@article {679, title = {Multiscale poromechanics of wet cement paste}, journal = {Proceedings of the National Academy of Sciences}, volume = {2}, year = {2019}, month = {May-09-2019}, pages = {201901160}, abstract = {

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.

}, issn = {0027-8424}, doi = {10.1073/pnas.1901160116}, url = {http://www.pnas.org/lookup/doi/10.1073/pnas.1901160116}, author = {Zhou, Tingtao and Katerina Ioannidou and Franz-Josef Ulm and Bazant, Martin Z. and Roland Jean-Marc Pellenq} } @article {534, title = {Atomistic and mesoscale simulation of sodium and potassium adsorption in cement paste}, journal = {The Journal of Chemical Physics}, volume = {14963}, year = {2018}, month = {Aug-21-2018}, pages = {074705}, abstract = {

An atomistic and mesoscopic assessment of the effect of alkali uptake in cement paste is performed. Semi-grand canonical Monte Carlo simulations indicate that Na and K not only adsorb at the pore surface of calcium silicate hydrates (C-S-H) but also adsorb in the C-S-H hydrated interlayer up to concentrations of the order of 0.05 and 0.1 mol/kg, respectively. Sorption of alkali is favored as the Ca/Si ratio of C-S-H is reduced. Long timescale simulations using the Activation Relaxation Technique indicate that characteristic diffusion times of Na and K in the C-S-H interlayer are of the order of a few hours. At the level of individual grains, Na and K adsorption leads to a reduction of roughly 5\% of the elastic moduli and to volume expansion of about 0.25\%. Simulations using the so-called primitive model indicate that adsorption of alkali ions at the pore surface can reduce the binding between C-S-H grains by up to 6\%. Using a mesoscopic model of cement paste, the combination of individual grain swelling and changes in inter-granular cohesion was estimated to lead to overall expansive pressures of up to 4 MPa\—and typically of less than 1 MPa\—for typical alkali concentrations observed at the proximity of gel veins caused by the alkali-silica reaction.

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}, issn = {0021-9606}, doi = {10.1063/1.5042755}, url = {https://aip.scitation.org/doi/10.1063/1.5042755}, author = {Dufresne, Alice and Arayro, Jack and Zhou, Tingtao and Katerina Ioannidou and Franz-Josef Ulm and Roland Jean-Marc Pellenq and B{\'e}land, Laurent Karim} } @article {571, title = {Griffith{\textquoteright}s postulate: Grand Canonical Monte Carlo approach for fracture mechanics of solids}, journal = {Engineering Fracture Mechanics}, volume = {199}, year = {2018}, month = {Aug-2018}, pages = {544 - 554}, abstract = {

A Grand Canonical Monte Carlo Approach (GCMC) is proposed for the fracture analysis of solids discretized as mass points and bond interactions. In contrast to classical load-driven fracture processes, the GCMC approach introduces an auxiliary field, the bond rupture potential , to which the system is subjected; in addition to changes in volume V and temperature T. In this VT-ensemble, bond isotherms that link the average number of bonds to the bond rupture potential (Nk-) are obtained that carry critical information for fracture analysis. Specifically, the slope of the bond isotherm reflects bond fluctuations, permitting identification of (1) a fluctuation-based damage variable, and (2) the competition in energy fluctuations between the redistribution of strain energy induced by bond rupture, and the dissipation of the groundstate energy. Based on these fluctuations, it is shown that the GCMC-approach allows the identification of a critical bond energy release rate of material samples, when strain energy fluctuations equal groundstate energy fluctuations \– much akin to Griffith\’s 1921 stationarity postulate to \“predicting the breaking loads of elastic solids\”. This is illustrated by means of thermodynamic integration of bond isotherms to determine force-displacement curves, for both notched and unnotched homogeneous samples discretized by regular 2-D lattices with bonds exhibiting harmonic potentials.

Fig. 1. Bond-Isotherms Nk-μfor three systems: (a) unnotched; (b) notched; (c) broken

Fig. 2. Fluctuation-based damage in function of the prescribed bond rupture potential,{\textellipsis}

Fig. 3. Energy dissipation due to fluctuations for (a) the unnotched and (b) the{\textellipsis}

Fig. 4. Thermodynamic integration of the bond isotherms of (a) an unnotched sample; and{\textellipsis}

}, keywords = {Grand Canonical Monte Carlo Simulations; Bond rupture; Bond rupture potential; Bond isotherms; Damage; Fluctuations}, issn = {00137944}, doi = {10.1016/j.engfracmech.2018.06.001}, url = {https://linkinghub.elsevier.com/retrieve/pii/S0013794418301747}, author = {Al-Mulla, Talal and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {576, title = {Impact of Nanoporosity on Hydrocarbon Transport in Shales{\textquoteright} Organic Matter}, journal = {Nano Letters}, volume = {18}, year = {2018}, month = {Jan-16-2018}, pages = {832 - 837}, abstract = {

In a context of growing attention for shale gas, the precise impact of organic matter (kerogen) on hydrocarbon recovery from unconventional reservoirs still has to be assessed. Kerogen\&$\#$39;s microstructure is characterized by a very disordered pore network that greatly affects hydrocarbon transport. The specific structure and texture of this organic matter at the nanoscale is highly dependent on its origin. In this study, by the use of statistical physics and molecular dynamics, we shed some new lights on hydrocarbon transport through realistic molecular models of kerogen at different level of maturity [Bousige et al. Nat. Mater. 2016, 15, 576]. Despite the apparent complexity, severe confinement effects controlled by the porosity of the various kerogens allow linear alkanes (from methane to dodecane) transport to be studied only via the self-diffusion coefficients of the species. The decrease of the transport coefficients with the amount of adsorbed fluid can be described by a free volume theory. Ultimately, the transport coefficients of hydrocarbons can be expressed simply as a function of the porosity (volume fraction of void) of the microstructure, thus paving the way for shale gas recovery predictions.

https://pubs-acs-org.libproxy.mit.edu/appl/literatum/publisher/achs/journals/content/nalefd/2018/nalefd.2018.18.issue-2/acs.nanolett.7b04079/20180208/images/medium/nl-2017-04079p_0004.gif

}, keywords = {Kerogen; microporosity; diffusion; hydrocarbons; shales}, issn = {1530-6984}, doi = {10.1021/acs.nanolett.7b04079}, url = {http://pubs.acs.org/doi/10.1021/acs.nanolett.7b04079}, author = {Ama{\"e}l Obliger and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {580, title = {Improving the practicality and safety of artificial corneas: Pre-assembly and gamma-rays sterilization of the Boston Keratoprosthesis}, journal = {The Ocular Surface}, volume = {16}, year = {2018}, month = {Jul-2018}, pages = {322 - 330}, abstract = {

Purpose: To make the Boston keratoprosthesis (B-KPro), together with its carrier corneal graft, more easily procured, transported and stored, as well as less expensive, easier for the surgeon to implant and safer for the patient, it is proposed that the B-KPro-graft combination be pre-assembled by an expert technician, followed by sterilization with gamma ray irradiation (GI) allowing long-term storage at room temperature. For this to be possible, it must be shown that the B-KPro itself (not only the graft) remains unharmed by the irradiation.

Methods: Polymethyl methacrylate (PMMA) discs and B-KPros were submitted to either ethylene oxide sterilization or different doses of GI. Cell biocompatibility, mechanical strength and optical quality were evaluated. The feasibility of assembling the B-KPro to a corneal graft, and gamma-radiate afterwards, was also assessed.

Results: There were no differences in cell biocompatibility between the samples. The optical evaluation showed high levels of transparency for all the groups. The absorbance of ultraviolet was higher for the groups treated with GI. The mechanical evaluation by nanoindentation showed no alterations of the PMMA discs after GI. The flexure test revealed a similar mechanical behavior. Technically, pre-assembly and GI of the B-KPro revealed no problems.

Conclusions: Sterilization of B-KPro using GI has no detrimental influence on the device. The pre-assembly of B-KPro to a donor cornea, followed by gamma sterilization, emerges as an efficient and safe procedure. (C) 2018 Elsevier Inc. All rights reserved.

}, keywords = {Artificial corneas; Boston keratoprosthesis; Gamma radiation; Gamma rays; Preassembly; Sterilization; Polymethyl methacrylate}, issn = {15420124}, doi = {10.1016/j.jtos.2018.04.002}, url = {https://linkinghub.elsevier.com/retrieve/pii/S1542012418300442}, author = {Gonzalez-Andrades, Miguel and Sharifi, Roholah and Islam, Mohammad Mirazul and Divoux, Thibaut and Haist, Michael and Paschalis, Eleftherios I. and Gelfand, Larisa and Mamodaly, Shamina and Di Cecilia, Luca and Cruzat, Andrea and Franz-Josef Ulm and Chodosh, James and Delori, Francois and Dohlman, Claes H.} } @article {575, title = {Le Ch{\^a}telier{\textquoteright}s conjecture: Measurement of colloidal eigenstresses in chemically reactive materials}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {112}, year = {2018}, month = {Mar-2018}, pages = {334 - 344}, abstract = {

Volume changes in chemically reactive materials, such as hydrating cement, play a critical role in many engineering applications that require precise estimates of stress and pressure developments. But a means to determine bulk volume changes in the absence of other deformation mechanisms related to thermal, pressure and load variations, is still missing. Herein, we present such a measuring devise, and a hybrid experimental-theoretical technique that permits the determination of colloidal eigenstresses. Applied to cementitious materials, it is found that bulk volume changes in saturated cement pastes at constant pressure and temperature conditions result from a competition of repulsive and attractive phenomena that originate from the relative distance of the solid particles- much as Henry Louis Le Chatelier, the father of modern cement science, had conjectured in the late 19th century. Precipitation of hydration products in confined spaces entails a repulsion, whereas the concurrent reduction in interparticle distance entails activation of attractive forces in charged colloidal particles. This cross-over from repulsion to attraction can be viewed as a phase transition between a liquid state (below the solid percolation) and the limit packing of hard spheres, separated by an energy barrier that defines the temperature-dependent eigenstress magnitude. (C) 2017 Elsevier Ltd. All rights reserved.

Fig. 1. Pressure vessel measurement device for volume changes under constant pressure{\textellipsis}

Fig. 2. Bulk Volume Change measurement results under drained and fluid saturated{\textellipsis}

Fig. 3. Eigenstress Scaling: (a) Normalized eigenstress (|σ*|/max|σ*|) vs

Fig. 4. Eigenstress interpretation: (a) volume fractions vs

}, keywords = {Poromechanics; Colloidal stresses; Cement-based materials; Expansion; Shrinkage}, issn = {00225096}, doi = {10.1016/j.jmps.2017.12.012}, url = {https://linkinghub.elsevier.com/retrieve/pii/S0022509617309985}, author = {Muhannad Abuhaikal and Katerina Ioannidou and Petersen, Thomas and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {630, title = {Mesoscale structure, mechanics, and transport properties of source rocks{\textquoteright} organic pore networks}, journal = {Proceedings of the National Academy of Sciences}, volume = {115}, year = {2018}, month = {Dec-04-2018}, pages = {12365-12370}, abstract = {

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\&$\#$39; 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.

}, keywords = {porous media; electron tomography; mechanics; fluid transport; mesoscale}, issn = {0027-8424}, doi = {10.1073/pnas.1808402115}, url = {http://www.pnas.org/lookup/doi/10.1073/pnas.1808402115}, author = {Berthonneau, Jeremie and Ama{\"e}l Obliger and Valdenaire, Pierre-Louis and Grauby, Olivier and Ferry, Daniel and Chaudanson, Damien and Pierre E. Levitz and Kim, Jae Jin and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {658, title = {A methodology to calibrate and to validate effective solid potentials of heterogeneous porous media from computed tomography scans and laboratory-measured nanoindentation data}, journal = {Acta Geotechnica}, volume = {13}, year = {2018}, month = {Jan-12-2018}, pages = {1369 - 1394}, abstract = {

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 .

}, issn = {1861-1125}, doi = {10.1007/s11440-018-0687-9}, url = {http://link.springer.com/10.1007/s11440-018-0687-9}, author = {Monfared, Siavash and Hadrien Laubie and Farhang Radja{\"\i} and Hubler, Mija H. and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {532, title = {Phase separation of stable colloidal clusters}, journal = {Physical Review Materials}, volume = {2}, year = {2018}, month = {Sep-25-2018}, abstract = {

This article presents a nonequilibrium thermodynamic theory for the mean-field precipitation, aggregation, and pattern formation of colloidal clusters. A variable gradient energy coefficient and the arrest of particle diffusion upon \“jamming\” of cluster aggregates in the spinodal region predicts observable gel patterns that, at high intercluster attraction, form system-spanning, out-of-equilibrium networks with glasslike, quasistatic structural relaxation. For reactive systems, we incorporate the free energy landscape of stable prenucleation clusters into the Allen-Cahn reaction equation. We show that pattern formation is dominantly controlled by the Damk\öhler number and the stability of the clusters, which modifies the autocatalytic rate of precipitation. As clusters individually become more stable, bulk phase separation is suppressed.

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}, doi = {10.1103/PhysRevMaterials.2.095602}, url = {https://journals.aps.org/prmaterials/abstract/10.1103/PhysRevMaterials.2.095602}, author = {Petersen, Thomas and Bazant, Martin Z. and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {570, title = {Poroelasticity of Methane-Loaded Mature and Immature Kerogen from Molecular Simulations}, journal = {Langmuir}, volume = {34}, year = {2018}, month = {Nov-13-2018}, pages = {13766 - 13780}, abstract = {

While hydrocarbon expulsion from kerogen is certainly the key step in shale oil/gas recovery, the poromechanical couplings governing this desorption process, taking place under a significant pressure gradient, are still poorly understood. Especially, most molecular simulation investigations of hydrocarbon adsorption and transport in kerogen have so far been performed under the rigid matrix approximation, implying that the pore space is independent of pressure, temperature, and fluid loading, or in other words, neglecting poromechanics. Here, using two hydrogenated porous carbon models as proxies for immature and overmature kerogen, that is, highly aliphatic hydrogen-rich vs highly aromatic hydrogen-poor models, we perform an extensive molecular-dynamics-based investigation of the evolution of the poroelastic properties of those matrices with respect to temperature, external pressure, and methane loading as a prototype alkane molecule. The rigid matrix approximation is shown to hold reasonably well for overmature kerogen even though accounting for flexibility has allowed us to observe the well-known small volume contraction at low fluid loading and temperature. Our results demonstrate that immature kerogen is highly deformable. Within the ranges of conditions considered in this work, its density can double and its accessible porosity (to a methane molecule) can increase from 0 to \∼30\%. We also show that these deformations are significantly nonaffine (i.e., nonhomogeneous), especially upon fluid adsorption or desorption.

}, keywords = {ADSORPTION-INDUCED DEFORMATION; ORGANIC-MATTER; COMPETITIVE ADSORPTION; NANOPOROUS MEDIA; POROUS CARBONS; GLASSY-CARBON; COAL; TRANSPORT; SORPTION; MODEL}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.8b02534}, url = {http://pubs.acs.org/doi/10.1021/acs.langmuir.8b02534}, author = {Obliger, Ama{\"e}l and Valdenaire, Pierre-Louis and Capit, Nicolas and Franz-Josef Ulm and Roland Jean-Marc Pellenq and Jean-Marc Leyssale} } @article {572, title = {Potential-of-Mean-Force Approach for Molecular Dynamics{\textendash}Based Resilience Assessment of Structures}, journal = {Journal of Engineering Mechanics}, volume = {144}, year = {2018}, month = {Aug-2018}, pages = {04018066}, abstract = {

A molecular dynamics (MD)-based structural mechanics approach is proposed for the assessment of resilience of buildings. At the core of the approach, potentials of mean force (PMFs) suitable for structural members for both two-body (stretch) and three-body (bending) interactions are derived to define the energy states between mass points discretizing structural members. An original potential parameter calibration procedure is proposed: for close-to-equilibrium potential parameters, the procedure is based on matching measured frequency of a structure with the frequency of the molecular model. In turn, for bond-rupture parameters, it is shown that classical interatomic potential expressions, such as Morse potential, can be used to calibrate the energy content of many structural members and connections. By way of example, the MD-based structural mechanics approach is applied to a large-scale structure. Compared with classical continuum-based approaches, the added value of the method thus proposed is a rational means of determining the progressive structural collapse load of structures based on thermodynamic integration. By redefining structural mechanics within the context of statistical physics, molecular simulations, and potentials of mean force, the approach provides a powerful means of determining fragility curves required for the assessment of resilience of buildings.

}, keywords = {Molecular dynamics; Structural mechanics; Potential of mean force; Morse potential; Progressive structural collapse; Fragility curves}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0001491}, url = {http://ascelibrary.org/doi/10.1061/\%28ASCE\%29EM.1943-7889.0001491}, author = {Keremides, Konstantinos and Abdolhosseini Qomi, Mohammad Javad and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {525, title = {A reaction model for cement solidification: Evolving the C{\textendash}S{\textendash}H packing density at the micrometer-scale}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {118}, year = {2018}, month = {Sep-2018}, pages = {58 - 73}, abstract = {

Cement paste is a multiphase material of complex chemistry, of which 60\% by volume is typically composed of calcium\–silicate\–hydrates (C\–S\–H), the phase that lends the material its strength and stiffness. Moreover, it has been shown that the C\–S\–H phase is a dispersion of nanometer-sized particles that are characterized by an attractive\–repulsive potential and densify in course of the hydration reaction. Herein, we model the nucleation and growth of the nanoparticles as a continuous density field subject to a reaction equation. Using this phase-field approach, we aim to reduce the parameter space present in similar hydration models and create a vehicle to upscale mechanical information from the nanometer-scale to the micrometer-scale. Despite the apparent simplification of the physics at play, we readily reproduce the cement paste reaction kinetics and microtexture\—functions of temperature, coarseness of the calcium\–silicate source particles, and initial water-to-cement ratio\—, and vet them against experimental observations. Presenting results for two-dimensional simulations, we achieve excellent agreement with measurements of hydration heat curves, pore-chord-length and solid-chord-length density functions, distributions of low- and high-density C\–S\–H products, and elasticity.

Illustration of the dissolution and nucleation and growth processes driving{\textellipsis}

A comparison between the mean coordination number ⟨z⟩ of the particles modeled{\textellipsis}

Gibb{\textquoteright}s free energy that interpolates between the source phase ψ=1 and open pore{\textellipsis}

Gibb{\textquoteright}s energy of reaction and (b) reaction rate for nanoparticle{\textellipsis}

Evolution of the mean packing fraction of C{\textendash}S{\textendash}H (〈ϕ〉V'; opaque) and the{\textellipsis}

Diagram of the volume fractions of hydrating cement paste

}, issn = {00225096}, doi = {10.1016/j.jmps.2018.05.010}, url = {https://www-sciencedirect-com.libproxy.mit.edu/science/article/pii/S0022509617308876}, author = {Petersen, Thomas and Valdenaire, Pierre-Louis and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {574, title = {Role of City Texture in Urban Heat Islands at Nighttime}, journal = {Physical Review Letters}, volume = {120}, year = {2018}, month = {Mar-09-2018}, pages = {Article Number: 108701 }, abstract = {

An urban heat island (UHI) is a climate phenomenon that results in an increased air temperature in cities when compared to their rural surroundings. In this Letter, the dependence of an UHI on urban geometry is studied. Multiyear urban-rural temperature differences and building footprints data combined with a heat radiation scaling model are used to demonstrate for more than 50 cities worldwide that city texture-measured by a building distribution function and the sky view factor-explains city-to-city variations in nocturnal UHIs. Our results show a strong correlation between nocturnal UHIs and the city texture.

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}, keywords = {IDEAL CONDITIONS; CLIMATE-CHANGE; CITIES; SIMULATION; GEOMETRY; ENERGY; HEALTH; IMPACT; MODEL}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.120.108701}, url = {https://link.aps.org/doi/10.1103/PhysRevLett.120.108701}, author = {Sobstyl, Jake M. and Emig, Thorsten and Qomi, M. J. Abdolhosseini and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {652, title = {Synthesis, characterization, and catalytic application in aldehyde hydrosilylation of half-sandwich nickel complexes bearing (κ1-C)- and hemilabile (κ 2-C, S)-thioether-functionalised NHC ligands}, journal = {Dalton Transactions}, volume = {47}, year = {2018}, month = {Dec-21-2018}, pages = {17134-17145}, abstract = {

Neutral nickel-N-heterocyclic carbene complexes, ((1)-C)-[NiCpBr{R-NHC-(CH2)(2)SR}] [Cp = (5)-C5H5; R-NHC-(CH2)(2)SR = 1-mesityl-3-[2-(tert-butylthio)ethyl]- (1a), 1-mesityl-3-[2-(phenylthio)ethyl]- (1b), 1-benzyl-3-[2-(tert-butylthio)ethyl]- (1c), 1-benzyl-3-[2-(phenylthio)ethyl]-imidazol-2-ylidene (1d)], which bear a N-bound thioether side arm, were prepared by the reaction of nickelocene with the corresponding imidazolium bromides [R-NHC-(CH2)(2)SRHBr] (a-d), via conventional or microwave heating. The H-1 NMR spectra of the benzyl-substituted species 1c and 1d showed signals for diastereotopic NCH2CH2S protons at room temperature. However, structural studies established the absence of coordination of the sulphur atom in the solid state, and solvent DFT calculations showed that bromide displacement by sulphur is an unfavourable process (G = +13.5 kcal mol(-1) for 1d), thereby suggesting that the observed disatereotopicity is more likely due to significant steric congestion rather than to a possible C,S-chelation in solution. Treatment of these complexes with KPF6 in tetrahydrofuran (THF) led to bromide abstraction to afford the cationic complexes [NiCp{R-NHC-(CH2)(2)SR}](PF6) (2a-c). Alternatively, 2a-c could also be prepared by the direct reaction of nickelocene with the corresponding imidazolium hexafluorophosphate salts [R-NHC-(CH2)(2)SRHPF6]. Inversely to the neutral species, whereas X-ray crystallography established C,S-chelation in the solid state, the H-1 NMR spectra (CDCl3, CD2Cl2, or thf-d(8)) at room temperature showed no diastereotopic NCH2CH2S protons, thus suggesting the possible displacement of the sulphur atom by the respective solvents and/or very fast sulphur inversion. DFT calculations established a low energy inversion process in all cases (+9 G(double dagger) +13 kcal mol(-1)) as well as a favourable solvent coordination process (G(double dagger) approximate to +11 kcal mol(-1); G approximate to -7 kcal mol(-1)) with a solvent such as THF, thus suggesting that sulphur inversion and/or solvent coordination can both account for the absence of diastereotopy at room temperature, depending on the solvent. While all complexes catalysed the hydrosilylation of benzaldehyde in the absence of any additive, the cationic C,S-chelated complexes 2 proved more active than the sterically constrained neutral species 1. In particular, 2c proved to be the most active pre-catalyst and its catalytic charge could be lowered down to 2 mol\% with PhSiH3 as the hydrogen source.

