22 Search Results

Abstract Ensuring the long-term chemical durability of glasses is critical for nuclear waste immobilization operations. Durable glasses usually undergo qualification for disposal based on their response to standardized tests such as the product consistency test or the vapor hydration test (VHT). The VHT uses elevated temperature and water vapor to accelerate glass alteration and the formation of secondary phases. Understanding the relationship between glass composition and VHT response is of fundamental and practical interest. However, this relationship is complex, non-linear, and sometimes fairly variable, posing challenges in identifying the distinct effect of individual oxides on VHT response. Here, we leveragemore » a dataset comprising 654 Hanford low-activity waste (LAW) glasses across a wide compositional envelope and employ various machine learning techniques to explore this relationship. We find that Gaussian process regression (GPR), a nonparametric regression method, yields the highest predictive accuracy. By utilizing the trained model, we discern the influence of each oxide on the glasses’ VHT response. Moreover, we discuss the trade-off between underfitting and overfitting for extrapolating the material performance in the context of sparse and heterogeneous datasets.« less

Metal cation identity determines the zeolite topology. Framework topology determines the total zeolite cationic content. Potassium predominantly counterbalances Al anions; sodium and calcium are predominantly structure-directing agents.

Not provided.

Silicate glasses have no long-range order and exhibit a short-range order that is often fairly similar to that of their crystalline counterparts. Hence, the out-of-equilibrium nature of glasses is largely encoded in their medium-range order. However, the ring size distribution—the key feature of silicate glasses’ medium-range structure—remains invisible to conventional experiments and, hence, is largely unknown. Here, by combining neutron diffraction experiments and force-enhanced atomic refinement simulations for two archetypical silicate glasses, we show that rings of different sizes exhibit a distinct contribution to the first sharp diffraction peak in the structure factor. On the basis of these results, wemore » demonstrate that the ring size distribution of silicate glasses can be determined solely from neutron diffraction patterns, by analyzing the shape of the first sharp diffraction peak. This method makes it possible to uncover the nature of silicate glasses’ medium-range order.« less

Not provided.

Abstract Quantitative Structure Property Relationship (QSPR) analysis based on molecular dynamics (MD) simulations is a promising approach for establishing the composition‐property relationships of glasses and other materials with complex structures. A series of 20 borosilicate, aluminosilicate, and boroaluminosilicate glasses have been modeled using MD simulations with recently developed effective potentials. Short‐ and medium‐range structures of these glasses were analyzed and, based on the structural information, QSPR analysis of the initial dissolution rates ( r ₀ ) of these glasses that were measured at 90°C and pH 9 by using various structural descriptors such as percentage of bridging oxygen species, networkmore » connectivity, and average ring size. The structural descriptor, F _net , which contains both energetic information such as single bond strength and structural information such as cation coordination number and Q _n distribution, was also used. It was found that while the overall network connectivity, average ring size and F _net provide reasonable correlations with r ₀ of studied glasses, F _net gives the best correlation among the descriptors. For glasses that show incongruent dissolution, it was found that modification of glass compositions to account for preferential release of modifier cations is necessary to achieve best correlations. The findings were discussed with results of recent studies on evaluating the compositional dependence of glass dissolution behavior using the topological‐constraints‐based models.« less

Not provided.

Alkaline industrial wastes (e.g., slags: ordered crystalline solids, and fly ashes: disordered solids) represent abundant reservoirs of elements such as silicon and calcium. Rapid elemental extractions from these wastes, however, have often relied on the use of “stoichiometric additives” (i.e., acids or bases). Herein, we demonstrate that acoustic stimulation enhances the release of network-forming Si species from crystalline blast furnace slags and amorphous fly ashes at reaction temperatures less than 65 °C. These additive-free enhancements are induced by cavitation processes which reduce the apparent activation energy of solute dissolution (E_a, kJ/mol) by up to 40% as compared to unstimulated conditions.more » Because of the reduction in the apparent activation energy, acoustic stimulation features an energy intensity that is up to 80% lower in promoting dissolution, as compared to other additive-free methods such as enhancing the solute’s surface area, introducing heat, or convectively mixing the solvent. Based on atomic topology analysis, we show that the reduction in apparent dissolution activation energy upon acoustic stimulation scales with the number of weak topological constraints per atom in the atomic network of the dissolving solute, independent of their ordered or disordered nature. This suggests that sonication breaks the weakest constraints in the solute’s atomic network, which, in turn, facilitates dissolution. Furthermore, the results suggest the ability of acoustic stimulation to enhance waste utilization and circularity, by enabling efficient resource extraction from industrial wastes.« less

Alkali-silica reaction (ASR) is a significant cause of the degradation of concrete structures. ASR results from the dissolution of reactive silicate aggregates and the subsequent formation of damaging, expansive ASR gels. Despite the prevalence of ASR, so far only lithium-based chemical admixtures have been shown to be successful in mitigating its deleterious effects. Herein, dissolved calcium nitrate (Ca(NO₃)₂: CN) is demonstrated to reduce ASR-induced expansion caused by the use of sodium borosilicate (NBS) glass as a model reactive aggregate. The significance of reductions of NBS-glass dissolution and mortar-bar expansion rates is discussed, with special focus on highlighting the mechanism bymore » which calcium nitrate mitigates ASR, i.e., by the inhibition of aggregate dissolution. This study reveals a new and cost-effective pathway to suppress aggregate dissolution and ASR in concrete based on the dosage of soluble alkaline-earth additives.« less

Not provided.