Computer Simulations of Polymers Close to Solid Interfaces: Some Selected Topics

This paper presents a topical overview of molecular-dynamics and Monte Carlo simulations for polymer systems close to solid interfaces. The simulations utilize simplified coarse-grained models: The polymers are represented by bead-spring chains, and the walls by a crystalline layer of Lennard-Jones particles or by a smooth impenetrable barrier. This approach has two advantages. First, it reduces the complexity of the simulation. Often, it is only then possible that the interesting length and time scales can be studied at all. Second, the approach concentrates on generic features that are believed to determine the physics of the problem under consideration. The results of the simulation can thus help to single out those features which should be incorporated in an analytical treatment. In this paper, we want to illustrate the versatility of these models by applying them to a broad spectrum of different problems. The situations considered range from the adsorption of a polymer from dilute solution onto a wall, over the importance of sub-monolayer monomeric or polymeric lubricants for kinetic friction, to the crystallization or glass transition of dense polymer films.     

Segregation of Aluminium at Nickel-Sapphire Interfaces

Sessile drop experiments of pure liquid Ni on the basal surface of pure sapphire were conducted under controlled atmosphere and temperature. This system has been traditionally considered as non-reactive, based on thermodynamic assessments. However, the results of this study demonstrate that a capillary driven interaction exists between the pure liquid Ni and the sapphire, which causes the dissolution of the sapphire substrate mainly at the triple junction. Oxygen and Al resulting from the dissolution process diffuse into Ni and segregate at its interfaces with the atmosphere and the sapphire (probably as Al _x O _y clusters), which reduces the interface energy. It is considered that this reduction is beneficial for the adhesion of both liquid and solid Ni on sapphire. The amount of Al introduced into the drop, and hence the segregation of Al that affects the interface energy (and adhesion), are related to the size of the sessile drop.     

Zero-Flux Plane Kinetics at Multicomponent Interfaces

Zero flux planes (ZFP's) are the locations in a diffusion couple where fluxes of individual components vanish. The conditions required for developing ZFP's between interdiffusing multicomponent alloys are now well understood through the works of Dayananda and Morral. In this paper we analyze the kinetics of multicomponent diffusion near ZFP's. In contrast to the usual mixing that occurs between end-member alloys in a diffusion couple, where the average component compositions are approached through “global” exchange of atoms, the presence of a stationary ZFP requires instead that mixing of the blocked component occurs through the release of a pair of coupled diffusion waves. In classical (thick) couples these waves spread symmetrically away from the Matano plane. The wave pair consists of a “depletion” wave that reduces the blocked component concentration in the component-rich alloy, and a conjugate “repletion” wave that increases the concentration in the adjacent component-poor alloy. Curiously, each of these waves establishes the average (equilibrium) concentration unilaterally on either side of the Matano plane. A stationary ZFP precludes net transport of one component across the Matano plane—a circumstance that has practical and theoretically interesting implications for the design of stable multicomponent films and coatings that must resist diffusive loss of a component.     

Coherency Strain-Assisted Equilibrium Segregation at Heterophase Interfaces

Theoretical work in the field of interfacial segregation is focused mainly on the sharp interface approach beginning with the Gibbs' introduction of the dividing surface. In this paper a continuum approach to the problem of interfacial segregation, which deals with continuous distributions of quantities at interfaces, is developed. The current study concentrates on heterophase interfaces in alloys as opposed to grain boundaries or antiphase domain boundaries. The important effect of coherency strains is taken into account. The Gibbs adsorption theorem is discussed in the framework of a continuum approach. A comparison is made between the sharp (Gibbsian) and diffuse interface approaches.     

Ordering at Solid-Liquid Interfaces Between Dissimilar Materials

In an earlier report we explored structural correlations at a liquid-solid interface with molecular dynamics simulations of a model aluminium system using the Ercolessi-Adams potential and up to 4320 atoms. Substrate atoms were pinned to their equilibrium fcc crystalline positions while liquid atoms were free to move. A direct correlation between the amount of ordering in the liquid phase and the underlying substrate orientation was found. In the present paper we extend this study to the case of a fixed bcc substrate in contact with liquid aluminium. We find surprisingly similar results for the density profiles of both (100) and (110) substrates. However, there is a far greater in-plane ordering in the (100) than for the (110) system. For the (100) substrates we observe adsorption of liquid atoms into the terminating plane of the bcc (100) substrate, effectively transforming the bcc (100) plane into an fcc (100) plane.     

A Numerical Approach to Copolymers at Selective Interfaces

We consider a model of a random copolymer at a selective interface which undergoes a localization/delocalization transition. In spite of the several rigorous results available for this model, the theoretical characterization of the phase transition has remained elusive and there is still no agreement about several important issues, for example the behavior of the polymer near the phase transition line. From a rigorous viewpoint non coinciding upper and lower bounds on the critical line are known. In this paper we combine numerical computations with rigorous arguments to get to a better understanding of the phase diagram. Our main results include:

Analysis of Gibbsian Segregation at Heterophase Cu-MnO Interfaces

An alternative methodology to analyze Gibbsian segregation at heterophase interfaces with transmission electron microscopy (TEM) is presented and discussed. In this approach the actual concentration of the segregating element in a monolayer at the interface is obtained. This is in contrast to line scans or maps where the concentrations determined are a convolution of the concentration profiles with the electron probe and where for general interfaces the deconvolution problem can not be solved accurately. This is possible because the present approach uses explicitly the information offered by hetero-interfaces. The method is tested on the possible segregation of indium and gallium dissolved in a Cu matrix to interfaces between MnO precipitates and the Cu matrix. The occurrence of indium segregation is clearly demonstrated and the In concentration in the terminating Cu monolayer at the parallel {111} Cu/MnO interface is determined to be 15 ± 3 at.%, whereas the average In concentration in the Cu matrix is 3.8 ± 0.4 at.%. Further it was found that indium effectively blocks gallium segregation towards the oxide side of the interface. On the other hand, the presence of gallium does not influence the segregation of indium. Explanation for the gallium segregation at the oxide side relies on a thin spinel type Ga _x Mn _y O₄, which reduces the misfit at the metal-oxide interface.     

