Developing accurate, transferable, and computationally-efficient interatomic forcefields is key to facilitate the modeling of silicate glasses. However, the high number of forcefield parameters that need to be optimized render traditional parameterization methods poorly efficient or potentially subject to bias. Here, we present a new forcefield parameterization methodology based on ab initio molecular dynamics simulations, Gaussian process regression, and Bayesian optimization. By taking the example of glassy silica, we show that our methodology yields a new interatomic forcefield that offers an unprecedented description of the atomic structure of silica. This methodology offers a new route to efficiently parameterize new empirical interatomic forcefields for silicate glasses with very limited need for intuition.
Understanding, predicting and eventually improving the resistance to fracture of silicate materials is of primary importance to design new glasses that would be tougher, while retaining their transparency. However, the atomic mechanism of the fracture in amorphous silicate materials is still a topic of debate. In particular, there is some controversy about the existence of ductility at the nano-scale during the crack propagation. Here, we present simulations of the fracture of three archetypical silicate glasses using molecular dynamics. We show that the methodology that is used provide realis…
Structure and properties of magnesium silicate and borate melts and glasses were investigated by using newly parameterized interaction potentials in molecular dynamics simulations and compared with those of calcium silicate and borate. The competition between the depolymerization of the silica network and the formation of new bonds with modifier ions leads to the enhancement of the elastic moduli with increasing modifier content in alkaline earth silicate glasses. Compared with calcium silicate, the higher elastic moduli of magnesium silicate result from a higher connectivity of the overall gl…
The existence of nanoscale ductility during the fracture of silicate glasses remains controversial. Here, based on molecular dynamics simulations coupled with topological constraint theory, we show that nano-ductility arises from the spatial heterogeneity of the atomic network's rigidity. Specifically, we report that localized floppy modes of deformation in under-constrained regions of the glass enable plastic deformations of the network, resulting in permanent change in bond configurations. Ultimately, these heterogeneous plastic events percolate, thereby resulting in a non-brittle mode of fr…
Alkaline earth silicate glasses $xCaO-(1-x)SiO_2$ exhibit a well marked threshold in Raman lineshapes which can be related to the onset of network rigidity as the concentration of calcium oxide $x$ is decreased. The present results are analyzed by constraint counting algorithms and more deeply characterized by a size increasing cluster approximation that allows to perform Maxwell mechanical constraint counting beyond the usual mean-field treatment. This permits to discuss under which structural conditions an elastic intermediate phase can be obtained.
Predicting the dissolution rates of silicate glasses in aqueous conditions is a complex task as the underlying mechanism(s) remain poorly understood and the dissolution kinetics can depend on a large number of intrinsic and extrinsic factors. Here, we assess the potential of data-driven models based on machine learning to predict the dissolution rates of various aluminosilicate glasses exposed to a wide range of solution pH values, from acidic to caustic conditions. Four classes of machine learning methods are investigated, namely, linear regression, support vector machine regression, random f…
Although molecular dynamics (MD) simulations are commonly used to predict the structure and properties of glasses, they are intrinsically limited to short time scales, necessitating the use of fast cooling rates. It is therefore challenging to compare results from MD simulations to experimental results for glasses cooled on typical laboratory time scales. Based on MD simulations of a sodium silicate glass with varying cooling rate (from 0.01 to 100 K/ps), here we show that thermal history primarily affects the medium-range order structure, while the short-range order is largely unaffected over…
The Brillouin elastic free energy change $DF$ between thermally annealed and quenched $(Na_2O)_x(SiO_2)_{1-x}$ glasses is found to decrease linearly at $x > 0.23$ (floppy phase), and to nearly vanish at $x < 0.18$ (stressed- rigid phase). The observed $D F(x)$ variation closely parallels the mean-field floppy mode fraction $f(x)$ in random networks, and fixes the two (floppy, stressed-rigid) elastic phases. In calorimetric measurements, the non-reversing enthalpy near $T_g$ is found to be large at $x < 0.18$ and at $x > 0.23$, but to nearly vanish in the $0.18 < x < 0.23$ range, suggesting exi…
We use \textit{ab initio} molecular dynamics simulations to investigate the properties of the dry surface of pure silica and sodium silicate glasses. The surface layers are defined based on the atomic distributions along the direction ($z-$direction) perpendicular to the surfaces. We show that these surfaces have a higher concentration of dangling bonds as well as two-membered (2M) rings than the bulk samples. Increasing concentration of Na$_2$O reduces the proportion of structural defects. From the vibrational density of states, one concludes that 2M rings have a unique vibrational signature …
