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At least 595 records · Page 33

Joint EM-NE-International Study of Glass Behavior over Geologic Time Scales - 12303

Vitrification has been chosen as the best demonstrated available technology for waste immobilization worldwide. To date, the contributions of physical and chemical processes controlling the long-term glass dissolution rate in geologic disposal remain uncertain, leading to a lack of international consensus on a rate law for glass corrosion. Existing rate laws have overcome uncertainty through conservatism, but a thorough mechanistic understanding of waste form durability in geologic environments would improve public and regulator confidence. If it is possible to take credit for the true durability of the waste form in repository system evaluations, then it is possible to design the repository with less conservatism with concomitant cost savings. To gain a fundamental understanding of the dissolution rate law, six nations have joined together to formulate a joint plan for collaborative research into the mechanisms controlling the long-term corrosion of glass. This report highlights the technical program plan behind the US portion of this effort, with an emphasis on the current understanding (and limitations) of several mechanistic theories for glass corrosion. Some recent results are presented to provide an example of the ongoing research. Atom probe tomography has been used to provide a high-resolution analysis of elemental concentration gradients present at the hydrated glass / pristine glass interface in SON68 after 25.75 years of corrosion in a simulated granitic groundwater at 90 deg. C. The most valuable result of these initial studies is the success of the technique. Characterization by APT had never been previously demonstrated for glass corrosion layers. The resolution of APT is a powerful addition to the tools with which we can investigate the mechanisms dominating glass corrosion. Some other key results of this study include the observation that the elemental interfacial width between the hydrated glass and pristine glass appears to be much sharper (∼2 nm for B, Na and Al) than had been previously measured using nanoSIMS (∼240 nm). It is not clear whether the APT analysis and nanoSIMS characterizations were possibly performed on topographically unique regions, or whether nanoSIMS overestimated the elemental width. However, the APT data seems very convincing that the elemental width can be much sharper than was previously thought. This result calls into question some of the assumptions made for the diffusion-control models of glass dissolution, since such a sharp profile would not match the diffusion coefficients used to date. Other results, such as the observation of apparently layered concentration profiles, show that gel evolution is not as simple as is currently assumed in nearly every model. This task is a good example of the collaborative nature of the I-TEAM effort. Based on experimental needs and differences in expertise, scientists from DOE and CEA worked together to change the level of understanding in the field. These types of interactions are nearly ubiquitous among the tasks in the technical program plan. With the excellence of the team in place and the willingness of the participants to work together for a common understanding, the stated goal of consensus on the mechanistic basis for radionuclide release from glass is well within reach. (authors)

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Process Control Approach to Implement High Waste Loading Glass Formulations for Hanford Low Activity Waste Vitrification - 18435

Acceptable glass formulations for vitrification of Hanford low activity waste (LAW) at The Hanford Tank Waste Treatment and Immobilization Plant (WTP) must meet a variety of product quality, processability, and waste loading requirements. The glass formulation development work underpinning the WTP baseline LAW glasses was captured in a vitrification process control approach developed by the Vitreous State Laboratory (VSL) and Atkins Energy Federal EPC, Inc. that permits the calculation of the glass formulation required for each particular batch of LAW delivered to the LAW vitrification facility. Since that time, we have developed a wide range of glass formulations that achieve considerably higher waste loadings and which therefore are more economically attractive in terms of reduced amounts of glass produced and decreased time for treatment. That work was done in support of the Department of Energy's Office of River Protection program that is examining options to optimize the LAW facility and LAW glass waste form. Implementation of these high waste loading formulations at the WTP requires the development of a new LAW vitrification process control algorithm, which is the subject of this paper. Waste loadings in LAW glasses are typically limited by either the alkali loading for LAW with low sulfate content or the SO{sub 3} loading for LAW with high sulfate content. In the former case, waste loadings are limited by refractory corrosion and glass corrosion on the vapor hydration test (VHT) and product consistency test (PCT), all of which tend to increase with higher alkali concentrations. In the latter case, waste loadings are limited by the formation of a molten sulfate phase in the melter, which has deleterious effects. The LAW vitrification process control strategy must mitigate these effects while optimizing waste loadings. Given the composition of any LAW stream, the new LAW vitrification process control algorithm permits the calculation of a suitable high waste loading glass composition and the required glass forming additives such that all processing, waste loading, and product quality requirements are met. This algorithm was developed from data for a large number of glasses that were formulated, and characterized with respect to a variety of properties affecting processability and product quality; many of these formulations were also subjected to melter testing to verify acceptable processing characteristics, processing rates, and the absence of secondary sulfate phase formation. This paper describes the development of the present algorithm, comparisons to the present lower waste loading baseline WTP process control approach, and plans for further development and testing. (authors)

