Durability of Adhesive Bonds to Zinc-Coated Steels: Effects of Corrosive Environments on Lap Shear Strength

The effects of corrosive environments on adhesive bonds to electro-galvanized, zinc/aluminum alloy coated, coated electro-galvanized, and cold-rolled steels have been investigated. Bonds prepared using a rubber-modified dicyandiamide-cured epoxy adhesive, an epoxy-modified poly(vinyl chloride)-based adhesive, an acrylic-modified poly(vinyl chloride)-based adhesive a one-part urethane adhesive, and a two-component epoxy-modified acrylic adhesive were exposed under no-load conditions to constant high humidity or cyclic corrosion exposure for 50 days or 50 cycles (10 weeks) respectively.

Over the course of this study, exposure to constant high humidity had little effect on lap shear strength for any of the systems studied. Bond failures were initially cohesive, and with few exceptions remained so.

Bond strength retention under the cyclic corrosion exposure conditions employed was strongly dependent on adhesive composition and on substrate type. On galvanized substrates, lap shear strengths for the poly(vinyl chloride)-based adhesives were reduced by 90–100% during the course of the corrosion exposure, and a change in the mode of bond failure (from cohesive to interfacial) was observed. On the coated electro-galvanized steel substrate, the poly(vinyl chloride)-based adhesives showed about 50% retention in lap shear strength and a cohesive failure throughout most of the corrosion test. The dicyandiamide-cured epoxy adhesive used in this study generally showed the best lap shear strength retention to zinc-coated substrates; bonds to cold-rolled steel were severely degraded by corrosion exposure. The performance of the acrylic and urethane adhesives were intermediate to the dicyandiamide-cured epoxy and poly(vinyl chloride)-based adhesives in strength retention.     

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.     

Nonlinear Analysis of theTorque Transmission Capability of Adhesively Bonded Tubular Lap Joints

Calculated torque transmission capability of adhesively bonded tubular lap joints using linear elastic material properties is usually much less than the experimentally-determined one because the majority of the load transfer of the adhesively bonded joints is accomplished by the nonlinear behavior of rubber-toughened epoxy adhesives.

Although the adhesively bonded tubular double lap joint has better torque transmission capability and reliability than the single lap joint, the nonlinear analytic or numerical analysis for the adhesively bonded tubular double lap joint has not been performed because of numerical complications.

An iterative solution that includes the nonlinear shear behavior of the adhesive was derived using the analytic solution. Since the iterative solution can be obtained very quickly due to the simplicity of the algorithm, it is an attractive method of designing adhesively bonded tubular single and double lap joints.     

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.     

Influence of aliphatic amine epoxy hardener on the adhesive properties of blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with epoxy resin

The adhesive properties have been investigated in blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with diglycidyl ether of bisphenol A and three different aliphatic amine epoxy hardener. The adhesives properties are evaluated in steel alloy substrate using single‐lap shear test. The copolymers are initially miscible in the stoichiometric blends of epoxy resin and hardener at room temperature. Phase separation is noted in the course of the polymerization reaction. Different morphologies are obtained according to the amine epoxy hardener. The most effective adhesive for steel–steel joints in single‐lap shear test is the blends using 1‐(2‐aminoethyl)piperazine (AEP) as hardener. This system shows the biggest lap shear strength. However, the modified adhesives show a reduction in the mechanical resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An Iterative Solution for the Torque Transmission Capability of Adhesively-Bonded Tubular Single Lap Joints with Nonlinear Shear Properties

The adhesively-bonded tubular single lap joint shows large nonlinear behavior in the load-displacement relationship, because structural adhesives for the joint are usually rubber-toughened, which endows adhesives with nonlinear shear properties. Since the majority of load transfer of the adhesively-bonded tubular single lap joint is accomplished by the nonlinear behavior of the adhesive, its torque transmission capability should be calculated using nonlinear shear properties. However, both the analytic and numerical analyses become complicated if the nonlinear shear properties of the adhesive are included during the calculation of torque transmission capabilities.

In this paper, in order to obtain the torque transmission capabilities easily, an iterative solution which includes the nonlinear shear properties of the adhesive was derived using the analytic solution with the linear shear properties of the adhesive. Since the iterative solution can be obtained very quickly due to its simplicity, it has been found that it can be used in the design of the adhesively-bonded tubular single lap joint.     

Transmission and Mechanical Properties of Optical Adhesives

The optical, mechanical and durability performance of selected epoxy, polyester, UV-curable acrylic, cyanoacrylate and silicone adhesives were evaluated and measured for bonding applications of optically transparent glasses in the visible and infra-red regions of the electromagnetic spectra.

