The Szego-Widom theorem provides an expression for the determinant of block Toeplitz matrices in the asymptotic limit of large matrix dimension n. We show that the presence of zero modes, i.e, eigenvalues that vanish as n, ||<1, when n, requires a modification of the Szego-Widom theorem. A new asymptotic expression for the determinant of a certain class of block Toeplitz matrices with one pair of zero modes is derived. The result is inspired by one-dimensional topological superconductors, and the relation with the latter systems is discussed.

VL - 174 UR - http://link.springer.com/10.1007/s10955-018-2177-8 JO - J Stat Phys ER - TY - JOUR T1 - Multiscale poromechanics of wet cement paste JF - Proceedings of the National Academy of Sciences Y1 - 2019 A1 - Zhou, Tingtao A1 - Katerina Ioannidou A1 - Franz-Josef Ulm A1 - Bazant, Martin Z. A1 - Roland Jean-Marc Pellenq AB -Capillary effects, such as imbibition drying cycles, impact the mechanics of granular systems over time. A multiscale poromechanics framework was applied to cement paste, which is the most common building material, experiencing broad humidity variations over the lifetime of infrastructure. First, the liquid density distribution at intermediate to high relative humidity is obtained using a lattice gas density functional method together with a realistic nanogranular model of cement hydrates. The calculated adsorption/desorption isotherms and pore size distributions are discussed and compare well with nitrogen and water experiments. The standard method for pore size distribution determination from desorption data is evaluated. Second, the integration of the Korteweg liquid stress field around each cement hydrate particle provided the capillary forces at the nanoscale. The cement mesoscale structure was relaxed under the action of the capillary forces. Local irreversible deformations of the cement nanograins assembly were identified due to liquid–solid interactions. The spatial correlations of the nonaffine displacements extend to a few tens of nanometers. Third, the Love–Weber method provided the homogenized liquid stress at the micrometer scale. The homogenization length coincided with the spatial correlation length of nonaffine displacements. Our results on the solid response to capillary stress field suggest that the micrometer-scale texture is not affected by mild drying, while nanoscale irreversible deformations still occur. These results pave the way for understanding capillary phenomena-induced stresses in heterogeneous porous media ranging from construction materials to hydrogels and living systems.

VL - 2 UR - http://www.pnas.org/lookup/doi/10.1073/pnas.1901160116 JO - Proc Natl Acad Sci USA ER - TY - JOUR T1 - Mechanical strength of wet particle agglomerates JF - Mechanics Research Communications Y1 - 2018 A1 - Vo, Thanh-Trung A1 - Patrick Mutabaruka A1 - Saeid Nezamabadi A1 - Jean-Yves Delenne A1 - Izard, Edouard A1 - Roland Jean-Marc Pellenq A1 - Farhang Radjaï AB -Using particle dynamics simulations, we investigate the strength and microstructure of agglomerates of wet frictional particles subjected to axial compression. The numerical model accounts for the cohesive and viscous effects of the binding liquid up to a debonding distance with the liquid assumed to be distributed homogeneously inside the agglomerate. We show that wet agglomerates undergo plastic deformation due to the rearrangements of primary particles during compression. The compressive strength is thus characterized by the plastic threshold before the onset of failure by the irreversible loss of wet contacts between primary particles. We find that the agglomerate plastic threshold is proportional to the characteristic cohesive stress defined from the liquid-vapor surface tension and the mean diameter of primary particles, with a prefactor that is a nearly linear function of the debonding distance and increases with size span. We analyze the agglomerate microstructure and, considering only the cohesive capillary forces at all bonds between primary particles, we propose an expression of the plastic strength as a function of the texture parameters such as the wet coordination number and packing fraction. This expression is shown to be consistent with our simulations up to a multiplicative factor reflecting the distribution of the capillary bridges. (C) 2018 Published by Elsevier Ltd.

VL - 92 UR - https://www-sciencedirect-com.libproxy.mit.edu/science/article/pii/S0093641318301216 JO - Mechanics Research Communications ER - TY - JOUR T1 - Mesoscale structure, mechanics, and transport properties of source rocks’ organic pore networks JF - Proceedings of the National Academy of Sciences Y1 - 2018 A1 - Berthonneau, Jeremie A1 - Amaël Obliger A1 - Valdenaire, Pierre-Louis A1 - Grauby, Olivier A1 - Ferry, Daniel A1 - Chaudanson, Damien A1 - Pierre E. Levitz A1 - Kim, Jae Jin A1 - Franz-Josef Ulm A1 - Roland Jean-Marc Pellenq KW - porous media; electron tomography; mechanics; fluid transport; mesoscale AB -Organic matter is responsible for the generation of hydrocarbons during the thermal maturation of source rock formation. This geochemical process engenders a network of organic hosted pores that governs the flow of hydrocarbons from the organic matter to fractures created during the stimulation of production wells. Therefore, it can be reasonably assumed that predictions of potentially recoverable confined hydrocarbons depend on the geometry of this pore network. Here, we analyze mesoscale structures of three organic porous networks at different thermal maturities. We use electron tomography with subnanometric resolution to characterize their morphology and topology. Our 3D reconstructions confirm the formation of nanopores and reveal increasingly tortuous and connected pore networks in the process of thermal maturation. We then turn the binarized reconstructions into lattice models including information from atomistic simulations to derive mechanical and confined fluid transport properties. Specifically, we highlight the influence of adsorbed fluids on the elastic response. The resulting elastic energy concentrations are localized at the vicinity of macropores at low maturity whereas these concentrations present more homogeneous distributions at higher thermal maturities, due to pores' topology. The lattice models finally allow us to capture the effect of sorption on diffusion mechanisms with a sole input of network geometry. Eventually, we corroborate the dominant impact of diffusion occurring within the connected nanopores, which constitute the limiting factor of confined hydrocarbon transport in source rocks.

VL - 115 UR - http://www.pnas.org/lookup/doi/10.1073/pnas.1808402115 IS - 49 JO - Proc Natl Acad Sci USA ER - TY - JOUR T1 - A methodology to calibrate and to validate effective solid potentials of heterogeneous porous media from computed tomography scans and laboratory-measured nanoindentation data JF - Acta Geotechnica Y1 - 2018 A1 - Monfared, Siavash A1 - Hadrien Laubie A1 - Farhang Radjaï A1 - Hubler, Mija H. A1 - Roland Jean-Marc Pellenq A1 - Franz-Josef Ulm AB -Built on the framework of effective interaction potentials using lattice element method, a methodology to calibrate and to validate the elasticity of solid constituents in heterogeneous porous media from experimentally measured nanoindentation moduli and imported scans from advanced imaging techniques is presented. Applied to computed tomography (CT) scans of two organic-rich shales, spatial variations of effective interaction potentials prove instrumental in capturing the effective elastic behavior of highly heterogeneous materials via the first two cumulants of experimentally measured distributions of nanoindentation moduli. After calibration and validation steps while implicitly accounting for mesoscale texture effects via CT scans, Biot poroelastic coefficients are simulated. Analysis of stress percolation suggests contrasting pathways for load transmission, a reflection of microtextural differences in the studied cases. This methodology to calibrate elastic energy content of real materials from advanced imaging techniques and experimental measurements paves the way to study other phenomena such as wave propagation and fracture while providing a platform to fine-tune effective behavior of materials given advancements in additive manufacturing and machine learning algorithms .

VL - 13 UR - http://link.springer.com/10.1007/s11440-018-0687-9 IS - 6 JO - Acta Geotech. ER - TY - JOUR T1 - A minimal power model for human running performance JF - PLOS ONE Y1 - 2018 A1 - Mulligan, Matthew A1 - Adam, Guillaume A1 - Emig, Thorsten ED - Piknova, Barbora KW - ENERGY-COST; OXYGEN-UPTAKE; ATHLETIC RECORDS; ECONOMY; RUNNERS; RUN; ENDURANCE; MARATHON; EXERCISE; EXHAUSTION AB -Models for human running performances of various complexities and underlying principles have been proposed, often combining data from world record performances and bio-energetic facts of human physiology. The purpose of this work is to develop a novel, minimal and universal model for human running performance that employs a relative metabolic power scale. The main component is a self-consistency relation for the time dependent maximal power output. The analytic approach presented here is the first to derive the observed logarithmic scaling between world (and other) record running speeds and times from basic principles of metabolic power supply. Our hypothesis is that various female and male record performances (world, national) and also personal best performances of individual runners for distances from 800m to the marathon are excellently described by this model. Indeed, we confirm this hypothesis with mean errors of (often much) less than 1%. The model defines endurance in a way that demonstrates symmetry between long and short racing events that are separated by a characteristic time scale comparable to the time over which a runner can sustain maximal oxygen uptake. As an application of our model, we derive personalized characteristic race speeds for different durations and distances.

