Search for: All records

Abstract The sodium aluminosilicate (NAS) glass family is important for many different industrial applications, but glass relaxation has not yet been thoroughly studied in this system. Thermal analysis techniques such as differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC) can provide insight into the enthalpy relaxation of glass by measuring the glass transition temperature (T_g), activation energy, and enthalpy of relaxation. MDSC is mostly used to study nonoxide and lowT_gglasses, and there is much debate about whether the nonreversing heat flow analysis method is accurate. To the authors’ knowledge, this is the first paper using MDSC to study these NAS compositions, and one of few papers to report MDSC on highT_goxide glasses. We report on one set of modulation conditions that obtain a linear response using Lissajous curves, as well as comparing the activation energy calculated from DSC with the enthalpy of relaxation obtained from MDSC. Our results show that the activation energy and enthalpy of relaxation do not give the same compositional minimum in relaxation, and therefore more work is needed to investigate the validity of the nonreversing heat flow approach for highT_goxide glasses. 

Abstract Previous research has shown a consistent discrepancy in the reported structure of alkaline earth aluminosilicate glasses using molecular dynamics (MD) simulations versus nuclear magnetic resonance (NMR) experiments. Past MD results have consistently shown less than 5% five‐coordinated Al units (Al^[5]) in peraluminous glass compositions, but with high fractions of triple‐bonded oxygens (TBO, i.e., triclusters). Experimental results have shown a high fraction of Al^[5]with no direct evidence for TBO. One of the main criticisms associated with high TBO content found in MD‐generated glass structures is the use of classical interatomic potentials. To investigate this issue, we analyze the formation of both TBO and Al^[5]using three independently developed potentials with varying silica content and [Al₂O₃]/[MgO] ratios for the magnesium aluminosilicate (MAS) system. We specifically choose compositions with high ratios of alumina to magnesium oxide as this region is not as commonly explored. Results indicate that Al^[5]charge compensates the Al network in metaluminous compositions (compositions with more Mg than Al) while both TBO and Al^[5]are prevalent in peraluminous ranges (high Al content compositions) to charge balance Al units. From the literature, NMR experiments report MAS glasses with varying Al^[5]fractions and show significant differences for the same reported compositions. When comparing MD results from this work, the fraction of calculated Al^[5]is within the experimental variation found in the literature. This indicates that classical potentials can accurately capture alumina environments and that both Al^[5]and TBO can coexist in relatively high fractions. From the consistency in our results, we conclude that TBOs are inherent to the aluminosilicate glass system and are not simulation artifacts. 

Abstract The impact of microstructure on hardness in phase‐separated calcium aluminosilicate glasses is investigated. Changes in hardness are governed by microstructure deformations that occur during indentation. Phase separation leads to decreased hardness due to the incongruent yielding of the droplet and matrix phases. Moreover, the deformation of microstructures possessing dilute, spherical droplets did not have a significant impact on hardness. Microstructures characterized by concentrated, acicular droplets were found to deform through a process of droplet coalescence. This process absorbs additional energy during yielding and results in glasses that deform through droplet coalescence possessing improved hardness. 

Abstract The field strength (FS) effect of six different network modifiers on the elastoplastic properties of aluminoborosilicate glasses was explored using a volumetric recovery study. This work, in conjunction with Part I, explored the intersection of hardness, crack resistance, and other physical properties with glass elasticity. Results showed that (1) the elastic volume fraction decreased with FS for both the alkali and alkaline earth (AE) glasses; (2) the Poisson's ratio did not trend with pile‐up or shear flow volume fraction; (3) the elastic‐to‐plastic deformation ratio increased with applied load and decreased with modifier FS for both the alkali and AE glasses; and (4) an increase in plasticity correlated with increased hardness, crack resistance, and elastic moduli. 

Abstract The modifier field strength (FS) is believed to play an important role in determining the elastic–plastic responses of aluminoborosilicate (ABS) glasses, but its effect is not well understood. Three novel alkali and three alkaline earth (AE) ABS compositions were created for this study which is the first part of two studies that explored the elastoplastic responses of these glasses. Six compositions were designed using different network modifiers (NWMs) to cover a range of cation FS. The glasses were also designed such that the concentrations of NWM and Al₂O₃were similar, which maximized the three‐coordinated boron fraction in the network. It is well known that modifier FS can affect the coordination number (CN) of Al and B in an ABS glass structure, for example, a higher FS modifier can promote B³ → B⁴and higher [Al^5,6], but the degree of this depends on network former (NWF) ratios. Previous work used solid‐state NMR spectroscopic analysis on the current glasses to find that there was variation between [B⁴] and [Al⁴] between the two glass series (alkali vs. AE) but that was attributed to synthesis factors and no trend with FS was associated with the varying NWF CN. Further,²⁹Si ssNMR showed no evidence of NBOs which made sense based on composition. The conclusion, therefore, was that there was a far greater correlation with modifier FS for the increased mechanical and physical properties rather than the CN of Al and B. Part I of the current work focused on the elastic moduli, Poisson's ratio, the indentation size effect (ISE), and the bow‐in parameter. This part laid out the foundation to investigate the intersection of these elastoplastic properties with hardness and crack resistance as a function of NWM FS. Results showed that: (i) the Young's, bulk, and shear moduli increased with modifier FS, whereas Poisson's ratio did not trend with FS; (ii) the alkali glasses had a significantly higher magnitudes of ISE compared to the AE glasses; and (iii) the bow‐in parameter was load dependent and decreased with modifier FS at the highest indentation load. 

