Theory for solvent, momentum, and energy transfer between a surfactant solution and a vapor atmosphere

We develop a complete set of equations governing the evolution of a sharp interface separating a volatile-solvent/nonvolatile-surfactant solution from a vapor atmosphere. In addition to a sorption isotherm equation and the conventional balances for mass, linear momentum, and energy, these equations include a counterpart of the Hertz???Knudsen???Langmuir equation familiar from conventional theories of evaporation-condensation. This additional equation arises from a consideration of configurational forces within a thermodynamical framework. While the notion of configurational forces is well-developed and understood for the description of materials, like crystalline solids, that possess natural reference configurations, very little has been done regarding their role in materials, such as viscous fluids, that do not possess preferred reference states. We therefore provide a comprehensive discussion of configurational forces, the balance of configurational momentum, and configurational thermodynamics that does not require a choice of reference configuration. The general evolution equations arising from our theory account for the thermodynamic structure of the solution and the interface and for sources of dissipation related to the transport of surfactant, momentum, and heat in the solution, the transport of surfactant and momentum within the interface, and the transport of solute, momentum, kinetic energy, and heat across the interface. Due to the complexity of these equations, we provide approximate equations which we compare to relations that appear in the literature.published or submitted for publicationis peer reviewe

The Stored Energy of Cold Work, Thermal Annealing, and Other Thermodynamic Issues in Single Crystal Plasticity at Small Length Scales

This paper develops a thermodynamically consistent gradient theory of single-crystal plasticity using the principle of virtual power as a paradigm to develop appropriate balance laws for forces and energy. The resulting theory leads to a system of microscopic force balances, one balance for each slip system, and to an energy balance that accounts for power expended during plastic flow via microscopic forces acting in concert with slip-rates and slip-rate gradients. Central to the theory are an internal energy and entropy, plastic in nature, dependent on densities that account for the accumulation of glide dislocations as well as geometrically necessary dislocations – and that, consequently, represent quantities associated with cold work. Our theory allows us to discuss – within the framework of a gradient theory – the fraction of plastic stress-power that goes into heating, as well as the reduction of the dislocation density in a cold-worked material upon subsequent (or concurrent) thermal annealing.National Science Foundation (U.S.) (NSF CMMI Award No.1063626)National Research Foundation (South Africa

First-principles calculation of mechanical properties of Si <001> nanowires and comparison to nanomechanical theory

We report the results of first-principles density functional theory calculations of the Young's modulus and other mechanical properties of hydrogen-passivated Si nanowires. The nanowires are taken to have predominantly {100} surfaces, with small {110} facets according to the Wulff shape. The Young's modulus, the equilibrium length and the constrained residual stress of a series of prismatic beams of differing sizes are found to have size dependences that scale like the surface area to volume ratio for all but the smallest beam. The results are compared with a continuum model and the results of classical atomistic calculations based on an empirical potential. We attribute the size dependence to specific physical structures and interactions. In particular, the hydrogen interactions on the surface and the charge density variations within the beam are quantified and used both to parameterize the continuum model and to account for the discrepancies between the two models and the first-principles results.Comment: 14 pages, 10 figure

Thermodynamics of non-local materials: extra fluxes and internal powers

The most usual formulation of the Laws of Thermodynamics turns out to be suitable for local or simple materials, while for non-local systems there are two different ways: either modify this usual formulation by introducing suitable extra fluxes or express the Laws of Thermodynamics in terms of internal powers directly, as we propose in this paper. The first choice is subject to the criticism that the vector fluxes must be introduced a posteriori in order to obtain the compatibility with the Laws of Thermodynamics. On the contrary, the formulation in terms of internal powers is more general, because it is a priori defined on the basis of the constitutive equations. Besides it allows to highlight, without ambiguity, the contribution of the internal powers in the variation of the thermodynamic potentials. Finally, in this paper, we consider some examples of non-local materials and derive the proper expressions of their internal powers from the power balance laws.Comment: 16 pages, in press on Continuum Mechanics and Thermodynamic

A statistical mechanics framework for static granular matter

The physical properties of granular materials have been extensively studied in recent years. So far, however, there exists no theoretical framework which can explain the observations in a unified manner beyond the phenomenological jamming diagram [1]. This work focuses on the case of static granular matter, where we have constructed a statistical ensemble [2] which mirrors equilibrium statistical mechanics. This ensemble, which is based on the conservation properties of the stress tensor, is distinct from the original Edwards ensemble and applies to packings of deformable grains. We combine it with a field theoretical analysis of the packings, where the field is the Airy stress function derived from the force and torque balance conditions. In this framework, Point J characterized by a diverging stiffness of the pressure fluctuations. Separately, we present a phenomenological mean-field theory of the jamming transition, which incorporates the mean contact number as a variable. We link both approaches in the context of the marginal rigidity picture proposed by [3, 4].Comment: 21 pages, 15 figure

Diffraction microstrain in nanocrystalline solids under load - heterogeneous medium approach

This is an account of the computation of X-ray microstrain in a polycrystal with anisotropic elasticity under uniaxial external load. The results have been published in the article "Microstrain in nanocrystalline solids under load by virtual diffraction", at Europhysics Letters 89, 66002 (2010). The present information was submitted to Europhysics Letters as part of the manuscript package, and was available to the reviewers who recommended the paper for publication.Comment: Supporting online material for J. Markmann, D. Bachurin, L.-H. Shao, P. Gumbsch, J. Weissm\"uller, Microstrain in nanocrystalline solids under load by virtual diffraction, Europhys. Lett. 89, 66002 (2010

Atomistic calculations of interface elastic properties in noncoherent metallic bilayers

The paper describes theoretical and computational studies associated with the interface elastic properties of noncoherent metallic bicrystals. Analytical forms of interface energy, interface stresses, and interface elastic constants are derived in terms of interatomic potential functions. Embedded-atom method potentials are then incorporated into the model to compute these excess thermodynamics variables, using energy minimization in a parallel computing environment. The proposed model is validated by calculating surface thermodynamic variables and comparing them with preexisting data. Next, the interface elastic properties of several fcc-fcc bicrystals are computed. The excess energies and stresses of interfaces are smaller than those on free surfaces of the same crystal orientations. In addition, no negative values of interface stresses are observed. Current results can be applied to various heterogeneous materials where interfaces assume a prominent role in the systems' mechanical behavior.open322