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Deciphering the non-linear impact of Al on chemical durability of silicate glass

The role of Al in aluminosilicate glasses remains somewhat a mystery: at low concentrations, it increases the resistance to hydrolysis of the glass, whereas at high concentrations an opposite effect is observed. To understand the origin of the phenomenon on a fundamental atomistic scale, we performed 577 MD simulations and applied potential mean force (PMF) calculations to estimate the activation barriers for hydrolysis and to statistically correlate them with local structural features of the glass. Models of pure silicate and aluminosilicate glasses are constructed and investigated. PMF simulation results are further validated by the experimental measurements and revealed that Al is very easy to dissociate, but it also increases the glass chemical durability through significantly increasing both the strength of Si and network connectivity of the glass. In contrast, at high Al concentration, preferential dissolution of Al weakens the silicate network, which it supposes to strengthen, and so the glass resistance becomes poor. Through PMF calculations, we evaluated the activation barriers for dissociating bonds around Al as 0.49 eV, which is less than a half of the energy to dissociate bonds around Si in pure silicate (1.22 eV) and around Si in aluminosilicate glass (1.34 eV), all these energy differences being statistically significant. Molecular structural level investigation revealed that Si with Al as a second neighbor in the glass network has a significantly higher activation energy for dissociation than Si in pure silicate glass. Furthermore, the proposed approach opens the way to the development of quantitative predictive models of glass durability.

36 MATERIALS SCIENCE↗

Effects of system size and cooling rate on the structure and properties of sodium borosilicate glasses from molecular dynamics simulations

We present that borosilicate glasses form an important glass forming system in both glass science and technologies. The structure and property changes of borosilicate glasses as a function of thermal history in terms of cooling rate during glass formation and simulation system sizes used in classical molecular dynamics (MD) simulation were investigated with recently developed composition dependent partial charge potentials. Short and medium range structural features such as boron coordination, Si and B Qn distributions, and ring size distributions were analyzed to elucidate the effects of cooling rate and simulation system size on these structure features and selected glass properties such as glass transition temperature, vibration density of states, and mechanical properties. Neutron structure factors, neutron broadened pair distribution functions, and vibrational density of states were calculated and compared with results from experiments as well as ab initio calculations to validate the structure models. The results clearly indicate that both cooling rate and system size play an important role on the structures of these glasses, mainly by affecting the 3B and 4B distributions and consequently properties of the glasses. It was also found that different structure features and properties converge at different sizes or cooling rates; thus convergence tests are needed in simulations of the borosilicate glasses depending on the targeted properties. Lastly, the results shed light on the complex thermal history dependence on structure and properties in borosilicate glasses and the protocols in MD simulations of these and other glass materials.

36 MATERIALS SCIENCE↗

Relationship between surface μ‐roughness and interface slurry particle spatial distribution during glass polishing

Abstract During optical glass polishing, a number of interactions between the workpiece (i.e., glass), polishing slurry, and pad can influence the resulting workpiece roughness at different spatial scale lengths. In our previous studies, the particle size distribution of the slurry, the pad topography, and the amount of material removed by a single particle on the workpiece were shown to strongly correlate with roughness at AFM scale lengths (nm‐μm) and weakly at μ‐roughness scale lengths (μm‐mm). In this study, the polishing slurry pH and the generation of glass removal products are shown to influence the slurry particle spatial and height distribution at the polishing interface and the resulting μ‐roughness of the glass workpiece. A series of fused silica and phosphate glass samples were polished with various ceria and colloidal silica slurries over a range of slurry pH , and the resulting AFM roughness and μ‐roughness were measured. The AFM roughness was largely invariant with pH , suggesting that the removal function of a single particle is unchanged with pH . However, the μ‐roughness changed significantly, increasing linearly with pH for phosphate glass and having a maximum at an intermediate pH for fused silica. In addition, the spatial and height distribution of slurry particles on the pad (as measured by laser confocal microscopy) was determined to be distinctly different at low and high pH during phosphate glass polishing. Also, the zeta potential as a function of pH was measured for the workpiece, slurry, and pad with and without surrogate glass products (K 3 PO 4 for phosphate glass and Si( OH ) 4 for silica) to assess the role of interfacial charge during polishing. The addition of K 3 PO 4 significantly raised the zeta potential, whereas addition of Si( OH ) 4 had little effect on the zeta potential. An electrostatic DLVO three‐body force model, using the measured zeta potentials, was used to calculate the particle–particle, particle–workpiece, and particle–pad attractive and repulsive forces as a function of pH and the incorporation of glass products at the interface. The model predicted an increase in particle–pad attraction with an increase in pH and phosphate glass products consistent with the measured slurry distribution on the pads during phosphate glass polishing. Finally, a slurry “island” distribution gap ( IDG ) model has been formulated which utilizes the measured interface slurry distributions and a load balance to determine the interface gap, the contact area fraction, and the load on each slurry “island”. The IDG model was then used to simulate the workpiece surface topography and μ‐roughness; the results show an increase in roughness with pH similar to that observed experimentally.

