On interfacial free energy versus interfacial stress of fluids adsorbed on chemically patterned surfaces: lessons from the special case of striped substrates

The statistical mechanics of fluids adsorbed on chemically patterned surfaces is far from straightforward when attempting to develop virial theorems for the interfacial free energy. This is because in general one would have to devise new procedures to distinguish surface tension from surface stress, even for wall-fluid models where the substrate atoms are replaced by an effective external field. However, the distinction may be made explicit for the special case of striped walls. This paper makes use of striped wall-fluid models to discuss the significance of fluid interfacial stress to patterned inhomogeneous fluids. In particular, it considers the adsorption of hemicylindrical drops on an array of high energy stripes. For the planar stripe geometry it is also possible to make effective use of the pressure tensor formalism. Beyond the special case of striped patterns it is not possible to use standard procedures based on virial theorems to directly evaluate interfacial free energy. The lessons learnt from these exercises apply especially to computer simulation studies of patterned inhomogeneous fluids.     

Fabrication of patterned polyaniline microstructure through microcontact printing and electrochemistry

Polyaniline (PANI) microstructures on ITO glass surface were achieved by microcontact printing of self-assembled film and electrochemical polymerization in an aqueous monoaniline solution. The patterned microstructures of PANI were easily transferred to an adhesive tape surface, which could be applied in the area of plastic circuit application. Optical microscope, atomic force microscopy (AFM), lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to examine the topography and properties of patterned PANI films. Optical microscope and AFM results showed that the PANI microstructure has regular pattern and clear boundary, while LFM and XPS results implied that this microstructure was completely covered by PANI. The data suggested that the interfacial properties of the surface control the rate of electrochemical polymerization, and the polymerization rate on the modified ITO surface is higher than that on the bare ITO area. In our experiments, cyclic voltammetric method, potentiostatic method and chronopotentiometry method were employed to deposited patterned PANI films on octadecyltrichorosilane modified ITO substrate.     

Stability of droplets and channels on homogeneous and structured surfaces

Wetting of structured or imprinted surfaces which leads to a variety of different morphologies such as droplets, channels or thin films is studied theoretically using the general framework of surface or interface thermodynamics. The first variation of the interfacial free energy leads to the well-known Laplace equation and a generalized Young equation which involves spatially dependent interfacial tensions. Furthermore, we perform the second variation of the free energy for arbitrary surface patterns and arbitrary shape of the wetting morphology in order to derive a new and general stability criterion. The latter criterion is then applied to cylindrical segments or channels on homogeneous and structured surfaces. Received 4 August 1999     

微矩形凹槽表面液滴各向异性浸润行为的研究

受自然界启发,仿生微结构被广泛用于调控固-液界面的性质.研究显示,液滴在微结构表面的各向异性浸润行为可用于实现微流动方向和速度的控制,且其各向异性浸润与微结构的尺寸和分布等密切相关.本文研究了微矩形凹槽尺寸对液滴各向异性浸润行为的影响规律.结果显示,液滴沿平行沟槽的方向具有较小的运动阻力、易铺展,因此具有较小接触角;而垂直于沟槽方向,由于沟槽的阻隔作用具有较大运动阻力,因而具有较大接触角,并且在垂直方向液滴的浸润过程是三相线一系列钉扎和跳跃行为.在微矩形凹槽表面,液滴沿平行方向接触角θ//与肋板宽度R和凹槽宽度G密切相关,其值与表面固体面积比成反比;而垂直于沟槽方向的接触角θ⊥随肋板宽度R和凹槽宽度G变化基本保持不变.同时各向异性液滴的变形比L/W、特征方向接触角比值θ⊥/θ//与表面固体面积比成正比.研究结果有助于加深理解微结构表面浸润行为的机制,并为微矩形凹槽在微流动控制方向的应用提供技术支持.     

