark lumps are included but a significant correlation (r(sup 2) = 0.44) if we limit consideration to central objects with radii >35 microns; a moderate correlation is also found in QUE 97990. We suggest that impact-induced shear of a plum-pudding-like precursor produced the observed "mantles"; these were shielded from comminution during impact events by the adjacent stronger chondrules and inclusions. Some mantles in CM chondrites with low degrees of alteration show distinct layers that may largely reflect differences in porosity. Typically, a gray, uniform inner layer is surrounded by an outer layer consisting of darker silicates with BSE-bright speckles. The CM-chondrite objects characterized as "primary accretionary rocks" by Metzler et al. did not form in the nebula, but rather on the parent body. The absence of solar-flare particle tracks and solar-wind-implanted rare gases in these clasts reflect their lithified nature and low surface/volume ratios during the period when they resided in the regolith and were subject to irradiation by solar particles. The clasts are analogous to the light-colored metamorphosed clasts in ordinary-chondrite regolith breccias (which also lack solar-flare particle tracks and solar-wind gas).

Trigo-Rodriquez, Josep M.↗
NASA NTRS2016

Application of Scanning-Imaging X-Ray Microscopy to Fluid Inclusion Candidates in Carbonates of Carbonaceous Chondrites

In order to search for such fluid inclusions in carbonaceous chondrites, a nondestructive technique using x-ray micro-absorption tomography combined with FIB sampling was developed and applied to a carbonaceous chondrite. They found fluid inclusion candidates in calcite grains, which were formed by aqueous alteration. However, they could not determine whether they are really aqueous fluids or merely voids. Phase and absorption contrast images can be simultaneously obtained in 3D by using scanning-imaging x-ray microscopy (SIXM). In refractive index, n=1-sigma+i(beta), in the real part, 1-sigma is the refractive index with decrement, sigma, which is nearly proportional to the density, and the imaginary part, beta, is the extinction coefficient, which is related to the liner attenuation coefficient, mu. Many phases, including water and organic materials as well as minerals, can be identified by SIXM, and this technique has potential availability for Hayabusa-2 sample analysis too. In this study, we examined quantitative performance of d and m values and the spatial resolution in SIXM by using standard materials, and applied this technique to carbonaceous chondrite samples. We used POM ([CH2O]n), silicon, quartz, forsterite, corundum, magnetite and nickel as standard materials for examining the sigma and mu values. A fluid inclusion in terrestrial quartz and bi-valve shell (Atrina vexillum), which are composed of calcite and organic layers with different thickness, were also used for examining the spatial resolution. The Ivuna (CI) and Sutter's Mill (CM) meteorites were used as carbonaceous chondrite samples. Rod- or cube-shaped samples 20-30 micron in size were extracted by using FIB from cross-sectional surfaces of the standard materials or polished thin sections of the chondrites, which was previously observed with SEM. Then, the sample was attached to a thin W-needle and imaged by SIXM system at beamline BL47XU, SPring-8, Japan. The slice thickness was 109.3 nm and the pixel size was mostly 100 nm.

