Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard–Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals.

International audienceThis paper reviews atomistic force field parameterizations for molecular simulations of cementitious minerals, such as tricalcium silicate (C3S), portlandite (CH), tobermorites (model C-S-H). Computational techniques applied to these materials include classical molecular simulations, density functional theory and energy minimization. Such simulations hold promise to capture the nanoscale mechanisms operating in cementitious materials and guide in performance optimization. Many force fields have been developed, such as Born–Mayer–Huggins, InterfaceFF (IFF), ClayFF, CSH-FF, CementFF, GULP, ReaxFF, and UFF. The benefits and limitations of these approaches are discussed and a database is introduced, accessible via a web-link (http://cemff.epfl.ch). The database provides information on the different force fields, energy expressions, and model validations using systematic comparisons of computed data with benchmarks from experiment and from ab-initio calculations. The cemff database aims at helping researchers to evaluate and choose suitable potentials for specific systems. New force fields can be added to the database

Simulations of a series of single comb copolymers on C-S-H model surfaces of different composition reveal adsorption mechanisms and conformations in atomic detail to better understand the role in cement hydration and design interfacial properties.

Cement and concrete are the most widely used building materials and contain comb copolymers such as polycarboxylate ethers (PCEs) as hydration and setting modifiers. The working mechanisms of these additives in cement hydration have remained uncertain, which limits the rational design of additives and of new cement materials with lower CO 2 footprint. We identified quantitative correlations between PCE copolymer structure, adsorption, and cement setting properties for a series of copolymer structures and concentrations, combined with insights into conformations and adsorption mechanisms by atomistic simulations. The PCE copolymers have only a small fraction of polydispersity compared to earlier studies, and molecular dynamics simulations utilize Interface force field models for C-S-H phases that enable order-of-magnitude more accurate insights into the dynamics of the nanoscale polymer interfaces compared to earlier models. Two distinct sets of property correlations were discovered. (1) The carboxylate content of the PCEs, i.e., the molar density of ionic side groups per unit mass, correlates with the adsorbed amount of polycarboxylate ethers onto cement pastes, the conductivity of the cement paste, and the retardation of the acceleration period of cement hydration. (2) The combination of the ionic character of the polymer backbone and the length of non-ionic polyethylene glycol (PEG) side chains correlates with the water-to-cement ratio necessary for processing, zeta potentials, and fluidity of the cement pastes in mini slump tests. Simulations indicate that PCE adsorption onto cement particles involves migration of calcium ions in the acrylate backbone onto the calcium silicate hydrate surface, or calcium hydroxide surfaces, followed by ion pairing of the anionic polymer backbone with the positively charged mineral surface. PEG side chains exhibit no affinity to the mineral surface. The best fluidity and water reduction are achieved using an optimum ratio of the volume of PEG side chains to the volume of the anionic backbone, balancing sufficient surface bonding through the ionic backbone and minimization of interparticle forces by the non-ionic PEG side chains. A charge density too low prevents effective adsorption, and a charge density too high leads to multilayer deposition and ionic agglomeration forces between coated particles that reduce the fluidity and increase the necessary water-to-cement ratio. The proposed mechanism supersedes prior models and provides quantitative metrics for the rational design of polymer additives for cement and related particle dispersions.

Polyacrylonitrile (PAN) is among the most promising precursor polymers to produce strong and lightweight carbon fiber. Conformations in solution and the extent of binding to carbon nanotubes (CNTs) are critical during gel spinning and for alignment of graphitic layers upon carbonization. First quantitative insights into these processes are reported using molecular dynamics simulations from the atomic scale including virtual π electrons and comparisons to experimental data. Common solvents for fiber spinning induce significant differences in PAN conformations in dilute solution at 25 C with persistence lengths between 0.5 and 2 nm.Variations in conformation become smaller at 75 C, in the presence of CNTs, and at higher PAN concentration. "Aging" of PAN conformations in dimethylformamide and dimethylsulfoxide at higher temperature is explained and a correlation between extended polymer conformations and increased binding to CNTs identified in dilute solutions. PAN is overall barely attracted to CNTs under common solution conditions and enters significant surface contact only at higher concentration as solvent is physically removed. The impact of temperature is small, whereby binding increases at lower temperature. The results provide first guidance to control interactions of polymers with CNTs to induce distinct conformations and specific binding at the early stages of assembly.

We describe the dynamics of gellan strands in solution, the interaction mechanisms with clay platelets of different composition, and design principles to tune the attraction.

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