Suratwala, Tayyab↗

Nematic-like stable glasses without equilibrium liquid crystal phases

We report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition.Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. While itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

36 MATERIALS SCIENCE↗

Glass-ceramics for nuclear-waste immobilization

Crystallization in glasses is usually considered to be a problem in the glass industry. However, controlled crystallization of glasses is an important prerequisite in the development of glass-ceramics with tailored useful properties. Similar boundary conditions apply when considering glass-ceramics for the immobilization of nuclear waste via vitrification. While uncontrolled crystallization in nuclear-waste glasses is problematic, chemically durable glass-ceramics with significantly high waste loadings can be produced with controlled crystallization of glasses. This article presents an overview of various aspects of nuclear-waste glasses where crystallization is either considered to be advantageous or problematic. The classification of glass-ceramic waste forms and strategies to design glass-ceramics for a given waste stream is discussed. In conclusion, some open and relevant problems faced by researchers developing nuclear-waste glass-ceramics are also offered.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Office of River Protection Advanced Low-Activity Waste Glass Research and Development Plan

The U.S. Department of Energy Office of River Protection (ORP) has initiated and leads an integrated Advanced Waste Glass (AWG) program to increase the loading of Hanford tank wastes in glass while meeting melter lifetime expectancies and process, regulatory, and product performance requirements. The integrated ORP program is focused on providing a technical, science-based foundation for making key decisions regarding the successful operation of the Hanford Tank Waste Treatment and Immobilization Plant (WTP) facilities in the context of an optimized River Protection Project (RPP) flowsheet. The fundamental data stemming from this program will support development of advanced glass formulations, key product performance and process control models, and tactical processing strategies to ensure safe and successful operations for both the low-activity waste (LAW) and high-level waste vitrification facilities. These activities will be conducted with the objective of improving the overall RPP mission by enhancing flexibility and reducing cost and schedule. The purpose of this advanced LAW glass research and development plan is to identify the near-term, mid-term, and longer-term research and development activities required to develop and validate advanced LAW glasses, property-composition models and their uncertainties, and an advanced glass algorithm to support WTP facility operations, including both Direct Feed LAW and full pretreatment flowsheets. Data are needed to develop, validate, and implement 1) new glass property-composition models and 2) a new glass formulation algorithm. Hence, this plan integrates specific studies associated with increasing the Na2O and SO3/halide concentrations in glass, because these components will ultimately dictate waste loadings for LAW vitrification. Of equal importance is the development of an efficient and economic strategy for 99Tc management. Specific and detailed studies are being implemented to understand the fate of Tc throughout the WTP flowsheet and the underlying mechanisms that dictate its partitioning between streams within the LAW vitrification facility. These studies are aimed at increasing the single-pass Tc retention in glass and the potential use of high-temperature mineral phases to capture Tc. The Tc-bearing mineral phases would be thermally stable and resistant to Tc release during feed melting reactions or they could serve as alternative waste forms. The LAW glass research and development is focused on reducing the total volume of LAW glass produced and minimizing the impact of (or potentially eliminating) the need for recycle.