VL - 13 UR - http://dx.plos.org/10.1371/journal.pone.0206645 IS - 11 JO - PLoS ONE ER - TY - JOUR T1 - Multi-periodic boundary conditions and the Contact Dynamics method JF - Comptes Rendus Mécanique Y1 - 2018 A1 - Farhang Radjaï AB -For investigating the mechanical behavior of granular materials by means of the discrete element approach, it is desirable to be able to simulate representative volume elements with macroscopically homogeneous deformations. This can be achieved by means of fully periodic boundary conditions such that stresses or displacements can be applied in all space directions. We present a general framework for periodic boundary conditions in granular materials and its implementation more specifically in the Contact Dynamics method. (c) 2017 Academie des sciences. Published by Elsevier Masson SAS.

VL - 346 UR - https://linkinghub.elsevier.com/retrieve/pii/S1631072117302346 IS - 3 JO - Comptes Rendus Mécanique ER - TY - JOUR T1 - Multiscale modeling for bioresources and bioproducts JF - Innovative Food Science & Emerging Technologies Y1 - 2018 A1 - Barnabe, M. A1 - Blanc, Nicolas A1 - Chabin, T. A1 - Jean-Yves Delenne A1 - Duri, A. A1 - Frank, Xavier A1 - Hugouvieux, V. A1 - Lutton, E. A1 - Mabille, F. A1 - Saeid Nezamabadi A1 - Perrot, N. A1 - Farhang Radjaï A1 - Ruiz, T. A1 - Tonda, A. AB -Designing and processing complex matter and materials are key objectives of bioresource and bioproduct research. Modeling approaches targeting such systems have to account for their two main sources of complexity: their intrinsic multi-scale nature; and the variability and heterogeneity inherent to all living systems. Here we provide insight into methods developed at the Food & Bioproduct Engineering division (CEPIA) of the French National Institute of Agricultural Research (INRA). This brief survey focuses on innovative research lines that tackle complexity by mobilizing different approaches with complementary objectives. On one hand cognitive approaches aim to uncover the basic mechanisms and laws underlying the emerging collective properties and macroscopic behavior of soft-matter and granular systems, using numerical and experimental methods borrowed from physics and mechanics. The corresponding case studies are dedicated to the structuring and phase behavior of biopolymers, powders and granular materials, and to the evolution of these structures caused by external constraints. On the other hand machine learning approaches can deal with process optimizations and outcome predictions by extracting useful information and correlations from huge datasets built from experiments at different length scales and in heterogeneous conditions. These predictive methods are illustrated in the context of cheese ripening, grape maturity prediction and bacterial production.

VL - 46 UR - https://linkinghub.elsevier.com/retrieve/pii/S1466856417302230 IS - Special Issue: SI JO - Innovative Food Science & Emerging Technologies ER - TY - JOUR T1 - Magnetism as indirect tool for carbon content assessment in nickel nanoparticles JF - Journal of Applied Physics Y1 - 2017 A1 - Oumellal, Y. A1 - Yann Magnin A1 - ínez de Yuso, A. A1 - Aguiar Hualde, J. M. A1 - Amara, H. A1 - Paul-Boncour, V. A1 - Matei Ghimbeu, C. A1 - Malouche, A. A1 - Christophe Bichara A1 - Roland Jean-Marc Pellenq A1 - Zlotea, C. AB -We report a combined experimental and theoretical study to ascertain carbon solubility in nickel nanoparticles embedded into a carbon matrix *via* the one-pot method. This original approach is based on the experimental characterization of the magnetic properties of Ni at room temperature and Monte Carlo simulations used to calculate the magnetization as a function of C content in Ni nanoparticles. Other commonly used experimental methods fail to accurately determine the chemical analysis of these types of nanoparticles. Thus, we could assess the C content within Ni nanoparticles and it decreases from 8 to around 4 at. % with increasing temperature during the synthesis. This behavior could be related to the catalytic transformation of dissolved C in the Ni particles into graphite layers surrounding the particles at high temperature. The proposed approach is original and easy to implement experimentally since only magnetization measurements at room temperature are needed. Moreover, it can be extended to other types of magnetic nanoparticles dissolving carbon.

Heat radiation and near-field radiative heat transfer can be strongly manipulated by adjusting geometrical shapes, optical properties, or the relative positions of the objects involved. Typically, these objects are considered as embedded in vacuum. By applying the methods of fluctuational electrodynamics, we derive general closed-form expressions for heat radiation and heat transfer in a system of N arbitrary objects embedded in a passive nonabsorbing background medium. Taking into account the principle of reciprocity, we explicitly prove the symmetry and positivity of transfer in any such system. Regarding applications, we find that the heat radiation of a sphere as well as the heat transfer between two parallel plates is strongly enhanced by the presence of a background medium. Regarding near- and far-field transfer through a gas like air, we show that a microscopic model (based on gas particles) and a macroscopic model (using a dielectric contrast) yield identical results. We also compare the radiative transfer through a medium like air and the energy transfer found from kinetic gas theory.

VL - 95 UR - https://link.aps.org/doi/10.1103/PhysRevB.95.085413 IS - 8 JO - Phys. Rev. B ER - TY - JOUR T1 - Mechanisms of jamming in the Nagel-Schreckenberg model for traffic flow JF - Physical Review E Y1 - 2017 A1 - Bette, Henrik M. A1 - Habel, Lars A1 - Emig, Thorsten A1 - Schreckenberg, Michael AB -We study the Nagel-Schreckenberg cellular automata model for traffic flow by both simulations and analytical techniques. To better understand the nature of the jamming transition, we analyze the fraction of stopped cars P(v=0) as a function of the mean car density. We present a simple argument that yields an estimate for the free density where jamming occurs, and show satisfying agreement with simulation results. We demonstrate that the fraction of jammed cars P(v∈{0,1}) can be decomposed into the three factors (jamming rate, jam lifetime, and jam size) for which we derive, from random walk arguments, exponents that control their scaling close to the critical density.

VL - 95 UR - https://link.aps.org/doi/10.1103/PhysRevE.95.012311 IS - 1 JO - Phys. Rev. E ER - TY - JOUR T1 - Mesoscale Poroelasticity of Heterogeneous Media JF - Journal of Nanomechanics and Micromechanics Y1 - 2017 A1 - Monfared, Siavash A1 - Hadrien Laubie A1 - Farhang Radjaï A1 - Roland Jean-Marc Pellenq A1 - Franz-Josef Ulm AB -The poromechanics of heterogeneous media is reformulated in a discrete framework using the lattice element method (LEM) that accounts for the presence of interfaces as well as local microtextural and elastic variations. The exchange of mechanical information between pore and solid(s) is captured by means of force field potentials for these domains, which eliminate the requirement of scale separability of continuum-based poromechanics approaches. In congruence with mu VT and NPT ensembles of statistical mechanics, discrete expressions for Biot poroelastic coefficients are derived. Considering harmonic-type interaction potentials for each link, analytical expressions for both isotropic and transversely isotropic effective elasticity are presented. The theory is validated against continuum-based expressions of Biot poroelastic coefficients for porous media with isotropic and transversely isotropic elastic solid behavior. (C) 2017 American Society of Civil Engineers.

