Boron coordination change in barium borate melts and glasses and its contribution to configurational heat capacity, entropy, and fragility
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O. L. G. Alderman↗
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Formulation and testing of a high-tin borosilicate nuclear waste glass for in-can melting
Here, borosilicate waste glasses were successfully developed to immobilize two high-level waste raffinate streams via an in-can melter process with an Inconel 601 canister at 1050 °C. Measured viscosity and crystallinity thermal profiles were within the targeted processing constraints for the in-can melter process. Measured chemical durability of the glass by ASTM C1285–21 (Method A), ranged from normalized loss of boron, NL(B) = 1.44 – 2.65 g•m -2 , and NL(B) decreased with increased waste loading, accompanied by increased SnO 2 crystallinity. Measured corrosion of the in-can melter canister by a glass melt showed that Inconel 601 performed well at 1100 °C for up to 500 hr. Resistance polarization measurements versus time revealed that Inconel 601 corrosion rates in (and by) glass melts decreased from an initial rate of 63 mm•y -1 down to 10.2 mm•y -1 after 137 h with increased duration, which was attributed to formation of an oxide passivation layer (mainly Cr 2 O 3 ) at the alloy-glass interface.
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In situ characterization of foam morphology during melting of simulated waste glass using x-ray computed tomography
Not Available
Luksic, Steven A.↗
Laboratory Shock Experiments on Basalt - Iron Sulfate Mixes at Approximately 40-50 GPa and Their Relevance to the Martian Regolith Component Present in Shergottites
Basaltic shergottites such as Shergotty, Zagami and EET79001 contain impact melt glass pockets that are rich in Martian atmospheric gases [1] and are known as gas-rich impact-melt (GRIM) glasses. These glasses show evidence for the presence of a Martian regolith component based on Sm and Kr isotopic studies [2]. The GRIM glasses are sometimes embedded with clusters of innumerable micron-sized iron-sulfide blebs associated with minor amounts of iron sulfate particles [3, 4]. These sulfide blebs are secondary in origin and are not related to the primary igneous sulfides occurring in Martian meteorites. The material comprising these glasses arises from the highly oxidizing Martian surface and sulfur is unlikely to occur as sulfide in the Martian regoilith. Instead, sulfur is shown to occur as sulfate based on APXS and Mossbauer results obtained by the Opportunity and Spirit rovers at Meridiani and Gusev [5]. We have earlier suggested that the micron-sized iron sulfide globules in GRIM glasses were likely produced by shock-reduction of iron sulfate occurring in the regolith at the time when the GRIM glasses were produced by the meteoroid impact that launched the Martian meteorites into space [6]. As a result of high energy deposition by shock (approx. 40-60 GPa), the iron sulfate bearing phases are likely to melt along with other regolith components and will get reduced to immiscible sulfide fluid under reducing conditions. On quenching, this generates a dispersion of micron-scale sulfide blebs. The reducing agents in our case are likely to be H2 and CO which were shock-implanted from the Martian atmosphere into these glasses along with the noble gases. We conducted lab simulation experiments in the Lindhurst Laboratory of Experimental Geophysics at Caltech and the Experimental Impact Laboratory at JSC to test whether iron sulfide globules can be produced by impact-driven reduction of iron sulfate by subjecting Columbia River Basalt (CRB) and ferric sulfate mixtures to shock pressures between 40 and 50 GPa under reducing conditions. The experimental products from the recovered samples were analyzed by SEM and microprobe techniques at JSC.
Rao, M. N.↗
Ferrule and use thereof for cooling a melt spun hollow glass fiber as it emerges from a spinnerette
An improvement in the process of melt spinning thin walled, hollow fibers from relatively low melting glasses results if cooling of the emerging fiber is accomplished by use of a thin layer of gas to transfer heat from the fiber to a ferrule which fits closely to the spinnerette face and the individual fiber. The ferrule incorporates or is in contact with a heat sink and is slotted or segmented so that it may be brought into position around the moving fiber. Thinner walled, more uniform fibers may be spun when this method of cooling is employed.
Brown, William E.↗
Preparation of optical materials used in non-visible region (M-17)
The purpose of the experiment was the following: development of containerless glass melting technique; fabrication of high purity glass; and development of acoustic levitation technique. For the space experiment, glass 65CaO-25Ga2O3-10GeO2 was selected out of various types of glasses. The expected results are: ultra-high purity glass and manipulation by acoustics.
