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At least 127 records · Page 7

The Effects of Gravity on the Crystallization Behavior of Heavy Metal Fluoride Glasses

Heavy metal fluoride glasses are used in such applications as fiber lasers and laser amplifiers. ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) is one of the more commonly used heavy metal fluoride glasses. ZBLAN is an infrared transmitter and has a theoretical attenuation coefficient of 0.002 db/km. However, due to impurities and small crystallites this attenuation coefficient has not been achieved to date. ZBLAN is a fragile glass which can lead to rapid crystallization, if the glass is not cooled rapidly to below the glass transition temperature or if the glass is reheated near the crystallization temperature for any period of time. Studies carried on at Marshall Space Flight Center and the University of Alabama in Huntsville since 1993 have shown that heating ZBLAN glass at the crystallization temperature in reduced gravity results in a suppression of crystallization when compared to ZBLAN processed in unit gravity. These studies utilized NASA's KC-135 aircraft and the Conquest sounding rocket. In the first series of experiments, short lengths of ZBLAN fiber were heated to the crystallization temperature in reduced gravity on board the KC- 135 and the Conquest sounding rocket and compared with fibers heated in unit gravity. The fibers processed in reduced gravity showed no evidence of crystallization when studied with x-ray diffraction and scanning electron microscopy. However, the fibers processed in unit gravity were completely crystallized. Subsequent experiments included heating small pieces of ZBLAN glass at the crystallization temperature while viewing with a video camera to follow the crystallization phenomenon. In this experiment crystallization was observed in reduced gravity, however, it was suppressed when compared to heating in unit gravity. In the most recent experiment on board the KC-135, rapid thermal analysis of ZBLAN was performed. A mechanism to explain the observations has been proposed. This mechanism is based on shear thinning whereby, the glass undergoes a reduction in viscosity in the 10(exp 5) - 10(exp 7) poise range, allowing more rapid diffusion and thus crystallization. It is proposed that this mechanism is suppressed in reduced gravity. An experiment is presently being conducted to test this theory. With increased knowledge of ZBLAN behavior in reduced gravity, three low earth orbit tiber drawing facilities have been designed. One would be suitable for use on the International Space Station, another while aboard the Space Shuttle and the third system is a fully automated facility which would operate independently of the ISS or Shuttle in a free float mode. The primary benefits of free floating a facility in LEO includes a higher quality of microgravity and reduced safety concerns since it is not in a manned environment.

Tucker, Dennis S.↗

Optical and Mechanical Properties of Glass Blown In Vacuo

Theoretically, the strength of glass processed in vacuum should be higher due to outgassing of contaminants normally present in the glass, such as bulk water in the form of OH bonds that tends to weaken the glass structure. In this research, small discs of a few types of glass have been subjected to various temperatures for extended periods of time in vacuum. Their strength was then tested using a standard flexure technique, facilitated by a custom-designed test fixture, and the results were compared to glass tested in air using the same fixture. The purpose of the glass blowing investigation was to prove the basic feasibility of a high-level concept for in-space manufacture of optical elements. The central requirement was that the glass bubble had to be blown into a support structure such that the bubble could be handled by manipulation of the structure. The blown bubble attached itself to a mullite ring geometrically and mechanically, as a demonstration in the initial experiments described here, by expanding through and around it. The vacuum system used was custom made, as were most of the components of the system, such as the heating element, the glass and ring support structure, and the gas inlet system that provided the pressure needed to blow the glass.

Manning, andrew↗

Picture Wall (Glass Structures)

Photo shows a subway station in Toronto, Ontario, which is entirely glass-enclosed. The all-glass structure was made possible by a unique glazing concept developed by PPG Industries, Pittsburgh, Pennsylvania, one of the largest U.S. manufacturers of flat glass. In the TVS glazing system, transparent glass "fins" replace conventional vertical support members used to provide support for wind load resistance. For stiffening, silicone sealant bonds the fins to adjacent glass panels. At its glass research center near Pittsburgh, PPG Industries uses the NASTRAN computer program to analyze the stability of enclosures made entirely of glass. The company also uses NASTRAN to simulate stresses on large containers of molten glass and to analyze stress effects of solar heating on flat glass.

