Increase in the molecular component of the adhesive pressure in polymer composites induced by electric charge

The effect of electric charge, present at a glass fiber–polymer interface during the composite material formation, on the adhesive pressure between the components was studied. Additional electric charge was delivered to the interface by means of the deposition of charged polymer particles onto the fiber surface from a fluidized bed in an electric field. The adhesive pressure was calculated using the results of the variational mechanics analysis by Scheer and Nairn from the data obtained with a single fiber microbond test. Our experiments showed that the adhesive pressure increased by 15–20% in the case of charged polymer matrices. This can be attributed to both intensification of van der Waals forces due to extra interfacial pressure and, for polar polymers, the increase of the surface concentration of local adhesive bonds. The mechanical and kinetic models have been proposed to describe the observed behavior of the adhesive pressure; theoretical curves for the adhesive pressure as a function of the time and temperature of the contact formation, including the effect of electric factors, have been obtained. From the kinetic model, the activation energies for the process of adhesive contact formation were determined. The effect of acceleration of adhesive bonding in the presence of electric charge can be explained in terms of a decrease of the activation energy for local bond formation in an electric field.     

Fabrication of continuous fiber-reinforced thermoplastic composites with structural gradient from sheath-core type bicomponent fibers

Sheath-core type bicomponent fibers of polypropylene (PP) as a sheath component and thermotropic liquid crystalline polymer (TLCP) as a core component were prepared by the highspeed melt spinning process. Continuous fiber reinforced thermoplastic composites, in which TLCP acts as a reinforcing fiber and PP as a matrix polymer, were fabricated by the compression molding of these fibers. In the melt spinning, the attainable highest take-up velocity of TLCP was improved by co-processing with PP. Tensile modulus and strength of the TLCP component in the PP/TLCP bicomponent fibers increased with an increase in the take-up velocity. Comparison of wide-angle X-ray diffraction patterns of starting bicomponent fibers and fabricated composites indicated that the orientation relaxation of TLCP did not occur in the compression molding process. Accordingly, the tensile modulus and strength of the PP/TLCP composites were similar to those of the bicomponent fibers. Continuous fiber reinforced thermoplastic composites with various types of fiber content distributions were fabricated from the bicomponent fibers in which sheath-core composition was changed gradually in the spinning process. In the three-point bending test, the composites with two different types of symmetric structural gradients, one with higher TLCP fiber content near the surfaces than in the center and the other with higher TLCP content in the center than near the surfaces, exhibited different flexural moduli even though the overall TLCP contents were comparable. In the three-point bending test of a composite with asymmetric structural gradient, the yielding behavior and maximum flexural load varied depending on the direction of load application although the initial flexural moduli were similar.     

The effect of organoclay on the properties of a reactive hot melt polyurethane adhesive

In order to improve the initial bond strength of a reactive hot melt polyurethane adhesive (RHA), organoclay was added as a modifier. The organoclay caused a viscosity increase as well as a solid-like yield behavior of the RHA in melt state. The enhanced initial and final bond strength and reduced setting time showed that the organoclay improved both the solidification rate after application upon cooling and the bonding interaction. We examined tensile properties and X-ray diffraction patterns of RHAs, and the morphology was observed by transmission electron microscopy.     

Dynamics of the strength of adhesive-bond joints between polymers and steel

We have investigated the time dependences of the strength of adhesive bonds between polymers (epoxy adhesive and polyamide) and steel 45 at various temperatures. These dependences have been determined based on the rates of two opposite processes, viz., an increase in strength due to the formation of coordination bonds between polymer molecules and Fe²⁺ ions and a decrease in strength due to ruptures of adhesive or polyamide molecules under the effect of internal stresses. The values of activation energy of these processes have been determined.     

Strengthening of highly heat-resistant liquid-crystal polymer fibers upon heat treatment

Fibers of fully aromatic thermotropic liquid-crystal polymers containing mesogenic groups in the backbone are prepared on laboratory machines that make it possible to vary the conditions of jet spinning and subsequent heat treatment. The thermal and mechanical properties of the polymer fibers are investigated using differential thermal and thermomechanical analyses and strength measurements. It is found that, after spinning under optimum conditions, the strength of the fibers at room temperature is approximately equal to 1 GPa. After heat treatment under specially chosen conditions, the strength increases by a factor of two or three due to an increase in the activation energy of fracture. The role of crystallization and cross-linking in strengthening of liquid-crystal polymer fibers is elucidated.     

