84,599 research outputs found

    Structure and dynamics of water at carbon-based interfaces

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    Water structure and dynamics are affected by the presence of a nearby interface. Here, first we review recent results by molecular dynamics simulations about the effect of different carbon-based materials, including armchair carbon nanotubes and a variety of graphene sheets—flat and with corrugation—on water structure and dynamics. We discuss the calculations of binding energies, hydrogen bond distributions, water’s diffusion coefficients and their relation with surface’s geometries at different thermodynamical conditions. Next, we present new results of the crystallization and dynamics of water in a rigid graphene sieve. In particular, we show that the diffusion of water confined between parallel walls depends on the plate distance in a non-monotonic way and is related to the water structuring, crystallization, re-melting and evaporation for decreasing inter-plate distance. Our results could be relevant in those applications where water is in contact with nanostructured carbon materials at ambient or cryogenic temperatures, as in man-made superhydrophobic materials or filtration membranes, or in techniques that take advantage of hydrated graphene interfaces, as in aqueous electron cryomicroscopy for the analysis of proteins adsorbed on graphene.Postprint (author's final draft

    A critical assessment of methods for the intrinsic analysis of liquid interfaces. 1. surface site distributions

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    Substantial progress in our understanding of interfacial structure and dynamics has stemmed from the recent development of algorithms that allow for an intrinsic analysis of fluid interfaces. These work by identifying the instantaneous location of the interface, at the atomic level, for each molecular configuration and then computing properties relative to this location. Such a procedure eliminates the broadening of the interface caused by capillary waves and reveals the underlying features of the system. However, a precise definition of which molecules actually belong to the interfacial layer is difficult to achieve in practice. Furthermore, it is not known if the different intrinsic analysis methods are consistent with each other and yield similar results for the interfacial properties. In this paper, we carry out a systematic and detailed comparison of the available methods for intrinsic analysis of fluid interfaces, based on a molecular dynamics simulation of the interface between liquid water and carbon tetrachloride. We critically assess the advantages and shortcomings of each method, based on reliability, robustness, and speed of computation, and establish consistent criteria for determining which molecules belong to the surface layer. We believe this will significantly contribute to make intrinsic analysis methods widely and routinely applicable to interfacial systems

    A fundamental mechanism for carbon-film lubricity identified by means of ab initio molecular dynamics

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    Different hypotheses have been proposed to explain the mechanism for the extremely low friction coefficient of carbon coatings and its undesired dependence on air humidity. A decisive atomistic insight is still lacking because of the difficulties in monitoring what actually happens at the buried sliding interface. Here we perform large-scale ab initio molecular dynamics simulations of both undoped and silicon-doped carbon films sliding in the presence of water. We observe the tribologically-induced surface hydroxylation and subsequent formation of a thin film of water molecules bound to the OH-terminated surface by hydrogen bonds. The comparative analysis of silicon-incorporating and clean surfaces, suggests that this two-step process can be the key phenomenon to provide high slipperiness to the carbon coatings. The water layer is, in fact, expected to shelter the carbon surface from direct solid-on-solid contact and make any counter surface slide extremely easily on it. The present insight into the wettability of carbon-based films can be useful for designing new coatings for biomedical and energy-saving applications with environmental adaptability.Comment: 22 pages, 4 figures, 1 tabl

    Soil Infrastructure, Interfaces & Translocation Processes in Inner Space (“Soil-it-is”): Towards a Road Map for the Constraints and Crossroads of Soil Architecture and Biophysical Processes

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    Soil functions and their impact on health, economy, and the environment are evident at the macro scale but determined at the micro scale, based on interactions between soil micro-architecture and the transport and transformation processes occurring in the soil infrastructure comprising pore and particle networks and at their interfaces. Soil structure formation and its resilience to disturbance are highly dynamic features affected by management (energy input), moisture (matric potential), and solids composition and complexation (organic matter and clay interactions). In this paper we review and put into perspective preliminary results of the newly started research program “Soil-it-is” on functional soil architecture. To identify and quantify biophysical constraints on soil structure changes and resilience, we claim that new approaches are needed to better interpret processes and parameters measured at the bulk soil scale and their links to the seemingly chaotic soil inner space behavior at the micro scale. As a first step, we revisit the soil matrix (solids phase) and pore system (water and air phases), constituting the complementary and interactive networks of soil infrastructure. For a field-pair with contrasting soil management, we suggest new ways of data analysis on measured soil-gas transport parameters at different moisture conditions to evaluate controls of soil matrix and pore network formation. Results imply that some soils form sponge-like pore networks (mostly healthy soils in terms of agricultural and environmental functions), while other soils form pipe-like structures (agriculturally poorly functioning soils), with the difference related to both complexation of organic matter and degradation of soil structure. The recently presented Dexter et al. (2008) threshold (ratio of clay to organic carbon of 10 kg kg-1) is found to be a promising constraint for a soil’s ability to maintain or regenerate functional structure. Next, we show the Dexter et al. (2008) threshold may also apply to hydrological and physical-chemical interface phenomena including soil-water repellency and sorption of volatile organic vapors (gas-water-solids interfaces) as well as polycyclic aromatic hydrocarbons (water-solids interfaces). However, data for differently-managed soils imply that energy input, soil-moisture status, and vegetation (quality of eluded organic matter) may be equally important constraints together with the complexation and degradation of organic carbon in deciding functional soil architecture and interface processes. Finally, we envision a road map to soil inner space where we search for the main controls of particle and pore network changes and structure build-up and resilience at each crossroad of biophysical parameters, where, for example, complexation between organic matter and clay, and moisture-induced changes from hydrophilic to hydrophobic surface conditions can play a role. We hypothesize that each crossroad (e.g. between organic carbon/clay ratio and matric potential) may control how soil self-organization will manifest itself at a given time as affected by gradients in energy and moisture from soil use and climate. The road map may serve as inspiration for renewed and multi-disciplinary focus on functional soil architecture