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Using Artificial Microstructures to Understand Microstructure Property Relationship-Toughening Mechanisms in Metallic Glass (Final Report)

Metallic glasses are a new class of structural materials which exhibit exciting mechanical properties including high strength and elasticity. In terms of fracture toughness, the material class of metallic glasses spans a wide range; Some metallic glasses are extremely brittle and exhibit near ideal brittle behavior whereas others can be exceptional tough with values comparable to the toughest metals out there. Such large range of observed fracture toughness within the material class of metallic glasses is surprising as they have seemingly a very similar atomic structure. Therefore, we developed “artificial microstructures” which allows to decouple the various contribution of sample geometry, imperfection and structure. Specifically, we decouple variations in the alloys’ chemical composition and the atomic structure and quantified the resulting fracture toughness. Atomic structure of a metallic glass can be modified by the fictive temperature. The fictive temperature of a glass is the temperature at which the liquid metallic glass falls out of equilibrium upon colling and forms a glass. Upon further cooling the structure is maintained only thermal oscillations decrease due to a lower absolute temperature. We found that the effect of fictive temperature (same chemistry, different structural stages of the glass) is comparable to the variations of fracture toughness when the chemistry is varied. Hence, it appears that the subtle differences in the glass structure are responsible for the large range of fracture toughness’s observed. Our results reveal that fracture toughness within the material class of metallic glasses varies significantly and we found some example alloys with exceptional high resistance to fracture and others that are almost ideally brittle. Significant influences on the fracture toughness have the structure of the glass, its chemistry, and some imperfections in the structure.

36 MATERIALS SCIENCE↗

Evaluation of a Sulfate Solubility Limit Greater Than 0.65 Weight Percent in Sludge Batch 10 Glasses

Previous laboratory-scale crucible testing with batch chemicals confirmed that the sulfate (SO 4 2- ) limit for Sludge Batch 10 (SB10) was 0.65 weight percent (wt.%) in glass. This limit signifies that 0.65 wt.% SO 4 2- can be retained in the glass without the formation of a sulfate phase. The Defense Waste Processing Facility imposes this constraint in the Material Tracking Program. Based on preliminary calculations to support the Material Tracking Program, it was anticipated that transfer volumes of the monosodium titanate/sludge solids (MST/SS) stream from the Salt Waste Processing Facility (SWPF) may need to be reduced to maintain projected sulfate concentrations below 0.65 wt.% in glass. Savannah River Mission Completion requested that the Savannah River National Laboratory perform additional sulfate testing to determine whether a sulfate solubility limit greater than 0.65 wt.% is feasible for SB10, which could allow for higher transfer volumes of the MST/SS stream. This report documents the results of the testing at higher sulfate concentrations for the glass composition region defined by the most recent SB10 projection (November 2022) and Frits 473 and 625. Frit 473 was recommended for SB10 and Frit 625 was used during SB9 processing and the SB9 to SB10 transition. A total of twenty-one glass compositions were developed based on the expected compositional variables, which include sludge-only (SO) and coupled processing with the SWPF, waste loading (WL), and frit composition. The target sulfate concentrations were varied from 0.65-0.85 wt.% at 32 and 40% WL. Each glass was prepared from reagent grade chemicals and melted at 1150 °C. Visual observations were used to confirm the presence of a sulfate salt phase on the cooled glass surfaces. Representative samples of each glass were submitted for chemical composition analysis by inductively coupled plasma-optical emission spectroscopy and Cs analysis by inductively coupled plasma-mass spectrometry. Overall the majority of mean measured values are consistent with the target values for each major oxide of interest with less than 5% error. The percent errors for the measured SO 4 2- concentrations are generally less than 10%, which is comparable with previous sulfate solubility study measurements and acceptable. Only the SO glasses based on Frit 625 formed a sulfate phase at a 0.80 wt.% SO 4 2- target concentration at both 32 and 40% WL. The remainder of the glasses did not form a sulfate layer. Due to the formation of the sulfate phase, the limit is conservatively set at 0.70 wt.% based on the measured sulfate concentrations of 0.71 wt.% and 0.75 wt.% for these two glasses. None of the SO or coupled operation glasses based on Frit 473 formed a sulfate salt phase, which supports a sulfate limit of 0.80 wt.%. The following SO 4 2- concentration limits are recommended during SO and coupled SB10 processing: (1) 0.70 wt.% during processing with Frit 625, and (2) 0.80 wt.% during processing with Frit 473.

