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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on Earth (1 g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on Earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials.

Day, Delbert E.↗
NASA NTRS2006

Computer Modeling of Thermal Convection in Melts to Explain Glass Formation in Low Gravity and on Earth

Experiments conducted up to this time on glass forming melts in the low gravity environment of space show that glasses prepared in low-g are more chemically homogeneous and more resistant to crystallization than the comparable glasses prepared at 1-g on Earth. This result is somewhat surprising and opposite to the accepted concept on glass formation for a melt. A hypothesis based on "shear thinning" of a melt, a decrease in viscosity with increasing shear stress, is proposed as an explanation for the observed low-gravity results. This paper describes detailed simulation procedures to test the role of thermal convection in introducing shear stress in glass forming melts, using a lithium disilcate melt as a model. The simulation system in its idealized version consists of a cylinder that is heated at one end and cooled at the other with gravity acting in a transverse direction to the thermal gradient. The side wall of the cylinder is assumed to be insulating. The governing equations of motion and energy are solved using variable properties for viscosity (Arrehenius and non-Arrehenius behaviors) and density (constant and temperature dependent). Other parametric variables in the calculations include gravity level and gravity vector orientation. The shear stress in the system are then computed as a function of gravity from the calculated values of maximum melt velocity, and its effect on melt viscosity (shear thinning) is predicted. Also included and discussed are the modeling efforts related to other potential convective processes in glass forming melts and their possible effects on melt viscosity.

Ray, Chandra S.↗
NASA NTRS2005

Tomographic Location of Potential Melt-Bearing Phenocrysts in Lunar Glass Spherules

In 1971, Apollo 17 astronauts collected a 10 cm soil sample (74220) comprised almost entirely of orange glass spherules. Below this, a double drive-tube core sampled a 68 cm thick horizon comprised of orange glass and black beads (crystallized equivalents of orange glass). Primitive lunar glass spherules (e.g.-A17 orange glasses) are thought to represent ejecta from lunar mare fire fountains [1, 2]. The fire-fountains were apparently driven by a combination of C-O gas ex-solution from orange glass melt and the oxidation of graphite [3, 4]. Upon eruption, magmas lost their volatiles (e.g., S, CO, CO2) to space. Evidence for volatile escape remains as volatile-rich coatings on the exteriors of many spherules [e.g., 5,6]. Moreover, [7] showed that Type I and II Fe-Ni-rich metal particles found within orange glass olivine phenocrysts, or free-floating in the glass itself, are powerful evidence for the volatile driving force for lunar fire fountains.

Ebel, D. S.↗
DOE OSTI2022

Synthesis of Nanoceria with Varied Ratios of Ce3+/Ce4+ Utilizing Soluble Borate Glass

Mixed-valence cerium oxide nanoparticles (nanoceria) have been investigated with pronounced interest due to a wide range of biomedical and industrial applications that arises from its remarkable redox catalytic properties. However, there is no understanding of how to control the formation of these two types of nanoceria to obtain Ce3+/Ce4+ ratios required in various applications. In this work, using a soluble borate glass, nanoceria with specific ratios of Ce3+/Ce4+ are created and extracted via controlled glass-melting parameters. Glass embedded with nanoceria as well as nanoceria extracted from the glass were studied via XANES and fitted with the Multivariate Curve Resolution (MCR) technique to calculate the ratio of Ce3+/Ce4+. Results show that mixed-valence nanoceria with specific ratios are hermetically sealed within the glass for long durations. When the glass dissolves, the mixed-valence nanoceria are released, and the extracted nanoceria have unchanged Ce3+/Ce4+ ratios. Furthermore, TEM investigation on released nanoceria show that the nanoceria consist of several different structures. Although nanocrystal structures of Ce7O12, Ce11O20, and Ce2O3 contribute to the reduced state, a new quasi-stable phase of CeO1.66 has been observed as well.

36 MATERIALS SCIENCE↗
NASA NTRS2005

Volatiles in the Desert: Subtle Remote-sensing Signatures of the Dakhleh Oasis Catastrophic Event, Western Desert, Egypt

Over the past decade members of the Dakhleh Oasis Project have studied enigmatic signatures in the Pleistocene geologic record of portions of the Dakhleh oasis and palaeo-oasis in Egypt's Western Desert [1,2]. In particular, Si-Ca-Al rich glass melt (Dakhleh Glass, Fig. 1) points to a catastrophic event between c.100,000-200,000 years ago [3] in this well-studied African savannah and freshwater lake Middle Stone Age environment [4,5].