Effect of ultrasonic vibration on adhesive enhancement of plasma-modified nickel surface

Poor adhesion of nickel surface limits its further application in the aerospace field. In this study, plasma modification was conducted on the surface of the nickel plate pretreated by sandblasting, and then ultrasonic vibration was applied during the adhesively bonding process of the CFRP(Carbon fibre-reinforced polymer)/Ni joints. The bonding strength of the joints was increased by 65%. The adherend surface and the bonding interface were analyzed from microstructure, element distribution and chemical bonding to study the strengthening mechanism. By the sandblasting, irregular pits were formed on the nickel surface, effectively increasing the surface roughness. The plasma modification could introduce active functional groups including hydroxyl, amino and carbonyl on the nickel surface, which improved the surface wettability macroscopically. However, at a microscopic level, the adhesive with high viscosity and poor fluidity did not form a compact interface with the nickel. The ultrasonic application could promote the filling of the adhesive in irregular micro-scale pits on the surface, thereby strengthening the mechanical anchoring effect. Furthermore, the ultrasonic application produced dynamic impingement at the interface, enhancing the contact between the adhesive and the nickel plate. The adhesive molecules could fully collide and react with the active functional groups introduced on the nickel surface to form more chemical bonds, thus effectively improving the bonding strength of the CFRP/Ni joints.     

Surface investigation of adhesive formulation consisting of UV sensitive triblock poly(styrene–b-butadiene–b-styrene) copolymer

Atomic force microscopy (AFM) analysis in conjunction with macroscopic studies such as peel testing and contact angle measurement have been undertaken to explain the nanomechanical properties of adhesive formulation consisting of triblock poly(styrene–b-butadiene–b-styrene) (SBS) copolymers. The cross-linking of this photosensitive copolymer was investigated by analyzing the mechanical and morphological changes of each phase induced by the UV exposure. Main result is that the adhesive properties are strongly influenced by the cross-linking of the polybutadiene (PB) phase leading to an increase in the surface stiffness without affecting the surface energy. AFM analysis shows that the adhesion force is mostly governed by the contact area between the adhesive and the probe. The surface mobility may explain the increase in adhesion for this pressure sensitive copolymer.     

Molecular dynamics study on the effects of stamp shape, adhesive energy, and temperature on the nanoimprint lithography process

Molecular dynamics simulations of nanoimprint lithography (NIL) were performed to investigate the effects of three critical process parameters in NIL: stamp shape, adhesive energy between the stamp and polymer film, and imprint temperature. The proposed simulation model of the NIL process consists of an amorphous SiO₂ stamp with a line pattern, an amorphous poly(methylmethacrylate) film, and a Si substrate under the periodic boundary condition in the horizontal direction to simulate a real NIL process imprinting periodical line patterns. The behavior of polymer deformation and the effects of adhesion on pattern transfer were investigated by observing the deformation process, calculating the imprint and separation forces, and analyzing the density and stress distribution inside the polymer film. In addition, their dependency on the process parameters is also discussed with reference to the changes in pattern shape, adhesive energy between the stamp and polymer atoms, and imprint temperature of the polymer film. During the imprint process, the rectangular pattern shows inferior cavity filling and higher stress concentration compared to trapezoidal and triangular patterns because it requires much larger flow and deformation of the polymer film. Low imprint temperature also produces high stress concentration and large imprint force due to the lower fluidity of polymer film. In the separation process, the rectangular pattern generates the largest separation force and causes the most serious defects of the transferred pattern and even the polymer film, while the triangular pattern shows the most satisfactory pattern transfer. In addition, the adhesive energy between the stamp and the polymer film also strongly influences the adhesion between the stamp and the polymer film. Low adhesive energy reduces the separation force of the stamp and transferred pattern defects, and therefore enhances the quality of pattern transfer.     

Characterization of Kovar-to-Kovar laser welded joints and its mechanical strength

For the packaging of a pump laser in butterfly package, the most crucial assembly step is the fiber-to-laser diode coupling and attachment. The use of laser welding as the joining method offers several advantages if compared with the adhesive joints: strong joining strength, short process time and less contamination. This paper reports on laser welding process characteristics; weld strength and its fracture mode. The penetration depth and melt area of laser spot welds were found to be complicated functions of laser pulse energy, intensity, and beam diameter. Effects of pulse width, input power and size of the focal spot on the rate of energy input to the workpieces and consequently, the weld strength were reported. The weld strength was found to be dependent on the overlapping area between the two joining materials. Surface roughness, R_a, has influence on the fraction of energy absorbed, A, and therefore, affecting the penetration depth. Thermal analysis was carried out on the laser-welded joints and its heat-affected zone (HAZ) induced by various power densities was examined. These data are important in order to optimize and utilize the laser welding process as an effective manufacturing tool for fabrication of reliable pump laser.     