}, issn = {1477-9226}, doi = {10.1039/C8DT03882A}, url = {http://xlink.rsc.org/?DOI=C8DT03882A}, author = {Franz-Josef Ulm and Poblador-Bahamonde, Amalia I. and Choppin, Sabine and Bellemin-Laponnaz, St{\'e}phane and Chetcuti, Michael J. and Achard, Thierry and Ritleng, Vincent} } @article {535, title = {Thermalizing and Damping in Structural Dynamics}, journal = {Journal of Applied Mechanics}, volume = {85}, year = {2018}, month = {Aug-2018}, abstract = {

Structural damping, that is the presence of a velocity dependent dissipative term in the equation of motion, is rationalized as a thermalization process between a structure (here a beam) and an outside bath (understood in a broad sense as a system property). This is achieved via the introduction of the kinetic temperature of structures and formalized by means of an extended Lagrangian formulation of a structure in contact with an outside bath at a given temperature. Using the Nose-Hoover thermostat, the heat exchange rate between structure and bath is identified as a mass damping coefficient, which evolves in time in function of the kinetic energy/temperature history exhibited by the structure. By way of application to a simple beam structure subjected to eigen-vibrations and dynamic buckling, commonality and differences of the Nose-Hoover beam theory with constant mass damping models are shown, which permit a handshake between classical damping models and statistical mechanics-based thermalization models. The solid foundation of these thermalization models in statistical physics provides new insights into stability and instability for engineering structures. Specifically, since two systems are considered in (thermodynamic) equilibrium when they have the same temperature, we show in the case of dynamic buckling that a persistent steady-state difference in kinetic temperature between structure and bath is but indicative of the instability of the system. This shows that the kinetic temperature can serve as a structural order parameter to identify and comprehend failure of structures, possibly well beyond the elastic stability considered here.

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}, keywords = {structural dynamics; damping; Nose-Hoover Bath; kinetic temperature; dynamic buckling}, issn = {0021-8936}, doi = {10.1115/1.4040080}, url = {http://appliedmechanics.asmedigitalcollection.asme.org.libproxy.mit.edu/article.aspx?articleid=2680040}, author = {Arghavan Louhghalam and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {573, title = {Thermodynamics, kinetics, and mechanics of cesium sorption in cement paste: A multiscale assessment}, journal = {Physical Review Materials}, volume = {2}, year = {2018}, month = {May-30-2018}, chapter = {Article Number: 053608 }, abstract = {

Cesium-137 is a common radioactive byproduct found in nuclear spent fuel. Given its 30 year half life, its interactions with potential storage materials-such as cement paste-is of crucial importance. In this paper, simulations are used to establish the interaction of calcium silicate hydrates (C-S-H)-the mam binding phase of cement paste-with Cs at the nano- and mesoscale. Different C-S-H compositions are explored, including a range of Ca/Si ratios from 1.0 to 2.0. These calculations are based on a set of 150 atomistic models, which qualitatively and quantitatively reproduce a number of experimentally measured features of C-S-H-within limits intrinsic to the approximations imposed by classical molecular dynamics and the steps followed when building the models. A procedure where hydrated Ca2+ ions are swapped for Cs1+ ions shows that Cs adsorption in the C-S-H interlayer is preferred to Cs adsorption at the nanopore surface when Cs concentrations are lower than 0.19 Mol/kg. Interlayer sorption decreases as the Ca/Si ratio increases. The activation relaxation technique nouveau is used to access timescales out of the reach of traditional molecular dynamics (MD). It indicates that characteristic diffusion time for Cs1+ in the C-S-H interlayer is on the order of a few hours. Cs uptake in the interlayer has little impact on the elastic response of C-S-H. It leads to swelling of the C-S-H grams, but mesoscale calculations that access length scales out of the range of MD indicate that this leads to practically negligible expansive pressures for Cs concentrations relevant to nuclear waste repositories.

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}, keywords = {CALCIUM-SILICATE-HYDRATE; C-S-H; MOLECULAR-DYNAMICS; CRYSTAL-STRUCTURE; MONTE-CARLO; IMMOBILIZATION; RADIONUCLIDES; SIMULATIONS; RELAXATION; COLLOIDS}, doi = {10.1103/PhysRevMaterials.2.053608}, url = {https://link.aps.org/doi/10.1103/PhysRevMaterials.2.053608}, author = {Arayro, Jack and Dufresne, Alice and Zhou, Tingtao and Katerina Ioannidou and Franz-Josef Ulm and Roland Jean-Marc Pellenq and B{\'e}land, Laurent Karim} } @article {318, title = {Carbon management of infrastructure performance: Integrated big data analytics and pavement-vehicle-interactions}, journal = {Journal of Cleaner Production}, volume = {142}, year = {2017}, month = {Jan-20-2017}, pages = {956 - 964 Part: 2}, abstract = {

As a crucial part of the transportation system, roadway network provides mobility to the society and is vital for the economy. At the same time it contributes significantly to the environmental footprint during its construction, operation and maintenance. Hence, the sustainable development of our Nation\&$\#$39;s roadway system requires quantitative means to link infrastructure performance to lifecycle energy use and greenhouse gas emissions. Recent developments in mechanistic models of roughness- and deflection-induced pavement-vehicle interaction aim at providing such engineering estimates. Herein, it is demonstrated that these models when implemented at a network scale are a powerful basis for big data analytics of excess-energy consumption and carbon dioxide emissions by integrating spatially and temporally varying road conditions, pavement properties, traffic loads and climatic conditions. A novel ranking algorithm is proposed, that allows upscaling of the local carbon dioxide emissions due to pavement vehicle interaction to the size of state-wide or national sustainability goals. Implemented for 5157 lane-miles of the interstate highway system in the State of Virginia, sections contributing significantly to carbon dioxide emissions are identified. It is shown that the proposed ranking algorithm based on the inferred emission that exhibits a power-law distribution, provides the shortest path for greenhouse gas emissions savings per maintenance at network scale. That is, maintaining a few lane miles allows for a significant synergetic improvement of both infrastructure performance and environmental impact of the interstate network and helps transportation agencies in making economic and environmentally sustainable decisions.

Unlabelled figure

Fig.1. Flow of network analysis; the inputs and the output of deflection- and{\textellipsis}

Fig.2. Spatial distribution of roughness- and deflection-induced excess CO2 emissions{\textellipsis}

Fig.3. Total annual excess CO2 emissions (Tons) for a 7-year period (2007{\textendash}2013) in{\textellipsis}

Fig.4. Excess CO2 emissions in function of its rank

Fig.5. Comparison of different road selection strategies for maintenance in terms of{\textellipsis}

}, issn = {09596526}, doi = {10.1016/j.jclepro.2016.06.198}, author = {Arghavan Louhghalam and Mehdi Akbarian and Franz-Josef Ulm} } @article {244, title = {Crystal-chemistry control of the mechanical properties of 2:1 clay minerals}, journal = {Applied Clay Science}, volume = {143}, year = {2017}, month = {Jul-2017}, pages = {387 - 398}, abstract = {

Clay minerals are the main constituents of the clay matrix of a wide variety of sedimentary deposits. When subjected to burial, some of these minerals undergo phase transitions accompanied by atomic substitutions which ultimately impact the cohesive interactions between their constitutive layers. The most common among such transitions is smectite illitization, which is also highly relevant for oil and gas exploration and production from source rocks. The impact of this transition on the mechanical properties of clay minerals as well as clay bearing rocks remains, however, to be properly addressed. To this end, a set of macroscopic single 2:1 clay minerals (pyrophyllite, talc, vermiculite, phlogopite, muscovite, and clintonite) representative of the two octahedral fillings and the variation in surface charge densities was investigated. A hybrid experimental-modeling approach is proposed, which combines nanoindentation in orthogonal directions (x1 and x3-directions) with analytical derivations of the cohesive energy (Ui) using XRD and TEM-EDS measurements. The results highlight that the interlayer energy defines the elasticity (modulus M), strength (hardness H) and ductility behavior (M/H) of these materials; and not the bond energy stored into the constituent layers. This finding permits the derivation of predictive stiffness and strength functional relations as derivatives of the interlayer energy that account for the arrangement of nanoscale layers and the interlayer composition. These relations suggest that as the cohesion increases with the coulombic interactions through progressive smectite illitization, the system loses its capacity to dissipate applied energy by dislocation mechanisms in between the layers, entailing an increase in brittleness of the clay particles with burial. By way of conclusion, the geophysics and geochemistry implications of these results for predicting the macroscopic mechanical performance of clay bearing geomaterials, such as economically valuable source rocks, are discussed.

}, issn = {01691317}, doi = {10.1016/j.clay.2017.04.010}, author = {Berthonneau, Jeremie and Christian G. Hoover and Grauby, Olivier and Alain Baronnet and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {239, title = {Disorder-induced stiffness degradation of highly disordered porous materials}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {106}, year = {2017}, month = {Sep-2017}, chapter = {207-228}, abstract = {

The effective mechanical behavior of multiphase solid materials is generally modeled by means of homogenization techniques that account for phase volume fractions and elastic moduli without considering the spatial distribution of the different phases. By means of extensive numerical simulations of randomly generated porous materials using the lattice element method, the role of local textural properties on the effective elastic properties of disordered porous materials is investigated and compared with different continuum micromechanics-based models. It is found that the pronounced disorder-induced stiffness degradation originates from stress concentrations around pore clusters in highly disordered porous materials. We identify a single disorder parameter, \φsa, which combines a measure of the spatial disorder of pores (the clustering index, sa) with the pore volume fraction (the porosity, \φ) to scale the disorder-induced stiffness degradation. Thus, we conclude that the classical continuum micromechanics models with one spherical pore phase, due to their underlying homogeneity assumption fall short of addressing the clustering effect, unless additional texture information is introduced, e.g. in form of the shift of the percolation threshold with disorder, or other functional relations between volume fractions and spatial disorder; as illustrated herein for a differential scheme model representative of a two-phase (solid\–pore) composite model material.

Fig. 1. Two-dimensional porous media: (a) ordered system, (b) type 1 disorder (pores{\textellipsis}

Fig. 2. Two-point probability functions and associated microstructures of four systems{\textellipsis}

Fig. 3. Probability Density Function (PDF) of the local porosity (φa) and associated{\textellipsis}

Fig. 4. (a) Degrees of freedom of a link element between points i and j, (b) D3Q18 unit{\textellipsis}

Fig. 5. Dimensionless effective Young{\textquoteright}s modulus: Eeff(φ)/Es as function of the porosity{\textellipsis}

Fig. 6. Dimensionless effective Young{\textquoteright}s modulus: Eeff(φ)/Es as function of the porosity

Fig. 7. Ordered system under uniaxial strain, (a) schematic stress map, the darker the{\textellipsis}

Fig. 8. Dimensionless effective Young{\textquoteright}s modulus: Eeff(φ)/Es as function of the porosity

Fig. 9. Probability Density Function (PDF) of the normalized stress (σxx/〈σxx〉) in the{\textellipsis}

Fig. 10. Dimensionless disordered Young{\textquoteright}s modulus: F(φsa)=Eeff(φ,sa)/Eordered(φ) as{\textellipsis}

Fig. 11. Two-phase periodic porous solid

Fig. 12. Dimensionless disordered Young{\textquoteright}s modulus: FMT(φsa)=Eeff(φ,sa)/EMT(φ) as{\textellipsis}

Fig. 13. Integration path for the lower bound differential scheme

Fig. 14. Dimensionless effective Young{\textquoteright}s modulus: Eeff(φ)/Es as function of porosity the

Fig. 15. Dimensionless disordered Young{\textquoteright}s modulus: FMT(φsa)=Eeff(φ,sa)/EMT(φ) as{\textellipsis}

Fig. B.16. (a) Porosity as a function of the number of pores

Fig. D.17. High porosity limit geometry

Fig. E.18. Calculation of the local porosity in a square observation window

}, doi = {10.1016/j.jmps.2017.05.008}, author = {Hadrien Laubie and Monfared, Siavash and Farhang Radja{\"\i} and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {591, title = {Effective Potentials and Elastic Properties in the Lattice-Element Method: Isotropy and Transverse Isotropy}, journal = {Journal of Nanomechanics and Micromechanics}, volume = {7}, year = {2017}, month = {Sep-2017}, pages = { Article Number: UNSP 04017007 }, abstract = {

Lattice approaches have emerged as a powerful tool to capture the effective mechanical behavior of heterogeneous materials using harmonic interactions inspired from beam-type stretch and rotational interactions between a discrete number of mass points. In this paper, the lattice element method (LEM) is reformulated within the conceptual framework of empirical force fields employed at the lattice scale. Within this framework, because classical harmonic formulations are but a Taylor expansion of nonharmonic potential expressions, they can be used to model both the linear and the nonlinear response of discretized material systems. Specifically, closed-form calibration procedures for such interaction potentials are derived for both the isotropic and the transverse isotropic elastic cases on cubic lattices, in the form of linear relations between effective elasticity properties and energy parameters that define the interactions. The relevance of the approach is shown by an application to the classical Griffith crack problem. In particular, it is shown that continuum-scale quantities of linear-elastic fracture mechanics, such as stress intensity factors (SIFs), are well captured by the method, which by its very discrete nature removes geometric discontinuities that provoke stress singularities in the continuum case. With its strengths and limitations thus defined, the proposed LEM is well suited for the study of multiphase materials whose microtextural information is obtained by, e.g., X-ray micro-computed tomography. (c) 2017 American Society of Civil Engineers.

}, issn = {2153-5434}, doi = {10.1061/(ASCE)NM.2153-5477.0000125}, url = {http://ascelibrary.org/doi/10.1061/\%28ASCE\%29NM.2153-5477.0000125}, author = {Hadrien Laubie and Monfared, Siavash and Farhang Radja{\"\i} and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {588, title = {From cellulose to kerogen: molecular simulation of a geological process}, journal = {Chemical Science}, volume = {8}, year = {2017}, month = {Dec-01-2017}, pages = {8325-8335}, abstract = {

The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man\&$\#$39;s land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.

}, issn = {2041-6520}, doi = {10.1039/C7SC03466K}, url = {http://xlink.rsc.org/?DOI=C7SC03466K}, author = {Atmani, Lea and Christophe Bichara and Roland Jean-Marc Pellenq and Henri Van Damme and Adri CT Van Duin and Raza, Zamaan and Truflandier, Lionel A. and Ama{\"e}l Obliger and Kralert, Paul G. and Franz-Josef Ulm and Jean-Marc Leyssale} } @article {245, title = {Inhomogeneity in Cement Hydrates: Linking Local Packing to Local Pressure}, journal = {Journal of Nanomechanics and Micromechanics}, volume = {7}, year = {2017}, month = {Mar-03-2017}, pages = {Article Number: UNSP 04017003}, abstract = {

Nanoscale structural heterogeneities were recently revealed in computational and experimental studies of calcium silicate hydrates in hardened cement pastes. In this work their consequences for the mechanics are analyzed by computing local pressures in model samples at different overall densities, corresponding to different initial water-to-cement ratios. The correlations between pore size distributions, local density, local cohesive energy, and local pressure clearly show how in these materials structural heterogeneities may be the origin of significant mechanical heterogeneities. The results indicate that even at high density pressure, heterogeneities develop during the densification of cement hydrates and result in the coexistence of regions of high positive pressure with regions of negative pressure, in spite of the overall mechanical stability of the samples. Furthermore, the regions of negative pressure, prone to mechanical instabilities and local plastic processes, tend to be localized close to the surface of large mesopores and hence to be more significant at higher initial water content.
Inhomogeneity in Cement Hydrates: Linking Local Packing to Local Pressure. Available from: https://www.researchgate.net/publication/314222493_Inhomogeneity_in_Cement_Hydrates_Linking_Local_Packing_to_Local_Pressure [accessed Oct 2, 2017].

}, issn = {2153-5434}, doi = {10.1061/(ASCE)NM.2153-5477.0000120}, author = {Katerina Ioannidou and Emanuela Del Gado and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {586, title = {Mesoscale Poroelasticity of Heterogeneous Media}, journal = {Journal of Nanomechanics and Micromechanics}, volume = {7}, year = {2017}, month = {Oct-19-2017}, pages = {Article Number: UNSP 04017016 }, abstract = {

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.

}, issn = {2153-5434}, doi = {10.1061/(ASCE)NM.2153-5477.0000136}, url = {http://ascelibrary.org/doi/10.1061/\%28ASCE\%29NM.2153-5477.0000136}, author = {Monfared, Siavash and Hadrien Laubie and Farhang Radja{\"\i} and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {587, title = {Methodology for Estimation of Nanoscale Hardness via Atomistic Simulations}, journal = {Journal of Nanomechanics and Micromechanics}, volume = {7}, year = {2017}, month = {Dec-2017}, pages = { Article Number: UNSP 04017011 }, abstract = {

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.

}, keywords = {Atomistic simulation; Friction; Cohesion; Hardness; Tobermorite; Montmorillonite}, issn = {2153-5434}, doi = {10.1061/(ASCE)NM.2153-5477.0000127}, url = {http://ascelibrary.org/doi/10.1061/\%28ASCE\%29NM.2153-5477.0000127}, author = {Qomi, M. J. Abdolhosseini and Ebrahimi, Davoud and Mathieu Bauchy and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {623, title = {Nano-granular texture of cement hydrates}, journal = {EPJ Web of Conferences}, volume = {140}, year = {2017}, month = {Jun-30-2017}, pages = {Article Number 15027}, abstract = {

Mechanical behavior of concrete crucially depends on cement hydrates, the \“glue\” of cement. The design of high performance and more environmentally friendly cements demands a deeper understanding of the formation of the multiscale structure of cement hydrates, when they precipitate and densify. We investigate the precipitation and setting of nano-grains of cement hydrates using a combination of Monte Carlo and Molecular Dynamics numerical simulations and study their texture from nano up to the micron scale. We characterize the texture of cement hydrates using the local volume fraction distribution, the pore size distribution, the scattering intensity and the chord length distribution and we compare them with experiments. Our nano-granular model provides cement structure with realistic texture and mechanics and can be further used to investigate degradation mechanisms.

}, doi = {10.1051/epjconf/201714015027}, url = {http://www.epj-conferences.org/10.1051/epjconf/201714015027}, author = {Katerina Ioannidou and Franz-Josef Ulm and Pierre E. Levitz and Emanuela Del Gado and Roland Jean-Marc Pellenq}, editor = {Farhang Radja{\"\i} and Saeid Nezamabadi and Luding, S. and Jean-Yves Delenne} } @article {242, title = {A potential-of-mean-force approach for fracture mechanics of heterogeneous materials using the lattice element method}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {105}, year = {2017}, month = {Aug-2017}, pages = {116 - 130}, abstract = {

Fracture of heterogeneous materials has emerged as a critical issue in many engineering applications, ranging from subsurface energy to biomedical applications, and requires a rational framework that allows linking local fracture processes with global fracture descriptors such as the energy release rate, fracture energy and fracture toughness. This is achieved here by means of a local and a global potential-of-mean-force (PMF) inspired Lattice Element Method (LEM) approach. In the local approach, fracture-strength criteria derived from the effective interaction potentials between mass points are shown to exhibit a scaling commensurable with the energy dissipation of fracture processes. In the global PMF-approach, fracture is considered as a sequence of equilibrium states associated with minimum potential energy states analogous to Griffith\’s approach. It is found that this global approach has much in common with a Grand Canonical Monte Carlo (GCMC) approach, in which mass points are randomly removed following a maximum dissipation criterion until the energy release rate reaches the fracture energy. The duality of the two approaches is illustrated through the application of the PMF-inspired LEM for fracture propagation in a homogeneous linear elastic solid using different means of evaluating the energy release rate. Finally, by application of the method to a textbook example of fracture propagation in a heterogeneous material, it is shown that the proposed PMF-inspired LEM approach captures some well-known toughening mechanisms related to fracture energy contrast, elasticity contrast and crack deflection in the considered two-phase layered composite material.

}, issn = {00225096}, doi = {10.1016/j.jmps.2017.05.006}, author = {Hadrien Laubie and Farhang Radja{\"\i} and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {590, title = {Production of H 2 by water radiolysis in cement paste under electron irradiation: A joint experimental and theoretical study}, journal = {Cement and Concrete Research}, volume = {100}, year = {2017}, month = {Oct-2017}, pages = {110 - 118}, abstract = {

Long-term confinement of nuclear waste is one of the main challenges faced by the nuclear industry. Fission products such as Sr-90 and Cs-137, both beta(-) emitters known to induce serious health hazards, represent the largest fraction of nuclear waste. Cement is a good candidate to store them, provided it can resist the effects of irradiation over time. Here, we have investigated the effects of beta(-) decay on cement by performing electron irradiation experiments on different samples. We show that H-2 production in cement, the main effect of water radiolysis, depends strongly on composition and relative humidity. First-principles calculations indicate that the water-rich interlayer regions with Ca2+ ions act as electron traps that promote the formation of H-2. They also show that holes localize in water-rich regions in low Ca content samples and are then able to participate in H-2 production. This work provides new understanding of radiolysis effects in cements.