From the initially selected adhesives only the UV-curable modified acrylic, two-component silicone and room temperature cured epoxy, were found to be of high performance characteristics, having good transmission properties and enhanced endurance in a combination of heat and humidity and following thermal cycling.

Sodium chloride substrates served as adherends for the transmission characterization of the optical adhesives, due to their high transmission properties in the 0.4-10 m μ spectral range. A modified lap shear specimen was designed for studying the mechanical properties and failure mechanisms of the adhesives and their durability in a humid and not environment. Finally, a two-piece glass doublet was used for investigating the optomechanical characteristics of the optical adhesive following environmental conditioning and thermal shock cycling.

Due to the inherent C-C bond, polymer adhesives are limited in utility, as far as transparency is concerned, close to 3.5 μm and in most of the 8-12 μm spectral range.     

New Developments in Structural Adhesives for the Automotive Industry

Recently developed epoxy paste adhesives, reactive hot melts, adhesive film tape and polyurethane adhesives are presented for structural bonding in the automotive industry. Paste adhesives usually require a precure stage to obtain handling strength of the joints and to guarantee wash-out resistance of the adhesive in the paint baths. This step can be omitted with reactive hot melts and adhesive film tape, which are solid before and after their application. In addition they allow an improved working hygiene. Some mechanical properties of the adhesives are shown such as lap shear strength and peel strength as well as lap shear strength as a function of the bondline thickness. Results of the excellent durability of epoxy one-component pastes, reactive hot melts and adhesive film tape are given from cyclic environmental and salt spray tests.     

Comparison of the Degradation Mechanisms of Zinc-Coated Steel, Cold-Rolled Steel, and Aluminium/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and zinc, zinc-coated steel, two different aluminium alloys or cold-rolled steel metal coupons have been investigated. The influence of the dicyandiamide content of the adhesive on the durability properties-has been assessed by salt spray testing or by storing the joints in water at 70°C or 90°C for periods of time up to five weeks. The degradation products formed during ageing of the epoxy adhesive in water have been investigated using high performance liquid chromatography (HPLC) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). The degradation mechanisms of aluminium/epoxy bonded joints have been thoroughly studied using X-ray photoelectron spectroscopy.

The performances of the bonded joints under a pure corrosive environment have been found to be little influenced by the quantity of dicyandiamide in the adhesive. When the bonded joints were aged in hot water, the stability of the interface toward an excess of dicyandiamide directly followed the sensitivity of the oxide layer at high pH values. Optimal durability properties without peel strength losses of the adhesive were aehieved both with zinc and aluminium-coated substrates by reducing the quantity of dicyandiamide in the epoxy adhesive by 20% (the initial dicyandiamide content in the commercial adhesive being ca. 9%, with respect to the epoxy resin).     

Factors Affecting the Durability of Ti-6Al-4V/Epoxy Bonds

Factors influencing the durability of Ti-6Al-4V/epoxy interphases were studied by determining chemical and physical properties of Ti-6Al-4V adherend surfaces and by characterizing the strength and durability of Ti-6Al-4V/epoxy bonds.

Ti-6Al-4V adherend surfaces were oxidized either by chemical etch or anodization. Four principal pretreatments were studied: chromic acid anodization (CAA), sodium hydroxide anodization (SHA), phosphate fluoride acid etch (P/F) and TURCO basic etch (TURCO). The oxides were characterized by SEM, STEM, profilometry, contact angles and XPS.

All adhesive bonding was carried out using a structural epoxy, FM-300U. Both lap shear and wedge test samples were tested in hot, wet environments. The results lead to the conclusion that the interfacial area between the adhesive and adherend is the primary factor affecting bond durability.     

Studies on the adhesion behavior of water-based adhesives blended with asan gum

The influence of asan gum, a locally available waste material obtained from the Terminalia alata tree, in blends with waterborne natural rubber adhesive and poly(vinyl acetate), on the lap shear strength and the peel strength has been investigated. Both the strength values increase, even with a small quantity of the gum. At a higher gum content, both these parameters, however, decrease. Fourier Transform Infrared studies reveal that there is no covalent bonding between the gum and the adhesives, although some hydrogen bonding exists in the poly(vinyl acetate) blend. Morphological studies reveal mechanical interlocking of the adhesive in the substrates. The pseudoplastic nature of the gum-modified waterborne adhesives has been confirmed from rheological studies using a Brookfield viscometer. The higher lap shear and peel strength values of the gum-modified adhesives compared to the control adhesives are attributed to the higher shear modulus of the former. The 100% modulus and tensile strength of the adhesives blended with the gum are also higher, compared to their controls.     

