Large-area three-dimensional molecular ordering of a polymer brush by one-step processing

Rational molecular design and processing, enabling large-area molecular ordering, are important for creating high-performance organic materials and devices. We show that, upon one-step hot-pressing with uniaxially stretched Teflon sheets, a polymer brush carrying azobenzene-containing mesogenic side chains self-assembles into a freestanding film, where the polymer backbone aligns homeotropically to the film plane and the side chains align horizontally. Such an ordered structure forms through translation of a one-dimensional molecular order of the Teflon sheet and propagates from the interface macroscopically on both sides of the film. The resultant wide-area bimorph configuration allows the polymer film to bend rapidly and reversibly when the azobenzene units are photoisomerized. The combination of polymer brushes with hot-pressing and Teflon sheets provides many possibilities in designing functional soft materials.     

The dynamics of the onset of frictional slip

The way in which a frictional interface fails is critical to our fundamental understanding of failure processes in fields ranging from engineering to the study of earthquakes. Frictional motion is initiated by rupture fronts that propagate within the thin interface that separates two sheared bodies. By measuring the shear and normal stresses along the interface, together with the subsequent rapid real-contact-area dynamics, we find that the ratio of shear stress to normal stress can locally far exceed the static-friction coefficient without precipitating slip. Moreover, different modes of rupture selected by the system correspond to distinct regimes of the local stress ratio. These results indicate the key role of nonuniformity to frictional stability and dynamics with implications for the prediction, selection, and arrest of different modes of earthquakes.     

均布荷载作用下钢-混凝土组合梁界面滑移近似计算及其效应分析

为了计算钢-混凝土组合梁的截面滑移及其对梁强度和刚度的影响。提出了具有界面滑移的钢-混凝土组合梁的总荷载及截面总弯矩由2部份组成。不考虑滑移的组合梁承担整体荷载及整体弯矩，能自由滑移的叠合梁承担局部荷载和局部弯矩。基于Bernoulli梁理论和抗剪连接件线性剪力-滑移模型。建立截面总弯矩分配的计算公式．给出均部荷载作用下简支组合梁的栓钉剪力及界面滑移近似计算公式。得到了考虑滑移的组合梁在弹性阶段截面弹性应力、跨中挠度的计算公式及挠度增大系数。     

From static to kinetic friction in confined liquid films

The transition from rest to sliding contact of atomically smooth solids separated by molecularly thin liquid films was studied. The films could be deformed nearly reversibly to a large fraction of the film thickness. The modulus of elasticity and yield stress were low, considerably less than for a molecular crystal or glass in the bulk. The transition to dissipative sliding was typically (but not always) discontinuous. The dissipative stress was then nearly velocity-independent. The similar response of monolayers strongly attached to the solid surfaces, presenting a well-defined interface for sliding, suggests that the physical mechanism of sliding may involve wall slip.     

Ultrastrong and stiff layered polymer nanocomposites

Nanoscale building blocks are individually exceptionally strong because they are close to ideal, defect-free materials. It is, however, difficult to retain the ideal properties in macroscale composites. Bottom-up assembly of a clay/polymer nanocomposite allowed for the preparation of a homogeneous, optically transparent material with planar orientation of the alumosilicate nanosheets. The stiffness and tensile strength of these multilayer composites are one order of magnitude greater than those of analogous nanocomposites at a processing temperature that is much lower than those of ceramic or polymer materials with similar characteristics. A high level of ordering of the nanoscale building blocks, combined with dense covalent and hydrogen bonding and stiffening of the polymer chains, leads to highly effective load transfer between nanosheets and the polymer.     

Laser ablation and the production of polymer films

The formation of high-quality thin films of polytetrafluoroethylene (PTFE) is important in many applications ranging from material reinforcement to molecular electronics. Laser ablation, a technique widely used to deposit a variety of inorganic materials, can also be used as a simple and highly versatile method for forming thin polymer films. The data presented show that PTFE films can be produced on various supports by the evaporation of a solid PTFE target with a pulsed ultraviolet laser. The composition of the ablation plume suggests that PTFE ablation and subsequent film formation occur by way of a laser-induced pyrolitic decomposition with subsequent repolymerization. The polymer films produced by this method are composed of amorphous and highly crystalline regions, the latter being predominantly in a chain-folded configuration with the molecular axis aligned parallel to the substrate surface.     