}, issn = {00088846}, doi = {10.1016/j.cemconres.2017.05.022}, url = {https://linkinghub.elsevier.com/retrieve/pii/S0008884617302065}, author = {Le Caer, Sophie and Dezerald, Lucile and Boukari, Khaoula and Laine, Maxime and Taupin, s{\'e}bastien and Kavanagh, Ryan M. and Johnston, Conrad S.N. and Foy, Eddy and Charpentier, Thibault and Konrad J. Krakowiak and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Tribello, Gareth A. and Kohanoff, Jorge J. and Andres Sa{\`u}l} } @article {589, title = {Role of Interfaces in Elasticity and Failure of Clay{\textendash}Organic Nanocomposites: Toughening upon Interface Weakening?}, journal = {Langmuir}, volume = {33}, year = {2017}, month = {Oct-24-2017}, pages = {11457 - 11466}, abstract = {

Synthetic organic-inorganic composites constitute a new class of engineering materials finding applications in an increasing range of fields. The interface between the constituting phases plays a pivotal role in the enhancement of mechanical properties. In exfoliated clay-organic nanocomposites, individual, high aspect ratio clay sheets are dispersed in the organic matrix providing large interfaces and hence efficient stress transfer. In this study, we aim at elucidating molecular-scale reinforcing mechanisms in a series of model clay-organic composite systems by means of reactive molecular simulations. In our models, two possible locations of failure initiation are present: one is the interlayer space of the clay platelet, and the other one is the clay-organic interface. We systematically modify the cohesiveness of the interface and assess how the failure mechanism changes when the different model composites are subjected to a tensile test. Besides a change in the failure mechanism, an increase in the released energy at the interface (meaning an increased overall toughness) are observed upon weakening the interface by bond removal. We propose a theoretical analysis of these results by considering a cohesive law that captures the effect of the interface on the composite mechanics. We suggest an atomistic interpretation of this cohesive law, in particular, how it relates to the degree of bonding at the interface. In a broader perspective, this work sheds light on the importance of the orthogonal behavior of interfaces to nanocomposites.

https://pubs-acs-org.libproxy.mit.edu/appl/literatum/publisher/achs/journals/content/langd5/2017/langd5.2017.33.issue-42/acs.langmuir.7b01071/20171025/images/medium/la-2017-01071k_0008.gif

}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.7b01071}, url = {http://pubs.acs.org/doi/10.1021/acs.langmuir.7b01071}, author = {Gy{\"o}rgy Hantal and Brochard, Laurent and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Benoit A. Coasne} } @article {593, title = {Stress Transmission and Failure in Disordered Porous Media}, journal = {Physical Review Letters}, volume = {119}, year = {2017}, month = {Aug-14-2017}, pages = { Article Number: 075501 }, abstract = {

By means of extensive lattice-element simulations, we investigate stress transmission and its relation with failure properties in increasingly disordered porous systems. We observe a non-Gaussian broadening of stress probability density functions under tensile loading with increasing porosity and disorder, revealing a gradual transition from a state governed by single-pore stress concentration to a state controlled by multipore interactions and metric disorder. This effect is captured by the excess kurtosis of stress distributions and shown to be nicely correlated with the second moment of local porosity fluctuations, which appears thus as a (dis)order parameter for the system. By generating statistical ensembles of porous textures with varying porosity and disorder, we derive a general expression for the fracture stress as a decreasing function of porosity and disorder. Focusing on critical sites where the local stress is above the global fracture threshold, we also analyze the transition to failure in terms of a coarse-graining length. These findings provide a general framework which can also be more generally applied to multiphase and structural heterogeneous materials.

}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.119.075501}, url = {https://link.aps.org/doi/10.1103/PhysRevLett.119.075501}, author = {Hadrien Laubie and Farhang Radja{\"\i} and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {243, title = {Topological Control on the Structural Relaxation of Atomic Networks under Stress}, journal = {Physical Review Letters}, volume = {119}, year = {2017}, month = {Jul-21-2017}, pages = {Article Number: 035502}, abstract = {

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

Figure

Figure

Figure

}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.119.035502}, author = {Mathieu Bauchy and Wang, Mengyi and Yu, Yingtian and Wang, Bu and Krishnan, M. Anoop and Enrico Masoero and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {643, title = {Cement As a Waste Form for Nuclear Fission Products: The Case of 90Sr and Its Daughters}, journal = {Environmental Science \& Technology}, volume = {49}, year = {2016}, month = {Nov-17-2016}, pages = {13676-13683}, abstract = {

One of the main challenges faced by the nuclear industry is the long-term confinement of nuclear waste. Because it is inexpensive and easy to manufacture, cement is the material of choice to store large volumes of radioactive materials, in particular the low-level medium-lived fission products. It is therefore of utmost importance to assess the chemical and structural stability of cement containing radioactive species. Here, we use ab initio calculations based on density functional theory (DFT) to study the effects of Sr-90 insertion and decay in C-S-H (calcium-silicate-hydrate) in order to test the ability of cement to trap and hold this radioactive fission product and to investigate the consequences of its beta-decay on the cement paste structure. We show that Sr-90 is stable when it substitutes the Ca2+ ions in C-S-H, and so is its daughter nucleus Y-90 after beta-decay. Interestingly, Zr-90, daughter of Y-90 and final product in the decay sequence, is found to be unstable compared to the bulk phase of the element at zero K but stable when compared to the solvated ion in water. Therefore, cement appears as a suitable waste form for Sr-90 storage.

}, issn = {0013-936X}, doi = {10.1021/acs.est.5b02609}, url = {http://pubs.acs.org/doi/10.1021/acs.est.5b02609}, author = {Dezerald, Lucile and Kohanoff, Jorge J. and Alfredo A. Correa and Caro, Alfredo and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Andres Sa{\`u}l} } @article {252, title = {Data analytics for simplifying thermal efficiency planning in cities}, journal = {Journal of The Royal Society Interface}, volume = {13}, year = {2016}, month = {Apr-2016}, pages = {Article Number: 20150971}, abstract = {

More than 44\% of building energy consumption in the USA is used for space heating and cooling, and this accounts for 20\% of national CO2emissions. This prompts the need to identify among the 130 million households in the USA those with the greatest energy-saving potential and the associated costs of the path to reach that goal. Whereas current solutions address this problem by analysing each building in detail, we herein reduce the dimensionality of the problem by simplifying the calculations of energy losses in buildings. We present a novel inference method that can be used via a ranking algorithm that allows us to estimate the potential energy saving for heating purposes. To that end, we only need consumption from records of gas bills integrated with a building\&$\#$39;s footprint. The method entails a statistical screening of the intricate interplay between weather, infrastructural and residents\&$\#$39; choice variables to determine building gas consumption and potential savings at a city scale. We derive a general statistical pattern of consumption in an urban settlement, reducing it to a set of the most influential buildings\&$\#$39; parameters that operate locally. By way of example, the implications are explored using records of a set of (N= 6200) buildings in Cambridge, MA, USA, which indicate that retrofitting only 16\% of buildings entails a 40\% reduction in gas consumption of the whole building stock. We find that the inferred heat loss rate of buildings exhibits a power-law data distribution akin to Zipf\&$\#$39;s law, which provides a means to map an optimum path for gas savings per retrofit at a city scale. These findings have implications for improving the thermal efficiency of cities\&$\#$39; building stock, as outlined by current policy efforts seeking to reduce home heating and cooling energy consumption and lower associated greenhouse gas emissions.

}, issn = {1742-5689}, doi = {10.1098/rsif.2015.0971}, author = {Mohammad Javad Abdolhosseini Qomi and Noshadravan, Arash and Sobstyl, Jake M. and Toole, Jameson and Ferreira, Joseph and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Gonzalez, Marta C.} } @article {321, title = {Early-Age Stress and Pressure Developments in a Wellbore Cement Liner: Application to Eccentric Geometries}, journal = {Journal of Applied Mechanics}, volume = {83}, year = {2016}, month = {Sep-2016}, pages = {Article Number: 091012}, abstract = {

This paper introduces a predictive model for the stress and pressure evolutions in a wellbore cement liner at early ages. A pressure state equation is derived that observes the coupling of the elastic changes of the solid matrix, the eigenstress developments in the solid and porespaces, and the mass consumption of water in course of the reaction. Here, the transient constitution of the solid volume necessitates advancing the mechanical state of the poroelastic cement skeleton incrementally and at constant hydration degree. Next, analytic function theory is employed to assess the localization of stresses along the steel\–cement (SC) and rock\–cement (RC) interfaces by placing the casing eccentrically with respect to the wellbore hole. Though the energy release rate due to complete debonding of either interface is only marginally influenced by the eccentricity, the risk of evolving a microcrack along the thick portion of the sheath is substantially increased. Additionally, it is observed that the risk of microannulus formation is principally affected by the pressure rebound, which is engendered by the slowing reaction rate and amplified for rock boundaries with low permeability.

}, issn = {0021-8936}, doi = {10.1115/1.4034013}, author = {Thomas Alexander Petersen and Franz-Josef Ulm} } @article {247, title = {Evolution of organo-clay composites with respect to thermal maturity in type II organic-rich source rocks}, journal = {Geochimica et Cosmochimica Acta}, volume = {195}, year = {2016}, month = {Dec-15-2016}, pages = {68 - 83}, abstract = {

Among the proposed pathways of sequestration and progressive transformation of organic matter (OM) during burial, the sorptive protection mechanism explains the strong relationship between total organic carbon (TOC) and mineral surface area (MSA) noted in numerous black shales around the globe. The complete mechanistic framework of preservation and evolution of OM in organo-mineral complexes remains, however, an enigma. On one hand, smectite layers composing the clay fraction are known to have a major influence on available surface area. OM maturation occurs, on the other hand, concurrently with the smectite illitization that provokes the closure of the interlayer spaces. The potential of smectite layers in the sequestration and preservation of organic molecules and the fate of these molecules with respect to the smectite illitization were therefore addressed. Here, the mineralogy of three organic-rich source rocks of various maturities was characterized in regards with the geochemistry of their OM. A thorough examination of the clay minerals present in the clay matrices provided evidences of mixed layer minerals containing smectite and illite layers with an increasing illite component with respect to maturity. The comprehensive interpretation of the X-ray diffractograms and analytical electron microscopy results suggested the presence of organic molecules in the inter-particulate and possibly the interlayer spaces of the smectite-rich components in immature source rocks. This eventuality was further supported by the presence of intercalated clay-organic nanocomposites observed by transmitted electron microscopy coupled with energy dispersive spectroscopy. Textural observations also showed that the increased illite content found in the overmature sample led to the reorganization of the OM and the clay particles into nano-scale aggregates. These results clarify the geochemical mechanism beyond the reported relationship between TOC and MSA and allow generalizing it to various organic-rich source rocks. Eventually, the understanding of the close organo-clay association raises prospects on the prediction of the evolution of the mechanical properties of economically valuable source rocks with respect to maturity.

}, issn = {00167037}, doi = {10.1016/j.gca.2016.09.008}, author = {Berthonneau, Jeremie and Grauby, Olivier and Muhannad Abuhaikal and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Henri Van Damme} } @article {248, title = {Fracture toughness anomalies: Viewpoint of topological constraint theory}, journal = {Acta Materialia}, volume = {121}, year = {2016}, month = {Dec-2016}, pages = {234 - 239}, abstract = {

The relationship between composition, structure, and resistance to fracture remains poorly understood. Here, based on molecular dynamics simulations, we report that sodium silicate glasses and calcium\–silicate\–hydrates feature an anomalous maximum in fracture toughness. In the framework of topological constraint theory, this anomaly is correlated to a flexible-to-rigid transition, driven by pressure or composition for sodium silicate and calcium\–silicate\–hydrates, respectively. This topological transition, observed for an isostatic network, is also shown to correspond to a ductile-to-brittle transition. At this state, the network is rigid but free of eigen-stress and features stress relaxation through crack blunting, resulting in optimal resistance to fracture. Our topological approach could therefore enable the computational design of tough inorganic solids, which has long been a \“holy grail\” within the non-metallic materials chemistry community.

Image 1

}, issn = {13596454}, doi = {10.1016/j.actamat.2016.09.004}, author = {Mathieu Bauchy and Wang, Bu and Wang, Mengyi and Yu, Yingtian and Mohammad Javad Abdolhosseini Qomi and Smedskjaer, Morten M. and Christophe Bichara and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {249, title = {Free Volume Theory of Hydrocarbon Mixture Transport in Nanoporous Materials}, journal = {The Journal of Physical Chemistry Letters}, volume = {7}, year = {2016}, month = {Jun-10-2016}, pages = {3712 - 3717}, abstract = {
Despite recent focus on shale gas, hydrocarbon recovery from the ultraconfining and disordered porosity of organic matter in shales (kerogen) remains poorly understood. Key aspects such as the breakdown of hydrodynamics at the nanoscale and strong adsorption effects lead to unexplained non-Darcy behaviors. Here, molecular dynamics and statistical mechanics are used to elucidate hydrocarbon mixture transport through a realistic molecular model of kerogen [Bousige, C.; et al. Nat. Mater. 2016, 15, 576]. Owing to strong adsorption effects, velocity cross-correlations between the mixture components and between molecules of the same species are shown to be negligible. This allows estimation of each component permeance from its self-diffusivity, which can be obtained from single-component data. These permeances are found to scale with the reciprocal of the alkane length and decrease with the number of adsorbed molecules following a simple free volume theory, therefore allowing mixture transport prediction as a function of the amount of trapped fluid.
Abstract Image
}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.6b01684}, author = {Ama{\"e}l Obliger and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Benoit A. Coasne} } @article {196, title = {Mesoscale texture of cement hydrates}, journal = {Proceedings of the National Academy of Sciences}, volume = {113}, year = {2016}, month = {Feb-23-2016}, pages = {2029 - 2034}, abstract = {

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.

Fig. 1.

}, issn = {0027-8424}, doi = {10.1073/pnas.1520487113}, author = {Katerina Ioannidou and Konrad J. Krakowiak and Mathieu Bauchy and Christian G. Hoover and Enrico Masoero and Sidney Yip and Franz-Josef Ulm and Pierre E. Levitz and Roland Jean-Marc Pellenq and Emanuela Del Gado} } @article {325, title = {A molecular informed poroelastic model for organic-rich, naturally occurring porous geocomposites}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {88}, year = {2016}, month = {Mar-2016}, pages = {186 - 203}, abstract = {

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\&$\#$39;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.

Fig.1. Clay type distribution in the studied samples

Fig.2. Schematics for the multi-scale maturity dependent model for organic-rich shales

Fig.3. A Scanning Electron Microscope (SEM) image on Haynesville sample

Fig.4. Calibration quality check by comparing predicted macroscopic values (drained{\textellipsis}

Fig.5. Validation by means of nanoindentation for Woodford on the left and Haynesville{\textellipsis}

Fig.6. Bulk modulus of kerogen against density for two of the samples studied by{\textellipsis}

}, issn = {00225096}, doi = {10.1016/j.jmps.2015.12.006}, author = {Monfared, Siavash and Franz-Josef Ulm} } @article {323, title = {Nanochemo-mechanical signature of organic-rich shales: a coupled indentation{\textendash}EDX analysis}, journal = {Acta Geotechnica}, volume = {11}, year = {2016}, month = {Jun-2016}, pages = {559 - 572}, abstract = {

The organic\–inorganic nature of organic-rich source rocks poses several challenges for the development of functional relations that link mechanical properties with geochemical composition. With this focus in mind, we herein propose a method that enables chemo-mechanical characterization of this highly heterogeneous source rock at the micron and submicron length scale through a statistical analysis of a large array of energy-dispersive X-ray spectroscopy (EDX) data coupled with nanoindentation data. The ability to include elemental composition to the indentation probe via EDX is shown to provide a means to identify pure material phases, mixture phases, and interfaces between different phases. Employed over a large array, the statistical clustering of this set of chemo-mechanical data provides access to the properties of the fundamental building blocks of clay-dominated organic-rich source rocks. The versatility of the approach is illustrated through the application to a large number of source rocks of different origin, chemical composition, and organic content. We find that the identified properties exhibit a unique scaling relation between stiffness and hardness. This suggests that organic-rich shale properties can be reduced to their elementary constituents, with several implications for the development of predictive functional relations between chemical composition and mechanical properties of organic-rich source rocks such as the intimate interplay between clay-packing, organic maturity, and mechanical properties of porous clay/organic phase.

}, issn = {1861-1125}, doi = {10.1007/s11440-015-0426-4}, author = {Abedi, Sara and Slim, Mirna and Hofmann, Ronny and Bryndzia, Taras and Franz-Josef Ulm} } @article {322, title = {Nanomechanics of organic-rich shales: the role of thermal maturity and organic matter content on texture}, journal = {Acta Geotechnica}, volume = {11}, year = {2016}, month = {Aug-2016}, pages = {775 - 787}, abstract = {

Despite the importance of organic-rich shales, microstructural characterization and theoretical modeling of these rocks are limited due to their highly heterogeneous microstructure, complex chemistry, and multiscale mechanical properties. One of the sources of complexity in organic-rich shales is the intricate interplay between microtextural evolution and kerogen maturity. In this study, a suite of experimental and theoretical microporomechanics methods are developed to associate the mechanical properties of organic-rich shales both to their maturity level and to the organic content at micrometer and sub-micrometer length scales. Recent results from chemomechanical characterization experiments involving grid nanoindentation and energy-dispersive X-ray spectroscopy (EDX) are used in new micromechanical models to isolate the effects of maturity levels and organic content from the inorganic solids. These models enable attribution of the role of organic maturity to the texture of the indented material, with immature systems exhibiting a matrix-inclusion morphology, while mature systems exhibit a polycrystal morphology. Application of these models to the interpretation of nanoindentation results on organic-rich shales allows us to identify unique clay mechanical properties that are consistent with molecular simulation results for illite and independent of the maturity of shale formation and total organic content. The results of this investigation contribute to the design of a multiscale model of the fundamental building blocks of organic-rich shales, which can be used for the design and validation of multiscale predictive poromechanics models.

}, issn = {1861-1125}, doi = {10.1007/s11440-016-0476-2}, author = {Abedi, Sara and Slim, Mirna and Franz-Josef Ulm} } @article {324, title = {Radial fracture in a three-phase composite: Application to wellbore cement liners at early ages}, journal = {Engineering Fracture Mechanics}, volume = {154}, year = {2016}, month = {Mar-2016}, pages = {272 - 287}, abstract = {

Little understanding exists between the early-age stress developments in a wellbore cement sheath and its risk of impairment. During hydration, the cement morphology and pore-pressure changes induce eigenstresses in the solid and pore volumes. Utilizing these stresses as the driving mechanism of fracture, this paper formalizes the inspection of a radial crack in an elastic cement sheath constrained by an inner steel casing and an outer rock formation. The solution is constructed in the framework of analytic function theory and seeks the Green\’s function for an edge dislocation in the intermediate cement phase. A dislocation pile-up along the line of fracture constructs a singular integral equation for the crack opening displacement derivative, from which the energy release rate is readily deduced.

Under the uniform development of eigenstresses, the stiffness ratios of steel-to-cement and rock-to-cement generally predict the crack to initiate along the steel-cement interface. Here, the impacts of (i) a rigid bond and (ii) a sliding interface with no shear are assessed. This leads to the primary result of the paper: the potential for radial fracture is substantially mitigated by ensuring the shear connection between the steel casing and the cement sheath.

Diagram of a wellbore cement system with a radial crack emanating from SC.

Simulated evolution of the shear modulus G, bulk modulus K, and Poisson{\textquoteright}s ratio ...

Simulated evolution of the effective hoop stress Σθθ=σθθ+p along SC (blue) and ...

Continuation of the annular region of the cement domain across SC and RC.

}, issn = {00137944}, doi = {10.1016/j.engfracmech.2016.01.005}, author = {Thomas Alexander Petersen and Franz-Josef Ulm} } @article {195, title = {Realistic molecular model of kerogen{\textquoteright}s nanostructure}, journal = {Nature Materials}, year = {2016}, month = {Feb-01-2016}, abstract = {

Despite kerogen\’s importance as the organic backbone for hydrocarbon production from source rocks such as gas shale, the interplay between kerogen\’s chemistry, morphology and mechanics remains unexplored. As the environmental impact of shale gas rises, identifying functional relations between its geochemical, transport, elastic and fracture properties from realistic molecular models of kerogens becomes all the more important. Here, by using a hybrid experimental\–simulation method, we propose a panel of realistic molecular models of mature and immature kerogens that provide a detailed picture of kerogen\’s nanostructure without considering the presence of clays and other minerals in shales. We probe the models\’ strengths and limitations, and show that they predict essential features amenable to experimental validation, including pore distribution, vibrational density of states and stiffness. We also show that kerogen\’s maturation, which manifests itself as an increase in the sp2/sp3 hybridization ratio, entails a crossover from plastic-to-brittle rupture mechanisms.

Kerogen in organic-rich shale formations.

Reconstruction of molecular models of kerogens.

Experimental validation of the molecular models.

Elastic properties of molecular models of kerogen.

