Structure, Properties, and Phase Transformations of Water Nanoconfined between Brucite-like Layers: The Role of Wall Surface Polarity.

The interaction of water with confining surfaces is primarily governed by the wetting properties of the wall material-in particular, whether it is hydrophobic or hydrophilic. The hydrophobicity or hydrophilicity itself is determined primarily by the atomic structure and polarity of the surface groups. In the present work, we used molecular dynamics to study the structure and properties of nanoscale water layers confined between layered metal hydroxide surfaces with a brucite-like structure. The influence of the surface polarity of the confining material on the properties of nanoconfined water was studied in the pressure range of 0.1-10 GPa. This pressure range is relevant for many geodynamic phenomena, hydrocarbon recovery, contact spots of tribological systems, and heterogeneous materials under extreme mechanical loading. Two phase transitions were identified in water confined within 2 nm wide slit-shaped nanopores: (1) at p1 = 3.3-3.4 GPa, the liquid transforms to a solid phase with a hexagonal close-packed (HCP) crystal structure, and (2) at p2 = 6.7-7.1 GPa, a further transformation to face-centered cubic (FCC) crystals occurs. It was found that the behavior of the confined water radically changes when the partial charges (and, therefore, the surface polarity) are reduced. In this case, water transforms directly from the liquid phase to an FCC-like phase at 3.2-3.3 GPa. Numerical simulations enabled determination of the amount of hydrogen bonding and diffusivity of nanoconfined water, as well as the relationship between pressure and volumetric strain.

Analysis of the Quasi-Static and Dynamic Fracture of the Silica Refractory Using the Mesoscale Discrete Element Modelling.

Computer modelling is a key tool in the optimisation and development of ceramic refractories utilised as insulation in high-temperature industrial furnaces and reactors. The paper is devoted to the mesoscale computer modelling of silica refractories using the method of homogeneously deformable discrete elements. Approaches to determine the local mechanical properties of the constituents from the global experimental failure parameters and respective crack trajectories are considered. Simulations of the uniaxial compressive and tensile failure in a wide range of quasi-static and dynamic loading rates (102 s-1) are performed. The upper limit of the dynamic loading rates corresponds to the most severe loading rates during the scrap loading on the refractory lining. The dependence of the strength, fracture energy, and brittleness at failure on the loading rate is analysed. The model illustrates that an increase in the loading rate is accompanied by a significant change in the mechanical response of the refractory, including a decrease in the brittleness at failure, a more dispersed failure process, and a higher fraction of the large grain failure. The variation of the grain-matrix interface's strength has a higher impact on the static compressive than on the static tensile properties of the material, while the material's dynamic tensile properties are more sensitive to the interface strength than the dynamic compressive properties.

Nonlinear Mechanical Effect of Free Water on the Dynamic Compressive Strength and Fracture of High-Strength Concrete.

It is well-known that the effect of interstitial fluid on the fracture pattern and strength of saturated high-strength concrete is determined by qualitatively different mechanisms at quasi-static and high strain rate loading. This paper shows that the intermediate range of strain rates (10-4 s-1 < ε˙ < 100 s-1) is also characterized by the presence of a peculiar mechanism of interstitial water effect on the concrete fracture and compressive strength. Using computer simulations, we have shown that such a mechanism is the competition of two oppositely directed processes: deformation of the pore space, which leads to an increase in pore pressure; and pore fluid flow. The balance of these processes can be effectively characterized by the Darcy number, which generalizes the notion of strain rate to fluid-saturated material. We have found that the dependence of the compressive strength of high-strength concrete on the Darcy number is a decreasing sigmoid function. The parameters of this function are determined by both low-scale (capillary) and large-scale (microscopic) pore subsystems in a concrete matrix. The capillary pore network determines the phenomenon of strain-rate sensitivity of fluid-saturated concrete and logistic form of the dependence of compressive strength on strain rate. Microporosity controls the actual boundary of the quasi-static loading regime for fluid-saturated samples and determines localized fracture patterns. The results of the study are relevant to the design of special-purpose concretes, as well as the assessment of the limits of safe impacts on concrete structural elements.

Suppression of wear in dry sliding friction induced by negative thermal expansion.

Surface temperature is among crucial factors which control wear during sliding dry contact. Using computer modeling, we study the possibility to achieve close to zero rate of surface wear during sliding friction of the special type of materials which possess negative thermal expansion. The numerical simulations reveal two wear regimes for materials with negative thermal expansion coefficient as dependent on the applied normal stress level. When the applied stress is lower than that of a critical level, a steady almost zero wear rate and nanorough surface are achieved during friction. Otherwise, wear rate is of the same order of magnitude as for "traditional" materials with positive thermal expansion coefficient. The critical stress value is analyzed depending on the material's mechanical, thermophysical, and surface roughness characteristics.

Computer-Aided Design of Boron Nitride-Based Membranes with Armchair and Zigzag Nanopores for Efficient Water Desalination.

