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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Preparation and characterization of novel foamed porous glass-ceramics

Foamed glass-ceramics without using foaming agent have been synthesized in a novel glass system of SrO-CaO-Al{sub 2}O{sub 3}-TiO{sub 2}-B{sub 2}O{sub 3}-SiO{sub 2}-P{sub 2}O{sub 5}-M{sub x}O{sub y} (where M = Ba, Mg, La, Ce and Ni) by a simple process of powder sintering. The glass and glass-ceramics are characterized by dilatometry, differential scanning calorimetry (DSC), heating stage microscopy (HSM), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), optical microscopy and Fourier transformed infrared spectroscopy (FTIR). All the glasses formed are amorphous and the glass transition temperature and dilatometric softening temperature of these glasses are found to be in the range 673–678 °C and 706–728 °C respectively. The glasses are highly stable as indicated by the DSC evaluated glass stability parameters of the range 195–240 °C. Quantitative sintering study of glass powder compacts revealed swelling in the samples with NiO and CeO{sub 2} corresponding to a geometry change of 75 and 108% around 900 °C respectively. With reference to this finding the glass powder compacts are heated to 900 °C and the foamed glass-ceramics are obtained. Characteristic crystalline silicate phases have been identified in the XRD studies and their microstructures are recorded by FESEM. Optical microscope study of the foamed samples revealed formation of bigger foamed cavity with residual pores in samples with NiO and CeO{sub 2} in comparison to samples with BaO, MgO and La{sub 2}O{sub 3}. The mean pore diameters of the samples with NiO and CeO{sub 2} are determined to be 43 and 32 μm, and their respective porosities are 2.34 and 1.82 cm{sup 3}/g respectively. Thus NiO and CeO{sub 2} are found to be very effective to obtain foamed glass-ceramics without using foaming agent by the viscous flow sintering of fine glass powder compacts along with the reduction of the respective polyvalent ions. - Highlights: • Synthesis of foamed porous glass-ceramics without foaming agent by sintering method • Only powder compact yielded foamed porous glass-ceramics but bulk glass did not. • Glasses containing NiO and CeO{sub 2} exhibited significant foaming efficiency. • Bloating of entrapped gas during viscous flow sintering is the origin of foaming. • Residual void created pores in the sintered glass-ceramics as evidenced in FESEM.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Composition-Based Density Model for High Level Waste Glasses

In this report, the Savannah River National Laboratory (SRNL) provides a first-principles model capable of predicting the density of high-level waste (HLW) glass based on the glass composition. The model relies on the additivity of the specific volume of bound glass oxides to obtain a quantitative evaluation of the approximate glass density. A database of glass densities and compositions was compiled from various sources including previous Defense Waste Processing Facility (DWPF) variability study glasses, HLW studies from other institutions, and literature references. There are a total of 1104 glass compositions in the database with densities ranging from 2.224 g/cm 3 to 3.997 g/cm 3 . The breadth of the compositional coverage space is reported as well. A predictive method was investigated in which the glass density was calculated as a function of the weighted partial molar volumes of the individual glass oxides and the molar mass of the glass. This method yielded a high correlation between the predicted density and the measured density. In addition, a linear regression of these predictions indicated that the predicted value was equal to the measured within the bounds of analytical uncertainty. The following conclusions were drawn from the results of these analyses: 1. Measured glass density is highly correlated with glass composition (R 2 ≈ 0.95). 2. The correlation between glass density and glass composition can be expressed as either: a. A weighted sum of the individual oxide glass-component densities, or b. A weighted sum of the individual oxide glass-component partial molar volumes. 3. A linear regression of the predicted density via partial molar volume method to the measured density yields a slope of 0.9975 and an intercept of -0.0007 – the uncertainty interval associated with these coefficients contain one and zero, respectively. 4. The fitted coefficients and associated uncertainty intervals of the linear regression of the predicted density via the partial molar volume method to the measured density suggest that the predicted theoretical density is, within analysis uncertainty, equal to the measured density of the glass. It is recommended that glass density measurements included with the variability study for each sludge batch be discontinued. In their place, SRNL will calculate a bounding glass density value for the frit/sludge system using the model. It is also recommended that DWPF implement the density model as part of the fissile loading determination portion of the SME acceptability process. Details for implementation are provided in this report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Effect of network connectivity on behavior of synthetic Broborg hillfort glasses