}, issn = {1476-1122}, doi = {10.1038/nmat4541}, author = {Bousige, Colin and Ghimbeu, Cam{\'e}lia Matei and Vix-Guterl, Cathie and Pomerantz, Andrew E. and Suleimenova, Assiya and Vaughan, Gavin and Garbarino, Gaston and Feygenson, Mikhail and Wildgruber, Christoph and Franz-Josef Ulm and Roland Jean-Marc Pellenq and Benoit A. Coasne} } @article {320, title = {Risk of Pavement Fracture due to Eigenstresses at Early Ages and Beyond}, journal = {Journal of Engineering Mechanics}, volume = {142}, year = {2016}, month = {Dec-2016}, pages = {Article Number: 04016105 }, abstract = {

Tensile cracks significantly affect the durability of concrete pavements, leading to an increase in the costs of maintenance and rehabilitation. A model is developed that relates thermal, chemical, and hygral evolutions at small scales due to different distress mechanisms to the risk of fracture at the structural scale. The method is based on application of linear elastic fracture mechanics (LEFM) to eigenstresses that develop in infinite- and finite-length beams on an elastic foundation that represents the subgrade. Axial and bending contributions to the energy release rate are determined for a worst-case scenario of an entirely cracked pavement section in functions of material properties, structural dimensions, and eigenstress forces and moments. By way of example, the model is used to study the risk of fracture of concrete pavements due to two different mechanisms: (1)\ autogeneous shrinkage at early ages of placing the concrete and (2)\ thermal cycles at the short term and long term after a temperature change. In addition, scaling relationships are developed that provide insight into the improvement of different structural and material properties for minimizing the risk of fracture.

}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0001167}, author = {Arghavan Louhghalam and Franz-Josef Ulm} } @article {319, title = {Size-Effect Law for Scratch Tests of Axisymmetric Shape}, journal = {Journal of Engineering Mechanics}, volume = {142}, year = {2016}, month = {Dec-2016}, pages = {Article Number: 04016094 }, abstract = {

This paper presents a theoretical and experimental framework for the application of size-effect analysis to microscratch testing as a means to quantify the fracture properties and internal friction of materials at the microscale. The energetic size-effect law (SEL) for microscratch tests is developed for a general monomeric probe shape in terms of an intrinsic size function. The fundamental idea of the proposed approach is to rescale the scratch response to that of the flat punch, a conjecture that allows one to compare the SEL for different probe geometries, and thus solve for the asymptotic fracture toughness and effective process zone length from scratch tests done on homogenous (acetal homopolymer resin and polycarbonate resin) and inhomogeneous materials (mica ceramic and gas shale). As a material of current interest for controlled fracture studies, two samples of gas shale cored from the Marcellus and Eagle Ford formations are tested and analyzed to quantify all material properties that may be derived from the scratch resistance; namely fracture parameters, asymptotic hardness, strength, cohesion, and internal friction.

}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0001159}, author = {Hubler, Mija H. and Franz-Josef Ulm} } @article {326, title = {Velocity statistics of the Nagel-Schreckenberg model}, journal = {Physical Review E}, volume = {93}, year = {2016}, month = {Feb-18-2016}, pages = {Article Number: 022305}, abstract = {

The statistics of velocities in the cellular automaton model of Nagel and Schreckenberg for traffic are studied. From numerical simulations, we obtain the probability distribution function (PDF) for vehicle velocities and the velocity-velocity (vv) correlation function. We identify the probability to find a standing vehicle as a potential order parameter that signals nicely the transition between free congested flow for sufficiently large number of velocity states. Our results for the vv correlation function resemble features of a second order phase transition. We develop a 3-body approximation that allows us to relate the PDFs for velocities and headways. Using this relation, an approximation to the velocity PDF is obtained from the headway PDF observed in simulations. We find a remarkable agreement between this approximation and the velocity PDF obtained from simulations.

}, issn = {2470-0045}, doi = {10.1103/PhysRevE.93.022305}, author = {Bain, Nicolas and Emig, Thorsten and Franz-Josef Ulm and Schreckenberg, Michael} } @article {128, title = {Bottom-up model of adsorption and transport in multiscale porous media.}, journal = {Phys Rev E Stat Nonlin Soft Matter Phys}, volume = {91}, year = {2015}, month = {Mar-20-2015}, pages = {Article Number: 032133 }, abstract = {

We develop a model of transport in multiscale porous media which accounts for adsorption in the different porosity scales. This model employs statistical mechanics to upscale molecular simulation and describe adsorption and transport at larger time and length scales. Using atom-scale simulations, which capture the changes in adsorption and transport with temperature, pressure, pore size, etc., this approach does not assume any adsorption or flow type. Moreover, by relating the local chemical potential \μ(r) and density \ρ(r), the present model accounts for adsorption effects and possible changes in the confined fluid state upon transport. This model constitutes a bottom-up framework of adsorption and transport in multiscale materials as it (1) describes the adsorption-transport interplay, (2) accounts for the hydrodynamics breakdown at the nm scale, and (3) is multiscale.

}, issn = {1550-2376}, doi = {10.1103/PhysRevE.91.032133}, author = {Botan, Alexandru and Franz-Josef Ulm and Roland Jean-Marc Pellenq and Benoit A. Coasne} } @article {136, title = {Capturing material toughness by molecular simulation: accounting for large yielding effects and limits}, journal = {International Journal of Fracture}, volume = {194}, year = {2015}, month = {Aug-2015}, pages = {149 - 167}, abstract = {

The inherent computational cost of molecular simulations limits their use to the study of nanometric systems with potentially strong size effects. In the case of fracture mechanics, size effects due to yielding at the crack tip can affect strongly the mechanical response of small systems. In this paper we consider two examples: a silica crystal for which yielding is limited to a few atoms at the crack tip, and a nanoporous polymer for which the process zone is about one order of magnitude larger. We perform molecular simulations of fracture of those materials and investigate in particular the system and crack size effects. The simulated systems are periodic with an initial crack. Quasi-static loading is achieved by increasing the system size in the direction orthogonal to the crack while maintaining a constant temperature. As expected, the behaviors of the two materials are significantly different. We show that the behavior of the silica crystal is reasonably well described by the classical framework of linear elastic fracture mechanics (LEFM). Therefore, one can easily upscale engineering fracture properties from molecular simulation results. In contrast, LEFM fails capturing the behavior of the polymer and we propose an alternative analysis based on cohesive crack zone models. We show that with a linear decreasing cohesive law, this alternative approach captures well the behavior of the polymer. Using this cohesive law, one can anticipate the mechanical behavior at larger scale and assess engineering fracture properties. Thus, despite the large yielding of the polymer at the scale of the molecular simulation, the cohesive zone analysis offers a proper upscaling methodology.

}, issn = {0376-9429}, doi = {10.1007/s10704-015-0045-y}, author = {Brochard, Laurent and Gy{\"o}rgy Hantal and Hadrien Laubie and Franz-Josef Ulm and Roland Jean-Marc Pellenq and Benoit A. Coasne} } @proceedings {98, title = {Is cement a glassy material?}, journal = {Euro-C Conference}, volume = {COMPUTATIONAL MODELLING OF CONCRETE STRUCTURES, VOL 1}, year = {2015}, month = {Jun-22-2015}, pages = {169-176}, publisher = {CRC PRESS-TAYLOR \& FRANCIS GROUP}, address = {MAR 24-27, 2014, St Anton am Alberg, AUSTRIA}, abstract = {

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

}, isbn = {978-1-138-02641-4; 978-1-315-76203-6}, doi = {10.1201/b16645-19}, author = {Mathieu Bauchy and Mohammad Javad Abdolhosseini Qomi and Roland Jean-Marc Pellenq and Franz-Josef Ulm}, editor = {Bicanic, N and Mang, H and Meschke, G and DeBorst, R} } @article {133, title = {Cement As a Waste Form for Nuclear Fission Products: The Case of 90 Sr and Its Daughters}, journal = {Environ Sci Technol}, volume = {49}, year = {2015}, month = {Oct-2015}, pages = {13676-83}, abstract = {

One of the main challenges faced by the nuclear industry is the long-term confinement of nuclear waste. Because it is inexpensive and easy to manufacture, cement is the material of choice to store large volumes of radioactive materials, in particular the low-level medium-lived fission products. It is therefore of utmost importance to assess the chemical and structural stability of cement containing radioactive species. Here, we use ab initio calculations based on density functional theory (DFT) to study the effects of (90)Sr insertion and decay in C-S-H (calcium-silicate-hydrate) in order to test the ability of cement to trap and hold this radioactive fission product and to investigate the consequences of its \β-decay on the cement paste structure. We show that (90)Sr is stable when it substitutes the Ca(2+) ions in C-S-H, and so is its daughter nucleus (90)Y after \β-decay. Interestingly, (90)Zr, daughter of (90)Y and final product in the decay sequence, is found to be unstable compared to the bulk phase of the element at zero K but stable when compared to the solvated ion in water. Therefore, cement appears as a suitable waste form for (90)Sr storage.

}, issn = {1520-5851}, doi = {10.1021/acs.est.5b02609}, author = {Dezerald, Lucile and Kohanoff, Jorge J and Alfredo A. Correa and Caro, Alfredo and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Andres Sa{\`u}l} } @proceedings {332, title = {Creep of Bulk C-S-H: Insights from Molecular Dynamics Simulations}, journal = {10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete StructuresCONCREEP 10}, volume = {CONCREEP 10: MECHANICS AND PHYSICS OF CREEP, SHRINKAGE, AND DURABILITY OF CONCRETE AND CONCRETE STRUCTURES }, year = {2015}, month = {Sep-17-2015}, pages = {511-516}, publisher = {American Society of Civil Engineers}, address = {September 21{\textendash}23, 2015, Vienna, AustriaReston, VA}, abstract = {

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

}, doi = {10.1061/978078447934610.1061/9780784479346.061}, author = {Mathieu Bauchy and Enrico Masoero and Franz-Josef Ulm and Roland Jean-Marc Pellenq}, editor = {Hellmich, Christian and Pichler, Bernhard and Kollegger, Johann} } @proceedings {331, title = {C-S-H across Length Scales: From Nano to Micron}, journal = {10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete StructuresCONCREEP 10}, volume = {CONCREEP 10: MECHANICS AND PHYSICS OF CREEP, SHRINKAGE, AND DURABILITY OF CONCRETE AND CONCRETE STRUCTURES }, year = {2015}, month = {Sep-17-2015}, pages = {39-48}, publisher = {American Society of Civil Engineers}, address = {September 21{\textendash}23, 2015, Vienna, AustriaReston, VA}, abstract = {

Despite their impact on longevity, serviceability, and environmental footprint of our built infrastructure, the chemo-physical origins of nanoscale properties of cementitious materials, and their link to macroscale properties still remain rather obscure. Here, we discuss a multi-scale approach that describes different aspects of physical properties of C-S-H at the nano- and meso-scales. These include dynamics of water, thermal properties and mechanical behavior of C-S-H and its effect on properties of cement paste at different scales.

}, doi = {10.1061/978078447934610.1061/9780784479346.006}, url = {http://ascelibrary.org/doi/book/10.1061/9780784479346http://ascelibrary.org/doi/pdf/10.1061/9780784479346http://ascelibrary.org/doi/10.1061/9780784479346.006http://ascelibrary.org/doi/pdf/10.1061/9780784479346.006}, author = {Mohammad Javad Abdolhosseini Qomi and Enrico Masoero and Mathieu Bauchy and Franz-Josef Ulm and Emanuela Del Gado and Roland Jean-Marc Pellenq}, editor = {Hellmich, Christian and Pichler, Bernhard and Kollegger, Johann} } @article {135, title = {Effect of Chain Length and Pore Accessibility on Alkane Adsorption in Kerogen}, journal = {Energy \& Fuels}, volume = {29}, year = {2015}, month = {Oct-28-2015}, pages = {7889 - 7896}, abstract = {
Abstract Image

Configurational-biased Grand Canonical Monte Carlo and Molecular Dynamics simulations were used to investigate the adsorption and structure of n-alkanes in realistic models of kerogen (the organic phase in gas shales). Both the effects of the n-alkane length (from methane to dodecane) and of the adsorbent porosity/density and connectivity were considered. For all n-alkanes, due to the subnano pore size of kerogen, adsorption follows a Langmuir-type adsorption isotherm as the adsorbed amount increases continuously with pressure until maximum loading is reached. While all n-alkanes get adsorbed very efficiently in low density kerogen, size exclusion in high density kerogen lead to low adsorbed amounts for molecules larger than hexane. Using Molecular Dynamics simulations reflecting the setup of actual adsorption experiments, we also probed the effect of pore accessibility on n-alkane adsorption in kerogen. All pores are connected to the surface and, hence, accessible for the low density kerogen. In contrast, most pores are isolated and inaccessible in the kerogen with the high density. We also address the effect of mesoporosity and its connection to nanoporosity on alkane adsorption in kerogen.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.5b02015}, author = {Kerstyn I. Falk and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Benoit A. Coasne} } @article {148, title = {Experimental chemo-mechanics of early-age fracture properties of cement paste}, journal = {Cement and Concrete Research}, volume = {75}, year = {2015}, month = {Sep-2015}, pages = {42 - 52}, abstract = {

The risk of early-age fracture of cementitious materials in ever more challenging environments provides a unique opportunity to employ an experimental chemo-mechanical platform to develop functional relations between hydration degree, fracture and strength properties, assessed by isothermal calorimetry, micro-scratching, splitting and microindentation on white cement paste at various curing ages from 7\ h to 28\ days. We show that the modulus, tensile strength, fracture toughness and energy all evolve with a natural logarithmic dependence on the hydration degree. These trends are linked to the densification of the material during the hydration process, explained by compaction mechanics and free volume theory. We show that while the fracture process zone size is essentially constant during the hydration process, the ductility of the material, quantified by M/H, decreases, and is consistent with the evolution of Kc/H. Both quantities provide a convenient way to experimentally assess the fracture sensitivity of early-age cement-based materials.

}, issn = {00088846}, doi = {10.1016/j.cemconres.2015.04.004}, author = {Christian G. Hoover and Franz-Josef Ulm} } @article {137, title = {Fracture toughness of calcium{\textendash}silicate{\textendash}hydrate from molecular dynamics simulations}, journal = {Journal of Non-Crystalline Solids}, volume = {419}, year = {2015}, month = {Jul-01-2015}, pages = {58 - 64}, abstract = {

Concrete is the most widely manufactured material in the world. Its binding phase, calcium\–silicate\–hydrate (C\–S\–H), is responsible for its mechanical properties and has an atomic structure fairly similar to that of usual calcium silicate glasses, which makes it appealing to study this material with tools and theories traditionally used for non-crystalline solids. Here, following this idea, we use molecular dynamics simulations to evaluate the fracture toughness of C\–S\–H, inaccessible experimentally. This allows us to discuss the brittleness of the material at the atomic scale. We show that, at this scale, C\–S\–H breaks in a ductile way, which prevents one from using methods based on linear elastic fracture mechanics. Knowledge of the fracture properties of C\–S\–H at the atomic scale opens the way for an upscaling approach to the design of tougher cement paste, which would allow for the design of slender environment-friendly infrastructures, requiring less material.

}, issn = {00223093}, doi = {10.1016/j.jnoncrysol.2015.03.031}, author = {Mathieu Bauchy and Hadrien Laubie and Mohammad Javad Abdolhosseini Qomi and Christian G. Hoover and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {151, title = {Inference of the phase-to-mechanical property link via coupled X-ray spectrometry and indentation analysis: Application to cement-based materials}, journal = {Cement and Concrete Research}, volume = {67}, year = {2015}, month = {Jan-2015}, pages = {271 - 285}, abstract = {

A novel approach for the chemo-mechanical characterization of cement-based materials is presented, which combines the classical grid indentation technique with elemental mapping by scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS). It is illustrated through application to an oil-well cement system with siliceous filler. The characteristic X-rays of major elements (silicon, calcium and aluminum) are measured over the indentation region and mapped back on the indentation points. Measured intensities together with indentation hardness and modulus are considered in a clustering analysis within the framework of Finite Mixture Models with Gaussian component density function. The method is able to successfully isolate the calcium-silica-hydrate gel at the indentation scale from its mixtures with other products of cement hydration and anhydrous phases; thus providing a convenient means to link mechanical response to the calcium-to-silicon ratio quantified independently via X-ray wavelength dispersive spectroscopy. A discussion of uncertainty quantification of the estimated chemo-mechanical properties and phase volume fractions, as well as the effect of chemical observables on phase assessment is also included.

}, issn = {00088846}, doi = {10.1016/j.cemconres.2014.09.001}, author = {Konrad J. Krakowiak and Wilson, William and James, Simon and Musso, Simone and Franz-Josef Ulm} } @proceedings {334, title = {Kinetic Simulations of Cement Creep: Mechanisms from Shear Deformations of Glasses}, journal = {10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete StructuresCONCREEP 10}, volume = {CONCREEP 10: MECHANICS AND PHYSICS OF CREEP, SHRINKAGE, AND DURABILITY OF CONCRETE AND CONCRETE STRUCTURES}, year = {2015}, month = {Sep-17-2015}, pages = {555-564}, publisher = {American Society of Civil Engineers}, address = {September 21{\textendash}23, 2015, Vienna, AustriaReston, VA}, abstract = {

The logarithmic deviatoric creep of cement paste is a technical and scientific challenge. Transition State Theory (TST) indicates that some nanoscale mechanisms of shear deformation, associated with a specific kind of strain hardening, can explain the type of deviatoric creep observed experimentally in mature cement pastes. To test this possible explanation, we simulate the shear deformations of a colloidal model of cement hydrates at the nanoscale. Results from quasi-static simulations indicate a strain hardening analogous to that postulated by the TST approach. Additional results from oscillatory shear (fatigue) simulations show an increase of deformation with number of loading cycles that is consistent with the observed creep. These findings indicate that nanoscale simulations can improve our current understanding of the mechanisms underlying creep, with potential to go beyond the logarithmic creep and explore the onset of failure during tertiary creep.

}, doi = {10.1061/978078447934610.1061/9780784479346.068}, author = {Enrico Masoero and Mathieu Bauchy and Emanuela Del Gado and Hegoi Manzano and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Sidney Yip}, editor = {Hellmich, Christian and Pichler, Bernhard and Kollegger, Johann} } @proceedings {330, title = {The Meso-Scale Texture of Cement Hydrate Gels: Out-of-Equilibrium Evolution and Thermodynamic Driving}, journal = {10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete Structures CONCREEP 10}, volume = {CONCREEP 10: MECHANICS AND PHYSICS OF CREEP, SHRINKAGE, AND DURABILITY OF CONCRETE AND CONCRETE STRUCTURES}, year = {2015}, month = {Sep-17-2015}, pages = {34-38}, publisher = {American Society of Civil Engineers}, address = {September 21{\textendash}23, 2015 Vienna, AustriaReston, VA}, abstract = {

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.

}, doi = {10.1061/978078447934610.1061/9780784479346.005}, author = {Emanuela Del Gado and Katerina Ioannidou and Enrico Masoero and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Sidney Yip}, editor = {Hellmich, Christian and Pichler, Bernhard and Kollegger, Johann} } @article {150, title = {Nano-chemo-mechanical signature of conventional oil-well cement systems: Effects of elevated temperature and curing time}, journal = {Cement and Concrete Research}, volume = {67}, year = {2015}, month = {Jan-2015}, pages = {103 - 121}, abstract = {

With ever more challenging (T,p) environments for cementing applications in oil and gas wells, there is a need to identify the fundamental mechanisms of fracture resistant oil well cements. We report results from a multi-technique investigation of behavior and properties of API class G cement and silica-enriched cement systems subjected to hydrothermal curing from 30\ \°C to 200\ \°C; including electron probe microanalysis, X-ray diffraction, thermogravimetry analysis, electron microscopy, neutron scattering (SANS), and fracture scratch testing. The results provide a new insight into the link between system chemistry, micro-texture and micro-fracture toughness. We suggest that the strong correlation found between chemically modulated specific surface and fracture resistance can explain the drop in fracture properties of neat oil-well cements at elevated temperatures; the fracture property enhancement in silica-rich cement systems, between 110\° and 175\ \°C; and the drop in fracture properties of such systems through prolonged curing over 1\ year at 200\ \°C.

Fig.1. Particle size distribution of the silica flour (ground quartz) incorporated{\textellipsis}

Fig.2. Location of the {\textquotedblleft}chemical poles{\textquotedblright} of the cement clinker and cement hydration{\textellipsis}

Fig.3. Simplified schematic of: (a) the cement paste microstructure cured at room{\textellipsis}

Fig.4. A schematic of the effect of adding an extra dimension, Al, to the statistical{\textellipsis}

Fig.5. X-ray powder diffraction spectra with qualitative analysis of the major phases{\textellipsis}

Fig.6. Thermal gravimetric analysis (TGA) carried out on samples cured in the{\textellipsis}

}, issn = {00088846}, doi = {10.1016/j.cemconres.2014.08.008}, author = {Konrad J. Krakowiak and Jeffrey J. Thomas and Musso, Simone and James, Simon and Ange-Therese Akono and Franz-Josef Ulm} } @article {142, title = {Optimized molecular reconstruction procedure combining hybrid reverse Monte Carlo and molecular dynamics}, journal = {The Journal of Chemical Physics}, volume = {142}, year = {2015}, month = {Mar-21-2015}, pages = {Article Number: 114112}, abstract = {

We report an efficient atom-scale reconstruction method that consists of combining the Hybrid Reverse Monte Carlo algorithm (HRMC) with Molecular Dynamics (MD) in the framework of a simulated annealing technique. In the spirit of the experimentally constrained molecular relaxation technique [Biswas et al., Phys. Rev. B 69, 195207 (2004)], this modified procedure offers a refined strategy in the field of reconstruction techniques, with special interest for heterogeneous and disordered solids such as amorphous porous materials. While the HRMC method generates physical structures, thanks to the use of energy penalties, the combination with MD makes the method at least one order of magnitude faster than HRMC simulations to obtain structures of similar quality. Furthermore, in order to ensure the transferability of this technique, we provide rational arguments to select the various input parameters such as the relative weight of the energy penalty with respect to the structure optimization. By applying the method to disordered porous carbons, we show that adsorption properties provide data to test the global texture of the reconstructed sample but are only weakly sensitive to the presence of defects. In contrast, the vibrational properties such as the phonon density of states are found to be very sensitive to the local structure of the sample.