Source record↗

Containerless Processing of a Lithium Disilicate Glass

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.

Ranasinghe, K. S.↗

Measuring Humidity in Sealed Glass Encasements

A technique has been devised for measuring the relative humidity levels in the protective helium/water vapor atmosphere in which the Declaration of Independence, the United States Constitution, and the Bill of Rights are encased behind glass panels on display at the National Archives in Washington, DC. The technique is noninvasive: it does not involve penetrating the encasements (thereby risking contamination or damage to the priceless documents) to acquire samples of the atmosphere. The technique could also be applied to similar glass encasements used to protect and display important documents and other precious objects in museums. The basic principle of the technique is straightforward: An encasement is maintained at its normal display or operating temperature (e.g., room temperature) while a portion of its glass front panel is chilled (see Figure 1) until condensed water droplets become visible on the inside of the panel. The relative humidity of the enclosed atmosphere can then be determined as a known function of the dew point, the temperature below which the droplets condense. Notwithstanding the straightforwardness of the basic principle, careful attention to detail is necessary to enable accurate determination of the dew point. In the initial application, the affected portion of the glass panel was cooled by contact with an aluminum plate that was cooled by a thermoelectric module, the exhaust heat of which was dissipated by a heat sink cooled by a fan. A thermocouple was used to measure the interior temperature of the aluminum plate, and six other thermocouples were used to measure the temperatures at six locations on the cooled outer surface of the glass panel (see Figure 2). Thermal grease was applied to the aluminum plate and the thermocouples to ensure close thermal contact. Power was supplied to the thermoelectric module in small increments, based on previous laboratory tests. A small flashlight and a magnifying glass were used to look for water droplets condensing on the inner surface of the glass. The temperature readings of the thermocouples were taken during cool-down and upon observing condensation. In determining the dew point, it was necessary to make a correction for the differences between the temperatures measured on the chilled outer surface of the glass and the temperature of the inner surface, where the condensation took place. The correction was derived from a laboratory test on a measurement setup that was nearly identical, except that the dew location on the inner surface was also instrumented with a thermocouple. The test showed that the temperature at the dew location on the inner surface of the glass panel was 0.9 C above the temperature determined from the measurements on the chilled outer surface of the panel.

West, James W.↗

Computational Fluid Dynamics Simulations of Glass Vitrification Refractory Coupon Tests

The Waste Treatment and Immobilization Plant (WTP) at the Hanford site is nearing the start of the Direct-Feed Low-Activity Waste (DFLAW) operations. DFLAW is destined to convert a pretreated low activity waste portion of the 56 million gallons of tank waste into a stable solid glass. In the subsequent decade completion of the high-level waste (HLW) facility is anticipated. Sustained operational missions of both LAW and HLW melter facilities are expected over multiple decades. In high-temperature glass melters, the refractory lining corrodes over time, which could potentially be an issue for longer term operations, this refractory corrosion is higher at the level of the glass-air interface due to surface tension driven flow. The glass viscosity, melt pool temperature, and glass chemical composition can impact the rate at which the refractory corrodes. This rate is important to quantify for the various waste glasses to be produced at the WTP since the integrity of the refractory should not be a limiting factor affecting the lifetime of the melter. To this end, a series of glasses representative of the first batches of waste glass produced by the WTP will be melted in small-scale crucibles with Monofrax® K-3 coupons inserted. The corrosion of the K-3 will be measured in the melt and at the meltline (or neckline). A model for the corrosion rate will be constructed and implemented into a previously developed framework for a computational fluid dynamics (CFD) model of the full-scale WTP. To assist with experimental design and validate the implementation of the model in the full-scale melter, CFD simulations of the small-scale crucible tests were performed. The bubbling that occurs in the small-scale crucible is initially validated here with a model that uses silicone oil at room temperature. The viscosity of the oil ranges from 1 to 100 Pa•s, which corresponds to operating glass pool temperatures near 1150 °C down to idling temperatures near 950 °C. The simulation results show good agreement with the bubble sizes that form during experiments. CFD modeling of the crucible setup was used to determine bubbling characteristics to match the range of near-wall velocities expected in the full-scale WTP. This study presents the initial CFD modeling results, corrosion testing plan, and some preliminary corrosion samples with an outline for the next steps for the development of the corrosion model.

