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NASA NTRSDate not supplied

Characterizing Martian X-Ray Amorphous Materials Through Terrestrial Analogs

X-ray amorphous materials (i.e., lacking long-range crystallographic order) have been identified on the martian surface from orbit and in-situ. Initial models of orbital IR spectral data identified volcanic glasses [e.g., 1], but subsequent interpretations suggested that amorphous silicates are dominantly secondary in nature and formed from water-rock interactions [e.g., 2-4]. Thermal IR spectra from the Mini-Thermal Emission Spectrometer on the Spirit rover show evidence for the amorphous secondary product opaline silica [e.g., 5]. X-ray diffraction (XRD) measurements by the CheMin instrument on the Mars Science Laboratory rover have identified 20-70 wt.% amorphous materials in every sample analyzed in Gale crater to date [e.g., 6]. Mass balance calculations using CheMin results and bulk elemental measurements by the Alpha Particle X-ray Spectrometer suggest the amorphous component in Gale crater is variably enriched in Si, Fe, and S [e.g., 7,8]. The compositions are not consistent with pure volcanic glass, indicating water must have been involved in the formation of amorphous materials in Gale crater. We seek to better constrain the conditions under which amorphous materials on Mars formed by studying the composition and short-range atomic order of amorphous materials in terrestrial analog environments via XRD and transmission electron microscopy (TEM).

E B Rampe↗
NASA NTRS2002

Cometary Science After Hale-Bopp

Comets and the chondritic porous interplanetary dust particles (CP IDPs) that they shed in their comae are reservoirs of primitive solar nebula materials. The high porosity and fragility of cometary grains and CP IDPs, and anomalously high deuterium contents of pyroxene-rich CP IDPs imply these aggregate particles contain significant interstellar grain components. Spectrophotometry of comets at thermal IR wavelengths (3-40 microns) reveal the presence of a warm (near-IR) featureless emission modeled by amorphous carbon grains, and mid-IR and far-IR broad and narrow resonances modeled by chondritic (50% Fe and 50% Mg) amorphous and Mg-rich crystalline silicate minerals, respectively. Cometary amorphous silicate resonances are well matched by IR spectra of CP IDPs dominated by 0.1 micron spherules of Glass with Embedded Metal and Sulfides (GEMS) that are thought to be the interstellar Fe-bearing amorphous silicates produced in the cooling outflows of Asymptotic Giant Branch (AGB) stars. Acid-etched microtomed CP IDP samples, however, show that both the carbon phase (aliphatic) and the amorphous silicate phase (Mg-rich) are not optically absorbing while the embedded Fe nanoparticles make the IDPs dark. The CP IDPs suggest either significant processing has occurred in the ISM or that the AGB amorphous silicates have Mg-rich stoichiometry and possibly grew on Fe particle condensates. Cometary crystalline silicate resonances are well matched by IR spectra of laboratory submicron Mg-rich olivine crystals, [Mg(sub y),Fe(sub 1-y)]2SiO4 with y/ge0.85, and in the case of Hale-Bopp at r(sub h) less than or equal to approx. 1.5 AU, by Mg-rich pyroxene crystals, [Mg(sub x),Fe(sub 1-x)]SiO3 with x/ge0.85. While a fraction of AGB stardust (less than or equal to 15%) are Mg-rich crystals, this interstellar star dust component is insufficient to account for the deduced abundance of crystalline minerals in comet dust. An insufficient source of ISM Mg-rich crystals leads to the inference that Mg-rich crystals in comets may be hot, early solar nebula condensates that traveled large radial distances out to the comet-forming zone.

