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Modified versions of thermoplastic polyimide LaRC(TM)-IA incorporate various amounts of additional, rigid moieties into backbones of LaRC(TM)-IA molecules. Modified versions more resistant to solvents and exhibit higher glass-transition temperatures, yet retain melt-flow processability of unmodified LaRC(TM)-IA.
The Chicxulub structure in Yucatan, Mexico, has recently been recognized as a greater then 200-km-diameter multi-ring impact crater of K-T boundary age. Crystalline impact melt rocks and breccias from within the crater, which have compositions similar to those of normal continental crustal rocks and which show shock metamorphic effects, have been studied for trace element and Re-Os isotope compositions. Re-Os isotope systematics allow the sensitive and selective determination of an extraterrestrial component in impact-derived rocks. A melt rock sample shows elevated iridium concentrations, an osmium concentration of 25 ppb, and a low Os-187/Os-188 ratio of 0.113, which are incompatible with derivation from the continental crust. Even though the Os-187/Os-188 ratio is slightly lower than the range so far measured in meteorites, a mantle origin seems unlikely for mass balance reasons and because the cratering event is unlikely to have excavated mantle material. The data support the hypothesis of a heterogeneously distributed meteoritic component in the Chicxulub melt rock. A sample of impact glass from the Haitian K-T boundary at Beloc yielded about 0.1 ppb osmium and an Os-187/0s-188 ratio of 0.251, indicating the presence of a small meteoritic component in the impact ejecta as well.
The ability to estimate oxygen fugacities for mare basalts and to extend these observations to the lunar mantle is limited using bulk analysis techniques based on buffering assemblages or the valence state of iron. These limitations are due to reequilibration of mineral assemblages at subsolidus conditions, deviations of mineral compositions from thermodynamic ideality, size requirements, and the limits of the iron valence at very low fO2. Still, these approaches have been helpful and indicate that mare basalts crystallized at fO2 between the iron-w stite buffer (IW) and the ilmenite breakdown reaction (ilmenite = rutile + iron). It has also been inferred from these estimates that the lunar mantle is also highly reduced lying at conditions below IW. Generally, these data cannot be used to determine if the mare basalts become increasingly reduced during transport from their mantle source and eruption at the lunar surface and if there are differences in fO2 among mare basalts or mantle sources. One promising approach to determining the fO2 of mare basalts is using the mean valence of vanadium (2+, 3+, 4+, 5+) determined on spots of a few micrometers in diameter using synchrotron x-ray absorption fine structure (XAFS) spectroscopy. The average valence state of V in basaltic glasses is a function of fO2, temperature, V coordination, and melt composition. Here, we report the initial results of this approach applied to lunar pyroclastic glasses.
We have shown earlier that the high SO3/Cl ratios found in secondary mineral assemblages in shergottite GRIM glasses (Gas-Rich Impact-Melt) likely resulted from interactions of regolith materials with sulfate-rich (and Cl-poor) solutions. The low SO3/Cl ratios determined in secondary salts in nakhalite fracture-fillings presumably formed by rock interactions with chloride-rich (and SO4-poor) solutions near Mars surface. The SO3 and Cl abundances determined by APXS in abraded rocks (RAT) from Endurance, Fram and Eagle craters indicate that these salt assemblages likely formed by evaporative concentration of brine fluids at Meridiani. The SO3/Cl ratios in the abraded rocks are examined here, instead of their absolute abundances, because the abundance ratios might provide better guide-lines for tracking the evolution of evaporating fluids at Meridiani. The SO3/Cl ratios in these samples, in turn, might provide clues for the mobile element ratios of the altering fluids that infiltrated into the Meridiani rocks.
Space weathering products, such as agglutinates and nanophaase iron-bearing rims are easily preserved through lithifcation in lunar regolith breccias, thus such products, if produced, should be preserved in asteroidal regotith breccias as well. A study of representative regolith breecia meteorites, Fayetteville (H4) and Kapoeta (howardite), was undertaken to search for physical evidence of space weathering on asteroids. Amorphous or npFe(sup 0)-bearing rim cannot be positively identified in Fayetteville, although possible glass rims were found. Extensive friction melt was discovered in the meteorite that is difficult to differentiate from weathered materials. Several melt products, including spherules and agglutinates, as well as one irradiated rim and one possible npFe(sup 0)-bearing rim were identified in Kapoeta. The existence of these products suggests that lunar-like space weathering processes are, or have been, active on asteroids.
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.
Abundant evidence now shows that the buried Chicxulub structure in northern Yucatan, Mexico, is indeed the intensely sought-after source of the ejecta found world-wide at the Cretaceous-Tertiary (K/T) boundary. In addition to large-scale concentric patterns in gravity and magnetic data over the structure, recent analyses of drill-core samples reveal a lithological assemblage similar to that observed at other terrestrial craters. This assemblage comprises suevite breccias, ejecta deposit breccias (Bunte Breccia equivalents), fine-grained impact melt rocks, and melt-matrix breccias. All these impact-produced lithologies contain diagnostic evidence of shock metamorphism, including planar deformation features in quartz, feldspar, and zircons; diaplectic glasses of quartz and feldspar; and fused mineral melts and whole-rock melts. In addition, elevated concentrations of Ir, Re, and Os, in meteoritic relative proportions, have been detected in some melt-rock samples from the center of the structure. Isotopic analyses, magnetization of melt-rock samples, and local stratigraphic constraints identify this crater as the source of K/T boundary deposits.