Modified YSZ/Ni structures with improved stability

The modification of the YSZ/Ni interface by the addition of lower surface energy oxides such as TiO₂, Cr₂O₃ and Mn₃O₄ on the YSZ-surface or alloying Ni-metal with Cr or Pd influences positively the interfacial bonding between ceramic and metallic phases. Wetting experiments in the modified-YSZ/liquid Ni and YSZ/liquid Ni-based alloys systems at 1773K in Ar+4vol%H₂ atmosphere gave contact angle values lower than that of the unmodified YSZ/liquid-Ni system. The present wettability results together with literature data were used for the determination of the surface energies for the modified YSZ-ceramics and the liquid Ni-based alloys as well as the interfacial energies of the ceramic-liquid metal systems examined. Lower interfacial energy values were achieved in the case of the modified YSZ-ceramics. The modification of the YSZ-surface was found to contribute positively also to the interfacial bonding of the ceramic-solid Ni interface, decreasing in this way the agglomeration rate of the metallic phase, when this is deposited as a thin layer onto the ceramic surface. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 16, 1996     

Effects of wettability and interfacial nanobubbles on flow through structured nanochannels: an investigation of molecular dynamics

Solid–fluid boundary conditions are strongly influenced by a number of factors, including the intrinsic properties of the solid/fluid materials, surface roughness, wettability, and the presence of interfacial nanobubbles (INBs). The interconnected nature of these factors means that they should be considered jointly. This paper employs molecular dynamics (MD) simulation in a series of studies aimed at elucidating the influence of wettability in boundary behaviour and the accumulation of interfacial gas. Specifically, we examined the relationship between effective slip length, the morphology of nanobubbles, and wettability. Two methods were employed for the promotion of hydrophobicity between two structured substrates with similar intrinsic contact angles. We also compared anisotropic and isotropic atomic arrangements in the form of graphite and Si(100), respectively. A physical method was employed to deal with variations in surface roughness, whereas a chemical method was used to adjust the wall–fluid interaction energy (?_wf). We first compared the characteristic properties of wettability, including contact angle and fluid density within the cavity. We then investigated the means by which variations in solid–fluid interfacial wettability affect interfacial gas molecules. Our results reveal that the morphology of INB on a patterned substrate is determined by wettability as well as the methods employed for the promotion of hydrophobicity. The present study also illustrates the means by which the multiple effects of the atomic arrangement of solids, surface roughness, wettability and INB influence effective slip length.     

Morphology of lamellae-forming block copolymer films between two orthogonal chemically nanopatterned striped surfaces

The structure of block copolymers results from the interplay between weak intermolecular forces, typically in the order of k(B)T per molecule. This is particularly true for block copolymer thin films in the presence of chemically patterned surfaces, where the different contributions to the total free energy, the interfacial and bulklike terms, have comparable magnitudes. Here, we report on the structures formed by block copolymers films equilibrated between two chemically patterned surfaces with orthogonal stripes. Our experiments and simulations reveal that the domains are continuous through the film and the interface between domains resembles the Scherk's first minimal surface. The impact of chemical patterns on block copolymer morphologies and the underlying physics gives insight into the nanofabrication of complex nanostructures with directed self-assembly using two engineered boundary conditions, as opposed to only one.     

Surface free energies of solid metals: Estimation from liquid surface tension measurements

An equation is derived on semi-theoretical grounds which expresses the solid-vapour surface free energy as a function of the liquid surface tension and the solid-liquid interfacial free energy. A means of calculating reliable values for the solid-liquid energy is presented, which then allows an accurate estimate of solid surface energy at the melting temperature, T_m, to be made for the large number of elements for which dependable liquid surface tension data exist. A method of estimating surface entropy is presented, and has been used to calculate the energies typical of “average”, high-index surfaces at temperatures ranging from 0 K to T_m. It is felt that this paper describes the most accurate method presently available for the calculation of the surface energy of solids in the absence of direct experimental measurement.     

Self-assembly of Ag nanopowder on OTS-patterned glass

Ag ink was spontaneously patterned on glass substrate by using the surface energy difference of a pre-patterned octadecyltrichlorosilane (OTS) layer. Ag ink was confined into the hydrophilic area, where OTS layer was not formed. OTS layer was selectively transferred by micro-contact printing (μCP) method and significantly decreased surface energy. As a result, surface of glass substrate was separated as hydrophobic and hydrophilic with and without OTS layer, respectively. Ag line could be successfully patterned with the width of below 10 μm on the glass. The patterned Ag line was dense and abrupt on the edge and the thickness was about 0.25 μm. Ag film showed good adhesion on a glass substrate after anneal above 200 °C. The minimum resistivity was about 4 μΩ cm.     