VL - 7 UR - http://ascelibrary.org/doi/10.1061/%28ASCE%29NM.2153-5477.0000136 IS - 4 JO - J. Nanomech. Micromech. ER - TY - JOUR T1 - Methodology for Estimation of Nanoscale Hardness via Atomistic Simulations JF - Journal of Nanomechanics and Micromechanics Y1 - 2017 A1 - Qomi, M. J. Abdolhosseini A1 - Ebrahimi, Davoud A1 - Mathieu Bauchy A1 - Roland Jean-Marc Pellenq A1 - Franz-Josef Ulm KW - Atomistic simulation; Friction; Cohesion; Hardness; Tobermorite; Montmorillonite AB -Statistical mechanics has provided powerful techniques to measure mechanical properties of materials at the nanoscale and paved the way for bottom-up computational materials design. The introduction of such techniques in civil engineering applications, namely construction and geotechnical materials, remains limited to the elastic and fracture properties. This paper presents an atomistic approach to calculate the nanoscale cohesion, friction angle, and hardness. This method is based on the application of biaxial external deformation, or stress, in the weakest crystallographic direction in the material. The onset of the failure is characterized by investigating the unloading paths from several points on the stress-strain curve. Such calculations of the failure stress along different deformation paths provide multiple failure Mohr circles in the normal-shear stress space, which is found to provide a failure envelope akin to the Mohr-Coulomb failure criterion that is widely used for the plastic analysis of granular geomaterials. The failure envelope characterizes the nanoscale cohesion and friction angle, which in conjunction with continuum mechanics can be utilized to estimate the nanoscale hardness of layered materials. Application of this method to tobermorite and Na-montmorillonite crystals yields values that are close to the experimental measurements obtained using nanoindentation and atomic force microscopy techniques. (C) 2017 American Society of Civil Engineers.

VL - 7 UR - http://ascelibrary.org/doi/10.1061/%28ASCE%29NM.2153-5477.0000127 IS - 4 JO - J. Nanomech. Micromech. ER - TY - JOUR T1 - Model representations of kerogen structures: An insight from density functional theory calculations and spectroscopic measurements JF - Scientific Reports Y1 - 2017 A1 - Weck, Philippe F. A1 - Kim, Eunja A1 - Wang, Yifeng A1 - Kruichak, Jessica N. A1 - Mills, Melissa M. A1 - Matteo, Edward N. A1 - Roland Jean-Marc Pellenq AB -Molecular structures of kerogen control hydrocarbon production in unconventional reservoirs. Significant progress has been made in developing model representations of various kerogen structures. These models have been widely used for the prediction of gas adsorption and migration in shale matrix. However, using density functional perturbation theory (DFPT) calculations and vibrational spectroscopic measurements, we here show that a large gap may still remain between the existing model representations and actual kerogen structures, therefore calling for new model development. Using DFPT, we calculated Fourier transform infrared (FTIR) spectra for six most widely used kerogen structure models. The computed spectra were then systematically compared to the FTIR absorption spectra collected for kerogen samples isolated from Mancos, Woodford and Marcellus formations representing a wide range of kerogen origin and maturation conditions. Limited agreement between the model predictions and the measurements highlights that the existing kerogen models may still miss some key features in structural representation. A combination of DFPT calculations with spectroscopic measurements may provide a useful diagnostic tool for assessing the adequacy of a proposed structural model as well as for future model development. This approach may eventually help develop comprehensive infrared (IR)-fingerprints for tracing kerogen evolution.

VL - 7 IS - 1 JO - Sci Rep ER - TY - JOUR T1 - Modeling Granular Materials: Century-Long Research across Scales JF - Journal of Engineering Mechanics Y1 - 2017 A1 - Farhang Radjaï A1 - Jean-Noel Roux A1 - Daouadji, Ali AB -Granular materials are the most recurrent form of solid-state matter on Earth. They challenge researchers and engineers in various fields not only because they occur with a broad variety of grain sizes, shapes and interactions in nature and industry, but also because they show a rich panoply of mechanical states. Despite this polymorphism, all these different types of soils, powders, granules, ores, pharmaceutical products, etc., are instances of the granular matter with the same least common denominator of being sandlike (psammoid in Greek), i.e., solid grains interacting via frictional contacts. This review describes milestone contributions to the field of granular materials since the early elastic-plastic models developed for soils in the 1950s. The research on granular materials has grown into a vast multidisciplinary field in the 1980s with increasing focus on the microstructure and owing to new experimental tools and discrete simulation methods. It turns out that the granular texture, particle-scale kinematics, and force transmission are far more complex than presumed in early micromechanical models of granular materials. Hence, constitutive relations cannot easily be derived from the particle-scale behavior although advanced continuum models have been developed to account for anisotropy, intermediate stress, and complex loading paths. The subtle elastic properties and origins of bulk friction will be discussed, as well as the effects of particle shape and size distributions. The review covers also recent developments in macroscopic modeling such as the thermomechanical approach, anisotropic critical state theory, nonlocal modeling approach, inertial flows, and material instabilities. Finally, a brief account is given of open issues and some new frontiers and challenges in the field.

VL - 143 IS - 4 JO - J. Eng. Mech. ER - TY - JOUR T1 - Modeling root growth in granular soils: effects of root stiffness and packing fraction JF - EPJ Web of Conferences Y1 - 2017 A1 - Fakih, Mahmoud A1 - Jean-Yves Delenne A1 - Farhang Radjaï A1 - Fourcaud, Thierry ED - Saeid Nezamabadi ED - Luding, S. AB -We use molecular dynamics simulations to investigate the effects of root bending stiffness and packing fraction on the path followed by a growing root in 2D packings of grains representing a soil. The root is modeled as a chain of elements that can grow in length and change their direction depending on the forces exerted by soil grains. We show that the root shape is mainly controlled by the bending stiffness of its apex. At low stiffness, the root randomly explores the pore space whereas at sufficiently high stiffness, of the order of soil hardness multiplied by mean grain size, the root follows a straight path across the soil. Between these two limits, the root shape can be characterized by the standard deviation of its re-directions at the scale of soil grains. We find that this shape parameter varies as a power-law function of the normalized bending stiffness.

VL - 140 UR - http://www.epj-conferences.org/10.1051/epjconf/201714014013 JO - EPJ Web Conf. ER - TY - JOUR T1 - Modeling soft granular materials JF - Granular Matter Y1 - 2017 A1 - Saeid Nezamabadi A1 - Thanh Hai Nguyen A1 - Jean-Yves Delenne A1 - Farhang Radjaï AB -Soft-grain materials such as clays and other colloidal pastes share the common feature of being composed of grains that can undergo large deformations without rupture. For the simulation of such materials, we present two alternative methods: (1) an implicit formulation of the material point method (MPM), in which each grain is discretized as a collection of material points, and (2) the bonded particle model (BPM), in which each soft grain is modeled as an aggregate of rigid particles using the contact dynamics method. In the MPM, a linear elastic behavior is used for the grains. In order to allow the aggregates in the BPM to deform without breaking, we use long-range center-to-center attraction forces between the primary particles belonging to each grain together with steric repulsion at their contact points. We show that these interactions lead to a plastic behavior of the grains. Using both methods, we analyze the uniaxial compaction of 2D soft granular packings. This process is nonlinear and involves both grain rearrangements and large deformations. High packing fractions beyond the jamming state are reached as a result of grain shape change for both methods. We discuss the stress-strain and volume change behavior as well as the evolution of the connectivity of the grains. Similar textures are observed at large deformations although the BPM requires higher stress than the MPM to reach the same level of packing fraction.

VL - 19 IS - 1 JO - Granular Matter ER - TY - Generic T1 - Modelling Transient Dynamics of Granular Slopes: MPM and DEM T2 - PROCEEDINGS OF THE 1ST INTERNATIONAL CONFERENCE ON THE MATERIAL POINT METHOD (MPM 2017) Book Series: Procedia Engineering Y1 - 2017 A1 - Krishna Kumar A1 - Kenichi Soga A1 - Jean-Yves Delenne A1 - Farhang Radjaï ED - Rohe, A ED - Kenichi Soga ED - Teunissen, H AB -Transient granular flows, such as rock falls, debris flows, and aerial and submarine avalanches, occur very often in nature. In the geotechnical context, transient movements of large granular slopes are a substantial factor of risk due to their destructive force and the transformations the y may produce in the landscape. This paper investigates the ability of MPM, a continuum approach, to reproduce the evolution of a granular slope destabilised by an external energy source. In particular, a central issue is whether the power-law dependence of run-out distance and time observed with respect to the initial geometry or energy can be reproduced by a simple Mohr-Coulomb plastic behaviour. The effect of base friction on the run-out kinematics is studied by comparing the data obtained from the DEM and MPM simulations. The mechanism of energy dissipation is primarily through friction and the MPM is able to predict the run-out response in good agreement with the DEM simulations. At very low excitation energies, the DEM simulations show longer run-out in comparison to the MPM due to local destabilization at the flow front. At low input energies, a larger fraction of the energy is consumed in the destabilisation process, hence the amount energy available for flow is less. However, at higher input energy, where most of the energy is dissipated during the spreading phase, the run-out distance has a weak dependence on the distribution of velocity in the granular mass.