Wooden, Diane H.↗
NASA NTRS2012

Formation and Processing of Amorphous Silicates in Primitive Carbonaceous Chondrites and Cometary Dust

Chondritic-porous interplanetary dust particles (CP IDPs) exhibit strongly heterogeneous and unequilibrated mineralogy at sub-micron scales, are enriched in carbon, nitrogen and volatile trace elements, and contain abundant presolar materials [1-4]. These observations suggest that CP IDPs have largely escaped the thermal processing and water-rock interactions that have severely modified or destroyed the original mineralogy of primitive meteorites. CP IDPs are believed to represent direct samples of the building blocks of the Solar System - a complex mixture of nebular and presolar materials largely unperturbed by secondary processing. The chemical and isotopic properties of CP IDPs and their atmospheric entry velocities are also consistent with cometary origins. GEMS (glass with embedded metal and sulfides) grains are a major silicate component of CP IDPs. GEMS grains are < 0.5 microns in diameter objects that consist of numerous 10 to 50 nm-sized Fe-Ni metal and Fe-Ni sulfide grains dispersed in a Mg-Si-Al-Fe amorphous silicate matrix [2, 5]. Based on their chemistry and isotopic compositions, most GEMS appear to be non-equilibrium condensates from the early solar nebula [2]. If GEMS grains are a common nebular product, then they should also be abundant in the matrices of the most physically primitive chondritic meteorites. Although amorphous silicates are common in the most primitive meteorites [6-9], their relationship to GEMS grains and the extent to which their compositions and microstructure have been affected by parent body processing (oxidation and aqueous alteration) is poorly constrained. Here we compare and contrast the chemical, microstructural and isotopic properties of amorphous silicates in primitive carbonaceous chondrites to GEMS grains in IDPs.

Keller, Lindsay P.↗
NASA NTRS1986

Roedderite in the Qingzhen (EH3) chondrite

The rare mineral roedderite, (Na1.09 K0.89 Ca0.02)2.00 (Mg4.71 Fe0.27)4.98 (Si11.80 Al0.09)11.89 O30 has been found in accessory amounts in the highly unequilibrated enstatite chondrite, Qingzhen. It occurs in association with minor amounts of albite and SiO2 as inclusions within the metal or sulfide phases of metal-sulfide assemblages. The roedderite crystals are connected through oxide and silicate veins to the surrounding matrix. The presence of glass coated vesicles on the surface of the assemblages strongly suggests that roedderite originated in the presence of a fluid phase, presumably during post-accretional planetary processes.

Rambaldi, E. R.↗
NASA NTRS1998

Fluoropolymer Films Deposited by RF Plasma Sputtering of Polytetrafluoroethylene Using Inert Gases

The FT-IR (Fourier Transform Infrared), UV (Ultraviolet) and XPS (X Ray Photoelectron Spectroscopy) spectra of fluoropolymer films (SPTFE) deposited by rf (radio frequency) plasma sputtering of polytetrafluoroethylene (PTFE), using Ne, Kr and Xe as sputtering gases, were obtained and compared with prior spectra for SPTFE formed using He and Ar. The F/C (fluorine / carbon) ratios for SPTFE films (1.44-1.55), obtained at a rf power of 10 W, were essentially the same for all five rare gases, there being no trend of decreasing fluorine content in the SPTFE product with increasing atomic weight of the sputtering gas - contrary to the momentum transfer notion advanced by M. E. Ryan, et al. Increasing rf power from 10 to 50 W resulted in successively lower F/C ratios for SPTFE (e.g., from 1.55 to 1.21 in the case of Xe plasma-sputtered PTFE), accompanied by sputtering of the glass reactor and deposition of fragments of sodium aluminum silicate occurring at 40 W and above. In order to achieve a "Teflon-like" SPTFE structure (i.e., products with as high a F/C ratio as possible) in a given plasma reactor, an optimum rf power must be found, which in the present case was approximately 10 W.

Golub, Morton A.↗
NASA NTRS1993

Strontium and oxygen isotope study of M-1, M-3 and M-4 drill core samples from the Manson impact structure, Iowa: Comparison with Haitian K-T impact glasses

Strontium and oxygen isotope analyses were performed on 8 samples from the M-1, M-3, and M-4 cores recently drilled at the Manson impact structure. The samples were three elastic sedimentary rocks (of probable Cretaceous age) which occurred as clasts within the sedimentary clast breccia, two samples of crystalline rock breccia matrix, and three samples of dolomite and limestone. The Sr-87/Sr-86 (corrected to 65 Ma) ratios were much higher than those in impact glasses from the Haitian Cretaceous-Tertiary (K-T) boundary. Isotope mixing calculations demonstrate that neither the silicate or carbonate rocks analyzed from the Manson crater, or mixtures of these rocks are appropriate source materials for the Haitian impact glasses. However, the Sr-87/Sr-86 (65Ma) ratio and delta O-18 value of the Ca-rich Haitian glasses are well reproduced by mixtures of Si-rich Haitian glass with platform carbonate of K-T age.

