A template-free, more environmentally friendly approach for glass micro-texturing.

Micron and nanometer size textured silicate glass surfaces are of interest in consumer electronics, photovoltaics, and biosensing applications. Typically, texturing glass surfaces requires applying a patterned mask or a pre-etching treatment (e.g. sandblasting) on the glass substrate, followed by a mask transferring or etching process using a fluoride-containing compound. The major challenges of such a process are the complexity and cost of masking, and the safety and environmental concerns around the usage and disposal of hydrofluoric acid. Here, we describe a template-free method to construct micron-sized and submicron-sized texture on isotropic glass surfaces in one step. The new texturing mechanisms are well supported by experimental data and peridynamic simulations. With this novel strategy, the etchant uses fluoride-free chemicals such as citric acid to texture silicate glass. Etchant concentration, etch temperature, time, and additives are the primary parameters that dictate the texturing process. Surface feature size and depth can be independently controlled by tuning the leaching and chemical polishing process. We hope this study can trigger more research on novel and more environmentally friendly texturing of isotropic materials.

Ab Initio Study of Hydrolysis Effects in Single and Ion-Exchanged Alkali Aluminosilicate Glasses.

Hydrolysis in alkali-doped aluminosilicate glasses is one of the most complicated mechanisms in glass science. There remain many fundamental and unresolved issues with implications on their potential applications. Herein, we address this challenge by carrying out detailed calculations on the structure and properties of both anhydrate (dry) and hydrated alkali aluminosilicate glasses on carefully constructed models. Specifically, the Na-, (Na + K)-, and K-doped aluminosilicate glasses with compositions (SiO2)0.6(Al2O3)0.2(Na2O)0.2 - x(K2O)x (x = 0, 0.10, and 0.20) are simulated using ab initio molecular dynamics (AIMD). The local short- and intermediate-range order in these glasses is analyzed in terms of atomic pair distribution, coordination number, bond length, and bond angle distributions to delineate the subtle variations due to different alkali sizes and hydrolysis. The electronic structure, interatomic bonding, mechanical, and optical properties for these models are calculated and validated with available experimental data. We use the novel concept of total bond order density (TBOD), the quantum mechanically derived metric, to characterize the internal cohesion and strength in the simulated glasses. Detailed analysis of the hydrolysis mechanism enables us to provide information on the complex interplay of various participating elements and their interactions at the atomic level. Such detailed information provides a new platform of knowledge, which is crucial for understanding the issues related to glass corrosion and durability, and ways and means for their special applications in commercial glass products. Both undissociated molecular water and dissociated water in the form of hydroxyl groups exist in the hydrated models in the presence of alkali ions. For the first time, we observed the opposite mixed alkali effect in the Poisson's ratio for anhydrate and hydrated glasses.

Glass-activated regeneration of volumetric muscle loss.

Volumetric muscle loss (VML) resulting from injuries to skeletal muscles has profound consequences in healthcare. Current VML treatment based on the use of soft materials including biopolymers and decellularized extracellular matrix (dECM) is challenging due to their incapability of stimulating the formation of satellite cells (SCs), muscle stem cells, which are required for muscle regeneration. Additional stem cells and/or growth factors have to be incorporated in these constructs for improved efficacy. Here we report an approach by using bioactive glasses capable of regenerating VML without growth factors or stem cells. One silicate and two borate compositions with different degradation rates (2.4% for silicate 45S5; 5.3% and 30.4% for borate 8A3B and 13-93B3, respectively, in simulated body fluid (SBF) at 37 °C for 30 days) were used for this study. Our in vitro models demonstrate the ability of ions released from bioactive glasses in promoting angiogenesis and stimulating cells to secrete critical muscle-related growth factors. We further show the activation of SCs and the regeneration of skeletal muscles in a rat VML model. Considering these promising results, this work reveals a potentially simple and safe approach to regenerating skeletal muscle defects. STATEMENT OF SIGNIFICANCE: (1) This is the first report on an inorganic material used in skeletal muscle regeneration through in vitro and in vivo models. (2) Bioactive glass is found to activate the production of satellite cells (SCs), muscle stem cells, without the incorporation of extra stem cells or growth factors. (3) The work represents a simple, safe, low-cost yet efficient means for healing muscle defects.

Ab Initio Modeling of Structure and Properties of Single and Mixed Alkali Silicate Glasses.

A density functional theory (DFT)-based ab initio molecular dynamics (AIMD) has been applied to simulate models of single and mixed alkali silicate glasses with two different molar concentrations of alkali oxides. The structural environments and spatial distributions of alkali ions in the 10 simulated models with 20% and 30% of Li, Na, K and equal proportions of Li-Na and Na-K are studied in detail for subtle variations among the models. Quantum mechanical calculations of electronic structures, interatomic bonding, and mechanical and optical properties are carried out for each of the models, and the results are compared with available experimental observation and other simulations. The calculated results are in good agreement with the experimental data. We have used the novel concept of using the total bond order density (TBOD), a quantum mechanical metric, to characterize internal cohesion in these glass models. The mixed alkali effect (MAE) is visible in the bulk mechanical properties but not obvious in other physical properties studied in this paper. We show that Li doping deviates from expected trend due to the much stronger Li-O bonding than those of Na and K doping. The approach used in this study is in contrast with current studies in alkali-doped silicate glasses based only on geometric characterizations.

Nanoscale effects of silica particle supports on the formation and properties of TiO2 nanocatalysts.

Small TiO2 crystals in the anatase phase are in high demand as photocatalysts. Stable TiO2 crystals in the anatase phase were obtained using a silica nanoparticle as a support. The focus of this study was to investigate the nanoscale effect of the silica support on the formation and properties of small anatase crystals. The experiments were carried out using powder X-ray diffraction, differential thermal analysis, transmission electron microscopy, and energy dispersion spectroscopy. The results showed that the size of the silica support played a crucial role in crystallization of TiO2 and regulation of TiO2 properties, including phase transition, crystal size, thermodynamic property and catalytic activity. A nanoscale curvature model of the spherical silica support was proposed to explain these size effects. Finally, the developed TiO2 catalysts were applied to the oxidation of methanol using a high-throughput photochemical reactor. The size effect of the silica supports on the TiO2 catalytic efficiency was demonstrated using this system.

Silica nanoparticles for template synthesis of supported Pt and Pt-Ru electrocatalysts.

A simple method was developed for the template synthesis of silica-supported Pt and bimetallic Pt-Ru nanocatalysts. The synthesis used amine-functionalized silica nanoparticles as both template and support for the formation of metal nanoclusters with a precise composition, narrow size distribution, uniform shape and close spatial association. The nanocatalysts were compared with a commercial Pt-C catalyst used in fuel cell applications. Electrochemical measurements of methanol oxidation demonstrated higher catalytic activity for silica-supported Pt nanocatalysts and a reduced CO poisoning effect from co-templating of Pt and Ru.