Image of FIG. 1.

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Image of FIG. 4.

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Image of FIG. 6.

Image of FIG. 7.

}, issn = {0021-9606}, doi = {10.1063/1.4914921}, author = {Bousige, Colin and Botan, Alexandru and Franz-Josef Ulm and Roland Jean-Marc Pellenq and Benoit A. Coasne} } @article {141, title = {Organic{\textendash}Clay Interfacial Chemical Bonds Probed by ab Initio Calculations}, journal = {The Journal of Physical Chemistry C}, volume = {119}, year = {2015}, month = {Mar-26-2015}, pages = {6511 - 6517}, abstract = {
Abstract Image

Evaluating the nature of binding of the organic phase (called kerogen) with clays and other minerals in gas and oil shale is of critical importance for developing optimal processes for hydrocarbon extraction and recovery. Here we report the results of an ab initio reactive study of a gaseous oil/clay interface, which consists of grafting fragments of sp3 methane and sp2 benzene onto the basal surface of illite. Methane and benzene fragments were selected as they correspond to the simplest monomers of the immature (aliphatic sp3 carbon atoms) and mature (aromatic sp2 carbon atoms) stages of the kerogen macromolecule while illite is encountered in many shale formations. We find that the methyl or phenyl radicals always bond upright to one of the outmost Si atoms of the clay phase, while the H atom attaches to the inner Al\–OH group forming a water molecule. The covalent attachment of the radicals to the oxygen atoms of the clay surface is always less favorable than to the silicon atoms. The energetics of these grafted adducts are discussed along with the maturation state of the shale. An unanticipated signature of the covalent Si\–C binding is the formation of hypervalent Si complexes, characterized by elongated bonds at the oil/clay interface. We complement our atomistic modeling by simulating IR spectra of the two covalently grafted interfaces (methyl\–illite and phenyl\–illite) which fingerprint elongated Si\–C bonds in the frequency range 1100\–1250 cm\–1. This novel finding should have a large impact on the understanding of fracking conditions in shales through this tight- and loose-bonded organic/inorganic interface.

}, issn = {1932-7447}, doi = {10.1021/jp510885f}, author = {Bocquet, Marie-Laure and Benoit A. Coasne and Roland Jean-Marc Pellenq and Franz-Josef Ulm} } @article {138, title = {Physical Origins of Thermal Properties of Cement Paste}, journal = {Physical Review Applied}, volume = {3}, year = {2015}, month = {Jun-17-2015}, pages = {Article Number: 064010}, abstract = {

Despite the ever-increasing interest in multiscale porous materials, the chemophysical origin of their thermal properties at the nanoscale and its connection to the macroscale properties still remain rather obscure. In this paper, we link the atomic- and macroscopic-level thermal properties by combining tools of statistical physics and mean-field homogenization theory. We begin with analyzing the vibrational density of states of several calcium-silicate materials in the cement paste. Unlike crystalline phases, we indicate that calcium silicate hydrates (CSH) exhibit extra vibrational states at low frequencies (\<2\ \ THz) compared to the vibrational states predicted by the Debye model. This anomaly is commonly referred to as the boson peak in glass physics. In addition, the specific-heat capacity of CSH in both dry and saturated states scales linearly with the calcium-to-silicon ratio. We show that the nanoscale-confining environment of CSH decreases the apparent heat capacity of water by a factor of 4. Furthermore, full thermal conductivity tensors for all phases are calculated via the Green-Kubo formalism. We estimate the mean free path of phonons in calcium silicates to be on the order of interatomic bonds. This satisfies the scale separability condition and justifies the use of mean-field homogenization theories for upscaling purposes. Upscaling schemes yield a good estimate of the macroscopic specific-heat capacity and thermal conductivity of cement paste during the hydration process, independent of fitting parameters.

Figure

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}, doi = {10.1103/PhysRevApplied.3.064010}, author = {Mohammad Javad Abdolhosseini Qomi and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {131, title = {Rigidity transition in materials: hardness is driven by weak atomic constraints.}, journal = {Phys Rev Lett}, volume = {114}, year = {2015}, month = {Mar-23-2015}, pages = {Article Number: 125502}, abstract = {

Understanding the composition dependence of the hardness in materials is of primary importance for infrastructures and handled devices. Stimulated by the need for stronger protective screens, topological constraint theory has recently been used to predict the hardness in glasses. Herein, we report that the concept of rigidity transition can be extended to a broader range of materials than just glass. We show that hardness depends linearly on the number of angular constraints, which, compared to radial interactions, constitute the weaker ones acting between the atoms. This leads to a predictive model for hardness, generally applicable to any crystalline or glassy material.

Figure

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}, issn = {1079-7114}, doi = {10.1103/PhysRevLett.114.125502}, author = {Mathieu Bauchy and Mohammad Javad Abdolhosseini Qomi and Christophe Bichara and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {147, title = {Roughness-Induced Vehicle Energy Dissipation: Statistical Analysis and Scaling}, journal = {Journal of Engineering Mechanics}, volume = {141}, year = {2015}, month = {Nov-2015}, pages = {Number: 04015046 }, abstract = {

The energy dissipated in a vehicle suspension system due to road roughness affects rolling resistance and the resulting fuel consumption and greenhouse gas emission. The key parameters driving this dissipation mechanism are identified via dimensional analysis. A mechanistic model is proposed that relates vehicle dynamic properties and road roughness statistics to vehicle dissipated energy and thus fuel consumption. A scaling relationship between the dissipated energy and the most commonly used road roughness index, the International Roughness Index (IRI), is also established. It is shown that the dissipated energy scales with IRI squared and scaling of dissipation with vehicle speed V depends on road waviness number w in the form of Vw\−2. The effect of marginal probability distribution of the road roughness profile on dissipated energy is examined. It is shown that although the marginal distribution of the road profile does not affect the identified scaling relationships, the multiplicative factor in these relationships does change from one distribution to another. As an example of practical application, the model is calibrated with the empirical HDM-4 model for different vehicle classes.

}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0000944}, author = {Arghavan Louhghalam and Tootkaboni, Mazdak and Franz-Josef Ulm} } @proceedings {329, title = {Shrinkage Due to Colloidal Force Interactions}, journal = {10th International Conference on Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete and Concrete Structures CONCREEP 10}, volume = {CONCREEP 10: MECHANICS AND PHYSICS OF CREEP, SHRINKAGE, AND DURABILITY OF CONCRETE AND CONCRETE STRUCTURES}, year = {2015}, month = {Sep-17-2015}, pages = {13-16}, publisher = {American Society of Civil Engineers}, address = {September 21{\textendash}23, 2015, Vienna, AustriaReston, VA }, abstract = {

It has long been argued that shrinkage in cementitious materials can occur even in the absence of drying phenomena. Herein we argue that such shrinkage is attributable to colloidal forces that develop between C-S-H particles during the hydration in an out-of-equilibrium process. We base our argument on meso-scale simulation results, and show via microporomechanics theory that such colloidal forces can lead to the build-up of solid eigenstresses causing macroscopic shrinkage deformation.

}, doi = {10.1061/978078447934610.1061/9780784479346.002}, author = {Franz-Josef Ulm and Roland Jean-Marc Pellenq}, editor = {Hellmich, Christian and Pichler, Bernhard and Kollegger, Johann} } @article {132, title = {Subcontinuum mass transport of condensed hydrocarbons in nanoporous media.}, journal = {Nat Commun}, volume = {6}, year = {2015}, month = {Apr-22-2015}, pages = {Article Number: 6949}, abstract = {

Although hydrocarbon production from unconventional reservoirs, the so-called shale gas, has exploded recently, reliable predictions of resource availability and extraction are missing because conventional tools fail to account for their ultra-low permeability and complexity. Here, we use molecular simulation and statistical mechanics to show that continuum description--Darcy\&$\#$39;s law--fails to predict transport in shales nanoporous matrix (kerogen). The non-Darcy behaviour arises from strong adsorption in kerogen and the breakdown of hydrodynamics at the nanoscale, which contradict the assumption of viscous flow. Despite this complexity, all permeances collapse on a master curve with an unexpected dependence on alkane length. We rationalize this non-hydrodynamic behaviour using a molecular description capturing the scaling of permeance with alkane length and density. These results, which stress the need for a change of paradigm from classical descriptions to nanofluidic transport, have implications for shale gas but more generally for transport in nanoporous media.

Figure 1

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Figure 6

}, issn = {2041-1723}, doi = {10.1038/ncomms7949}, author = {Kerstyn I. Falk and Benoit A. Coasne and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Lyd{\'e}ric Bocquet} } @article {102, title = {Anomalous composition-dependent dynamics of nanoconfined water in the interlayer of disordered calcium-silicates}, journal = {Journal of Chemical Physics}, volume = {140}, year = {2014}, month = {Feb-07-2014}, pages = {Article Number: 054515}, type = {Article}, abstract = {

With shear interest in nanoporous materials, the ultraconfining interlayer spacing of calcium-silicate-hydrate (C-S-H) provides an excellent medium to study reactivity, structure, and dynamic properties of water. In this paper, we present how substrate composition affects chemo-physical properties of water in ultraconfined hydrophilic media. This is achieved by performing molecular dynamics simulation on a set of 150 realistic models with different compositions of calcium and silicon contents. It is demonstrated that the substrate chemistry directly affects the structural properties of water molecules. The motion of confined water shows a multi-stage dynamics which is characteristic of supercooled liquids and glassy phases. Inhomogeneity in that dynamics is used to differentiate between mobile and immobile water molecules. Furthermore, it is shown that the mobility of water molecules is composition-dependent. Similar to the pressure-driven self-diffusivity anomaly observed in bulk water, we report the first study on composition-driven diffusion anomaly, the self diffusivity increases with increasing confined water density in C-S-H. Such anomalous behavior is explained by the decrease in the typical activation energy required for a water molecule to escape its dynamical cage. (C) 2014 AIP Publishing LLC.

Image of FIG. 1.
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}, issn = {0021-9606}, doi = {10.1063/1.4864118}, author = {Mohammad Javad Abdolhosseini Qomi and Mathieu Bauchy and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {84, title = {Atomic-scale modelling of elastic and failure properties of clays}, journal = {Molecular Physics}, volume = {112}, year = {2014}, month = {May-19-2014}, pages = {1294-1305}, type = {Article}, abstract = {

The elastic and failure properties of a typical clay, illite, are investigated using molecular simulation. We employ a reactive (ReaxFF) and a non-reactive (ClayFF) force field to assess the elastic properties of the clay. As far as failure is concerned, ReaxFF was used throughout the study; however, some calculations were also performed with ClayFF. A crack parallel to the clay layers is found to have low fracture resistance when submitted to a tensile loading perpendicular to the crack. The mechanism of both yield and fracture failures is decohesion in the interlayer space. In contrast, under shear loading, the nanoscale failure mechanism is a stick-slip between clay layers. No fracture propagation is observed as the clay layers slide on top of each other. The low fracture resistance in mode I and the stick-slip failure in mode II are both the consequence of the lack of chemical bonds between clay layers where the cohesion is provided by non-covalent interactions. This work, which provides a description of the failure of clays at the microscopic scale, is the first step towards describing the failure of clays at a larger scale where the polycrystalline distribution of clay grains must be taken into account.

}, keywords = {clay, elastic properties, fracture, reactive molecular simulation}, issn = {0026-8976}, doi = {10.1080/00268976.2014.897393}, author = {Gy{\"o}rgy Hantal and Brochard, Laurent and Hadrien Laubie and Ebrahimi, Davoud and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Benoit A. Coasne} } @article {309, title = {Chemoelastic Fracture Mechanics Model for Cement Sheath Integrity}, journal = {Journal of Engineering Mechanics}, volume = {140}, year = {2014}, month = {Jul-04-2014}, pages = {Article Number: 04013009 }, abstract = {

A linear elastic fracture mechanics (LEFM) model for the engineering fracture design of cement sheath integrity at early ages in oil and gas well applications is proposed. The model considers the specific worst-case scenario of a single radial crack and estimates the energy release rate (stress intensity factor) that potentially develops in a cement sheath as a result of the buildup of eigenstresses at early ages, considering the loss of axisymmetry. Specifically, the model involves a two-step solution procedure: a chemoelastic stress solver and a LEFM solver using an Airy-stress function approach together with the method of complex variables. For the first, an appropriate constitutive model for cement slurries at early ages is required as a backbone for chemoelastic stress development. Second, the LEFM solver uses the stresses to estimate the energy release rate and the stress intensity, and thus provide a means to evaluate the driving force of fracture propagation and the fracture risk as a function of the degree of hydration. The functional relationships thus established between the LEFM quantities and the degree of the chemical reaction are expected to become an indispensable tool in safely designing well cements for operation under extreme bore hole conditions.

}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0000690}, author = {Ardakani, Sina Moeini and Franz-Josef Ulm} } @article {72, title = {Combinatorial molecular optimization of cement hydrates}, journal = {Nat Commun}, volume = {5}, year = {2014}, month = {Sep-24-2014}, pages = {Article Number: 4960}, abstract = {

Despite its ubiquitous presence in the built environment, concrete\â\€$(1s (Bmolecular-level properties are only recently being explored using experimental and simulation studies. Increasing societal concerns about concrete\â\€$(1s (Benvironmental footprint have provided strong motivation to develop new concrete with greater specific stiffness or strength (for structures with less material). Herein, a combinatorial approach is described to optimize properties of cement hydrates. The method entails screening a computationally generated database of atomic structures of calcium-silicate-hydrate, the binding phase of concrete, against a set of three defect attributes: calcium-to-silicon ratio as compositional index and two correlation distances describing medium-range silicon-oxygen and calcium-oxygen environments. Although structural and mechanical properties correlate well with calcium-to-silicon ratio, the cross-correlation between all three defect attributes reveals an indentation modulus-to-hardness ratio extremum, analogous to identifying optimum network connectivity in glass rheology. We also comment on implications of the present findings for a novel route to optimize the nanoscale mechanical properties of cement hydrate.

Figure 1

}, doi = {10.1038/ncomms5960}, author = {Mohammad Javad Abdolhosseini Qomi and Konrad J. Krakowiak and Mathieu Bauchy and Stewart, K.L. and Rouzbeh Shahsavari and Jagannathan, D. and Brommer, D.B. and Alain Baronnet and Markus J Buehler and Sidney Yip and Franz-Josef Ulm and Krystyn J. Van Vliet and Roland Jean-Marc Pellenq} } @article {306, title = {Discussion: Strength-to-fracture scaling in scratching}, journal = {Engineering Fracture Mechanics}, volume = {119}, year = {2014}, month = {Mar-2014}, pages = {21 - 28}, abstract = {

In their paper, Lin and Zhou (2013) add a new dimension to the scratch test analysis, challenging the applicability of Linear Elastic Fracture Mechanics to scratch tests. The question raised is how to integrate the three-dimensionality of scratch tests into the energetic Size Effect Law (SEL) formulated by Ba{\v z}ant for quasi-brittle materials. We show that Lin and Zhou\’s analysis, although relevant is incomplete, as it neglects the blade width, which is critical for the fracture property assessment. In return, if the blade width is properly taken into account, the SEL here proposed is a formidable means to ascertain the fracture toughness from scratching.

Fig. 1. Description of macroscopic scratch tests

Fig. 2. Influence of cutter width w on the intrinsic specific energy ε and the{\textellipsis}

Fig. 3. Strength scaling of scratch tests for different geometries (straight vs

Fig. 4. (a) Presence of a horizontal propagating crack during scratch testing{\textellipsis}

Fig. 5. Application of Ba{\v z}ant{\textquoteright}s Size Effect Law to scratch tests for different{\textellipsis}

}, issn = {00137944}, doi = {10.1016/j.engfracmech.2014.02.025}, author = {Ange-Therese Akono and Franz-Josef Ulm and Zden{\v e}k P Ba{\v z}ant} } @article {313, title = {Fl{\"u}gge{\textquoteright}s Conjecture: Dissipation- versus Deflection-Induced Pavement{\textendash}Vehicle Interactions}, journal = {Journal of Engineering Mechanics}, volume = {140}, year = {2014}, month = {Aug-2014}, pages = {Article Number: 04014053 }, abstract = {

The dissipation occurring below a moving tire in steady-state conditions in contact with a viscoelastic pavement is expressed using two different reference frames: a fixed observer attached to the pavement and a moving observer attached to the pavement\–tire contact surface. The first approach is commonly referred to as dissipation-induced pavement\–vehicle interaction (PVI), the second as deflection-induced PVI. Based on the principle of frame independence, it is shown that both approaches are strictly equal, from a thermodynamic point of view, and thus predict the same amount of dissipated energy. This equivalence is illustrated through application to two pavement systems: a viscoelastic beam and a viscoelastic plate both resting on an elastic foundation. The amount of dissipated energy in the pavement structure needs to be supplied by the vehicle to maintain constant speed, thus contributing to the rolling resistance, associated excess fuel consumption, and greenhouse gas emissions. The model here proposed can be used to quantify the dissipated energy and contribute to the development of engineering methods for the sustainable design of pavements.

}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0000754}, author = {Arghavan Louhghalam and Mehdi Akbarian and Franz-Josef Ulm} } @article {311, title = {An improved technique for characterizing the fracture toughness via scratch test experiments}, journal = {Wear}, volume = {313}, year = {2014}, month = {May-15-2014}, pages = {117 - 124}, abstract = {

The scratch test consists in pushing a tool across the surface of a weaker material at a given penetration depth; and it has several applications in Science and Engineering including strength testing of rocks and ceramics, damage of polymers and metals and quality control of thin films and coatings. Despite numerous attempts in the scientific literature, the application of scratch tests to the characterization of fracture properties remains a challenge and a heavily controversial topic. Therefore, this investigation aims at articulating a rigorous theoretical and experimental framework in order to assess the fracture toughness at both the macroscopic and the microscopic length scales, using scratch tests. First, we apply optical microscopy and scanning electron microscopy to investigate the physical evidence of crack initiation, crack propagation and material removal mechanisms during scratch tests. Then, we employ Finite Element simulations of crack growth during macroscopic scratch tests to assess the influence of the blade back-rake angle, the friction coefficient between the blade and the material and the wear flat of the blade on the scratching forces, thus testing the robustness of our Linear Elastic Fracture Mechanics scratch model. Finally, at the microscopic scale, a meticulous scratch probe calibration procedure is described to improve the accuracy of the fracture properties determination by addressing important issues such as moisture content, specimen surface cleanliness and choice of reference material. In summary, we bring forward a robust, convenient and accurate method that is applied to polymers, ceramics and metals and can be further applied to the multi-scale study of fracture processes in complex and challenging materials such as gas shale, cement paste and cortical bone.

Fig.1. (color online) (a) Macroscopic scratch tests experiments on paraffin wax with a{\textellipsis}

Fig.2. (color online) Fracture processes in scratch tests at both the macroscopic and{\textellipsis}

Fig.3. (color online) (a) Numerical Scratch Fracture model: 0<=θ<=20{\textdegree} is the blade{\textellipsis}

Fig.4. (color online) (a) Ratio of the stress intensity factor in mode II (in-plane{\textellipsis}

Fig.5. (color online) Wear flat configuration: the interface between the blade and the{\textellipsis}

Fig.6. (color online) Example of damage to the scratch probe as a result of misuse or{\textellipsis}

}, issn = {00431648}, doi = {10.1016/j.wear.2014.02.015}, author = {Ange-Therese Akono and Franz-Josef Ulm} } @article {312, title = {Irwin׳s conjecture: Crack shape adaptability in transversely isotropic solids}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {68}, year = {2014}, month = {Aug-2014}, pages = {1 - 13}, abstract = {

The planar crack propagation problem of a flat elliptical crack embedded in a brittle elastic anisotropic solid is investigated. We introduce the concept of crack shape adaptability: the ability of three-dimensional planar cracks to shape with the mechanical properties of a cracked body. A criterion based on the principle of maximum dissipation is suggested in order to determine the most stable elliptical shape. This criterion is applied to the specific case of vertical cracks in transversely isotropic solids. It is shown that contrary to the isotropic case, the circular shape (i.e. penny-shaped cracks) is not the most stable one. Upon propagation, the crack first grows non-self-similarly before it reaches a stable shape. This stable shape can be approximated by an ellipse of an aspect ratio that varies with the degree of elastic anisotropy. By way of example, we apply the so-derived crack shape adaptability criterion to shale materials. For this class of materials it is shown that once the stable shape is reached, the crack propagates at a higher rate in the horizontal direction than in the vertical direction. We also comment on the possible implications of these findings for hydraulic fracturing operations.

Fig.1. Top view of an elliptical crack (en, et and eb are the unit vectors normal to{\textellipsis}

Fig.2. Definition of the θ angle for a penny-shaped crack

Fig.3. Definition of the α-angle for an elliptical vertical crack (θ=π/2)

Fig.4. Zoom at the crack tip (vertical crack)

Fig.5. Comparison of the H(ϕ)/H2 obtained numerically {\textendash} solid line {\textendash} and its{\textellipsis}

Fig.6. Comparison of the H(ϕ)/H2 obtained numerically {\textendash} solid line {\textendash} and its{\textellipsis}

}, issn = {00225096}, doi = {10.1016/j.jmps.2014.03.004}, author = {Hadrien Laubie and Franz-Josef Ulm} } @article {109, title = {Magnetic interactions in 3d metal chains on Cu2X/Cu(001) (X = N, O): Comparison with corresponding unsupported chains}, journal = {Physical Review B}, volume = {90}, year = {2014}, month = {Nov-2014}, pages = {195423}, type = {Article}, abstract = {

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.

