Semi-Structural Hot Melt Adhesives Based on Crosslinkable Functionalized Polyolefins

A structural or semi-structural adhesive is usually applied to the substrates as monomers, oligomers, or melts of polymers with reactive groups and is then polymerized or crosslinked in situ in the joint between the substrates. We have been studying a number of crosslinked functionalized polyolefins blended with tackifier used as semi-structural adhesives for bonding to oily galvanized steel surfaces. The functions of takifier, surface properties of adhesive and substrate, geometry effects of lap joints, adhesive T_β, chain end defects, network chain length, and cure kinetics of these systems will be discussed. Our experimental results indicate that lap shear strengths of galvanized steel joints depend on adhesive storage modulus to the power of roughly 1/2. A rough estimate of the fracture energy of the adhesive bond, G_a could be obtained from this relation. Although some estimated G_a values are too low while the others are too high, they seem to be in rough accord with the degree of interfacial bonding and the locus of failure of the lap shear bonds.     

Benchmark tests on adhesive strengths in butt, single and double lap joints and double-cantilever beams

The RC99 committee of the Japan Society for Mechanical Engineers conducted the benchmark tests on strengths of adhesive joints using different testing methods. The effects of joint configuration, loading mode, adherend yield strength and so on, on the strength and data scatter were investigated using two typical epoxy adhesives. The strengths obtained by various tests were compared with each other. The relationships among strengths of butt, single lap and double lap joints and fracture toughness were given. Thirteen member institutes of the committee participated in this project. The benchmark results allow us to recognize that the joint strengths are strongly affected by the curing process. The key to obtaining the appropriate joint strength, is precise temperature control inside the adhesive layer for curing. Toughened adhesives do not always give higher joint strengths than untoughened adhesives. The yield strength of adherends much affects the observed lap joint strength of adhesives.     

The effect of curing temperature on thermal,physical and mechanical characteristics of two types of adhesives for aerospace structures

The effects of cure temperatures on the thermal, physical and mechanical characteristics of two types of thermosetting structural epoxy film adhesives were determined in detail. The aim of this paper is to assess the effect of cure temperatures (82–121 °C) on the degree of cure of the two adhesives and the relevant void formations that need to be addressed in bonded part production and repair. Two thermal parameters were used to characterize the advancement of the reaction, such as degree of cure and glass transition temperature. The joint properties with respect to the cure temperatures were characterized by void content and bond-line thickness measurements and lap shear strength tests. Experimental results presented that all lap shear strengths were well within minimum shear strength (29 MPa) required by the specification of the film-type adhesive. However, the lap shear strength testing after aging at 82 °C and 95%R.H for 1000 h showed that the improved durability when the adhesive is cured at 121 °C did not occur for the 82 °C cure. Low curing conversion (75–77% degree of cure) combined with high voids (over 2 areal%) has a catastrophic effect on the bonding qualities at the metal-adhesive interface and due to lack of cohesion in the adhesive. The changes in the interface caused by the low temperature curing may contribute to an increased susceptibility of the bonded joint to moisture and consequent bond-line degradation.     

Thermal characteristics of tubular single lap adhesive joints under axial loads

When an adhesive joint is exposed to high environmental temperature, the tensile load capability of the adhesive joint decreases because both the elastic modulus and failure strength of the adhesive decrease. The thermo-mechanical properties of a structural adhesive can be improved by addition of fillers to the adhesive. In this paper, the elastic modulus and failure strength of adhesives as well as the tensile load capability of tubular single lap adhesive joints were experimentally and theoretically investigated with respect to the volume fraction of filler (alumina) and the environmental temperature. Also the tensile modulus of the filler containing epoxy adhesive was predicted using a new equation which considers filler shape, filler content, and environmental temperature. The tensile load capability of the adhesive joint was predicted by using the effective strain obtained from the finite element analysis and a new failure model, from which the relation between the bond length and the crack length was developed with respect to the volume fraction of filler.     

Epoxy-based composite adhesives with improved lap shear strengths at high temperatures for steel-steel bonded joints

High-performance room temperature-cure epoxy structural adhesives utilizing simplified formulation are developed. The developed structural adhesive consists of diglycidyl ether of bisphenol A (DGEBA) and novolac epoxy blend as a base resin, micrometer-sized silica particles as a reinforcing filler, and triethylenetetramine as a curing agent. The developed ambient temperature-cure epoxy structural adhesive with optimized formulation exhibits outstanding properties including high glass transition temperature of 95°C, high thermal stability with degradation temperature at 5% weight loss of 364°C, exceptionally high rubbery plateau modulus of 320 MPa, good flame-retardant characteristics with limiting oxygen index of 40, and high single lap shear strength for single lap steel-steel bonded joint of 548 MPa at the temperature of 80°C. The silica-filled DGEBA/novolac epoxy composite adhesive is a potential candidate for applying as a structural adhesive for construction with long-term durability.     

