SEARCH · Engineering Papers
Results for “Glasses”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments
During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.
High-entropy induced a glass-to-glass transition in a metallic glass
Glass-to-glass transitions are useful for us to understand the glass nature, but it remains difficult to tune the metallic glass into significantly different glass states. Here, we have demonstrated that the high-entropy can enhance the degree of disorder in an equiatomic high-entropy metallic glass NbNiZrTiCo and elevate it to a high-energy glass state. An unusual glass-to-glass phase transition is discovered during heating with an enormous heat release even larger than that of the following crystallization at higher temperatures. Dramatic atomic rearrangement with a short- and medium-range ordering is revealed by in-situ synchrotron X-ray diffraction analyses. This glass-to-glass transition leads to a significant improvement in the modulus, hardness, and thermal stability, all of which could promote their applications. Based on the proposed high-entropy effect, two high-entropy metallic glasses are developed and they show similar glass-to-glass transitions. These findings uncover a high-entropy effect in metallic glasses and create a pathway for tuning the glass states and properties.
Glass length: Workability and meltability of glass as a function of glass melt fragility
Workability and meltability of molten glass are properties important for balancing glass formulation with the design and operations of glass melting and forming facilities. The working and melting “lengths” are the temperature intervals within which glass viscosity allows the melting and forming glass to be performed. They are related to glass melt structure through the glass melt fragility, which, by the augmented Adam-Gibbs equation, is a function of configuration entropy. Both working length and melting length are high for strong glasses and decrease as the melt fragility increases. In this work, analytical formulas are obtained for three-parameter viscosity models VFT, AM, and MYEGA. These models agree with each other and with the Adam-Gibbs equation on the relationship between workability and fragility of glasses but diverge at high-temperatures. The compositional effects on workability and meltability are mediated via the fragility as a function of glass composition expressed in terms of mass and mole component coefficients.
Overall Performance Losses and Activated Mechanisms in Double Glass and Glass-backsheet Photovoltaic Modules with Monofacial and Bifacial PERC Cells, under Accelerated Exposures
Commercial PV modules have various packaging choices nowadays, which influence their long-term reliability. This study compared the degradation behaviors of sixteen module variants from two brands with varying encapsulant materials (EVA or POE), encapsulant types, module architectures (GB or DG), and cell types (monofacial or bifacial) using null hypothesis testing to determine statistical significant findings. The modules were exposed for 2,520 hours under two accelerated exposures: modified damp heat (mDH) and modified damp heat with full-spectrum light (mDH+FSL). For both brands, two DG module variants with UV-Cutoff rear encapsulant are found to have significantly lower average power loss than the module variants of EVA+GB with opaque rear encapsulant after each accelerated exposure. Metallization interconnect corrosion is identified as the primary degradation mechanism. Furthermore, unsupervised hierarchical clustering finds that the degradation behaviors of modules from one brand with a more strict manufacturing quality control depends on module architectures only.
