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At least 73 records · Page 4

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Ming, Douglas W.↗

Shock Effects in the Metal-rich Chondrites QUE 94411, Hammadah al Hamra 237 and Bencubbin

We have studied the metal-rich chondrites QUE94411 (QUE), Hammadah al Hamra 237 (HH237) and Bencubbin with an emphasis on the petrographical and mineralogical effects of the shock processing that these meteorite assemblages have undergone. Iron-nickel metal and chondrule silicates are the main components in these meteorites. These high-temperature components are held together by shock melts consisting of droplets of dendritically intergrown FeNi metal/sulfide embedded in ferrous silicate glass. The silicate glass component of the shock melt is substantially more FeO-rich (FeO: 30 to 40 wt%) than the prevailing chondrule silicates (FeO less than 5 wt%). Fine-grained matrix material, which is a major component in most other chondritic assemblages, is extremely scarce in QUE4411 and HH237; it has not been observed in Bencubbin. This material occurs as rare, hydrated, and fine-grained matrix lumps with major and minor element abundances roughly similar to the ferrous silicate shock melts (and CI). We infer that hydrated, fine-grained material, compositionally similar to these matrix lumps, was originally present between the FeNi metal grains and chondrules, but was preferentially heated by the shock wave and melted. Other shock-related features in QUE94411, HH237, and Bencubbin include a distinct alignment and occasionally strong plastic deformation of metal and chondrule fragments. However, the existence of chemically zoned and metastable FeNi metal condensates condensates in direct contact with shock melts indicates that the shock did not substantially increase the average temperature of the aggregate. TEM analyses of the FeNi metal droplets embedded in the shock melts show martensitic crystal structures, indicating rapid cooling, essentially quenching, of the shock melts. These findings indicate that the preshock temperature of the assemblage was low. Because porphyritic olivine-pyroxene chondrules are absent in QUE94411, HH237, and Bencubbin, it is difficult to determine the precise shock stage of these meteorites, but the shock was probably relatively light (S2- S3; 5-20 GPa) consistent with a bulk temperature increase of the assemblages of less than 200 C. The higher pressures within this range (i.e. 15-20 GPa) are consistent with the findings of shock produced diamonds in Bencubbin. The many mineralogical, petrological and isotopic (e.g. O and N) similarities between Bencubbin, Weatherford, Gujba and QUE/HH237 have been used to argue for a common origin of these meteorites on a single asteroidal parent body. The findings of this study, which indicate similar shock processing, lend support to this view.

Meibom, A.↗

Vacuum melting and mechanical testing of simulated lunar glasses

Lunar silicate glasses may possess superior mechanical properties compared to terrestrial glasses because the anhydrous lunar environment should prevent hydrolytic weakening of the strong Si-O bonds. This hypothesis was tested by melting, solidifying, and determining the fracture toughness of simulated mare and highlands composition glasses in a high vacuum chamber. The fracture toughness, K(IC), of the resulting glasses was obtained via microindentation techniques. K(IC) increased as the testing environment was changed from air to a vacuum of 10 exp -7 torr. However, this increase in toughness may not result solely from a reduction in the hydrolytic weakening effect; the vacuum-melting process produced both the formation of spinel crystallites on the surfaces of the glass samples and significant changes in the compositions which may have contributed to the improved K(IC).

Carsley, J. E.↗

Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K -edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems

