Morten Mattrup Smedskjær

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.

Structure and properties of sodium aluminosilicate glasses from molecular dynamics simulations.

Addition of alumina to sodium silicate glasses considerably improves the mechanical properties and chemical durability and changes other properties such as ionic conductivity and melt viscosity. As a result, aluminosilicate glasses find wide industrial and technological applications including the recent Corning(®) Gorilla(®) Glass. In this paper, the structures of sodium aluminosilicate glasses with a wide range of Al∕Na ratios (from 1.5 to 0.6) have been studied using classical molecular dynamics simulations in a system containing around 3000 atoms, with the aim to understand the structural role of aluminum as a function of chemical composition in these glasses. The short- and medium-range structures such as aluminum coordination, bond angle distribution around cations, Q(n) distribution (n bridging oxygen per network forming tetrahedron), and ring size distribution have been systematically studied. In addition, the mechanical properties including bulk, shear, and Youngs moduli have been calculated and compared with experimental data. It is found that aluminum ions are mainly four-fold coordinated in peralkaline compositions (Al∕Na < 1) and form an integral part of the rigid silicon-oxygen glass network. In peraluminous compositions (Al∕Na > 1), small amounts of five-fold coordinated aluminum ions are present while the concentration of six-fold coordinated aluminum is negligible. Oxygen triclusters are also found to be present in peraluminous compositions, and their concentration increases with increasing Al∕Na ratio. The calculated bulk, shear, and Youngs moduli were found to increase with increasing Al∕Na ratio, in good agreement with experimental data.

Near-infrared emission from Eu–Yb doped silicate glasses subjected to thermal reduction

Quantum cutting (QC) is a promising approach for enhancing the energy conversion efficiency of solar cells since it allows for conversion of one ultraviolet photon from the sun into two near-infrared photons with energy comparable to the band gap of silicon solar cells. We find that QC can occur by cooperative energy transfer from Eu2+ to Yb3+ in soda-lime-silicate glasses subjected to thermal reduction around the glass transition temperature. Besides the QC effect, the thermal reduction results in improvement of surface performances, e.g., hardness. This synergy effect potentially makes the thermally reduced glass an ideal solar cell substrate material.

Impact of network topology on cationic diffusion and hardness of borate glass surfaces

The connection between bulk glass properties and network topology is now well established. However, there has been little attention paid to the impact of network topology on the surface properties of glass. In this work, we report the impact of the network topology on both the transport properties (such as cationic inward diffusion) and the mechanical properties (such as hardness) of borate glasses with modified surfaces. We choose soda lime borate systems as the object of this study because of their interesting topological features, e.g., boron anomaly. An inward diffusion mechanism is employed to modify the glass surface compositions and hence the surface topology. We show that accurate quantitative predictions of the hardness of the modified surfaces can be made using topological constraint theory with temperature-dependent constraints. Experimental results reveal that Ca(2+) diffusion is most intense in glasses with lowest BO(4) fraction, whereas Na(+) diffusion is only significant when nonbridging oxygens start to form. These phenomena are interpreted in terms of the atomic packing and the local electrostatic environments of the cations.

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.

Mixed alkaline earth effect in the compressibility of aluminosilicate glasses

The mixed modifier effect (MME) in oxide glasses manifests itself as a non-additive variation in certain properties when one modifier oxide species is substituted by another one at constant total modifier content. However, the structural and topological origins of the MME are still under debate. This study provides new insights into the MME by investigating the effect of isostatic compression on density and hardness of mixed MgO/CaO sodium aluminosilicate glasses. This is done using a specially designed setup allowing isostatic compression of bulk glass samples up to 1 GPa at elevated temperature. A mixed alkaline earth effect is found in the compressibility and relative change of hardness, viz., a local maximum of density as a function of Mg/Ca ratio appears following compression, whereas a local minimum of hardness in the uncompressed glasses nearly disappears after compression. Moreover, the densification of these glasses is found to occur at temperatures much below the glass transition temperature, indicating that a non-viscous mechanism is at play. This is further supported by the fact that density relaxes in a stretched exponential manner upon subsequent annealing at ambient pressure with an exponent of ∼0.62. This is close to the Phillips value of 3/5 for relaxation in three dimensions when both short- and long-range interactions are activated.

