The mixed modifier effect (MME) is one of the most challenging puzzles in the field of oxide glasses, as there exists no universal quantitative theoretical model for accurately describing and predicting the nonlinear deviation of property values. In this paper, pairwise and ternary interactions are examined experimentally to understand the MME in a series of aluminosilicate glasses. By keeping the glass network former concentration constant and adjusting the molar ratios of three network modifiers (Na2O, K2O, and CaO), the MMEs in glass transition temperature (
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−
- Award ID(s):
- 2011410
- PAR ID:
- 10433619
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Journal of the American Ceramic Society
- Volume:
- 106
- Issue:
- 11
- ISSN:
- 0002-7820
- Page Range / eLocation ID:
- p. 6541-6554
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Mixed modifier effect in Na 2 O·K 2 O·CaO aluminosilicate glasses: Pairwise and ternary interactionsmore » « less
Abstract T g), Vickers hardness (H v), and activation energy (E a) for aqueous dissolution for each modifier cation are investigated. We examine whether a pairwise interaction model is sufficient, or if ternary interactions also need to be included to predict the MME in these aluminosilicate glass systems. This work reveals that the pairwise model can be used to predict the MME forT gin complex multiple‐modifier glass systems using only two‐body interaction factors. However, ternary mixed‐modifier interactions are present in other properties such asH vandE a. -
more » « less
Abstract Resorbable glasses with nominal molar compositions of 20Na2O·30[(1−
x )CaO·x SrO]∙50P2O5, wherex = 0, 0.25, 0.50, 0.75, and 1, were prepared and characterized. With the replacement of CaO by SrO, the molar volume, refractive index, and coefficient of thermal expansion increased, and the glass transition temperature, crystallization temperature, and viscosity decreased. The replacement of CaO by SrO decreased the dissolution rate in 37°C water by nearly an order of magnitude. Resorbable glass fibers drawn from melts of the 20Na2O·30CaO·50P2O5glass exhibited decreasing transmission of laser light (632 nm) in a predictable way as the fiber dissolved in a phosphate buffer solution. This demonstrated that these glasses could be used to produce resorbable fibers for temporary biosensing or therapeutic applications. -
more » « less
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 of
R = [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 asR increases 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 ofR and 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. -
more » « less
Abstract Topological constraint theory (TCT) has enabled the prediction of various properties of oxide glasses as a function of their composition and structure. However, the robust application of TCT relies on accurate knowledge of the network structure and topology. Here, based on classical molecular dynamics simulations, we derive a fully analytical model describing the topology of the calcium aluminosilicate [(CaO)
x (Al2O3)y (SiO2)1−x −y , CAS] ternary system. This model yields the state of rigidity (flexible, isostatic, or stressed‐rigid) of CAS systems as a function of composition and temperature. These results reveal the existence of correlations between network topology and glass‐forming ability. This study suggests that glass‐forming ability is encoded in the network topology of the liquid state rather than that of the glassy state. -
more » « less
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.