Study on the Non-isothermal Melt Crystallization Kinetics of PTT/PBT Blends

Macro-kinetic models, namely the modified Avrami, Ozawa, Mo, and Kissinger models, were applied to investigate the non-isothermal melt crystallization process of PTT/PBT blends by DSC measurements. It was found that the modified Avrami model can describe the non-isothermal melt crystallization processes of PTT/PBT blends fairly well. When the cooling rates range from 5 to 20°C/min, the Ozawa model could be used to satisfactorily describe the early stage of crystallization. However, the Ozawa model didn't fit the polymer blends in the late stage of crystallization, because it ignored the influence of secondary crystallization. Under the conditions of the non-isothermal melt crystallization, it was found that the cooling rates and the blend composition affect the crystallization for blends according to Kissinger crystallization kinetics parameters. The crystallization kinetics constant K_a increases with increasing cooling rate, indicating the crystallization rates of PTT, PBT, and PTT/PBT blends were improved. The crystallization kinetic activation energy parameters are good agreement with the results from isothermal crystallization processes of the polymer blends. The crystallization activation energy of PTT/PBT blends is higher than the activation energy of PTT and PBT.     

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.     

摩擦导致的聚合物表层微观结构改变

应用大规模分子动力学方法, 模拟了锥形探头在非晶态聚合物薄膜表面的滑动摩擦过程, 研究了摩擦导致的聚合物薄膜表层微观结构改变, 以及探头与基体间黏着作用、滑动速度和分子链长度对基体表层微观结构改变的影响. 当探头与基体之间为黏着作用时, 摩擦导致基体表面滑痕区域的键取向沿滑动方向重新取向, 导致表层分子链回转半径沿滑动方向伸长, 并且这些表层微观结构的改变程度随滑动速度的减小而增大. 在摩擦导致结构改变的过程中, 链端单体和链中单体的贡献作用不同, 形成了不同的分子链拉伸变形机制. 当样本缠结度较大或探头滑动速度较小时, 相比于链中单体, 探头对链端单体的拖曳作用使更多分子链发生拉伸变形. 研究还发现, 在探头与聚合物薄膜系统中, 使薄膜表层微观结构发生改变是摩擦能量耗散的重要途径.     

Classical stochastic model of laser-stimulated surface processes and the selective nature of laser excitation via multiphonon couplings

The dynamical behavior of laser-stimulated surface processes (LSSP) is studied by the generalized Langevin equation via the memory effects of the damping kernel, the dephasing kernel and mode-mode interactions. The temperature-dependent averaged energy absorption rate (which characterizes the line shape) is calculated by solving the Laplace-Fourier transform of the velocity correlation function. The features of the response function and its overall line broadening are discussed in terms of Markovian processes. The nature of LSSP and laser-selective effects are discussed in terms of the multiphonon coupling strength and the related “internal resonant” condition. It is shown that laser-selective bond breaking is possible for a slow intramolecular vibrational relaxation rate which is governed by a high-order multiphonon process or a far off “internal resonance”.     

聚苯乙烯/纳米铝复合材料的流变特性及纺丝研究

为有效制得Z箍缩氘代聚苯乙烯/纳米铝(DPS/AlNPs)导电丝阵材料，采用PS中掺入AlNPs制备PS/AlNPs复合材料纤维进行模拟研究。研究了温度及剪切速率等因素对PS/AlNPs复合材料流变性能的影响、复合材料熔体的结构变化及流动状态与可纺性能的关系，以及PS/AlNPs纤维的形貌、热稳定性能和力学性能。结果表明:PS/AlNPs熔体属于典型剪切变稀型非牛顿流体，熔体的表观粘度与温度呈现负相关，240~260 ℃时复合材料的非牛顿指数介于0.462~0.546，结构黏度系数介于1.8~2.1，黏流活化能介于77.2~104.6 kJ·mol-1，具有良好的可纺性。PS/AlNPs纤维表面光滑，对AlNPs粒子包覆良好且对其抗氧化非常有利，其中当AlNPs质量分数为1%时纤维的断裂伸长率突出、掺量为5%时其断裂强度较高。     

准分子激光增强高分子材料粘着力的机理研究

 由热方程计算激光与液体薄膜材料相互作用时的温度场,分析高分子材料表面熔化及材料表面液体膜汽化产生的材料的表面粗化;近一步分析高分子的断裂、F原子 替代等光化学反应;从而提出激光增强高分子材料的粘着力的表面粗化和光化学反应的机理。     

Experimental evidence for an intrinsic route to polymer melt fracture phenomena: a nonlinear instability of viscoelastic Poiseuille flow

The production rate of polymer fibers by extrusion is usually limited by the appearance of a series of instabilities ("melt fracture") that lead to unwanted undulations of the surface. We present both qualitative and quantitative experimental evidence that-in addition to previously known polymer-specific scenarios-there is an intrinsic route towards melt fracture type phenomena: a nonlinear ("subcritical") instability of viscoelastic Poiseuille flow.     