Haldemann, A. F. C.↗
NASA NTRSDate not supplied

High Resolution Imaging and Analysis of Terrestrial Impact Glass: Amorphous Materials, Phyllosilicates and Everything in Between

Introduction: Impact cratering is one of the most ubiquitous geologic processes shaping the surface of all solid bodies in our solar system. Impacts are also a major source of clay minerals, poorly crystalline clay-like phases and amorphous (i.e., lacking long-range atomic order) materials on Earth and Mars. Phyllosilicates and amorphous materials have consistently formed a major component (~20-70 wt%) of every single drilled rock and soil sample in Gale Crater on Mars, as determined by the CheMin instrument on Curiosity. The origin of the amorphous component is speculative, but could be primary impact or volcanic-produced glass(es) deposited via aeolian or fluvial processes, secondary aqueous alteration products or chemical precipitates; it is likely to be a combination of all three possibilities. Efforts to determine the composition of these materials across the rover’s traverse through Gale Crater are ongoing. Naturally occurring amorphous phases are found in a variety of environments on Earth, and terrestrial analogue studies may help shed light on how they may have formed on Mars. Primary and altered impact glass are likely widespread on Mars and may have contributed to the amorphous component found throughout Gale Crater. In its pristine, unaltered state, impact glass (i.e., melt glass) is considered amorphous. However, truly unaltered glass is rarely preserved in crater fill impactites as it quickly alters in the post-impact environ-ment, commonly forming a mixture of hydrated aluminosilicate phases whose structures are not always discernable at the microscale (i.e., they may be amorphous or contain short-range order). These phases are part of an incredibly complex group of materials; differences in their composition and crystalline structure (or lack thereof) and genetic relationship to the more well-crystalline clay minerals are often only discernable at the nanoscale, beyond the resolution of traditional X-ray diffractometers (XRD) and scanning electron microscopes/microprobes (SEM/EPMA) alone. In this contribution, we summarize recent results from ongoing characterization of clay minerals, poorly crystalline clay-like phases, and amorphous materials preserved in altered terrestrial impact glass from the Chicxulub (~66 Ma) and Ries (~15 Ma) impact structures. This work has been performed using a combination of high-resolution transmission electron microscopy (HR-TEM), SEM, microprobe/EPMA, Raman spectroscopy and XRD.

Impact crater↗
DOE OSTI2022

Liquid fragility maximum in lithium borate glass‐forming melts related to the local structure

Abstract The structure of liquid lithium pyroborate, Li 4 B 2 O 5 ( J = Li/B = 2), has been measured over a wide temperature range by high‐energy X‐ray diffraction, and compared to that of its glass and borate liquids of other compositions. The results indicate a gradual increase in tetrahedral boron fraction from 3(1)% to 6(1)% during cooling from T = 1271(15) to 721(8) K, consistent with the larger N 4 = 10(1)% found for the glass, and literature 11 B nuclear magnetic resonance measurements. van't Hoff analysis based on a simple boron isomerization reaction BØ 3 O 2 – ⇌ BØO 2 2– yields Δ H = 13(1) kJ mol –1 and Δ S = 40(1) J mol –1 K –1 for the boron coordination change from 4 to 3, which are, respectively, smaller and larger than found for singly charged isomers for J ≤ 1. With these, we extend our model for N 4 ( J , T ), nonbridging oxygen fraction f nbr ( J , T ), configurational heat capacity , and entropy S conf ( J , T ) contributions up to J = 3. A maximum is revealed in at J = 1, and shown semi‐quantitatively to lead to a corresponding maximum in fragility contribution, akin to that observed in the total fragilities by temperature‐modulated differential scanning calorimetry. Lithium is bound to 4.6(2) oxygen in the pyroborate liquid, with 2.7(1) bonds centered around 1.946(8) Å and 1.9(1) around 2.42(1) Å. In the glass, n LiO = 5.4(4), the increase being due to an increase in the number of short Li–O bonds.

36 MATERIALS SCIENCE↗
NASA NTRS1983

MEA/A-1 experiment 81F01 conducted on STS-7 flight, June 1983. Containerless processing of glass forming melts

The space processing of containerless, glassforming melts on board the space shuttle flight STS-7 is investigated. Objectives include; (1) obtain quantitative evidence for the supression of heterogeneous nucleation/crystallization, (2) study melt homogenization without gravity driven convection, (3) procedural development for bubble free, high purity homogeneous melts inmicro-g, (4) comparative analysis of melts on Earth and in micro g, and (5) assess the apparatus for processing multicomponent, glass forming melts in a low gravity environment.

