Force-field dependence on the interfacial structure of oil–water interfaces

We investigate the performance of different force-fields for alkanes, united (TraPPE) and all atom (OPLS-AA) models, and water (SPC/E and TIP4P-2005), in the prediction of the interfacial structure of alkane (n-octane, and n-dodecane)–water interfaces. We report an extensive comparison of the interfacial thermodynamic properties as well as the interfacial structure (translational and orientational). We use the recently introduced intrinsic sampling method, which removes the averaging effect of the interfacial capillary waves and provides a clear view of the interface structure. The alkane interfacial structure is sensitive to the environment, i.e. alkane–vapour or alkane–water interfaces, showing a stronger structure when it is in contact with the water phase. We find that this structure is fairly independent of the level of detail, full or united atom, employed to describe the alkane phase. The water surface properties show a small dependence on the water model. The dipole moment of the SPC/E model shows asymmetric fluctuations, with a tendency to point both towards the alkane and water phases. On the other hand the dipole moment of the TIP4P-2005 model shows a tendency to point towards the water phase only. Analysis of the intrinsic electrostatic field indicates that the surface water potential is confined to an interfacial region of about 8 Å. Overall we find that the intrinsic structure of alkane–water interfaces is a robust interfacial property, which is independent of the details of the force-field employed. Hence, it should provide a good reference to interpret experimental data.     

Spreading and two-dimensional mobility of long-chain alkanes at solid/gas interfaces

Long-chain n alkanes on solid surfaces can form partially wetting liquid alkane droplets coexisting with solid multilayer terraces. We propose a diffusivelike alkane flow between terrace edge and droplet perimeter through a molecularly thin "precursorlike" film. Depending on the (uniform!) sample temperature, either droplet or terrace edge are not in thermodynamic equilibrium. This leads to a chemical potential gradient, which drives the reversible alkane flow. The gradient can be adjusted and calculated independently from the phenomenological diffusion coefficient.     

Heteroepitaxial growth of oxides on sapphire induced by laser radiation in the solid–liquid interface

2 O₃, Fe₂O₃ and MnO₂ on sapphire from an aqueous solutions of either CrO₃, FeCl₃, or KMnO₄, respectively, under laser irradiation of the interface sapphire/liquid. The interface is exposed through the sapphire substrate to the radiation of a copper vapor laser (wavelength of 510 nm). The etching of sapphire is accompanied by the deposition of oxide films, which are shown to grow epitaxially on the sapphire substrate, while the deposition of the polycrystalline oxide film occurs on a glass substrate under the same experimental conditions. Similarly, the epitaxial growth of cubic Fe₂O₃ and orthorhombic MnO₂ is observed, though their crystallographic structure is different from the hexagonal structure of sapphire. Received: 26 June 1997/Accepted: 7 July 1997     

一种外延生长高质量GaN薄膜的新方法

采用化学方法腐蚀c-面蓝宝石衬底，以形成一定的图案；利用LP-MOCVD在经过表面处理的蓝宝石衬底上以及常规c-面蓝宝石衬底上外延生长GaN薄膜.采用高分辨率双晶X射线衍射(DCXRD)、三维视频光学显微镜(OM)、扫描电子显微镜(SEM)和原子力显微镜(AFM)进行分析，结果表明，在经过表面处理形成一定图案的蓝宝石衬底上外延生长的GaN薄膜明显优于在常规蓝宝石衬底上外延生长的GaN薄膜，其(0002)面上的XRD FWHM为208.80弧秒，(1012)面上的为320.76弧秒.同时，此方法也克服了传统 关键词： 表面处理 MOCVD 横向外延生长 GaN薄膜     

Anchoring of alkyl chain molecules on oxide surface using silicon alkoxide

Chemical states of the interfaces between octadecyl-triethoxy-silane (ODTS) molecules and sapphire surface were measured by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) using synchrotron soft X-rays. The nearly self-assembled monolayer of ODTS was formed on the sapphire surface. For XPS and NEXAFS measurements, it was elucidated that the chemical bond between silicon alkoxide in ODTS and the surface was formed, and the alkane chain of ODTS locates upper side on the surface. As a result, it was elucidated that the silicon alkoxide is a good anchor for the immobilization of organic molecules on oxides.     