JF - PROCEEDINGS OF THE 1ST INTERNATIONAL CONFERENCE ON THE MATERIAL POINT METHOD (MPM 2017) Book Series: Procedia Engineering PB - Elsevier Ltd. CY - JAN 10-13, 2017, Delft, NETHERLANDS VL - 175 JO - Procedia Engineering ER - TY - JOUR T1 - Molecular Modeling and Adsorption Properties of Ordered Silica-Templated CMK Mesoporous Carbons JF - Langmuir Y1 - 2017 A1 - Jain, Surendra Kumar A1 - Roland Jean-Marc Pellenq A1 - Keith E. Gubbins A1 - Peng, Xuan AB -Realistic molecular models of silica-templated CMK-1, CMK-3, and CMK-5 carbon materials have been developed by using carbon rods and carbon pipes that were obtained by adsorbing carbon in a model MCM-41 pore. The interactions between the carbon atoms with the silica matrix were described using the PN-Traz potential, and the interaction between the carbon atoms was calculated by the reactive empirical bond order (REBO) potential. Carbon rods and pipes with different thicknesses were obtained by changing the silica–carbon interaction strength, the temperature, and the chemical potential of carbon vapor adsorption. These equilibrium structures were further used to obtain the atomic models of CMK-1, CMK-3, and CMK-5 materials using the same symmetry as found in TEM pictures. These models are further refined and made more realistic by adding interconnections between the carbon rods and carbon pipes. We calculated the geometric pore size distribution of the different models of CMK-5 and found that the presence of interconnections results in some new features in the pore size distribution. Argon adsorption properties were investigated using GCMC simulations to characterize these materials at 77 K. We found that the presence of interconnection results greatly improves the agreement with available experimental data by shifting the capillary condensation to lower pressures. Adding interconnections also induces smoother adsorption/condensation isotherms, and desorption/evaporation curves show a sharp jump. These features reflex the complexity of the nanovoids in CMKs in terms of their pore morphology and topology.

VL - 33 IS - 9 ER - TY - Generic T1 - MPM with Frictional Contact for Application to Soft Particulate Materials T2 - PROCEEDINGS OF THE 1ST INTERNATIONAL CONFERENCE ON THE MATERIAL POINT METHOD (MPM 2017) Book Series: Procedia Engineering Y1 - 2017 A1 - Saeid Nezamabadi A1 - Thanh Hai Nguyen A1 - Jean-Yves Delenne A1 - Julien Averseng A1 - Frank, Xavier A1 - Farhang Radjaï ED - Rohe, A ED - Kenichi Soga ED - Teunissen, H AB -Soft particle materials are composed of discrete particles that can undergo large deformations without rupture. Most food products, many powders, colloidal pastes, vesicles and biological cells are soft particle systems. In order to model such materials, we present an efficient numerical approach combining an implicit formulation of the Material Point Method (MPM) and Contact Dynamics (CD) method. The MPM deals with bulk variables of an individual particle by discretizing it as a collection of material points, whereas the CD allows for the treatment of frictional contacts between particles. This model is applied for the simulation of the uniaxial compression of 2D soft-particle packings. The compaction is a nonlinear process in which new contacts are formed between particles and the contact areas increase. The change of particle shapes allows these materials to reach high packing fraction. We find that the contact specific surface, the orientation anisotropy and the aspect ratio of particles increase as a function of the packing fraction but at different rates. We also evidence the effect of friction, which favors strong stress chains and thus the elongation of particles, leading to larger values of the orientation anisotropy and the aspect ratio at a given level of packing fraction as compared to a frictionless particle packing.

JF - PROCEEDINGS OF THE 1ST INTERNATIONAL CONFERENCE ON THE MATERIAL POINT METHOD (MPM 2017) Book Series: Procedia Engineering PB - Elsevier Ltd. CY - JAN 10-13, 2017, Delft, NETHERLANDS VL - 175 JO - Procedia Engineering ER - TY - JOUR T1 - Mesoscale texture of cement hydrates JF - Proceedings of the National Academy of Sciences Y1 - 2016 A1 - Katerina Ioannidou A1 - Konrad J. Krakowiak A1 - Mathieu Bauchy A1 - Christian G. Hoover A1 - Enrico Masoero A1 - Sidney Yip A1 - Franz-Josef Ulm A1 - Pierre E. Levitz A1 - Roland Jean-Marc Pellenq A1 - Emanuela Del Gado AB -Strength and other mechanical properties of cement and concrete rely upon the formation of calcium–silicate–hydrates (C–S–H) during cement hydration. Controlling structure and properties of the C–S–H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C–S–H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C–S–H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C–S–H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C–S–H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials.

VL - 113 IS - 8 JO - Proc Natl Acad Sci USA ER - TY - JOUR T1 - A molecular informed poroelastic model for organic-rich, naturally occurring porous geocomposites JF - Journal of the Mechanics and Physics of Solids Y1 - 2016 A1 - Monfared, Siavash A1 - Franz-Josef Ulm AB -

Molecular simulation results on organic maturity (mature and immature kerogen as the two asymptotic cases) are introduced into a continuum micromechanics based model for organic-rich shales. Through a fundamental functional relationship that constrains microporous kerogen density and elasticity variable spaces and within the framework of effective media theory; the model bridges the gap between asymptotic cases of organic maturity with texture as the overriding theme, specifically a matrix/inclusion (Mori–Tanaka) texture for immature systems and a granular (self-consistent) texture for mature ones. The utility of the molecular results merged into a continuum framework is demonstrated by estimating kerogen's microporosity () from nanoindentation measurements. The effect of burial and diagenetic processes on the effective poroelasticity of these porous, naturally occurring geocomposites are captured by introduction of imperfect interfaces. Finally, the performance of the model is fully characterized by ranking the normalized contribution of uncertainty of input to the overall behavior and parameters of interest to geophysicists and geomechanicians such as degree of anisotropy and *in situ* stresses.

Magnetic materials having competing, i.e., frustrated, interactions can display magnetism prolific in intricate structures, discrete jumps, plateaus, and exotic spin states with increasing applied magnetic fields. When the associated elastic energy cost is not too expensive, this high potential can be enhanced by the existence of an omnipresent magnetoelastic coupling. Here we report experimental and theoretical evidence of a nonnegligible magnetoelastic coupling in one of these fascinating materials, SrCu2(BO3)(2) (SCBO). First, using pulsed-field transversal and longitudinal magnetostriction measurements we show that its physical dimensions, indeed, mimic closely its unusually rich field-induced magnetism. Second, using density functional-based calculations we find that the driving force behind the magnetoelastic coupling is the CuOCu superexchange angle that, due to the orthogonal Cu2+ dimers acting as pantographs, can shrink significantly (0.44%) with minute (0.01%) variations in the lattice parameters. With this original approach we also find a reduction of similar to 10% in the intradimer exchange integral J, enough to make predictions for the highly magnetized states and the effects of applied pressure on SCBO.

VL - 112 UR - http://www.pnas.org/lookup/doi/10.1073/pnas.1421414112 IS - 7 JO - Proc Natl Acad Sci USA ER - TY - JOUR T1 - Magnetic nanopantograph in the SrCu2(BO3)2 Shastry–Sutherland lattice JF - Proceedings of the National Academy of Sciences Y1 - 2015 A1 - Guillaume Radtke A1 - Andres Saùl A1 - Dabkowska, Hanna A. A1 - Salamon, Myron B. A1 - Jaime, Marcelo AB -Magnetic materials having competing, i.e., frustrated, interactions can display magnetism prolific in intricate structures, discrete jumps, plateaus, and exotic spin states with increasing applied magnetic fields. When the associated elastic energy cost is not too expensive, this high potential can be enhanced by the existence of an omnipresent magnetoelastic coupling. Here we report experimental and theoretical evidence of a nonnegligible magnetoelastic coupling in one of these fascinating materials, SrCu2(BO3)2 (SCBO). First, using pulsed-field transversal and longitudinal magnetostriction measurements we show that its physical dimensions, indeed, mimic closely its unusually rich field-induced magnetism. Second, using density functional-based calculations we find that the driving force behind the magnetoelastic coupling is the CuOCu^ superexchange angle that, due to the orthogonal Cu2+ dimers acting as pantographs, can shrink significantly (0.44%) with minute (0.01%) variations in the lattice parameters. With this original approach we also find a reduction of ∼10% in the intradimer exchange integral J, enough to make predictions for the highly magnetized states and the effects of applied pressure on SCBO.