Moisture absorption effect on adhesive filled bonded joints

The effect of filler type and content on the performance and durability of adhesive bonded joints upon exposure to damp heat (water immersion) has been investigated using concurrently step lap shear and thermo mechanical analysis (TMA) experiments. A TMA based approach is developed in order to predict the strength of the bonded constructions. Two types of fillers were used in order to achieve the objectives: glass beads (GB) and alumina ceramic powder (ACP). It is shown that ACP filled adhesives have higher strength retention than GB filled ones. It is also demonstrated that valuable information can be extracted from TMA measurements. Generally, the increase of the coefficient of thermal expansion (CTE) of the bonded joints is found to be in agreement with the decrease of the step lap joint strengths after exposure. The increase of the CTE of the bonded joints resulting from exposure to hot water seems to increase the stresses, which in turn affect the overall strength. Similarly, bulk adhesive results show that GB filled systems are more susceptible to water than ACP filled ones, which confirms the decrease in strength of GB filled bonded constructions.     

Influence of the filler material on the thermal stability of one‐component moisture‐curing polyurethane adhesives

Filler materials are part and parcel for the adjustment of adhesives, in particular, their rheological and mechanical properties. Furthermore, the thermal stability of adhesives can be positively influenced by the addition of an expedient filler, with inorganic types common practice in most cases. In this study, one‐component moisture‐curing polyurethane adhesives for engineered wood products based on isocyanate prepolymers with different polymer‐filled polyether polyols were investigated with regard to the filler's potential to increase the thermal stability of bonded wood joints. The property changes due to the addition of fillers were determined by means of mechanical tests on bonded wood joints and on pure adhesive films at different temperatures up to 200°C. Additional analyses by atomic force and environmental scanning electron microscopy advanced the understanding of the effects of the filler. The tested organic fillers, styrene acrylonitrile, a polyurea dispersion, and polyamide, caused increases in the cohesive strength and stiffness over the whole temperature range. However, the selected filler type was hardly important with regard to the tensile shear strength of the bonded wood joints at high temperatures, although the tensile strength and Young's modulus of the adhesive films differed over a wide range. Prepolymers with a lower initial strength and stiffness resulted in worse cohesion, in particular, at high temperatures. This disadvantage, however, could be compensated by means of the filler material. Ultimately, the addition of filler material resulted in optimized adhesive properties only in a well‐balanced combination with the prepolymer used. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A Method of Predicting the Stresses in Adhesive Joints after Cyclic Moisture Conditioning

The durability of adhesive joints is of special concern in structural applications and moisture has been identified as one of the major factors affecting joint durability. This is especially important in applications where joints are exposed to varying environmental conditions throughout their life. This paper presents a methodology to predict the stresses in adhesive joints under cyclic moisture conditioning. The single lap joints were manufactured from aluminium alloy 2024 T3 and the FM73®-BR127® adhesive-primer system. Experimental determination of the mechanical properties of the adhesive was carried out to measure the effect of moisture uptake on the strength of the adhesive. The experimental results revealed that the tensile strength of the adhesive decreased with increasing moisture content. The failure strength of the single lap joints also progressively degraded with time when conditioned at 50°C, immersed in water; however, most of the joint strength recovered after drying the joints. A novel finite element based methodology, which incorporated moisture history effects, was adopted to determine the stresses in the single lap joints after curing, conditioning, and tensile testing. A significant amount of thermal residual stress was present in the adhesive layer after curing the joints; however, hygroscopic expansion after the absorption of moisture provided some relief from the curing stresses. The finite element model used moisture history dependent mechanical properties to predict the stresses after application of tensile load on the joints. The maximum stresses were observed in the fillet areas in both the conditioned and the dried joints. Study of the stresses revealed that degradation in the strength of the adhesive was the major contributor in the strength loss of the adhesive joints and adhesive strength recovery also resulted in recovered joint strength. The presented methodology is generic in nature and may be used for various joint configurations as well as for other polymers and polymer matrix composites.     

Effect of Aging Time at High Temperature on the Shear Strength of Adhesively Bonded Aluminum Composite Foam Joints

In this study, the shear strength behavior of adhesively bonded joints, made of aluminum composite foams subjected to high-temperature processes, has been investigated. Aluminum composite foam and solid aluminum blocks were used to form single lap joints and as the binder, a methacrylate-based structural adhesive has been selected. Foam-foam and solid-foam joints were formed and cured at room temperature for 24 hours. After curing process, aging at 200 ^oC was performed on the samples for 15, 30, 45, 60 minutes. The aged samples were subjected to lap shear testing for adhesively bonded metals and the influences of aging duration on joint strength and failure type were investigated.