Abstract The nonexponential relaxation behavior of glass is governed by the dimensionless stretching exponent,β, which is typically assumed to be a constant but is more accurately described as a function of temperature. Herein, relaxation calculations of glassy materials are undertaken via an iterative differential equation‐based algorithm to determine when the use of a temperature‐dependent (or dynamic) stretching exponent is required to capture the industrially relevant evolution of fictive temperature components, which is necessary for process engineering. Results reveal a range of liquid fragility index (m) in which a staticβdescription is roughly equivalent to the behavior observed with a dynamicβ. However, fast primary (α) relaxation modes demonstrate unique behavior in systems exhibiting excessively strong or fragile liquid behavior when a temperature‐dependent stretching exponent is considered. In this special issue dedicated to the International Year of Glass, we also provide broader perspectives regarding the importance and impact of a temperature‐dependentβ. 

Abstract Glasses with nanoscale phase separation have the potential to possess improved hardness and fracture toughness while maintaining their optical transparency. Here we present the results of isothermal heat treatments of phase‐separated calcium aluminosilicate glasses. Our results indicate that a transition from Lifshitz–Slozof–Wagner (LSW)‐type kinetics to a diffusion‐controlled pseudo‐coalescence mechanism occurs at ~17% droplet volume fraction, which results in the droplets becoming increasingly elongated and interconnected. The activation barrier for both mechanisms suggests that calcium diffusion is the underlying means for the coarsening of the silica‐rich domains. Simple approximations show the transition cannot be explained by Brownian motion or Van der Waals attraction between domains, and instead suggest various osmotic forces may be responsible. 

Abstract Although the interactions among glass formers and modifiers, for example, connectivity and charge distribution, have been studied extensively in oxide glasses, the impact of a particular modifier species on the mechanical performance of aluminoborosilicate (ABS) glasses is not well understood. This work compares the indentation properties of six ABS glasses, each of which contains a different network modifier (NWM) with varying field strength (FS). Three alkali and three alkaline earth ABS glasses were designed with low NWM content and [NWM] ≈ [Al₂O₃], to test the modifier FS effect at low concentrations and to maximize three‐coordinated boron. It has been found that both hardness and crack resistance increase with increasing FS in these ABS systems, which is surprising in the context of historical reports. Using¹¹B,²⁷Al, and²⁹Si solid‐state nuclear magnetic resonance, this work provides evidence of how charge distributions differ as a function of NWM species, and how this relates to the observed indentation behaviors. 

Abstract Glass properties are governed by the interplay between network formers and network modifiers; for a given composition of network formers, the ratio of different cationic modifiers compensating the anionic species in the network has a profound effect, which is often nonlinear, called a mixed modifier effect (MME). We have investigated the MME of sodium (Na) and calcium (Ca) in an aluminosilicate (NCAS) glass series following the formula [Na₂O]_30−x[CaO]_x[Al₂O₃]₁₀[SiO₂]₆₀, wherex = 0, 7.5, 15, 22.5, and 30. A nonadditive trend was observed in hardness and indentation toughness, with aqueous corrosion resistance exhibiting a shift from incongruent to congruent corrosion, whereas the network structure determined by molecular dynamics simulations revealed no significant trend with composition. Additionally, the NCAS glass containing both [Na₂O] and [CaO] within an intermediate range exhibited superior resistance to wear at high humidity, a clear MME phenomenon previously only observed in soda–lime silica. 

Abstract Glass for pharmaceutical packaging requires high chemical durability for the safe storage and distribution of newly developed medicines. In borosilicate pharmaceutical glasses which typically contain a mixture of different modifier ions (alkali or alkaline earth), the dependence of the chemical durability on alkaline earth oxide concentrations is not well understood. Here, we have designed a series of borosilicate glasses with systematic substitutions of CaO with MgO while keeping their total concentrations at 13 mol% and a fixed Na₂O concentration of 12.7 mol%. We used these glasses to investigate the influence ofR = [MgO]/([MgO] + [CaO]) on the resistance to aqueous corrosion at 80°C for 40 days. It was found that this type of borosilicate glass undergoes both leaching of modifier ions through an ion exchange process and etching of the glass network, leading to dissolution of the glass surface. Based on the concentration analysis of the Si and B species dissolved into the solution phase, the dissolved layer thickness was found to increase from ~100 to ~170 nm asRincreases from 0 to 1. The depth profiling analysis of the glasses retrieved from the solution showed that the concentration of modifier ions (Na⁺, Ca²⁺, and Mg²⁺) at the interface between the solution and the corroded glass surface decreased to around 40%–60% of the corresponding bulk concentrations, regardless ofRand the leaching of modifier cations resulted in a silica‐rich layer in the surface. The leaching of Ca²⁺and Mg²⁺ions occurred within ~50 and <25 nm, respectively, from the glass surface and this thickness was not a strong function ofR. The leaching of Na⁺ions varied monotonically; the thickness of the Na⁺depletion layer increased from ~100 nm atR = 0 to ~200 nm atR = 1. Vibrational spectroscopy analysis suggested that the partial depletion of the ions may have caused some degree of the network re‐arrangement or re‐polymerization in the corroded layer. Overall, these results suggested that for the borosilicate glass, replacing [CaO] with [MgO] deteriorates the chemical durability in aqueous solution.