arXiv subjects

Mathieu Bauchy

Publications and source records attributed to Mathieu Bauchy.

34 records · Page 2Linked to original sources

arXiv2017

Predicting the dissolution kinetics of silicate glasses using machine learning

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 forest, and artificial neural network. We observe that, although linear methods all fail to describe the dissolution kinetics, the artificial neural network approach offers excellent predictions, thanks to its inherent ability to handle non-linear data. Overall, we suggest that a more extensive use of machine learning approaches could significantly accelerate the design of novel glasses with tailored properties.

cond-mat.dis-nn↗

arXiv2017

Cooling-Rate Effects in Sodium Silicate Glasses: Bridging the Gap between Molecular Dynamics Simulations and Experiments

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 range of cooling rates simulated. This results in a decoupling between the enthalpy and volume relaxation functions, where the enthalpy quickly plateaus as the cooling rate decreases, whereas density exhibits a slower relaxation. Finally, we demonstrate that the outcomes of MD simulations can be meaningfully compared to experimental values if properly extrapolated to slower cooling rates.

cond-mat.mtrl-sci↗

arXiv2016

Topological Control on Atomic Networks' Relaxation Under Stress

Upon loading, atomic networks can feature delayed viscoplastic relaxation. However, the effect of composition and structure on such a relaxation remains poorly understood. Herein, relying on accelerated molecular dynamics simulations and topological constraint theory, we investigate the relationship between atomic topology and stress-induced relaxation, by taking the example of creep deformations in calcium--silicate--hydrates, the binding phase of concrete. Under constant shear stress, C--S--H is found to feature delayed logarithmic shear deformations. We demonstrate that the propensity for relaxation is minimum for isostatic atomic networks, which are characterized by the simultaneous absence of floppy internal modes of relaxation and eigen stress. This suggests that topological nano-engineering could lead to the discovery of non-aging materials.

cond-mat.mtrl-sci↗

arXiv2015

Nano-Ductility in Silicate Glasses is Driven by Topological Heterogeneity

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 fracture. This suggests that nano-ductility is intrinsic to multi-component silicate glasses having nanoscale heterogeneities.

cond-mat.mtrl-sci↗

arXiv2015

Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

Concrete, a mixture formed by mixing cement, water, and fine and coarse mineral aggregates is used in the construction of nuclear power plants (NPPs), e.g., to construct the reactor cavity concrete that encases the reactor pressure vessel, etc. In such environments, concrete may be exposed to radiation (e.g., neutrons) emanating from the reactor core. Until recently, concrete has been assumed relatively immune to radiation exposure. Direct evidence acquired on Ar$^+$-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. Specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, i.e., similar to glassy silica, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica; i.e., an increase of around 3 orders of magnitude. Calcite however, shows little change in dissolution rates - although its density noted to reduce by around 9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral's atomic network that is characterized by the number of topological constraints (n$_c$) that are imposed on the atoms in the network. The outcomes are discussed within the context of the durability of concrete structural elements formed with calcitic/quartzitic aggregates in nuclear power plants.

cond-mat.mtrl-sci↗

arXiv2015

Topological Control on Silicates Dissolution Kinetics

Like many others, silicate solids dissolve when placed in contact with water. In a given aqueous environment, the dissolution rate depends highly on the composition and the structure of the solid, and can span several orders of magnitude. Although the kinetics of dissolution depends on the complexities of both the dissolving solid and the solvent, a clear understanding of which critical structural descriptors of the solid control its dissolution rate is lacking. Through pioneering dissolution experiments and atomistic simulations, we correlate the dissolution rates - ranging over four orders of magnitude - of a selection of silicate glasses and crystals, to the number of chemical topological constraints acting between the atoms of the dissolving solid. The number of such constraints serves as an indicator of the effective activation energy, which arises from steric effects, and prevents the network from reorganizing locally to accommodate intermediate units forming over the course of the dissolution.

cond-mat.mtrl-sci↗

arXiv2015

Does a dissolution-precipitation mechanism explain concrete creep in moist environments?

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of creep remains poorly understood, and controversial. Here, we propose that concrete creep at RH (relative humidity) > 50%, but fixed moisture-contents (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as is often observed in a geological context, e.g., when rocks are exposed to sustained loads, in moist environments. Based on micro-indentation and vertical scanning interferometry experiments, and molecular dynamics simulations carried out on calcium-silicate-hydrates (C-S-H's), the major binding phase in concrete, of different compositions, we show that creep rates are well correlated to dissolution rates - an observation which supports the dissolution-precipitation mechanism as the origin of concrete creep. C-S-H compositions featuring high resistance to dissolution, and hence creep are identified - analysis of which, using topological constraint theory, indicates that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.

cond-mat.mtrl-sci↗

arXiv2015

Creep of Bulk C--S--H: Insights from Molecular Dynamics Simulations

Understanding the physical origin of creep in calcium--silicate--hydrate (C--S--H) is of primary importance, both for fundamental and practical interest. Here, we present a new method, based on molecular dynamics simulation, allowing us to simulate the long-term visco-elastic deformations of C--S--H. Under a given shear stress, C--S--H features a gradually increasing shear strain, which follows a logarithmic law. The computed creep modulus is found to be independent of the shear stress applied and is in excellent agreement with nanoindentation measurements, as extrapolated to zero porosity.

cond-mat.mtrl-sci↗

arXiv2015

Is Cement a Glassy Material?