As a result, lower strengths were obtained in all samples that aged under high temperature compared to non-aged samples. After the application of short-term (15-30 min) aging processes on samples, it is observed that they have joint strength values about 50% of the joint strength of non-aged samples. However, strength values of short-term aged joints (15, 30 min) remain higher than the strength values of the foam materials used in the tests. These results show that methacrylate-based adhesives subjected to short-term thermal loads up to 200 °C can be used in constructions.     

Rubber solution adhesives for wood-to-wood bonding

Rubber solutions were prepared and used for bonding wood pieces. The effect of the variation of chlorinated natural rubber (CNR) and phenolformaldehyde (PF) resin in the adhesive solutions on lap shear strength was determined. Natural rubber and neoprene-based adhesive solutions were compared for their lap shear strength. The storage stability of the adhesive prepared was determined. The change in lap shear strength before and after being placed in cold water, hot water, acid, and alkali was tested. The bonding character of these adhesives was compared with different commercially available solution adhesives. The room-temperature aging resistance of wood joints was also determined. In all the studies, the adhesive prepared in the laboratory was found to be superior compared to the commercial adhesives. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1185–1189, 1998     

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.     

Flexibilized Copolyimide Adhesives

Two copolyimides, LARC-STPI and STPI-LARC-2, with flexible backbones were prepared and characterized as adhesives. The processability and adhesive properties were compared to those of a commercially available form of LARC-TPI.

Lap shear specimens were fabricated using adhesive tape prepared from each of the three polymers. Lap shear tests were performed at room temperature, 177°C, and 204°C before and after exposure to water-boil and to thermal aging at 204°C for up to 1000 hours.

The three adhesive systems possess exceptional lap shear strengths at room temperature and elevated temperatures both before and after thermal exposure. LARC-STPI, because of its high glass transition temperature provided high lap shear strengths up to 260°C. After water-boil, LARC-TPI exhibited the highest lap shear strengths at room temperature and 177°C, whereas the LARC-STPI retained a higher percentage of its original strength when tested at 204°C [68% versus 50% (STPI-LARC-2) and 40% (LARC-TPI)].

These flexible thermoplastic copolyimides show considerable potential as adhesives based on this study and because of the ease of preparation with low cost, commercially available materials.     

Boundary Layers and Physico-Mechanical Properties of Adhesive Joints: Part I Experimental Background

Abstract

Various hypotheses of boundary layer formation in adhesive joints are reviewed. The features of boundary layers in joints obtained by means of thermoplastic and thermoreactive adhesives are studied, and substrate boundary layers are estimated. The examples of influence of density, elasticity modulus and other properties of boundary layers upon adhesive joint properties are presented.

An original method to design adhesive joints is proposed, based on the concept of special boundary layer properties. By means of this method the problem of mechanical performance of an adhesive lap shear joint is solved. The effects of various parameters of the theoretical model are compared with the experimental data.     

The surface treatment and adhesive bonding of polyetheretherketone. Part I. Adhesive joint strength

A range of surface treatments including degreasing, abrasion, chromate etching, plasma etching and nitric-sulfuric acid etching were applied to unreinforced and 20 vol. % glass fiber reinforced polyetheretherketone. Single lap shear adhesive joints were prepared using a nylon-fabric-supported epoxy resin film adhesive. Plasma ashing produced adhesive joint strengths of 13 MPa in lap shear and correlated with substantial cohesive failure within the adhesive resin. Adhesion to the abraded surface was very low but it was significantly improved by grit blasting and by chromate etching.     

Influence of Fabrication Residual Thermal Stresses on Rubber-toughened Adhesive Tubular Single Lap Steel-Steel Joints under Tensile Load

The tensile load bearing capability of adhesively-bonded tubular single lap joints which is calculated under the assumption of linear mechanical adhesive properties is usually much less than the experimentally-determined because the majority of the load transfer of adhesively-bonded joints is accomplished by the nonlinear behavior of rubber-toughened epoxy adhesives. Also, as the adhesive thickness increases, the calculated tensile load bearing capability with the linear mechanical adhesive properties increases, while, on the contrary, the experimentally-determined tensile load bearing capability decreases.

In this paper, the stress analysis of adhesively-bonded tubular single lap steel-steel joints under tensile load was performed taking into account the nonlinear mechanical properties and fabrication residual thermal stresses of the adhesive. The nonlinear tensile properties of the adhesive were approximated by an exponential equation which was represented by the initial tensile modulus and ultimate tensile strength of the adhesive.

