Spectroscopic Detection of Chiral Aggregation at Liquid-Liquid Interfaces

Introduction Optical activity is a fundamental property, which pro-vides valuable information on the structure of mole-cules and the conformation of their assemblies. There-fore, it is widely used in many fields including organic chemistry, coordination c…     

Annealing-induced interfacial toughening using a molecular nanolayer

Self-assembled molecular nanolayers (MNLs) composed of short organic chains and terminated with desired functional groups are attractive for modifying surface properties for a variety of applications. For example, organosilane MNLs are used as lubricants, in nanolithography, for corrosion protection and in the crystallization of biominerals. Recent work has explored uses of MNLs at thin-film interfaces, both as active components in molecular devices, and as passive layers, inhibiting interfacial diffusion, promoting adhesion and toughening brittle nanoporous structures. The relatively low stability of MNLs on surfaces at temperatures above 350-400 degrees C (refs 12, 13), as a result of desorption or degradation, limits the use of surface MNLs in high-temperature applications. Here we harness MNLs at thin-film interfaces at temperatures higher than the MNL desorption temperature to fortify copper-dielectric interfaces relevant to wiring in micro- and nano-electronic devices. Annealing Cu/MNL/SiO2 structures at 400-700 degrees C results in interfaces that are five times tougher than pristine Cu/SiO2 structures, yielding values exceeding approximately 20 J m(-2). Previously, similarly high toughness values have only been obtained using micrometre-thick interfacial layers. Electron spectroscopy of fracture surfaces and density functional theory modelling of molecular stretching and fracture show that toughening arises from thermally activated interfacial siloxane bridging that enables the MNL to be strongly linked to both the adjacent layers at the interface, and suppresses MNL desorption. We anticipate that our findings will open up opportunities for molecular-level tailoring of a variety of interfacial properties, at processing temperatures higher than previously envisaged, for applications where microlayers are not a viable option-such as in nanodevices or in thermally resistant molecular-inorganic hybrid devices.     

Electric-field-induced capillary attraction between like-charged particles at liquid interfaces

Nanometre- and micrometre-sized charged particles at aqueous interfaces are typically stabilized by a repulsive Coulomb interaction. If one of the phases forming the interface is a nonpolar substance (such as air or oil) that cannot sustain a charge, the particles will exhibit long-ranged dipolar repulsion; if the interface area is confined, mutual repulsion between the particles can induce ordering and even crystallization. However, particle ordering has also been observed in the absence of area confinement, suggesting that like-charged particles at interfaces can also experience attractive interactions. Interface deformations are known to cause capillary forces that attract neighbouring particles to each other, but a satisfying explanation for the origin of such distortions remains outstanding. Here we present quantitative measurements of attractive interactions between colloidal particles at an oil-water interface and show that the attraction can be explained by capillary forces that arise from a distortion of the interface shape that is due to electrostatic stresses caused by the particles' dipolar field. This explanation, which is consistent with all reports on interfacial particle ordering so far, also suggests that the attractive interactions might be controllable: by tuning the polarity of one of the interfacial fluids, it should be possible to adjust the electrostatic stresses of the system and hence the interparticle attractions.     

Experimental study of oil-water interface layers dilatation rheological properties

Oil-water interface layers dilatation rheological properties have been measured with the liquid-liquid interface film pressure measurement apparatus, which was based on the principles of Langmuir film balance. Experimental results show that it is possible to form the interface-associ- ated material caused by the attraction of the dispersion forces at the pure alkane-water interface. The type of material is sensitive to the interfacial pressure. Under the influence of the interfacial pressure, the stability of the interface associated materials decreases with the increase of the number of alkane carbons.     

含弱界面的复合材料层合板对水平剪切波的散射

对含有弱界面的复合材料层合板,采用弱连接界面的剪切弹簧模型,借助波函数法研究了水平剪切波入射时层合板对波的散射,得到了解析结果.数值计算结果表明,弱界面处在不同位置时,对以一定角度入射到复合材料层合板的水平剪切波,其反射和透射系数有明显变化;当层合板中弱界面的力学性能参数强弱不同时,以入射角为变量所得到的透射系数和反射系数曲线呈现出明显差异.证明了根据含弱界面复合材料层合板所得到的水平剪切波的散射规律,不仅能够确定反映弱界面力学性质的参数R的大小,而且还能够判明弱界面所在的位置,这将为复合材料层合板中弱界面的超声无损检测提供依据.     