There is wide industrial interest in developing robust models of long-term (>100 years) glass durability. Archeological glass analogs, glasses of similar composition, and alteration conditions to those being tested for durability can be used to evaluate and inform such models. Two such analog glasses from a 1500-year-old vitrified hillfort near Uppsala, Sweden have previously been identified as potential analogs for low concentration Fe-bearing aluminosilicate nuclear waste glasses. However, open questions remain regarding the melting environment from which these historic glasses were formed and the effect of these conditions on their chemical durability. A key factor to answering the previous melting and durability questions is the redox state of Fe in the starting and final materials. Past work has shown that the melting conditions of a glass-forming melt may influence the redox ratio value (Fe +3 /ΣFe), a measure of a glass's redox state, and both melting conditions and the redox ratio may influence the glass alteration behavior. Synthetic analogs of the hillfort glasses have been produced using either fully oxidized or reduced Fe precursors to address this question. In this study, the melting behavior, glass transition temperature, oxidation state, network structure, and chemical durability of these synthesized glass analogs is presented. Resulting data suggests that the degree of network connectivity as impacted by the oxidation state of iron impacted the behavior of the glass-forming melt but in this case does not affect the chemical durability of the final glass. Glasses with a lower degree of melt connectivity were found to have a lower viscosity, resulting in a lower glass transition temperature and softening temperature, as well as in a lower temperature of foam onset and temperature of foam maximum. This lower degree of network connectivity most likely played a more significant role in accelerating the conversion of batch chemicals into glass than the presence of water vapor in the furnace's atmosphere. Future work will focus on using the results from this work with outcomes from other aspects of this project to evaluate long-term glass alteration models.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products

Glass-ceramic waste form development began in FY 2010 examining two combined waste stream options: (1) alkaline earth (CS) + lanthanide (Ln), and (2) + transition metal (TM) fission-product waste streams generated by the uranium extraction (UREX+) separations process. Glass-ceramics were successfully developed for both options however; Option 2 was selected over Option 1, at the conclusion of 2010, because Option 2 immobilized all three waste streams with only a minimal decrease in waste loading. During the first year, a series of three glass (Option 2) were fabricated that varied waste loading-WL (42, 45, and 50 mass%) at fixed molar ratios of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali both at 1.75. These glass-ceramics were slow cooled and characterized in terms of phase assemblage and preliminary irradiation stability. This fiscal year, further characterization was performed on the FY 2010 Option 2 glass-ceramics in terms of: static leach testing, phase analysis by transmission electron microscopy (TEM), and irradiation stability (electron and ion). Also, a new series of glass-ceramics were developed for Option 2 that varied the additives: Al{sub 2}O{sub 3} (0-6 mass%), molar ratio of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali (1.75 to 2.25) and waste loading (50, 55, and 60 mass%). Lastly, phase pure powellite and oxyapatite were synthesized for irradiation studies. Results of this fiscal year studies showed compositional flexibility, chemical stability, and radiation stability in the current glass-ceramic system. First, the phase assemblages and microstructure of all of the FY 2010 and 2011 glass-ceramics are very similar once subjected to the slow cool heat treatment. The phases identified in these glass-ceramics were oxyapatite, powellite, cerianite, and ln-borosilicate. This shows that variations in waste loading or additives can be accommodated without drastically changing the phase assemblage of the waste form, thus making the processing and performance characteristics of the waste form more predictable/flexible. However, in the future, the glass phase still needs to be accurately characterized to determine the effects of waste loading and additives on the glass structure. Initial investigations show a borosilicate glass phase rich in silica. Second, the normalized concentrations of elements leached from the waste form during static leach testing were all below 0.6 g/L after 28d at 90 C, by the Product Consistency Test (PCT), method B. These normalized concentrations are on par with durable waste glasses such as the Low-Activity Reference Material (LRM) glass. The release rates for the crystalline phases (oxyapatite and powellite) appear to be lower (more durable) than the glass phase based on the relatively low release rates of Mo, Ca, and Ln found in the crystalline phases compared to Na and B that are mainly observed in the glass phase. However, further static leach testing on individual crystalline phases is needed to confirm this statement. Third, Ion irradiation and In situ TEM observations suggest that these crystalline phases (such as oxyapatite, ln-borosilicate, and powellite) in silicate based glass ceramic waste forms exhibit stability to 1000 years at anticipated doses (2 x 10{sup 10}-2 x 10{sup 11} Gy). This is adequate for the short lived isotopes in the waste, which lead to a maximum cumulative dose of {approx}7 x 10{sup 9} Gy, reached after {approx}100 yrs, beyond which the dose contributions are negligible. The cumulate dose calculations are based on a glass-ceramic at WL = 50 mass%, where the fuel has a burn-up of 51GWd/MTIHM, immobilized after 5 yr decay from reactor discharge.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2012