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Characterization of the Sulfur-Saturated Melt Versions of the LAW ML1 Glasses

This report provides the results from the chemical analyses of the sulfur-saturated melt versions of the Low-Activity Waste Machine Learning study glasses, a series of simulated nuclear waste glasses designed and fabricated at Pacific Northwest National Laboratory. These data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. Chemical analyses were performed on a representative sample of each of the sulfur-saturated melt versions of the glasses to allow for comparisons with targeted compositions as well as the measured compositions of the quenched glasses. The relative differences between the targeted and measured concentrations of F- for one glass, K 2 O for one glass, Na 2 O, for one glass, P 2 O 5 for one glass, and ZrO 2 for several of the glasses were greater than ±10%. As expected, the measured concentrations of SO 3 in most of the glasses were higher than targeted due to the use of the sulfur saturation method in fabricating these glasses.

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Apollo 17 ropy glasses

Ropy glasses are a major soil component in the Apollo 17 gray soils 74240 and 74260. These particles form a distinct morphological type characterized by a wide range of dynamic shapes with a diagnostic sorted and welded fine-grained debris coating. Apollo 17 ropy glasses show abundant evidence for shock. Shocked lithic and mineral inclusions, lack of any igneous textures, and lechatelierite, all indicate an impact origin. A striking similarity is observed between the lunar ropy glasses and the glass impact bombs (Flaedle) of the Ries Crater in Germany. A highland basaltic composition was observed for the Apollo 17 ropy glasses in contrast to the KREEP composition of ropy glasses from the Apollo 12 and Apollo 14 landing sites. Other workers have presented convincing evidence that ejecta from Tycho reached the Taurus-Littrow Valley, and these ropy glasses may represent Tycho ejecta. However, the close stratigraphic association of the ropy glasses with the greater than 3.5 b.y. old orange glass suggests the ropy glasses may be too old to be Tycho ejecta, which should be only about 100 m.y. old. If this is the case, the ropy glasses represent impact glasses from a very old impact in an unknown highlands source area.

Fruland, R. M.↗

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

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

Day, Delbert E.↗

Surface Coatings on Lunar Volcanic Glasses

We are undertaking a detailed study of surface deposits on lunar volcanic glass beads. These tiny deposits formed by vapor condensation during cooling of the gases that drove the fire fountain eruptions responsible for the formation of the beads. Volcanic glass beads are present in most lunar soil samples in the returned lunar collection. The mare-composition beads formed as a result of fire-fountaining approx.3.4-3.7 Ga ago, within the age range of large-scale mare volcanism. Some samples from the Apollo 15 and Apollo 17 landing sites are enriched in volcanic spherules. Three major types of volcanic glass bead have been identified: Apollo 15 green glass, Apollo 17 orange glass, and Apollo 17 "black" glass. The Apollo 15 green glass has a primitive composition with low Ti. The high-Ti compositions of the orange and black glasses are essentially identical to each other but the black glasses are opaque because of quench crystallization. A poorly understood feature common to the Apollo 15 and 17 volcanic glasses is the presence of small deposits of unusual materials on their exterior surfaces. For example, early studies indicated that the Apollo 17 orange glasses had surface enrichments of In, Cd, Zn, Ga, Ge, Au, and Na, and possible Pb- and Zn-sulfides, but it was not possible to characterize the surface features in detail. Technological advances now permit us to examine such features in detail. Preliminary FE-TEM/X-ray studies of ultramicrotome sections of Apollo 15 green glass indicate that the surface deposits are heterogeneous and layered, with an inner layer consisting of Fe with minor S and an outer layer of Fe and no S, and scattered Zn enrichments. Layering in surface deposits has not been identified previously; it will be key to defining the history of lunar fire fountaining.

