A theory of finite tensile deformation of double-network hydrogels

A continuum damage model was developed to describe the finite tensile deformation of tough double-network (DN) hydrogels synthesized by polymerization of a water-soluble monomer inside a highly crosslinked rigid polyelectrolyte network. Damage evolution in DN hydrogels was characterized by performing loading-unloading tensile tests and oscillatory shear rheometry on DN hydrogels synthesized from 3-sulfopropyl acrylate potassium salt (SAPS) and acrylamide (AAm). The model can explain all the mechanical features of finite tensile deformation of DN hydrogels, including idealized Mullins effect and permanent set observed after unloading, qualitatively and quantitatively. The constitutive equation can describe the finite elasto-plastic tensile behavior of DN hydrogels without resorting to a yield function. It was showed that tensile mechanics of DN hydrogels in the model is controlled by two material parameters which are related to the elastic moduli of first and second networks. In effect, the ratio of these two parameters is a dimensionless number that controls the behavior of material. The model can capture the stable branch of material response during neck propagation where engineering stress becomes constant. Consistent with experimental data, by increasing the elastic modulus of the second network the finite tensile behavior of the DN hydrogel changes from necking to strain hardening.     

Modeling of Solute-Solvent Interactions Using an External Electric Field—From Tautomeric Equilibrium in Nonpolar Solvents to the Dissociation of Alkali Metal Halides

An implicit account of the solvent effect can be carried out using traditional static quantum chemistry calculations by applying an external electric field to the studied molecular system. This approach allows one to distinguish between the effects of the macroscopic reaction field of the solvent and specific solute–solvent interactions. In this study, we report on the dependence of the simulation results on the use of the polarizable continuum approximation and on the importance of the solvent effect in nonpolar solvents. The latter was demonstrated using experimental data on tautomeric equilibria between the pyridone and hydroxypyridine forms of 2,6-di-tert-butyl-4-hydroxy-pyridine in cyclohexane and chloroform.     

1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its ³¹P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this ³¹P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported.     

Accuracy assessment of the linear Poisson–Boltzmann equation and reparametrization of the OBC generalized Born model for nucleic acids and nucleic acid–protein complexes

The generalized Born model in the Onufriev, Bashford, and Case (Onufriev et al., Proteins: Struct Funct Genet 2004, 55, 383) implementation has emerged as one of the best compromises between accuracy and speed of computation. For simulations of nucleic acids, however, a number of issues should be addressed: (1) the generalized Born model is based on a linear model and the linearization of the reference Poisson–Boltmann equation may be questioned for highly charged systems as nucleic acids; (2) although much attention has been given to potentials, solvation forces could be much less sensitive to linearization than the potentials; and (3) the accuracy of the Onufriev–Bashford–Case (OBC) model for nucleic acids depends on fine tuning of parameters. Here, we show that the linearization of the Poisson Boltzmann equation has mild effects on computed forces, and that with optimal choice of the OBC model parameters, solvation forces, essential for molecular dynamics simulations, agree well with those computed using the reference Poisson–Boltzmann model. © 2015 Wiley Periodicals, Inc.     

计算材料科学中桥域多尺度方法的若干进展

材料科学中存在固有的多尺度特性,桥域多尺度方法是在宏观尺度(如连续介质力学)中引入不同的细微观尺度的计算区域,乃至纳米尺度的分子动力学、量子力学计算区域,将不同尺度的研究方法通过一定的数学模型耦合在一起。该方法既能节约计算成本,又能保证所研究问题的物理特性。本文对多尺度方法的基本概念、跨尺度桥域多尺度方法的发展、基本原理、耦合方法和离散方程进行了讨论,给出了几个应用算例,并在最后进行了总结,展望了今后的可能发展方向。     

A new two-point deformation tensor and its relation to the classical kinematical framework and the stress concept