VL - 112 ER - TY - JOUR T1 - The Maya blue nanostructured material concept applied to colouring geopolymers JF - RSC Adv. Y1 - 2015 A1 - Ouellet-Plamondon, Claudiane A1 - Aranda, Pilar A1 - Favier, Aurélie A1 - Habert, Guillaume A1 - Henri Van Damme A1 - Ruiz-Hitzky, Eduardo AB -Maya blue is an ancient nanostructured pigment synthetized by assembling indigo, a natural dye, with palygorskite, a microfibrous clay mineral. The novelty of our approach is to mimic “pre-Columbian nanotechnology” and to functionalize geopolymers with a sepiolite-based hybrid organic–inorganic nanocomposite inspired from the Maya blue. It is acid- and UV-resistant, as confirmed by the stability of Maya mural paintings over time. We synthesized analogous pigments, using methylene blue (MB) and methyl red (MR) as organic dyes and sepiolite as fibrous clay mineral. We used an aqueous and a solid-state method, both leading to encapsulation of dye monomers into the clay micropores, as confirmed by UV-vis spectroscopy. This nanostructured pigment was then included into a geopolymer matrix at room temperature. The stability of the new material to UV and acid was tested. It was confirmed that it is the prior encapsulation of the dye into sepiolite that leads to the stability of the pigment in the geopolymer matrix. This first study opens the way to numerous possibilities for functionalizing inorganic binder materials with organic elements that would be otherwise sensitive to thermal treatment in conventional ceramic processing.

VL - 5 IS - 120 JO - RSC Adv. ER - TY - JOUR T1 - Mechanism of H2O Insertion and Chemical Bond Formation in AlPO 4-54·x H2O at High Pressure JF - Journal of the American Chemical Society Y1 - 2015 A1 - Alabarse, Frederico G. A1 - Rouquette, Jérôme A1 - Benoit A. Coasne A1 - Haidoux, Abel A1 - Paulmann, Carsten A1 - Cambon, Olivier A1 - Haines, Julien AB -The insertion of H2O in AlPO4-54•xH2O at high pressure was investigated by single-crystal x-ray diffraction and Monte Carlo molecular simulation. H2O molecules are concentrated, in particular near the pore walls. Upon insertion, the additional water is highly disordered. Insertion of H2O (superhydration) is found to impede pore collapse in the material, thereby strongly modifying its mechanical behavior. However, instead of stabilizing the structure with respect to amorphization, the results provide evidence for the early stages of chemical bond formation between H2O molecules and tetrahedrally coordinated aluminum, which is at the origin of the amorphization/reaction process.

VL - 137 IS - 2 JO - J. Am. Chem. Soc. ER - TY - JOUR T1 - Mechanism of strength reduction along the graphenization pathway JF - Science Advances Y1 - 2015 A1 - Antonio Gamboa A1 - Baptiste Farbos A1 - Aurel, P. A1 - Gérard L. Vignoles A1 - Jean-Marc Leyssale AB -Even though polycrystalline graphene has shown a surprisingly high tensile strength, the influence of inherent grain boundaries on such property remains unclear. We study the fracture properties of a series of polycrystalline graphene models of increasing thermodynamic stability, as obtained from a long molecular dynamics simulation at an elevated temperature. All of the models show the typical and well-documented brittle fracture behavior of polycrystalline graphene; however, a clear decrease in all fracture properties is observed with increasing annealing time. The remarkably high fracture properties obtained for the most disordered (less annealed) structures arise from the formation of many nonpropagating prefracture cracks, significantly retarding failure. The stability of these reversible cracks is due to the nonlocal character of load transfer after a bond rupture in very disordered systems. It results in an insufficient strain level on neighboring bonds to promote fracture propagation. Although polycrystallinity seems to be an unavoidable feature of chemically synthesized graphenes, these results suggest that targeting highly disordered states might be a convenient way to obtain improved mechanical properties.

VL - 1 IS - 10 JO - Science Advances ER - TY - Generic T1 - The Meso-Scale Texture of Cement Hydrate Gels: Out-of-Equilibrium Evolution and Thermodynamic Driving T2 - 10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete Structures CONCREEP 10 Y1 - 2015 A1 - Emanuela Del Gado A1 - Katerina Ioannidou A1 - Enrico Masoero A1 - Roland Jean-Marc Pellenq A1 - Franz-Josef Ulm A1 - Sidney Yip ED - Hellmich, Christian ED - Pichler, Bernhard ED - Kollegger, Johann AB -

By the end of cement hydration calcium-silicate-hydrate (C-S-H) gels extends over tens and hundreds of nanometers. Their complex texture affects directly, and to a large extent, the macroscopic hygrothermal and mechanical behavior of cement. Here we review a statistical physics approach recently developed, which allows us to investigate the gel formation under the out-of-equilibrium conditions typical of cement hydration and the role of the nano-scale structure in C—S—H mechanics upon hardening. Our investigations have unveiled the role, in the C-S-H gels, of nano-scale structural and mechanical heterogeneities that develop due to the the far-from-equilibrium physico-chemical environment in which the material forms. A subtle interplay between the out-of-equilibrium evolution and the effective interactions emerging between the nano-scale units of the gels at different stages of the hydration process ultimately determines the mesoscale texture of cement hydrates and their material properties.

JF - 10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete Structures CONCREEP 10 PB - American Society of Civil Engineers CY - September 21–23, 2015 Vienna, AustriaReston, VA VL - CONCREEP 10: MECHANICS AND PHYSICS OF CREEP, SHRINKAGE, AND DURABILITY OF CONCRETE AND CONCRETE STRUCTURES ER - TY - Generic T1 - Micromechanical analysis of the surface erosion of a cohesive soil by means of a coupled LBM-DEM model T2 - IV International Conference on Particle-based Methods (PARTICLES 2015) Y1 - 2015 A1 - Cuellar, Pablo A1 - Pierre Philippe A1 - Stéphane Bonelli A1 - Benahmed, Nadia A1 - Brunier-Coulin, Florian A1 - Jeff Ngoma A1 - Jean-Yves Delenne A1 - Farhang Radjaï ED - Onate, E ED - Bischoff, M ED - Owen, DRJ KW - Cohesion KW - DEM KW - LBM KW - Surface erosion AB -The elementary mechanisms driving the ubiquitous surface erosion of cohesive geomaterials can be analysed from a micromechanical perspective combining well-known numerical techniques. Here, a coupled model combining the Discrete Element and Lattice Boltzmann methods (DEM-LBM) provides an insight into the solid-fluid interaction during the transient erosion caused by a vertical fluid jet impinging on the surface of a granular assembly. The brittle cementation providing cohesion between the solid grains is described here by means of a simple bond model with a single-parameter yield surface. The initial topology of the surface erosion tends to mimic the profile of fluid velocity directly above the soil surface. We find that both the rate of erosion and the magnitude of eroded mass depend directly on the micromechanical strength of the single solid bonds.

JF - IV International Conference on Particle-based Methods (PARTICLES 2015) PB - International Center for Numerical Methods in Engineering (CIMNE) CY - SEP 28-30 2015 Barcelona, SPAIN VL - PARTICLE-BASED METHODS IV-FUNDAMENTALS AND APPLICATIONS UR - https://hal.archives-ouvertes.fr/hal-01269324 ER - TY - JOUR T1 - Modeling force transmission in granular materials JF - Comptes Rendus Physique Y1 - 2015 A1 - Farhang Radjaï AB -The probability density function of contact forces in granular materials has been extensively studied and modeled as an outstanding signature of granular microstructure. Arguing that particle environments play a fundamental role in force transmission, we analyze the effects of steric constraints with respect to force balance condition and show that each force may be considered as resulting from a balance between lower and larger forces in proportions that mainly depend on steric effects. This idea leads to a general model that predicts an analytical expression of force density with a single free parameter. This expression fits well our simulation data and generically predicts the exponential fall-off of strong forces, a small peak below the mean force and the non-zero probability of vanishingly small forces.