Tsuchiyama, Akira↗
DOE OSTI2025

Pathway to tune sputter coated Nb$_3$Sn with Zr

Superconducting radio frequency (SRF) cavities are essential elements of many modern-day particle accelerators such as, European XFEL (DESY), LCLS II-HE (SLAC) and PIP II (Fermilab). Nb$_3$Sn superconducting material promises significant potential to exceed the performance of conventional niobium based SRF cavities. We aim to advance the ongoing R$&$D efforts to achieve Nb$_3$Sn coated cavities with high material quality. In this work, we have developed to achieve a route for effectively reducing the intrinsic defects in magnetron sputter coated Nb$_3$Sn SRF cavities and eventually improve the overall RF performance. We have observed that Zr is mainly being incorporated as ZrO$_2$ precipitates of average dimensions ranging from 20-100nm. By increasing the concentration of Zr, we have three major effects in the physical properties. Firstly, we noted that the density of the surface and bulk voids as well as their average dimensions are dramatically reduced on increasing the Zr content in Nb$_3$Sn. These surface voids are believed to be detrimental to cavity applications due to increase the local dissipation of electric and magnetic fields. These results indicate that inclusion of Zr in Nb$_3$Sn sputtered coating will improve the material quality and might help to reduce the overall RF power dissipation. Secondly, we observed that increasing Zr concentration from 0 to 2.4% substantially improves both superconducting transition temperature (Tc) and upper critical magnetic field (Hc2). However, on further increasing the Zr concentration to 24%, we noticed a small decrement in the Hc2 value. These results infer that the increase in Zr concentration up to an optimal concentration will be beneficial to enhance the superconducting properties. Increase in Tc promises lesser RF losses and improvement in accelerating gradient, whereas the increase in Hc2 suggests more efficient flux pinning which could give rise to high quality factors in presence of multi-Tesla magnetic field. Additionally, we also observed that increasing Zr concentration possibly prevents the oxygen diffusion and leads to thinner formation of primary surface oxide (Nb$_2$O$_5$ and SnO). This study gives a route to tune Zr fraction in Nb3Sn to modify the physical properties that control the high field performance of Nb3Sn RF cavities.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1987

Nondestructive evaluation of structural ceramics by photoacoustic microscopy

A photoacoustic microscopy (PAM) digital imaging system was developed and utilized to characterize silicon nitride material at the various stages of the ceramic fabrication process. Correlation studies revealed that photoacoustic microscopy detected failure initiating defects in substantially more specimens than microradiography and ultrasonic techniques. Photoacoustic microscopy detected 10 to 100 micron size surface and subsurface pores and inclusions, respectively, up to 80 microns below the interrogating surface in machined sintered silicon nitride. Microradiography detected 50 micron diameter fracture controlling pores and inclusions. Subsurface holes were detected up to a depth of 570 microns and 1.00 mm in sintered silicon nitride and silicon carbide, respectively. Seeded voids of 20 to 30 micron diameters at the surface and 50 microns below the interrogating surface were detected by photoacoustic microscopy and microradiography with 1 percent X-ray thickness sensitivity. Tight surface cracks of 96 micron length x 48 micron depth were detected by photoacoustic microscopy. PAM volatilized and removed material in the green state which resulted in linear shallow microcracks after sintering. This significantly limits the use of PAM as an in-process NDE technique.

Khandelwal, Pramod K.↗
NASA NTRS1990

Impact fracture experiments simulating interstellar grain-grain collisions

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

Freund, Friedemann↗
NASA NTRS2021

Predicting near-saturated hydraulic conductivity in urban soils

Pedotransfer functions (PTFs) provide point predictions of soil hydraulic properties from more readily measured soil characteristics, yet uncertainties and biases in measurement methods, sampling distributions, and boundary conditions can limit accuracy when estimating near-saturated hydraulic conductivity (K(n)). These limitations may be particularly problematic in understudied urban landscapes that often contain altered hydraulic properties. To better treat deficiencies in PTF performance, we addressed three objectives, which were to: 1) develop PTFs to predict urban K(n), 2) assess bulk density and coarse fragments as explanatory variables; and 3) evaluate the predictive capability of these PTFs by comparing their output to measured hydraulic conductivity values from three other studies of urban soil hydraulics. We used artificial neural networks (ANN) and random forest (RF) approaches to predict urban K(n), with the training dataset including 307 tension infiltrometer tests and other measurements drawn from urban soil assessments in 11 U.S. cities. The PTFs utilized a hierarchy of inputs, starting with percentage sand, silt, clay, and then adding percentage coarse fragments and bulk density. The ANN models performed similar to the RF models, and all models exhibited similar or better predictive performance as models results collected from published articles. The inclusion of bulk density or coarse fragments did not improve accuracy over soil texture alone. Possible reasons for this result include low correlation between K(n) and bulk density and the exclusion of large voids during flow measurements with tension infiltrometers. The models have been made available as an open-source software package to encourage adoption by users working in urban systems.

