This study examines the incorporation of TiO₂ into sodium borosilicate glasses and its effect on the formation of glassy and crystalline microphases. Glasses in the composition range: 7Na₂O–23B₂O₃–(70 ‐ X)SiO₂–XTiO₂ (where X = 0–14.6 mol.% TiO₂) which exhibit phase separation were investigated. Raman studies confirm the formation of two different TiO₂ coordinations depending on the molar content of TiO₂. Thermal properties of glasses are unaffected by TiO₂ addition. The domain size of microphase development in TiO₂‐containing glass indicates competition between phase separation and crystallization. Enrichment of titanium on the interphase between glassy microphases reduces the mass transfer and consequently limits the growth rate of glassy phases. This competes with the formation of anatase for which a nucleation‐controlled mechanism is proposed.

Excursion sets of Gaussian random fields are used to model the three-dimensional (3D) morphology of differently manufactured porous glasses (PGs), which vary with respect to their mean pore widths measured by mercury intrusion porosimetry. The stochastic 3D model is calibrated by means of volume fractions and two-point coverage probability functions estimated from tomographic image data. Model validation is performed by comparing model realizations and image data in terms of morphological descriptors which are not used for model fitting. For this purpose, we consider mean geodesic tortuosity and constrictivity of the pore space, quantifying the length of the shortest transportation paths and the strength of bottleneck effects, respectively. Additionally, a stereological approach for parameter estimation is presented, i.e., the 3D model is calibrated using merely two-dimensional (2D) cross-sections of the 3D image data. Doing so, on average, a comparable goodness of fit is achieved as well. The variance of the calibrated model parameters is discussed, which is estimated on the basis of randomly chosen, individual 2D cross-sections. Moreover, interpolating between the model parameters calibrated to differently manufactured glasses enables the predictive simulation of virtual but realistic PGs with mean pore widths that have not yet been manufactured. The predictive power is demonstrated by means of cross-validation. Using the presented approach, relationships between parameters of the manufacturing process and descriptors of the resulting morphology of PGs are quantified, which opens possibilities for an efficient optimization of the underlying manufacturing process. Published by the American Physical Society 2024

Research and development in the field of glass-based laser additive manufacturing continues to receive significant interest within scientific and industrial contexts. In particular, powder bed fusion by laser radiation (PBF-LB) enables the additive manufacturing of porous and vitrified, complex three-dimensional components. The present study investigates the glass morphology that can be achieved using PBF-LB for components made from alkali borosilicate glass. The investigations focus on the comprehensive analysis of the entire process window, including the characterisation of porous and molten glass morphology. In particular, the influence of different laser-beam diameters, which are achieved through defocusing, and the variation in volume energy density are examined in detail and compared with conventional shaping. It was determined that the process of mechanically stable shaping is constrained to temperatures above the softening temperature and relative component densities within the range of ρrel = 37.8…94.2%. Furthermore, it has been demonstrated that the process-related line-like energy input results in the formation of characteristic vitrification strands. This research contributes to the overall understanding of the producible glass morphology and the process limitations of the PBF-LB process. In addition, the entire range of glass morphologies, ranging from open-pored to closed-melt configurations, could be analysed for the first time.

A new preparation concept of a partially porous solid-state bilayer electrolyte (BE) for high-temperature sodium-ion batteries has been developed. The porous layer provides mechanical strength and is infiltrated with liquid and highly conductive NaAlCl₄ salt, while the dense layer prevents short circuits. Both layers consist, at least partially, of Na-β-alumina. The BEs are synthesized by a three-step procedure, including a sol-gel synthesis, the preparation of porous, calcined bulk material, and spin coating to deposit a dense layer. A detailed study is carried out to investigate the effect of polyethylene oxide (PEO) concentration on pore size and crystallization of the bulk material. The microstructure and crystallographic composition are verified for all steps via mercury intrusion, X-ray diffraction, and scanning electron microscopy. The porous bulk material exhibits an unprecedented open porosity for a Na_xAlO_y bilayer-system of ≤57% with a pore size of ≈200–300 nm and pore volume of ≤0.3 cm³∙g⁻¹. It contains high shares of crystalline α-Al₂O₃ and Na-β-alumina. The BEs are characterized by impedance spectroscopy, which proved an increase of ionic conductivity with increasing porosity and increasing Na-β-alumina phase content in the bulk material. Ion conductivity of up to 0.10 S∙cm⁻¹ at 300 °C is achieved.