VL - 16 IS - 1 JO - Comptes Rendus Physique ER - TY - JOUR T1 - Magnetic interactions in 3d metal chains on Cu2X/Cu(001) (X = N, O): Comparison with corresponding unsupported chains JF - Physical Review B Y1 - 2014 A1 - Urdaniz, M. C. A1 - Barral, M. A. A1 - Llois, A. M. A1 - Andres Saùl AB -In this work we present a systematic study of the magnetic interactions within 3d transition-metal chains adsorbed on Cu2N and Cu2O monolayers grown on Cu(001). We are interested in the particular geometric adsorption configuration which gives rise, after relaxation, to the development of diatomic TM-X (X = N, O) chains. By using density functional theory (DFT), we calculate the energy difference between the ferromagnetic and antiferromagnetic intrachain configurations for Ti, V, Cr, Mn, Fe, and Co. Both substrates give rise, with minor differences, to the same magnetic trends, the only chains which are ferromagnetic after adsorption are Cr chains. By performing similar calculations in unsupported chains and introducing a tight-binding-model Hamiltonian based on physically reasonable assumptions we reproduce the magnetic trends obtained from the DFT calculations.

VL - 90 ER - TY - JOUR T1 - Mesoscale properties of clay aggregates from potential of mean force representation of interactions between nanoplatelets JF - Journal of Chemical Physics Y1 - 2014 A1 - Ebrahimi, Davoud A1 - Andrew J. Whittle A1 - Roland Jean-Marc Pellenq AB -Face-to-face and edge-to-edge free energy interactions of Wyoming Na-montmorillonite platelets were studied by calculating potential of mean force along their center to center reaction coordinate using explicit solvent (i.e., water) molecular dynamics and free energy perturbation methods. Using a series of configurations, the Gay-Berne potential was parametrized and used to examine the mesoscale aggregation and properties of platelets that are initially random oriented under isothermal-isobaric conditions. Aggregates of clay were defined by geometrical analysis of face-to-face proximity of platelets with size distribution described by a log-normal function. The isotropy of the microstructure was assessed by computing a scalar order parameter. The number of platelets per aggregate and anisotropy of the microstructure both increases with platelet plan area. The system becomes more ordered and aggregate size increases with increasing pressure until maximum ordered state at confining pressure of 50 atm. Further increase of pressure slides platelets relative to each other leading to smaller aggregate size. The results show aggregate size of (3-8) platelets for sodium-smectite in agreement with experiments (3-10). The geometrical arrangement of aggregates affects mechanical properties of the system. The elastic properties of the meso-scale aggregate assembly are reported and compared with nanoindentation experiments. It is found that the elastic properties at this scale are close to the cubic systems. The elastic stiffness and anisotropy of the assembly increases with the size of the platelets and the level of external pressure. (C) 2014 AIP Publishing LLC.

VL - 140 IS - 15 ER - TY - Generic T1 - Mesoscale simulation of clay aggregate formation and mechanical properties T2 - 3rd International Symposium on Geomechanics from Micro to Macro Y1 - 2014 A1 - Ebrahimi, Davoud A1 - Roland Jean-Marc Pellenq A1 - Andrew J. Whittle ED - Kenichi Soga ED - Krishna Kumar ED - Giovanna Biscontin AB -This paper proposes a novel methodology for understanding the meso-scale aggregation of clay platelets in water. We use Molecular Dynamics simulations using the CLAYFF force fields to represent the interactions between two layers of Wyoming montmorillonite (Na-smectite) in bulk water. The analyses are used to establish the potential of mean force at different spacings between the layers for edge-to-edge and face-to-face interactions. This is accomplished by finding the change in free energy as a function of the separation distance between the platelets using thermodynamic perturbation theory with a simple overlap sampling method. These nanoscale results are then used to calibrate the Gay–Berne (GB) potential that represents each platelet as a single-site ellipsoidal body. A coarse-graining upscaling approach then uses the GB potentials and molecular dynamics to represent the meso-scale aggregation of clay platelets (at submicron length scale). Results from meso-scale simulations obtain the equilibrium/jamming configurations for mono-disperse clay platelets. The results show aggregation for a range of clay platelets dimensions and pressures with mean stack size ranging from 3 to 8 platelets. The particle assemblies become more ordered and exhibit more pronounced elastic anisotropy at higher confining pressures. The results are in good agreement with previously measured nano-indentation moduli over a wide range of clay packing densities.

JF - 3rd International Symposium on Geomechanics from Micro to Macro CY - SEP 01-03 2014 Univ Cambridge, Cambridge, ENGLAND VL - Geomechanics from Micro to Macro: Granular Matter IS - 3 JO - Granular Matter ER - TY - Generic T1 - Modelling cement at fundamental scales: From atoms to engineering strength and durability T2 - Euro-C Conference Y1 - 2014 A1 - Enrico Masoero A1 - Hamlin M. Jennings A1 - Franz-Josef Ulm A1 - Emanuela Del Gado A1 - Hegoi Manzano A1 - Roland Jean-Marc Pellenq A1 - Sidney Yip ED - Bicanic, N ED - Mang, H ED - Meschke, G ED - DeBorst, R AB -The mechanics and rheology of cement pastes are largely determined by the Calcium-Silicate-Hydrate (C-S-H) gel, which is normally the main binding phase. The C-S-H gel is an amorphous material with a nanoscale pore network. Here we consider a model structure of the gel, where a continuous molecular model of non-porous C-S-H is combined with a colloidal model that incorporates the porosity of the gel. Numerical simulations predict mechanical properties and microscopic processes associated with yielding under shear. The proposed model can now be used to extract further properties and to contribute to a broader effort aimed at describing and engineering the multi-scale structure and mechanical behaviour of the cement paste. We finally discuss the opportunities offered by our model with respect to the scientific and technological challenges of modelling and controlling ageing and creep over long time scales.

JF - Euro-C Conference PB - CRC Press-Taylor & Francis Group CY - MAR 24-27, 2014, St Anton am Alberg, AUSTRIA VL - COMPUTATIONAL MODELLING OF CONCRETE STRUCTURES, VOL 1 SN - 978-1-138-02641-4; 978-1-315-76203-6 ER - TY - Generic T1 - Modelling soft-particle materials T2 - 3rd International Symposium on Geomechanics from Micro to Macro Y1 - 2014 A1 - Saeid Nezamabadi A1 - Farhang Radjaï A1 - Julien Averseng ED - Kenichi Soga ED - Krishna Kumar ED - Giovanna Biscontin AB -Soft-particle materials include colloidal pastes, vesicles, many powders, microgels and suspensions. They share the common feature of being composed of particles that can undergo large deformations without rupture. For the simulation of such materials, we present a modelling approach based on an implicit formulation of the Material Point Method (MPM) interfaced with the Contact Dynamics (CD) method for the treatment of frictional contacts between particles. Each particle is discretized as a collection of material points. The information carried by the material points is projected onto a background mesh, where equations of motion are solved. The mesh solution is then used to update the material points. The implicit formulation of MPM allows for unconditional numerical stability and efficient coupling with implicit treatment of unilateral contacts and friction between the particles by the CD method. We use this model to analyse the compaction process of 2D soft-particle packings. The packing can reach high solid fractions by particle shape change and still flow plastically. The compaction is a nonlinear process in which new contacts are formed between particles and the contact areas increase. We find that the evolution of the packing fraction is a slow logarithmic function of the driving stress as a consequence of increasing contact area. We also evidence the effect of friction, which favours strong stress chains and thus the elongation of particles, leading to a larger packing fraction at a given level of compressive stress as compared to a frictionless particle packing.

JF - 3rd International Symposium on Geomechanics from Micro to Macro PB - CRC Press CY - SEP 01-03-2014 Univ Cambridge, Cambridge, ENGLAND VL - Geomechanics from Micro to Macro UR - http://prodinra.inra.fr/record/370208 ER - TY - JOUR T1 - Molecular dynamics simulation of amorphous HfOHfO2 is widely investigated as the favoured material for resistive RAM device implementation. The structural features of HfO2 play a fundamental role in the switching mechanisms governing resistive RAM operations, and a comprehensive understanding of the relation between the atomistic properties and final device behaviour is still missing. In addition, despite the fact that ultra-scaled 10 nm resistive RAM will probably be made of amorphous HfO2, a deeper investigation of the structure is necessary. In this paper, the classical molecular dynamics technique was used to investigate the disordered atomic configuration of amorphous HfO2. The influence of density on both the atomistic structure and the diffusion of O species was carefully analysed. The results achieved show that the atomistic structure of an amorphous HfO2 system is strongly affected by the density, and the amorphous system is rearranged in an atomic configuration similar to the crystalline configuration at similar densities. The diffusion of oxygen atoms increases with the decrease of the density, consistent with a less-packed atomic structure which allows for easier movement of this species.