Blum, Joel D.↗
NASA NTRS2002

PMR-15/Layered Silicate Nanocomposites For Improved Thermal Stability And Mechanical Properties

Montmorillonite clay was organically modified by co-exchange of an aromatic diamine and a primary alkyl amine. The clay was dispersed into a PMR (Polymerization of Monomer Reactants)-15 matrix and the glass transition temperature and thermal oxidative stability of the resulting nanocomposites were evaluated. PMR-15/ silicate nanocomposites were also investigated as a matrix material for carbon fabric reinforced composites. Dispersion of the organically modified silicate into the PMR-15 matrix enhanced the thermal oxidative stability, the flexural strength, flexural modulus, and interlaminar shear strength of the polymer matrix composite.

Campbell, Sandi↗
NASA NTRS1994

Craters in aluminum 1100 targets using glass projectiles at 1-7 km/s

We report on impact experiments using soda-lime glass spheres of 3.2 mm diameter and aluminum targets (1100 series). The purpose is to assist in the interpretation of LDEF instruments and in the development of future cosmic-dust collectors in low-Earth orbit. Because such instruments demand understanding of both the cratering and penetration process, we typically employ targets with thicknesses that range from massive, infinite half-space targets, to ultrathin films. This report addresses a subset of cratering experiments that were conducted to fine-tune our understanding of crater morphology as a function of impact velocity. Also, little empirical insight exists about the physical distribution and shock-metamorphism of the impactor residues as a function of encounter speed, despite their recognized significance in the analysis of space-exposed surfaces. Soda-lime glass spheres were chosen as a reasonable analog to extraterrestrial silicates, and aluminum 1100 was chosen for targets, which among the common Al-alloys, best represents the physical properties of high-purity aluminum. These materials complement existing impact studies that typically employed metallic impactors and less ductile Al-alloys. We have completed dimensional analyses of the resulting craters and are in the process of investigating the detailed distribution of the unmelted and melted impactor residues via SEM methods, as well as potential compositional modifications of the projectile melts via electron microprobe.

Bernhard, R. P.↗
NASA NTRSDate not supplied

Chemical and petrographic characterization of amorphous silicate material in cometary GEMS

Amorphous silicate material (ASM) is found in the matrix of GEMS (glass with embedded metal and sulfides) in chondritic porous interplanetary dust particles (CP-IDPs) and in the matrices of primitive chondritic meteorites. It either formed by irradiation of crystalline precursors in the interstellar medium or by non-equilibrium condensation in the solar nebula. However, the origins of ASM in IDPs and chondrites and their possible relationship are still not well constrained. Here we performed a petrographic and chemical characterization of ASM in five CP-IDPs by Transmission Electron Microscopy (TEM)techniques. We also analyzed carbon and nitrogen isotopic compositions of organic matter by Nano SIMS to constrain the pristine character of analyzed IDPs. ASM in IDPs is depleted in all major element/Si ratios with respect to the solar value. Compared to bulk GEMS analyses, the ASM contains less Fe, because nanophase inclusions of Fe-Ni-metal and FeS are mostly excluded by our approach. In contrast, ASM in meteorites has higher-than-solar Fe/Si ratios, maybe due to aqueous alteration on the meteorite parent bodies. Chemical composition of GEMS ASM indicates a non-equilibrium condensation origin. Silicone oil contamination of particles during collection is excluded, because GEMS collected in dry polyurethane show similar compositions. Magnetite rims around GEMS in our IDP samples indicate heating of some particles during atmospheric entry. However, preserved 15N and13C isotopic anomalies in organic matter around GEMS and in IDP matrix link the IDPs to a cold environment and overall validate their primitiveness.