Figure

Figure

Figure

Figure

Figure

Figure

Figure

}, issn = {1098-0121}, doi = {10.1103/PhysRevB.90.195423}, author = {Urdaniz, M. C. and Barral, M. A. and Llois, A. M. and Andres Sa{\`u}l} } @proceedings {99, title = {Modelling cement at fundamental scales: From atoms to engineering strength and durability}, journal = {Euro-C Conference}, volume = {COMPUTATIONAL MODELLING OF CONCRETE STRUCTURES, VOL 1}, year = {2014}, month = {2014}, pages = {139-148}, publisher = {CRC Press-Taylor \& Francis Group}, address = {MAR 24-27, 2014, St Anton am Alberg, AUSTRIA}, abstract = {

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.

}, isbn = {978-1-138-02641-4; 978-1-315-76203-6}, doi = {10.1201/b16645-16}, author = {Enrico Masoero and Hamlin M. Jennings and Franz-Josef Ulm and Emanuela Del Gado and Hegoi Manzano and Roland Jean-Marc Pellenq and Sidney Yip}, editor = {Bicanic, N and Mang, H and Meschke, G and DeBorst, R} } @article {96, title = {Nano-scale mechanics of colloidal C-S-H gels}, journal = {Soft Matter}, volume = {10}, year = {2014}, month = {Jan-21-2014}, pages = {491-499}, type = {Article}, abstract = {

Gels of calcium-silicate-hydrates (C-S-H) are the glue that is largely responsible for the mechanical properties of cement. Despite their practical relevance, their nano-scale structure and mechanics are still mainly unexplored, because of the difficulties in characterizing them in a complex material like cement. We propose a colloidal model to investigate the gel mechanics emerging in the critical range of length-scales from several tens to hundreds of nanometers. We show that the size polydispersity of the hydrates and size-dependent effective interactions can explain the mechanical heterogeneities detected in nano-indentation experiments. We also show how these features control the arising of irreversible structural rearrangements under deformation, which are good candidates as nano-scale mechanisms underlying mechanical aging and slow structural relaxation in the gels.

Graphical abstract: Nano-scale mechanics of colloidal C{\textendash}S{\textendash}H gels
}, issn = {1744-683X}, doi = {10.1039/c3sm51815a}, author = {Enrico Masoero and Emanuela Del Gado and Roland Jean-Marc Pellenq and Sidney Yip and Franz-Josef Ulm} } @article {115, title = {Nanoscale Structure of Cement: Viewpoint of Rigidity Theory}, journal = {Journal of Physical Chemistry C}, volume = {118}, year = {2014}, month = {Jun-12-2014}, pages = {12485-12493}, type = {Article}, abstract = {
Abstract Image

Rigidity theory is a powerful tool to predict the properties of glasses with respect to composition. By reducing such molecular networks to simple mechanical trusses, topological constraint theory filters out all the unnecessary details that ultimately do not affect macroscopic properties. However, the usual constraint enumeration is restricted to networks that are amorphous, homogeneous, and fully connected. On the contrary, calcium\–silicate\–hydrate (C\–S\–H), the binding phase of cement, is partially crystalline and heterogeneous and shows some isolated water molecules. Here, we report how rigidity theory can be used to describe the nanoscale structure of this material by relying on molecular dynamics simulations. The distinction between intact and broken constraints is clearly defined at the atomic scale, thus allowing a precise enumeration of the topological constraints. We show that the rigidity of the C\–S\–H network can be increased by decreasing the Ca/Si molar ratio, which, as predicted by rigidity theory, allows improvement of the hardness of the material. This study suggests that rigidity theory could be applied with great rewards to a broader range of materials than glasses.

}, issn = {1932-7447}, doi = {10.1021/jp502550z}, author = {Mathieu Bauchy and Mohammad Javad Abdolhosseini Qomi and Christophe Bichara and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {262, title = {Order and disorder in calcium{\textendash}silicate{\textendash}hydrate}, journal = {The Journal of Chemical Physics}, volume = {140}, year = {2014}, month = {Jun-07-2014}, pages = {Article Number: 214503}, abstract = {

Despite advances in the characterization and modeling of cement hydrates, the atomic order in Calcium\–Silicate\–Hydrate (C\–S\–H), the binding phase of cement, remains an open question. Indeed, in contrast to the former crystalline model, recent molecular models suggest that the nanoscale structure of C\–S\–H is amorphous. To elucidate this issue, we analyzed the structure of a realistic simulated model of C\–S\–H, and compared the latter to crystalline tobermorite, a natural analogue of C\–S\–H, and to an artificial ideal glass. The results clearly indicate that C\–S\–H appears as amorphous, when averaged on all atoms. However, an analysis of the order around each atomic species reveals that its structure shows an intermediate degree of order, retaining some characteristics of the crystal while acquiring an overall glass-like disorder. Thanks to a detailed quantification of order and disorder, we show that, while C\–S\–H retains some signatures of a tobermorite-like layered structure, hydrated species are completely amorphous.

}, issn = {0021-9606}, doi = {10.1063/1.4878656}, author = {Mathieu Bauchy and Mohammad Javad Abdolhosseini Qomi and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @proceedings {348, title = {Pavement infrastructures footprint: The impact of pavement properties on vehicle fuel consumption}, journal = {Euro-C Conference}, volume = {COMPUTATIONAL MODELLING OF CONCRETE STRUCTURES}, year = {2014}, month = {Mar-2014}, pages = {1051-1058}, address = {MAR 24-27 2014 St Anton am Alberg, AUSTRIA}, abstract = {

A novel mechanistic model based on an infinite beam on elastic foundation is developed to
quantify the impact of pavement structural and material properties on pavement deflection and consequently on
vehicle fuel consumption. The model can also account for the effect of temperature and vehicle speed on fuel
consumption. A simplified expression for evaluating the energy dissipation for practical purposes is proposed
and used to investigate the impact of various pavement design systems on fuel consumption. GPS (General Pave-
ment Studies) sections from the FHWA\’s Long Term Pavement Performance program (FHWA 2011) are used
for this study. These sections consist of asphalt concrete (AC), portland cement concrete (PCC) and composite
pavements. The model quantifies the impact of temperature and vehicle speed on the fuel consumption and
confirms that those impacts are negligible for PCC and significant for AC pavements due to their viscoelasticity.

}, url = {https://cshub.mit.edu/sites/default/files/documents/louhghalam-Euro-C-2014.pdf}, author = {Arghavan Louhghalam and Mehdi Akbarian and Franz-Josef Ulm}, editor = {Bicanic, N and Mang, H and Meschke, G} } @article {327, title = {Plane-Strain Crack Problem in Transversely Isotropic Solids for Hydraulic Fracturing Applications}, journal = {Journal of Engineering Mechanics}, volume = {140}, year = {2014}, month = {Dec-2014}, pages = {Article Number: 04014092 }, abstract = {

This paper aims at understanding and predicting how pressurized cracks propagate in anisotropic brittle solids, a situation frequently encountered in hydraulic fracturing. Special attention is paid to transverse isotropy, often used to model shale. Although the theory of linear elastic fracture mechanics of anisotropic solids is well established at present, this paper shows that the application of Muskhelishvili\’s formalism to Lekhnitskii\’s anisotropic complex potentials provides a powerful tool to extend the validity of the classical tools of isotropic fluid-driven crack models to the anisotropic case, provided that the appropriate elastic constants are used. These elastic constants are identified and derived in closed form for transversely isotropic solids. The constants are shown to be directly related to quantities easily measured in a laboratory at macroscopic scale through indentation tests and acoustic measurements. Moreover, several crack-kinking criteria are compared. Contrary to the isotropic case, the crack-kinking criteria are not consistent among themselves, even in the case of a pure pressure loading. The orientation at which it is easier to propagate an already existing crack is sought. A critical crack length, below which this crack orientation is the one of minimal stiffness felt by the crack, is identified.

}, issn = {0733-9399}, doi = {10.1061/(ASCE)EM.1943-7889.0000807}, author = {Hadrien Laubie and Franz-Josef Ulm} } @proceedings {100, title = {Poro-chemo-fracture-mechanics ... bottom-up: Application to risk of fracture design of oil and gas cement sheath at early ages}, journal = {Euro-C Conference}, volume = {COMPUTATIONAL MODELLING OF CONCRETE STRUCTURES, VOL 1 }, year = {2014}, month = {Jan-2014}, pages = {61-67}, publisher = {CRC PRESS-TAYLOR \& FRANCIS GROUP}, address = {MAR 24-27, 2014, St Anton am Alberg, AUSTRIA}, abstract = {

With ever more challenging (T, p) environments for cementing applications in oil and gas wells, there is a need to change the classical paradigm of constitutive modeling of the early-age behavior of cementitious materials in oil-and gas well applications. Herein, we propose a bottom-up approach, which starts at the molecular scale of calcium-silicate-hydrates (C-S-H), and propagates this understanding via incremental poroelastic upscaling methods to the meso-and macroscale, and ultimately to the scale of engineering applications. With a clear focus on engineering risk-of-fracture evaluations, we show how to integrate this bottom-up approach with fracture mechanics.

}, isbn = {978-1-138-02641-4; 978-1-315-76203-6}, doi = {10.1201/b16645-8}, author = {Franz-Josef Ulm and Muhannad Abuhaikal and Thomas Alexander Petersen and Roland Jean-Marc Pellenq}, editor = {Bicanic, N and Mang, H and Meschke, G and DeBorst, R} } @article {149, title = {Roughness-induced Pavement-Vehicle Interactions Key Parameters and Impact on Vehicle Fuel Consumption}, journal = {Transportation Research Record: Journal of the Transportation Research Board}, volume = {2525}, year = {2014}, month = {Dec-30-2014}, pages = {62 - 70}, abstract = {

Pavement roughness affects rolling resistance and thus vehicle fuel consumption. When a vehicle travels at constant speed on an uneven road surface, the mechanical work dissipated in the vehicle\’s suspension system is compensated by vehicle engine power and results in excess fuel consumption. This dissipation depends on both road roughness and vehicle dynamic characteristics. This paper proposes, calibrates, and implements a mechanistic model for roughness-induced dissipation. The distinguishing feature of the model is its combination of a thermodynamic quantity (energy dissipation) with results from random vibration theory to identify the governing parameters that drive the excess fuel consumption caused by pavement roughness, namely, the international roughness index (IRI) and the waviness number, w (a power spectral density parameter). It is shown through sensitivity analysis that the sensitivity of model output, that is, excess fuel consumption, to the waviness number is significant and comparable to that of IRI. Thus, introducing the waviness number as a second roughness index, in addition to IRI, allows a more accurate quantification of the impact of surface characteristics on vehicle fuel consumption and the corresponding greenhouse gas emissions. This aspect is illustrated by application of the roughness\–fuel consumption model to two road profiles extracted from FHWA\’s Long-Term Pavement Performance database.

}, issn = {0361-1981}, doi = {10.3141/2525-07}, author = {Arghavan Louhghalam and Mehdi Akbarian and Franz-Josef Ulm} } @article {304, title = {Scaling Relationships of Dissipation-Induced Pavement-Vehicle Interactions}, journal = {Transportation Research Record: Journal of the Transportation Research Board}, volume = {2457}, year = {2014}, month = {Jan-2014}, pages = {95 - 104}, abstract = {

Rolling resistance is one of the key factors that affect the fuel efficiency of the national pavement system. In addition to pavement texture and pavement roughness, the dissipation of mechanical work provided by the vehicle because of viscous deformation within the pavement structure has been recognized as a relevant factor contributing to the environmental footprint of pavement systems. This dissipation depends on material and structural parameters that can be optimized to increase the fuel efficiency of pavements. Identifying the key material and structural parameters that drive this dissipation is the focus of this paper. This identification is achieved by a combination of dimensional analysis and model-based simulations of the dissipation of a viscoelastic beam on an elastic foundation. For linear viscoelastic systems, the dissipation is found to scale with the square of the vehicle weight and with the inverse of the viscous relaxation time, in addition to distinct power relations of top-layer stiffness, thickness, and subgrade modulus. These scaling relations can be used by pavement engineers to reduce such pavement-inherent dissipation mechanisms and increase the fuel efficiency of a pavement design. An example shows the application of these scaling relations with data extracted from FHWA\&$\#$39;s Long-Term Pavement Performance database for seven road classes. The scaling relations provide a means for evaluating the performance of the various road classes in terms of the fuel efficiency related to dissipation.

}, issn = {0361-1981}, doi = {10.3141/2457-10}, author = {Arghavan Louhghalam and Mehdi Akbarian and Franz-Josef Ulm} } @article {300, title = {Scratch hardness-strength solutions for cohesive-frictional materials}, journal = {International Journal for Numerical and Analytical Methods in Geomechanics}, volume = {36}, year = {2014}, month = {Feb-25-2014}, pages = {307 - 326}, abstract = {

In this paper we develop analytical solutions for scratch hardness\–strength relations for cohesive-frictional materials of the Mohr\–Coulomb and Drucker\–Prager type. Based on the lower bound yield design approach, closed-form solutions are derived for frictionless scratch devices, and validated against computational upper bound and elastoplastic finite element solutions. The influence of friction at the blade\–material interface is also investigated, for which a simple computational optimization is proposed. Illustrated for scratch tests on cement paste, we show that the proposed solutions provide a convenient way to determine estimates of cohesion and friction parameters from scratch data, and may serve as a benchmark to identify the relevance of strength models for scratch test analysis. Copyright \© 2011 John Wiley \& Sons, Ltd.

}, doi = {10.1002/nag.1008}, author = {Bard, Romain and Franz-Josef Ulm} } @article {110, title = {Simultaneous assessment of phase chemistry, phase abundance and bulk chemistry with statistical electron probe micro-analyses: Application to cement clinkers}, journal = {Cement and concrete Research}, volume = {55}, year = {2014}, month = {Jan-2014}, pages = {35-48}, type = {Article}, abstract = {

According to recent developments in cement clinker engineering, the optimization of chemical substitutions in the main clinker phases offers a promising approach to improve both reactivity and grindability of clinkers. Thus, monitoring the chemistry of the phases may become part of the quality control at the cement plants, along with the usual measurements of the abundance of the mineralogical phases (quantitative X-ray diffraction) and the bulk chemistry (X-ray fluorescence). This paper presents a new method to assess these three complementary quantities with a single experiment. The method is based on electron microprobe spot analyses, performed over a grid located on a representative surface of the sample and interpreted with advanced statistical tools. This paper describes the method and the experimental program performed on industrial clinkers to establish the accuracy in comparison to conventional methods. (C) 2013 Elsevier Ltd. All rights reserved.

SEM micrographs of coarsely ground sample C-C4. (a) The 500{\texttimes} magnification ...
Ca vs. Si representation for bulk samples (a) B-C2 focused on the entire range ...
(a) SEM micrograph of clinker C4 at 1000{\texttimes} magnification: the spacing between ...
Additional representations of the clustered results for bulk samples: Fe vs. Si ...
Si vs. Ca representation for coarsely ground samples (a) C-C2a and (b) C-C4b and ...
}, keywords = {Characterization, Clinker, EPMA, X-ray diffraction}, issn = {0008-8846}, doi = {10.1016/j.cemconres.2013.09.013}, author = {Wilson, William and Konrad J. Krakowiak and Franz-Josef Ulm} } @article {261, title = {A soft matter in construction {\textendash} Statistical physics approach to formation and mechanics of C{\textendash}S{\textendash}H gels in cement}, journal = {The European Physical Journal Special Topics}, volume = {223}, year = {2014}, month = {Oct-2014}, pages = {2285 - 2295}, abstract = {

Calcium-silicate hydrate (C-S-H) is the main binding agent in cement and concrete. It forms at the beginning of cement hydration, it progressively densifies as cement hardens and is ultimately responsible of concrete performances. This hydration product is a cohesive nano-scale gel, whose structure and mechanics are still poorly understood, in spite of its practical importance. Here we review some of the open questions for this fascinating material and 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 approach unveils how some distinctive features of the kinetics of cement hydration can be related to changes in the morphology of the gels and elucidates the role of nano-scale mechanical heterogeneities in the hardened C-S-H.

}, issn = {1951-6355}, doi = {10.1140/epjst/e2014-02264-1}, author = {Emanuela Del Gado and Katerina Ioannidou and Enrico Masoero and Alain Baronnet and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Sidney Yip} } @article {310, title = {Stimuli-Responsive Cement-Reinforced Rubber}, journal = {ACS Applied Materials \& Interfaces}, volume = {6}, year = {2014}, month = {May-14-2014}, pages = {6962 - 6968}, abstract = {
Abstract Image

In this work, we report the successful development of a cement\–rubber reactive composite with reversible mechanical properties. Initially, the composite behaves like rubber containing inert filler, but when exposed to water, it increases in volume and reaches a stiffness that is intermediate between that of hydrogenated nitrile butadiene rubber (HNBR) and hydrated cement, while maintaining a relatively large ductility characteristic of rubber. After drying, the modulus increases even further up to 400 MPa. Wet/drying cycles prove that the elastic modulus can reversibly change between 150 and 400 MPa. Utilizing attenuated total reflection Fourier transform infrared spectroscopy), we demonstrate that the high pH produced by the hydration of cement triggers the hydrolysis of the rubber nitrile groups into carboxylate anions. Thus, the salt bridges, generated between the carboxylate anions of the elastomer and the cations of the filler, are responsible for the reversible variations in volume and elastic modulus of the composite as a consequence of environmental moisture exposure. These results reveal that cement nanoparticles can successfully be used to accomplish a twofold task: (a) achieve an original postpolymerization modification that allows one to work with carboxylate HNBR (HXNBR) not obtained by direct copolymerization of carboxylate monomers with butadiene, and (b) synthesize a stimuli-responsive polymeric composite. This new type of material, having an ideal behavior for sealing application, could be used as an alternative to cement for oil field zonal isolation applications.

}, issn = {1944-8244}, doi = {10.1021/am500774k}, author = {Musso, Simone and Robisson, Agathe and Sudeep Maheshwar and Franz-Josef Ulm} } @article {32, title = {Surface Chemistry and Atomic-Scale Reconstruction of Kerogen-Silica Composites}, journal = {The Journal of Physical Chemistry C}, volume = {118}, year = {2014}, month = {Feb-6-2014}, pages = {2429-2438}, abstract = {
Abstract Image

Interest in gas shale, a novel source rock of natural gas, has increased tremendously in recent years. Better understanding of the kerogen\–rock interaction is of crucial importance for efficient gas extraction and, hence, asset management. In this study, we explore the possible chemical bonds between kerogen and silica, one of the most predominant mineral constituents of gas shale, by means of quantum chemistry. Energetically favorable bond formation reactions are found between alcoholic hydroxyl, carboxylate, and aldehyde groups, as well as aliphatic double bonds of kerogen and the silica surface. The performance of a reactive force field was also assessed in a representative set of chemical reactions and found to be satisfactory. The potential impact of bond formation reactions between the two phases on the actual kerogen\–silica interface is discussed as a function of the kerogen type, maturity, and density. Finally, a methodology aiming to reconstruct realistic kerogen\–silica interfaces is presented.

}, doi = {10.1021/jp406329n}, author = {Gy{\"o}rgy Hantal and Brochard, Laurent and Dias Soeiro Cordeiro, M Natalia and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @proceedings {365, title = {AIP Conference Proceedings A multiscale description of failure in granular materials}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jun-18-2013}, pages = {585-588}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

This paper presents conditions of initiation and development of failure in granular materials through a twodimensional discrete element model. General condition for the effective development of failure and its physical characteristics are recalled. Then relation between failure and the second order work expressed in terms of microscopic variables is discussed. Eventually, correspondence between a localized mode of failure marked with shear band patterns and space distribution of negative values of microscopic second-order work is investigated.

}, doi = {10.1063/1.4811999}, author = {Hadda, Nejib and Fran{\c c}ois Nicot and Sibille, Luc and Farhang Radja{\"\i} and Tordesillas, Antoinette and Darve, F{\'e}lix}, editor = {Yu, A and Dong, K and Yang, R} } @proceedings {366, title = {AIP Conference ProceedingsTumbling sandpiles in a fluid}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jul-2013}, pages = {662-665}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

By means of contact dynamics simulations interfaced with computational fluid dynamics, we analyze the effect of a suspending fluid on the dynamics of collapse and spread of a granular column. We find that the runout distance increases as a power law with the aspect ratio of the column and, for a given aspect ratio, it may be the same in the grain-inertial and fluid-inertial regimes but with considerably longer duration in the latter case. We show that, in both viscous and fluid-inertial regimes, this behavior results from compensation between two effects of the fluid: 1) reduction of the kinetic energy during collapse and 2) enhancement of the flow by lubrication during spread.

}, doi = {10.1063/1.4812018}, author = {Farhang Radja{\"\i} and Vincent Topin and Perales, F. and Yann Monerie}, editor = {Yu, A and Dong, K and Yang, R} } @proceedings {367, title = {A benchmark for particle shape dependence}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jun-18-2013}, pages = {883-886}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

Particle shape is a major parameter for the space-filling and strength properties of granular materials. For a systematic investigation of shape effect, a numerical benchmark test was set up within a collaborative group using different numerical methods and particles of various shape characteristics such as elongation, angularity and nonconvexity. Extensive 2D shear simulations were performed in this framework and the shear strength and packing fraction were compared for different shapes. We show that the results may be analyzed in terms of a low-order shape parameter \η describing the degree of distortion from a perfectly circular shape. In particular, the shear strength is an increasing function of \η with nearly the same trend for all shapes, the differences being of second order compared to \η. We also observe a nontrivial behavior of packing fraction which, for all our simulated shapes, increases with \η from the random close packing fraction for disks, reaches a peak considerably higher than that for disks, and subsequently declines as \η is further increased. Finally, the analysis of contact forces for the same value of \η leads to very similar statistics regardless of our specific particle shapes.