Contact mechanics analysis of oscillatory sliding of a rigid fractal surface against an elastic–plastic half-space

Oscillatory sliding contact between a rigid rough surface and an elastic–plastic half-space is examined in the context of numerical simulations. Stick-slip at asperity contacts is included in the analysis in the form of a modified Mindlin theory. Two friction force components are considered – adhesion (depending on the real area of contact, shear strength and interfacial adhesive strength) and plowing (accounting for the deformation resistance of the plastically deformed half-space). Multi-scale surface roughness is described by fractal geometry, whereas the interfacial adhesive strength is represented by a floating parameter that varies between zero (adhesionless surfaces) and one (perfectly adhered surfaces). The effects of surface roughness, apparent contact pressure, oscillation amplitude, elastic–plastic properties of the half-space and interfacial adhesion on contact deformation are interpreted in the light of numerical results of the energy dissipation, maximum tangential (friction) force and slip index. A non-monotonic trend of the energy dissipation and maximum tangential force is observed with increasing surface roughness, which is explained in terms of the evolution of the elastic and plastic fractions of truncated asperity contact areas. The decrease of energy dissipation with increasing apparent contact pressure is attributed to the increase of the elastic contact area fraction and the decrease of the slip index. For a half-space with fixed yield strength, a lower elastic modulus produces a higher tangential force, whereas a higher elastic modulus yields a higher slip index. These two competing effects lead to a non-monotonic dependence of the energy dissipation on the elastic modulus-to-yield strength ratio of the half-space. The effect of interfacial adhesion on the oscillatory contact behaviour is more pronounced for smoother surfaces because the majority of asperity contacts deform elastically and adhesion is the dominant friction mechanism. For rough surfaces, higher interfacial adhesion yields less energy dissipation because more asperity contacts exhibit partial slip.     

Interfacial Stress,Interfacial Energy,and Phase Equilibria in Binary Alloys

A simple model is presented in order to explore the influence of interfacial stress, interfacial energy, and surface stress on the characteristics of phase equilibria in stressed, two-phase binary alloys. Two different system geometries are employed: concentric spheres and thin plates. The conditions for thermodynamic equilibrium are solved and equations of state for each geometry are obtained in terms of the phase fraction, alloy composition, system dimension, and several dimensionless materials parameters. Elastic stress introduces new equilibrium states that are further modified by the interfacial quantities. Those conditions for which interfacial quantities can induce significant changes in the equilibrium phase fraction and phase compositions are identified.     

同质硅分子束外延层的界面缺陷的研究

对同质硅分子束外延层的界面缺陷进行了测试与分析．对存在高浓度施主型界面缺陷的Ｐ型材料，通过解泊松方程计算了该材料的肖特基势垒的能带图，得到了该缺陷能级上电子的填充与发射随外加反向偏压变化的情况．并分析了用深能级瞬态谱（ＤＬＴＳ）对其进行测试所需的条件，以及与常规的ＤＬＴＳ测试结果的不同之处．提出了可同时对该缺陷上电子的发射和俘获过程进行ＤＬＴＳ测量的方法．实验测量结果表明，该高密度的界面缺陷的能级位置位于Ｅ_c－０．３０ｅＶ． 关键词：     

Surface energy and mechanical behaviour of hardened cement paste

The Bangham equation indicates a direct proportionality between the length change of a porous body and a change of surface energy. In our experiments surface energy of hardened cement paste has been modified by desorbing or adsorbing water molecules. The internal pressure created by surface energy could be directly determined with the help of Mössbauer experiments. Based on these results it is possible to determine to what extent shrinkage or swelling is caused by a change of surface energy. Using Griffith's criterion our findings can explain quantitatively the decrease of stength as a function of increasing water content. Results are in good agreement with other methods of studying surface energy such as experiments to determine van der Waals forces.     