Hayakawa, J.↗
Martian soil component in impact glasses in a Martian meteorite
Chemical compositions of impact melt glass veins, called Lithology C (Lith C) in Martian meteorite EET79001 were determined by electron microprobe analysis. A large enrichment of S, and significant enrichments of Al, Ca, and Na were observed in Lith C glass compared to Lithology A (Lith A). The S enrichment is due to mixing of plagioclase- enriched Lith A material with Martian soil, either prior to or during impact on Mars. A mixture of 87% Lith A, 7% plagioclase, and 6% Martian soil reproduces the average elemental abundances observed in Lith C. Shock melting of such a mixture of plagioclase-enriched, fine-grained Lith A host rock and Martian soil could yield large excesses of S (observed in this study) and Martian atmospheric noble gases (found by Bogard et al., 1983) in Lith C. These mixing proportions can be used to constrain the elemental abundance of phosphorus in Martian soil.
NASA Center JSC↗
Apollo Sample 64455: Petrologic and Geochemical Characterization of a Glass-Coated Impact Melt Rock
Introduction and Background: Impact melts are a key product of the impact cratering process. Impact melts can turbulently entrain pre-existing rock fragments, and melt part of those entrained materials until thermal equilibrium is achieved [1–3]. Lunar impact melt rocks are valuable for determining the precise ages of basin-forming and cratering events, which anchor the cratering chronology and dynamics of the entire solar system [4, and references therein]. Additionally, entrained clasts can inform on the petrology and age of crustal materials that predate the melt-forming impact. In lithologies where no pristine samples are available, entrained materials may hold the record of endogenous lunar volatiles, provided we can untangle their impact histories as high temperature impact melt can heat the clasts and may alter their native volatiles or isotopic signatures [5–6]. Here, we characterize an Apollo 16 sample, 64455,70B, in an effort to understand the physical, microstructural, and geochemical consequences of impact melt contact metamorphism. We acquired optical light and x-ray maps of the sample, as well as quantitative analyses via electron probe microanalysis (EPMA). These tasks allow us to better understand the interaction between impact melts and entrained clasts, ultimately closing knowledge gaps in high-temperature impact processing on planetary surfaces. Sample Description: Sample 64455 is an oblong crystalline rock encased in glass to form an egg-like shape [7–8]. The impact melt coating has altered the outer (1 to 2 mm) rind of the crystalline rock and has preserved schlieren. The interior crystalline rock is likely a crystalline impact melt rock based on its bulk Ir content of 2.25 parts per billion [9]. The composition of the impact melt glass rind cannot be solely derived from the crystalline interior, the glassy rind is more aluminous and less magnesian [10]. Neither the crystalline interior nor the glassy rind were radiometrically age dated, although several studies investigated its cosmogenic isotopes and exposure ages, which reveal the sample was exposed on the lunar surface for ~1–2 Ma [11–13]. Preliminary Results: The interior crystalline rock consists primarily of plagioclase with interstitial pyroxene and olivine. Plagioclase grains are zoned and compositions range from An97–89, while pyroxene compositions generally range from En68Fs19Wo13 to En82Fs15Wo3 and olivine are Fo77 to Fo85. Minor phases include Fe-Ni metal, Ca-phosphates, a K- and Si-rich phase, sulfides, and Fe-phosphides. The glass rind contains approximately 44 wt.% SiO2, 25 wt.% Al2O3, 6 wt.% FeO, 8 wt.% MgO, and 14 wt.% CaO, with other oxides at <1 wt.% each, although the composition of the glass becomes more variable closest to the crystalline rock. The rind consists of rounded plagioclase, pyroxene, and olivine crystals with interstitial melt. In some locations, the rounded crystals are surrounded by closely-packed, blade-like crystals, <5 µm in width. These results indicate that the crystalline interior has partially melted where in contact with the high-temperature impact melt and while further investigation is needed, pyroxene may have preferentially melted relative to olivine and plagioclase. Future Work: We plan to conduct electron backscatter diffraction (EBSD) mapping in order to determine crystallinity and crystal orientation. Next using transmission electron microscopy (TEM) data in conjunction with EBSD and EPMA information, we will model the diffusion of moderately volatile elements between the melt and remnant crystals.
A C Stadermann↗
Water Content of Lunar Alkali Fedlspar
Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites crystallized between 4.3-3.8 Ga from relatively wet melts that degassed upon crystallization. The formation of these granites likely removed significant amounts of water from some mantle source regions, e.g. later mare basalts predicting derivation from a mantle with <10 ppm water. However, this would have been a heterogeneous pro-cess based on K distribution. Thus some, if not most of the mantle may not have been devolatilized by this process; as seen by water in volcanic glasses and melt inclusions.