Testing of High S Matrix Glasses to Expand DFHLW Glass Compositional Ranges (Rev.1)
Gaps in glass composition-property data for direct-feed high-level waste (DFHLW) have recently been identified. One such gap is the region of high sulfur solubility since previous, pretreated, high-level wastes contained very little sulfur. Filling this data gap will significantly broaden the range of process flowsheet options including minimal washing and will allow for optimized waste loading in DFHLW glasses. This report summarizes the data collected during the characterization of the DFHLW High S Glass Matrix (HS24). A glass matrix of 50 glass compositions was developed to evenly cover the DFHLW composition region for high sulfur glass. Matrix glasses were designed to expand the composition region outside the current component concentration and property limits so as to reduce uncertainties at the limits. The 50 matrix glasses were fabricated and tested for properties important to the success of DFHLW vitrification including: compositions, canister centerline cooling (CCC) crystallinity and isothermal crystallinity, density, viscosity, electrical conductivity (EC), product consistency test (PCT) response, toxicity, and sulfate solubility. Melter materials corrosion testing is reported elsewhere. These glasses were intentionally designed to have high SO 3 solubilities (0.7 to 2.2 SO 3 wt%) in compositional regions that had not been previously explored. Forty-eight glasses showed the measured SO 3 content retained >80% of the target SO 3 and the densities of all the glasses ranged from 2.49 g·cm -3 to 2.74 g·cm -3 . While the model predicted nepheline formation in 5 glasses, one of the tested 50 CCC glasses formed nepheline, and 35 glasses formed Cr-containing phases such as spinels and eskolaite. Only five glasses were amorphous after CCC treatment where 44 glasses with detectable crystals contained =10 wt% crystals and only one glass had > 10 wt% crystals. None of the glasses exceeded the allowable T 2% for spinel crystal formation at 950 ºC (i.e., no glasses had >2 wt% spinel at 950 ºC) during isothermal crystal fraction tests where 10 glasses showed no crystalline phases at or below 950 ºC. All the glasses (except one which failed being slightly lower than the target) satisfied the SO 3 constraint while 98 glasses did not meet the viscosity constraints and 4 failed the EC constraints. Six quenched (Q) and six CCC glasses failed the Defense Waste Processing Facility (DWPF) Environmental Assessment (EA) glass PCT threshold and 3 Q and 4 CCC failed the PCT design constraint. One glass exceeded the WTP delisting limits for Cr via EPA Method 1311 (i.e., Toxicity Characteristic Leaching Procedure, TCLP). It should be emphasized that some of these glasses were specifically designed to approach or even exceed certain property constraints, as filling data gaps in these regions will provide the greatest benefit for future model development by improving accuracy and reducing uncertainties. These insights will ultimately support the development of more robust glass formulation strategies, enabling higher waste loading, reducing operational risks, and expanding the processing envelope.
Rare Earth and Transition Metal Containing Glasses
Transition metal (TM) and rare earth (RE) ions have been incorporated into many glass systems such as silicate, phosphate, and borosilicate-based oxide glasses, as well as in halide and chalcogenide glasses, that find applications ranging from optical, photonic, and magnetic devices, solid-state battery, to nuclear waste disposal. Understanding the structural role of RE and TM in these glasses can help to develop glass compositions for targeted applications with either high-optical emission efficiency, electrical conductivity, or chemical durability. In this chapter, we first provide a general introduction of the applications and structural features of RE and TM in glasses, then the critical aspects of molecular dynamics (MD) simulations of these glasses such as interatomic potentials, structural analysis tools to study RE and TM ions in glasses and their clustering behaviors, Quantitative Structure–Property Analysis (QSPR), diffusion and dynamic property calculations, and electronic structure calculations to understand electronic defects such as charge trapping and radiation effects are introduced. Three representative case studies are presented: the first one is on MD simulations of erbium- and europium-doped silica and silicate glasses, as well as cerium doped aluminophosphate glasses, that revealed the effect of glass composition on RE ion local structure and clustering behavior. Electronic structure calculations of cerium-doped glass show how the existence of multioxidation states help to mediate radiation-induced damages caused by excited electron–hole pairs was also discussed. The second one focuses on alkali vanadophosphate glasses where the existence of two vanadium oxidation states help to provide electronic conduction in the glasses while alkali ions provide ionic conduction. MD simulations were used to understand vanadium environments and other structural aspects in the phosphate glasses, as well as the ionic transport behaviors of alkali ions. The third case study is on zirconium-containing borosilicate and aluminosilicate glasses that find wide applications in nuclear waste disposal. MD simulations help to provide structural details of zirconium ions that are validated by diffraction and EXAFS spectra. The structural information was used to interpret changes of mechanical properties and chemical durability by using QSPR and other analyses-based MD-generated structure models.