Polymerization-induced epitaxy: scanning tunneling microscopy of a hydrogen-bonded sheet of polyamide on graphite

A molecularly thin film of a two-dimensional polymer network formed by hydrogen bonding was synthesized and investigated with scanning tunneling microscopy. Poly(in-caprolactam) (nylon 6) was epitaxially grown on the basal plane of graphite and an ultrathin film of the polymer was obtained after the bulk materials had been washed away with solvents. The polymer chain has a planar, all-trans conformation and adjacent chains run in the antiparallel direction. This produces complete pairing of hydrogen bonding groups, with each amide group lying on a straight line perpendicular to the polymer backbone. This hydrogen-bonded sheet is oriented so that each polymer backbone lies in the (1010) direction on the graphite hexagonal lattice, as opposed to the (1120) direction taken by other paraffinic molecules studied so far. This experiment shows that hydrogen bonding can be used to control the orientation of macromolecules in two dimensions.     

Supramolecular Materials: Self-Organized Nanostructures

Miniaturized triblock copolymers have been found to self-assemble into nanostructures that are highly regular in size and shape. Mushroom-shaped supramolecular structures of about 200 kilodaltons form by crystallization of the chemically identical blocks and self-organize into films containing 100 or more layers stacked in a polar arrangement. The polar supramolecular material exhibits spontaneous second-harmonic generation from infrared to green photons and has an adhesive tape-like character with nonadhesive-hydrophobic and hydrophilic-sticky opposite surfaces. The films also have reasonable shear strength and adhere tenaciously to glass surfaces on one side only. The regular and finite size of the supramolecular units is believed to be mediated by repulsive forces among some of the segments in the triblock molecules. A large diversity of multifunctional materials could be formed from regular supramolecular units weighing hundreds of kilodaltons.     

Method for estimation of ocean current velocity from satellite images

Barotropic instability waves on a shear interface propagate at the average speed of the water on the two sides. Assuming the instability to be excited by tidal oscillations, the phase speed is the wavelength divided by the tidal period. If the water is at rest on one side of the shear layer the current speed on the other side can be calculated. This method, applied to the Gulf Stream beyond Cape Hatteras as seen in satellite images, gives estimates of current speed in general agreement with in situ observations.     

聚合物复合材料界面粘合理论研究进展

文章对聚合物复合材料界面粘合理论的研究进展进行了综述,认为各种理论均有一定的合理性及局限性,而在实际的复合材料中,其界面情况要比理论复杂得多,只有灵活运用各种粘接理论,才可加深对界面的理解.同时,文章对粘合理论的研究前景和发展方向进行了展望.     

The use of graft copolymers to bind immiscible blends

Computer simulations and experimental studies were combined to design copolymers that enhance the strength of polymer composites. These copolymers contain side chains that associate across the boundary between phase-separated regions to form a "molecular velcro" that effectively binds the regions together. This behavior significantly improves the structural integrity and mechanical properties of the material. Because the side chains can be fabricated from a large class of compounds, the technique greatly increases the variety of copolymers that can be used in forming high-strength polymer blends.     

Effects of basal debris on glacier flow

Glacier movement is resisted partially by debris, either within glaciers or under glaciers in water-saturated layers. In experiments beneath a thick, sliding glacier, ice containing 2 to 11% debris exerted shear traction of 60 to 200 kilopascals on a smooth rock bed, comparable to the total shear traction beneath glaciers and contrary to the usual assumption that debris-bed friction is negligible. Imposed pore-water pressure that was 60 to 100% of the normal stress in a subglacial debris layer reduced shear traction on the debris sufficiently to halt its deformation and cause slip of ice over the debris. Slip resistance was thus less than debris shearing resistance.     

A tough, thermally conductive silicon carbide composite with high strength up to 1600 degreesC in Air

A sintered silicon carbide fiber-bonded ceramic, which consists of a highly ordered, close-packed structure of very fine hexagonal columnar fibers with a thin interfacial carbon layer between fibers, was synthesized by hot-pressing plied sheets of an amorphous silicon-aluminum-carbon-oxygen fiber prepared from an organosilicon polymer. The interior of the fiber element was composed of sintered beta-silicon carbide crystal without an obvious second phase at the grain boundary and triple points. This material showed high strength (over 600 megapascals in longitudinal direction), fibrous fracture behavior, excellent high-temperature properties (up to 1600 degreesC in air), and high thermal conductivity (even at temperatures over 1000 degreesC).     

