Marcel Potuzak

Topological Principles of Borosilicate Glass Chemistry

Borosilicate glasses display a rich complexity of chemical behavior depending on the details of their composition and thermal history. Noted for their high chemical durability and thermal shock resistance, borosilicate glasses have found a variety of important uses from common household and laboratory glassware to high-tech applications such as liquid crystal displays. In this paper, we investigate the topological principles of borosilicate glass chemistry covering the extremes from pure borate to pure silicate end members. Based on NMR measurements, we present a two-state statistical mechanical model of boron speciation in which addition of network modifiers leads to a competition between the formation of nonbridging oxygen and the conversion of boron from trigonal to tetrahedral configuration. Using this model, we derive a detailed topological representation of alkali-alkaline earth-borosilicate glasses that enables the accurate prediction of properties such as glass transition temperature, liquid fragility, and hardness. The modeling approach enables an understanding of the microscopic mechanisms governing macroscopic properties. The implications of the glass topology are discussed in terms of both the temperature and thermal history dependence of the atomic bond constraints and the influence on relaxation behavior. We also observe a nonlinear evolution of the jump in isobaric heat capacity at the glass transition when substituting SiO(2) for B(2)O(3), which can be accurately predicted using a combined topological and thermodynamic modeling approach.

Irreversibility of Pressure Induced Boron Speciation Change in Glass

It is known that the coordination number (CN) of atoms or ions in many materials increases through application of sufficiently high pressure. This also applies to glassy materials. In boron-containing glasses, trigonal BO3 units can be transformed into tetrahedral BO4 under pressure. However, one of the key questions is whether the pressure-quenched CN change in glass is reversible upon annealing below the ambient glass transition temperature (Tg). Here we address this issue by performing 11B NMR measurements on a soda lime borate glass that has been pressure-quenched at ~0.6 GPa near Tg. The results show a remarkable phenomenon, i.e., upon annealing at 0.9Tg the pressure-induced change in CN remains unchanged, while the pressurised values of macroscopic properties such as density, refractive index, and hardness are relaxing. This suggests that the pressure-induced changes in macroscopic properties of soda lime borate glasses compressed up to ~0.6 GPa are not attributed to changes in the short-range order in the glass, but rather to changes in overall atomic packing density and medium-range structures.

Communication: Resolving the vibrational and configurational contributions to thermal expansion in isobaric glass-forming systems

A fundamental understanding of isobaric thermal expansion behavior is critical in all areas of glass science and technology. Current models of glass transition and relaxation behavior implicitly assume that the thermal expansion coefficient of glass-forming systems can be expressed as a sum of vibrational and configurational contributions. However, this assumption is made without rigorous theoretical or experimental justification. Here we present a detailed statistical mechanical analysis resolving the vibrational and configurational contributions to isobaric thermal expansion and show experimental proof of the separability of thermal expansion into vibrational and configurational components for Corning Jade glass.

Influence of Aluminum Speciation on the Stability of Aluminosilicate Glasses against Crystallization

In this letter, we investigate the correlation between glass microstructure and glass stability (GS) in soda lime aluminosilicates. We find a loss of GS (i.e., an onset of crystallization) in the glasses above a critical concentration of Al2O3 when heating at the standard rate of 20 K/min. This loss in GS may be attributed to formation of five-fold coordinated Al species when [Al2O3]/[Na2O] > 1. The primary crystalline phase is identified as nepheline, in which Al exists in four-fold coordination. This implies that the five-fold coordinated Al is energetically less stable compared to Al in a tetrahedral environment.

Are the dynamics of a glass embedded in its elastic properties

The low temperature dynamics of glass are critically important for many high-tech applications. According to the elastic theory of the glass transition, the dynamics of glass are controlled by the evolution of shear modulus. In particular, the elastic shoving model expresses dynamics in terms of an activation energy required to shove aside the surrounding atoms. Here, we present a thorough test of the shoving model for predicting the low temperature dynamics of an oxide glass system. We show that the nonequilibrium viscosity of glass is governed by additional factors beyond changes in shear modulus.

Role of elastic deformation in determining the mixed alkaline earth effect of hardness in silicate glasses

Glasses deform permanently as a result of indentation and the total resistance to deformation consists of three individual resistances, i.e., those to elastic deformation, densification, and plastic flow. The link between Vickers hardness and the resistances to densification and plastic flow has been investigated previously, but the link between the resistance to elastic deformation and hardness has not yet been studied. In this work, we investigate the link between elastic deformation during indentation and Vickers hardness in a series of mixed magnesium-barium boroaluminosilicate glasses. We show that the mixed alkaline earth effect manifests itself as deviations from linearity in shear modulus, Poissons ratio, glass transition temperature, liquid fragility index, hardness, volume of densification, and volume of plastic flow. We find no correlation between the elastic part of the indentation and hardness, and we thus infer that elastic deformation does not play a dominant role in determining the mixed ...

Laser texturing of doped borosilicate glasses

We describe a novel process of laser-assisted fabrication of surface structures on doped oxide glasses with heights reaching 10 - 13% of the glass thickness. This effect manifests itself as a swelling of the irradiated portion of the glass, and occurs in a wide range of glass compositions. The extent of such swelling depends on the glass base composition. Doping with Fe, Ti, Co, Ce, and other transition metals allows for adjusting the absorption of the glass and maximizing the feature size. In the case of bumps grown on borosilicate glasses, we observe reversible glass swelling and the bump height can increase or decrease depending on whether the consecutive laser pulse has higher or lower energy compared with the previous one. To understand the hypothetical mechanism, which includes laser heating of glass, glass melting, and directional flow, we explored density, refractive index, fictive temperature, and phase separation dynamics.

A partial molar volume for ZnO in silicate melts

Abstract The densities of 8 Zn-bearing silicate melts have been determined, in equilibrium with air, in the temperature range of 1363 to 1850 K. The compositional joins investigated [sodium disilicate (NS2)-ZnO; anorthite-diopside 1 bar eutectic (AnDi)-ZnO; and diopside-petedunnite] were chosen based on the pre-existing experimental density data set, on their petrological relevance, and in order to provide a test for significant compositionally induced variations in the structural role of ZnO. The ZnO concentrations investigated range up to 25 mol% for sodium disilicate, 20 mol% for the anorthitediopside 1 atm eutectic, and 25 mol% for petedunnite. Molar volumes and expansivities have been derived for all melts. The molar volumes of the present liquids decrease with increasing ZnO content. The partial molar volume of ZnO derived here from the volumetric measurements for each binary system is the same within error. A multicomponent fit to the volumetric data for all compositions yields a value of 13.59(0.55) cm3/mol at 1500 K. We find, herewith, no volumetric evidence for compositionally induced coordination number variations for ZnO in alkali-bearing vs. alkali-free silicate melts nor for Al-free vs. Al-bearing silicate melts.