Mills, R. D.↗
Hanford low-activity waste glass composition-temperature-melt viscosity relationships
This study developed a model for predicting viscosity of alkali-alumino-borosilicate glass melts as functions of composition and temperature. The model is based on a total of 3935 viscosity-temperature data from 574 glasses with viscosity values ranging from 2.53 to 7260 Poise (P) in the temperature range of 900–1260°C. Several different model forms were surveyed, including those based on Arrhenius, Vogel-Fulcher-Tammann, Avramov-Milchev, and Mauro-Yue-Ellison-Gupta-Allen. For each of these models, combinations of the temperature-independent parameters were fitted to composition. It was found that generally fitting more than one temperature-independent parameter as functions of composition resulted in overfitting. The Avramov-Milchev-based model was found to best represent the Hanford low-activity waste glass melt viscosity data based on model fit and validation statistics. A 21-term partial quadratic mixture model was recommended for use. This model predicts melt viscosity with a root-mean square error of .1736 ln(P), which is similar to the error in viscosity measurements from replicate glass analyses of .1383 ln(P). Viscosity was found to be most increased by SiO 2 > Al 2 O 3 > ZrO 2 > SnO 2 and most decreased by Li 2 O > Na 2 O > B 2 O 3 > CaO > K 2 O > MgO, at temperatures from 900 to 1260°C.
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Cold-cap structure in a slurry-fed electric melter
We report as glass batch is charged into an electric melter, a cold cap forms on the glass melt surface. Heat transfer to the cold cap from the molten glass below and the melter atmosphere above determines the melting rate. A mathematical model of the cold cap and the experimental kinetic data of the feed-to-glass conversion that were collected for several simulated low-activity and high-level waste melter feeds allowed us to develop relationships between the internal structure of the cold cap, its properties, its thickness, and the internal heat transfer. This contribution shows the distribution of major crystalline phases and the cumulative evolution of gases within the cold cap. It also examines the temperature, conversion degree, and heating rate the melter feed is experiencing during the passage through the cold cap and their effects on the cold-cap bottom temperature and morphology, which are important for the computational fluid dynamics simulations of melters.
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Rb, Sr and strontium isotopic composition, K/Ar age and large ion lithophile trace element abundances in rocks and glasses from the Wanapitei Lake impact structure
Shock metamorphosed rocks and shock-produced melt glasses from the Wanapitei Lake impact structure have been examined petrographically and by electron microprobe. Eleven clasts exhibiting varying degrees of shock metamorphism and eight impact-produced glasses have been analyzed for Rb, Sr and Sr isotopic composition. Five clasts and one glass have also been analyzed for large ion lithophile (LIL) trace element abundances including Li, Rb, Sr, and Ba and the REE's. The impact event forming the Wanapitei Lake structure occurred 37 m.y. ago based on K/Ar dating of glass and glassy whole-rock samples. Rb/Sr isotopic dating failed to provide a meaningful whole-rock or internal isochron. The isotopic composition of the glasses can be explained by impact-produced mixing and melting of metasediments.
Winzer, S. R.↗
Glass Crystallization Constraints for WTP LAW Operations: Assessment of Isothermal Treatments on Crystal Formation
Much work has been done to expand the glass composition region available for operation of the Hanford Tank Waste Treatment and Immobilization Plant. This includes the development of updated glass property-composition models as well as constraints. This report supports this effort by suggesting constraints for avoiding excessive, and likely detrimental, crystallization during melter operation while processing advanced low-activity glasses. The constraints target Cassiterite and ZrO 2 -containing phases (ZCP, e.g., Baddeleyite and Zircon) that can form when melter temperatures drop below 1100 °C. These types of crystals were found to be potentially detrimental during processing as they are denser than low-activity waste glass melts; with densities of 6.95 g/cm 3 for Cassiterite and 5.68 g/cm 3 for Baddeleyite (the most prevalent ZCP). Compared to melt densities of approximately 2.65 g/cm 3 . Thus, they have the potential to form during melter idling and settle to the bottom of the melter or inside the melter. If the crystals are present in appreciable amounts, they can result in blockages of the pour-spout riser, which impacts glass pouring and melter operation. Additionally, SnO 2 and ZrO 2 are added to glass formulations to improve glass durability. Their precipitation from the melt may reduce overall glass durability. Using previously acquired results and results from testing during this effort, the following constraints (Table S.1) were determined and are recommended to reduce the risk of forming crystals of the types and concentrations that are likely detrimental to melter operation.
