SH ultrasonic guided waves for the evaluation of interfacial adhesion

Shear-Horizontally (SH) polarized, ultrasonic, guided wave modes are considered in order to infer changes in the adhesive properties at several interfaces located within an adhesive bond joining two metallic plates. Specific aluminium lap-joint samples were produced, with different adhesive properties at up to four interfaces when a glass–epoxy film is inserted into the adhesive bond. EMAT transducers were used to generate and detect the fundamental SH₀ mode. This is launched from one plate and detected at the other plate, past the lap joint. Signals are picked up for different propagation paths along each sample, in order to check measurement reproducibility as well as the uniformity of the adhesively bonded zones. Signals measured for four samples are then compared, showing very good sensitivity of the SH₀ mode to changes in the interfacial adhesive properties. In addition, a Finite Element-based model is used to simulate the experimental measurements. The model includes adhesive viscoelasticity, as well as spatial distributions of shear springs (with shear stiffness K_T) at both metal–adhesive interfaces, and also at the adhesive–film interfaces when these are present. This model is solved in the frequency domain, but temporal excitation and inverse FFT procedure are implemented in order to simulate the measured time traces. Values of the interfacial adhesive parameters, K_T, are determined by an optimization process so that best fit is obtained between both sets of measured and numerically predicted waveforms. Such agreement was also possible by adjusting the shear modulus of the adhesive component. This work suggests a promising use of SH-like guided modes for quantifying shear properties at adhesive interfaces, and shows that such waves can be used for inferring adhesive and cohesive properties of bonds separately. Finally, the paper considers improvements that could be made to the process, and its potential for testing the interfacial adhesion of adhesively bonded composite components.     

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.     

Improving the adhesion between a aqueous PU and a polyamide fibre with silane

Glycidoxypropyltrimethoxysilane (GPS) and γ-aminopropyltrimethoxysilane (APS) were used to modify the surface chemistry of polyamide fibre. The surface chemistry was characterised using X-ray photoelectron spectroscopy. The silanol functional group was designed to be introduced on the surface of polyamide fibre to increase its chemical activity by N-alkylation of GPS and hydrolysis of APS, and to improve the poor interfacial adhesion between a polyamide 66 fibre and an aqueous polyurethane polymer adhesive. The microbond test was used to measure the interfacial shear strength between the waterborne PU adhesive and the polyamide fibre. It has been found that APS hydrolysis and GPS-alkylated fibre surface can be used to improve the interfacial adhesion of polyamide fibre to PU. The IFSS can be improved by N-alkylation of GPS from 5.0 to 8.4?MPa. After water immersion at 50?°C for 48?h, then drying, the IFSS increased to 8.8?MPa due to the plasticisation of PU in water. Better interfacial adhesion was also observed by the hydrolysis of APS, but not significantly improved by this method due to the relatively weak hydrogen bond at the interface between APS and polyamide fibre.     

Measurement of adhesion energies and Young's modulus in thin polymer films using a novel axi-symmetric peel test geometry

We present a novel method of probing adhesion energies of solids, particularly polymers. This method uses the axi-symmetric deformation of a thin spincast polymer membrane brought into contact with a flat substrate to probe the work of adhesion. The use of a thin membrane minimizes uncertainty in the radius of contact, while the use of spincast films provides very smooth surfaces by means of a very simple method. The experimental profile of the deformed membrane shows good agreement with the expected logarithmic profile. The experimental setup enables the measurement of Young's modulus and the solid-solid work of adhesion for thin films. The value obtained for Young's modulus of polystyrene (PS) was found to be in agreement with other conventional measurement techniques. In addition, measurement of the work of adhesion at the PS/silicon oxide interface was possible. The apparatus is well suited to studying the dependence of Young's modulus, work of adhesion and fracture energy on membrane thickness, temperature, pulling rate, and ageing of the interface, and can readily be modified to study biologically relevant samples.     