VL - 22 UR - http://stacks.iop.org/0965-0393/22/i=6/a=065006?key=crossref.b7d708e3a43b9124ea539668eee311b0 IS - 6 JO - Modelling Simul. Mater. Sci. Eng. ER - TY - JOUR T1 - Molecular dynamics simulations of the formation of 1D spin-valves from stretched Au-Co and Pt-Co nanowires JF - J. Phys.: Condens. Matter Y1 - 2014 A1 - Robinson Cortes-Huerto A1 - T. Sondon A1 - Andres Saùl AB -We have performed molecular dynamics (MD) simulations of stretched Aux-Co1 - x and Ptx-Co1 - x nanowires to investigate the formation of bimetallic monoatomic wires between two electrodes. We have considered nanowires with two concentrations x = 0.2 and 0.8, aspect ratio of 13, a cross section of 1 nm(2) and a wide range of temperatures (from 10 to 400 K). For the MD simulations we have used a semi-empirical interatomic potential based on the second moment approximation (SMA) of the density of states to the tight-binding Hamiltonian.For Au-Co alloys, Au atoms tends to migrate towards the narrowed region to form almost pure Au wires. In the PtCo case the formed chains usually consist of Pt enriched alternating structures. The most striking result is probably the Au(0.2)-Co(0.8) alloy where pure monoatomic Au chains form between two Co electrodes constituting a potential 1D spin valve. Despite the known ease with which the 5d metals (Pt, Ir, and Au) form monoatomic chains (MACS), our results show that in the presence of Co (x = 0.2), the percentage of chain formation is higher than in the Pt and Au rich cases (x = 0.8).

VL - 26 IS - Special issue: Break junctions ER - TY - JOUR T1 - Multiphase equation of state for carbon addressing high pressures and temperatures JF - Phys Rev. B Y1 - 2014 A1 - L. X. Benedict A1 - K. P. Driver A1 - S. Hamel A1 - B. Militzer A1 - T. Qi A1 - Alfredo A. Correa A1 - Andres Saùl A1 - E. Schwegler AB -We present a 5-phase equation of state for elemental carbon which addresses a wide range of density and temperature conditions: 3g/cc<ρ<20g/cc,0K<T<∞. The phases considered are diamond, BC8, simple cubic, simple hexagonal, and the liquid/plasma state. The solid phase free energies are constrained by density functional theory (DFT) calculations. Vibrational contributions to the free energy of each solid phase are treated within the quasiharmonic framework. The liquid free energy model is constrained by fitting to a combination of DFT molecular dynamics performed over the range 10000K<T<100000K, and path integral quantum Monte Carlo calculations for T>100000K (both for ρ between 3 and 12 g/cc, with select higher- ρ DFT calculations as well). The liquid free energy model includes an atom-in-jellium approach to account for the effects of ionization due to temperature and pressure in the plasma state, and an ion-thermal model which includes the approach to the ideal gas limit. The precise manner in which the ideal gas limit is reached is greatly constrained by both the highest-temperature DFT data and the path integral data, forcing us to discard an ion-thermal model we had used previously in favor of a new one. Predictions are made for the principal Hugoniot and the room-temperature isotherm, and comparisons are made to recent experimental results.

VL - 89 ER - TY - JOUR T1 - Mesoscopic Monte Carlo simulations of microstructure and conductivity of zirconia-based ceramics JF - J. Eur. Ceram. Soc. Y1 - 2013 A1 - P. Epicoco A1 - Benoit A. Coasne A1 - A. Gioia A1 - P. Papet A1 - I. Cabodi A1 - M. Gaubil AB -Zirconia-based refractories are ceramics that serve as furnaces for the production of high-quality speciality glasses. These materials are obtained by cooling a melt composed of different oxides and oxide precursors. The microstructure of these refractories consists of monoclinic zirconia embedded in a three-dimensional interconnected amorphous phase. Using mesoscopic Monte Carlo simulations, the present paper addresses the effect of the amount of amorphous phase and temperature on the microstructure of the material. The simulated microstructures resemble those obtained using tomography experiments. A theoretical model describing the electrical behavior of the material as a function of temperature and composition is also reported. In this model, the conductivity of the ZrO2 particles is assumed to be constant, but the overall conductivity of the sample depends on its tortuosity s. Comparison with experimental data suggests that the present model provides a realistic picture of the electrical behavior of zirconia-based ceramics and leads to quantitative predictions.

VL - 61 IS - 13 ER - TY - JOUR T1 - Micromechanical analysis of second order work in granular media JF - Granular Matter Y1 - 2013 A1 - Hadda, Nejib A1 - François Nicot A1 - Bourrier, Franck A1 - Sibille, Luc A1 - Farhang Radjaï A1 - Darve, Félix AB -This paper examines instabilities in granular materials from a microscopic point of view through numerical simulations conducted using a discrete element method on two three-dimensional specimens. The detection and the tracking of grain scale deformation mechanisms constitute the key point for a better understanding the failure process and puzzling out what lies behind the vanishing of the macroscopic second order work. For this purpose, the second order work from microscopic variables, involving contact force and branch vector, was introduced and tracked numerically. Then, all contacts depicting negative values of the second order work were deeply investigated, especially their spatial distribution (homogeneity, agglomeration, dispersion

Numerous natural and manufactured systems such as colloidal suspensions, geological pore networks, catalysts, and nanofluidic devices develop a large and sometimes complex interface strongly influencing the dynamics of the fluid entrapped inside these materials. A coarse grain picture of this molecular dynamics can be considered as an intermittence of adsorption steps and bulk relocations from one point to another point of the interface. Adsorption statistics such as the adsorption time distribution and its first moment reflect the degree of interaction of the molecule with the colloidal interface. Relocation statistics strongly depend on the shape of the pore, the surface forces and the bulk confinement. In this paper, a theoretical analysis of this intermittent dynamics is presented. A direct comparison with molecular dynamics simulations is proposed in the case of liquid water confined inside a hydrophilic substrate (silica slit pore with hydroxylated surfaces) or inside a hydrophobic substrate (carbon nanotube). Analysis of this intermittent dynamics allows quantification of the level of interaction of the vicinal water with the solid interface inside an independent adsorption region in exchange with the confined bulk fluid. The possibility of experimentally probing this dynamics using NMR relaxometry is emphasized.

VL - 9 IS - 36 ER - TY - JOUR T1 - On the molecular origin of high-pressure effects in nanoconfinement: The role of surface chemistry and roughness JF - Journal of Chemical Physics Y1 - 2013 A1 - Yun Long A1 - Jeremy C. Palmer A1 - Benoit A. Coasne A1 - Malgorzata Sliwinska-Bartkowiak A1 - George Jackson A1 - Erich A. Mueller A1 - Keith E. Gubbins AB -Experiments and simulations both suggest that the pressure experienced by an adsorbed phase confined within a carbon nanoporous material can be several orders of magnitude larger than the bulk phase pressure in equilibrium with the system. To investigate this pressure enhancement, we report a molecular-simulation study of the pressure tensor of argon confined in slit-shaped nanopores with walls of various models, including carbon and silica materials. We show that the pressure is strongly enhanced by confinement, arising from the effect of strongly attractive wall forces; confinement within purely repulsive walls does not lead to such enhanced pressures. Simulations with both the Lennard-Jones and Barker-Fisher-Watts intermolecular potentials for argon-argon interactions give rise to similar results. We also show that an increase in the wall roughness significantly decreases the in-pore pressure due to its influence on the structure of the adsorbate. Finally, we demonstrate that the pressures calculated from the mechanical (direct pressure tensor calculations) and the thermodynamic (volume perturbation method) routes yield almost identical results, suggesting that both methods can be used to calculate the local pressure tensor components in the case of these planar geometries. (C) 2013 AIP Publishing LLC.