Abstract The synchrotron technique of micro X-ray absorption near-edge structure spectroscopy at the sulfur K-edge (S-XANES) provides a unique opportunity to measure the proportion of different oxidation states of sulfur (S) in silicate glasses. Although applied extensively in the analysis of basaltic silicate glasses, few S-XANES studies have investigated variations in S oxidation states with fO2 in felsic silicate glasses. In addition, no study has systematically compared the S-XANES results obtained from the same samples at different photon flux densities to quantify the relationship between exposure time and changes in S speciation in silicate glass, as has been done for Fe and V. This study evaluates observed differences in S speciation measured in experimentally produced H2O-saturated dacitic glasses over a range of reducing to oxidizing conditions (from log fO2 = ΔFMQ-0.7 to ΔFMQ+3.3; FMQ is the fayalite-magnetite-quartz mineral redox buffer) and equilibrated at 1000 °C and 300 MPa. S-XANES spectra were collected at three different photon flux densities using three microspectroscopy beamlines. As is observed in S-XANES analyses of basaltic silicate glasses, beam-induced changes to the S6+/ΣS are observed as a function of photon flux density and beam exposure time. Our results demonstrate that silicate glasses of dacitic composition undergo beam-induced photo-reduction in samples equilibrated at ΔFMQ > +1.75 and photo-oxidation if equilibrated at ΔFMQ < +1. The time required to observe beam-induced changes in the spectra varies as a function of flux density, and our study establishes an upper photon density limit at ~1.0 × 1012 photons/µm2. The S6+/ΣS calculated from spectra collected below this absorbed photon limit at intermediate flux densities (~1–4 × 109 photons/s per µm2) are affected by beam damage, as no conditions were found to be completely free of beam-induced changes. However, the S6+/ΣS ratios calculated below the limit at intermediate flux densities are consistent with thermodynamic constraints, demonstrating that S6+/ΣS ratios calculated from S-XANES spectra can be considered reliable for estimating the oxygen fugacity. Our results carry important implications for the S budget of felsic magmas and dissolution mechanisms in evolved melts. While our results from all three flux densities show the presence of S4+ dissolved in relatively oxidized (ΔFMQ > +1.75) dacitic glass, even in the spectra exposed to the lowest photon densities, we are unable to rule out the possibility that the S4+ signal is the result of instantaneous X-ray irradiation induced beam damage using S-XANES alone. When our spectra are compared to S-XANES spectra from basaltic silicate glasses, important differences exist in the solubility of S2– and S6+ between dacitic silicate melts, pointing to differences in solubility mechanisms as melt composition changes. This study highlights the need for further investigation into beam damage systematics, presence of S4+, and the solubility mechanisms of different oxidation states of S as silicate melt composition changes.

Geochemistry & Geophysics↗

Method for estimating the density of high-level nuclear waste glass

A database of over 1100 silicate glass compositions and densities was compiled and used to evaluate the efficacy of an algorithm for estimating the density of silicate glass compositions. We sought to develop a parsimonious algorithm based on the additivity of partial molar volumes of individual oxide components weighted by their mole fraction in a glass composition. Bound molar volumes were used for oxides in which the density of the oxide bound in a glass matrix was previously determined. The bound molar volumes were known for oxides covering 97.5 mole percent of the database compositional space. The measured glass densities were plotted against the estimated glass densities and a linear regression yielded an R 2 adj. = 0.95 and a slope and intercept of approximately one and zero, respectively. This regression suggests that glass densities estimated by the algorithm, within analysis uncertainty, are equal to the measured densities of the glasses. In addition to the development of the density estimation, we corroborated many of the referenced bound molar volume data used in the parameterization of the estimation algorithm via linear regression of the individual partial molar volumes versus the inverse measured densities (specific volumes) of the glasses in the database.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Chemistry and surface morphology of soil particles from Luna 20 LRL sample 22003.

Optical and scanning electron microscopy, scanning electron microprobes and energy dispersion techniques were applied in an analysis of six siliceous glass spheres, five siliceous glass-bonded agglutinates and one breccia fragment from Luna 20 sample 22003. It is theorized that local meteor impact processes might have been responsible for the formation of most of the glass spheres and that the impacts of relatively high velocity particles might have been responsible for the craters observed on the surfaces of the spheres. The concentrations of iron spherules on the surfaces of the glass spheres were generally lower than in similar Apollo 11 and 12 glass spheres.