Low Velocity Sphere Impact of a Borosilicate Glass

This report summarizes US Army TARDEC sponsored work at Oak Ridge National Laboratory (ORNL) involving low velocity (< 30 m/s or < 65 mph) ball impact testing of Borofloat borosilicate glass, and is a follow-up to a similar study completed by the authors on Starphire soda-lime silicate glass last year. The response of the borosilicate glass to impact testing at different angles was also studied. The Borofloat glass was supplied by the US Army Research Laboratory and its tin-side was impacted or indented. The intent was to better understand low velocity impact response in the Borofloat. Seven sphere materials were used whose densities bracket that of rock: borosilicate glass, soda-lime silicate glass, silicon nitride, aluminum oxide, zirconium oxide, carbon steel, and a chrome steel. A gas gun or a ball-drop test setup was used to produce controlled velocity delivery of the spheres against the glass tile targets. Minimum impact velocities to initiate fracture in the Borofloat were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the seven sphere-Borofloat-target combinations. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) BS glass responded similarly to soda-lime silicate glass when spherically indented but quite differently under sphere impact conditions; (2) Frictional effects contributed to fracture initiation in BS glass when it spherically indented. This effect was also observed with soda-lime silicate glass; (3) The force necessary to initiate fracture in BS glass under spherical impact decreases with increasing elastic modulus of the sphere material. This trend is opposite to what was observed with soda-lime silicate glass. Friction cannot explain this trend and the authors do not have a legitimate explanation for it yet; (4) The force necessary to initiate contact-induced fracture is higher under dynamic conditions than under quasi-static conditions. That difference decreases with increasing elastic modulus mismatch between the sphere material and borosilicate This trend was opposite in soda-lime silicate glass; (5) Fracture in borosilicate glass occurs at lower velocities (i.e., easier) at 24° than at 0° (orthogonal) and 46° of impact for the same probability of failure. Though not analyzed yet, this suggests that a convolution of kinetic energy and friction is contributing to that trend; (6) There is a subtle indication there was intra-tile differences in spherical indentation RCIF. This likely is not a material property nor exclusive to borosilicate glass, rather, it is a statistical response of a combination of local, surface-located flaw and imposed tensile stress. Understanding of the surface flaw population and flaw positioning can likely enable prediction of spherical indentation RCIF; and (7) Contact-induced fracture did not initiate in the Borofloat BS for impact kinetic energies up to ~ 20 mJ. For kinetic energies between ~ 20-150 mJ, fracture sometimes initiated. Contact-induced fracture would always occur for impact energies > 150 mJ. The energy values, and their boundaries, were much lower for BS glass than they were for soda-lime silicate glass.

36 MATERIALS SCIENCE↗
DOE OSTI2013

HGMS: Glasses and Nanocomposites for Hydrogen Storage

The primary goal of this project is to fabricate and investigate different glass systems and glass-derived nanocrystalline composite materials. These glass-based, two-phased materials will contain nanocrystals that can attract hydrogen and be of potential interest as hydrogen storage media. The glass materials with intrinsic void spaces that are able to precipitate functional nanocrystals capable to attract hydrogen are of particular interest. Proposed previously, but never practically implemented, one of promising concepts for storing hydrogen are micro-containers built of glass and shaped into hollow microspheres. The project expanded this concept to the exploration of glass-derived nanocrystalline composites as potential hydrogen storage media. It is known that the most desirable materials for hydrogen storage do not interact chemically with hydrogen and possess a high surface area to host substantial amounts of hydrogen. Glasses are built of disordered networks with ample void spaces that make them permeable to hydrogen even at room temperature. Glass-derived nanocrystalline composites (two-phased materials), combination of glasses (networks with ample voids) and functional nanocrystals (capable to attract hydrogen), appear to be promising candidates for hydrogen storage media. Key advantages of glass materials include simplicity of preparation, flexibility of composition, chemical durability, non-toxicity and mechanical strength, as well as low production costs and environmental friendliness. This project encompasses a fundamental research into physics and chemistry of glasses and nanocrystalline composite materials, derived from glass. Studies are aimed to answer questions essential for considering glass-based materials and composites as potential hydrogen storage media. Of particular interest are two-phased materials that combine glasses with intrinsic voids spaces for physisorption of hydrogen and nanocrystals capable of chemisorption. This project does not directly address any hydrogen storage technical barriers or targets in terms of numbers. Specifically, hydrogen sorption and desorption tests or kinetics measurements were not part of the project scope. However, the insights gained from these studies could help to answer fundamental questions necessary for considering glass-based materials as hydrogen storage media and could be applied indirectly towards the DOE hydrogen storage technical targets such as system weight and volume, system cost and energy density. Such questions are: Can specific macro-crystals, proven to attract hydrogen when in a macroscopic form (bulk), be nucleated in glass matrices as nanocrystals to create two-phased materials? What are suitable compositions that enable to synthetize glass-based, two-phase materials with nanocrystals that can attract hydrogen via surface or bulk interactions? What are the limits of controlling the microstructure of these materials, especially limits for nanocrystals density and size? Finally, from a technological point of view, the fabrication of glass-derived nanocomposites that we explore is a very simple, fast and inexpensive process that does not require costly or specialized equipment which is an important factor for practical applications.