Abboud, Alexander W. [Idaho National Lab]↗

The corrosion behavior of borosilicate glass in the presence of cementitious waste forms

Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. Here, the results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na + , K + , Ca 2+ , and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were “sealed” in the presence of Ca 2+ ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions.

36 MATERIALS SCIENCE↗

LionGlass™: A low‐melting, carbonate‐free alternative to soda lime silicate glass

LionGlass™ is Penn State University's patent-pending alumino-silicophosphate glass compositional family that offers, for the first time, a viable low-melting, carbonate-free alternative to soda lime silicate glass by (a) lowering the melting temperature by up to 400°C compared to soda lime silicate glass and (b) eliminating the use of carbonate batch materials. The viscosity curve of LionGlass is shifted downward in temperature compared to soda lime silicate glass, enabling melting at much lower temperatures. LionGlass also has significantly improved resistance to crack initiation compared to soda lime silicate glass. Other properties, such as thermal expansion coefficient and optical dispersion curve, are comparable to those of traditional soda lime silicate glass.

Lion-Glass↗

Ultrafast Laser Welding and Terahertz Time-domain Spectroscopy of Soda Lime Silicate Glass

Joining and welding techniques of similar and dissimilar materials have reached their limits due to the inflexibility of adapting dielectric materials, e.g., glasses and ceramics, reproducibility for transparent materials, and cycle process time. The ability to join pieces of glasses using laser irradiation allows rapid processing of vacuum insulating glass (VIG) for a widening range of commercial energy-efficient applications. We have used a 1064-nm laser wavelength with 15 picoseconds pulse width and a 155-kHz repetition rate to weld commercial plate glass pieces. The welded samples were characterized via x-ray fluorescence (XRF), time-of-flight secondary ion mass spectrometry (TOF–SIMS), polarimetry, and terahertz time-domain spectroscopy (THz-TDS) to determine the integrity of the weld and chemical changes in the welded areas. Our data shows no significant changes in glass chemistry and structure on average over nano- to micro-scales occurred from the welding process within the limits of the characterization tools. Our results demonstrate successful welding of glass plates without significant changes in the glass chemistry, structure, or properties in the laser-modified region or strains in the bulk glass.

Matthies, Kathleen [ORNL] (ORCID:0009000213135441)↗

Effects of Composition and Oxidation States on the Structures of Chromium-Containing Sodium Silicate Glasses: Molecular Dynamics Simulations using Machine Learning Interatomic Potentials

Chromium represents a significant challenge for the vitrification of high-level nuclear waste into silicate and borosilicate glasses due to its low solubility and variable oxidation states, which can limit the waste loading due to promotion of crystallization or phase separation during processing. In this study, we modeled chromium containing silicate glasses using molecular dynamics simulations with three machine learning interatomic potentials (MLIPs), MACE, CHGNet, and PFP were employed, to gain insights on glass composition and oxidation states on the structures of these glasses. One of the goals is to evaluate their ability of these MLIPs to accurately represent the general structure of silicate glasses and chromium local environments as a function of chromium oxidation states. Density Functional Theory (DFT) based calculations and experimental data such as neutron structure factors were used to validate the structural models. It was found that the foundation models of all three MLIPs are able to reproduce general structural features of the sodium silicate glass structure consistent with experimental and DFT data, but only CHGNet and PFP can accurately capture the oxidation states and local environment of chromium: tetrahedral for Cr6+ and octahedral for Cr3+. Furthermore, we studied the effect of varying Cr3+/ Cr6+ (Cr3+/Crtotal) ratio and total chromium content using PFP. Our results show that Cr6+ enhances network polymerization by reducing non-bridging oxygens through Na? charge compensation required due to the formation of chromate (CrO42-) species, while Cr³? acts as a network modifier that disrupts connectivity. System size effects on the structural characteristics and chromium environments were also tested using the PFP potential. This work highlights the importance of careful validation on the precision, transferability, and potential of MLIPs for modeling glasses containing transition metal elements that can exist in multiple oxidation states. It is also encouraging to see the foundational models are all three MLFFs are able to reproduce the basic sodium silicate glass structures, while suggesting additional training or refining is needed to improve the description of more complex systems containing transition metals.

