Strength, deformation and relaxation of joints bonded with modified cyanoacrylate adhesives

The introduction of high molecular weight poly(methyl methacrylate) or poly(butadiene-co-acrylonitrile) into ethyl 2-cyanoacrylate produced viscous adhesives with a homogeneous or heterogeneous structure after cure. Steel joints bonded with these adhesives are shown to have improved tensile shear strength, deformability and stress relaxation of bonds compared with pure cyanoacrylate adhesive. Poly(methyl methacrylate)-modified adhesive is recommended for static load-bearing joints while poly(butadiene-co-acrylonitrile)-modified adhesive is more suited to cyclic or vibrating loads.     

Comparison of fracture behavior between acrylic and epoxy adhesives

An experimental study was conducted on the strength of adhesively bonded steel joints, prepared epoxy and acrylic adhesives. At first, to obtain strength characteristics of these adhesives under uniform stress distributions in the adhesive layer, tensile tests for butt, scarf and torsional test for butt joints with thin-wall tube were conducted. Based on the above strength data, the fracture envelope in the normal stress-shear stress plane for the acrylic adhesive was compared with that for the epoxy adhesive. Furthermore, for the epoxy and acrylic adhesives, the effect of stress triaxiality parameter on the failure stress was also investigated. From those comparison, it was found that the effect of stress tri-axiality in the adhesive layer on the joint strength with the epoxy adhesive differed from that with the acrylic adhesive. Fracture toughness tests were then conducted under mode l loading using double cantilever beam (DCB) specimens with the epoxy and acrylic adhesives. The results of the fracture toughness tests revealed continuous crack propagation for the acrylic adhesive, whereas stick-slip type propagation for the epoxy one. Finally, lap shear tests were conducted using lap joints bonded by the epoxy and acrylic adhesives with several lap lengths. The results of the lap shear tests indicated that the shear strength with the epoxy adhesive rapidly decreases with increasing lap length, whereas the shear strength with the acrylic adhesive decreases gently with increasing the lap length.     

Adhesion Studies of Mixtures of Ethyl Cyanoacrylate with a Difunctional Cyanoacrylate Monomer and with other Electron-deficient Olefins

Alkyl cyanoacrylate instant adhesives are widely used because of their fast cure speed and versatility on a large number of substrates. Recent performance improvements, such as increased thermal resistance, resulted from the addition of latent acids and polymers, which do not copolymerize with the adhesive monomer, to the adhesive formulations. However, use of these additives can increase fixture time or reduce the final adhesive strength.

Two methods for possibly improving alkyl cyanoacrylate instant adhesives, without loss of cure speed or adhesive properties, could be either crosslinking the alkyl cyanoacrylate monomer with a dicyanoacrylate or copolymerizing it with a second 1, 1 disubstituted electron-deficient olefin. A crosslinker. 1,4 butanediol dicyanoacrylate (BDDCA) and two monofunctional monomers, diethyl methylenemalonate (DEMM) and N,N diethyl-2-cyanoacrylamide (DECA), were prepared, in good purity, for adhesion studies with ethyl cyanoacrylate (ECA). Crosslinking ECA with BDDCA does improve solvent resistance, as determined by solvent swelling experiments. Glass fixture times are approximately the same for ECA, crosslinked ECA, the pure monomers, and monomer mixtures with ECA, while steel fixture times are generally slower. Crosslinking ECA with BDDCA does not improve lap-shear adhesion, either at room temperature or after thermal exposure at 121°C. Lap-shear strength data, before and after heat exposure, revealed that the ECA/DEMM and the ECA/DECA monomer mixtures exhibit weaker lap-shear adhesive strength than ECA alone.     

Effect of silicon carbide nanoparticles on the adhesion strength of steel–epoxy composite joints bonded with acrylic adhesives

This paper reports a study on the effect of silicon carbide nanoparticles on the adhesion strength of steel–glass/epoxy composite joints bonded with two-part structural acrylic adhesives. The introduction of nanosilicon carbide in the two-part acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strengths of the adhesive joints increased with adding the filler content up to 1.5?wt%, after which decreased with adding more filler content. Also, addition of nanoparticles caused a reduction in the peel strength of the joints. DSC analysis revealed that Tg values of the adhesives rose with increase in the nanofiller content. The equilibrium water contact angle was decreased for adhesives containing nanoparticles. SEM micrographs revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.     

