Dispersion forces effects in the instability of polymer films

We have investigated the dispersion forces effects in the instability of polystyrene films within the framework of the frequency-dependent theory. The calculated results of excess free energy, wavelength and growth rate show that the stability of the film can be tuned by the properties and the variation of the thickness of the coating. As the film thickness increases, the retardation effects can be significant and the full results of free energy must be used to deal with the instability of the polystyrene films.     

Heterogeneous hole nucleation in electron-charged 4He wetting films

4He wetting layers on Cs exhibit an unusually long-lived metastable state upon undercooling to temperatures well below the wetting temperature T(w) approximately 1.9 K. The decay of this state by homogeneous thermal nucleation of holes is disfavored by the incipient divergence of the free energy barrier separating the metastable thick film from the stable thin-film state. We propose that interface deformations ("dimples") created by electrons bound at the 4He liquid-vapor interface can be used as nuclei for the heterogeneous nucleation of holes. The size and excess free energy of the dimple can be tuned by an applied electric field E which allows the lifetime of the metastable film to be controlled.     

Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit^® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.     

Calculation of anisotropic strain-engineered patterns of monolayer islands

The self-organization of monolayer epitaxy islands in presence of anisotropies in surface stress, applied stress, and lattice mismatch between the film and substrate materials is investigated. The fundamental nature of island interactions is addressed in the context of a model wherein the system free energy consists of the excess energy and strain energy of atomic surface steps. It is shown the anisotropy can change the character of island interactions. An energy-reducing kinetic relation is adopted to evolve an initially random morphology towards a generally metastable minimum energy state. It is found the self-organization of islands into a regular array requires both the repulsion between islands and tendency for islands to aligned in a particular direction. Small anisotropies provide the required repulsion but not the tendency for islands to align and large anisotropies provide the necessary alignment but cause islands to attract. Modest levels of anisotropy provide the most favorable conditions of self-organization.     

Effect of different Ge predeposition amounts on SiC grown on Si (1 1 1)

The SiC films were grown by solid source molecular beam epitaxy (SSMBE) on Si (1 1 1) with different amounts of Ge predeposited on Si prior to the epitaxial growth of SiC. The samples were investigated with reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM), and X-ray diffraction (XRD). The results indicate that there is an optimized Ge predeposition amount of 0.2 nm. The optimized Ge predeposition suppress the Si outdiffusion and reduce the formation of voids. For the sample without Ge predeposition, the Si outdiffusion can be observed in RHEED and the results of XRD show the worse quality of SiC film. For the sample with excess amount of Ge predeposition, the excess Ge can increase the roughness of the surface which induces the poor quality of the SiC film.     

Free energies of interfaces from quasi-harmonic theory: A critical appraisal

A critical assessment is given of the quasi-harmonic approximation, and various approximations to the quasi-harmonic approximation, with regard to predicting the free energy and atomic structure of grain boundaries in silicon at elevated temperatures. The quasi-harmonic results are compared with those obtained by molecular dynamics and thermodynamic integration. It is found that the quasi-harmonic approximation yields accurate excess free energies and atomic structures of grain boundaries at 1,000 K. The anharmonic contribution to the free energy that is absent in the quasi-harmonic contribution is virtually the same at a grain boundary in Si and in the perfect crystal. The second-moment and Einstein approximations to the full quasi-harmonic theory yield unreliable free energies, but reasonably accurate atomic structures. However, excess free energies are quite well described by the Einstein model. It is concluded that the quasi-harmonic approximation works remarkably well in silicon. The simplest approximations to the phonon density of states lead to unreliable results for the free energy, but cancellation of errors occurs to a large extent when excess free energies are computed.     

Ab initio investigation of the surface properties of Cu(111) and Li diffusion in Cu thin film

Ab initio density-functional calculations have been performed to investigate the surface properties of Cu(111) and lithium diffusion in copper thin film. The calculation results including lattice constant, cohesive energy, work function and surface energy are in fair agreement with that derived from corresponding experiments. The various diffusion pathways such as diffusion of lithium as a substitution atom and various mechanisms are investigated with ab initio molecular dynamics. The energy barrier has been calculated corresponding to each possible pathway. Theoretically, we have identified that lithium can diffuse through copper thin film by successive nearest neighbor vacancy-atom exchanges, therefore, the nearest neighbor vacancy assisted jumping is deduced to be the most probable by comparing the different mechanisms. It is found that more free diffusion may be observed by increasing the number of copper vacancies in the thin film. It is also confirmed that the diffusion is more obvious as temperature is increased.     