}, doi = {10.1063/1.4812073}, author = {Gael Combe and C{\'e}cile Nouguier-Lehon and Emilien Az{\'e}ma and Krzysztof Szarf and Baptiste Saint-Cyr and Marie Chaze and Farhang Radja{\"\i} and Pascal Villard and Jean-Yves Delenne and Vincent Richefeu and Philippe Sornay and Charles Voivret and CEGEO Group}, editor = {Yu, A and Dong, K and Yang, R} } @proceedings {369, title = {Capillary states of granular materials in the funicular state}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jun-18-2013}, pages = {1023-1026}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

Using a multi-phase lattice Boltzmann model, we investigate the capillary states of a 2D granular packing gradually saturated by condensation from a homogeneously injected vapor phase. The internal stresses induced by surface tension and Laplace pressure are directly calculated from the forces acting on the grains with increasing amount of liquid. The evolution of cohesive strength with the amount of liquid reveals four different states reflecting the connectivity of the liquid phase and local grain environments. It increases in the pendular state, characterized by binary liquid bridges holding the grains together, and within the funicular state with an increasing number of liquid clusters connected to several grains. Beyond 40\% of saturation, the cohesive strength falls off due to a decreasing Laplace pressure of liquid clusters.

}, doi = {10.1063/1.4812108}, author = {Jean-Yves Delenne and Vincent Richefeu and Farhang Radja{\"\i}}, editor = {Yu, A and Dong, K and Yang, R} } @proceedings {368, title = {Comparison of the effects of rolling resistance and angularity in sheared granular media}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jul-2013}, pages = {891-894}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

In this paper, we compare the effect of rolling resistance at the contacts in granular systems composed of disks with the effect of angularity in granular systems composed of regular polygonal particles. For this purpose, we use contact dynamics simulations. By means of a simple shear numerical device, we investigate the mechanical behavior of these materials in the steady state in terms of shear strength, solid fraction, force and fabric anisotropies, and probability distribution of contact forces. We find that, based on the energy dissipation associated with relative rotation between two particles in contact, the effect of rolling resistance can explicitly be identified with that of the number of sides in a regular polygonal particle. This finding supports the use of rolling resistance as a shape parameter accounting for particle angularity and shows unambiguously that one of the main influencing factors behind the mechanical behavior of granular systems composed of noncircular particles is the partial hindrance of rotations as a result of angular particle shape.

}, keywords = {angularity, anisotropy, force distribution, Granular material, rolling resistance, Shear strength, solid fraction}, url = {https://hal.archives-ouvertes.fr/hal-00842799}, author = {Estrada, Nicolas and Emilien Az{\'e}ma and Farhang Radja{\"\i} and Taboada, Alfredo}, editor = {Yu, A and Dong, K and Yang, R} } @article {218, title = {Environmental scanning electron microscopy (ESEM) and nanoindentation investigation of the crack tip process zone in marble}, journal = {Acta Geotechnica}, volume = {8}, year = {2013}, month = {Jun-2013}, pages = {223 - 245}, abstract = {

This study explores the interaction between crack initiation and nanomechanical properties in the crack-tip fracture process zone of Carrara marble. Specimens with preexisting cracks were loaded in a uniaxial testing machine until the process zone appeared at the tips of the preexisting cracks. ESEM analysis reveals an increase in microcrack density in the process zone with increased loading of the specimen. Nanoindentation testing comprised of lines and grids of single nanoindentations located both near and far from the process zone shows a decrease in both indentation modulus and indentation hardness near grain boundaries in intact material, and with closeness to the process zone. Ultimately, the study confirms that the crack-tip process zone manifests itself as an area of reduced indentation hardness and indentation modulus in marble.

}, issn = {1861-1125}, doi = {10.1007/s11440-013-0213-z}, author = {Brooks, Z. and Franz-Josef Ulm and Einstein, H. H.} } @article {45, title = {Molecular simulations of supercritical fluid permeation through disordered microporous carbons}, journal = {Langmuir}, volume = {29}, year = {2013}, month = {Aug-13-2013}, pages = {9985{\textendash}9990}, abstract = {
Abstract Image

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.

}, doi = {10.1021/la402087r}, author = {Botan, Alexandru and Vermorel, Romain and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {31, title = {Nanoindentation investigation of creep properties of calcium silicate hydrates}, journal = {Cement and Concrete Research}, volume = {52}, year = {2013}, month = {Oct-2013}, pages = {38{\textendash}52}, abstract = {

The creep properties of calcium silicate hydrates (C-S-H) are assessed by means of nanoindentation creep experiments on a wide range of substoichiometric cement pastes. We observe that, after a few seconds, the measured creep compliance of C-S-H is very well captured by a logarithmic time function. The rate of the logarithmic creep is found to scale in a unique manner with indentation modulus, indentation hardness, and packing density, independent of processing, mix proportions, indenter geometry and load history. The comparison with macroscopic creep experiments on concrete shows that minutes-long nanoindentations enable a quantitative assessment of the long-term creep properties of cementitious materials, orders of magnitude faster than macroscopic testing. Finally, we show that a strong analogy exists between this logarithmic creep behavior of C-S-H and that of soils, which suggests a granular origin of creep of geomaterials.

Typical measurement of variation Δh(t) in penetration depth during the creep ...

Coefficient γ governing the linear part of the fitting function (16) versus (a) ...

}, doi = {10.1016/j.cemconres.2013.05.006}, author = {Matthieu Vandamme and Franz-Josef Ulm} } @proceedings {360, title = {Penetration strength of coarse granular materials from DEM simulations}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013 }, year = {2013}, month = {Jun-18-2013}, pages = { 241-244}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

Field tests are widely used for soil characterization in geotechnical applications in spite of implementation difficulties. The light penetrometer test is a well-known testing tool for fine soils, but the physical interpretation of the output data in the case of coarse granular materials is far less evident. In fact, the data are considerably more sensitive to various parameters such as fabric structure, particles shape or the applied impact energy. In order to achieve a better understanding of the underlying phenomena, we performed a numerical study by means contact dynamics DEM simulations. We consider the penetration of a moving tip into a sample composed of irregular grain shapes and we analyze the influence of the driving velocity and applied energy on the penetration strength. We find that the latter grows with both the penetration rate and energy. Force fluctuations on the tip involve a jamming-unjamming process. The typology of contact network and inter-granular friction play a major role in the fluctuations and measured values of the cone penetration strength.

}, doi = {10.1063/1.4811912}, author = {Quezada, Juan Carlos and Saussine, Gilles and Breul, Pierre and Farhang Radja{\"\i}}, editor = {Yu, A and Dong, K and Yang, R} } @article {219, title = {Reactive elastomeric composites: When rubber meets cement}, journal = {Composites Science and Technology}, volume = {75}, year = {2013}, month = {Feb-11-2013}, pages = {77 - 83}, abstract = {

This paper describes a novel reactive composite material comprised of hydrogenated nitrile butadiene rubber (HNBR) compounded with slag cement. The composite initially looks and behaves like rubber, but when exposed to water it simultaneously swells and stiffens due to hydration of the cement component. The material eventually reaches a stiffness that is intermediate between that of HNBR and hydrated cement, while maintaining a relatively large ductility that is more characteristic of rubber. This behavior, which is ideal for sealing applications, differentiates this material from conventional swellable materials that become less stiff upon swelling. The development of this new type of material was motivated by the requirements of oilfield zonal isolation, where alternatives to cement are needed for some challenging sealing applications. A mechanism for the swelling and stiffening of the reactive composite is proposed: water diffuses into the HNBR matrix and is converted to bound water through hydration reactions with the cement, causing the effective solid filler content of the composite to increase. A model is proposed that treats the composite as a cellular solid with a continuous filler phase (hydrated cement). This model is able to reproduce the observed increase in the elastic modulus with time during exposure to water.

Elastic modulus ratio (current/initial) as a function of swelling, for HNBR ...

Kinetics of swelling of all three materials during approximately 1month of ...

Evolution of the elastic modulus of all three materials during approximately ...

Tensile stress{\textendash}strain curves for HNBR-cement (61{\textendash}39\% by volume, pre-exposure) ...

Schematic of the hydration process occurring inside the HNBR-cement material, ...

SEM images of HNBR-cement material before (left) and after (right) hydration. It ...

}, issn = {02663538}, doi = {10.1016/j.compscitech.2012.11.012}, author = {Robisson, Agathe and Sudeep Maheshwar and Musso, Simone and Jeffrey J. Thomas and Auzerais, Francois M. and Han, Dingzhi and Qu, Meng and Franz-Josef Ulm} } @proceedings {361, title = {Settlement statistics of a granular layer composed of polyhedral particles}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jun-18-2013}, pages = {333-336}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

We use 3D contact dynamics simulations to investigate the mechanical equilibrium and settlement of a granular material composed of irregular polyhedral particles confined between two horizontal frictional planes. We show that, as a consequence of mobilized wall-particle friction force at the top and bottom boundaries, the transient deformation induced by a constant vertical load increment is controlled by the aspect ratio (thickness over width) of the packing as well as the stress ratio. The transient deformation declines considerably for increasingly smaller aspect ratios and grows with the stress ratio. From the simulation data for a large number of independent configurations, we find that sample-to-sample fluctuations of the deformation have a broad distribution and they scale with the average deformation.

}, doi = {10.1063/1.4811935}, author = {Quezada, Juan Carlos and Saussine, Gilles and Breul, Pierre and Farhang Radja{\"\i}}, editor = {Yu, A and Dong, K and Yang, R} } @proceedings {363, title = {Shear strength and microstructure of 3D assemblies of platy particles}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {Jul-09-2013}, pages = {519-522}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

As a first step towards particle-scale modeling of clayey soils, we investigate the mechanical behavior and microstructure of assemblies of three-dimensional rectangular platy particles by means of the discrete element method. Several samples composed of particles of different levels of platyness (ratio of width to thickness) were numerically prepared and sheared to large deformations. We analyze the shear strength, packing fraction, connectivity, contact and force anisotropies, and mobilization of friction forces as functions of platyness.We find that both the mechanical behavior and microstructure are strongly dependent on the degree of platyness. This happens, in particular, because of the alignment of particle faces along a particular direction. Additionally, as observed for other granular materials with complex shapes, the packing fraction passes by a peak value before decreasing for larger values of platyness.

}, keywords = {Clays, DEM, Microstructure, Shear strength}, url = {https://hal.archives-ouvertes.fr/hal-00842787}, author = {Boton, Mauricio and Emilien Az{\'e}ma and Estrada, Nicolas and Farhang Radja{\"\i} and Lizcano, Arcesio}, editor = {Yu, A and Dong, K and Yang, R} } @proceedings {362, title = {Shear strength, force distributions and friction mobilization in sheared packings composed of angular particles}, journal = {7th International Conference on Micromechanics of Granular Media (Powders and Grains)}, volume = {Book Series: AIP Conference Proceedings POWDERS AND GRAINS 2013}, year = {2013}, month = {2013}, pages = {511-514}, publisher = {AIP}, address = {JUL 08-12 2013 Sydney, AUSTRALIA}, abstract = {

In this paper, we explore the effect of particle shape angularity on the mechanical behavior of sheared granular packings. A first series of contact dynamics simulations is performed in 2D with regular polygons with an increasing number of sides ranging from 3 (triangles) to 60. Then, in order to approach \“idealized\” angular particles, a second series of simulations is performed in 3D with irregular polyhedra with the number of faces ranging from 8 (octahedron-like) to 596. A counterintuitive finding is that the shear strength increases with angularity up to a maximum value and saturates as the particles become more angular (below 6 sides in 2D and 46 faces in 3D). A micromechanical analysis of force and contact orientations, all enhanced by face-face and face-side contacts, reveals that this increase is due to an increase of both contact and force anisotropies, and the saturation for higher angularities is a consequence of a rapid fall-off of the contact and normal force anisotropies compensated by an increase of the tangential force anisotropy.

}, doi = {10.1063/1.4811980}, author = {Emilien Az{\'e}ma and Estrada, Nicolas and Farhang Radja{\"\i}}, editor = {Yu, A and Dong, K and Yang, R} } @article {220, title = {Strength Homogenization of Double-Porosity Cohesive-Frictional Solids}, journal = {Journal of Applied Mechanics}, volume = {80}, year = {2013}, month = {Mar-2013}, pages = {Article Number: 020902}, abstract = {

The strength homogenization of cohesive-frictional solids influenced by the presence of two pressurized pore spaces of different characteristic sizes is addressed in this study. A two-scale homogenization model is developed based on limit analysis and the second-order method (SOM) in linear comparison composite theory, which resolves the nonlinear strength behavior through the use of linear comparison composites with optimally chosen properties. For the scale of the classical configuration of a porous solid, the formulation employs a compressible thermoelastic comparison composite to deliver closed-form expressions of strength criteria. Comparisons with numerical results reveal that the proposed homogenization estimates for drained conditions are adequate except for high triaxialities in the mean compressive strength regime. At the macroscopic scale of the double-porosity material, the SOM results are in agreement with strength criteria predicted by alternative micromechanics solutions for materials with purely cohesive solid matrices and drained conditions. The model predictions for the cohesive-frictional case show that drained strength development in granularlike composites is affected by the partitioning of porosity between micro-and macropores. In contrast, the drained strength is virtually equivalent for single-and double-porosity materials with matrix-inclusion morphologies. Finally, the second-order linear comparison composite approach confirms the applicability of an effective stress concept, previously proposed in the literature of homogenization of cohesive-frictional porous solids, for double-porosity materials subjected to similar pressures in the two pore spaces. For dissimilar pore pressures, the model analytically resolves the complex interplays of microstructure, solid properties, and volume fractions of phases, which cannot be recapitulated by the effective stress concept.

}, issn = {0021-8936}, doi = {10.1115/1.4007905}, author = {J. Alberto Ortega and Franz-Josef Ulm} } @conference {36, title = {Water Isotherms, Shrinkage and Creep of Cement Paste: Hypotheses, Models and Experiments}, booktitle = {Mechanics and Physics of Creep, Shrinkage, and Durability of Concrete: A Tribute to Zdenek P. Ba{\.z}ant}, year = {2013}, month = {Sep-25-2013}, publisher = {ASCE Publications}, organization = {ASCE Publications}, abstract = {

Cement paste has a complex mesoscale structure, and small changes in its pore network potentially cause large variation in measurements such as the water isotherm (also nitrogen). We deconvolute the water isotherm with the help of advanced computational techniques, hypotheses, and a re-examination of published data. The pore system is divided into four different categories, each containing water with its own physical properties. By viewing the highly interdependent roles of water in each of the pore categories as a system, new insights are gained regarding possible mechanisms that control drying, shrinkage, and creep, and experimental strategies for verification.

}, doi = {10.1061/9780784413111.015}, author = {Hamlin M. Jennings and Enrico Masoero and Pinson, Matthew B and Strekalova, Elena G and Patrick A Bonnaud and Hegoi Manzano and Qing Ji and Jeffrey J. Thomas and Roland Jean-Marc Pellenq and Franz-Josef Ulm and others} } @article {104, title = {Concrete Innovation Potential: From Atoms to Green Infrastructure}, journal = {Beton- UND Stahlbetonbau}, volume = {107}, year = {2012}, month = {Aug-01-2012}, pages = {504-U79}, type = {Article}, abstract = {

Concrete Innovation Potential: From Atoms to Green Infrastructure The sustainable development of concrete opens new possibilities for concrete engineers. This contribution aims at identifying the innovation potential of concrete for a sustainable development. It is shown that breakthroughs in Materials Science of concrete release new degrees of freedom for design and construction of concrete infrastructure that can contribute to reducing the material\&$\#$39;s ecological footprint. Integrated in a Life-Cycle Analysis of concrete structures, which considers both the embodied energy and the use phase, acomprehensive picture is obtained how molecular and nanometric modifications can contribute to a sustainable development of concrete. Given the more than 20 million tons of concrete produced annually, it is readily understood that new intellectual challenges are opening for concrete engineers to design buildings not only for function and safety but as well for ecological soundness.

}, issn = {0005-9900}, doi = {10.1002/best.201200020}, author = {Franz-Josef Ulm} } @article {57, title = {Confined water dissociation in microporous defective silicates: Mechanism, dipole distribution, and impact on substrate properties}, journal = {Journal of the American Chemical Society}, volume = {134}, year = {2012}, month = {Feb-01-2012}, pages = {2208{\textendash}2215}, abstract = {
Abstract Image

Interest in microporous materials has risen in recent years, as they offer a confined environment that is optimal to enhance chemical reactions. Calcium silicate hydrate (C-S-H) gel, the main component of cement, presents a layered structure with sub-nanometer-size disordered pores filled with water and cations. The size of the pores and the hydrophilicity of the environment make C-S-H gel an excellent system to study the possibility of confined water reactions. To investigate it, we have performed molecular dynamics simulations using the ReaxFF force field. The results show that water does dissociate to form hydroxyl groups. We have analyzed the water dissociation mechanism, as well as the changes in the structure and water affinity of the C-S-H matrix and water polarization, comparing the results with the behavior of water in a defective zeolite. Finally, we establish a relationship between water dissociation in C-S-H gel and the increase of hardness due to a transformation from a two- to a three-dimensional structure.

}, doi = {10.1021/ja209152n}, author = {Hegoi Manzano and Moeini, Sina and Marinelli, Francis and Adri CT Van Duin and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {54, title = {Evidence on the Dual Nature of Aluminum in the Calcium-Silicate-Hydrates Based on Atomistic Simulations}, journal = {Journal of the American Ceramic Society}, volume = {95}, year = {2012}, month = {Jan-23-2012}, pages = {1128{\textendash}1137}, abstract = {

Hydration of tri-calcium silicate (C3S) and di-calcium silicate (C2S) precipitates calcium-silicate-hydrate (CSH) which is the bonding phase responsible for the strength of cementitious materials. Substitution of part of C3S and C2S with aluminum-containing additives alters the chemical composition of hydration products by precipitating calcium-aluminate-silicate-hydrate (CASH). Incorporation of aluminum in the molecular building blocks of CSH entails structural and chemo-mechanical consequences. These alterations can be measured through solid state nuclear magnetic resonance (NMR) experiments. By conducting a wide spectrum of atomistic simulation methods on thousands of aluminum-containing molecular CASH structures, an overall molecular approach for determination of CASH nanostructure is presented. Through detailed analysis of different order parameters, it is found that aluminum can exhibit a tetra-/penta-/octahedral behavior which is fully consistent with the recent NMR observations. This corresponds to the formation of a class of complex three-dimensional alumino-silicate skeletons with partial healing effect in the CASH nanostructure potentially increasing durability and strength of hydration products. We explored the variation of mechanical observables by increasing aluminum content in CASH structures of varying calcium to silicon ratio. Finally, deformation of CSHs and CASHs of different chemical formula in a multi-scale fashion unravels the effect of chemical composition on the strength and kinematics of deformation in this particular type of composites.

}, doi = {10.1111/j.1551-2916.2011.05058.x}, author = {Mohammad Javad Abdolhosseini Qomi and Franz-Josef Ulm and Roland Jean-Marc Pellenq} } @article {259, title = {Experimental determination of the fracture toughness via microscratch tests: Application to polymers, ceramics, and metals}, journal = {Journal of Materials Research}, volume = {27}, year = {2012}, month = {Jan-2012}, pages = {485 - 493}, abstract = {

This article presents a novel microscratch technique for the determination of the fracture toughness of materials from scratch data. While acoustic emission and optical imaging devices provide quantitative evidence of fracture processes during scratch tests, the technique proposed here provides a quantitative means to assess the fracture toughness from the recorded forces and depth of penetration. We apply the proposed method to a large range of materials, from soft (polymers) to hard (metal), spanning fracture toughness values over more than two orders of magnitude. The fracture toughness values so obtained are in excellent agreement with toughness values obtained for the same materials by conventional fracture tests. The fact that the proposed microscratch technique is highly reproducible, almost nondestructive, and requires only small material volumes makes this technique a powerful tool for the assessment of fracture properties for microscale materials science and engineering applications.

}, issn = {0884-2914}, doi = {10.1557/jmr.2011.402}, author = {Ange-Therese Akono and Randall, Nicholas X. and Franz-Josef Ulm} } @article {301, title = {Fracture scaling relations for scratch tests of axisymmetric shape}, journal = {Journal of the Mechanics and Physics of Solids}, volume = {60}, year = {2012}, month = {Mar-2012}, pages = {379 - 390}, abstract = {

Scratch testing and scratch test analysis continues to gain momentum in Applied Mechanics, due to the possibility offered by this method to assess fracture properties at very fine scales. In this paper, we derive general scratch force scaling relations for axisymmetric scratch probes defined by single variable monomial functions. These relations are used to define fracture criteria with and without consideration of the development of shear stresses at the probe\–material interface. The approach is illustrated for common scratch probe geometries: conical probe, flat punch, and hemi-spherical probe. Application of the proposed method to micro-scratch tests on two materials (an aluminum alloy and a thermoplastic polymer) using a Rockwell probe (a conical probe ending in a hemi-spherical shape) illustrates the versatility of the approach: First, the scratch force-depth scaling relations provide a means to determine the degree of the homogeneous function characterizing the scratch probe. Second, the fracture criteria enable an experimental assessment of the fracture toughness. The good agreement between the fracture toughness determined by scratching and values reported in the open literature show the potential of the proposed method for determining fracture properties of materials at even smaller scales.