Wentworth, Susan J.↗

Cooling Rates of Lunar Volcanic Glass Beads

It is widely accepted that the Apollo 15 green and Apollo 17 orange glass beads are of volcanic origin. The diffusion profiles of volatiles in these glass beads are believed to be due to degassing during eruption (Saal et al., 2008). The degree of degassing depends on the initial temperature and cooling rate. Therefore, the estimations of volatiles in parental magmas of lunar pyroclastic deposits depend on melt cooling rates. Furthermore, lunar glass beads may have cooled in volcanic environments on the moon. Therefore, the cooling rates may be used to assess the atmospheric condition in an early moon, when volcanic activities were common. The cooling rates of glasses can be inferred from direct heat capacity measurements on the glasses themselves (Wilding et al., 1995, 1996a,b). This method does not require knowledge of glass cooling environments and has been applied to calculate the cooling rates of natural silicate glasses formed in different terrestrial environments. We have carried out heat capacity measurements on hand-picked lunar glass beads using a Netzsch DSC 404C Pegasus differential scanning calorimeter at University of Munich. Our preliminary results suggest that the cooling rate of Apollo 17 orange glass beads may be ~12 K/min, based on the correlation between temperature of the heat capacity curve peak in the glass transition range and glass cooling rate. The results imply that the parental magmas of lunar pyroclastic deposits may have contained more water initially than the early estimations (Saal et al., 2008), which used higher cooling rates, 60-180 K/min in the modeling. Furthermore, lunar volcanic glass beads could have been cooled in a hot gaseous medium released from volcanic eruptions, not during free flight. Therefore, our results may shed light on atmospheric condition in an early moon.

Hui, Hejiu↗

Eco-efficient waste glass recycling: Integrated waste management and green product development through LCA

Highlights: Black-Right-Pointing-Pointer A new eco-efficient recycling route for post-consumer waste glass was implemented. Black-Right-Pointing-Pointer Integrated waste management and industrial production are crucial to green products. Black-Right-Pointing-Pointer Most of the waste glass rejects are sent back to the glass industry. Black-Right-Pointing-Pointer Recovered co-products give more environmental gains than does avoided landfill. Black-Right-Pointing-Pointer Energy intensive recycling must be limited to waste that cannot be closed-loop recycled. - Abstract: As part of the EU Life + NOVEDI project, a new eco-efficient recycling route has been implemented to maximise resources and energy recovery from post-consumer waste glass, through integrated waste management and industrial production. Life cycle assessment (LCA) has been used to identify engineering solutions to sustainability during the development of green building products. The new process and the related LCA are framed within a meaningful case of industrial symbiosis, where multiple waste streams are utilised in a multi-output industrial process. The input is a mix of rejected waste glass from conventional container glass recycling and waste special glass such as monitor glass, bulbs and glass fibres. The green building product is a recycled foam glass (RFG) to be used in high efficiency thermally insulating and lightweight concrete. The environmental gains have been contrasted against induced impacts and improvements have been proposed. Recovered co-products, such as glass fragments/powders, plastics and metals, correspond to environmental gains that are higher than those related to landfill avoidance, whereas the latter is cancelled due to increased transportation distances. In accordance to an eco-efficiency principle, it has been highlighted that recourse to highly energy intensive recycling should be limited to waste that cannot be closed-loop recycled.

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Chemical Composition Measurements of LAWA44 Glass Samples

DOE is building the Hanford Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site in Washington to remediate 55 million gallons of radioactive waste that is temporarily stored in 177 underground tanks. Both low-activity and high-level wastes will then be vitrified into borosilicate glass using Joule-heated ceramic melters. Efforts are being made to increase the loading of Hanford tank wastes in the glass. One area of work is enhancing waste glass composition/property models and broadening the compositional regions over which those models are applicable. In this report, the Savannah River National Laboratory provides chemical analysis results for several samples of a simulated low-activity waste glass, LAWA44, provided by the Pacific Northwest National Laboratory as part of an ongoing development task. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. A detailed review showed no indications of errors in the preparation or measurement of the study glasses. All of the measured sums of oxides for the study glasses fell within the interval of 97.9 to 102.6 wt %, indicating acceptable recovery of the glass components. Comparisons of the targeted and measured chemical compositions showed that the measured values for the glasses met the targeted concentrations within 10% for those components present at more than 5 wt %. It was noted that the measured B 2 O 3 concentrations are somewhat above the targeted values for the study glasses. No obvious trends were observed with regard to the multiple melting steps used to prepare the study glasses, indicating that any potential effects of volatility were below measurable thresholds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic timescales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models be validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test B, and pressurized unsaturated flow (PUF)], thereby reducing the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year-long PUF experiment was conducted with the Subsurface Transport Over Reactive Multiphases (STORM) code. Results show that parameterization of the computer model by combining direct bench scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year-long test duration, the rate decreased from 0.2 to 0.01 g/(m2 day) based on B release for low-activity waste glass LAWA44. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by four orders of magnitude) and suggests that the gel-layer properties are less protective under these dynamic conditions.

aluminoborosilicate nuclear waste glass↗