Process optimization of solvent based polybenzimidazole adhesive for aerospace applications

The use of adhesive bonding for high temperature applications is becoming more challenging because of low thermal and mechanical properties of commercially available adhesives. However, the development of high performance polymers can overcome the problem of using adhesive bonding at high temperature. Polybenzimidazole (PBI) is one such recently emerged high performance polymer with excellent thermal and mechanical properties. It has a tensile strength of 160 MPa and a glass transition of 425 °C. Currently, PBI is available in solution form with only 26% concentration in Dimethyl-acetamide solvent. Due to high solvent contents, the process optimization required lot of efforts to form PBI adhesive bonded joints with considerable lap shear strength. Therefore, in present work, efforts are devoted to optimize the adhesive bonding process of PBI in order to make its application possible as an adhesive for high temperature applications. Bonding process was optimized using different curing time and temperatures. Epoxy based carbon fiber composite bonded joints were successfully formed with single lap shear strength of 21 Mpa. PBI adhesive bonded joints were also formed after performing the atmospheric pressure plasma treatment of composite substrate. Plasma treatment has further improved the lap shear strength of bonded joints from 21 MPa to 30 MPa. Atmospheric pressure plasma treatment has also changed the mode of failure of composite bonded joints.     

Adhesive strength of steel–epoxy composite joints bonded with structural acrylic adhesives filled with silica nanoparticles

This paper reports a study on the effect of silica nanoparticles on the adhesion strength of steel–glass/epoxy composite joints bonded with two-part structural acrylic adhesives. The introduction of nano-silica in the two-part acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strengths of the adhesive joints increased with addition of the filler content up to 1.5 wt%, after which decreased with addition of more filler content. Also, addition of nanoparticles caused a reduction in the peel strength of the joints. Differential scanning calorimeter analysis revealed that T_g values of the adhesives rose with increasing the nanofiller content. The equilibrium water contact angle was decreased for adhesives containing nanoparticles. Scanning electron microscope micrographs revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.     

Shear behaviour of structural silicone adhesively bonded steel-glass orthogonal lap joints

This paper outlines an experimental study on the shear behaviour of structural silicone adhesively bonded steel-glass orthogonal lap joints. In the combination of steel plate and glass panel to form a hybrid structural glazing system, bonded joints with structural silicones can provide certain flexibility which relieves stress peaks at critical points of glass panel. The cohesive failure and its related fracture pattern of test joints with varied geometries of adhesives are examined experimentally. It is shown that the presence of two failure modes as discrete voids and macro cracks is closely related to the adhesive thickness. The effects of geometric parameters of adhesives on the joint shear strength are examined. It is demonstrated that the joint shear strengths are increased with increased individual overlap length, reduced adhesive thickness or increased adhesive width while the shear deformation corresponding to maximum shear force is mostly influenced by adhesive thickness. Mechanical contributions for those effects are analyzed accordingly. Finally, an analytical formula allowing for the equilibrium of strain and force on the adhesive and adherend is proposed for the analysis of shear strength. It is demonstrated that calculated normalized shear force ratios predicted by proposed formula agree well with those from experimental results.     

Failure behavior of adhesively bonded joints with a rubber modified epoxy adhesive under tensile-shear combined cyclic loading

Rubber-modified epoxy adhesives are used widely as structural adhesive owing to their properties of high fracture toughness. In many cases, these adhesively bonded joints are exposed to cyclic loading. Generally, the rubber modification decreases the static and fatigue strength of bulk adhesive without flaw. Hence, it is necessary to investigate the effect of rubber-modification on the fatigue strength of adhesively bonded joints, where industrial adhesively bonded joints usually have combined stress condition of normal and shear stresses in the adhesive layer. Therefore, it is necessary to investigate the effect of rubber-modification on the fatigue strength under combined cyclic stress conditions. Adhesively bonded butt and scarf joints provide considerably uniform normal and shear stresses in the adhesive layer except in the vicinity of the free end, where normal to shear stress ratio of these joints can cover the stress combination ratio in the adhesive layers of most adhesively bonded joints in industrial applications.