08 HYDROGEN↗
DOE OSTI2019

Characterization of Hanford LAW Phase 3 Glasses

This report provides analyses of glass compositions, wash solution compositions, and Product Consistency Test (PCT) leachate compositions for a series of simulated low-activity waste (LAW) glasses fabricated at the Pacific Northwest National Laboratory (PNNL). These data will be used in the development of improved property/composition models for LAW glass at Hanford. Chemical analyses were performed on a representative sample of each of the quenched and sulfur saturated glasses to allow for comparisons with the targeted compositions. For some of the quenched glasses, measured concentrations of Cr 2 O 3 , K 2 O, Na 2 O, P 2 O 5 , and ZrO 2 were below the targeted values. For some of the sulfur saturated glasses, the measured concentrations of Al 2 O 3 , Cl - , Cr 2 O 3 , F - , K 2 O, Na 2 O, P 2 O 5 , V 2 O 5 , and ZrO 2 were generally low relative to the targeted values. A comparison of the measured compositions of the quenched and sulfur saturated versions of the study glasses showed that the measured concentrations of Al 2 O 3 , Cl - , and F - were lower for most of the sulfur saturated glasses. The measured Cr 2 O 3 and K 2 O concentrations were markedly lower for the sulfur saturated versions of the glasses as compared to the quenched versions, which may indicate that these elements partitioned to the soluble sulfur salts. A set of modified glasses was received from PNNL later in this study. Chemical analysis showed that these glasses generally met their targeted compositions with the exception of Cr 2 O 3 concentrations, which were considerably higher than the targeted values. The measured SO 3 concentrations were higher for most of the sulfur saturated glasses relative to those of the quenched versions, as expected. Chemical analysis of the wash solutions that resulted from preparation of the sulfur saturated melts identified Cr, K, Na, P, S, and V as the major elements in solution. With the exception of sulfur, this may explain why the measured concentrations of these components in the study glasses were generally below the targeted values. PNNL performed PCTs on quenched and canister centerline cooled (CCC) versions of the study glasses, as well as the modified glasses. The leachates were sent to SRNL for chemical analysis. Minor scatter in the measured values among the triplicate samples for each glass was noted, with significant differences among the triplicate values noted for four of the CCC glasses. Normalized concentration values for some of the study glasses were greater than the 100 g/L maximum (total dissolution), which may indicate an error in the test. It is recommended that PNNL review their performance of the PCTs to determine the cause of these potential outliers and errors.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Anisotropic Vapor-Deposited Glasses: Hybrid Organic Solids

CONSPECTUS: The term "organic solids" encompasses both crystals and glasses. Organic crystals are commonly grown for purification and structure determination and are being extensively explored for applications in organic electronics including field effect transistors. The ability to control the packing of one molecule relative to its neighbors is of critical importance for most uses of organic crystals. Often, anisotropic packing is also highly desirable as it enhances charge transport and optimizes light absorption/emission. When compared to crystals, the local packing in organic glasses is highly disordered and often isotropic. Glasses, however, offer two key advantages with respect to crystals. First, glasses typically lack grain boundaries and thus exhibit better macroscopic homogeneity. Second, glass composition can often be varied over a wide range while maintaining homogeneity. Besides electronic materials, many modern plastics used in a wide range of technologies are organic glasses, and the glassy state is being increasingly utilized to deliver pharmaceuticals because of higher bioavailability. In this article, we introduce vapor-deposited organic glasses as hybrid materials that combine some of the useful features of crystals and traditional liquid-cooled glasses. Physical vapor deposition produces glasses by directly condensing molecules from the gas phase onto a temperature-controlled substrate and allows film thickness to be controlled with nanometer precision. Just as liquid-cooled glasses, vapor-deposited glasses have smooth surfaces and lack grain boundaries. These attributes are critical for applications such as organic light emitting diodes (OLEDs), in which vapor-deposited glasses of organic semiconductors form the active layers. In common with crystals, vapor-deposited glasses can exhibit anisotropic packing, and the extent of anisotropy can be comparable to that of the typical organic crystal. For vapor-deposited glasses, in contrast to crystals, anisotropic packing can generally be controlled as a continuous variable. Deposition conditions can be chosen to produce glasses with significant molecular orientation (molecules "standing up" or "lying down" relative to the substrate), and pr-stacking can be directed along different directions relative to the substrate. Over the last five years, we have gained a fundamental understanding of the mechanism that controls the anisotropy of vapor-deposited glasses and learned how to control many aspects of anisotropic packing. Two key elements that enable such control are the high mobility present at the surface of an organic glass and the tendency of the surface to promote anisotropic packing of molecules. In contrast to traditional epitaxial growth, for vapor-deposited glasses, the free surface (not the substrate) acts as a template that controls the structure of a growing film. Lastly, the structure of any given layer is decoupled from those beneath it, thereby providing considerable freedom in producing layered glassy structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Preshaping clear glass at low temperatures