5.5-7.5 MeV proton generation by a moderate-intensity ultrashort-pulse laser interaction with H2O nanowire targets

We report on the first generation of 5.5-7.5 MeV protons by a moderate-intensity short-pulse laser (～5×10(17) W/cm(2), 40 fsec) interacting with frozen H(2)O nanometer-size structure droplets (snow nanowires) deposited on a sapphire substrate. In this setup, the laser intensity is locally enhanced by the snow nanowire, leading to high spatial gradients. Accordingly, the nanoplasma is subject to enhanced ponderomotive potential, and confined charge separation is obtained. Electrostatic fields of extremely high intensities are produced over the short scale length, and protons are accelerated to MeV-level energies.     

On the formation of low molecular weight hydrocarbons in liquid n-alkanes γ-radiolysis: The yields affected by free radical and electron scavengers

The data on radical and/or electron scavengers' effects on liquid n-alkanes fragmentation by γ-radiation are explained in terms of the decomposition of parent alkyl radicals, resulting at least partly from the process of ion-electron pair neutralization. It is suggested that the decomposition of excited parent radicals in nearly statistical amounts gives rise to practically all olefins with corresponding yields of shorter alkyl radicals (low molecular weight alkanes) and the mechanism of “molecular decomposition” of parent alkane to alkane+olefin does not contribute significantly in n- alkanes fragmentation.

Electron scavengers, like N₂O, decrease the yields of parent radicals decomposition products by about only 45%. A certain amount of short alkyl radicals, resulting from other processes is being scavenged in N₂O containing systems. Oxygen scavenges all the radicals complementary to olefins, both scavengeable and unscavengeable, and also radical fraction of another origin, inhibited in N₂O containing systems.     

The behaviour of liquid alkanes near interfaces

Simulations of thick films of liquid alkanes supported on a wax-like substrate were carried out at a number of temperatures in order to investigate the structure and dynamics of molecules near the solid-liquid and the liquid-vapour interfaces. Films of butane, octane and a mixture were investigated. Near the solid surface the liquids were found to be structured and molecular diffusion slowed. However, there was no evidence of a frozen layer at this interface even near the bulk freezing temperature. The mixed liquid showed considerable segregation at both interfaces with preferential absorption of butane at the liquid-vapour interface and octane at the liquid-solid interface.     

Peculiarities of self-diffusion of alkane molecules in kaolinite

Self-diffusion of alkanes in kaolinite has been explored by pulsed field gradient nuclear magnetic resonance. The concentration dependences of average self-diffusion coefficient (SDC) of liquid have been studied in the wide temperature interval (T=253?383 K). The translational mobility of alkane molecules in kaolinite was shown to have some specific peculiarities. An anomalous rise was found in the average self-diffusion coefficient of the liquid as its content in kaolinite decreased. To explain this we should introduce a new “gas-like” state for the diffusant, whose mobility exceeds that of pure liquid. The possibility of the existence of such a state is explained by kaolinite’s ability to increase the specific surface area of the induced liquid. Analysis of a shape of the spin-echo diffusion attenuation leads one to suppose that there are heterogeneities in the medium’s porous space.     

Surface precrystallization of normal C24 alkane in porous glass

The behavior of the enthalpy and specific heat of normal C24 alkane in the bulk and in porous glasses is investigated using an adiabatic scanning microcalorimeter. Enthalpy jumps, which precede a phase transition in the entire volume of the pores, are found in porous glass with characteristic pore size 1000 Å at a transition from the isotropic liquid into the rotator phase RII. The enthalpy jumps are interpreted as a layerwise growth of a crystal phase on the surface of porous glass. It is also found that porous glass substantially changes the phase behavior of alkanes.     

Rate effects on layering of a confined linear alkane

We perform drainage experiments of a linear alkane fluid (n-hexadecane) down to molecular thicknesses, and we focus on the role played by the confinement rate. We show that molecular layering is strongly influenced by the velocity at which the confining walls are approached: under high enough shear rates, the confined medium behaves as a structureless liquid of enhanced viscosity for a film thickness below approximately 10 nm. Our results also lead us to conclude that a rapidly confined film can be quenched in a metastable disordered state, which might be related with recent intriguing results on the shear properties of confined films produced at different rates [Zhu and Granick, Phys. Rev. Lett. 93, 096101 (2004)].     