In this study, to investigate the effect of rubber modification on fatigue strength with various combined stress conditions in the adhesive layers, fatigue tests were conducted for adhesively bonded butt and scarf joints bonded with rubber modified and unmodified epoxy adhesives, wherein damage evolution in the adhesive layer was evaluated by monitoring strain the adhesive layer and the stress triaxiality parameter was used for evaluating combined stress conditions in the adhesive layer. The main experimental results are as follows: S–N characteristics of these joints showed that the maximum principal stress at the endurance limit indicated nearly constant values independent of combined stress conditions, furthermore the maximum principal stress at the endurance limit for the unmodified adhesive were nearly equal to that for the rubber modified adhesive. From the damage evolution behavior, it was observed that the initiation of the damage evolution shifted to early stage of the fatigue life with decreasing stress triaxiality in the adhesive layer, and the rubber modification accelerated the damage evolution under low stress triaxiality conditions in the adhesive layer.     

结构胶胶接接头耐久性的研究进展

结构胶是胶黏剂中具有高强度、耐高温、高耐久特性的一类胶黏剂的总称,主要用于部件中承受载荷的胶接连接。胶接接头的耐久性能是结构胶应用中的一个重要指标。主要从影响胶接接头耐久性的内在因素和外在因素以及实验室研究方法对结构胶胶接接头耐久性的研究进展进行综述。     

Rheological investigation of cure kinetics and adhesive strength of polyurethane acrylate adhesive

In this work, we used rheological techniques to study both the cure characteristics and the degree of cure of polyurethane acrylate adhesive, a type of reactive adhesive used in hard disk component assembly. These results were then correlated with the tensile shear strengths of adhesives. Here, the cure characteristics of polyurethane adhesive were investigated at isothermal conditions ranging from 25 to 120°C. From the rheological results, the gelation time, the vitrification time, as well as the time required to reach the maximum degree of cure, decreased when increasing the curing temperature. The cure rates of adhesive increased with temperature in three temperature ranges, which were retardation zone, vitrification zone, and reaction‐controlled zone. The cure rates in these zones were controlled by slow diffusion, fast diffusion, and the rate of reaction, respectively. From the temperature sweep of fully‐cured adhesives, we found that the crosslinking level of adhesives increased with curing temperatures at different rates depending on the temperature zones as well. Moreover, the adhesive strength measured by tensile shear test was found to also increase correspondingly with the adhesives' T_g, indicating that the crosslinking level directly affected the adhesive strength. The strong dependence of adhesive strength with crosslinking level indicates that the crosslinking level was essential for high adhesive strength. The correlation of cure characteristics and adhesive strengths at various curing temperatures performed in this study can further provide useful information for planning appropriate curing schemes of polyurethane acrylate adhesives used in electronic and other industries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Steel-Epoxy Composite Joints Bonded with Nano-TiO2 Reinforced Structural Acrylic Adhesive

This article reports a study on the effect of TiO₂ nanoparticles on the adhesion strength of steel–glass/epoxy composite joints bonded with two-part structural acrylic adhesives. The introduction of nano-TiO₂ in the two-part acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strengths of the adhesive joints increased with adding the filler content up to 3 wt.%, after which it decreased with adding more filler content. Also, addition of nanoparticles caused a reduction in the peel strength of the joints. Differential scanning calorimeter analysis revealed that glass transition temperature (T_g) values of the adhesives rose with increasing the nano-filler content. The equilibrium water contact angle decreased for adhesives containing nanoparticles. Scanning electron microscope micrographs revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.     

Assessments for impact of adhesive properties: modeling strength of metallic single lap joints

Adhesively bonded joints are widely used in a variety of industrial and engineering activities. Their overall strength is dependent on the properties of the adhesives. In the present research, assessments of adhesive properties were performed systematically through defining both strength mixity and energy rate mixity and using them to characterize the overall strength of metallic single lap joints. By means of the cohesive zone model, the adhesive strength mixity was defined as the ratio of the shear and tensile separation strength, and the energy rate mixity was defined as the ratio of the area below the shear cohesive curve and the area below the tensile cohesive curve. For each specified group of mixity parameters, corresponding to the properties of a specified adhesive, the overall strengths and the critical displacements of bonded joints were characterized. A series of strength and energy rate mixities were taken into account in the present calculations. A comparison of the present calculations with some existing experiments was carried out for both brittle and ductile adhesives. Finally, in the calculations presented here, damage initiation and evolution of the adhesive layer were also undertaken. The results showed that the overall strength of the joints was significantly depended on the adhesive properties, which were characterized by the strength and energy rate mixities of the adhesive. Furthermore, the shear adhesive stress components played a dominate role in both the damage initiation and evolution in the adhesives, which were also affected by the overlap length of the joints.     