Jinshi Jian↗
DOE OSTI2022

Collapse of helium-filled voids in extreme deformation: Dislocation mechanisms

The mechanisms responsible for the collapse of helium-filled bubbles during the passage of shock waves in monocrystalline copper are revealed. Both internal pressure (caused by pre-existing helium atoms) and bubble size are varied in molecular dynamics simulations to understand the atomistic scale deformation as they are subjected to shock compression at pressures of 48, 123, and 170 GPa, corresponding to particle velocities of 1.0, 2.0, and 2.5 km/s. Both empty and helium filled bubbles serve as dislocation sources, generating intense, localized plastic regions. There are distinct differences in the collapse of empty voids compared to He-filled bubbles, the former requiring less stress and generating a greater density of dislocations for a given shock strength. Additionally, a generalized model for dislocation emission is proposed, where the inclusion of shear stress generated by the helium bubble increases the critical stress to generate dislocations at the defect surface, demonstrating the change in plastic deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effects of secondary void-initiating particles on the steady-state crack growth resistance of high-strength steel

In this investigation, we focus on the dependence of stable crack growth resistance, as measured by the short-rod fracture toughness test, on secondary void-initiating particles such as AlN and Ti-based grain-refining precipitates in a variety of high-strength steels with tempered martensitic microstructures. The model developed by Ritchie and Thompson is modified to illustrate the significant amounts of toughening that can result from the refinement of secondary particles. Analysis of the data suggests that material strength is a predominant factor in increasing the short-rod fracture toughness relative to linear-elastic measures of initiation fracture toughness, but the extent of toughening is limited by the size and number density of secondary particles in the microstructure. The variation in estimates of secondary microvoid initiation and growth strains with precipitate size reinforce the notion that primary fracture at non-metallic inclusions and secondary fracture at smaller particles occur as sequential processes with a degree of concurrence that is dependent on the state of precipitation in both particle dispersions. Toughening in this connection is maximized by increases in microvoid growth strain that result from decreases in the size and areal number density of secondary void-initiating particles. Finally, the occurrence of transient instabilities during crack extension in short-rod specimens is explained with a phenomenological model that relates crack growth stability to natural variations in the dispersion of secondary void-initiating particles in the microstructure.

42 ENGINEERING↗
NASA NTRSDate not supplied

Multiscale and Multifidelity Modeling of a 3D Woven Composite Thermal Protection System

Complex three-dimensional (3D) woven composites have been considered by multiple NASA projects in recent years as a means of offering improved mechanical and thermal performance over traditional laminated composite systems. Parallel efforts have focused on developing simulation capabilities for these systems, which have traditionally and heavily relied on experimental testing to evaluate composite performance. One system is the Heatshield for Extreme Entry Environment Technology (HEEET), which is being considered for the thermal protection system on reentry spacecraft. Optical microscopy was used to characterize the blended carbon and phenolic fiber tows. A section of HEEET insulation layer was imaged with high-resolution micro-computed tomography (microCT) and segmented to separate individual tows, porous matrix, and voids. These data were used to develop multiscale thermomechanical computational models within the NASA Multiscale Analysis Tool (NASMAT). Two NASMAT modeling approaches were considered to capture the details of the 3D woven architecture: a coarse model appropriate for inclusion in multiscale structural analyses and a high-fidelity model created by downsampling the microCT data. Both elastic and thermal properties were computed and compared. The feasibility and challenges associated with modeling complex, hybrid 3D woven composites were also addressed.

NASMAT↗
DOE OSTI2021

Infiltration metasomatism of the Allende coarse-grained calcium-aluminum-rich inclusions