Recent studies have shown that the use of membranes based on artificial nanoporous materials can be effective for desalination and decontamination of water, separation of ions and gases as well as for solutions to other related problems. Before the expensive stages of synthesis and experimental testing, the search of the optimal dimensions and geometry of nanopores for the water desalination membranes can be done using computer-aided design. In the present study, we propose and examine the assumption that rectangular nanopores with a high aspect ratio would demonstrate excellent properties in terms of water permeation rate and ion rejection. Using the non-equilibrium molecular dynamic simulations, the properties of promising hexagonal boron nitride (h-BN) membranes with rectangular nanopores were predicted. It has been found that not only the nanopore width but also its design ("armchair" or "zigzag") determines the permeability and ion selectivity of the h-BN-based membrane. The results show that membranes with a zigzag-like design of nanopores of ~6.5 Å width and the armchair-like nanopores of ~7.5 Å width possess better efficiency compared with other considered geometries. Moreover, the estimated efficiency of these membranes is higher than that of any commercial membranes and many other previously studied single-layer model membranes with other designs of the nanopores.

Role of Adhesion Stress in Controlling Transition between Plastic, Grinding and Breakaway Regimes of Adhesive Wear.

A discrete-element based model of elastic-plastic materials with non-ideal plasticity and with an account of both cohesive and adhesive interactions inside the material is developed and verified. Based on this model, a detailed study of factors controlling the modes of adhesive wear is performed. Depending on the material and loading parameters, we observed three main modes of wear: slipping, plastic grinding, cleavage, and breakaway. We find that occurrence of a particular mode is determined by the combination of two dimensionless material parameters: (1) the ratio of the adhesive stress to the pure shear strength of the material, and (2) sensitivity parameter of material shear strength to local pressure. The case study map of asperity wear modes in the space of these parameters has been constructed. Results of this study further develop the findings of the widely discussed studies by the groups of J.-F. Molinari and L. Pastewka.

Strength of shear bands in fluid-saturated rocks: a nonlinear effect of competition between dilation and fluid flow.

This study shows the significant and nonlinear effect of the competition between dilation and fluid flow on the shear strength of constrained shear bands in fluid-saturated rocks. This effect is conditioned by the contribution of the pore pressure to the yield stress and strength. The pore pressure is controlled by the dilation of the pore space in the solid skeleton of the shear band during plastic deformation and by squeezing of pores in surrounding blocks by the dilating shear band due to the high stiffness of the host massif. A generalized equation has been derived to describe the dependence of the shear band strength on the ratio of strain rate to fluid flow rate.

The Continuum Approach to the Description of Semi-Crystalline Polymers Deformation Regimes: The Role of Dynamic and Translational Defects.

This paper presents a new approach to describe the mechanical behavior of semi-crystalline polymers, the plastic deformation of which is determined by their two-phase structure. To describe the plastic behavior of semi-crystalline polymers, a two-phase model is used. In the framework of this model, one phase is in a hard (crystalline) state, and the other in a soft (amorphous) state. The two-phase material is modeled by a single-phase homogeneous continuum based on the approximation of the effective medium. It is assumed that two infinitely close material points of the continuum are connected in series by elastic and viscous bonds, which corresponds to the Maxwell model. It is shown that, in this case, the Maxwell continuum is a pseudo-Euclidean space. Generalizing the definition of defects from a three-dimensional space to a four-dimensional pseudo-Euclidean space, we obtained a dynamic system of nonlinear, interrelated equations to describe the behavior of translational-type defects in the solid phase and dynamic defects in the amorphous phase. As an example of an application for these equations, the phenomenon of creep under uniaxial loading is considered. It is shown that the formalism of the proposed two-phase model makes it possible to describe creep phenomenon regularities, which correspond to both the aging theory and the flow theory.

Nonlinear effect of elastic vortexlike motion on the dynamic stress state of solids.

We present a theoretical analysis of the dynamic stress-strain state of regions in a solid body that are involved in a collective elastic vortexlike motion. It is shown that the initiation of elastic vortexlike motion in the material is accompanied by the appearance of dilatancy and equivalent strain, the magnitudes of which are proportional to the square of the ratio of linear velocity on the periphery of the elastic vortex to the velocity of longitudinal elastic waves (P wave). Under conditions of dynamic loading the described dynamic effects are able to initiate inelastic deformation or destruction of the material at loading speeds of a few percent of the P-wave speed. The obtained analytical estimates suggest that dynamic nonlinear strains can make a significant contribution in a number of widely studied nonlinear dynamic phenomena in solids. Among them are the effect of acoustic (dynamic) dilatancy in solids and granular media, which leads to the generation of longitudinal elastic waves by transverse waves [V. Tournat et al., Phys. Rev. Lett. 92, 085502 (2004)10.1103/PhysRevLett.92.085502] and the formation of an array of intense "hot spots" (reminiscent of shear-induced hydrodynamic instabilities in fluids) in adiabatic shear bands [P. R. Guduru et al., Phys. Rev. E 64, 036128 (2001)10.1103/PhysRevE.64.036128].

Key role of elastic vortices in the initiation of intersonic shear cracks.

Using the particle-based method of movable cellular automata, we analyze the initiation and propagation of intersonic mode II cracks along a weak interface. We show that the stress concentration in front of the crack tip, which is believed to be the mechanism of acceleration of the crack beyond the speed of shear waves, is due to the formation of an elastic vortex. The vortex develops in front of the crack during the short initial period of crack propagation. It expands and moves away from the crack tip and finally detaches from it. Maximum stress concentration in the vortex is achieved at the moment of detachment of the vortex. The crack can accelerate towards the longitudinal wave speed if the magnitude of shear stresses in the elastic vortex reaches the material shear strength before vortex detachment. We have found that for given material parameters, the condition for the unstable accelerated crack propagation depends only on the ratio of the initial crack length to its width (e.g., due to surface roughness).