A Thermo-Mechanical Study of Some Epoxy Adhesives Subjected to Combined Dynamic and Static Stresses

The object of the present study was to investigate the effect of superimposed dynamic and static stresses on mechanical and thermal properties of some epoxy adhesives. It was found that combinations of shear creep and torsional oscillations, applied simultaneously to adhesive joints at temperatures within the glassy range of the adhesive, led to strengthening of the joints in shear and to an increase in the glass transition temperature of the adhesive. Similar loading stresses applied at temperatures close to the T_g of the adhesive, led to opposite effects on the above mentioned properties of the joints. The width of the glassy-rubbery transition of the adhesives increased, in the whole range of temperatures used in this study and for all epoxy compositions, as a result of subjecting the joints to superimposed dynamic and static stresses. The broadening of the glass transition was interpreted as a result of the stiffening of polymer network during the combined stressing experiments. A linear relationship was found between the area of endothermal peaks in the first DSC scan of specimens subjected prior to test to superimposed dynamic and static stresses at temperatures below T_g, and the shear strength of the joints. In agreement with this observation and with literature data, a linear relationship was revealed also between the glass transition temperature of the resins (measured in the first DSC scan) and the shear strength of the joints. Based on experimental observations and on some literature information, it was suggested that the strengthening of the joint, as well as the changes in thermal properties of the adhesives, are mainly due to physical processes, such as short-range orientation of network chains and an increase in intermolecular interaction between highly polar sites of the network. The possibility that superimposed stressing led to changes in chemical crosslinking was discussed but it seems that no such reactions occurred.     

Investigation of formaldehyde-free wood adhesives from kraft lignin and a polyaminoamide–epichlorohydrin resin

A formaldehyde-free wood adhesive system consisting of kraft lignin and a polyaminoamide-epichlorohydrin (PAE) resin (a paper wet strength agent) has been investigated in detail. The lignin-PAE adhesives were prepared by mixing an alkaline kraft lignin solution and a PAE solution. Mixing times longer than 20 min had little impact on the shear strength of the wood composites bonded with the lignin-PAE adhesives. The shear strength of the wood composites bonded with the lignin-PAE adhesives increased and then flattened out when the press time and the press temperature increased. The shear strength and water resistance of the wood composites bonded with the lignin-PAE adhesives depended strongly on the lignin/PAE weight ratio. Of the weight ratios studied, the 3:1 lignin/PAE weight ratio resulted in the highest shear strength and the highest water resistance of the resulting wood composites. The wood composites bonded with the lignin-PAE adhesives did not delaminate and retained very high strengths even after they underwent a boiling-water test. The lignin-PAE adhesives could be stored at room temperature for two days without losing their adhesion ability. PAE was the crosslinking agent in this lignin-PAE adhesive. Possible reactions between lignin and PAE are discussed in detail.     

双组分高强度环氧胶粘剂的研制

根据车间内钢梁上吊车轨道安装底板与钢梁粘接的具体要求,研制了一种中温固化双组分环氧胶粘剂。探讨了E-51、E-39D和纳米碳酸钙用量对甲组分粘度的影响,测试了不同促进剂的胶粘剂凝胶时间并研究了粘接表面处理、中温固化时间对胶粘剂剪切强度的影响。结果表明,通过选用不同粘度的环氧树脂并添加纳米碳酸钙,控制甲组分粘度在8～20Pa.s,选用促进剂M3份,表面制备并采用偶联剂处理后,100℃下固化2h后,该胶铝-铝、钢-钢剪切强度可达45MPa和51MPa,实现了胶粘体系中温高强度快速固化。室温放置20h后钢-钢剪切强度为5.8MPa,可以安装加热设备以便后固化。     

Effect of creep on the mode II residual fracture energy of adhesives

Viscous flow that often occurs in adhesive materials leads to a permanent deformation when adhesives are subjected to creep loading. Creep loading has a significant influence on the strength of bonded structures. Due to the viscous behavior, the fracture energy also may change with time for joints that experience creep loading in service. In this work the effects of two creep parameters (creep load and time) on the residual mode II fracture energy of an adhesive was investigated using end notched flexure (ENF) specimens. To achieve this, ENF samples were subjected to different creep loading levels at different creep times followed by quasi static tests to obtain the residual shear fracture energy of the adhesive. Experimental results showed that pre-creep loading of the bonded structures can significantly improve the fracture energy and the static strength of the joints.     