Fig.1. Axisymmetric scratch probe geometry

Fig.2. Scaling of the normalized fracture force and the perimeter function, β, of the{\textellipsis}

Fig.3. Forces in three scratch tests on aluminum alloy 2024 (AA 2024) obtained with a{\textellipsis}

Fig.4. Fracture toughness determination from the scratch response of AA 2024 with a{\textellipsis}

Fig.5. Response and analysis of three scratch tests on a thermoplastic polymer (Delrin{\textellipsis}

}, issn = {00225096}, doi = {10.1016/j.jmps.2011.12.009}, author = {Ange-Therese Akono and Franz-Josef Ulm} } @article {51, title = {Hydration of calcium oxide surface predicted by reactive force field molecular dynamics}, journal = {Langmuir}, volume = {28}, year = {2012}, month = {Mar-06-2012}, pages = {4187{\textendash}4197}, abstract = {
Abstract Image

In this work, we present the parametrization of Ca\–O/H interactions within the reactive force field ReaxFF, and its application to study the hydration of calcium oxide surface. The force field has been fitted using density functional theory calculations on gas phase calcium\–water clusters, calcium oxide bulk and surface properties, calcium hydroxide, bcc and fcc Ca, and proton transfer reactions in the presence of calcium. Then, the reactive force field has been used to study the hydration of the calcium oxide {001} surface with different water contents. Calcium oxide is used as a catalyzer in many applications such as CO2 sequestration and biodiesel production, and the degree of surface hydroxylation is a key factor in its catalytic performance. The results show that the water dissociates very fast on CaO {001} bare surfaces without any defect or vacancy. The surface structure is maintained up to a certain amount of water, after which the surface undergoes a structural rearrangement, becoming a disordered calcium hydroxyl layer. This transformation is the most probable reason for the CaO catalytic activity decrease.

}, doi = {10.1021/la204338m}, author = {Hegoi Manzano and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Markus J Buehler and Adri CT Van Duin} } @article {299, title = {Mechanistic Approach to Pavement-Vehicle Interaction and Its Impact on Life-Cycle Assessment}, journal = {Transportation Research Record: Journal of the Transportation Research Board}, year = {2012}, month = {Dec-2012}, pages = {171 - 179}, abstract = {

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\&$\#$39;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.

}, issn = {0361-1981}, doi = {10.3141/2306-20}, author = {Mehdi Akbarian and Moeini-Ardakani, Seyed and Franz-Josef Ulm and Nazzal, Munir} } @proceedings {354, title = {Microscopic Origins of Shear Strength in Packings Composed of Elongated Particles}, journal = {9th International Workshop on Bifurcation and Degradation in Geomaterials (IWBDG 2011)}, volume = {Springer Series in Geomechanics and Geoengineering - ADVANCES IN BIFURCATION AND DEGRADATION IN GEOMATERIALS}, year = {2012}, month = {Apr-11-2012}, pages = {21-27}, address = {MAY 23-26 2011 Porquerolles, FRANCE}, abstract = {

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.

}, keywords = {Elongated particles, Fabric properties, force transmission, Harmonic decomposition}, url = {https://hal.archives-ouvertes.fr/hal-00686728}, author = {Emilien Az{\'e}ma and Farhang Radja{\"\i}}, editor = {St{\'e}phane Bonelli and Dascalu, Cristian and Fran{\c c}ois Nicot} } @article {303, title = {Nanochemomechanical assessment of shale: a coupled WDS-indentation analysis}, journal = {Acta Geotechnica}, volume = {7}, year = {2012}, month = {Dec-2012}, pages = {271 - 295}, abstract = {

Establishing the links between the composition, microstructure and mechanics of shale continues to be a formidable challenge for the geomechanics community. In this study, a robust methodology is implemented to access the in situ chemomechanics of this sedimentary rock at micrometer length scales. Massive grids of coupled wave dispersive spectroscopy (WDS) and instrumented indentation experiments were performed over representative material surfaces to accommodate the highly heterogeneous composition and microstructure of shale. The extensive datasets of compositional and mechanical properties were analyzed using multi-variate clustering statistics to determine the attributes of active phases present in shale at microscales. Our chemomechanical analysis confirmed that the porous clay (PC) mechanical phase inferred by statistical indentation corresponds to the clay mineral phase defined strictly on chemical grounds. The characteristic stiffness and hardness behaviors of the PC are realized spatially in regions removed from silt inclusions of quartz and feldspar. At the microscale shared by indentation and WDS experiments, a consistent chemomechanical signature for shale emerges in which the heterogeneities of the PC are captured by the standard deviations of indentation properties and concentrations of chemical elements. However, these local behaviors are of second order compared to the global trend observed for mean mechanical properties and the clay packing density, which synthesizes the relative volumes of clay and nanoporosity in the material. The coupled statistical indentation and WDS technique represents a viable approach to characterize the chemomechanics of shale and other natural porous composites at a consistent scale below the macroscopic level.

}, issn = {1861-1125}, doi = {10.1007/s11440-012-0185-4}, author = {Deirieh, A. and J. Alberto Ortega and Franz-Josef Ulm and Younane N. Abousleiman} } @article {302, title = {Nano-Engineering of Concrete}, journal = {Arabian Journal for Science and Engineering}, volume = {37}, year = {2012}, month = {Mar-2012}, pages = {481 - 488}, abstract = {

This paper summarizes recent developments in the field of nanoindentation analysis of highly heterogeneous composites. The fundamental idea of the proposed approach is that it is possible to assess nanostructure from the implementation of micromechanics-based scaling relations for a large array of nanoindentation tests on heterogeneous materials. We illustrate this approach through the application to calcium-silicate-hydrate (C-S-H), the binding phase of all cement-based materials. For this important class of materials, we show that C-S-H exists in at least three structurally distinct but compositionally similar forms: low density, high density and ultra-high density. These three forms differ merely in the packing density of 5-nm sized particles. The proposed approach also gives access to the solid particle properties of C-S-H, which can now be compared with results from atomistic simulations. By way of conclusion, we show how this approach provides a new way of analyzing complex hydrated nanocomposites, in addition to classical microscopy techniques and chemical analysis. This approach will turn out invaluable in our quest of adding the necessary \“green\” value to a commodity, concrete, by nano-engineering higher strength and toughness from first principles.

}, issn = {1319-8025}, doi = {10.1007/s13369-012-0181-x}, author = {Franz-Josef Ulm} } @article {48, title = {Nanostructure and nanomechanics of cement: polydisperse colloidal packing}, journal = {Physical review letters}, volume = {109}, year = {2012}, month = {Oct-10-2012}, pages = { Article Number: 155503}, abstract = {

Cement setting and cohesion are governed by the precipitation and growth of calcium-silicate-hydrate, through a complex evolution of microstructure. A colloidal model to describe nucleation, packing, and rigidity of calcium-silicate-hydrate aggregates is proposed. Polydispersity and particle size dependent cohesion strength combine to produce a spectrum of packing fractions and of corresponding elastic properties that can be tested against nanoindentation experiments. Implications regarding plastic deformations and reconciling current structural characterizations are discussed.

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}, doi = {10.1103/PhysRevLett.109.155503}, author = {Enrico Masoero and Emanuela Del Gado and Roland Jean-Marc Pellenq and Franz-Josef Ulm and Sidney Yip} } @article {260, title = {Quantifying plasticity-independent creep compliance and relaxation of viscoelastoplastic materials under contact loading}, journal = {Journal of Materials Research}, volume = {27}, year = {2012}, month = {Jan-2012}, pages = {302 - 312}, abstract = {

Here we quantify the time-dependent mechanical properties of a linear viscoelastoplastic material under contact loading. For contact load relaxation, we showed that the relaxation modulus can be measured independently of concurrent plasticity exhibited during the loading phase. For indentation creep, we showed that the rate of change of the contact creep compliance can be measured independently of any plastic deformation exhibited during loading through , where a(t) is the contact radius, h(t) is the displacement of the contact probe, and Pmax is the constant applied load during the creep phase. These analytical relations were compared with numerical simulations of conical indentation creep for a viscoelastoplastic material and validated against sharp indentation creep experiments conducted on polystyrene. The derived relations enable extraction of viscoelastic material characteristics, even if sharp probes confer concurrent plasticity, applicable for a general axisymmetric contact probe geometry and a general time-independent plasticity.

}, issn = {0884-2914}, doi = {10.1557/jmr.2011.302}, author = {Matthieu Vandamme and Tweedie, Catherine A. and Constantinides, Georgios and Franz-Josef Ulm and Krystyn J. Van Vliet} } @article {53, title = {Set in stone? A perspective on the concrete sustainability challenge}, journal = {MRS bulletin}, volume = {37}, year = {2012}, month = {Apr-09-2012}, pages = {395{\textendash}402}, abstract = {

As the most abundant engineered material on Earth, concrete is essential to the physical infrastructure of all modern societies. There are no known materials that can replace concrete in terms of cost and availability. There are, however, environmental concerns, including the significant CO2 emissions associated with cement production, which create new incentives for university\–industry collaboration to address concrete sustainability. Herein, we examine one aspect of this challenge\—the translation of scientific understanding at the microscale into industrial innovation at the macroscale\—by seeking improvements in cement-paste processing, performance, and sustainability through control of the mechanisms that govern microstructure development. Specifically, we consider modeling, simulation, and experimental advances in fracture, dissolution, precipitation, and hydration of cement paste precursors, as well as properties of the hardened cement paste within concrete. The aim of such studies is to optimize the chemical reactivity, mechanical performance, and other physical properties of cement paste to enable more sustainable processing routes for this ubiquitous material.

}, doi = {10.1557/mrs.2012.55}, author = {Krystyn J. Van Vliet and Roland Jean-Marc Pellenq and Markus J Buehler and Jeffrey C Grossman and Hamlin M. Jennings and Franz-Josef Ulm and Sidney Yip} } @article {298, title = {Use of UHPC in Bridge Structures: Material Modeling and Design}, journal = {Advances in Materials Science and Engineering}, year = {2012}, month = {Feb-11-2012}, pages = {Article Number: 319285}, abstract = {

Ultra-high-performance concrete (UHPC) is a promising new class of concrete material that is likely to make a significant contribution to addressing the challenges associated with the load capacity, durability, sustainability, economy, and environmental impact of concrete bridge infrastructures. This paper focuses on the material modeling of UHPC and design of bridge girders made of UHPC. A two-phase model used for modeling the behavior of UHPC was briefly discussed, and the model was implemented in a preliminary design case study. Based on the implemented design and the reported use of UHPC in bridge applications, the advantages, limitations, and future prospects of UHPC bridges were discussed, highlighting the need for innovative research and design to make optimum use of the favorable properties of the material in bridge structures.

}, issn = {1687-8434}, doi = {10.1155/2012/319285}, author = {Gunes, Oguz and Yesilmen, Seda and Gunes, Burcu and Franz-Josef Ulm} } @article {291, title = {Impact of Chemical Impurities on the Crystalline Cement Clinker Phases Determined by Atomistic Simulations}, journal = {Crystal Growth \& Design}, volume = {11}, year = {2011}, month = {Jul-2011}, pages = {2964 - 2972}, abstract = {
Abstract Image

The presence of chemical substitutions is believed to play a crucial role in the hydration reactions, structure, and elastic properties of cement clinker phases. Hence, substitutions are of great technological interest, as more efficient production of cement clinkers would result in a reduction of CO2 emissions, as well as possible economic benefits. Here we use a combination of classical and quantum mechanical simulation methods to study the detailed physicochemical changes of the clinker phases alite (Ca3SiO5) and belite (Ca2SiO4) when Mg2+, Al3+ and Fe3+ guest ions are incorporated into their structure. Using classical force field methods, we considered random substitutions among possible sites and different compositions in order to identify the preferential substitution sites on the crystalline structures. Then, the resulting structural changes that take place to accommodate the guest ions are investigated and discussed in detail. Using quantum mechanical density functional theory calculations the electronic structure of representative configurations has been computed to determine the potential impact of impurities on the reactivity.

}, issn = {1528-7483}, doi = {10.1021/cg200212c}, author = {Hegoi Manzano and Engin Durgun and Mohammad Javad Abdolhosseini Qomi and Franz-Josef Ulm and Roland Jean-Marc Pellenq and Jeffrey C Grossman} } @proceedings {352, title = {Modeling Porous Granular Aggregates}, journal = {9th International Workshop on Buifurcation and Degradation in Geomaterials (IWBDG 2011)}, volume = {Springer Series in Geomechanics and Geoengineering - ADVANCES IN BIFURCATION AND DEGRADATION IN GEOMATERIALS}, year = {2011}, month = {May-28-2011}, pages = {249 - 254}, publisher = {Springer Netherlands}, address = {MAY 23-26 2011 Porquerolles, FRANCE}, abstract = {

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.

}, isbn = {978-94-007-1420-5}, issn = {1866-8755}, doi = {10.1007/978-94-007-1421-2_32}, author = {Rafik Aff{\`e}s and Vincent Topin and Jean-Yves Delenne and Yann Monerie}, editor = {St{\'e}phane Bonelli and Dascalu, Cristian and Fran{\c c}ois Nicot} } @article {257, title = {Multitechnique Investigation of Extruded Clay Brick Microstructure}, journal = {Journal of the American Ceramic Society}, volume = {94}, year = {2011}, month = {Sept-2011}, pages = {3012 - 3022}, abstract = {

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.

}, doi = {10.1111/jace.2011.94.issue-910.1111/j.1551-2916.2011.04484.x}, author = {Konrad J. Krakowiak and Lourenco, Paulo B. and Franz-Josef Ulm} } @article {258, title = {The nanogranular origin of friction and cohesion in shale-A strength homogenization approach to interpretation of nanoindentation results}, journal = {International Journal for Numerical and Analytical Methods in Geomechanics}, volume = {35}, year = {2011}, month = {Dec-10-2011}, pages = {1854 - 1876}, abstract = {

An inverse micromechanics approach allows interpretation of nanoindentation results to deliver cohesive-frictional strength behavior of the porous clay binder phase in shale. A recently developed strength homogenization model, using the Linear Comparison Composite approach, considers porous clay as a granular material with a cohesive-frictional solid phase. This strength homogenization model is employed in a Limit Analysis Solver to study indentation hardness responses and develop scaling relationships for indentation hardness with clay packing density. Using an inverse approach for nanoindentation on a variety of shale materials gives estimates of packing density distributions within each shale and demonstrates that there exists shale-independent scaling relations of the cohesion and of the friction coefficient that vary with clay packing density. It is observed that the friction coefficient, which may be interpreted as a degree of pressure-sensitivity in strength, tends to zero as clay packing density increases to one. In contrast, cohesion reaches its highest value as clay packing density increases to one. The physical origins of these phenomena are discussed, and related to fractal packing of these nanogranular materials. Copyright \© 2010 John Wiley \& Sons, Ltd.

}, doi = {10.1002/nag.v35.1710.1002/nag.984}, author = {Bobko, Christopher P. and Gathier, Benjamin and J. Alberto Ortega and Franz-Josef Ulm and Borges, Lavinia and Younane N. Abousleiman} } @proceedings {353, title = {Onset of Immersed Granular Avalanches by DEM-LBM Approach}, journal = {9th International Workshop on Buifurcation and Degradation in Geomaterials (IWBDG 2011)}, volume = {Springer Series in Geomechanics and Geoengineering - ADVANCES IN BIFURCATION AND DEGRADATION IN GEOMATERIALS}, year = {2011}, month = {May-28-2011}, pages = {109 - 115}, publisher = {Springer Netherlands}, address = {MAY 23-26 2011 Porquerolles, FRANCE}, abstract = {

We present 3D grain-fluid simulations based on the discrete element method interfaced with the lattice Boltzmann method and applied to investigate the initiation of underwater granular flows. We prepare granular beds of 800 spherical grains with different values of the initial solid fraction in a biperiodic rectangular box. In order to trigger an avalanche, the bed is instantaneously tilted to a finite slope angle above the maximum angle of stability. We simulate the dynamics of the transient flow for different solid fractions. In agreement with the experimental work of Iverson (Water Resour Res 36(7):1897\–1910, 2000) and Pailha et\ al. (Phys Fluids 20(11):111701, 2008), we find that the flow onset is controlled by the initial solid fraction.

}, isbn = {978-94-007-1420-5}, issn = {1866-8755}, doi = {10.1007/978-94-007-1421-210.1007/978-94-007-1421-2_14}, author = {Jean-Yves Delenne and Mansouri, M. and Farhang Radja{\"\i} and Moulay Sa{\"\i}d El Youssoufi and Seridi, A.}, editor = {St{\'e}phane Bonelli and Dascalu, Cristian and Fran{\c c}ois Nicot} } @article {256, title = {The scratch test for strength and fracture toughness determination of oil well cements cured at high temperature and pressure}, journal = {Cement and Concrete Research}, volume = {41}, year = {2011}, month = {sept-2011}, pages = {942 - 946}, abstract = {

Recent advances in scratch test analysis provide new ways to relate measured scratch test properties not only to strength properties but fracture properties of materials as well. Herein, we present an application of such tools to oil well cements cured at high temperatures and pressures. We find a concurrent increase of strength and toughness of different oil well cement baseline formulations which we relate to the water-to-binder ratio for a series of cementitious materials prepared with cement and silica flour. The scratch test thus emerges as a self-consistent technique for both cohesive\–frictional strength and fracture properties that is highly reproducible, almost non-destructive, and not more sophisticated than classical compression tests, which makes this \‘old\’ test highly attractive for performance-based field applications.

}, issn = {00088846}, doi = {10.1016/j.cemconres.2011.04.014}, author = {Franz-Josef Ulm and James, Simon} } @article {254, title = {Scratch test model for the determination of fracture toughness}, journal = {Engineering Fracture Mechanics}, volume = {78}, year = {2011}, month = {Jan-2011}, pages = {334 - 342}, abstract = {

We revisit the scratch test within the framework of linear elastic fracture mechanics. In the analysis, we employ an Airy stress function approach to determine stresses and displacement in the vicinity of the scratch-blade\–material interface, which serve as input for the evaluation of the energy release rate by means of the J-Integral. In contrast to previous models, the energy release rate thus found scales with the sum of the applied forces squared. This entails a linear relation between the applied forces and , where w is the scratch width and d the scratch depth. This analytical scaling is validated using experimental scratch data on cement paste and sandstone, which shows that the proposed approach provides a convenient way to determine the fracture toughness from scratch tests carried out with different scratch widths and depths

}, issn = {00137944}, doi = {10.1016/j.engfracmech.2010.09.017}, author = {Ange-Therese Akono and Franz-Josef Ulm} } @article {255, title = {Scratching as a Fracture Process: From Butter to Steel}, journal = {Physical Review Letters}, volume = {106}, year = {2011}, month = {May-20-2011}, pages = {Article Number: 204302}, abstract = {

We present results of a hybrid experimental and theoretical investigation of the fracture scaling in scratch tests and show that scratching is a fracture dominated process. Validated for paraffin wax, cement paste, Jurassic limestone and steel, we derive a model that provides a quantitative means to relate quantities measured in scratch tests to fracture properties of materials at multiple scales. The scalability of scratching for different probes and depths opens new venues towards miniaturization of our technique, to extract fracture properties of materials at even smaller length scales.

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}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.106.204302}, author = {Ange-Therese Akono and Reis, P. M. and Franz-Josef Ulm} } @proceedings {347, title = {STRENGTH HOMOGENIZATION FOR COHESIVE-FRICTIONAL COMPOSITES: A LINEAR COMPARISON COMPOSITE APPROACH}, journal = {International Workshop on Multiscale and Multiphysics Processes in Geomechanics}, volume = {Springer Series in Geomechanics and Geoengineering}, year = {2011}, month = {Jan-2011}, pages = {57 - 60}, publisher = {Springer Berlin Heidelberg}, address = {JUN 23-25 2010 Stanford Univ, Stanford, CA}, abstract = {

In this work, we address the homogenization of cohesive-frictional strength properties of composite materials through the application of the Linear Comparison Composite (LCC) theory. The LCC methodology is implemented in a multiscale strength model relevant to geomaterials with heterogeneities associated with pore spaces and rigid-like grains. The proposed micromechanics solutions offer quantitative assessments of the effects of grain-scale properties and microstructure on the overall strength of the composite material Keywordscohesive-frictional materials\–linear comparison composite

}, isbn = {978-3-642-19629-4}, issn = {1866-8755}, doi = {10.1007/978-3-642-19630-0_15}, author = {J. Alberto Ortega and Gathier, Benjamin and Franz-Josef Ulm}, editor = {Wu, Wei and Borja, Ronaldo I.} } @article {293, title = {Empirical force fields for complex hydrated calcio-silicate layered materials}, journal = {Phys. Chem. Chem. Phys.}, volume = {13}, year = {2010}, month = {Nov-10-2010}, pages = {1002 - 1011}, abstract = {

The use of empirical force fields is now a standard approach in predicting the properties of hydrated oxides which are omnipresent in both natural and engineering applications. Transferability of force fields to analogous hydrated oxides without rigorous investigations may result in misleading property predictions. Herein, we focus on two common empirical force fields, the simple point charge ClayFF potential and the core-shell potential to study tobermorite minerals, the most prominent family of Calcium-Silicate-Hydrates that are complex hydrated oxides. We benchmark the predictive capabilities of these force fields against first principles results. While the structural information seem to be in close agreement with DFT results, we find that for higher order properties such as elastic constants, the core-shell potential quantitatively improves upon the simple point charge model, and shows a larger degree of transferability to complex materials. In return, to remedy the deficiencies of the simple point charge potential for hydrated calcio-silicates, we suggest using both structural data and elasticity data for potential calibration, a new force field potential, CSH-FF. This re-parameterized version of ClayFF is then applied to simulating an atomistic model of cement (Pellenq et al., PNAS, 2009). We demonstrate that this force field improves the predictive capabilities of ClayFF, being considerably less computational intensive than the core-shell model.

}, issn = {1463-9076}, doi = {10.1039/C0CP00516A}, author = {Rouzbeh Shahsavari and Roland Jean-Marc Pellenq and Franz-Josef Ulm} }