SiC过渡层对氟化类金刚石薄膜附着特性的影响

采用射频反应磁控溅射法在316L不锈钢基片上分别沉积了两种薄膜:一种是氟化类金刚石薄膜(F-DLC),另一种是先镀上一定厚度的SiC过渡层再沉积F-DLC.着重研究了薄膜的附着力随过渡层制备条件的变化规律.结果显示,增加SiC过渡层后薄膜的附着力明显增加,且附着力随SiC过渡层的制备条件有所变化,在射频输入功率为200 W,沉积时间5min制备出的SiC过渡层上再沉积F-DLC时,附着力可达8.7 N,远高于未加过渡层时F-DLC膜的附着力(4 N).通过研究SiC的沉积速率曲线、表面形貌和红外光谱,探讨了SiC过渡层及其制备条件影响薄膜附着力的相关机制.     

Adhesive fracture of heterogeneous interfaces

We have studied the effect of interface heterogeneity on fracture, at both local and global scales. The single cantilever beam adhesion test was used to investigate interfacial fracture between polycarbonate plates and an elastic/fragile epoxy adhesive. Two surface treatments were applied to a (given) polycarbonate plate giving zones of strong and weak adhesion parallel to the crack direction. Calculated fracture energies differed from those expected from a simple rule-of-mixtures. A perturbation method, proposed by Rice, was used and results compared with crack fronts observed in situ. The technique was applied successfully but the difference in values of stress intensity factor between the zones was found substantially different from the experimental value. In an attempt to explain discrepancies, specimens with discontinuous crack fronts (adhesive and/or plates severed along the strong/weak adhesion frontier) were tested. Good agreement was found with the rule-of-mixtures predictions raising questions about the role of crack front continuity in load transfer.     

Energy release rate and stress field calculation for debonding crack extension at the fibre-matrix interface during single-fibre pull-out

For the micromechanical modelling of the macroscopic failure of fibre-reinforced composites the formulation of a critical parameter for initiation and extension of debonding cracks at the fibre-matrix interface is essential. This point is discussed for the 'fibre pull-out' specimen, a test commonly used to measure the adhesion quality of fibre-matrix systems. Some of the simplifying assumptions fundamental to shear lag theory-based models of the fibre pull-out test are compared with results from a detailed finite element (FE) model to examine their validity. The FE model strongly contradicts assumptions made with the shear lag theory that the axial stress gradient in the matrix can be neglected from the equilibrium equation. A critical interface shear strength is commonly used as a measure of adhesion quality. But for elastic materials the nature of the stress concentrations at the fibre end and interface crack-tip are singular. Therefore a fracture mechanic approach is better suited for a debonding criterion than a simple finite shear strength. The energy release rate shows a minimum for short crack lengths and may stabilize the moving crack.     

三层介质超声谐振模式随材料和界面粘接性能变化的演变规律

在用超声波谐振对粘接材料的粘接强度进行无损评估时, 不同模式对粘接强度的敏感程度受到众多因素和参数的影响, 对检测结果的可靠性至关重要. 基于多层介质中声传播和界面弱粘接边界条件的理论模型, 将一个上下非对称的金属-粘接剂-金属三层结构的平面波反射系数函数中的谐振模式看作是上下铝金属层各自的Lamb波频散模式通过夹心粘接剂层相互耦合后叠加组成. 改变影响结构粘接强度的因素, 即粘接剂的性能参数(声阻抗、密度、厚度)和界面切向劲度系数k_t来分析三层结构谐振模式耦合方式的变化,得出结论: 粘接结构粘接性能的变化基本上不改变与被粘铝层相关的固有部分的Lamb波模式, 而它们的耦合模式则在谐振频率上产生平移并会与固有模式进行交换和替代; 不同参数的变化引起的模式演变有各自的规律, 大多可彼此区分.     

