Molecular simulation of the confined crystallization of ice in cement nanopore.

Freezing of water under nanoconfinement exhibits physical peculiarities with respect to the bulk water. However, experimental observations are extremely challenging at this scale, which limits our understanding of the effect of confinement on water properties upon freezing. In this study, we use molecular dynamic simulations to investigate how confinement affects the kinetics of growth of ice and the thermodynamic equilibrium of ice-liquid coexistence. TIP4P/Ice water model and CSH-FF model were applied to simulate ice crystallization in a confined cement system at temperatures down to 220 K. We adapted an interface detection algorithm and reparameterized the CHILL/CHILL+ algorithm to capture ice growth. The confinement leads to a shift of the maximum growth rate of ice to a higher temperature than for bulk water. Both the confinement and surface impurities contribute to slowing down the ice growth. For the ice-liquid coexistence at equilibrium, we derive a formulation of Thomson's equation adapted to statistical physics quantities accessible by molecular simulation, and we show that this adapted equation predicts accurately the melting line of bulk and confined ice Ih as a function of pressure. The confinement decreases systematically the melting temperature of ice of about 5 K compared with bulk ice Ih. A premelted water film about 1 nm thick is observed between the solid wall and ice, and its thickness is found to decrease continuously as temperature is lowered. We note that the surface impurities are key to the formation of the premelted water nanofilm when the temperature is lower than 250 K.

Solubility of NaCl under anisotropic stress state.

Salt solubility is generally determined under isotropic stress conditions. Yet, in the context of salt weathering of porous media, mechanical constraints on the in-pore growth of salt crystals are likely to be orientation-dependent, resulting in an anisotropic stress state on the crystal. In this paper, we determine by molecular simulation the solubility of NaCl in water when the crystal is subjected to anisotropic stress. Such anisotropy causes the chemical potential of the crystal to be orientation-dependent, and proper thermodynamic formulation requires describing the chemical potential as a tensor. The solute and crystal chemical potentials are computed from free energy calculations using Hamiltonian thermodynamic integration, and the usual condition of solubility is reformulated to account for the tensorial nature of the crystal chemical potential. We investigate in detail how the uniaxial compression of the crystal affects its solubility. The molecular simulation results led to revisiting the Correns law under anisotropic stress. Regarding the solute, the non-ideal behavior of the liquid phase is captured using Pitzer's ion interaction approach up to high concentrations of interest for in-pore crystallization and beyond the concentrations addressed in the existing literature. Regarding NaCl crystals, the validity of the generalized Gibbs-Duhem equation for a tensorial chemical potential is carefully verified, and it is found that crystallization progresses almost orthogonally to the crystal surface even under high shear stresses. Comparing uniaxial and isotropic compression highlights the major differences in solubility caused by stress anisotropy, and the revisited Correns law offers an appropriate framework to capture this phenomenon.

A meso-scale model of clay matrix: the role of hydration transitions in geomechanical behavior.

While much progress has been made on the modeling of swelling clays at the molecular scale in recent decades, up-scaling to the macroscopic scale remains a challenge, in particular because the mesoscopic scale (between a few nanometers and a few hundreds of nanometers) is still poorly understood. In this article, we propose a new 2D granular model of clay at the mesoscale. This model is adapted to the modeling of a dense clay matrix representing geomechanical conditions (up to pressures of 10-100 MPa). Some salient features of this model with respect to the existing literature are: (1) its ability to capture hydration transitions occurring at small basal spacings (essential to model complex hydro-mechanical behaviors such as drying shrinkage), (2) the flexibility of the clay layers that becomes important at pressures exceeding 1 MPa, and (3) the control of the inter-layer shear strength critical to model plasticity. The model calibration is purely bottom-up, based on molecular modeling results only. The case of Na-montmorillonite (Na-Mnt) is investigated in detail, regarding isotropic compression (elasticity and plasticity), yield surface and desiccation. The behavior of the granular model appears well consistent with what is known experimentally for pure Na-Mnt, and offers valuable insight into meso-scale processes that could not be reached so far (role of hydration transition, layer flexibility, and impact of loading history). This granular model is a first step toward quantitative up-scaling of molecular modeling of swelling clay for geomechanical applications.