The development by machine learning of models predicting materials' properties usually requires the use of a large number of consistent data for training. However, quality experimental datasets are not always available or self-consistent. Here, as an alternative route, we combine machine learning with high-throughput molecular dynamics simulations to predict the Young's modulus of silicate glasses. We demonstrate that this combined approach offers excellent predictions over the entire compositional domain. By comparing the performance of select machine learning algorithms, we discuss the natur…
For small tension the response of a solid to an applied stress is given by Hooke's law. Outside this linear regime the relation between stress and strain is no longer universal and at present there is no satisfactory insight on how to connect for disordered materials the stress-strain relation to the microscopic properties of the system. Here we use atomistic computer simulations to establish this connection for the case of silicate glasses containing modifiers. By probing how in the highly non-linear regime the stress-strain curve depends on composition, we are able to identify the microscopi…
We use large-scale simulations to investigate the dynamic fracture of silica and sodium-silicate glasses under uniaxial tension. The stress-strain curves demonstrate that silica glass is brittle whereas the glasses rich in Na show pronounced ductility. A strong composition dependence is also seen in the crack velocity which is on the order of 1800 m/s for glasses with low Na concentration and decreases to 700 m/s if the concentration is high. We find that during the fracture of Na-rich glasses very irregular cavities as large as 3-4 nm form ahead of the crack front, indicating the presence of …
We present results of molecular dynamics simulations on lithium metasilicate over a broad range of temperatures for which the silicate network is frozen in but the lithium ions can still be equilibrated. The lithium dynamics is studied via the analysis of different correlation functions. The activation energy for the lithium mobility agrees very well with experimental data. The correlation of the dynamics of adjacent ions is weak. At low temperatures the dynamics can be separated into local vibrational dynamics and hopping events between adjacent lithium sites. The derivative of the mean squar…
Differential scanning calorimetry (DSC) is one of the most versatile probes for silicate glasses, allowing determination of, e.g., transition temperatures (glass, crystallization, melting) and the temperature dependence of heat capacity. However, complications arise for glasses featuring overlapping transitions and low sensitivity, e.g., arising from SiO2-rich compositions with small change in heat capacity during glass transition or the low sensitivity of thermocouples at high temperature. These challenges might be overcome using temperature-modulated DSC (TM-DSC), which enables separation of…
Although experiments can offer some fingerprints of the atomic structure of glasses (coordination numbers, pair distribution function, etc.), atomistic simulations are often required to directly access the structure itself (i.e., the positions of the atoms). On the one hand, molecular dynamics (MD) simulations can be used to generate by quenching a liquid - but MD simulations remain plagued by extremely high cooling rates. On the other hand, reverse Monte Carlo (RMC) modeling bypasses the melt-quenching route - but RMC often yields non-unique glass structures. Here, we adopt the force-enhanced…
A model is derived for the viscoelastic response of glasses at isothermal uniaxial deformation with small strains. A glass is treated as an ensemble of relaxing units with various activation energies for rearrangement. With reference to the energy-landscape concept, the rearrangement process is thought of as a series of hops of relaxing units (trapped in their potential wells on the energy landscape) to higher energy levels. Stress-strain relations are developed by using the laws of thermodynamics. Adjustable parameters are found by fitting experimental data in torsional dynamic tests on a mul…
Ion conducting $(CaO)_x(SiO_2)_{1-x}$ glasses and melts show a threshold behaviour in dc conductivity near $x=x_t=0.50$, with conductivities increasing linearly at $x>x_t$. We show that the behaviour can be traced to a rigid ($x<0.50$) to floppy ($x>0.50$) elastic phase transition near $x=x_t$. In the floppy phase, conductivity enhancement is traced to increased mobility or diffusion of $Ca^{2+}$ carriers as the modified network elastically softens.
The mixed-alkali effect on the cation dynamics in silicate glasses is analyzed via molecular dynamics simulations. Observations suggest a description of the dynamics in terms of stable sites mostly specific to one ionic species. As main contributions to the mixed--alkali slowdown longer residence times and an increased probability of correlated backjumps are identified. The slowdown is related to the limited accessibility of foreign sites. The mismatch experienced in a foreign site is stronger and more retarding for the larger ions, the smaller ions can be temporarily accommodated. Also correl…
The original electronic structure of the Pb$^{2+}$ ion explains its particular structural role in crystalline phases and silicate glasses. After a description of the structural role of lead in crystalline phases (PbO, silicates), this chapter presents a summary of the main structural studies carried out on glasses from the SiO$_2$-PbO, SiO$_2$-PbO-R$_2$O (R: alkaline) and SiO$_2$-PbO-Al$_2$O$_3$ systems, using various spectroscopic and simulation techniques.