在介质内表面处柱面波的反射和减反射

应用转移矩阵法研究柱面介质内表面处柱面波的反射,发现在小半径内表面上的反射为全反射,当半径较大时,它只是部分反射.这种特性对于设计光源和小半径接收器有用.同时研究了柱面波的柱面多层减反射涂层,发现这些涂层不能应用通常的四分之一膜层设计,在此基础上叙述了新的设计原理.     

Deconstructing Classical Water Models at Interfaces and in Bulk

Using concepts from perturbation and local molecular field theories of liquids we divide the potential of the SPC/E water model into short and long ranged parts. The short ranged parts define a minimal reference network model that captures very well the structure of the local hydrogen bond network in bulk water while ignoring effects of the remaining long ranged interactions. This deconstruction can provide insight into the different roles that the local hydrogen bond network, dispersion forces, and long ranged dipolar interactions play in determining a variety of properties of SPC/E and related classical models of water. Here we focus on the anomalous behavior of the internal pressure and the temperature dependence of the density of bulk water. We further utilize these short ranged models along with local molecular field theory to quantify the influence of these interactions on the structure of hydrophobic interfaces and the crossover from small to large scale hydration behavior. The implications of our findings for theories of hydrophobicity and possible refinements of classical water models are also discussed.     

Modelling of Transport Phenomena at Cement Matrix—Aggregate Interfaces

The performance of a heterogeneous material like concrete is largely determined by the many interfaces in this material. This contribution focuses on the potential of numerical simulation models to investigate the character of the matrix-aggregate interfacial zone and to simulate hydration-induced moisture transport from the water-rich interfacial zone to the drying bulk paste. Typical features of the simulation model are presented, as well as results of the numerical analysis of the effect of moisture transport within the hardening paste.     

Dynamics of Impurity Redistribution at Solution Interfaces: Phase-Field Approach

JETP Letters - A thermodynamically consistent phase-field model of locally nonequilibrium solidification of concentrated two-phase binary solutions is proposed. The model is based on the division...     

金属-砷化镓界面的电调制反射光谱与Franz-Keldysh效应研究

通过调制光谱这种基础的光学方法来研究Au-GaAs,Al-GaAs,Ni-GaAs的金属半导体界面的一些电学性质,并且加以比较,其中包括电场、费米能级扎钉和界面态密度等情况。这些界面是通过在SIN+ GaAs样品上沉积金属(Au,Al,Ni)生长成的。通过观察电反射谱来研究金属GaAs的界面电场和费米能级扎钉的情况,然后通过傅里叶变换这些所取得的电反射谱来分析这些材料的界面性质。通过测量氦氖激光器诱导产生的光电压和激光器光强之间的关系来得到这些材料的界面态密度情况,从而进行进一步的研究。     

Instability of Interfaces in the Antiferromagnetic XXZ Chain at Zero Temperature

 For the antiferromagnetic, highly anisotropic XZ and XXZ quantum spin chains, we impose periodic boundary conditions on chains with an odd number of sites to force an interface (or kink) into the chain. We prove that the energy of the interface depends on the momentum of the state. This shows that at zero temperature the interface in such chains is not stable. This is in contrast to the ferromagnetic XXZ chain for which the existence of localized interface ground states has been proven for any amount of anisotropy in the Ising-like regime. Received: 15 August 2002 / Accepted: 8 January 2003 Published online: 14 April 2003 RID="⋆" ID="⋆" ? Copyright rests with the authors. Reproduction of the entire article for non-commercial purposes is permitted. Communicated by M. Aizenman     

非水体系的表面增强拉曼光谱研究

本文主要报告了本研究小组自八十年代末至今应用SERS效应对电极/非水溶液界面现象进行研究的一些结果。研究电极从具有强SERS效应的金、银、铜等贵金属,拓宽至铁、镍、铂等过渡金属。借助非水体系SERS的特殊性,我们主要开展了非水体系中溶剂的界面特性、溶质的表面吸附及表面化学反应如C1分子在铂族金属表面的解离反应等研究。此外,对作为非水体系中无法彻底去除的水分子的表面吸附模型也进行了较详细的研究。     

Atomic-Scale Simulation Study of Equilibrium Solute Adsorption at Alloy Solid-Liquid Interfaces

Equilibrium structural properties of solid-liquid interfaces in Cu-Ni alloys are studied by Monte-Carlo simulations employing interatomic potentials based on the embedded-atom method. We describe a thermodynamic-integration approach used to derive bulk concentrations and densities for solid and liquid phases in two-phase thermodynamic equilibrium. These results are used as a basis for constructing three-dimensional supercell geometries employed in Monte-Carlo-simulation studies of solid-liquid interface properties for {100} and {111} crystallographic orientations. At a temperature of 1750 K (four percent below the calculated melting point of pure Ni) equilibrium density and concentration profiles have been derived, allowing a calculation of the relative Gibbsian adsorption, , of Cu (solute) relative to Ni (solvent) at solid-liquid interfaces in Ni-rich alloys. We derive absorption values of and –0.23 ± 0.50 atoms/nm² for {100} and {111} interfaces, respectively. These results are discussed in the context of available experimental measurements and continuum-theory results for adsorption at heterophase interfaces.