In situ interfacial mass detection with piezoelectric transducers

The converse piezoelectric effect, in which an electric field applied across a piezoelectric material induces a stress in that material, has spurred many recent developments in mass measurement techniques. These methods commonly rely on the changes in the vibrational resonant frequency of piezoelectric quartz oscillators that result from changes in mass on the surface of the oscillator. The dependence of frequency on mass has been exploited extensively for mass measurements in vacuum or gas phase, for example, thickness monitors for thin-film preparation and sensors for chemical agents. Advances in piezoelectric methodology in the last decade now allow dynamic measurements of minute mass changes (< 10(-9) grams per square centimeter) at surfaces, thin films, and electrode interfaces in liquid media as well. Mass measurements associated with a diverse collection of interfacial processes can be readily performed, including chemical and biological sensors, reactions catalyzed by enzymes immobilized on surfaces, electron transfer at and ion exchange in thin polymer films, and doping reactions of conducting polymers.     

Chain mobility in the amorphous region of nylon 6 observed under active uniaxial deformation

A specially designed solid-state deuterium nuclear magnetic resonance probe was used to examine the effect of uniaxial elongation on the chain mobility in the amorphous region of semicrystalline nylon 6. In measurements conducted near the glass transition temperature, there was measurable deformation-induced enhancement of the mobility of the amorphous chains up to the yield point. This enhanced mobility decayed once deformation was stopped. Enhanced mobility was not observed in deformation at room temperature. The mechanics of deformation can be explained by the Robertson model for glassy polymers near the glass transition temperature, which states that applied stress induces liquid-like behavior in the polymer chains.     

桥跨分析模型薄板剪力的精确计算

对于两对边简支、两对边自由的矩形析，经典薄板理论不能求得Ｑ的精确解，根源在于Ｋｉｒｃｈｈｏｆｆ变换剪力Ｖｙ＝０在静力等效上的局限性。对上述板，通过一个实例，用Ｒｅｉｓｓｎｅｒ中厚板理论和经典板理论的解做比较，发现苦自由边板的边界条件Ｍｙ＝Ｖｙ＝０用梁的边界条件Ｍｙ＝Ｑｙ＝０替代，就能得到与用Ｒｅｉｓｓｎｅｒ板理论相同的精确内力Ｑｘ，Ｑｙ。这样，就提供了一个科教片上述薄板精确剪力Ｑｘ，Ｑｙ的简化方法     

Ad Hoc网络的安全策略

为了在恶劣的环境中在移动节点之间提供受保护的通信,安全问题已经越来越受到关注。移动Ad Hoc的特点为实现安全带来了一系列挑战,如：公开的对等网络结构、共享的无线资源和高度动态的网络拓扑等。主要着眼于在MANET网络中保护移动节点间的多跳网络连接这个基本安全问题。从这个问题入手提出了相应的安全方案。完整的安全解决方案必须包括全部的三个安全部分：防御攻击、检测入侵节点和对于攻击的反应。     

Void structure in colloidal dispersions

The time evolution of void structures in highly purified polymer latex dispersions was studied with a confocal laser scanning microscope. In such dispersions, which were initially homogeneous, the voids grew with time when the dispersions were kept standing and formed more quickly in the internal material than in material close to the glass-dispersion interface. Void formation is thus not an artifact arising from the presence of the interface. A similar structural inhomogeneity, in apparently homogeneous systems, is discussed for simple ionic solutions, ionic polymer solutions, and Langmuir-Blodgett films.     

Mechanism diversity of the loma prieta aftershocks and the mechanics of mainshock-aftershock interaction

The diverse aftershock sequence of the 1989 Loma Prieta earthquake is inconsistent with conventional models of mainshock-aftershock interaction because the aftershocks do not accommodate mainshock-induced stress changes. Instead, the sense of slip of the aftershocks is consistent with failure in response to a nearly uniaxial stress field in which the maximum principal stress acts almost normal to the mainshock fault plane. This orientation implies that (i) stress drop in the mainshock was nearly complete, (ii) mainshock-induced decreases of fault strength helped were important in controlling the occurrence of after-shocks, and (iii) mainshock rupture was limited to those sections of the fault with preexisting shear stress available to drive fault slip.     

Transition between frictional slip and ductile flow for halite shear zones at room temperature

A complete transition from frictional slip to ductile shearing flow upon decreasing velocity (or slip rate) or increasing confining pressure is documented for a thin layer of halite undergoing large shearing deformation. The results indicate that the logarithmic law for steady-state friction with a negative velocity dependence breaks down when friction becomes nearly equal to the shear resistance required for ductile flow and that the law changes into a flow law in shear upon further decrease in velocity. The frictionvelocity relation is crucial in stability analyses of fault motion, and the results are important for earthquake and state-of-stress problems, especially in the application of laboratory data to the slow average motion of natural faults and to the behavior of deep faults along which ductile deformation becomes increasingly predominant.