驱油用聚丙烯酰胺溶液的界面扩张流变特征研究

借助界面扩张流变测量方法,研究了聚合物与正十二烷形成的界面膜特征。主要探讨了液膜稳定过程与界面扩张粘弹模量随测量时间变化的关系、聚合物溶液浓度的影响以及不同聚合物、不同界面膜的流变特征。结果表明,界面粘弹模量的变化反映了膜的吸附平衡过程;正十二烷/聚合物体系膜强度以弹性为主,只是随聚合物浓度增加,粘性模量对膜强度的贡献比例有所上升。聚合物溶液与不同物质所形成的界面具有不同的粘弹性特征,与空气、正十二烷、原油所形成界面的界面扩张粘弹模量E的大小次序为E空气>E正十二烷>E原油,即E随着两相密度差的减小而减小。     

光激发引起的菌紫质人工膜系统界面自由能

应用界面双层模型和界面固有化学势的概念 ,对菌紫质人工膜系统C(N)端界面受光激发所引起的界面自由能变化进行了初步的探讨 ,导出了bR相、C或N端界面能的一般表达式 ,及三类具体的菌紫质人工膜系统 (液 bR 液 ,固 bR 固 ,液 bR 固 )界面自由能的表达式 .可以看出 ,光照下的bR人工膜系统界面自由能的变化 ,不仅与物质组分相关 ,还与跨膜电势相联系 .据此 ,在一定范围内提高bR膜系统溶液的温度、pH值 ,以及降低跨膜电压 ,都将减少界面自由能 ,从而对系统的光驱质子泵过程产生影响 .本文研究仅局限于光照的影响 ,暂不涉及体系相结构变化的情形 .     

Some effects of interface on fluid flow and heat transfer on micro- and nanoscale

The interfacial effects on flow and heat transfer on micro/nano scale are discussed in this paper. Different from bulk cases where interfaces can be simply treated as a boundary, the interfacial effects are not limited to the interface on a microscale but could extend into a significant, even the whole domain of the flow and heat transfer field when the characteristic size of the domain is close to the mean free path （MFP） of the carriers inside an object. Most of microscale thermal phenomena result from interfacial interactions. Any changes in the interactions between the object and boundary particles, such as the force between fluid and solid wall particles, microstructure of interfaces, could affect thermal properties, flow and heat transfer characteristics and hence change thermal conductivity, velocity and temperature profiles, friction coefficient and thermal radiative properties, etc. The properties of nanostructure or flow and heat transfer features of fluid in micro/nanostructures not only depend on themselves, but also on the interaction with the interface because the interface impact can go deep inside the flow. The same fluid, same channel geometry but different wall materials could have different flow and heat transport characteristics on microscale.     

Liquid-crystal-mediated self-assembly at nanodroplet interfaces

Technological applications of liquid crystals have generally relied on control of molecular orientation at a surface or an interface. Such control has been achieved through topography, chemistry and the adsorption of monolayers or surfactants. The role of the substrate or interface has been to impart order over visible length scales and to confine the liquid crystal in a device. Here, we report results from a computational study of a liquid-crystal-based system in which the opposite is true: the liquid crystal is used to impart order on the interfacial arrangement of a surfactant. Recent experiments on macroscopic interfaces have hinted that an interfacial coupling between bulk liquid crystal and surfactant can lead to a two-dimensional phase separation of the surfactant at the interface, but have not had the resolution to measure the structure of the resulting phases. To enhance that coupling, we consider the limit of nanodroplets, the interfaces of which are decorated with surfactant molecules that promote local perpendicular orientation of mesogens within the droplet. In the absence of surfactant, mesogens at the interface are all parallel to that interface. As the droplet is cooled, the mesogens undergo a transition from a disordered (isotropic) to an ordered (nematic or smectic) liquid-crystal phase. As this happens, mesogens within the droplet cause a transition of the surfactant at the interface, which forms new ordered nanophases with morphologies dependent on surfactant concentration. Such nanophases are reminiscent of those encountered in block copolymers, and include circular, striped and worm-like patterns.     

Electronic reconstruction at an interface between a Mott insulator and a band insulator

Surface science is an important and well-established branch of materials science involving the study of changes in material properties near a surface or interface. A fundamental issue has been atomic reconstruction: how the surface lattice symmetry differs from the bulk. 'Correlated-electron compounds' are materials in which strong electron-electron and electron-lattice interactions produce new electronic phases, including interaction-induced (Mott) insulators, many forms of spin, charge and orbital ordering, and (presumably) high-transition-temperature superconductivity. Here we propose that the fundamental issue for the new field of correlated-electron surface/interface science is 'electronic reconstruction': how does the surface/interface electronic phase differ from that in the bulk? As a step towards a general understanding of such phenomena, we present a theoretical study of an interface between a strongly correlated Mott insulator and a band insulator. We find dramatic interface-induced electronic reconstructions: in wide parameter ranges, the near-interface region is metallic and ferromagnetic, whereas the bulk phase on either side is insulating and antiferromagnetic. Extending the analysis to a wider range of interfaces and surfaces is a fundamental scientific challenge and may lead to new applications for correlated electron materials.     