We report on the mineralogy, petrography, and O and Al-Mg isotopic systematics of secondary mineralization in the metasomatically altered igneous Ca,Al-rich inclusions (CAIs) [compact type A (CTA), B1, B2, forsterite-bearing B (FoB), and C] from the CV3 carbonaceous chondrite Allende. This alteration affected mainly melilite, and to a lesser degree anorthite, and resulted in the formation of a variety of secondary minerals, including adrianite, Al-diopside, andradite, anorthite, calcite, celsian, clintonite, corundum, dmisteinbergite, ferroan olivine, ferroan monticellite, ferroan Al-diopside, forsterite, grossular, heazlewoodite, hedenbergite, hutcheonite, kushiroite, margarite, monticellite, Na-melilite, nepheline, pentlandite, pyrrhotite, sodalite, spinel, tilleyite, wadalite, and wollastonite. The secondary mineral assemblages are mainly defined by chemical compositions of the primary melilite replaced and elements introduced by an aqueous fluid. Gehlenitic melilite (Åk <35 ) in CTAs and mantles of B1s is mainly replaced by anorthite + grossular; clintonite, corundum, spinel, and Al-diopside are minor. Åkermanitic melilite (Åk 35-90 ) in type B2s, FoBs, and cores of B1s is replaced by the grossular + monticellite + wollastonite, grossular + monticellite, and grossular + Al-diopside assemblages; forsterite, spinel, clintonite, and Na-melilite are minor. In type Cs, lacy melilite (åkermanitic melilite with rounded inclusions of anorthite) is pseudomorphically replaced by the grossular + forsterite + monticellite and grossular + Al-diopside assemblages; Na-melilite is minor. Primary and secondary anorthites in the peripheral portions of CAIs are replaced by nepheline, sodalite, and ferromagnesian olivine. Some CAIs contain voids and cracks filled by andradite, hedenbergite, wollastonite, ±sodalite, ±grossular, ±monticellite, ±tilleyite, and ±calcite. All CAIs studied are surrounded by Wark-Lovering rims, fine-grained matrix-like rims composed of lath-shaped ferroan olivine and abundant nepheline grains, and a layer of salite-hedenbergite pyroxenes + andradite + wollastonite. Grossular associating with monticellite, Al-diopside, and forsterite and replacing åkermanitic melilite ( 27 Al/ 24 Mg ~ 2) has high 27 Al/ 24 Mg ratios (30–100) and shows no resolvable excess of radiogenic 26 Mg (26Mg*). The 27 Al/ 24 Mg ratios (7–10) and 26 Mg* (2–3‰) in the nearly monomineralic grossular veins crosscutting gehlenitic melilite are similar to those of the host melilite and plot along a regression line with 26 Al/ 27 Al ratio of ~5×10 –5 . Oxygen isotopic compositions of secondary minerals in the most Type Bs measured in situ with the UH Cameca ims-1280 and matrix-matched standards plot along mass-dependent fractionation line with Δ 17 O of ~ –3±2‰ with δ 18 O ranging from ~0 to ~10‰. Primary melilite and anorthite in the host CAIs are similarly 16 O-depleted, whereas spinel, forsterite, and most Al,Ti-diopside grains have 16 O-rich compositions (Δ 17 O ~ –25±2‰). Secondary grossular and forsterite in type Cs and type B1 CAI TS-34 show a range of Δ 17 O, from ~ –15 to ~ –1‰; the 16 O-enriched compositions of grossular and forsterite plot along the carbonaceous chondrite anhydrous mineral line. The similar ranges of Δ 17 O and positions on the three-isotope oxygen diagram are observed for primary anorthite; melilite is generally 16 O-depleted compared to anorthite (Δ 17 O ~ –5 to –1±2‰); spinel and fassaite are 16 O-rich (except very Ti-rich fassaite in TS-34 and CTA CAIs). We conclude that Allende CAIs experienced an open-system in situ metasomatic alteration at relatively high temperatures (200-250 °C) in the presence of CO 2 - and H 2 O-bearing fluid with Δ 17 O of ~ –3±2‰ followed by thermal metamorphism at ~ 500 °C on the CV chondrite parent asteroid. During the alteration, most elements were mobile: Si, Na, Cl, K, Fe, S, and Ni were introduced; Al, Ti, Mg, and Ba were locally mobilized; Ca and some Mg and Al were lost from the host inclusions. The alteration occurred after nearly complete decay of 26 Al, >3 Ma after crystallization of CAIs with the canonical ( 26 Al/ 27 Al) 0 of (5.25±0.02)×10 -5 ; 26 Mg* in grossular was inherited from the primary melilite and provide no chronological significance. Oxygen isotopic heterogeneity of primary minerals in the Allende CAIs at least partly is due to isotopic exchange with an aqueous fluid that largely affected melilite, anorthite, perovskite, Zr- and Sc-rich oxides and silicates, and possibly very Ti-rich fassaite.

58 GEOSCIENCES↗