Predicting the Dissolution Rate of Borosilicate Glasses using QSPR analysis based on molecular dynamics simulations
Quantitative Structure Property Relationship (QSPR) analysis based on molecular dynamics (MD) simulations is a promising approach for establishing the composition-property relationships of glass and other materials with complex structures. A series of 20 borosilicate and boroaluminosilicate glasses have been modeled by using MD simulations with recently developed effective potentials. Short- and medium-range structures of these glasses were analyzed and, based on these structural information, QSPR analysis of the initial dissolution rate (r0) was made and compared with measured r0 at 90°C and pH 9 using various structural descriptors such as percentage of bridging oxygen species, network connectivity and average ring size. The structural descriptors, Fnet, containing energetic information such as single bond strength and other structural information were also used. It was found that overall network connectivity, average ring size and Fnet give reasonable predictions of the r0 of studied glasses, given the conditions that the glasses are homogeneous and dissolve congruently. Modifying glass compositions to account preferential release of modifiers gives a better prediction for incongruently dissolving glasses. The results were compared with our recent work of predicting glass dissolution behavior from compositions using the topological-constraints-based models.
Application of the immobilized low-activity waste glass corrosion model to the static dissolution of 24 statistically-designed alkali-borosilicate waste glasses
Glass corrosion models that capture the complex mechanisms of the glass-water reaction enable the prediction of nuclear waste glass durability in disposal scenarios. Parameterization of such models is challenging because of the need to capture changes in corrosion behavior with time, reaction conditions, and glass composition. In this report we describe and employ the immobilized low activity waste (ILAW) glass corrosion model (IGCM) in geochemical simulations of static dissolution tests, at two temperatures (40 °C and 90 °C), for a matrix of 24 enhanced low activity waste (eLAW) glasses statistically designed to cover a processable composition space defined by 8 major glass components (Al 2 O 3 , B 2 O 3 , CaO, Na 2 O, SiO 2 , SnO 2 , ZrO 2 , and Others as defined in the text). The IGCM includes a first-order chemical affinity term and an ion-exchange term that represents the net exchange of Na+ ions in the pristine glass with protons in aqueous solution. Constant, time-dependent, and time- and pH-dependent functional forms of the ion-exchange term are evaluated to reproduce the change in corrosion behavior with time in saturated, static dissolution tests. The agreement with measured aqueous concentrations of the main glass components (B, Na, and Si) improved significantly upon addition of a time-dependent term, which therefore constitutes a simple representation of the glass-water reaction progress. Due to the limited changes in pH in the static dissolution tests, past a short initial period of rapid increase, addition of a pH dependent term did not appreciably improve the fits, indicating that comprehensive model parameterization requires more than one type of glass corrosion test to capture a wide range of solution chemistries. IGCM parameters were found to be dependent on glass composition, and the parameter sets generated in this work will enable the development of composition–parameter correlation models that offer the promise of predicting IGCM parameters, and thus glass corrosion behavior, solely based on glass composition.
Seeded Stage III glass dissolution behavior of a statistically designed glass matrix
The glass dissolution rate of some glasses accelerates after prolonged time spent at a slow, residual glass dissolution rate. This phenomenon is referred to as Stage III behavior. Here, the acceleration in glass dissolution rate linked to Stage III behavior is significant and may be the most impactful to long-term performance of glass in a repository. This work is aimed at understanding the effect of glass composition on Stage III behavior to add a level of technical defensibility to glass disposal. To this end, a set of twenty-four glass compositions were statistically designed, where eight glass components (SiO 2 , B 2 O 3 , Al 2 O 3 , CaO, Na 2 O, SnO 2 , ZrO 2 , and Others) have been independently varied in order to study the individual effects of each. These glasses have been subjected to static dissolution tests at 90 °C in deionized water and then seeded with zeolite Na-P2 28 days into the testing to induce Stage III behavior. The response of the glasses to the zeolite seeds fell into four primary types: 1) no response to seeds; 2) an immediate linear sustained acceleration in the rate; 3) an immediate linear acceleration in the rate followed by a decrease; and, 4) a progressive acceleration in the rate that is concurrent with the addition of the seeds. The main glass components observed to influence these behaviors were CaO, Al 2 O 3 , B 2 O 3 , and ZrO 2 , where: 1) CaO influenced which glasses showed a Stage III response to seeds (high CaO: Types 2, 3, and 4) or did not respond to seeds (low CaO: Type 1), 2) Al 2 O 3 and B 2 O 3 influenced which glasses showed a sustainable Stage III response (high Al 2 O 3 : Types 2 and 4) versus transitory response (low Al 2 O 3 and high B 2 O 3 : Type 3), and 3) ZrO 2 concentration influenced whether glasses showed a linear (high ZrO 2 : Type 2) versus progressive (low ZrO 2 : Type 4) response to seeds.