The nature of Calcium--Silicate--Hydrate (C--S--H), the binding phase of cement, remains a controversial question. In particular, contrary to the former crystalline model, it was recently proposed that its nanoscale structure was actually amorphous. To elucidate this issue, we analyzed the structure of a realistic simulation of C--S--H, and compared the latter to crystalline tobermorite, a natural analogue to cement, and to an artificial ideal glass. Results clearly support that C--S--H is amorphous. However, its structure shows an intermediate degree of order, retaining some characteristics of the crystal while acquiring an overall glass-like disorder. Thanks to a detailed quantification of order and disorder, we show that its amorphous state mainly arises from its hydration.

cond-mat.mtrl-sci↗

arXiv2015

Topological Constraints and Rigidity of Network Glasses from Molecular Dynamics Simulations

Due to its non-crystalline nature, the glassy state has remained one the most exciting scientific challenges. To study such materials, Molecular Dynamics (MD) simulations have been extensively used because they provide a direct view into its microscopic structure. MD is therefore used not only to reproduce real system properties but also benefits from detailed atomic scale analysis. Unfortunately, MD shows inherent limitations because of the limited computational power. For instance, only the simulations of small systems are currently permitted, which prevents from studying small compositional changes, although it is well known that they can dramatically alter system properties. At this stage, it is tempting to follow topological constraint theory, which aims at describing macroscopic properties of the glass relying only on the connectivity of individual atoms, thus considering the complicated glass network as simple mechanical trusses. Thanks to only basic hand calculations, this theory has been successful in predicting complex composition and temperature behavior of glass properties, such as the glass forming ability, the viscosity of the corresponding liquid or the elasticity. The purpose of my PhD work is to connect these successful approaches based only on the topology of the underlying low-temperature network with properties that can be obtained from MD calculations. It should thus allow for an increased applicability of rigidity theory.

cond-mat.mtrl-sci↗

arXiv2015

Fracture Toughness of Silicate Glasses: Insights from Molecular Dynamics Simulations

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 realistic values of fracture energy and toughness. In addition, the simulations clearly suggest that silicate glasses can show different degrees of ductility, depending on their composition.

cond-mat.mtrl-sci↗

arXiv2015

Ion-Exchange Strengthening of Glasses: Atomic Topology Matters

Ion-exchange is commonly used to chemically strengthen glasses, by replacing small atoms by larger ones at sub T$_g$ temperature, thereby inducing a compressive stress. However, the resulting expansion of the glass remains lower than that predicted by the difference of molar volumes of the as-cooled glasses, an anomaly that remains poorly understood. Here, based on molecular dynamcis simulations of permanently densified sodium silicate glasses coupled with topological constraint theory, we show that the rigidity of the network controls the extent of the dilatation. Isostatic networks, which are rigid but free of eigenstress, show maximal expansion and, therefore, appear to be an attractive option to improve the toughness of glass.

cond-mat.mtrl-sci↗

arXiv2015

Nature of Radiation-Induced Defects in Quartz

Although quartz ($\rm α$-form) is a mineral used in numerous applications wherein radiation exposure is an issue, the nature of the atomistic defects formed during radiation-induced damage have not been fully clarified. Especially, the extent of oxygen vacancy formation is still debated, which is an issue of primary importance as optical techniques based on charged oxygen vacancies have been utilized to assess the level of radiation damage in quartz. In this paper, molecular dynamics (MD) simulations are applied to study the effects of ballistic impacts on the atomic network of quartz. We show that the defects that are formed mainly consist of over-coordinated Si and O, as well as Si--O connectivity defects, e.g., small Si--O rings and edge-sharing Si tetrahedra. Oxygen vacancies, on the contrary, are found in relatively low abundance, suggesting that characterizations based on $E^{\prime}$ centers do not adequately capture radiation-induced structural damage in quartz. Finally, we evaluate the dependence on the incident energy, of the amount of each type of the point defects formed, and quantify unambiguously the threshold displacement energies for both O and Si atoms. These results provide a comprehensive basis to assess the nature and extent of radiation damage in quartz.

cond-mat.mtrl-sci↗

arXiv2015

Stretched Exponential Relaxation of Glasses at Low Temperature

The question of whether glass continues to relax at low temperature is of fundamental and practical interest. Here, we report a novel atomistic simulation method allowing us to directly access the long-term dynamics of glass relaxation at room temperature. We find that the potential energy relaxation follows a stretched exponential decay, with a stretching exponent $β= 3/5$, as predicted by Phillips' diffusion-trap model. Interestingly, volume relaxation is also found. However, it is not correlated to the energy relaxation, but is rather a manifestation of the mixed alkali effect.

cond-mat.dis-nn↗

arXiv2014

Structure and dynamics of liquid AsSe4 from ab initio molecular dynamics simulation

Structural and dynamical properties of AsSe4 liquids have been studied by ab initio molecular dynamics simulations as a function of temperature. Calculated neutron structure factors are in good agreement with experimental data. Results show the existence of a significant amount of As-As homopolar bonds and of SeI and AsIV units which are not part of the picture of the cross-linking As(Se1/2)3 pyramids usually proposed for the glassy state.

cond-mat.dis-nn↗

arXiv2012

Structural, vibrational and thermal properties of densified silicates : insights from Molecular Dynamics

Structural, vibrational and thermal properties of densified sodium silicate (NS2) are investigated with classical molecular dynamics simulations of the glass and the liquid state. A systematic investigation of the glass structure with respect to density was performed. We observe a repolymerization of the network manifested by a transition from a tetrahedral to an octahedral silicon environment, the decrease of the amount of non-bridging oxygen atoms and the appearance of three-fold coordinated oxygen atoms (triclusters). Anomalous changes in the medium range order are observed, the first sharp diffraction peak showing a minimum of its full-width at half maximum according to density. The previously reported vibrational trends in densified glasses are observed, such as the shift of the Boson peak intensity to higher frequencies and the decrease of its intensity. Finally, we show that the thermal behavior of the liquid can be reproduced by the Birch-Murnaghan equation of states, thus allowing us to compute the isothermal compressibility.

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