Concentration gradients in glass adjacent to skeletal olivines in a basalt have been examined by electron probe. The glass is depleted in Mg, Fe, and Cr and enriched in Si, Al, Na, and Ca relative to that far from olivine. Ionic diffusion coefficients for the glass compositions are calculated from temperature, ionic radius and melt viscosity, using the Stokes-Einstein relation. At 1170 C, the diffusion coefficient of Mg(2+) ions in the basalt is 4.5 billionths sq cm per sec. Comparison with measured diffusion coefficients in a mugearite suggests this value may be 16 times too small. The concentration gradient data and the diffusion coefficients are used to calculate instantaneous olivine growth rates. Growth necessarily preceded emplacement such that the composition of the crystals plus the enclosing glass need not be that of a melt. The computed olivine growth rates are compatible with the rate of crystallization deduced for the Skaegaard intrusion.
Glasses of Li2O.2SiO2 (LS2) and LS2 doped with 0.001 wt% platinum (LS2 + 0.001 wt% Pt) compositions were melted, cooled and re-heated at controlled rates while levitated (containerless) inside an Electrostatic Levitator (ESL) furnace at NASA Marshall Space Flight Center. The experiments were conducted in vacuum using spherical 2.5 - 3.0 mm diameter glass samples. The measured critical cooling rate for glass formation, Rc, for the LS2 and LS2 + 0.001 wt% Pt glasses processed at ESL were 14 plus or minus 2 C/min and 130 plus or minus 5 C/min, respectively. The values of Rc for the same LS2 and LS2 + 0.001 wt% Pt glasses processed in a container were 62 plus or minus 3 C/min and 162 plus or minus 5 C/min, respectively. The effective activation energy for crystallization, E, for the LS2 glass processed without a container at ESL was higher than that for an identical glass processed in a container. These results suggest that the glass formation tendency for a containerless LS2 melt is significantly increased compared to an identical melt in contact with a container. The absence of heterogeneous nucleation sites that are inherently present in all melts held in containers is believed to be the reason for the increased glass forming tendency of this containerless melt.
Large abundance of Martian atmospheric gases and neutron-induced isotopic excesses as well as Rb-Sr isotopic variations determined in some impact glasses in basaltic shergottites (e.g., Shergotty #DBS, Zagami #H1 and EET79001 #27, #8 and #104) provide definitive evidence for the occurrence of a Martian regolith component in their constituent mineral assemblages. Some of these glass-es, known as gas-rich impact-melts (GRIM), contain numerous micron-sized iron sulfide blebs along with minor amounts of iron sulfate particulates. As these GRIM glasses contain a Martian regolith component and as iron sulfates (but not sulfides) are found to occur abundantly on the Mars surface, we suggested that the sulfide blebs in GRIMs were likely generated by shock-reduction of the parental iron sulfate bearing regolith material that had been incorporated into the cavities/crevices of basaltic host rock prior to the impact event on Mars. To test whether the sulfates could be reduced to sulfides by impact shock, we carried out laboratory shock experiments on a basalt plus ferric sulfate mixture at 49 GPa at the Caltech Shock Wave Laboratory and at 21 GPa at Johnson Space Center (JSC) Experimental Impact Laboratory. The experimental details and the preliminary results for the Caltech 49 GPa experiment were presented at LPSC last year. Here, we report the results for the 21 GPa experiment at JSC and compare these results to obtain further insight into the mechanism of the bleb formation in the GRIM glasses.
Glasses are important parts of every lunar regolith sample, whether in the form of indigenous melts such as mesostasis or pyroclastics, or as quenched impact melts. The modal proportions of agglutinitic impact melts alone can exceed 50 percent for some mature regoliths, and glasses are commonly the most dominant single component of lunar soils. They therefore participate in and possibly affect all evolutionary processes to which regoliths are subjected, such as comminution and attendant chemical fractionation as a function of grain size, the retention of solar-wind products, the production of superparamagnetic iron, and others. Because they are such an integral part of lunar regoliths, a more complete understanding of regolith evolution must include the role played by these vitreous components. This contribution examines the comminution behavior of a variety of glasses and a fine-grained basalt under conditions of repetitive impact, and compares this behavior to those of crystalline components, such as lithic fragments and major rock-forming minerals.
Optical examination of nine polished grain mounts of Luna-24 drill-core material (0.09-0.50 mm size) revealed melt inclusions in olivine crystals. Two inclusions consist of clear glass with exceptionally high Si, yet contain no visible daughter minerals and have had no reaction effects with the olivine walls. Their compositions (one has SiO2 93.8, Al2O3 1.51, FeO 2.32, MgO 1.61, CaO 0.06, Na2O less than 0.05, K2O 0.11, total 99.41%; the other is similar) are unique and quite unlike the high-Si high-K melt of granitic composition that is found as inclusions in late-stage minerals of these (and the Apollo) samples, from silicate liquid immiscibility. The host olivines are Fo73 and Fo51. The origin of the melt in the inclusions and the lack of reaction effects are perplexing unsolved problems.