Corrosion Testing of Refractory inContact with Molten Glasses Designed for Waste Vitrification - VSL Touchpoint Matrix Glasses
It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests. Refractory corrosion is generally reported as physical material loss, measured in units of distance (e.g., inch) or as physical material loss rate, measured in units of distance per time (e.g., inch/day). In post-operational melters, the refractory corrosion is measured directly, sometimes reported as corrosion depth. Crucible tests are used in the laboratory to accelerate the refractory corrosion to facilitate a meaningful measurement in a commensurate amount of time. Crucible tests are particularly useful in understanding refractory corrosion across a large glass composition space, where operational testing would be prohibitive. Some of the critical parameters that are known to influence refractory corrosion by molten glass in a crucible test are temperature, system redox, molten salt phases, glass chemistry, and test duration. The majority of data collected for Monofrax® K-3 (hereafter referred to as K-3) corrosion is from crucible tests, but a small amount comes directly from scaled and production melters. Crucible test data has been collected under varying conditions, whereas data collected from operational melters is relatively fewer and represents conditions specific to the melter campaign. The result is that the published data can be grouped and analyzed in multiple ways, not all of which are readily comparable. The Standard Test Method for Isothermal Corrosion Resistance of Refractories to Molten Glass (ASTM C621) outlines the general guidelines used across industry. That method describes a sealed, static test in which the surface area of the refractory coupon and the volume of glass are fixed. A significant portion of the crucible data pertaining to nuclear waste glasses has been collected in a modified configuration; the most notable differences being the surface area of the refractory coupon to volume of the glass and use of a method for bubbling the melt. To our knowledge, the influence of those parameters on the refractory corrosion has not been quantified. In this work, it was determined that static tests and bubbled tests would be performed. Savannah River National Laboratory (SRNL) was tasked with setting up and performing static testing while PNNL was tasked with setting up and performing bubbled testing. Initial activities were performed to establish laboratory methods that reproduce data comparable to existing data sets of K-3 refractory corrosion by low activity waste (LAW) and high-level waste (HLW) glass compositions. Later activities were focused on refining the test parameters to establish a standard test practice to be used between Laboratories and collecting additional data to be used in the enhanced waste glass model development. This document serves primarily to convey the refractory loss measurement results from corrosion testing of K-3 refractory with waste glass compositions developed for use in the WTP melters. The data will be used in the enhanced property/composition models being developed for waste glass vitrification and melter operations.
Designing Glass and Crystalline Phases of Metal–Bis(acetamide) Networks to Promote High Optical Contrast
Owing to their high tunability and predictable structures, metal–organic materials offer a powerful platform to study glass formation and crystallization processes and to design glasses with unique properties. In this work, we report a novel series of glass-forming metal–ethylenebis(acetamide) networks that undergo reversible glass and crystallization transitions below 200 °C. The glass-transition temperatures, crystallization kinetics, and glass stability of these materials are readily tunable, either by synthetic modification or by liquid-phase blending, to form binary glasses. Pair distribution function (PDF) analysis reveals extended structural correlations in both single and binary metal–bis(acetamide) glasses and highlights the important role of metal–metal correlations during structural evolution across glass–crystal transitions. Notably, the glass and crystalline phases of a Co–ethylenebis(acetamide) binary network feature a large reflectivity contrast ratio of 4.8 that results from changes in the local coordination environment around Co centers. These results provide new insights into glass–crystal transitions in metal–organic materials and have exciting implications for optical switching, rewritable data storage, and functional glass ceramics.