Oedometric-like setup for the study of water transport in porous media by quasi-elastic neutron scattering.

In comparison to condensed matter, soft matter is subject to several interplaying effects (surface heterogeneities and swelling effect) that influence transport at the nanoscale. In consequence, transport in soft and compliant materials is coupled to adsorption and deformation phenomena. The permeance of the material, i.e., the response of the material to a pressure gradient, is dependent on the temperature, the chemical potential, and the external constraint. Therefore, the characterization of water dynamics in soft porous materials, which we address here, becomes much more complex. In this paper, the development of an original setup for scattering measurements of a radiation in the transmitted geometry in oedometric conditions is described. A specially designed cell enables a uniaxial compression of the investigated material, PIM-1 (Polymers of Intrinsic Microporosity), in the direction perpendicular to the applied hydraulic pressure gradient (up to 120 bars). High pressure boosting of the circulating water is performed with a commercially available high-pressure pump Karcher. This particular setup is adapted to the quasi-elastic neutron scattering technique, which enables us to probe diffusion and relaxation phenomena with characteristic times of 10-9 s-10-12 s. Moreover, it can easily be modified for other scattering techniques.

Collapse and cavitation during the drying of water-saturated PDMS sponges with closed porosity.

In this paper, we study the drying of water-saturated porous polydimethylsiloxane (PDMS) elastomers with closed porosity in which the evaporation of water is possible only via the diffusion across PDMS. Starting from water/PDMS emulsions, we fabricate soft macroporous samples with different pore diameter distributions and average diameters ranging from 10 to 300 µm. In these materials, the drying may lead to either a collapsed state with low porosity or the cavitation and reopening of a fraction of the pores. Using optical microscopy and porosity measurements, we showed the influence of the pore diameters and interactions on the result of drying. At pore diameters lower than 30 µm, the majority of pores remain collapsed. We attribute the permanence of the collapse of most small pores to a low probability of cavitation and to the adhesion of the pore walls. Pores with diameters larger than 100 µm reopen via cavitation of the water they contain. The behavior of pores with diameters ranging from 30 to 100 µm depends on the porosity and drying temperature. We also visualize collective cavitation upon the drying of sponges initially saturated with sodium chloride solution. In this case, the cavitation in the largest pores leads to the reopening of small pores in a neighboring zone of the sample. To our knowledge, our results present the first experimental proof of the pore-size-dependent and cooperative nature of the response of soft sponges with closed porosity to drying.

Flexibility of nanolayers and stacks: implications in the nanostructuration of clays.

The basic structural units of adsorbing microporous materials such as clays and cementitious materials are flexible nanolayers. The flexibility of these layers is reported to play a crucial role in the structuration of these materials, potentially affecting therefore the thermo-mechanical behavior of such materials. Adsorbed fluids are structured in a discrete number of layers within the space between the nanolayers in these materials. This discrete nature of adsorption states may lead to micro-instabilities due to non-convex energy profiles. The transition between adsorption states may involve the bending of layers. Bending contributes to metastability, which is reported to be a potential source of the irreversibilities notably in clay behavior. In this paper, we determine the bending modulus of clay nanolayers by the combination of plate theory with molecular simulations of sodium montmorillonite. The case of clays is illustrative of the behavior of phyllosilicates (i.e. sheet-silicates) which are ubiquitous minerals in the Earth's crust. We discuss the conditions in which clay particles, i.e. a stack of nanolayers, can be viewed as thin plates. Estimations of the bending modulus according to the hydration state and dimensions of clay particles are provided. We analyze the implications of the flexibility of the layers in the behavior of a stack of layers as well as in the transitions between adsorption states. The energy barrier associated with bending of clay layers and the characteristic length of bending in such transitions are provided. Our results contribute to a better understanding of the nanostructure of layered adsorbing materials.