Containerless melting and solidification provides a powerful tool for investigation and synthesis of ceramic and glass materials. The work described in this article explored and extended the limits of ground-based experimentation by using aero-acoustic and aerodynamic levitation in combination with laser beam heating and melting to investigate ceramic and glass processing. Results of liquid-phase processing experiments on calcia-gallia and calcia-gallia-silica glass-forming mixtures, aluminum oxide, and ceramic superconductors are summarized. The work is discussed in the context of low gravity experimental and materials synthesis requirements and opportunities.
Analytical scanning electron microscopy, using combined energy dispersive and wavelength dispersive spectrometry, was used to determine the major-element compositions of some natural and artificial glasses and their crystalline equivalents derived by the frictional melting of acid to intermediate protoliths. The major-element compositions are used to calculate the viscosities of their melt precursors using the model of Shaw at temperatures of 800-1400 C, with Fe(2+)/Fe(tot) = 0.5 and for 1-3 wt percent H2O. These results are then modified to account for suspension effects in order to determine viscosities. The results have implications for the generation of pseudotachylitic breccias as seen in the basement lithologies of the Sudbury and Vredefort structures and possibly certain dimict lunar breccias. Many of these breccias show similarities with the more commonly developed pseudotachylite fault and injection veins seen in endogenic fault zones that typically occur in thicknesses of a few centimeters or less. The main difference is one of scale: Impact-induced pseudotachylite breccias can attain several meters in thickness. This would suggest that they were generated under exceptionally high slip rates and hence high strain rates and that the friction melts generated possessed extremely low viscosities.
New modal data are presented for continuous polished thin sections from double drive tube 14210/14211, and single drive tube 14220, and for polished grain mounts of four soils from the double drive tube, one from the single drive tube, and the soils 14148 (trench top), 14149 (trench bottom), and 14141 (Cone Crater). Modal data show that the Cone Crater soil is immature, whereas the 'smooth plains' soils are mature and rich in agglutinates and breccias. Neither core exhibits any major variations with depth. Microprobe analyses of mineral and glass fragments are consistent with derivation of the soils predominantly from the local rocks, with about 5-11% exotic mare component indicated by the modal data. About 4% of the glasses are SiO2- and K2O-rich granitic glasses which are comminuted mesostasis from the local melt rocks. The soils are depleted in feldspar relative to the source rocks. The preferred explanation for this depletion is that feldspar is concentrated in the less than 10 microns fines and is consumed in the formation of agglutinates, regolith breccias, and feldspathic glass.
The Apollo 16 site polymict breccia 66055 contains abundant brown KREEP glass, as well as related brown glassy breccias having fluid forms. Most of the rock is composed of clasts of poikiloblastic breccia and mesostasis-rich impact melt which predate 66055's assembly, while the KREEP glass was created in the rock-producing impact. KREEP compositions are not common at the Apollo 16 site, leading to the speculation that 66055 originated in terrains to the west of the landing site. The presence of a granitic glass fragment that is embedded in the KREEP glass suggests that it is igneous, with a local volcanic origin which is more consistent with spatial relationships deduced from orbital geochemical data than with a basin ejecta deposit origin.
The experiments discussed were conducted for the purpose of placing additional constraints on the origin of lunar highlands noritic compositions. The sample 63545 represents a fine-grained, crystalline melt rock consisting of pink spinel, plagioclase, divine, interstitial glass, minor oxides, and metal. According to Chao (1973), 76055 is an olivine-bearing micronorite hornfels with abundant xenocrysts and xenoliths. The sample 76015 is a vesicular, poikilitic impact melt with a homogeneous matrix. The obtained experimental melting relations of 63545, 76055, and 76015, are examined, taking into account experimental petrology and trace element chemistry of mare basalts. It is concluded that the studied compositions do not represent magmas derived by partial melting of either cosmic or differentiated source regions at any pressure in the moon. Presently available information would seem to favor an origin by impact-fusion of several highlands components.
A new series of low-melt viscosity imide resins (10-20 poise at 280 C) were formulated from asymmetric 2,3,3',4' -benzophenone dianhydride (a-BTDA) and 4-phenylethynylphthalic endcaps, along with 3,4' -oxydianiline, 3,3' -methylenedianiline and 3,3'- diaminobenzophenone, using a solvent-free melt process. a-BTDA RTM resins exhibited higher glass transition temperatures (Tg's = 330-400 C) compared to those prepared by asymmetric 2,3,3',4' -biphenyl dianhydride, (a-BPDA, Tg's = 320-370 C). These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fiber composites by a RTM process. Composites properties of a-BTDA resins, such as open-hole compression and short-beam shear strength, are compared to those of composites made from a-BPDA based resin at room temperature, 288 C and 315 C. These novel, high temperature RTM imide resins exhibit outstanding properties beyond the performance of conventional RTM resins, such as epoxy and BMI resins which have use-temperatures around 177 C and 232 C for aerospace applications.