Advances in available glass chemistries and glass processing methods have accompanied and enabled some of the biggest technology revolutions, from the development and mass production of light bulbs to low-loss fiber optics and durable smartphone touchscreens. An emerging generation of low-temperature processing technologies aims to continue this important trend and make a broader array of glass components mass producible. In the issue, Mader et al. (1) describe one such innovation in glass processing—the use of low-temperature injection molding to preshape silica particle–filled composites that can later be transformed into transparent fused silica glass objects. Traditionally, transparent glass objects are manufactured in high volume from molten or softened glass, which is floated, drawn, blown, cast, or blow-molded to a desired shape (see the figure, top). The glass composition and processing technique dictate the working temperature, which is usually quite high (near 1000°C) and often restricts the choice of compatible equipment or limits the choice of glass composition. Because geometry-specific capital investment is required for production, drastic or frequent component design changes or small batches may be cost prohibitive. Alternatively, transparent glass components can also be shaped at ambient temperature from solid glass by a series of subtractive processes, including cutting or multiple stages of grinding, followed by slower processing steps, such as polishing or etching. This approach is somewhat less amenable to mass production, and certain geometries containing tool-inaccessible regions cannot be fabricated in this way. Several emerging glass-shaping technologies aim to reduce the required manufacturing temperatures and still provide access to a broader range of glass compositions and component geometries (see the figure). These approaches use a three-step process. First, a desired shape is preformed at low temperature from a glass-forming, organic-inorganic composite. Next, the preform is dried, and organic materials used to bind particles are removed. Finally, the preform is heated (sintered) well below the glass-melting temperature to densify to transparent glass. Although the second and third steps do occur at increased temperatures, only standard, geometry-agnostic driers and furnaces are required. This strategy builds on the well-studied sol-gel approach to forming monolithic glass, where silica network–forming chemical solutions are poured into molds, slowly dried, and condensed into dense glass without melting (2). In a departure from the sol-gel process, these new technologies use solvents, cross-linkers, and polymers to formulate organic-inorganic composites tuned for compatibility with a particular shaping process, with formats ranging from photocurable liquids to shear-thickening pastes to solids. The composite inorganic loadings are also typically higher than those in the pure sol-gel approach, which drastically reduces shrinkage in comparison.

36 MATERIALS SCIENCE↗
DOE OSTI2019

X-Ray Diffraction and Product Consistency Test Results for the Phase 6 Study of Nepheline Formation in High-Level Waste Glasses

Hanford high-level waste (HLW) contains relatively high concentrations of Al 2 O 3 . A major constraint limiting the waste loading of high-Al 2 O 3 glasses is nepheline (nominally NaAlSiO 4 ) formation upon slow cooling of HLW glasses after melts are poured into steel canisters. The model currently planned to be used at the Hanford Waste Treatment and Immobilization Plant (WTP) for avoiding nepheline formation is too conservative and drastically limits waste loading. To increase operational flexibility and effectively operate the WTP, the effects of glass composition on glass properties must be determined and glass property-composition models must be developed. Determining the impacts of glass composition on nepheline formation and the effects of nepheline on Product Consistency Test (PCT) response is an important part of this effort. As a part of this effort, data related to the Hanford high-Al 2 O 3 HLW composition region was generated to supplement existing data for model development. Twenty glasses were fabricated, heat treated, and analyzed for crystallinity and PCT response. The heat treatment was designed to mimic the canister centerline cooling (CCC) profile of Hanford HLW glass canisters. It was found that only 6 of the 20 prepared glasses (#4, #7, #8, #10, #19, and #20) formed nepheline upon heat treatment. All glasses except for one (#19) precipitated spinel upon quenching and no glasses contained nepheline upon quenching. Of the 20 glasses, the PCT-normalized boron release of the quenched glasses and all but five of the CCC glasses satisfied the environmental assessment glass benchmark value (16.695 g/L). The CCC glass samples that exceeded the limit were #8 (48.21 g/L), #10 (19.77 g/L), #13 (20.17 g/L), #19 (60.85 g/L), and #20 (61.08 g/L). Those glasses coincide with the highest amounts of nepheline found in the CCC glasses, except for #13, which did not form nepheline after CCC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2003

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 one1 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 (1g). 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. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be more resistant to crystallization than equivalent glasses prepared on earth. Similarly, the gravity-driven convection in a fluid melt is believed to be the primary force field that is responsible for melt homogenization on earth. Thus, it is not obvious why a glass prepared in space, where gravity-driven convection is ideally absent, would be more chemically homogeneous than a glass identically prepared on earth. The primary objective of the present research is to obtain experimental data for the nucleation rate and crystal growth rate for a well characterized silicate melt (lithium disilicate) processed entirely in space (low gravity) and compare these rates with the nucleation and crystal growth rates for a similar glass prepared identically on earth (1g).

Day, Delbert E.↗
DOE OSTI2013

Ferric oxide quantum dots in stable phosphate glass system and their magneto-optical study