Relationship between fibre-matrix adhesion and the interfacial shear strength in polymer-based composites

A model is proposed to correlate the interfacial shear strength at the fibre-matrix interface, measured by means of a fragmentation test on single fibre composites, to the reversible work of adhesion between both solids, this quantity being defined as the sum of the dispersive and the acid-base interactions (physical interactions) between the fibre and the matrix. Whatever the nature of the fibres and the matrices, a linear relationship, passing through the origin, is established between the interfacial shear strength and the reversible work of adhesion. However, the slope of this straight line depends on the elastic properties and, more precisely, on the elastic moduli of both the fibre and the matrix. This leads us to express the reversible work of adhesion as the product of a mean intermolecular distance at the interface and an adhesive pressure related to the interfacial shear strength. The limits of the theoretical and experimental approaches leading to the establishment of such a model, as well as its domain of validity, are discussed.     

Vapor Pressure Assisted Void Growth and Cracking of Polymeric Films and Interfaces

Pores and cavities form at filler particle-polymer matrix interfaces, at polymer film-silicon substrate interfaces as well as in molding compounds of IC packages. Moisture diffuses to these voids. During reflow soldering, surface mount plastic encapsulated devices are exposed to temperatures between 210 to 260°C. At these temperatures, the condensed moisture vaporizes. The rapidly expanding water vapor can create internal pressures within the voids that reach 3–6 MPa. These levels are comparable to the yield strengths of epoxy molding compounds and epoxy adhesives, whose glass transition temperatures T _g range between 150 to 300°C. Under the combined action of thermal stress and high vapor pressure (relative to the yield strength at T _g), both pre-existing and newly nucleated voids grow rapidly and coalesce. In extreme situations, vapor pressure alone could drive voids to grow and coalesce unstably causing film rupture, film-substrate interface delamination and cracking of the plastic package.Vapor pressure effects on void growth have been incorporated into Gurson's porous material model and a cohesive law. Crack growth resistance-curve calculations using these models show that high vapor pressure combined with high porosity bring about severe reduction in the fracture toughness. In some cases, high vapor pressure accelerates void growth and coalescence resulting in brittle-like interface delamination. Vapor pressure also contributes a strong tensile mode component to an otherwise shear dominated interface loading. An example of vapor pressure related IC package failure, known as popcorn cracking, is discussed.     

A novel surface treatment process for enhanced adhesion of ultra-high modulus polyethylene fibres to epoxy resins

Ultra-high modulus polyethylene (UHMPE) fibres have been treated using a novel 'non-plasma' treatment allowing the incorporation of various chemical functional groups onto the polymer surface. The process comprises two steps: corona discharge treatment, followed by silanization of the polymer surface by a solution of an organo-functional silane. Corona discharge treatment incorporates oxygen-containing functionalities, e.g. reactive hydroxyl groups, onto the polymer surface. The presence of reactive -OH groups provides the possibility of covalent linkage of any organo-functional silane to the corona discharge-treated polymer in the form of a fibre, film, sheet, or powder. The effectiveness of the process was assessed by examining the interlaminar fracture energy and flexural modulus and by SEM analysis of the fracture surfaces of composites fabricated from the untreated, corona discharge-treated, ammonia plasma-treated, and the amine-grafted (using the novel process) UHMPE fabric. A significant improvement in interfacial adhesion was confirmed by increases in the interlaminar fracture energies and flexural moduli. The effectiveness of the process investigated is similar to the ammonia plasma treatment. SEM analysis of the fracture surfaces indicated a change in the fracture mode from purely adhesive for unmodified fibres, through to mixed failure mode for corona-treated material, to highly cohesive-in-fibre surface for amine-grafted UHMPE fibres. XPS analysis confirmed the incorporation of the amine groups onto the surface of polyethylene treated using the novel method.     