VL - 139 ER - TY - JOUR T1 - Molecular simulation of adsorption and transport in hierarchical porous materials JF - Langmuir Y1 - 2013 A1 - Benoit A. Coasne A1 - Anne Galarneau A1 - Gerardin, Corine A1 - Fajula, François A1 - François Villemot AB -<>

Adsorption and transport in hierarchical porous solids with micro- (∼1 nm) and mesoporosities (>2 nm) are investigated by molecular simulation. Two models of hierarchical solids are considered: microporous materials in which mesopores are carved out (model A) and mesoporous materials in which microporous nanoparticles are inserted (model B). Adsorption isotherms for model A can be described as a linear combination of the adsorption isotherms for pure mesoporous and microporous solids. In contrast, adsorption in model B departs from adsorption in pure microporous and mesoporous solids; the inserted microporous particles act as defects, which help nucleate the liquid phase within the mesopore and shift capillary condensation toward lower pressures. As far as transport under a pressure gradient is concerned, the flux in hierarchical materials consisting of microporous solids in which mesopores are carved out obeys the Navier–Stokes equation so that Darcy’s law is verified within the mesopore. Moreover, the flow in such materials is larger than in a single mesopore, due to the transfer between micropores and mesopores. This nonzero velocity at the mesopore surface implies that transport in such hierarchical materials involves slippage at the mesopore surface, although the adsorbate has a strong affinity for the surface. In contrast to model A, flux in model B is smaller than in a single mesopore, as the nanoparticles act as constrictions that hinder transport. By a subtle effect arising from fast transport in the mesopores, the presence of mesopores increases the number of molecules in the microporosity in hierarchical materials and, hence, decreases the flow in the micropores (due to mass conservation). As a result, we do not observe faster diffusion in the micropores of hierarchical materials upon flow but slower diffusion, which increases the contact time between the adsorbate and the surface of the microporosity.

VL - 29 IS - 25 ER - TY - JOUR T1 - Molecular simulations of supercritical fluid permeation through disordered microporous carbons JF - Langmuir Y1 - 2013 A1 - Botan, Alexandru A1 - Vermorel, Romain A1 - Franz-Josef Ulm A1 - Roland Jean-Marc Pellenq AB -Fluid transport through microporous carbon-based materials is inherent in numerous applications, ranging from gas separation by carbon molecular sieves to natural gas production from coal seams and gas shales. The present study investigates the steady-state permeation of supercritical methane in response to a constant cross-membrane pressure drop. We performed dual control volume grand canonical molecular dynamics (DCV-GCMD) simulations to mimic the conditions of actual permeation experiments. To overcome arbitrary assumptions regarding the investigated porous structures, the membranes were modeled after the CS1000a and CS1000 molecular models, which are representative of real microporous carbon materials. When adsorption-induced molecular trapping (AIMT) mechanisms are negligible, we show that the permeability of the microporous material, although not significantly sensitive to the pressure gradient, monotonically decreases with temperature and reservoir pressures, consistent with diffusion theory. However, when AIMT occurs, the permeability increases with temperature in agreement with experimental data found in the literature.

VL - 29 IS - 32 ER - TY - JOUR T1 - Mechanistic Approach to Pavement-Vehicle Interaction and Its Impact on Life-Cycle Assessment JF - Transportation Research Record: Journal of the Transportation Research Board Y1 - 2012 A1 - Mehdi Akbarian A1 - Moeini-Ardakani, Seyed A1 - Franz-Josef Ulm A1 - Nazzal, Munir AB -The accuracy and the comprehensiveness of any pavement life-cycle assessment are limited by the ability of the supporting science to quantify the environmental impact. Pavement-vehicle interaction represents a significant knowledge gap that has important implications for many pavement life-cycle assessment studies. In the current study, the authors assumed that a mechanistic model that linked pavement structure and properties to fuel consumption could contribute to closing the uncertainty gap of pavement-vehicle interaction in life-cycle assessment of pavements. The simplest mechanistic pavement model, a Bernoulli-Euler beam on a viscoelastic foundation subjected to a moving load, was considered. Wave propagation properties derived from falling weight deflectometer time history data of FHWA's Long-Term Pavement Performance program were used to calibrate top-layer and substrate moduli for various asphalt and concrete systems. The model was validated against recorded deflection data. The mechanistic response was used to determine gradient force and rolling resistance to link deflection to vehicle fuel consumption. A comparison with independent field data provided realistic order-of-magnitude estimates of fuel consumption related to pavement-vehicle interaction as predicted by the model.

IS - 2306 JO - Transportation Research Record: Journal of the Transportation Research Board ER - TY - Generic T1 - Microscopic Origins of Shear Strength in Packings Composed of Elongated Particles T2 - 9th International Workshop on Bifurcation and Degradation in Geomaterials (IWBDG 2011) Y1 - 2012 A1 - Emilien Azéma A1 - Farhang Radjaï ED - Stéphane Bonelli ED - Dascalu, Cristian ED - François Nicot KW - Elongated particles KW - Fabric properties KW - force transmission KW - Harmonic decomposition AB -We investigate the rheology, force transmission and texture of granular materials composed of elongated particles by means of contact dynamics simulations. The particles have a rounded-cap rectangular (RCR) shape described by a single elongation parameter varying from 0 for a circular particle to 1 for an infinitely thin or long particle. We study the quasi-static behavior, structural and force anisotropies as a function of the elongation parameter for packings submitted to biaxial compression. The shear strength is found to increase linearly with this parameter whereas the solid fraction both at the initial isotropic state and in the critical state is nonmonotonous. We show that for these elongated particles a harmonic decomposition of the stress tensor provides a fairly good approximation of the internal state. Our data suggest that the increase of shear strength with reflects both enhanced friction mobilization and anisotropic particle orientation as the elongation of the particles increases.

JF - 9th International Workshop on Bifurcation and Degradation in Geomaterials (IWBDG 2011) CY - MAY 23-26 2011 Porquerolles, FRANCE VL - Springer Series in Geomechanics and Geoengineering - ADVANCES IN BIFURCATION AND DEGRADATION IN GEOMATERIALS UR - https://hal.archives-ouvertes.fr/hal-00686728 ER - TY - Generic T1 - Modeling Porous Granular Aggregates T2 - 9th International Workshop on Buifurcation and Degradation in Geomaterials (IWBDG 2011) Y1 - 2011 A1 - Rafik Affès A1 - Vincent Topin A1 - Jean-Yves Delenne A1 - Yann Monerie ED - Stéphane Bonelli ED - Dascalu, Cristian ED - François Nicot AB -We rely on 3D simulations based on the Lattice Element Method (LEM) to analyze the failure of porous granular aggregates under tensile loading. We investigate crack growth by considering the number of broken bonds in the particle phase as a function of the matrix volume fraction and particle-matrix adhesion. Three regimes are evidenced, corresponding to no particle damage, particle abrasion and particle fragmentation, respectively. We also show that the probability density of strong stresses falls off exponentially at high particle volume fractions where a percolating network of jammed particles occurs. Decreasing the matrix volume fraction leads to increasingly broader stress distribution and hence a higher stress concentration. Our findings are in agreement with 2D results previously reported in the literature.

JF - 9th International Workshop on Buifurcation and Degradation in Geomaterials (IWBDG 2011) PB - Springer Netherlands CY - MAY 23-26 2011 Porquerolles, FRANCE VL - Springer Series in Geomechanics and Geoengineering - ADVANCES IN BIFURCATION AND DEGRADATION IN GEOMATERIALS SN - 978-94-007-1420-5 ER - TY - JOUR T1 - Multitechnique Investigation of Extruded Clay Brick Microstructure JF - Journal of the American Ceramic Society Y1 - 2011 A1 - Konrad J. Krakowiak A1 - Lourenco, Paulo B. A1 - Franz-Josef Ulm AB -Despite the omnipresence of clay brick as construction material since thousands of years, fundamental knowledge about the link between composition, microstructure, and mechanical performance is still scarce. In this paper, we use a variety of advanced techniques of experimental mechanics and material characterization for extruded clay brick for masonry, that range from scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy, mercury intrusion porosimetry, to instrumented nanoindentation and macroscopic strength and durability tests. We find that extruded clay brick possesses a hierarchical microstructure: depending on the firing temperature, a “glassy” matrix phase, which manifests itself at submicrometer scales in form of neo-crystals of mullite, spinel-type phase, and other accessory minerals, forms either a granular or a continuum matrix phase that hosts at submillimeter scale the porosity. This porous composite forms the backbone for macroscopic material performance of extruded brick, including anisotropic strength, elasticity, and water absorption behavior.

VL - 94 IS - 9 ER -