Nucleation is generally viewed as a structural fluctuation that passes a critical size to eventually become a stable emerging new phase. However, this concept leaves out many details, such as changes in cluster composition and competing pathways to the new phase. In this work, both experimental and computer modeling studies are used to understand the cluster composition and pathways. Monte Carlo and molecular dynamics approaches are used to analyze the thermodynamic and kinetic contributions to the nucleation landscape in barium silicate glasses. Experimental techniques examine the resulting p…
We present a detailed analysis of the ion hopping dynamics and the related nearby oxygen dynamics in a lithium meta silicate glass via molecular dynamics simulation. For this purpose we have developed numerical techniques to identify ion hops and to sample and average dynamic information of the particles involved. This leads to an instructive insight into the microscopic interplay of ions and network. It turns out that the cooperative dynamics of lithium and oxygen can be characterized as a sliding door mechanism. It is rationalized why the local network fluctuations are of utmost importance f…
Optical materials with semiconductor nanoparticles within dielectric matrices are of interest for construction of non-linear optical elements, selective filters, spectral converters, etc. In the present work, we concern the glasses with PbS and PbSe fabricated by the two-step technique on the basis of silicate glass matrix and report the recent studied using the small-angle neutron scattering (SANS) technique. A proper understanding the structure of material, size of particles and spectral features need to control optical functionality of glasses. SANS is efficient non-destructive technique al…
Density is one of the most commonly measured or estimated materials properties, especially for glasses and melts that are of significant interest to many fields, including metallurgy, geology, materials science and sustainable cements. Here, two types of machine learning (ML) models (i.e., random forest (RF) and artificial neural network (ANN)) have been developed to predict the room-temperature density of glasses in the compositional space of CaO-MgO-Al2O3-SiO2-TiO2-FeO-Fe2O3-Na2O-K2O-MnO (CMASTFNKM), based on ~2100 data points mined from ~140 literature studies. The results show that the RF …
Over the past 40 years measurements of the nucleation rates in a large number of silicate glasses have indicated a breakdown in the widely used Classical Nucleation Theory (CNT) for temperatures below that of the peak nucleation rate. The data show that instead of steadily decreasing with decreasing temperature, the work of critical cluster formation enters a plateau, and even starts to increase. While many explanations have been offered to explain this anomaly, none have provided a satisfactory answer. We present the first experimental results that demonstrate that the anomaly is not real, bu…
The present review is intended to revisit the advances and debates in the comprehension of the mechanisms of subcritical crack propagation in silicate glasses almost a century after its initial developments. Glass has inspired the initial insights of Griffith into the origin of brittleness and the ensuing development of modern fracture mechanics. Yet, through the decades the real nature of the fundamental mechanisms of crack propagation in glass has escaped a clear comprehension which could gather general agreement on subtle problems such as the role of plasticity, the role of the glass compos…
In this work, we use molecular dynamics simulations to study the enhancement of surface over bulk diffusion (surface enhanced diffusion) in (PbO)x(SiO2)1-x glasses. This work is motivated to better understand surface diffusion in glasses and its connection to fragility, and to enhance surface diffusion in silica and related glasses for greater thermodynamic stability during vapor-deposition. By adding PbO to silica, the fragility of glass increases continuously for 10% <= x <= 70% during experiments. The increase in fragility may correspond to an increase in surface enhanced diffusion, as frag…
Oxide glasses are made of a network of glass former polyhedra, and modifiers which have a role in neutralizing the charge of the glass former polyhedra or depolymerize the glass network. The effect of the modifier content on the structure and properties of the glass are to some extent, well known. However, the effect of the type of modifiers on the clustering and the tendency to form a phase separation in the glass is not investigated in detail and still not fully understood until now. Here, we use molecular dynamics to investigate the effect of the modifier type on the structure and the clust…
Multiscale Experimental Evidence of a Transitory State in the HDA-LDA Transition in Alumino-sodo-silicate Glasses
Institut Lumière Matière UMR CNRS 5306, Université Claude Bernard Lyon 1, CNRS（里昂第一大学物质与光研究所）；Institute of Glass and Ceramics, Department of Materials Science and Engineering, Friedrich Alexander University Erlangen Nuremberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学玻璃与陶瓷研究所）