Graphical abstract: We report synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles (NCs) content on the optical and magneto-optical properties of the glasses. Faraday rotation of the glass nanocomposites was measured and showed variation in Verdet constant with concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and there is a threefold enhancement in the Verdet constant of ferric oxide quantum dot-glass nanocomposite. Highlights: ► We synthesize ferric oxide embedded low melting stable phosphate glass nanocomposite. ► Glasses doped with 0.25 and 2% ferric oxide show particle size in the range of 4–12 nm. ► The host phosphate glass itself shows fairly good Verdet constant (11.5°/T cm). ► Glasses doped with 0.25% ferric oxide show high Verdet constant (30.525°/T cm). ► The as synthesis glasses may have potential application in magneto optical devices. -- Abstract: Herein, we report the synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles content on the optical and magneto-optical properties of the glasses. The optical study clearly showed red shift in optical cut off with increasing ferric oxide concentration. The band gap of the host glass was observed to be 3.48 eV and it shifted to 3.14 eV after doping with ferric oxide. The glasses doped with 0.25 and 2% ferric oxide showed particle size of 4–6 nm and 8–12 nm, respectively. Faraday rotation of the glass nanocomposites was measured and showed variation in the Verdet constant as per increasing concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and threefold enhancement was observed in the Verdet constant of ferric oxide quantum dot-glass nanocomposite.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Direction of CRT waste glass processing: Electronics recycling industry communication

Highlights: Black-Right-Pointing-Pointer Given a large flow rate of CRT glass {approx}10% of the panel glass stream will be leaded. Black-Right-Pointing-Pointer The supply of CRT waste glass exceeded demand in 2009. Black-Right-Pointing-Pointer Recyclers should use UV-light to detect lead oxide during the separation process. Black-Right-Pointing-Pointer Recycling market analysis techniques and results are given for CRT glass. Black-Right-Pointing-Pointer Academic initiatives and the necessary expansion of novel product markets are discussed. - Abstract: Cathode Ray Tube, CRT, waste glass recycling has plagued glass manufacturers, electronics recyclers and electronics waste policy makers for decades because the total supply of waste glass exceeds demand, and the formulations of CRT glass are ill suited for most reuse options. The solutions are to separate the undesirable components (e.g. lead oxide) in the waste and create demand for new products. Achieving this is no simple feat, however, as there are many obstacles: limited knowledge of waste glass composition; limited automation in the recycling process; transportation of recycled material; and a weak and underdeveloped market. Thus one of the main goals of this paper is to advise electronic glass recyclers on how to best manage a diverse supply of glass waste and successfully market to end users. Further, this paper offers future directions for academic and industry research. To develop the recommendations offered here, a combination of approaches were used: (1) a thorough study of historic trends in CRT glass chemistry; (2) bulk glass collection and analysis of cullet from a large-scale glass recycler; (3) conversations with industry members and a review of potential applications; and (4) evaluation of the economic viability of specific uses for recycled CRT glass. If academia and industry can solve these problems (for example by creating a database of composition organized by manufacturer and glass source) then the reuse of CRT glass can be increased.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

SLUDGE BATCH 7B GLASS VARIABILITY STUDY

The Defense Waste Processing Facility (DWPF) is preparing to initiate processing Sludge Batch 7b (SB7b). In support of the upcoming processing, the Savannah River National Laboratory (SRNL) provided a recommendation to utilize Frits 418 with a 6% Na{sub 2}O addition (26 wt% Na{sub 2}O in sludge) and 702 with a 4% Na{sub 2}O addition (24 wt% Na{sub 2}O in sludge) to process SB7b. This recommendation was based on assessments of the compositional projections for SB7b available at the time from the Savannah River Remediation (SRR). To support qualification of SB7b, SRNL executed a variability study to assess the applicability of the current durability models for SB7b. The durability models were assessed over the expected composition range of SB7b, including potential caustic additions, combined with Frits 702 and 418 over a 32-40% waste loading (WL) range. Thirty four glasses were selected based on Frits 418 and 702 coupled with the sludge projections with an additional 4-6% Na{sub 2}O to reflect the potential caustic addition. Six of these glasses, based on average nominal sludge compositions including the appropriate caustic addition, were developed for both Frit 418 and Frit 702 at 32, 36 and 40% WL to provide coverage in the center of the anticipated SB7b glass region. All glasses were fabricated and characterized using chemical composition analysis, X-ray diffraction (XRD) and the Product Consistency Test (PCT). To comply with the DWPF Glass Product Control Program, a total of thirty four glasses were fabricated to assess the applicability of the current DWPF PCCS durability models. Based on the measured PCT response, all of the glasses were acceptable with respect to the Environmental Assessment (EA) benchmark glass regardless of thermal history. The NL[B] values of the SB7b variability study glasses were less than 1.99 g/L as compared to 16.695 g/L for EA. A small number of the D-optimally selected 'outer layer' extreme vertices (EV) glasses were not predictable using the current Product Composition Control System (PCCS) models for durability, but were acceptable compared to the EA glass when tested. These glasses fell outside of the lower 95% confidence band, which demonstrates conservatism in the model. A few of the glasses fell outside of the upper 95% confidence band; however, these particular glasses have normalized release values that were much lower than the values of EA and should be of no practical concern. Per the requirements of the DWPF Glass Product Control Program, the PCCS durability models have been shown to be applicable to the SB7b sludge system with a range of Na{sub 2}O concentrations blended with Frits 418 or 702. PCT results from the glasses fabricated as part of the variability study were shown to be predictable by the current DWPF PCCS models and/or acceptable with respect to the EA benchmark glass regardless of thermal history or compositional view.