Birgit Schulz↗
NASA NTRS1991

Altered spherules of impact melt and associated relic glass from the K/T boundary sediments in Haiti

Partially to wholly altered glass spherules produced by impact-induced shock melting have been found in the K/T boundary sediments of Haiti which also contain grains of shocked quartz. The relic glass has an approximately dacitic composition, and although grossly similar in composition to most previously described tektite glasses, it is slightly enriched in Ca and slightly depleted in Si, suggesting the Haitian glass was produced either from a target with a greater fraction of carbonate and anhydrite lithologies and fewer silicate units than the targets from which most other tektites were produced, and/or from one with a significant mafic component. The composition of the glass can best be reconciled with a continental margin terrane, consistent with studies of shocked mineral phases reported elsewhere. The thickness of the deposit in which the impact spherules occur indicates the source of the ejecta was in the proto-Caribbean region.

Kring, David A.↗
NASA NTRS1974

EPR measurement of the effect of glass composition on the oxidation states of europium

An investigation was conducted concerning the dependence of the concentration ratio of Eu(2+) to Eu(3+) on composition for silicate liquids whose compositional end members are CaAl2Si2O8 and MgSiO3, MG2SiO4, CaMgSi2O6, CaMgSiO4, CaSiO3, or Ca2SiO4. The liquids were quenched to produce glasses. An electron paramagnetic resonance spectrometer was used to determine the concentration ratios of Eu(2+) to Eu(3+) in the glasses.

Morris, R. V.↗
NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗
NASA NTRS1972

Highly differentiated subalkaline rhyolite from Glass Mountain, Mono County, California.

Available data on the partition of Sr between coexisting feldspar and melt phases re interpreted as an indication that a rhyolite from Glass Mountain represents about 25% of a hypothetical 'parent' magma of silicic composition having a norm ntent of 150 ppm. Available Sr and Pb isotope data on nearby Pleistocene rhyolite lavas suggest that the 'parent' magmas of volcanic rocks of the area came from mafic or ultramafic source marl.

Noble, D. C.↗
NASA NTRS1984

Chondrule rims and interchondrule matrix in UOC

Opaque rims around chondrules and clasts were distinguished from opaque, interchondrule matrix apparently unrelated spatially to chondrules and clasts. Microprobe and electron microscope techniques were used. The mean chemical composition for dark rim and matrix in Bishunpur and Tieschitz are similar to the opaque matrix of Huss, et al. However, the mean dark rim compositions in Bishunpur have significantly higher Fe, and lower Na, K, Al and Si than opaque interchondrule matrix. The opaque matrix of Huss, et al, essentially lies between these compositions. In Tieschitz only rim material was observed. In Tieschitz the rims are Si-poor and dominated by normative olivine (Fo50). Again there is an Na, K, Al component but is often nepheline normative rather than albitic. It too is probably present as glass, Ashworth (pers.comm.). In Bishunpur rims as well as the silicate-FeS, FeNi layering described by Allen, et al, discontinuous layering was observed within the silicate portion. This is apparently due to variations in the proportions of the components, particularly in the glassy phase. In Bishunpur there is a strong genetic link between matrix and rims, although rims seem to have formed under different, possibly more oxidizing, conditions. Also the presence of the same component in rims, matrix chondrules, and clasts suggests a common source.