Individual cationic site--energies are explicitly determined from molecular dynamics simulations of alkali silicate glasses, and the properties and relevance of this local energetics to ion transport are studied. The absence of relaxations on the timescale of ion transport proves the validity of a static description of the energy landscape, as it is generally used in hopping models. The Coulomb interaction among the cations turns out essential to obtain an average energy landscape in agreement with typical simplified hopping models. Strong correlations exist both between neighboring sites and …
The slow advance of a crack in sodo-silicate glasses was studied at nanometer scale by in situ and real time atomic force microscopy (AFM) in a well controlled atmosphere. An enhanced diffusion of sodium ions in the stress gradient field at the submicrometric vicinity of the crack tip was revealed through several effects: growth of nodules in AFM height images, changes in the AFM tip/sample energy dissipation. The nodules patterns revealed a dewetting phenomenon evidenced by 'breath figures'. Complementary chemical micro-analyses were done. These experimental results were explained by a two-st…
The synthesis of Ag nanoclusters in sodalime silicate glasses and silica was studied by optical absorption (OA) and electron spin resonance (ESR) experiments under both low (gamma-ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution - notably via their interaction with defects - are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image f…
A systematic review of main physical effects generated by ion exchange in silicate glasses is presented. Ion concentration distributions, residual stress profiles, and refractive index effects are discussed with particular attention on the physical and mathematical underpinnings of the ion exchange process. The study has the purpose of presenting a scientific foundation to enable future developments in the field. In this respect, the objective of this article is more educational than to present new research results. Appendixes are included to consider the detail of some specific topics without…
The local structural environment and the spatial distribution of iron and aluminum ions in sodosilicate glasses with composition NaFexAl1-xSi2O6 (x = 1, 0.8, 0.5 and 0) is studied by high-resolution neutron diffraction combined with structural modeling using the Empirical Potential Structure Refinement (EPSR) code. This work gives evidence of differences in the structural behavior of Al3+ and Fe3+, which are both often considered to act as network formers in charge-balanced compositions. The short-range environment and the structural role of the two cations are not composition dependent, and h…
Borosilicate glasses are traditionally challenging to model using atomic scale simulations due to the composition and thermal history dependence of the coordination state of B atoms. Here, we report a new empirical interatomic potential that shows a good transferability over a wide range of borosilicate glasses--ranging from pure silicate to pure borate end members--while relying on a simple formulation and a constant set of energy parameters. In particular, we show that our new potential accurately predicts the compositional dependence of the average coordination number of boron atoms, glass …
Information about the nature of the low-temperature anomalies and in particular the properties of the tunneling systems in silica and lithium silica glasses are revealed via computer simulations. The potential energy landscape of these systems is systematically explored for adjacent pairs of local minima which may act as double-well potentials (DWP) at low temperatures. Three different types of DWP are distinguished, related to perfectly coordinated silica, intrinsic silica defects, and extrinsic defects. Their properties like the spatial extension and the dipole moment are characterized in de…
Using molecular dynamics simulations we investigate the dependence of the structural and vibrational properties of the surfaces of sodo-silicate glasses on the sodium content as well as the nature of the surface. Two types of glass surfaces are considered: A melt-formed surface (MS) in which a liquid with a free surface has been cooled down into the glass phase and a fracture surface (FS) obtained by tensile loading of a glass sample. We find that the MS is more abundant in Na and non-bridging oxygen atoms than the FS and the bulk glass, whereas the FS has higher concentration of structural de…
Machine learning (ML) methods are becoming popular tools for the prediction and design of novel materials. In particular, neural network (NN) is a promising ML method, which can be used to identify hidden trends in the data. However, these methods rely on large datasets and often exhibit overfitting when used with sparse dataset. Further, assessing the uncertainty in predictions for a new dataset or an extrapolation of the present dataset is challenging. Herein, using Gaussian process regression (GPR), we predict Young's modulus for silicate glasses having sparse dataset. We show that GPR sign…
Fractoluminescence experiments are performed on two kinds of silicate glasses. All the light spectra collected during dynamic fracture reveal a black body radiator behaviour, which is interpreted as a crack velocity-dependent temperature rise close to the crack tip. Crack velocities are estimated to be of the order of 1300 m.s$^{-1}$ and fracture process zones are shown to extend over a few nanometers.