Carter, J. L.↗

Glass corrosion in natural environments

Experiments carried out during the progress period are summarized. Experiments carried out involving glass samples exposed to solutions of Tris have shown the appearance of 'spikes' upon monitoring glass dissolution as a function of time. The periodic 'spikes' observed in Tris-based media were interpreted in terms of cracking due to excessive stress in the surface region of the glass. Studies of the interactions of silicate glasses with metal ions in buffered media were extended to systems containing Al. Caps buffer was used to establish the pH. The procedures used are described and the results are given. Preliminary studies were initiated as to the feasibility of adding a slowly dissolving solid compound of the additive to the glass-water system to maintain a supply of dissolved additive. It appears that several magnesium compounds have a suitable combination of solubility and affinity towards silicate glass surfaces to have a pronounced retarding effect on the extraction of uranium from the glass. These preliminary findings raise the possibility that introducing a magnesium source into geologic repositories for nuclear waste glass in the form of a sparingly soluble Mg-based backfill material may cause a substantial reduction in the extent of long-term glass corrosion. The studies described also provide mechanistic understanding of the roles of various metal solutes in the leachant. Such understanding forms the basis for developing long-term predictions of nuclear waste glass durability under repository conditions. From what is known about natural highly reduced glasses such as tektites, it is clear that iron is dissolved as ferrous iron with little or no ferric iron. The reducing conditions were high enough to cause metallic iron to exsolve out of the glass in the form of submicroscopic spherules. As the nuclear waste glass is much less reduced, a study was initiated on other natural glasses in addition to the nuclear waste glass. Extensive measurements were carried out on these glasses in order to characterize their magnetic properties. Results of these studies are described.

Thorpe, Arthur N.↗

Chondrule-like objects and brown glasses in howardites

Chondrulelike objects and brown glasses were analyzed in the howardites, Bununu, Malvern, Monticello, Pavlovka, and Yamato 7308. The objects are very similar to chondrules in ordinary and carbonaceous chondrites. Like the brown glasses, the chondrulelike objects could have been produced by impact melting that left some crystalline nuclei, followed by a slower cooling rate than for the glasses. Alternatively, these objects are chondrules implanted from chondrite impactors. They are, however, without rims or any adhering matrix. The brown glasses appear to represent melting of average regolithic surface material, except for Monticello and Y7308, both of which have some siliceous glasses. The siliceous glasses could not have been produced by vapor fractionation but by melting of differentiated lithologies such as fayalitic granites. Impact mechanics indicates that howardites with abundant brown glasses came from an asteroid larger than Vesta (greater than 400 km radius), upon which impacts occurred at relative velocities of up to 5 km/s. Howardites with little or no brown glasses came from a smaller parent body. It is concluded that at least two parent bodies are likely sources for the basaltic achondrites.

Olsen, Edward J.↗

Technologies for Non-Destructive Evaluation of Surfaces and Thin Coating

A study was made on two commercially available terbium-doped silicate glasses. There is an increased interest in silicate glasses doped with rare-earth ions for use in high-energy particle detection and radiographic applications. These glasses are of interest due to the fact that they can be formed into small fiber sensors; a property that can be used to increase the spatial resolution of a detection system. Following absorption of radiation, the terbium ions become excited and then emit photons via 4f-4f electronic transitions as they relax back to the ground state. The lifetime of these transitions is on the order of milliseconds. A longer decay component lasting on the order of minutes has also been observed. While radiative transitions in the 4f shell of rare-earth ions are generally well understood by the Judd-Olfelt theory, the presence of a longer luminescence decay component is not. Experimental evidence that the long decay component is due, in part, to the thermal release of trapped charge carriers will be presented. In addition, a theoretical model describing the time evolution of the radiation-induced luminescence will be presented.

Manos, Dennis M.↗

29Si solid state NMR and Ti K-edge XAFS pre-edge spectroscopy reveal complex behavior of Ti in silicate melts

Abstract An understanding of the mechanisms of Ti is incorporation into silicate glasses and melts is critical for the field of petrology. Trace-element thermobarometry, high-field-strength element partitioning, and the physical properties of magmas are all be influenced by Ti incorporation into glasses and changes therein in response to changes in composition and temperature. In this study, we combine 29 Si solid state NMR and Ti K -edge XAFS spectroscopy to investigate how Ti is incorporated into quenched Na-silicate glasses, and the influence of Ti on the structure of silicate species in these glasses. 29 Si NMR shows that in both Ti-bearing Na 2 O•4SiO 2 (NS4) and Na 2 O•8SiO 2 (NS8) glasses, increasing the amount of Ti in the melt results in a shift of Si Q 4 peak in the 29 Si NMR spectra reflecting Ti nearest neighbors for Si in Q 4 speciation. The Ti XAFS results from NS8 glass indicate that Ti is primarily incorporated in [5]-fold coordination. At higher Ti content, there is a shift of the XAFS pre-edge feature suggesting mixing of [4]-fold Ti into the spectra. Combined, the 29 Si NMR and XAFS pre-edge data are consistent with Ti incorporation as isolated [5] Ti atoms and the formation of [5] Ti clusters at relatively low Ti concentrations, with no evidence for Ti–Na interactions as suggested by previous studies. As the Ti content increases, the Ti atoms begin to occupy 4-fold coordinated sites interacting primarily with Si in Q 4 speciation (no significant Na– [4] Ti bonding). The internal consistency of these two techniques provides a uniquely complete snapshot of the complexity of Ti incorporation in silicate melts and underlies the importance of understanding Ti incorporation mechanisms in natural magmatic systems.