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DOE OSTI2020

Characterization of Hanford LAW Phase 3 Glasses

This report provides analyses of glass compositions, wash solution compositions, and Product Consistency Test (PCT) leachate compositions for a series of simulated low-activity waste (LAW) glasses fabricated at the Pacific Northwest National Laboratory (PNNL). These data will be used in the development of improved property/composition models for LAW glass at Hanford. Chemical analyses were performed on a representative sample of each of the quenched and sulfur saturated glasses to allow for comparisons with the targeted compositions. For some of the quenched glasses, measured concentrations of Cr₂O₃, K₂O, Na₂O, P₂O₅, and ZrO₂ were below the targeted values. For some of the sulfur saturated glasses, the measured concentrations of Al₂O₃, Cl⁻, Cr₂O₃, F⁻, K₂O, Na₂O, P₂O₅, V₂O₅, and ZrO₂ were generally low relative to the targeted values. A comparison of the measured compositions of the quenched and sulfur saturated versions of the study glasses showed that the measured concentrations of Al₂O₃, Cl⁻, and F⁻ were lower for most of the sulfur saturated glasses. The measured Cr₂O₃ and K₂O concentrations were markedly lower for the sulfur saturated versions of the glasses as compared to the quenched versions, which may indicate that these elements partitioned to the soluble sulfur salts. A set of modified glasses was received from PNNL later in this study. Chemical analysis showed that these glasses generally met their targeted compositions. The measured SO₃ concentrations were higher for most of the sulfur saturated glasses relative to those of the quenched versions, as expected. Chemical analysis of the wash solutions that resulted from preparation of the sulfur saturated melts identified Cr, K, Na, P, S, and V as the major elements in solution. With the exception of sulfur, this may explain why the measured concentrations of these components in the study glasses were generally below the targeted values. PNNL performed PCTs on quenched and canister centerline cooled (CCC) versions of the study glasses, as well as the modified glasses. The leachates were sent to SRNL for chemical analysis. Minor scatter in the measured values among the triplicate samples for each glass was noted. Several of the study glasses, both quenched and CCC, have NCi values that are greater than the immobilized LAW constraint of 4 g/L for B, Na, and Si.

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DOE OSTI2012

Summary of FY11 Sulfate Retention Studies for Defense Waste Processing Facility Glass

This report describes the results of studies related to the incorporation of sulfate in high level waste (HLW) borosilicate glass produced at the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF). A group of simulated HLW glasses produced for earlier sulfate retention studies was selected for full chemical composition measurements to determine whether there is any clear link between composition and sulfate retention over the compositional region evaluated. In addition, the viscosity of several glasses was measured to support future efforts in modeling sulfate solubility as a function of predicted viscosity. The intent of these studies was to develop a better understanding of sulfate retention in borosilicate HLW glass to allow for higher loadings of sulfate containing waste. Based on the results of these and other studies, the ability to improve sulfate solubility in DWPF borosilicate glasses lies in reducing the connectivity of the glass network structure. This can be achieved, as an example, by increasing the concentration of alkali species in the glass. However, this must be balanced with other effects of reduced network connectivity, such as reduced viscosity, potentially lower chemical durability, and in the case of higher sodium and aluminum concentrations, the propensity for nepheline crystallization. Future DWPF processing is likely to target higher waste loadings and higher sludge sodium concentrations, meaning that alkali concentrations in the glass will already be relatively high. It is therefore unlikely that there will be the ability to target significantly higher total alkali concentrations in the glass solely to support increased sulfate solubility without the increased alkali concentration causing failure of other Product Composition Control System (PCCS) constraints, such as low viscosity and durability. No individual components were found to provide a significant improvement in sulfate retention (i.e., an increase of the magnitude necessary to have a dramatic impact on blending, washing, or waste loading strategies for DWPF) for the glasses studied here. In general, the concentrations of those species that significantly improve sulfate solubility in a borosilicate glass must be added in relatively large concentrations (e.g., 13 to 38 wt % or more of the frit) in order to have a substantial impact. For DWPF, these concentrations would constitute too large of a portion of the frit to be practical. Therefore, it is unlikely that specific additives may be introduced into the DWPF glass via the frit to significantly improve sulfate solubility. The results presented here continue to show that sulfate solubility or retention is a function of individual glass compositions, rather than a property of a broad glass composition region. It would therefore be inappropriate to set a single sulfate concentration limit for a range of DWPF glass compositions. Sulfate concentration limits should continue to be identified and implemented for each sludge batch. The current PCCS limit is 0.4 wt % SO 4 2- in glass, although frit development efforts have led to an increased limit of 0.6 wt % for recent sludge batches. Slightly higher limits (perhaps 0.7-0.8 wt %) may be possible for future sludge batches. An opportunity for allowing a higher sulfate concentration limit at DWPF may lay lie in improving the laboratory experiments used to set this limit. That is, there are several differences between the crucible-scale testing currently used to define a limit for DWPF operation and the actual conditions within the DWPF melter. In particular, no allowance is currently made for sulfur partitioning (volatility versus retention) during melter processing as the sulfate limit is set for a specific sludge batch. A better understanding of the partitioning of sulfur in a bubbled melter operating with a cold cap as well as the impacts of sulfur on the off-gas system may allow a higher sulfate concentration limit to be established for the melter feed. This approach would have to be taken carefully to ensure that a sulfur salt layer is not formed on top of the melt pool while allowing higher sulfur based feeds to be processed through DWPF.