流体混合物热力学性质计算的混合法则新进展

回顾近期关于流体混合物热物性混合法则的研究新进展,特别是余吉布斯自由能(GE)和余亥姆霍兹自由能(AE)型混合法则的拓展及应用,重点介绍一种基于AE,仅通过偏微分方程便可计算混合物所有热力学性质的混合法则。可为发展未知流体混合物热物性计算方法以及各种常见混合物热物性的工程应用提供参考和依据。     

Near-equilibrium measurements of nonequilibrium free energy

A central endeavor of thermodynamics is the measurement of free energy changes. Regrettably, although we can measure the free energy of a system in thermodynamic equilibrium, typically all we can say about the free energy of a nonequilibrium ensemble is that it is larger than that of the same system at equilibrium. Herein, we derive a formally exact expression for the probability distribution of a driven system, which involves path ensemble averages of the work over trajectories of the time-reversed system. From this we find a simple near-equilibrium approximation for the free energy in terms of an excess mean time-reversed work, which can be experimentally measured on real systems. With analysis and computer simulation, we demonstrate the accuracy of our approximations for several simple models.     

Effects of severe-strain-induced defects on the mechanical response of two kinds of high-angle grain boundaries

ABSTRACT

Grain boundaries of metallic materials subjected to severe plastic deformation exhibit significantly enhanced diffusivity and excess energy compared with their relaxed poly- or bi-crystalline counterparts even when the macroscopic degrees of freedom are the same in both types of grain boundaries. Boundaries of excess energy are/can be relaxed by annealing. As a first step in accounting for this experimentally observed high-energy state of general high-angle grain boundaries subjected to severe plastic deformation, a concept of localised basic shear units and the presence of localised extra free volume in these units situated in different locations in the grain boundaries, which was originally proposed to explain steady-state structural superplastic flow, is made use of. Using MD simulation, the mechanical response of these modified grain boundaries is compared with that of their relaxed state. The results are also compared with a case of a homogeneous distribution of extra free volume within the grain boundary. The localised shear units containing extra free volume introduced in the grain boundaries are found to alter their physical and mechanical features strongly, which, in turn, drastically affect, consistent with experimental results, the mechanical response of the heavily deformed material.     

Surface free energy of laser-produced bond percolators

Pulsed laser irradiation of thin metallic films on non-wetted substrates creates two-dimensional bond percolator structures. We show that these can be understood as frozen minimum free energy configurations. The spacing between nodes is found to depend linearly on the initial film thickness, as verified experimentally for the case of a Ti film on sapphire.     

Investigations of electron beam induced conductivity in silicon oxide thin films

Silicon oxide thin film conductivity under electron beam irradiation is studied. An induced current in the films is varied in a range from a few tenths to a few values of the beam current. The dependence of the current normalized to a product of the applied voltage and the beam current on the beam energy is found to have a maximum determined by the film thickness, beam energy, and sign of the applied voltage. For the negative voltage applied to the metal electrode deposited on the film, this maximum is observed at the beam energy, at which the depth generation function is smaller by several tens of nanometers than the film thickness. For the positive voltage on the metal electrode, the maximum is observed at higher beam energies. The obtained result could be qualitatively explained under the assumption that a stationary excess carrier distribution is formed under the electron beam. This distribution is shifted with respect to the generation function due to diffusion and drift of excess carriers. A value of this shift is of about a few tens of nanometers, and its sign indicates that the majority carriers providing the induced conductivity in the films studied are electrons.     

Effect of electrodes on the properties of a thin ferroelectric film

The effect of various metal electrodes on the properties of thin ferroelectric films is considered using the phenomenological Ginzburg-Landau theory. The electric field produced by charges on electrodes is taken into account (with allowance for the screening of the charges in the metals) in the free energy functional and in the Euler-Lagrange equation for the film polarization. This equation is solved using the variational method, and the free energy functional is reduced to the conventional free energy with a renormalized coefficient of P ². This coefficient is dependent on the properties and thickness of the film and the properties of the electrode. Therefore, the physical characteristics of the size effect can be found by merely substituting the renormalized coefficient into the usual formulas from phenomenological theory. The calculations are shown to be in good agreement with the experimental data for Pt, Ir, IrO₂, and SrRuO₃.     

Variations of Casimir energy from a superconducting transition

We consider a five-layer Casimir cavity, including a thin superconducting film. We show that when the cavity is cooled below the critical temperature for the onset of superconductivity, the sharp variation (in the microwave region) of the reflection coefficient of the film produces a variation in the value of the Casimir energy. Even though the relative variation in the Casimir energy is very small, its magnitude can be comparable to the condensation energy of the superconducting film, and thus causes a significant increase in the value of the critical magnetic field, required to destroy the superconductivity of the film. The proposed scheme might also help clarifying the current controversy about the magnitude of the contribution to Casimir free energy from the TE zero mode, as we find that alternative treatments of this mode strongly affect the shift of critical field.     