Starting from the issue of what is the correct form for a Legendre transformation of the strain energy in terms of Eulerian and two-point tensor variables we introduce a new two-point deformation tensor, namely H=(F−F^−T)/2, as a possible deformation measure involving points in two distinct configurations. The Lie derivative of H is work conjugate to the first Piola–Kirchhoff stress tensor P. The deformation measure H leads to straightforward manipulations within a two-point setting such as the derivation of the virtual work equation and its linearization required for finite element implementation. The manipulations are analogous to those used for the Lagrangian and Eulerian frameworks. It is also shown that the Legendre transformation in terms of two-point tensors and spatial tensors require Lie derivatives. As an illustrative example we propose a simple Saint Venant–Kirchhoff type of a strain-energy function in terms of H. The constitutive model leads to physically meaningful results also for the large compressive strain domain, which is not the case for the classical Saint Venant–Kirchhoff material.     

The Influence of Moduli Slope of a Linearly Graded Matrix on the Bulk Moduli of Some Particle- and Fiber-Reinforced Composites

The stored energy functional of a homogeneous isotropic elastic body is invariant with respect to translation and rotation of a reference configuration. One can use Noether's Theorem to derive the conservation laws corresponding to these invariant transformations. These conservation laws provide an alternative way of formulating the system of equations governing equilibrium of a homogeneous isotropic body. The resulting system is mathematically identical to the system of equilibrium equations and constitutive relations, generally, of another material. This implies that each solution of the system of equilibrium equations gives rise to another solution, which describes the reciprocal deformation and solves the system of equilibrium equations of another material. In this paper we derive conservation laws and prove the theorem on conjugate solutions for two models of elastic homogeneous isotropic bodies – the model of a simple material and the model of a material with couple stress (Cosserat continuum). This revised version was published online in August 2006 with corrections to the Cover Date.     

零维物质体和微态物质体

在这篇文章里,R.G Muncaster的零维弹性体被推广到一般的高阶零维物质体。从非极连续介质力学理论出发,我们推出了零维物质体的所有平衡方程和热力学不等式。再从这些方程和不等式推出微态物质体的相应平衡方程和热力学不等式。这样,我们在零维物质体理论和微态物质体理论之间建立了一个类似于刚性质点力学和古典非极连续介质力学之间关系的关系。     

Drained and Undrained Poroelastic Properties of Healthy and Pathological Bone: A Poro-Micromechanical Investigation

Poro-micromechanics allows for the quantification of poroelastic properties such as the Biot and Skempton coefficients, once a continuum micromechanics model for the material under consideration has been developed and validated. Employing such a model for the transversely isotropic elasticity of cortical and trabecular bone, we determine the tensors of Biot and Skempton coefficients as functions of the volume fractions of mineral, collagen, and the micropore space (Haversian and Volkmann canals, and the inter-trabecular space). Increase of microporosity, as experienced in osteoporosis, as well as decrease of mineral content, as experienced in osteomalacia, lead to an increase of Biot and Skempton coefficients, i. e. to magnification of the mechanical role of the marrow filling the micropore space. For quantification of the marrow pressure rise upon downfall, undrained conditions are appropriate, as can be shown by model predictions of non-destructive impact experiments.     

A generalised model of hydrogen diffusion in metals with multiple trap types

Continuum modelling of hydrogen diffusion in metals, which accounts for both trapping and an imposed force field, is revisited. A generalised model of hydrogen diffusion and trapping is developed as a continuous interpretation of the discrete random-walk theory. A system of nonlinear equations describing the phenomenon of diffusion with multiple types of traps is derived without the assumption of a local equilibrium among hydrogen populations in dissimilar positions. Lattice-trap interchange kinetics can degenerate into local equilibrium as a limit case. Moreover, certain terms in general equations may be negligible in specific situations. By removing these terms, known particularised models of hydrogen diffusion and trapping are recovered. Determining the terms, which are disregarded in reduced models, enables a straightforward assessment of the applicability of these models. The advantages and limitations of particularised models applied to hydrogen embrittlement analyses are discussed.