Propagation of ultrasonic guided waves in lap-shear adhesive joints: case of incident a0 Lamb wave

This paper deals with the propagation of ultrasonic guided waves in adhesively bonded lap-shear joints. The topic is relevant to bond inspection by ultrasonic testing. Specifically, the propagation of the lowest-order, antisymmetric a0 mode through the joint is examined. An important aspect is the mode conversion at the boundaries between the single-plate adherents and the multilayer overlap. The a0 strength of transmission is studied for three different bond states in aluminum joints, namely a fully cured adhesive bond, a poorly cured adhesive bond, and a slip bond. Theoretical predictions indicate that the dispersive behavior of the guided waves in the multilayer overlap is highly dependent on bond state. Experimental tests are conducted in lap-shear joints by a hybrid, broadband laser/air-coupled ultrasonic setup in a through-transmission configuration. The Gabor wavelet transform is employed to extract energy transmission coefficients in the 100 kHz 1.4 MHz range for the three different bond states examined. The cross-sectional mode shapes of the guided waves are shown to have a substantial role in the energy transfer through the joint.     

原子力显微镜在轻敲模式下的动力学模型

基于Hamaker假设、Lennard-Jones势能定律及经典弹性理论建立了一种新型的球体与平面黏着接触的弹性模型，该模型显示黏着力在原子力显微镜(AFM)针尖趋近和撤离样品表面，即加载和卸载的两个过程中存在黏着滞后现象，表明了AFM在轻敲工作模式中存在能量耗散.同时，根据所建的黏着接触弹性模型，建立了AFM在轻敲工作模式下的动力学模型，研究了AFM在轻敲工作模式下的振动幅度、相位差及耗散功率随针尖与样品表面间距的变化规律，仿真结果与现有的实验结果相一致.     

Mechanics of plasma exposed spin-on-glass (SOG) and polydimethyl siloxane (PDMS) surfaces and their impact on bond strength

Silicone polymer (PDMS), widely used for micro-fluidic and biosensor applications, possesses an extremely dynamic surface after it is subjected to an oxygen plasma treatment process. The surface becomes extremely hydrophilic immediately after oxygen plasma exposure by developing silanol bond (SiOH), which promotes its adhesion to some other surfaces like, silicon, silicon dioxide, glass, etc. Such a surface, if left in ambient dry air, shows a gradual recovery of hydrophobicity. We have found an identical behavior to occur to surfaces coated with a thin continuous film of SOG (methyl silsesquioxane). The chemistry induced by oxygen plasma treatment of a spin-on-glass (SOG) coated surface provides a much higher density of surface silanol groups in comparison to precleaned glass, silicon or silicon dioxide substrates thus providing a higher bond strength with polydimethyl siloxane (PDMS). The bonding protocol developed by using the spin coated and cured SOG intermediate layer provides an universal regime of multi level wafer bonding of PDMS to a variety of substrates. The paper describes a contact angle based estimation of bond strength for SOG and PDMS surfaces exposed to various combinations of plasma parameters. We have found that the highest bond strength condition is achieved if the contact angle on the SOG surface is less than 10°.     

Vertical manipulation of native adatoms on the InAs(111)A surface

We achieved the repositioning of native In adatoms on the polar III-V semiconductor surface InAs(111)A-(2?×?2) with atomic precision in a scanning tunnelling microscope (STM) operated at 5?K. The repositioning is performed by vertical manipulation, i.e., a reversible transfer of an individual adatom between the surface and the STM tip. Surface-to-tip transfer is achieved by a stepwise vibrational excitation of the adsorbate-surface bond via inelastic electron tunnelling assisted by the tip-induced electric field. In contrast, tip-to-surface back-transfer occurs upon tip-surface point contact formation governed by short-range adhesive forces between the surface and the In atom located at the tip apex. In addition, we found that carrier transport through the point contact is not of ballistic nature but is due to electron tunnelling. The vertical manipulation scheme used here enables us to assemble nanostructures of diverse sizes and shapes with the In adatoms residing on vacancy sites of the (2?×?2)-reconstructed surface (nearest-neighbour vacancy spacing: 8.57??).