Ackerson, Michael R.↗

Sources of Li isotope bias during SIMS analysis of standard glasses

The 7 Li/ 6 Li ratios in fourteen USGS, MPI-DING, and NIST glass reference materials (RMs) were analyzed by LG-SIMS to assess compositional matrix effects, evaluate RM δ 7 Li homogeneity, and calculate the useful yield of lithium in silicate glasses. The analyzed RMs cover a range of SiO 2 contents from 45.5 to 75.6% (komatiite to rhyolite), the largest compositional range yet evaluated for δ 7 Li matrix effects. We observe a matrix-induced bias (matrix effect) of up to 18‰ over the studied range that linearly correlates with SiO 2 content, demonstrating that SiO 2 content is a critical factor that must be considered when using silicate glasses to standardize for silicate samples of unknown δ 7 Li composition. All RMs were found to be sufficiently reproducible to aid in standardization of variable SiO 2 contents and appear isotopically homogeneous at the precision of our measurements. Lithium ionizes very efficiently in these RMs, with measurable yields >5% in all fused-rock RMs and >15% in low SiO 2 fused-rock RMs measured at high beam intensities. Finally, fused-rock RMs ionize lithium 2-3x more efficiently than synthetic glass RMs, which may be related to differences in major oxide chemistry and the reduced nature of the synthetic glasses relative to their fused counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of modifier-rich coatings on the ionic transport of glasses [Poster]

Ionic conduction in silicate glasses is mainly influenced by the nature, concentration, and mobility of the network-modifying (NWM) cations. The electrical conduction in SLS is dominated by the ionic migration of sodium moving from the anode to the cathode. An activation energy for this conduction process was calculated to be 0.82eV and in good agreement with values previously reported. The conduction process associated to the leakage current and relaxation peak in TSDC for HPFS is attributed to conduction between nonbridging oxygen hole centers (NBOHC). It is suggested that ≡Si-OH = ≡Si-O - + H 0 under thermo-electric poling, promoting hole or proton injection from the anode and responsible for the 1.5eV relaxation peak. No previous TSDC data have been found to corroborate this mechanism. The higher activation energy and lower current intensity for the coated HPFS might be attributed to a lower concentration of NBOHC after heat treatment (Si-OH + OH-Si = SiO-Si + H 2 O). This could explain the TSDC signal around room temperature for the coated HPFS. Another possible explanation could be a redox reaction at the anode region dominating the current response.

36 MATERIALS SCIENCE↗

Microscope Cells Containing Multiple Micromachined Wells

Tech Briefs, May 2003 19 Manufacturing Microscope Cells Containing Multiple Micromachined Wells The cost per cell has been reduced substantially. John H. Glenn Research Center, Cleveland, Ohio An improved design for multiple-well microscope cells and an associated improved method of fabricating them have been devised. [As used here, "well" denotes a cavity that has a volume of about 1 or 2 L and that is used to hold a sample for examination under a microscope. As used here, "cell" denotes a laminate, based on a standard 1- by 3-in. (2.54- by 7.62-cm) microscope slide, that comprises (1) the slide as the lower layer, (2) an intermediate layer that contains holes that serve as the wells, and (3) a top layer that either consists of, or is similar to, a standard microscope-slide cover slip.] The improved design and method of fabrication make it possible to increase (relative to a prior design and method of fabrication) the number of wells per cell while reducing the fabrication loss and reducing the cost per cell to about one-tenth of the prior value. In the prior design and method, the slide, well, and cover-slip layers were made from silicate glass. The fabrication of each cell was a labor-intensive process that included precise cutting and grinding of the glass components, fusing of the glass components, and then more grinding and polishing to obtain desired dimensions. Cells of the prior design were expensive and fragile, the rate of loss in fabrication was high, and the nature of the glass made it difficult to increase the number of cells per well. Efforts to execute alternative prior designs in plastic have not yielded satisfactory results because, for typical applications, plastics are not sufficiently thermally or chemically stable, not sufficiently optically clear, and/or not hard enough to resist scratching. The figure depicts a cell of the present improved type. The slide and cover-slip layers are made of a low-thermal-expansion glass (Pyrex(TradeMark) or equivalent) and the intermediate (well layer) is made of SiO2 - a combination of materials that results in a laminate stronger than one made from layers of silicate glass. Before the layers are assembled into the laminate, the SiO2 layer is micromachined to form the wells plus shallow grooves that, when subsequently covered with the cover slip, become capillary channels that are used to fill the wells with samples. The micromachining is accomplished by use of the same patterning and etching techniques used to fabricate microelectromechanical systems (MEMS).