小角X射线散射研究2091Al-Li合金δ′相的生长

采用小角X射线散射技术对2091Al-Li合金时效过程中 δ′相的生长机制和相界特性进行了研究. 结果表明, 在时效初期, 析出的δ′相粒子与基体之间存在过渡界面层, 这说明δ′相是通过调幅分解形成的. 在时效后期, δ′相粒子与基体之间有清晰的界面, 表明δ′相粒子是以成核生长的方式进行的.     

Simulation of mesoscale interfacial properties using the lattice Boltzmann method

We derive the mesoscopic interparticle potentials from macroscopic thermodynamics for van der Waals, Redlich-Kwong, and Redlich-Kwong-Soave equations of state and find that all these potentials are very similar to the Lennard-Jones potential. To in-vestigate the interfacial property at the mesoscale level, we incorporate free energy functions into the single-component multiphase lattice Boltzmann model and obtain the saturated density coexistence curves and interface mass density profiles across the interface using this method with different equations of state. The simulation results accurately reproduce the properties of equilibrium thermodynamics. Numerical results for single-component phase transitions indicate that a bubble-growth process is obtained and the equilibrium phase diagram is achieved at a given temperature. Bulk free energy, the interfacial energy coefficient, and other properties of nonequilibrium thermodynamic parameters, which are used to examine interfacial properties, are obtained in these simulations, and all these parameters are found to obey irreversible thermodynamics.     

MD膜驱剂和单季铵盐对界面Zeta电位的影响

MD膜驱油技术是一种新型提高原油采收率技术。为对比MD膜驱剂(单分子双季铵盐)和几种单季铵盐在界面作用中的差别,运用微电泳法分别考察了这些化合物与高岭土/水和沥青质对二甲苯溶液/水的界面作用。结果表明,Zeta电位能够反映出MD膜驱剂与单季铵盐在界面的静电作用及范德华力作用的差别。MD膜驱剂和单季铵盐与沥青质对二甲苯溶液/水界面的作用比与高岭土/水界面的作用大;范德华力在单季铵盐与沥青质对二甲苯溶液/水界面作用中的比重比在单季铵盐与高岭土/水界面作用中的比重大。MD膜驱剂和单季铵盐与两界面的作用大小顺序为:MD膜驱剂 四丁基溴化铵>四乙基溴化铵和四甲基溴化铵。MD膜驱剂与单季铵盐的不同主要在于其电荷量大,单季铵盐之间的不同则在于与界面的范德华力不同。     

Electrode/electrolyte interface and interface reactions of solid oxide cells:Recent development and advances

High temperature solid oxide cells(SOCs) consisted of solid oxide fuel cells(SOFCs) and solid oxide electrolysis cells(SOECs) are considered one of the most environmentally friendly and efficient energy conversion technology to store renewal energy from sun and wind in hydrogen and generate electricity from the fuels such as hydrogen and natural gas with high efficiency and very low greenhouse gas emission. Over the last few decades, the development of SOC technologies in particularly SOFCs has experienced significant progress and much of the recent research have paid great efforts in understanding the processes occurring at the electrode/electrolyte interfaces. As electrochemical reactions mainly proceed at the gas, electrode and electrolyte three phase boundaries(TPBs), the microstructure and properties of the electrode/electrolyte interfaces thus play a crucial role in determining the overall cell performance and durability. Herein, we review the progress and achievements in the fundamental researches of the electrode/electrolyte(mainly oxygen-conducting) interface evolution behavior under open circuit and polarization conditions. Studies involving interfacial phenomena such as interface formation and reactions, element segregation and diffusion, micropore formation and delamination are summarized and discussed in detail. Besides, the state of the art characterization techniques that have been employed to examine the interface behavior are reviewed. Finally, the challenges and prospects of the interface research in the improvement of the performance and durability of a SOC device are discussed.     