Evaluation of GlassNet for physics-informed machine learning of glass stability and glass-forming ability
Glassy materials form the basis of many modern applications, including nuclear waste immobilization, touch-screen displays, and optical fibers, and also hold great potential for future medical and environmental applications. However, their structural complexity and large composition space make design and optimization challenging for certain applications. Of particular importance for glass processing and design is an estimate of a given composition's glass-forming ability (GFA). However, there remain many open questions regarding the underlying physical mechanisms of glass formation, especially in oxide glasses. It is apparent that a proxy for GFA would be highly useful in glass processing and design, but identifying such a surrogate property has proven itself to be difficult. While glass stability (GS) parameters have historically been used as a GFA surrogate, recent research has demonstrated that most of these parameters are not accurate predictors of the GFA of oxide glasses. Here, in this work, we explore the application of an open-source pre-trained neural network model, GlassNet, that can predict the characteristic temperatures necessary to compute GS with reasonable performance and assess the feasibility of using these physics-informed machine learning (PIML)-predicted GS parameters to estimate GFA. In doing so, we track the uncertainties at each step of the computation—from the original ML prediction errors to the compounding of errors during GS estimation, and finally to the final estimation of GFA. While GlassNet exhibits reasonable accuracy on all individual properties, we observe a large compounding of error in the combination of these individual predictions for the PIML prediction of GS, finding that random forest models offer similar accuracy to GlassNet. We also break down the performance of GlassNet on different glass families and find that the error in GS prediction is correlated with the error in crystallization peak temperature prediction. Lastly, we utilize this finding to assess the relationship between top-performing GS parameters and GFA for two ternary glass systems: sodium borosilicate and sodium iron phosphate glasses. We conclude that to obtain true ML predictive capability of GFA, significantly more data needs to be collected.
Predicting nepheline precipitation in waste glasses using ternary submixture model and machine learning
Nepheline precipitation in nuclear waste glasses during vitrification can be detrimental due to its negative effect on chemical durability. Developing models to accurately predict nepheline precipitation from compositions is important to increase waste loading since existing models can be overly conservative. In this study, an expanded dataset containing 955 glasses was compiled from literature data, where 355 glasses are for high-level waste (HLW). Previously developed submixture models were refitted using the new dataset, where a misclassification rate of 7.8% was achieved. Nine machine learning (ML) algorithms (e.g., k-nearest neighbor, Gaussian process regression, artificial neural network, support vector machine, decision tree, etc.) were applied to evaluate their ability of predicting nepheline precipitation from compositions. Model accuracy, precision, recall/sensitivity, and F1 score were systemically compared between different ML algorithms and modeling protocols. Good model prediction with an accuracy ~0.9 (misclassification rate of ~10%) was observed with different algorithms under certain protocol. This study evaluated various ML models to predict nepheline precipitations in waste glasses, highlighting the importance of data preparation, modeling protocol, and their effect on model stability and reproducibility. The results provide insights into applying ML to predict glass properties and suggest areas for future research on modeling nepheline precipitations.
Structure–property relations of sodium iron phosphate nuclear waste glasses: Effects of iron redox ratio and glass composition
Iron phosphate glasses, known for their exceptional chemical durability and potential applicability in nuclear waste management, have gained significant attention over the years. The structures of these glasses are complicated by the coexistence of Fe 3+ and Fe 2+ , which plays a crucial role in determining their structures and properties. Here, this work uses molecular dynamics simulations to study the structural changes in Na 2 O–Fe 2 O 3 –P 2 O 5 glasses with varying glass composition and Fe 2+ /Fe 3+ redox ratio. It was found that the redox ratio and modifier contents significantly affected the short-range and medium-range orders in the glasses. Significant changes in the local environments around P 5+ and Fe 3+ were observed, as reflected by the bond distances and coordination numbers. Na + cations are found to preferentially associate with Fe 3+ (rather than Fe 2+ ), whereas Fe 2+ has stronger association with P 5+ than Na + , confirming the structural role of Fe 2+ as a glass modifier. The disruptions in P–O–P linkages upon increasing FeO suggest that FeO causes glass depolymerization. These glasses achieved higher connectivity with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, conerting phosphorous Q 2 to Q 3 units and iron Q 5 units to Q 4 units. The decrease of nonbridging oxygen fractions with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, through creating P–O–Fe linkages, is the main reason of enhanced network connectivity. Quantitative structure–property relationship analyses with different structural descriptors were used to correlate with measured properties. The analyses provided valuable insights into structure–property relationships, emphasizing the importance of choosing relevant energy parameters and defining glass network connectivity, particularly in F net descriptors. It was found the Fe–O–P linkage density exhibits strong correlations to measured dissolution rates, supporting the importance of these linkages in improving the chemical durability in iron phosphate glasses.