Two models based on local microscopic relaxations to explain long-term basic creep of concrete.

In this study, we propose an exhaustion model and an adapted work-hardening model to explain the long-term basic creep of concrete. In both models, the macroscopic creep strain originates from local microscopic relaxations. The two models differ in how the activation energies of those relaxations are distributed and evolve during the creep process. With those models, at least up to a few dozen MPa, the applied stress must not modify the rate at which those relaxations occur, but only enables the manifestation of each local microscopic relaxation into an infinitesimal increment of basic creep strain. The two models capture equally well several phenomenological features of the basic creep of concrete. They also make it possible to explain why the indentation technique enables the quantitative characterization of the long-term kinetics of logarithmic creep of cement-based materials orders of magnitude faster than by macroscopic testing. The models hint at a physical origin for the relaxations that is related to disjoining pressures.

Hydration Phase Diagram of Clay Particles from Molecular Simulations.

Adsorption plays a fundamental role in the behavior of clays. Because of the confinement between solid clay layers on the nanoscale, adsorbed water is structured in layers, which can occupy a specific volume. The transition between these states is intimately related to key features of clay thermo-hydro-mechanical behavior. In this article, we consider the hydration states of clays as phases and the transition between these states as phase changes. The thermodynamic formulation supporting this idea is presented. Then, the results from grand canonical Monte Carlo simulations of sodium montmorillonite are used to derive hydration phase diagrams. The stability analysis presented here explains the coexistence of different hydration states at clay particle scale and improves our understanding of the irreversibilities of clay thermo-hydro-mechanical behavior. Our results provide insights into the mechanics of the elementary constituents of clays, which is crucial for a better understanding of the macroscopic behavior of clay-rich rocks and soils.

Transient effects of drying creep in nanoporous solids: understanding the effects of nanoscale energy barriers.

The Pickett effect is the phenomenon of creep enhancement during transient drying. It has been observed for many nanoporous solids, including concrete, wood and Kevlar. While the existing micromechanical models can partially explain this effect, they have yet to consider nanoscale dynamic effects of water in nanopores, which are believed to be of paramount importance. Here, we examine how creep deformations in a slit pore are accelerated by the motion of water due to drying forces using coarse-grained molecular dynamics simulations. We find that the drying that drives water flow in the nanopores lowers both the activation energy of pore walls sliding past one another and the apparent viscosity of confined water molecules. This lowering can be captured with an analytical Arrhenius relationship accounting for the role of water flow in overcoming the energy barriers. Notably, we use this model and simulation results to demonstrate that the drying creep strain is not linearly dependent on the applied creep stress at the nanopore level. Our findings establish the scaling relationships that explain how the creep driving force, drying force and fluid properties are related. Thus, we establish the nanoscale origins of the Pickett effect and provide strategies for minimizing the additional displacements arising from this effect.

Effect of Water on Elastic and Creep Properties of Self-Standing Clay Films.

We characterized experimentally the elastic and creep properties of thin self-standing clay films, and how their mechanical properties evolved with relative humidity and water content. The films were made of clay montmorillonite SWy-2, obtained by evaporation of a clay suspension. Three types of films were manufactured, which differed by their interlayer cation: sodium, calcium, or a mixture of sodium with calcium. The orientational order of the films was characterized by X-ray diffractometry. The films were mechanically solicited in tension, the resulting strains being measured by digital image correlation. We measured the Young's modulus and the creep over a variety of relative humidities, on a full cycle of adsorption-desorption for what concerns the Young's modulus. Increasing relative humidity made the films less stiff and made them creep more. Both the elastic and creep properties depended significantly on the interlayer cation. For the Young's modulus, this dependence must originate from a scale greater than the scale of the clay layer. Also, hysteresis disappeared when plotting the Young's modulus versus water content instead of relative humidity. Independent of interlayer cation and of relative humidity greater than 60%, after a transient period, the creep of the films was always a logarithmic function of time. The experimental data gathered on these mesoscale systems can be of value for modelers who aim at predicting the mechanical behavior of clay-based materials (e.g., shales) at the engineering macroscopic scale from the one at the atomistic scale, for them to validate the first steps of their upscaling scheme. They provide also valuable reference data for bioinspired clay-based hybrid materials.