蓝宝石表面处理对氮化镓薄膜的影响

采用化学方法腐蚀c-面蓝宝石衬底,以形成一定的图案;利用LP-MOCVD在经过不同腐蚀时间的蓝宝石衬底上外延生长GaN薄膜。采用高分辨率双晶X射线衍射（DCXRD）、三维视频光学显微镜（OM）、扫描电子显微镜（SEM）和原子力显微镜（AFM）进行分析。结果表明,对蓝宝石衬底腐蚀50min情况下,外延生长的GaN薄膜晶体质量最优,其（0002）面上的XRD 半峰全宽为202.68arcsec,（10-12）面上的XRD 半峰全宽为300.24arcsec;其均方根粗糙度（RMS）为0.184nm。     

Graphene films grown on sapphire substrates via solid source molecular beam epitaxy

A method for growing graphene on a sapphire substrate by depositing an SiC buffer layer and then annealing at high temperature in solid source molecular beam epitaxy (SSMBE) equipment was presented. The structural and electronic properties of the samples were characterized by reflection high energy diffraction (RHEED), X-ray diffraction Φ scans, Raman spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results of the RHEED and Φ scan, as well as the Raman spectra, showed that an epitaxial hexagonal α-SiC layer was grown on the sapphire substrate. The results of the Raman and NEXAFS spectra revealed that the graphene films with the AB Bernal stacking structure were formed on the sapphire substrate after annealing. The layer number of the graphene was between four and five, and the thickness of the unreacted SiC layer was about 1--1.5 nm.     

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.     

用微波ECR等离子体溅射法在蓝宝石(0112)晶面上生长ZnO薄膜的研究

蓝宝石上外延生长ZnO薄膜在表面波和声光器件中有重要的应用．用微波电子回旋共振(ECR)等离子体溅射法在蓝宝石(0112)晶面上外延生长了ZnO薄膜,膜无色透明,并且表面光滑,基片温度为380℃,为探索沉积工艺参数对薄膜结构的影响,用XRD对不同基片温度和沉积速率生长的ZnO薄膜进行了研究．     

First-order and critical wetting of alkanes on water

Ellipsometry measurements of the wetting behavior of different alkanes on water show a sequence of two wetting transitions: a first-order (discontinuous) transition followed by a critical (continuous) one. We report temperature-induced wetting transitions for different alkanes and a novel pressure-induced wetting transition for an alkane mixture. The experiments enable us to determine the global wetting phase diagram as a function of chain length and temperature which we subsequently calculate theoretically. The two transition lines are found to be approximately parallel, in accordance with basic theoretical arguments.     

骨架柔性对短链烷烃分子在金属-有机骨架材料中扩散的影响

采用分子动力学方法,对短链烷烃在柔性和刚性具有相似拓扑结构的金属有机骨架材料(isoreticular metal-organic frameworks, IRMOFs)中的分子扩散进行了研究. 结果表明,分子在柔性骨架中的自扩散系数大于在刚性骨架中的自扩散系数,在柔性骨架中的活化能小于在刚性骨架中的活化能. 骨架的柔性对自扩散系数的影响随着温度的升高而增加,随着扩散分子数目以及扩散分子链长的增长而降低. 因此,在利用分子模拟方法研究烷烃在金属-有机骨架材料中的扩散行为时,尤其对于较高温度以及较短的烷烃分 关键词： 分子模拟 金属-有机骨架材料 柔性骨架 扩散     

ZnO外延膜与蓝宝石衬底的取向偏差及其弯曲变形

采用常压MOCVD方法在Al2O3(00．1)衬底上生长出了高质量ZnO单晶薄膜。由ZnO(00．2)面和Al2O3(00．6)面及ZnO(10．2)面和Al2O3(11．6)面X射线双晶(w／2θ衍射曲线的相对峰位,得到ZnO外延膜的晶格常数及外延层和衬底间的取向差异角。结果表明外延层和衬底在应力作用下产生了取向差和晶格畸变,并且取向倾斜方向与衬底的切割倾角方向一致;高温直接生长的样品的取向差比有低温缓冲层样品更大,晶格畸变也更严重。高温直接生长的样品弯曲半径小而应力更大;实验测量的应力值和理论计算的热应力值之间存在差异,原因主要是晶格失配应力的存在。有缓冲层的样品由于能更好地弛豫晶格失配引入的应力,热应力所占整个残余应力的比例相对更大。