Durability testing of actual Hanford waste glasses and their non-radioactive simulant glasses
The low-activity waste (LAW) fraction of Hanford tank waste will be converted to glass at the Waste Treatment and Immobilization Plant (WTP) and disposed on the Hanford site. The chemical durability of LAW glasses has been researched for decades to satisfy contract requirements. Most LAW glass durability data has been generated on non-radioactive simulant glasses fabricated via crucible melts. These non-radioactive glasses were chosen due to safety and cost reasons with confidence that radioactive waste glasses would exhibit similar behavior. To reduce the risk of significant differences in laboratory test response data between WTP melter waste glass and simulant glass, Product Consistency Tests (PCT, i.e., ASTM C1285-21) and Environmental Protection Agency (EPA) 1313 durability tests were performed on actual and simulant LAW glasses fabricated using laboratory-scaled melters. Actual and simulant glass durability test results are presented and statistically compared. Finally, differences in test responses were found to be within experimental uncertainty.
Glass Design Using Machine Learning Property Models with Prediction Uncertainties: Nuclear Waste Glass Formulation
The United States Department of Energy is responsible for managing the legacy nuclear waste stored in underground tanks at the Hanford Site. The waste will be separately vitrified as low-activity waste and high-level waste fractions. Waste glass formulation algorithms have been traditionally developed using partial quadratic mixture property-composition models. Recently, machine learning (ML) techniques have been used to predict glass properties and discover new glass materials for nuclear waste vitrification, and these advancements can be utilized to improve waste glass composition design. In this proof-of-principle study, ML algorithms such as Gaussian process regression (GPR) were used to interpolate glass properties (e.g., viscosity, electrical conductivity, chemical durability). After selecting appropriate sets of GPR hyper-parameters for each property, an optimization program was developed to formulate glass compositions to maximize waste loading while simultaneously satisfying property within constraints. The results of the ML-based waste loadings and glass compositions were compared to those obtained using the traditional methods. Comparing to the previous glass design framework, the ML-based optimization methods offer improved glass designs and a streamlined approach to generation of optimally designed data and near real-time updates.
Origin of the Apollo 15 very low Ti green glass. A perspective from the compositional diversity in the very low Ti glasses
The very low Ti green glasses from the Apollo 15 site have intrigued scientists for over 20 years. Their primitive composition has been used to understand magmatic processes and the structure of the moon. The compositional variability observed in the Apollo 15 glass population has long been a point of debate. Initial studies did not recognize the compositional diversity in the glasses. Stolper et al. documented the major element variability and concluded it could not be produced by magmatic processes and therefore concluded that these glasses must be of impact origin. Subsequent studies confirmed a volcanic origin for the glass population and attempted to elucidate magmatic processes to account for its compositional variability. Models that have been proposed for these glasses include the following: (1) the crystallization of single or multiple phases (olivine, pyroxene, Fe metal, immiscible sulfide); (2) the incompatible behavior of Ni and Co during multiple phase crystallization at extremely low fO2; and (3) magma or source mixing. All of these models have problems. Type (1) models appear not to be consistent with recent trace element studies on the glasses; model (2) is dependent on the debatable incompatible behavior of Ni and Co, and, in models of type (3), the origin and nature of mixing models are somewhat unconstrained. This study compares the Apollo 15 green glasses with the very low Ti picritic glasses from other landing sites.