SmCo7纳米晶合金晶粒组织热稳定性的热力学分析与计算机模拟

推导出了单相纳米晶合金的晶界过剩体积与晶粒尺寸之间的定量关系, 建立了纳米晶合金的晶界热力学性质随温度和晶粒尺寸发生变化的确定性函数. 针对SmCo₇纳米晶合金, 通过纳米晶界热力学函数计算和分析, 研究了单相纳米晶合金的晶粒组织热稳定性. 研究表明, 当纳米晶合金的晶粒尺寸小于对应于体系中晶界自由能最大值的临界晶粒尺寸时, 纳米晶组织处于相对稳定的热力学状态; 当纳米晶粒尺寸达到和超过临界尺寸时, 纳米晶组织将发生热力学失稳, 导致不连续的快速晶粒长大. 利用纳米晶合金热力学理论与元胞自动机算法相耦合的模型对SmCo₇纳米晶合金在升温过程中的晶粒长大行为进行了计算机模拟, 模拟结果与纳米晶合金热力学模型的计算预测结果一致, 由此证实了关于纳米晶合金晶粒组织热稳定性的研究结论. 关键词： 纳米晶合金热力学 7纳米晶合金')" href="#">SmCo₇纳米晶合金 热稳定性 计算机模拟     

Helmholtz free energy of a multilayer system of highly charged plates immersed in an electrolyte

The Helmholtz free energy of highly charged plates immersed in an electrolyte solution in a finite container is investigated using mean field theory. Exact solutions of the Poisson-Boltzmann equation under Dirichlet and Neumann boundary conditions lead to analytical expressions for the free energies. Adiabatic potentials of the charged plates, which are derived from the free energy, have long-range weak attractive parts and medium-range strong repulsive parts, irrespective of the type of boundary conditions. The repulsion results mainly from the osmotic pressure of the excess ions trapped between the plates by the large surface charges and the attraction arises essentially from an electric pull from the intermediate cloud of excess counterions shared by the plates.     

Thickness transitions in thin films: The equilibrium

The thermodynamic and thickness equilibria of planar solid, liquid or gaseous thin films are described in terms of the film excess chemical potential μ_ex. A general formula is given which relates μ_ex to the short- and/or long-range surface forces associated with the two film surfaces and the dependence of the film specific surface free energy σ on the film thickness h is expressed through μ_ex. The conditions under which the thin films are in stable or metastable thermodynamic equilibrium are analyzed and it is shown that the metastable thin films are subject to thickness transitions involving abrupt changes of h. The thin film thickness equilibrium, i.e. the coexistence between two films of different thickness, is also considered and the film equilibrium chemical potential characterizing this equilibrium is determined by means of μ_ex and σ.     

LJ模型的热力学特性、相平衡及用于真实分子的研究

结合描述硬球固体Helmholtz自由能的自由体积方法与描述硬球固体径向分布函数的拟合的分析表达式与一阶热力学摄动理论,用于描述Lennard Jones(LJ)固体的Helmholtz自由能.按照一个修正的WCA方法将LJ势分为短程排斥部分与长程吸引部分,将文献中一个用于求取液相的等价的硬球直径的简单的迭代法扩展到固相,用于求取固相的等价的硬球直径.在固体Helmholtz自由能的计算中,使用200壳层,以便获得精确的结果.体相LJ液体的热力学特性由一个最近提出的状态方程求取.该方法很好地描述了LJ固体的过量Helmholtz自由能与状态方程,满意地描述了Lennard Jones模型的相平衡;通过选取合适的LJ势参数,能很好地描述了真实分子的融化曲线.     

Surface induced mixed state of a superconducting film

Presented in this paper is a theoretical analysis of a planar surface induced mixed state for a superconducting film in parallel applied field. An analytical solution of the internal magnetic field is obtained based on Saint-James and de Gennes' order parameter in a film. An expression of Gibbs free energy per unit volume without restriction of a geometry is derived from non-linear Ginzburg-Landau (GL) equation in terms of a renormalized GL parameter and a modified geometric factor. Based on the Gibbs free energy, a phase diagram of distinguishing a first and second order phase transition for a type I superconducting film is calculated. The numerical results for exact solutions of spatial variation of order parameter, current density and internal magnetic field in the film geometry in parallel applied field case are presented. Near the upper critical field, the first entry of an applied field in the film exhibits a laminar structure.     

铜膜中锂离子扩散的第一性原理研究

基于第一性原理，采用“adiabatic trajectory”方法计算了锂离子在铜膜中的扩散势垒。通过比较可能的扩散机制，理论上证实了室温下锂离子可以最近邻空位扩散机制穿过铜膜。同时，解释了随着铜膜中空位数量的增加，锂离子的扩散势垒减小，从而更易在铜膜中扩散的物理现象。