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Nonlinear optical properties of lanthanum titanate glasses prepared by levitation melting
Lanthanum titanate glasses (17 La 2 O 3 -83 TiO 2 ) are fabricated via aerodynamic levitation melting. Here, nonlinear refraction and absorption were measured with the Z scan technique using ps optical pulses at 532 nm wavelength with peak intensities in the range of 0.25–2.5 GW/cm 2 . The two-photon absorption coefficient (β) and the effective nonlinear refraction coefficient ($n^{eff}_{2}$) are found to be, respectively, 2.19 cm/GW and 152 × 10 -16 cm 2 /W (85 × 10 -13 esu). The Raman gain is measured to be 106 × 10 -11 cm/W. The nonlinearity strength is found to be nearly 60 times larger in lanthanum titanate glasses relative to silica.
36 MATERIALS SCIENCE↗
LAW Glass Formulation to Support Melter Runs with Simulants
The major objective of this work was to prepare and characterize glass formulations in order to develop and select formulations that are compliant with contractual and processing requirements to support melter tests with each of the LAW Sub-Envelopes. Glasses that cover composition ranges of interest were prepared and characterized to ensure that selected glass compositions can tolerate expected composition variations resulting from process errors without adversely affecting processing characteristics or product quality. Glass compositions that are expected to result during transitions from one waste stream to another were also prepared and characterized. Other objectives of the work included preparation and characterization of glasses with respect to the properties of interest, optimization of sulfate loading in the glasses, evaluation of ability to achieve waste loading limits, testing to demonstrate compatibility of glass melts with melter materials of construction, and identification of glass formulation issues with respect to contract specifications and processing requirements.
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Vitrification Testing of HLW with High Phosphate
Projections of the number of high level waste (HLW) canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) (e.g., [1]) are based upon the inventory of the tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier Department of Energy (DOE) melter designs, incorporates a glass bubbler system. The bubblers create active glass pool mixing and thereby improve heat and mass transfer and glass melting rate. The WTP HLW melters each have a glass surface area of 3.75 m 2 and depth of ~1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by optimization of the feed and glass formulations, increasing the melter operating temperature above 1150⁰C, and by increasing the waste loading in the glass product. Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage.
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Ultrapure glass optical waveguide development in microgravity by the sol-gel process
Multicomponent, homogeneous, noncrystalline oxide gels can be prepared by the sol-gel process and these gels are promising starting materials for melting glasses in the space environment. The sol-gel process referred to here is based on the polymerization reaction of alkoxysilane with other metal alkoxy compounds or suitable metal salts. Many of the alkoxysilanes or other metal alkoxides are liquids and thus can be purified by distillation. The use of gels offers several advantages such as high purity and lower melting times and temperatures. The sol-gel process is studied for utilization in the preparation of multicomponent ultrapure glass batches for subsequent containerless melting of the batches in space to prepare glass blanks for optical waveguides.
Mukherjee, S. P.↗
Development of Property Composition Models For RPP-WTP LAW Glasses (Final Report)
This report describes the development of property-composition models for low-activity waste (LAW) glasses for the River Protection Project Waste Treatment Plant (RPP-WTP) at the Hanford site. The RPP-WTP will separate Hanford tank wastes into LAW and high-level waste (HLW) streams and each stream will be vitrified separately. The development of LAW and HLW glass formulations for the RPP-WTP has been reported previously and is an ongoing activity. Acceptable formulations must meet a variety of processability, product quality, and waste loading requirements that are dictated either by the RPP-WTP contract or by the characteristics of the particular treatment processes that have been selected. These requirements amount to constraints on the acceptable ranges of certain glass properties. These properties are determined first and foremost by the composition of the glass or glass melt. Thus, while there is no direct way of controlling the glass properties of interest during production, there are simple and extremely effective methods of achieving the same result by instead controlling the glass composition. This basic principle is no different from that used to produce enormous volumes of commercial glass to meet exacting product specifications. An essential difference in waste vitrification, however, is that one of the raw materials (the waste itself) can be subject to considerable compositional uncertainty and variability. Thus, waste vitrification facilities and associated process control systems (of which, the operating envelope in glass formulation space is a key part) must, of course, be designed to be robust with respect to such variations. The determination of quantitative relationships between the glass properties that must be controlled and the glass composition can play an important role in the development of such facilities.
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