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DOE OSTI2017

Toward Molecular Engineering of Polymer Glasses

Glass formation has been central to fabrication technologies since the dawn of civilization. Glasses not only encompass window panes, the insulation in our homes, the optical fibers supplying our cable TV, and vessels for eating and drinking, but they also include a vast array of ‘‘plastic’’ polymeric materials. Glasses find applications in high technology (e.g., producing microelectronic materials, etc., amorphous semiconductors), and recent advances have created ‘‘plastic metallic glasses’’ that are promising for fabricating everyday structural materials. Many commercially relevant systems, such as microemulsions and colloidal suspensions, have complex molecular structures and thus solidify by glass formation. Despite the importance of understanding the fundamental nature of glass formation for the synthesis of new materials, a predictive molecular theory has been lacking. Much of our understanding of glass formation derives from the analysis of experimental data, a process that has uncovered a number of interesting universal behaviors, namely, relations between properties that are independent of molecular details. However, these empirically derived relations and their limitations remain to be understood on the basis of theories, and, more importantly, there is strong need for theories of the explicit variation with molecular system to enable the rational design and tailoring of new materials. We have recently developed the generalized entropy theory, the only analytic, theory that enables describing the dependence of the properties of glass-formation on monomer molecular structures. These properties include the two central quantities of glass formation, the glass transition temperature and the glass fragility parameter, material dependent properties that govern how a material may be processed (e.g., by extrusion, ink jet, molding, etc.) Our recent works, which are further described below, extend the studies of glass formation in polymer systems to test the theory by directly comparing between the predictions of our generalized entropy theory with experiment and with simulations and to expand the vistas of the theory to describe a wider range of important systems (e.g. glass formation in binary blends and systems with specific interactions) and phenomena that are describable by the generalized entropy theory. In addition, we have addressed longstanding fundamental problems associated with the validity of the Adam-Gibbs theory, one of the underpinnings of the general entropy theory. Theoretical advances to enable describing the properties of glass-formation over a wider class of important polymeric systems, included semi-flexible systems, the more general situation of specific interactions, and more. Our recent work removes the simplest approximation uses the simplest model in which the interaction is approximated by a single, monomer average. Thus, the theory has been extended to allow some variations of the energy parameters between the atoms within the monomers. The theory has also been extended to include all the contributions from chain semi-flexibility. Both projects are extremely difficult, but the payback is that the process of solving the problems developed strong theoretical skills in Dr. Xu, who has recently begun a postdoc position at ORNL. The theory has also been extended to describe glass formation in partially miscible blends, with good general agreement with experiment. Again, the development of the theory presented an extremely difficult problem, but the payback is the development of a theory for a very important class of systems. Another project provides an extremely simple approximation for certain properties of glass formation in polymer melts and should make the theory more accessible to everyone.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Expansion of the Direct Feed High-Level Waste Glass Composition in the High Al Range

Baseline glass compositions have been developed and demonstrated for successful immobilization of Hanford high-level waste (HLW) prepared through a pretreatment process. Recent enhanced waste glass formulations have shown promise to increase the waste loading of pretreated sludge compositions from a broader range of HLW feeds. This project proposes to increase the loading of minimally pretreated Hanford HLW in glass by expanding the existing database and glass property-composition models. Estimated direct-feed high level waste (DFHLW) compositions were generated by the Hanford Tank Operations Contractor and used by Pacific Northwest National Laboratory to determine target glass compositions. Gaps in existing data were identified including one high-priority gap in the high Al compositional region. This report summarizes the data collected during the characterization of the DFHLW High Al Glass Matrix. These glasses were intentionally designed with high aluminum concentrations (15 to 30 wt%) and a high likelihood of nepheline formation, which is known to negatively affect glass durability. Some glasses were expected to either fail or approach property constraints to fill data gaps in poorly understood regions of the compositional space due to lack of data. Out of the 50 glasses tested, 14 glasses formed nepheline, while the model predicted nepheline formation in 20 glasses. All quenched glasses met the product consistency test durability constraint; however, 8 glasses failed this constraint after undergoing the canister centerline cooling treatment. Additionally, 17 glasses did not meet the viscosity constraints, 4 failed the EC constraints, and 2 exceeded the allowable T2% for spinel crystal formation. All glasses satisfied the SO 3 solubility limit. The resulting dataset provides valuable information to improve model accuracy and reduce prediction uncertainty. These insights will ultimately support the development of more robust glass formulation strategies, enabling higher waste loadings, reducing operational risks, and expanding the processing envelope.

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