    The ReaxFF reactive force-field : development, applications and future directions

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    The reactive force-field (ReaxFF) interatomic potential is a powerful computational tool for exploring, developing and optimizing material properties. Methods based on the principles of quantum mechanics (QM), while offering valuable theoretical guidance at the electronic level, are often too computationally intense for simulations that consider the full dynamic evolution of a system. Alternatively, empirical interatomic potentials that are based on classical principles require significantly fewer computational resources, which enables simulations to better describe dynamic processes over longer timeframes and on larger scales. Such methods, however, typically require a predefined connectivity between atoms, precluding simulations that involve reactive events. The ReaxFF method was developed to help bridge this gap. Approaching the gap from the classical side, ReaxFF casts the empirical interatomic potential within a bond-order formalism, thus implicitly describing chemical bonding without expensive QM calculations. This article provides an overview of the development, application, and future directions of the ReaxFF method

    Adsorption and grafting on colloidal interfaces studied by scattering techniques

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    The adsorption of polymer and surfactant molecules onto colloidal particles or droplets in solution can be characterized non-destructively by scattering techniques. In a first part, the general framework of Dynamic Light Scattering, Small Angle Neutron and X-ray Scattering for the determination of the structure of adsorbed layers, and namely of the density profile, is presented. We then review recent studies of layers of the model polymer poly(ethylene oxide), as homopolymer or part of a block copolymer. In this field, scattering with contrast variation has been shown to be a powerful tool to obtain a detailed description of the layer structure. Adsorption of chemically more complex systems, including polyelectrolytes, polymer complexes, grafted chains and biomacromolecules are also discussed in this review, as well as surfactant adsorption

    Emergent behavior of soil fungal dynamics:influence of soil architecture and water distribution

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    Macroscopic measurements and observations in two-dimensional soil-thin sections indicate that fungal hyphae invade preferentially the larger, air-filled pores in soils. This suggests that the architecture of soils and the microscale distribution of water are likely to influence significantly the dynamics of fungal growth. Unfortunately, techniques are lacking at present to verify this hypothesis experimentally, and as a result, factors that control fungal growth in soils remain poorly understood. Nevertheless, to design appropriate experiments later on, it is useful to indirectly obtain estimates of the effects involved. Such estimates can be obtained via simulation, based on detailed micron-scale X-ray computed tomography information about the soil pore geometry. In this context, this article reports on a series of simulations resulting from the combination of an individual-based fungal growth model, describing in detail the physiological processes involved in fungal growth, and of a Lattice Boltzmann model used to predict the distribution of air-liquid interfaces in soils. Three soil samples with contrasting properties were used as test cases. Several quantitative parameters, including Minkowski functionals, were used to characterize the geometry of pores, air-water interfaces, and fungal hyphae. Simulation results show that the water distribution in the soils is affected more by the pore size distribution than by the porosity of the soils. The presence of water decreased the colonization efficiency of the fungi, as evinced by a decline in the magnitude of all fungal biomass functional measures, in all three samples. The architecture of the soils and water distribution had an effect on the general morphology of the hyphal network, with a "looped" configuration in one soil, due to growing around water droplets. These morphologic differences are satisfactorily discriminated by the Minkowski functionals, applied to the fungal biomass

    Interfacial thermal conductance in graphene/black phosphorus heterogeneous structures

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    Graphene, as a passivation layer, can be used to protect the black phosphorus from the chemical reaction with surrounding oxygen and water. However, black phosphorus and graphene heterostructures have low efficiency of heat dissipation due to its intrinsic high thermal resistance at the interfaces. The accumulated energy from Joule heat has to be removed efficiently to avoid the malfunction of the devices. Therefore, it is of significance to investigate the interfacial thermal dissipation properties and manipulate the properties by interfacial engineering on demand. In this work, the interfacial thermal conductance between few-layer black phosphorus and graphene is studied extensively using molecular dynamics simulations. Two critical parameters, the critical power Pcr to maintain thermal stability and the maximum heat power density Pmax with which the system can be loaded, are identified. Our results show that interfacial thermal conductance can be effectively tuned in a wide range with external strains and interracial defects. The compressive strain can enhance the interfacial thermal conductance by one order of magnitude, while interface defects give a two-fold increase. These findings could provide guidelines in heat dissipation and interfacial engineering for thermal conductance manipulation of black phosphorus-graphene heterostructure-based devices.Comment: 33 pages, 22 figure
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