Alexander, C.↗
NASA NTRS2014

3D Observation of GEMS by Electron Tomography

Amorphous silicates in chondritic porous interplanetary dust particles (CP-IDPs) coming from comets are dominated by glass with embedded metal and sulfides (GEMS). GEMS grains are submicron-sized rounded objects (typically 100-500) nm in diameter) with anaometer-sized (10-50 nm) Fe-Ni metal and sulfide grains embedded in an amorphous silicate matrix. Several formation processes for GEMS grains have been proposed so far, but these models are still being debated [2-5]. Bradley et al. proposed that GEMS grains are interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk and that they are amorphiation products of crystalline silicates in the interstellar medium by sputter-deposition of cosmic ray irradiation, similar to space weathering [2,4]. This consideration is based on the observation of nano-sized crystals (approximately 10 nm) called relict grains in GEMS grains and their shapes are pseudomorphs to the host GEMS grains. On the other hand, Keller and Messenger proposed that most GEMS formed in the protoplanetary disk as condensates from high temperature gas [3,5]. This model is based on the fact that most GEMS grains have solar isotopic compositions and have extremely heterogeneous and non-solar elemental compositions. Keller and Messenger (2011) also reported that amorphous silicates in GEMS grains are surrounded by sulfide grains, which formed as sulfidization of metallic iron grains located on the GEMS surface. The previous studies were performed with 2D observation by using transmission electron microscopy (TEM) or scanning TEM (STEM). In order to understand the structure of GEMS grains described above more clearly, we observed 3D structure of GEMS grains by electron tomography using a TEM/STEM (JEM-2100F, JEOL) at Kyoto University. Electron tomography gives not only 3D structures but also gives higher spatial resolution (approximately a few nm) than that in conventional 2D image, which is restricted by sample thickness ) approx. or greater than 50 nm). Three cluster IDPs (L2036AA5 cluster4, L2009L8 cluster 13 and W726A2) were used for the observations. ID W726A2 was collected without silicon oil, which is ordinary used to collect IDPs, so this sample has no possibility of contaminations caused by silicon oil or solvent to rinse it [6]. The samples were embedded in epoxy risin and sliced into ultrathin sections (50-300 nm) using an ultramicotome. The sections were observed by BF-TEM and HAADF-STEM (high angle annular dark field-scanning TEM) modes. Images were obtained by rotating the sample tilt angle over a range of +/- 65 deg in 1 deg steps. The obtained images were reconstructed to slice images. Mineral phases in the slice images were estimated by comparing with a 2D elemental map obtained by an EDS (energy dispersive X-ray spectroscopy) system equipped in the TEM/STEM. Careful examination of the slice images confirmed that iron grains are embedded in the amorphous silicate matrix of the GEMS grains, but sulfide grains were mainly present on the surface of the amorphous silicate. These results are consistent with the model that GEMS grains formed as condensates [3,5], although more data are needed to conclude the origin of GEMS grains. The present study is the first successful example adapting the electron tomography to the IDPs. This type of analysis will be important for planetary material sciences in the future.

Matsuno, Junya↗
NASA NTRS1997

Laboratory Measurements of Celestial Solids

Our experimental study has focused on laboratory measurements of the low temperature optical properties of a variety of astronomically significant materials in the infrared and mm-wave region of the spectrum. Our far infrared measurements of silicate grains with an open structure have produced a variety of unusual results: (1) the low temperature mass opacity coefficient of small amorphous 2MgO(central dot)SiO2 and MgO(central dot)2SiO2 grains are many times larger than the values previously used for interstellar grain material; (2) all of the amorphous silicate grains studied possess the characteristic temperature dependent signature associated with two level systems in bulk glass; and (3) a smaller but nonzero two level temperature dependence signature is also observed for crystalline particles, its physical origin is unclear. These laboratory measurements yield surprisingly large and variable values for the mm-wave absorption coefficients of small silicate particles similar to interstellar grains, and suggest that the bulk absorptivity of interstellar dust at these long wavelengths will not be well known without such studies. Furthermore, our studies have been useful to better understand the physics of the two level absorption process in amorphous and crystalline grains to gain confidence in the wide applicability of these results.

Sievers, A. J.↗
NASA NTRS1993

Siderophile elements in the upper mantle of the Earth: New clues from metal-silicate partition coefficients

New, precise data on the solubilities of Ni, Co, and Mo in silicate melts at 1400 C and fO2 from IW to IW-2 are presented. The results suggest NiO, CoO as stable species in the melt. No evidence for metallic Ni or Co was found. Equilibrium was ensured by reversals with initially high Ni and Co in the glass. Mo appears to change oxidation state at IW-1, from MoO3 to MoO2. Metal-silicate partition coefficients calculated from these data and recent data on Pd indicate similar partition coefficients for Pd and Mo at the conditions of core formation. This unexpected result constrains models of core formation in the Earth.

Holzheid, A.↗