Day, D. E.↗
DOE OSTI2020

Fluorine Limits and Impacts in High-Level Waste Glass Compositions

The impact of elevated fluorine (F) content on Hanford high-level waste (HLW) glasses has not previously been studied in detail. This effort represents the first systematic study to determine what F concentration limits should be used for the design of alkali-borosilicate-based Hanford Waste Treatment and Immobilization Plant (WTP) HLW glasses, and to document the technical basis for that limit. If alkali borosilicate glass made from Hanford HLW can accommodate a large amount of F, the large capital costs for complex sludge washing facilities may be avoided, as would much of the operational costs and negative schedule impacts associated with handling the large volumes of water required to dissolve these salts. In order to determine a limit for F in likely HLW glass compositions, an evaluation was conducted on glasses with F ≤ 0.90 mass% from previous nuclear waste glass studies. The collected dataset contains 239 glasses (232 HLW glasses and 7 LAW glasses) including 109 glasses with 0.9 ≤ F mass% ≤ 2.5, 116 with 2.5 < F mass% ≤ 8.0, and 14 with F mass% ≥ 8 (max. F mass% = 17.42). The collected composition and property data were analyzed to determine the basis for the F tolerance, i.e. the maximum F concentration that can be processed without potential issues. Fluorine volatility, product consistency test (PCT) response, liquidus temperature (T L ), glass melt viscosity, and crystallinity have been investigated. No limits for F concentration can be made based on F volatility, T L , or glass melt viscosity, because the data show that high F in glasses do not indicate, with high probability, being restricted by those property constrains. However, crystallinity and PCT response were used to estimate the F tolerance. The results show that glasses with high F (≥ 0.90 mass%) are more likely to form large fractions of F-containing crystal phases which may increase PCT responses, i.e. decrease the glass durability. Based on the results of crystallinity and PCT data, the F tolerance of 4.5 mass% is estimated. There is no evidence of other glass components, such as calcium oxides and alkali metal oxides have combined impacts with F on the glass properties. Overall, the available high-F glass data is limited, especially in the designed HLW glass composition regions. Future work on formulation and testing of HLW glasses with F ≥ 0.9 mass% will close the data gaps and expand operational flexibility with respect to the fluoride tolerances. Volatility of F from melters and corrosion of materials in contact with glass melts are important for processing of high-F wastes; yet no test data are currently available. It is recommended tests be conducted to address these two potential issues.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1989

Study Of Phase Separation In Glass

Report describes an experimental study of effect of hydroxide content on phase separation in soda/silica glasses. Ordinary and gel glasses melted at 1,565 degree C, and melts stirred periodically. "Wet" glasses produced by passing bubbles of N2 saturated with water through melts; "dry" glasses prepared in similar manner, except N2 dried before passage through melts. Analyses of compositions of glasses performed by atomic-absorption and index-of-refraction measurements. Authors conclude hydroxide speeds up phase separation, regardless of method (gel or ordinary) by which glass prepared. Eventually helps material scientists to find ways to control morphology of phase separation.

Neilson, George F.↗
NASA NTRS1984

An electromotive force series in a borosilicate glass-forming melt

An electromotive force series for redox couples was defined as a function of oxygen fugacity in a borosilicate melt at 1150 C. The resulting order of relative reduction potentials can be used to estimate the amounts of redox species in glass during processing. The electromotive force series in this melt is comparable to those in other silicate glass-forming melts and in aqueous systems but differs in detail because of interaction of the solvents with individual redox couples.

Schreiber, H. D.↗
NASA NTRS1986

Containerless processing of glass forming melts: D-1, MEA/A-2 experiment 81F01 conducted on STS-61A flight, October 1985

Results of experiment 81F01, which was conducted in the Material Experiment Assembly MEA/A-2 on the D-1 Spacelab Mission (STS-61A), are presented. The general plan of the experiment was to heat, melt, and quench six spherical samples of different glass forming compositions while they were levitated in a single axis acoustic levitator furnace (SAAL). In addition, two non-melting sintered alumina samples were used to check the operational characteristics of the SAAL under reduced gravity conditions. Three of the eight samples were levitated between 1250 and 1500 C before the lack of coolant created an over-temperature condition that caused the SAAL to shut down prematurely. Two of the three samples processed were calcia-gallia-silica and soda-lime-silica glass forming compositions. Evidence of a two to three times increase in the tendency for glass formation was obtained for the calcia-gallia-silica. The final glass appeared reasonably homogeneous even though it was made from hot pressed powders containing deliberate heterogeneities. A photographic record was obtained of the microgravity sample processing sequences.