Generalized stacking fault energy surfaces in the molecular crystal αRDX

The generalized stacking fault (GSF) energy surfaces in the organic energetic molecular crystal, hexahydro-1,3,5-trinitro-s-triazine (RDX), were studied through atomistic simulations. Using a fully flexible molecular potential in highly damped molecular dynamics simulations, we determined quenched 0?K GSF energy surfaces and structures for a set of planes in the α-polymorph RDX crystal and subsequently compare predictions of slip or cleavage with available experimental observations. To account for the steric contributions and elastic shearing due to the presence of flexible molecules, a modified calculation procedure for the GSF energy surface is proposed that enables the distinction of elastic shear energy from the energy associated with the interfacial displacement discontinuity at the slip plane. Comparisons of the unstable stacking fault energy with the surface energy are used to differentiate cleavage planes from likely slip planes, and the calculations are found to be largely in agreement with available experimental data.     

Hydrodynamic boundary conditions: An emergent behavior of fluid–solid interactions

By using the Onsager principle of minimum energy dissipation, the hydrodynamic boundary conditions at the fluid–solid interface are shown to be the natural emergent behavior of microscopic interactions that lead to the interfacial tension and the tangential friction at the fluid–solid interface [T. Qian, C. Qiu, P. Sheng, J. Fluid Mech. 611 (2008) 333]. This is satisfying because the equations of motion, e.g., the Stokes equation, and the hydrodynamic boundary conditions can now be derived from a unified framework. The resulting continuum hydrodynamic formulation yields predictions for immiscible two-phase flows that are in quantitative agreement with molecular dynamic simulations. In particular, the classical problem of the moving contact line is resolved. We also show results on the moving contact line over chemically patterned surfaces which exhibit striking nanoscale characteristics as well as sub-quadratic dependence of the moving contact line dissipation on its average velocity.     

The classical spin-1/2 tachyon field

We present the classical theory of a set of two spinor fields patterned closely after the Dirac theory in two-component form, but each field obeys a modified Klein-Gordon equation, in which the sign ofm ² has been changed. The solution contains parts with real and imaginary frequencies, that contribute differently to conserved quantities such as the charge and the energy-momentum vector. We also show how the minimal interaction with the electromagnetic field is obtained.     

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with ?386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.     

Fabrication of complex three-dimensional nanostructures from self-assembling block copolymer materials on two-dimensional chemically patterned templates with mismatched symmetry

A study is presented of the self-assembly of a lamella-forming blend of a diblock copolymer and its respective homopolymers on periodically patterned substrates consisting of square arrays of spots, that preferentially attract one component, as a function of pattern dimensions and film thickness. The blend morphology follows the pattern at the substrate and forms a single quadratically perforated lamella (QPL). At intermediate film thicknesses necks connect this QPL to the film surface, resulting in a bicontinuous morphology. The necks do not register with the underlying square lattice but exhibit a substantial amount of hexagonal short-range order. For thicker films we observe bicontinuous morphologies consisting of parallel lamellae with disordered perforations. These results demonstrate a promising strategy for the fabrication of complex interfacial nanostructures from two-dimensional chemically patterned templates.     

求解带有锥形交叉区域薛定谔方程的改进界面跃迁格式

改进一种欧拉框架下的界面跃迁格式.原格式是为求解带有多个能级,不同能级之间存在锥形交叉区域的薛定谔方程提出的.石墨烯中的电子输运与上述过程相似.Kammerer等人提出带有跳跃算子的数值格式能够更好地保持石墨烯中电子输运的能量守恒.引入这种跳跃算子可以改进原有的界面跃迁格式.改进格式的数值结果取得了预期的效果.     

Enhanced surface free energy of polyimide fibers by alkali treatment and its interfacial adhesion behavior to epoxy resins

In this article, polyimide (PI) fibers were modified by alkali treatment, and PI fiber-reinforced epoxy composites were fabricated. The effects of different alkali treatment times on the surface properties of the PI fibers and the adhesion behaviors of PI fiber/epoxy composites were studied. The surface morphologies, chemical compositions, mechanical properties, and surface free energy of the PI fibers were characterized by atomic force microscopy, X-ray photoelectron spectroscopy, single-fiber tensile strength analysis, and dynamic contact angle analysis, respectively. The results show that alkali treatment plays an important role in the improvement of the surface free energy and the wettability of PI fibers. We also found that, after the 3 min, 30 °C, 20 wt% NaOH solution treatment, the fibers possessed good mechanical properties and surface activities, and the interlaminar shear strength of the composites increased to 64.52 MPa, indicating good interfacial adhesion properties.