Adhesive and curing properties of chicken feather/blood-based adhesives for the fabrication of medium-density fiberboards

This study was conducted to investigate the adhesive properties of chicken feather (CF)-based adhesives for wood-based panels. CF was hydrolysed in sodium hydroxide solutions of 5%, 7.5% and 10% (CF-AK). Chicken blood (CB) hydrolysed in sulfuric acid solution of 5% (CB-AC) was used as a hardener. The adhesives were formulated by crosslinking 60% CF-AK, 10% CB-AC and 30% formaldehyde-based crosslinking agents (formalin, melamine-urea-formaldehyde and phenol-formaldehyde prepolymers) on a solid weight basis. The CF-based adhesives were very viscous at room temperature, but the viscosity at 50 °C ranged from 300 to 600 mPa·s resulting in a sprayable adhesive. From the DSC analysis, the use of CF-AK-10% in the CF-based adhesives need longer curing time compared with that of CF-AK-5%. Most mechanical strength properties and dimensional stability of MDF bonded with CF-based adhesives were similar to those of commercial urea-formaldehyde (UF) resin. However, internal bonding strength of most MDF bonded with CF-based adhesives was higher than that with the UF resin. Most adhesive properties of the MDF manufactured with the new CF adhesive met the Korean Standard requirements for interior MDF. These results suggest that CF and/or CB can be used as raw materials for environment-friendly adhesives for producing wood panels.     

Eco-Friendly Adhesives Based on Tannin and N,N-Bis(2-Hydroxy-Ethyl) Fatty Amides (HEFAs) from Non-Traditional Oils for Wood Bonding

Abstract

Wood adhesives were formulated using tannin and N,N-bis(2-hydroxyethyl) fatty amides (HEFAs). The natural tannin-based adhesives can be used to replace formaldehyde-based adhesive systems and thereby reduce formaldehyde and volatile organic compound (VOC) emissions from adhesives used for plywoods. Performance properties of the adhesively bonded wood joints viz., tensile strength, impact strength and chemical resistance were measured. N,N-bis(2-hydroxyethyl) fatty amides (HEFAs) from non-traditional oils were mixed with a pure tannin-based adhesive as a crosslinker, and this increased the tensile strength, impact strength and chemical resistance of wood joints. The results revealed that a high performance and eco-friendly adhesive system for wood can be successfully formulated using tannin and HEFA.     

A Preliminary Study of the Use of Kynar® Piezoelectric Film to Measure Peel Stresses in Adhesive Joints

A variety of test techniques have been developed to test the performance of adhesives bonded in situ within joints. Most of these techniques measure strength, fracture toughness, or adhesive modulus of the bonded joint. Techniques to measure actual stress or strain values within a bonded joint are quite few in number. The Krieger gage¹ is able to measure the average shear displacement along a 12.5 mm. gage length of a thick adherend joint. It has been used primarily to measure in situ shear moduli of adhesives. Brinson and his colleagues² proposed bonding strain gages within adhesive joints to measure strains within the adhesive. Unfortunately, these gages are only sensitive to the lateral strains and not shear or peel strains. Because the lateral strains are dominated by the behavior of the adherends rather than the adhesive, the information which can be gained is incomplete.     

胶接接头在静态负载条件下的蠕变和松弛行为

Modern high performance adhesives are designed to offer an optimized balance of elasticity,toughness and plastic deformation capacity for the individual fields of application in e.g. the building and construction or transportation and vehicle industry. The long-term life prediction for adhesive joints based on laboratory tests requiring only days,weeks,or months is still a demanding challenge. Testing in practice is carried out with the intention of accelerating time dependent aging effects that may occur in a bonded joint during its service time. Initial strength values of bonded joints,such as shear or peel properties can often be obtained from the adhesive manufacturers or retrieved from literature. They are useful to compare different adhesives and to demonstrate the effect of parameters such as bond line thickness,overlap length or curing conditions,and,in some cases,the surface state. On the other hand only few data are available describing the mechanical long-term properties of adhesives related to creep and relaxation under static load conditions. Due to the nature of the polymer network of organic adhesives their viscoelastic-plastic deformation behavior is strongly time-and temperature dependent. The objective of this paper is to illustrate effective methods for investigating and predicting the creep and relaxation properties of adhesively bonded joints in the long-term region and for creating basic data for the design and engineering with adhesives.