Turner, Walter↗

Formation of Nanophase Iron in Lunar Soil Simulant for Use in ISRU Studies

For the prospective return of humans to the Moon and the extensive amount of premonitory studies necessary, large quantities of lunar soil simulants are required, for a myriad of purposes from construction/engineering purposes all the way to medical testing of its effects from ingestion by humans. And there is only a limited and precious quantity of lunar soil available on Earth (i.e., Apollo soils) - therefore, the immediate need for lunar soil simulants. Since the Apollo era, there have been several simulants; of these JSC-1 (Johnson Space Center) and MLS-1 (Minnesota Lunar Simulant) have been the most widely used. JSC-1 was produced from glassy volcanic tuff in order to approximate lunar soil geotechnical properties; whereas, MLS-1 approximates the chemistry of Apollo 11 high-Ti soil, 10084. Stocks of both simulants are depleted, but JSC-1 has recently gone back into production. The lunar soil simulant workshop, held at Marshall Space Flight Center in January 2005, identified the need to make new simulants for the special properties of lunar soil, such as nanophase iron (np-Fe(sup 0). Hill et al. (2005, this volume) showed the important role of microscale Fe(sup 0) in microwave processing of the lunar soil simulants JSC-1 and MLS-1. Lunar soil is formed by space weathering of lunar rocks (e.g., micrometeorite impact, cosmic particle bombardment). Glass generated during micrometeorite impact cements rock and mineral fragments together to form aggregates called agglutinates, and also produces vapor that is deposited and coats soil grains. Taylor et al. (2001) showed that the relative amount of impact glass in lunar soil increases with decreasing grain size and is the most abundant component in lunar dust (less than 20 micrometer fraction). Notably, the magnetic susceptibility of lunar soil also increases with the decreasing grain size, as a function of the amount of nanophase-sized Fe(sup 0) in impact-melt generated glass. Keller et al. (1997, 1999) also discovered the presence of abundant np-Fe(sup 0) particles in the glass patinas coating most soil particles. Therefore, the correlation of glass content and magnetic susceptibility can be explained by the presence of the np-Feo particles in glass: small particles contain relatively more np-Fe(sup 0) as glass coatings because the surface area versus mass ratio of the grain size is so increased. The magnetic properties of lunar soil are important in dust mitigation on the Moon (Taylor et al. 2005). Thus material simulating this property is important for testing mitigation methods using electromagnetic field. This np- Fe(sup 0) also produces a unique energy coupling to normal microwaves, such as present in kitchen microwave ovens. Effectively, a portion of lunar soil placed in a normal 2.45 GHz oven will melt at greater than 1200 C before your tea will boil at 100 C, a startling and new discovery reported by Taylor and Meek (2004, 2005). Several methods have been investigated in attempts to make nanophase-sized Feo dispersed within silicate glass; like in the lunar glass. We have been successful in synthesizing such a product and continue to improve on our recipe. We have performed extensive experimentation on this subject to date. Ultimately it will probably be necessary to add this np-Fe(sup 0) bearing silicate glass to lunar soil stimulant, like JSC-1, to actually produce the desired magnetic and microwave coupling properties for use in appropriate ISRU experimentation.

Liu, Yang↗