Puga, Christina L.↗

Ab Initio Simulation of Medium-Range Ordering in Ionic Glass Electrolytes LiSiPON and LiNaSiPON

Ionic glasses can exhibit a unique combination of optical transparency, electronic resistivity, ionic conductivity, and mechanical ductility. The origin of the relatively high ionic conductivity and ductility is poorly understood. Recently, these ionic glasses were found to have medium-range ordering (MRO) similar to that of metallic glasses. This MRO significantly impacts the properties of metallic glasses and is also expected to significantly impact the properties of ionic glasses. Here, this work used ab initio molecular dynamics (AIMD) simulations to study the effect of ionic glass composition on the MRO. The AIMD models showed that the degree of MRO increased as the temperature of the LiSiPON ionic glass decreased. The modeling also showed that the MRO is suppressed when 50% of Li is substituted with Na. This work lays the foundation for using AIMD to identify clear structure–property relationships in ionic glasses, allowing their properties to be optimized.

Osetsky, Yuri N. [Oak Ridge National Laboratory (O↗

Enhanced HLW glass property-composition models - phase 3

During the present phase (Phase 3) of work to enhance and expand the HLW glass property-composition models, test data for 137 glasses were collected and incorporated into the combined WTP/ORP database. The new data include those collected on glasses from two statistically designed matrices to augment the moderate alumina region (the HLW16-MA matrix covering the region of 9 wt% < Al2O3 < 12 wt% with 16 glasses) and the ultra-high alumina region (the HLW16-UHA matrix covering the region of 26 wt% < Al2O3 < 29 wt% with 29 glasses). The addition of ORP glasses over the different phases of testing has significantly expanded the combined WTP/ORP database. The compiled data include glass compositions, PCT (B, Li and Na) releases, spinel T1%, electrical conductivity, viscosity, TCLP-Cd releases, and nepheline formation upon CCC. With the exception of the CCC spinel formation data – the CCC data will be used to support the further development of nepheline models for Hanford HLW glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The kinetics of crystallization of molten binary and ternary oxide systems and their application to the origination of high modulus glass fibers

Emphasis on the consideration of glass formation on a kinetic process made it possible to think of glass compositions different from those normally employed in the manufacture of glass fibers. Approximately 450 new glass compositions were prepared and three dozen of these compositions have values for Young's modulus measured on bulk specimens greater than nineteen million pounds per square inch. Of the new glasses about a hundred could be drawn into fibers by mechanical methods at high speeds. The fiber which has a Young's modulus measured on the fiber of 18.6 million pounds per square inch and has been prepared in quantity as a monofilament (to date more than 150 million lineal feet of 0.2 to 0.4 mil fiber have been produced). This fiber has also been successfully incorporated both in epoxy and polyimide matrices. The epoxy resin composite has shown a modulus forty percent better than that achievable using the most common grade of competitive glass fiber, and twenty percent better than that obtainable with the best available grade of competitive glass fiber. Other glass fibers of even higher modulus have been developed.

