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This study focuses on understanding the relationship between iron redox, composition, and heat‐treatment atmosphere in nepheline‐based model high‐level nuclear waste glasses. Glasses in the Na2O–Al2O3–B2O3–Fe2O3–SiO2 system with varying Al2O3/Fe2O3 and Na2O/Fe2O3 ratios have been synthesized by melt‐quench technique and studied for their crystallization behavior in different heating atmospheres—air, inert (N2), and reducing (96%N2–4%H2). The compositional dependence of iron redox chemistry in glasses and the impact of heating environment and crystallization on iron coordination in glass‐ceramics have been investigated by Mossbauer spectroscopy and vibrating sample magnetometry. While iron coordination in glasses and glass‐ceramics changed as a function of glass chemistry, the heating atmosphere during crystallization exhibited minimal effect on iron redox. The change in heating atmosphere did not affect the phase assemblage but did affect the microstructural evolution. While glass‐ceramics produced as a result of heat treatment in air and N2 atmospheres developed a golden/brown colored iron‐rich layer on their surface, those produced in a reducing atmosphere did not exhibit any such phenomenon. Furthermore, while this iron‐rich layer was observed in glass‐ceramics with varying Al2O3/Fe2O3 ratio, it was absent from glass‐ceramics with varying Na2O/Fe2O3 ratio. An explanation of these results has been provided on the basis of kinetics of diffusion of oxygen and network modifiers in the glasses under different thermodynamic conditions. The plausible implications of the formation of iron‐rich layer on the surface of glass‐ceramics on the chemical durability of high‐level nuclear waste glasses have been discussed.

2D monolayers represent some of the most deformable inorganic materials, with bending stiffnesses approaching those of lipid bilayers. Achieving 2D heterostructures with similar properties would enable a new class of deformable devices orders of magnitude softer than conventional thin-film electronics. Here, by systematically introducing low-friction twisted or heterointerfaces, interfacial engineering is leveraged to tailor the bending stiffness of 2D heterostructures over several hundred percent. A bending model is developed and experimentally validated to predict and design the deformability of 2D heterostructures and how it evolves with the composition of the stack, the atomic arrangements at the interfaces, and the geometry of the structure. Notably, when each atomic layer is separated by heterointerfaces, the total bending stiffness reaches a theoretical minimum, equal to the sum of the constituent layers regardless of scale of deformation-lending the extreme deformability of 2D monolayers to device-compatible multilayers.

We report on the influence of Fe2O3 on the crystallization kinetics of nepheline (Na2O·Al2O3·2SiO2)-based sodium aluminosilicate glasses. A series of glasses with varying Al2O3/Fe2O3 content were synthesized in the system 25Na2O–(25–x) Al2O3–xFe2O3–50SiO2 (x varies between 0 and 5 mol%) through melt-quench technique. A systematic set of experiments were performed to elucidate the influence of iron speciation (Fe2+/Fe3+) on the crystallization kinetics of these glasses including: (1) obtaining the details of nonisothermal crystallization kinetics by differential scanning calorimetry, (2) determining the influence of heat treatment on the structure and iron coordination in glasses by X-ray photoelectron spectroscopy and wet chemistry, and (3) following the crystalline phase evolution in glasses in air and inert environments by X-ray diffraction and scanning electron microscopy. The crystallization of two polymorphs of NaAlSiO4—carnegieite (orthorhombic) and nepheline (hexagonal)—was observed in all the glasses, wherein the incorporation of iron promotes the formation of nepheline over carnegieite while shifting the crystallization mechanism from surface to volume. The influence of environment (air versus inert) and iron content on the crystallization kinetics of these glasses is contextualized from the perspective of the devitrification problem usually observed in sodium- and alumina-rich high level nuclear waste glasses.