ESEM study of the humidity-induced swelling of clay film.

We measured the humidity-induced swelling of thin self-standing films of montmorillonite clay by a combination of environmental scanning electron microscopy (ESEM) and digital image correlation (DIC). The films were about 40 µm thick. They were prepared by depositing and evaporating a suspension of clay and peeling off the highly oriented deposits. The rationale for creating such original samples was to obtain mesoscopic samples that could be used to bridge experimentally the gap between the scale of the clay layer and the engineering scale of a macroscopic clay sample. Several montmorillonite samples were used: the reference clay Swy-2, the same clay homoionized with sodium or calcium ions, and a sodium-exchanged Cloisite. The edges of the clay films were observed by ESEM at various relative humidity values between 14% and 95%. The ESEM images were then analyzed by DIC to measure the swelling or the shrinkage of the films. We also measured the adsorption/desorption isotherms by weighing the film samples in a humidity-controlled environment. In order to analyze our results, we compared our swelling/shrinkage and adsorption/desorption data with previously published data on the interlayer spacing obtained by X-ray diffraction and with numerical estimates of the interlayer water obtained by molecular dynamics simulation. The swelling and the hysteresis of this swelling were found to be comparable for the overall macroscopic films and for the interlayer space. The same correspondence between film and interlayer space was observed for the amount of adsorbed water. This suggests that, in the range of relative humidities values explored, the films behave like freely swelling oriented stacks of clay layers, without any significant contribution from the mesoporosity. The relevance of this result for the behavior of clayey sedimentary rocks and the differences with the behavior of nonoriented samples (powders or compacted powders) are briefly discussed.

Adsorption-induced deformation of microporous materials: coal swelling induced by CO2-CH4 competitive adsorption.

Carbon dioxide injection in coal seams is known to improve the methane production of the coal seam, while ensuring a safe and long-term carbon sequestration. This improvement is due to the preferential adsorption of CO(2) in coal with respect to CH(4): an injection of CO(2) thus results in a desorption of CH(4). However, this preferential adsorption is also known to cause a differential swelling of coal, which results in a significant decrease in the reservoir permeability during the injection process. Recent studies have shown that adsorption in coal micropores (few angströms in size) is the main cause of the swelling. In this work, we focus on the competitive adsorption behavior of CO(2) and CH(4) in micropores. We perform molecular simulations of adsorption with a realistic atomistic model for coal. The competitive adsorption is studied at various temperatures and pressures representative of those in geological reservoirs. With the help of a poromechanical model, we then quantify the subsequent differential swelling induced by the computed adsorption behaviors. The differential swelling is almost insensitive to the geological temperatures and pressures considered here and is proportional to the CO(2) mole fraction in the coal.

Nanogranular origin of concrete creep.

Concrete, the solid that forms at room temperature from mixing Portland cement with water, sand, and aggregates, suffers from time-dependent deformation under load. This creep occurs at a rate that deteriorates the durability and truncates the lifespan of concrete structures. However, despite decades of research, the origin of concrete creep remains unknown. Here, we measure the in situ creep behavior of calcium-silicate-hydrates (C-S-H), the nano-meter sized particles that form the fundamental building block of Portland cement concrete. We show that C-S-H exhibits a logarithmic creep that depends only on the packing of 3 structurally distinct but compositionally similar C-S-H forms: low density, high density, ultra-high density. We demonstrate that the creep rate ( approximately 1/t) is likely due to the rearrangement of nanoscale particles around limit packing densities following the free-volume dynamics theory of granular physics. These findings could lead to a new basis for nanoengineering concrete materials and structures with minimal creep rates monitored by packing density distributions of nanoscale particles, and predicted by nanoscale creep measurements in some minute time, which are as exact as macroscopic creep tests carried out over years.