Bonding Interface Imaging and Shear Strength Prediction by Ultrasound

The propagation of a longitudinal ultrasonic wave normally incident upon an adhesively bonded structure is studied. The structure consists of adherend and adhesive layers with finite thickness. Interfaces between adherend and adhesive are regarded as distributed springs. Theoretical and experimental results show that resonant frequencies of the bonded structure vary sensitively with the interface stiffness constants and adhesive thickness, and these interface characteristics are inversed by the simulation annealing (SA) method. Furthermore, the distribution image of interface stiffnesses is compared with the state of fracture interface, and quantitative prediction of shear strength is achieved based on the distribution of interface stiffnesses and adhesive thicknesses by using a back-propagation neutral network. The average relative error of the shear strength from prediction to real value is 10.7%.     

Interfacial adhesion between semi-crystalline polymers (polypropylene and nylon-6): in situ compatibilized interface and fracture mechanism

The interfacial fracture toughness between semi-crystalline polymers (polyamide/polypropylene) were studied to understand the failure mechanisms at the interface, especially when the interface was reinforced by an in situ compatibilizer. Based on the observation of the interface using scanning electron microscopy and wide angle X-ray spectroscopy, it was revealed that crystalline structure of polypropylene was not affected by the in situ compatibilizer at the interface. The reinforcing mechanism could be qualitatively identified by investigating the evolution of fracture toughness as a function of annealing time and temperature. The adhesion strength increased with the annealing time. Depending on the annealing temperature, the fracture toughness passed a peak value and then reached a plateau after some bonding time. As long as the chain length of the compatibilizer is long enough to form entanglements with the molecules at both bulk sides, the fracture at the interface is decided by the balance between adhesion strength at the interface and cohesive strength in the weak modulus side; the failure locus follows the lower one. Thus, adhesive failure occurred first when the reaction at the interface did not occur long enough to provide high adhesive strength at the interface, but the cohesive failure occurred in the crack propagation side after the adhesive strength value became higher than the cohesive strength value.     

Calculation of the Viscosity of Polymer Melts Based on Measurements of the Recovered Rubber-Like Deformation

On the basis of a model of polymer flow, considering the forces of entropic elasticity of extended macromolecules within the Eyring's concept, the relationships between the shear rate, shear stress, viscosity, and recovered rubber-like deformation were derived. The reduction of activation energy of the flow, by an amount proportional to the recovered rubber-like deformation, leads to an exponential decrease of viscosity with increasing shear rates; this nonlinear dependence of viscosity on shear rate (and shear stress) is defined as the viscosity anomaly of polymers. The measurement of deformation recovery after the cessation of polymer flow in the mode of constant shear rate or shear stress on a rotational viscometer confirmed the validity of the theoretical dependences.     

单层单晶石墨烯与柔性基底界面性能的实验研究

单晶石墨烯具有更优异的力学及电学性能,有望成为新一代柔性电子器件的核心材料.因此,有必要从实验的角度精细分析化学气相沉积法制得的大尺度单晶石墨烯与柔性基底复合结构的界面力学行为.本文通过显微拉曼光谱实验方法测量了不同长度的单层单晶石墨烯/PET(聚对苯二甲酸乙二醇酯)基底的界面力学性能参数及其在长度方向上界面边缘的尺度效应.实验给出了石墨烯在PET基底加载过程中与基底间黏附、滑移、脱黏三个界面状态的演化过程与应力分布规律.实验发现,单晶石墨烯与柔性基底间由范德瓦耳斯力控制的界面应变传递过程存在明显的边缘效应,并且与石墨烯的长度有关.界面的切应力具有尺度效应,其值随石墨烯长度的增加而减小,而石墨烯界面传递最大应变以及界面脱黏极限则不受试件尺度的影响.     

Effect of surface-grafted molecular brushes on the adhesion performance of bonded polymers and composite interfaces

This paper reviews the theoretical principles of the macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion and fracture performance of composite materials and adhesively bonded assemblies. Subsequently, a relatively simple and industry-feasible technology for surface grafting molecular brushes is discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesive, elastomer or matrix material. This occurs even after prolonged exposure of investigated systems to adverse environments such as hot water.     