Bacon, J. F.↗

Determining and analyzing the strength and impact resistance of high modulus glass

A number of new glass compositions have been prepared with increased emphasis on compositions without beryllia. Glass preparations have been much more broadly based and have included the eutectic glass fields, and the mullite-rare earth glass systems. Of the new glasses, the best non-toxic composition is UARL 472 with a bulk modulus of only 18.20 million psi. A second experimental glass, UARL 417, was chosen for research in making large quantities of fiber in monofilament form. Tests of these UARL 417 epoxy resin samples in comparison to similar composites made with the DuPont organic fiber, PRD-49-1, show that the UARL composites have a compressive strength 41/2 times higher and a specific compressive strength at least 21/2 times greater. Much of the research effort attempted to answer the question of why a given glass should have an impact strength superior to other glasses. No definitive answer to the question was found.

Bacon, J. F.↗

Study of recrystallization and devitrification of lunar glass

The technique of differential thermal analysis (DTA) was applied to the study of the Apollo 17 orange soil (74220,63) and the Apollo 16 glass coated anorthite (64455,21). These glasses show accentuated exotherms of strain relief in the annealing range which is indicative of rapid cooling. These are amenable to interpretation by comparison to the known history of synthetic glasses. Synthetic glasses were prepared whose similarity in behavior between the lunar glasses and their synthetic analogs is striking. Approximate rates of cooling of the lunar glasses were determined from comparative DTA of lunar and synthetic glasses and from the determination of the relation of strain relief in the annealing range to quench rate. At higher temperatures the glasses show exotherms of crystallization. The crystallization products associated with the exothermic reactions have been identified by X-ray diffraction and the surface morphologies developed by strain relief and crystallization have been characterized with scanning electron microscopy.

Ulrich, D. R.↗

Oxide glass processing in space

The experimental work performed thus far has resulted in the preparation of new glass compositions not reported heretofore in the open literature. Recent experiments which have resulted in the formation of 1/4-inch-diameter glass samples from two compositions, suggest that containerless melting and cooling as envisioned for space operations is of real technological significance. To date studies of space glasses have by choice been confined to oxide glasses only. It is felt that the applications for such glasses are more readily predictable than for the other materials, and that many of the principles that will evolve from a study of oxide glasses, which can be melted in air, permit a more direct approach to non-oxide materials in the future. The compositions being studied are all very simple in terms of traditional glass practices, none of them containing more than three major constituents. Future efforts should be concerned with more complex compositions, both to cover a broader range of optical properties and to enhance glass-forming tendencies.

Happe, R. A.↗

High modulus high temperature glass fibers

The search for a new high-modulus, high-temperature glass fiber involved the preparation of 500 glass compositions lying in 12 glass fields. These systems consisted primarily of low atomic number oxides and rare-earth oxides. Direct optical measurements of the kinetics of crystallization of the cordierite-rare earth system, for example, showed that the addition of rare-earth oxides decreased the rate of formation of cordierite crystals. Glass samples prepared from these systems proved that the rare-earth oxides made large specific contributions to the Young's modulus of the glasses. The best glasses have moduli greater than 21 million psi, the best glass fibers have moduli greater than 18 million psi, and the best glass fiber-epoxy resin composites have tensile strengths of 298,000 psi, compressive strengths of at least 220,000 psi, flexural strengths of 290,000 psi, and short-beam shear strengths of almost 17,000 psi.

Bacon, J. F.↗

Lunar glass compositions - Apollo 16 core sections 60002 and 60004

Approximately 500 glasses between 1 mm and 125 microns in size have been analyzed from fourteen samples from the Apollo 16 core sections 60002 and 60004. The majority of glasses have compositions comparable to those found in previous studies of lunar surface soils; however, two new and distinct glass compositions that are probably derived in part from mare material occur in the core samples. The major glass composition in all samples is that of Highland Basalt glass, but it also appears that high-K Fra Mauro Basalt (KREEP) glass is more common at the Apollo 16 site than was previously thought. The relative abundance of glasses within the core samples is random in distribution: each sample is characterized by a particular assemblage and distribution of the constituent glass compositions.

Meyer, H. O. A.↗