Ionic diffusion and the topological origin of fragility in silicate glasses

Mass transport in liquids and glass is intimately connected to the structure and topology of the disordered network. To investigate this problem, we measure the ionic diffusivity and fragility of a series of iron-bearing alkali-alkaline earth silicate glasses, substituting different types of alkali and alkaline earth cations while keeping the same ratio of network modifiers. Diffusion is studied around the glass transition temperature (T(g)) under a reducing atmosphere, leading to a reduction of Fe(3+) to Fe(2+), and inward diffusion of the modifier cations. In the SiO(2)-CaO-Fe(2)O(3)-A(2)O (A=Na, K, Rb, or Cs) glass series, we find that the Ca(2+) ions diffuse faster than alkali ions and that the activation energy of the Ca(2+) diffusion decreases with alkali size, a trend that is coincident with a decrease in liquid fragility. We have established a simple model for accurately describing the correlation between the fragility index (m) and T(g) based on a topological consideration of the glass network. The model builds on a temperature-dependent constraint approach where the Vogel temperature serves as a rigidity percolation threshold. This follows from our derivation of the Vogel-Fulcher-Tammann equation of viscosity from the more accurate Mauro-Yue-Ellison-Gupta-Allan equation. The established model provides an excellent prediction of the relationship between fragility and T(g), except for the MgO-containing glass where Mg(2+) is known to play a unique topological role in the network. This trend is in coincidence with the considerably faster inward diffusion of Mg(2+) in comparison to other alkaline earth cations.

Hardness and incipient plasticity in silicate glasses: Origin of the mixed modifier effect

The scaling of Vickers hardness (Hv) in oxide glasses with varying network modifier/modifier ratio is manifested as either a positive or negative deviation from linearity with a maximum deviation at the ratio of about 1:1. In an earlier study [J. Kjeldsen et al., J. Non-Cryst. Solids 369, 61 (2013)], we observed a minimum of Hv in CaO/MgO sodium aluminosilicate glasses at CaO/MgO = 1:1 and postulated that this minimum is linked to a maximum in plastic flow. However, the origin of this link has not been experimentally verified. In this work, we attempt to do so by exploring the links among Hv, volume recovery ratio (VR) and plastic deformation volume (VP) under indentation, glass transition temperature (Tg), Youngs modulus (E), and liquid fragility index (m) in CaO/MgO and CaO/Li2O sodium aluminosilicate glasses. We confirm the negative deviations from linearity and find that the maximum deviation (i.e., the so-called mixed modifier effect) of Hv, Tg, and m is at the modifier ratio of 1:1. These deviation...

Topological Model for Boroaluminosilicate Glass Hardness

*Correspondence: Morten M. Smedskjaer , Section of Chemistry, Aalborg University, Fredrik Bajers Vej 7H, Aalborg 9220, Denmark e-mail: mos@bio.aau.dk For various advanced glass applications, it is important to understand the composition dependence of indentation hardness. Boroaluminosilicate glasses form the basis of many industrial products and they exhibit complex structural behavior due to the mixed networkformer effect. Based on available structural nuclear magnetic resonance data and a previously proposed approach, we here establish a temperature-dependent constraint model of indentation hardness of sodium boroaluminosilicate glasses. The model correctly predicts the trends of hardness with varying Si/Al and Na/B ratios, including local minima and maxima at intermediate compositions. This topological approach is thus proving to be a valuable tool for exploring and designing new boroaluminosilicate glass compositions with tailored hardness.

Unique effects of thermal and pressure histories on glass hardness: Structural and topological origin

The properties of glass are determined not only by temperature, pressure, and composition, but also by their complete thermal and pressure histories. Here, we show that glasses of identical composition produced through thermal annealing and through quenching from elevated pressure can result in samples with identical density and mean interatomic distances, yet different bond angle distributions, medium-range structures, and, thus, macroscopic properties. We demonstrate that hardness is higher when the density increase is obtained through thermal annealing rather than through pressure-quenching. Molecular dynamics simulations reveal that this arises because pressure-quenching has a larger effect on medium-range order, while annealing has a larger effect on short-range structures (sharper bond angle distribution), which ultimately determine hardness according to bond constraint theory. Our work could open a new avenue towards industrially useful glasses that are identical in terms of composition and density, but with differences in thermodynamic, mechanical, and rheological properties due to unique structural characteristics.