Day, D. E.↗
NASA NTRS2003

Characterization of Martian Soil Fines Fraction in SNC Meteorites

Some impact-melt glasses in shergottite meteorites contain large abundances of martian atmospheric noble gases with high (129)Xe/(132)Xe ratios, accompanied by varying (87)Sr/(86)Sr (initial) ratios. These glasses contain Martian Soil Fines (MSF) probably from young volcanic terrains such as Tharsis or Elysium Mons. The composition of the MSF bearing samples is different from the average bulk composition of the host rock. These samples show the following charecteristics: a) simultaeneous enrichment of the felsic component and depletion of the mafic component relative to the host phase and b) significant secondary sulfur/sulfate excesses over the host material. The degree of enrichment and associated depletion varies from one sample to another. Earlier, we found large enrichments of felsic (Al, Ca, Na and K) component and depletion of mafic (Fe, Mg, Mn and Ti) component in several impact melt glass veins and pods of samples ,77 ,78 , 18, and ,20A in EET79001 accompanied by large sulfur/sulfate excesses. Based on these results, we proposed a model where the comminution of basaltic rocks takes place by meteoroid bombardment on the martian surface, leading to the generation of fine-grained soil near the impact sites. This fine-grained soil material is subsequently mobilized by saltation and deflation processes on Mars surface due to pervasive aeolian activity. This movement results in mechanical fractionation leading to the felsic enrichment and mafic depletion in the martian dust. We report, here, new data on an impact-melt inclusion ,507 (PAPA) from EET79001, Lith B and ,506 (ALPHA) from EET79001, Lith A and compare the results with those obtained on Shergotty impact melt glass (DBS).

Rao, M. N.↗
NASA NTRS1983

Description of the containerless melting of glass in low gravity

A brief description is given of a single-axis, acoustic levitator/furnace apparatus used to position, heat, melt, and quench multicomponent oxide, glass-forming compositions in low gravity. This apparatus is capable of processing eight approximately spherical samples (about 6 mm diameter) at temperatures up to 1550 C in a dry air atmosphere. Results are also presented for a containerless melting experiment conducted on SPAR VI where a ternary CaO-Ga2O3-SiO2 composition was levitated and quenched to a glass. Selected properties of the glass prepared on SPAR VI are compared with the properties of glass samples of identical composition prepared on earth.

Ray, C. S.↗
DOE OSTI2021

Effect of water vapor and thermal history on nuclear waste feed conversion to glass

Water affects the glass melting process by interacting with the foam layer at the glass melt surface and by influencing the batch conversion reactions. Water vapor from the nuclear waste slurry feed maintains a high water vapor pressure in the melter atmosphere. To investigate to what extent water vapor affects the vitrification of nuclear waste in joule-heated, cold-top melters, a series of feed expansion experiments were performed under humid and dry atmospheres using samples of low-activity waste (LAW) melter feed simulants. Melting of feed pellets in the presence of water vapor slightly decreased the temperature of primary foam onset, but did not significantly affect the feed volume expansion by foaming or the foam-collapse temperature. Sets of feed expansion experiments and evolved gas analyses were also performed to check the effect of thermal history on LAW feed samples tested as direct slurry, loose powder, and slow- and fast-dried pellets.

Marcial, Jose↗
NASA NTRS1978

Residual glasses and melt inclusions in basalts from DSDP Legs 45 and 46 - Evidence for magma mixing

Microprobe analyses of natural glasses in basalts recovered by Legs 45 and 46 of the Deep Sea Drilling Project are reported and interpreted in the context of other geochemical, petrographic and experimental data on the same rocks (Rhodes et al., 1978). Residual glass compositions in the moderately evolved aphyritic and abundantly phyric basalts within each site indicate that none of the units is related to any other or to a common parent by simple fractional crystallization. The compositional trends, extensive disequilibrium textures in the plagioclase phenocrysts and the presence in evolved lavas of refractory plagioclase and olivine phenocrysts bearing primitive melt inclusions provide evidence that magma mixing had a major role in the genesis of the Leg 45 and 46 basalts. The magma parental to these basalts was most likely characterized by high Mg/(Mg + Fe/+2/), CaO/Al2O3, CaO/Na2O and low lithophile concentrations. A mixing model involving incremental enrichment of magmaphile elements by repeated episodes of mixing of relatively primitive and moderately evolved magmas, followed by a small amount of fractionation is consistent with the characteristics of the basalts studied.

Dungan, M. A.↗
DOE OSTI2024

Modeling the Behavior of Noble Metals During HLW Vitrification in the DM1200 Melter

The noble metals ruthenium (Ru), rhodium (Rh), and palladium (Pd) are present to various extents in defense and commercial high-level nuclear waste streams. Usually, their concentrations are higher in commercial waste. Ru, Rh, and Pd are sparingly soluble in silicate glass melts and they therefore form separate metal, oxide, or other phases. These phases are generally denser than the glass melt and tend to sediment to the bottom of the melter, where they form a "sludge" layer. Since the sludge layer has a higher electrical conductivity than the molten glass, accumulation of sludge can ultimately lead to electrical disruption of the operation of the melter. In addition, the sludge reduces the melt volume, which also changes the operational characteristics of the melter. The noble metals sludge is a highly viscous mixture of melt and noble metal phases. The concentration of noble metals in the sludge may be 10 to 100 times higher than that in the drained glass.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