界面强度对柔颗粒增强复合材料破裂特性的影响

界面强度对复合材料的破裂特性和破裂机理具有非常重要的影响。研究了不同界面强度的柔颗粒增强脆性基复合材料在单轴拉伸荷载下的力学性能和破坏过程。在细观尺度上考虑了材料介质力学参数的非均匀分布,采用基于细观损伤力学开发的针对材料破坏过程分析的RFPA2D数值模拟程序,对复合材料从裂纹萌生、扩展直至失稳破坏的全过程进行数值模拟。结果表明,当界面结合较强时,复合材料主要发生穿晶破坏,材料韧性较好但强度较差;当界面结合较弱时,复合材料主要产生沿晶破坏,材料韧性较差而强度较好。     

Mesoscopic fast ion conduction in nanometre-scale planar heterostructures

Ion conduction is of prime importance for solid-state reactions in ionic systems, and for devices such as high-temperature batteries and fuel cells, chemical filters and sensors. Ionic conductivity in solid electrolytes can be improved by dissolving appropriate impurities into the structure or by introducing interfaces that cause the redistribution of ions in the space-charge regions. Heterojunctions in two-phase systems should be particularly efficient at improving ionic conduction, and a qualitatively different conductivity behaviour is expected when interface spacing is comparable to or smaller than the width of the space-charge regions in comparatively large crystals. Here we report the preparation, by molecular-beam epitaxy, of defined heterolayered films composed of CaF2 and BaF2 that exhibit ionic conductivity (parallel to the interfaces) increasing proportionally with interface density--for interfacial spacing greater than 50 nanometres. The results are in excellent agreement with semi-infinite space-charge calculations, assuming a redistribution of fluoride ions at the interfaces. If the spacing is reduced further, the boundary zones overlap and the predicted mesoscopic size effect is observed. At this point, the single layers lose their individuality and an artificial ionically conducting material with anomalous transport properties is generated. Our results should lead to fundamental insight into ionic contact processes and to tailored ionic conductors of potential relevance for medium-temperature applications.     

求解开腔体时谐散射问题的数值算法

针对一类开腔体时谐散射问题提出一种有效的数值算法. 该算法先对计算区域进行简单剖分, 再利用Fourier Bessel函数和平面波函数去近似解的局部性态, 并利用散射场的多极展开式逼近解在无穷远处的性态; 然后借助最小二乘算法迫使数值解在子区域内边界处近似满足连续性条件. 数值模拟验证了算法的有效性.     

新型缔合聚合物与表面活性剂的相互作用

通过对新型疏水缔合聚合物和表面活性剂二元体系的流变性及其聚表体系与模拟油之间的界面张力的研究,发现新型疏水缔合聚合物NAPs与表面活性剂SDBS之间存在明显的相互作用,并在一定条件下出现协同效应,聚表体系的体相粘度在某一表面活性剂浓度下出现最大值。聚表相互作用使它与模拟油之间出现最低界面张力的表面活性剂浓度增加,且界面张力要高于单独表面活性剂溶液与模拟油之间的界面张力。     

Water conduction through the hydrophobic channel of a carbon nanotube.

Confinement of matter on the nanometre scale can induce phase transitions not seen in bulk systems. In the case of water, so-called drying transitions occur on this scale as a result of strong hydrogen-bonding between water molecules, which can cause the liquid to recede from nonpolar surfaces to form a vapour layer separating the bulk phase from the surface. Here we report molecular dynamics simulations showing spontaneous and continuous filling of a nonpolar carbon nanotube with a one-dimensionally ordered chain of water molecules. Although the molecules forming the chain are in chemical and thermal equilibrium with the surrounding bath, we observe pulse-like transmission of water through the nanotube. These transmission bursts result from the tight hydrogen-bonding network inside the tube, which ensures that density fluctuations in the surrounding bath lead to concerted and rapid motion along the tube axis. We also find that a minute reduction in the attraction between the tube wall and water dramatically affects pore hydration, leading to sharp, two-state transitions between empty and filled states on a nanosecond timescale. These observations suggest that carbon nanotubes, with their rigid nonpolar structures, might be exploited as unique molecular channels for water and protons, with the channel occupancy and conductivity tunable by changes in the local channel polarity and solvent conditions.     

超晶格薄膜热传导的分子动力学模拟

采用非平衡态分子动力学方法模拟了超晶格薄膜的热传导性能，并对其主要影响因素作了分析．模拟结果显示，周期长度固定的超晶格薄膜，界面热阻在总热阻中的比例和导热系数同周期数无关；当超晶格薄膜的膜厚不变时，导热系数将随着周期长度的增大而增大，但由于超晶格薄膜晶格常数的不匹配，使其内部发生明显的几何形变，这种变化关系也愈加复杂，同时周期长度的增加，平均界面热阻也随着增大，揭示了界面热阻不仅取决于界面层的物理条件，而且也与构成的介质内部形变有着重要关系．