Classical molecular dynamics simulations have been used to investigate the structural role of Mg and its effect when it is incorporated in sodium aluminoborosilicate glasses. The simulations have been performed using three interatomic potentials; one is based on the rigid ionic model parameterized by Wang et al. (2018) and two slightly different parameterization of the core-shell model provided by Stevensson et al. (2018) and Pedone et al. (2020) The accuracies of these models have been assessed by detailed structural analysis and comparing the simulated nuclear magnetic resonance (NMR) spectra for spin active nuclei (Si-29, Al-27, B-11, O-17, Mg-25, and Na-23) with the experimental counterparts collected in a previous work. Our simulations reveal that the core-shell parameterizations provide better structural models. In fact, they better reproduce the NMR spectra of all the investigated nuclei and give better agreement with known experimental data. Magnesium is found to be five coordinated on average with distances with oxygen in between a network modifier (like Na) and an intermediate network formed (like Al). It prefers to lay closer to three-coordinated B atoms, forming B-NBO bonds, with respect to Si and especially Al. This can explain the formation of AlO5 and AlO6 units in the investigated Na-free glass, together with a Si clusterization.

The initial dissolution rate of a series of multicomponent glasses is studied in order to discuss the influence of increasing magnesium content in the glass on this alteration regime and to highlight differences in behavior between calcium- and magnesium-bearing glasses. The application of MD-based topological constraint theory (TCT) is confronted to glass transition temperature ( T g ) and initial dissolution rate ( r 0 ) on a glass series containing the main oxides of a French nuclear glass (AVM). In addition, a comparison between a reference magnesium-containing nuclear waste glass, AVMV4 and a proposed derived simplified composition N19M8 is performed regarding r 0 values. Results indicate a similar behavior in this alteration regime for the two glasses, suggesting that this simple glass might be a good analogue to the complex one. Substituting calcium for magnesium decreases the initial dissolution rate by a factor two in the series, while an overall increase of magnesium leads to an increased dissolution rate. Analyses performed with TCT suggests that magnesium environment is better defined than calcium or sodium and may behave as an intermediate species. Finally, a correlation between the number of constraints per atom and T g is established, while the model failed to link structural features to r 0 .

The alteration of a four-oxide alumino-borosilicate glass close to International Simple Glass (ISG) was studied in Si saturation conditions at pH 3, pH 7, and pH 9 using solution and post mortem solid analyses. In particular, the study examined the impact of structural disorder on the glass alteration generated by swift heavy ion irradiation. It is shown that the pre-irradiated glass altered three to four times more than the non-irradiated glass, depending on the pH. This increased alteration can be attributed to two factors: an increased hydrolysis speed of the Si–O–B bonds, which control the glass dissolution under these Si saturation conditions, and a less passivating alteration layer. The latter effect suggests that the glass structural disorder is retained by the first gel formed, which means very low Si atom mobility during alteration. However, gel maturation tends to mitigate the detrimental effect of radiation damages. These results will contribute to the development of a predictive residual rate model.

Seven magnesium-containing aluminoborosilicate glasses, with three to five oxides, have been studied through comprehensive multi-nuclear solid-state NMR ( 11 B, 27 Al, 29 Si, 23 Na, 17 O and 25 Mg) and Raman spectroscopy. The progressive addition of cations and the substitution of sodium and calcium by magnesium illuminate the impact of magnesium on the glass structure. The proportion of tri-coordinated boron drastically increased with magnesium addition, demonstrating the poor charge-compensating capabilities of magnesium in tetrahedral boron units. Oxygen-17 NMR showed the formation of mixing sites containing both Na and Mg near non-bridging oxygen sites. Furthermore, a high magnesium content appears to result in the formation of two sub-networks (boron and silicon rich) with different polymerisation degrees as well as to promote the formation of high-coordination aluminium sites (Al[V] and Al[VI]). Finally, magnesium coordination ranging from four to six, with a mean value shifting from five to six along the series, suggests that magnesium might endorse an intermediate role in these glasses.

A series of multicomponent glasses containing up to five oxides are studied using classical molecular dynamics simulations and neutron scattering experiments. The focus is on the role of magnesium in determining the structural properties of these glasses and the possible mixed effect during a sodium/magnesium substitution. Calculated structure functions (pair correlation function and structure factor) rather accurately reproduce their experimental counterpart, and we show that more fine structural features are qualitatively reproduced well, despite some discrepancies in the preferential spatial distribution between sodium and magnesium to aluminum and boron, as well as the nonbridging oxygen, distribution. The simulated systems offer a solid basis to support previous experimental findings on the composition-structure relationship, allowing for further analysis and property calculation. It is confirmed that the substitution of sodium by magnesium leads to the decrease of four-fold boron and a modification of the alkali coordinations with a significant change of the network structure. Specifically, magnesium coordination extracted from numerical simulations highlights a potential dissociation from penta- to tetra- and hexahedral units with increasing MgO contents along the glass series, which could not be resolved experimentally.

Quantitative Structure Property Relationship (QSPR) analysis based on molecular dynamics (MD) simulations is a promising approach for establishing the composition-property relationships of glasses and other materials with complex structures. A series of 20 borosilicate, aluminosilicate, and boroaluminosilicate glasses have been modeled using MD simulations with recently developed effective potentials. Short- and medium-range structures of these glasses were analyzed and, based on the structural information, QSPR analysis of the initial dissolution rates (r(0)) of these glasses that were measured at 90 degrees C and pH 9 by using various structural descriptors such as percentage of bridging oxygen species, network connectivity, and average ring size. The structural descriptor, F-net, which contains both energetic information such as single bond strength and structural information such as cation coordination number and Q(n) distribution, was also used. It was found that while the overall network connectivity, average ring size and F-net provide reasonable correlations with r(0) of studied glasses, F-net gives the best correlation among the descriptors. For glasses that show incongruent dissolution, it was found that modification of glass compositions to account for preferential release of modifier cations is necessary to achieve best correlations. The findings were discussed with results of recent studies on evaluating the compositional dependence of glass dissolution behavior using the topological-constraints-based models.

Tuning glass composition to obtain targeted properties generally relies on empirical approaches. However, a deep understanding of the physical and chemical mechanisms linking glass composition to its structure and properties would enable developing reliable predictive models. Indeed, although empirical models are usually able to interpolate composition–property relationships within a given compositional envelope, they often fail at extrapolating predictions far from their training domain. Here, as an alternative route to empirical models, we show that a structural descriptor based on the number of topological constraints per atom can be used to predict the initial dissolution rate of aluminosilicate and borosilicate glasses after being parameterized on different families of glasses (specific series of borosilicate glasses). Sixteen glasses belonging to these families were studied and their initial dissolution rates were determined at 90 °C and pH 90 °C = 9, covering rates spanning over 5 orders of magnitude. The model based on topological constraints was trained based on seven select borosilicate glasses ( R 2 = 0.997) and used to predict the dissolution rate of nine additional borosilicate and aluminosilicate glasses. We show that, provided that corrections are made for high alkali content glasses that dissolve incongruently (preferential release of Na), the model gives reasonable predictions, even far from its training domain.