Using the results of stress analysis, the failure criterion for the adhesively-bonded tubular single lap steel-steel joints under tensile load was developed, which can be used to predict the load-bearing capability of the joint. From the failure criterion, it was found that the fracture of the adhesively-bonded joint was much influenced by the fabrication residual thermal stresses.     

The Shear Stress-Strain Behaviour of Low-modulus Structural Adhesives

The shear stress-strain behaviour of two low-modulus structural adhesives has been measured using the butt-torsion test. The Nadai correction for non-linear shear behaviour is explained as it is necessary to understand how this correction can be applied to butt joints. The results for one adhesive were accurately used to predict the strength of a lap joint, and it was shown that the strength of such a joint can approach that of a conventional, modern, structural epoxy. Structural adhesives are usually reckoned to be those with a high strength (50 MPa and upwards) and (these days), a strain to failure of at least 10% in tension, and which usually have a tensile modulus of 2 GPa or so. However, adhesives which are significantly less stiff, less strong, but much more ductile are entering the 'structural' arena. In order to evaluate their effectiveness and use in design, it is necessary to be able to measure accurately their stress-strain behaviour. Two such materials are 3M 9245 Structural Bonding Tape (SBT) and 3M 7838 B/A.     

Experimental study of the effect of microspheres and milled glass in the adhesive on the mechanical adhesion of single lap joints

This article describes several experiments conducted on single lap joints (SLJ) subjected to tensile mechanical loads. Two epoxy adhesives, with slow and fast curing, were used, with a weight of 0%, 3%, and 10% of glass microspheres and milled glass particles, respectively. The adherends used in the construction of the specimens were fiber-reinforced polymers. The types of failures produced in the SLJ specimens were classified according to ASTM standards. The results of the experimental tests on the SLJ with fast-curing epoxy adhesive showed that the use of milled glass and glass microspheres improved the strength of the joint compared with the neat fast-curing epoxy adhesive. As for the experimental test on the joint with slow-curing epoxy adhesive, the results showed that the use of milled glass and glass microspheres decreased its strength when using different additive concentrations compared with the neat slow-curing epoxy adhesive.     

Aging and performance of structural film adhesives. I. A comparison of two high-temperature curing,epoxy-based systems

The room temperature aging of two epoxy adhesives, both of which are cured at 177°C and contain the moisture sensitive resin triglycidyl (4-aminophenol), has been examined. It has been found that hydrolysis of this resin is the major cause of reduction in epoxide content during aging. This in turn is largely responsible for the deterioration in the performance, especially at high temperatures, of bonded joints made with aged adhesive. The advantages of using high purity resins in adhesive formulations have been demonstrated.     

Finite element analysis of torsional free vibration of adhesively bonded single-lap joints

Adhesively bonding is a high-speed fastening technique which is suitable for joining advanced lightweight sheet materials that are dissimilar, coated and hard to weld. In this paper, the free torsional vibration characteristics of adhesively bonded single-lap joints are investigated in detail using finite element method. The effectiveness of finite element analysis technique used in the study is validated by experimental tests. The focus of the analysis is to reveal the influence on the torsional natural frequencies and mode shapes of these joints caused by variations in the material properties of adhesives. It is shown that the torsional natural frequencies and the torsional natural frequency ratios of the adhesively bonded single-lap joints increases significantly as the Young′s modulus of the adhesives increase, but only slight changes are encountered for variations of Poisson's ratio. The mode shapes analysis show that the adhesive stiffness has a significant effect on the torsional mode shapes. When the adhesive is relatively soft, the torsional mode shapes at the lap joint are slightly distorted. But when the adhesive is relatively very stiff, the torsional mode shapes at the lap joint are fairly smooth and there is a relatively higher local stiffening effect. The consequence of this is that higher stresses will be developed in the stiffer adhesive than in the softer adhesive.     

Adhesive Bonding to Galvanized Steel: I. Lap Shear Strengths and Environmental Durability

Initial (i.e., unaged) adhesion, as well as adhesion after seven day, 60°C water immersion and six week scab corrosion accelerated environmental exposures, has been assessed for five different one and two-part epoxy adhesives, bonded to three different types of galvanized steel substrates. We have shown that adhesion, as measured by lap shear strength, is specific to the galvanized substrate type. In general, for a given adhesive, adhesion to “hot-dipped” galvanized substrates is harder to achieve and maintain under accelerated environmental exposure than is adhesion to “electroplated” galvanized. Also, for a given type of galvanized steel, the one-part epoxies evaluated generally showed higher initial strengths, as well as better strength retention under environmental exposure than did the two-part epoxies.