Structural, morphological, wettability and thermal resistance properties of hydro-oleophobic thin films prepared by a wet chemical process

The structural properties of fluorine containing polymer compounds make them highly attractive materials for hydro-oleophobic applications. However, most of these exhibit low surface energy and poor adhesion on the substrates. In the present investigation, crack free, smooth and uniform thin films of poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole]-co-tetrafluoroethylene (TFD-co-TFE) with good adhesion have been deposited by wet chemical spin-coating technique on polished AISI 440C steel substrates. The as-deposited films (xerogel films) have been subjected to annealing for 1 h at different temperatures ranging from 100 to 500 °C in an argon atmosphere. The size growth of the nano-hemispheres increased from 8 nm for xerogel film to 28 nm for film annealed at 400 °C. It was found that as the annealing temperature increased from 100 to 400 °C, nano-hemisphere-like structures were formed, which in turn have shown increase in the water contact angle from 122° to 147° and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80 °C as well as exposed to steam for 8 days for 8 h/day indicating thermal stability of the film.     

Water and oil repellency of flexible silica-coated polymeric substrates

A facile coating technique was used for the one-step creation of silica-sphere layers onto flexible polypropylene (PP) substrates, which showed the enhanced repellency toward liquid droplets with different surface tensions, ranging from 25.6 to 72.3 mN/m. One-step solution preparation comprised the homogenous mixing of colloidal silica nanospheres and perfluoroalkyl methacrylic copolymer, and the resulting F-silica slurry was subsequently deposited over the PP films, which showed good adhesion. The flexible silica-coated polymeric film displayed a remarkable repellency toward water and oil drops, when compared with the F-coated PP flat film. The silica-stacking layers on the PP substrate generated a roughened surface, owing to the creation of bionic surface hierarchically combined with multiple-scale architecture. To clarify this, the wetted fraction was determined from Cassie-Baxter equation, and the work of adhesion, based on Young-Duprè equation, was used to examine the sliding ability of the resulting polymeric films. The cross-cut test incorporated with film bending proved the excellent adherence between silica layer and PP substrate. A satisfactory durability in water and oil immersions for 10 days showed that the resulting PP film possesses strong adhesion and better repellency for a long period, confirming a promising commercial feasibility.     

Fracture Mechanics Studies of Adhesion in Biological Systems

A fracture mechanics based methodology for quantifying adhesive interactions between soft solids, or between a soft solid and a rigid substrate, is reviewed. An emphasis is placed on the application of these techniques to the characterization of adhesive interactions in biological systems. Results from experiments involving the adhesion of gelatin hydrogels to hydrophilic and hydrophobic substrates are described as an illustration of the application of these methods. In these experiments a hemispherical gelatin cap is brought into contact with a flat surface. Separation of the two materials is described in terms of crack propagation along the gelatin/substrate interface. Simultaneous measurements of the applied load, the resulting displacement, and the contact area between the two materials enable us to determine the elastic modulus of the cap, in addition to the crack driving force, or energy release rate. The adhesive behavior of the interface is quantified by the relationship between the energy release rate and the crack velocity. Analogies are made to information obtained from contact angle measurements, and from measurements made with the Israelachvili surface forces apparatus.     

Castor Oil-Based Polyurethane/Epoxy Intercross-linked Polymer Network Adhesives for Metal Substrates

Castor oil based polyurethane (CO-PU) was first synthesized from castor oil and 4, 4’-diphenyl-methane-diisocyanate (MDI). Then, a series of CO-PU/epoxy (EP) intercross-linked polymer network (ICPN) adhesives for metal substrates were prepared by a sequential method. The functional groups, tack -free time, mechanical properties, adhesive properties, and thermal stability were studied. Fourier transform infrared spectroscopy analysis indicated that an ICPN structure was formed through the introduction of CO-PU into EP. Results of adhesive measurements showed that the maximal value of lap shear strength was achieved at the CO-PU content of 20%. Thermogravimetric analysis results indicated that thermal stability of the adhesive film decreased with increased CO-PU content.