Stainless steel coupled with carbon nanotube-modified epoxy and carbon fibre composites: Electrochemical and mechanical study

The aim of this work is the study of the electrochemical and mechanical behaviour of stainless steel (SS304) adhesively bonded with carbon nanotube (CNT)-reinforced epoxies to either SS304 or carbon-reinforced composites substrates. For metal to metal (MtM) joints, the shear strength of nano-reinforced adhesives was studied using single lap shear specimen geometries. The lap shear strength was improved by almost 50% and the highest shear strength appeared for 0.6% CNT weight content in the adhesive. The metal to composite joint performed altogether better compared to the MtM joint, although the CNT inclusion had an adverse effect on the lap shear strength attributed to the physical property change of the epoxy. Although the incorporation of CNTs was found to increase the galvanic effect, it also enhanced corrosion protection, as the modified adhesives exhibited increased resistance to uniform corrosion and localised corrosion and prevented the electrolyte from reaching the substrate.     

Hygrothermal Properties of Adhesively Bonded Joints and Their Correlation with Bulk Adhesive Properties

The combined effects of heat (50[ddot]C) and humidity (95% R.H.) on the lap shear and T-peel strengths of 120[ddot]C, 150[ddot]C and 215[ddot]C service epoxy film adhesives have been characterized. Experimental results have indicated that effects of hygrothermal conditioning on lap shear and peel properties vary with exposure time and final testing temperatures and type of adhesive tested. In the cases where cohesive failure was observed in the shear and peel specimens, a correlation could be established between the bulk properties of the adhesives (tensile strength and elongation) and their adhesively bonded joint properties (shear and peel). When testing was carried out at room temperature, a general correlation between the tensile elongation and T-peel or shear could be obtained. At below freezing temperatures, lap shear strength seemed to be correlated with bulk tensile strength while peel correlated with bulk tensile elongation. At elevated temperatures, the relative contributions of bulk strength and elongation were the decisive factors as far as shear and peel strengths are concerned.     

A Test Method for Accelerated Humidity Conditioning and Estimation of Adhesive Bond Durability

The ability to determine the durability of adhesive bonds remains an elusive task, especially when the service environment involves exposure to diluents such as water. Moisture continues to be of major concern for many adhesive bond systems for a number of reasons including:

1) many adhesives are hydrophilic, picking up significant amounts of moisture over time;

2) most adhesives and some adherends allow moisture permeation, eventually reaching the adhesive/adherend interface;

3) the high surface energies of metallic and certain other substrates result in moisture migrating to the adherend surfaces and displacing the adhesive from the substrates, and possibly oxidizing the adherend, etc., and

4) absorbed moisture induces swelling stresses which can reduce the bond strength.

Recognition of this susceptibility to moisture has led to extensive studies aimed at evaluating the effects of moisture, developing an understanding of the responsible mechanisms, and predicting the performance of adhesive bonds subjected to humid environments. While some studies have focused on the effect of humidity on neat adhesive samples, most studies have recognized the significance of the adhesive/adherend interactions, and have evaluated strength of actual bonded joints. Unfortunately, the time required for typical bonded geometries to reach moisture equilibrium can be quite long. Single lap joints (SLJ) and double cantilever beam (DCB) specimens with a width of 25mm may take several years to equilibrate, depending on the temperature and adhesive. Such lengthy conditioning times hamper the development of improved adhesives, and may delay the acceptance of these adhesives because of the time required to certify them. Methods to accelerate the conditioning of test specimens would be of significant benefit to adhesive formulators and users.     

Durable adhesives for large laminated timber

Large laminated timber (LT) made of hardwood is widely used as the main constitutional element of goods such as furniture, pianos and doors. A high durability of LT is essential to these products. This study focused on finding as to what adhesives were acceptable as highly durable adhesives for LT. Twelve different adhesives such as resorcinol-formaldehyde resin, aqueous emulsion-type isocyanate resin, poly(vinyl acetate) emulsion, epoxy resin, etc. were used. The durability of LT, i.e., the percentage of delamination length of LT under tests such as humidity and temperature cycling tests, and outdoor tests, was discussed in relation to the adhesive shear strength of a lap joint (LJ). The results showed that the percentage of delamination length under both low ?20°C for 16 h and high-temperature 50°C for 8 h cycling tests (temperature-resistance) on LT indicated a strong trend with the adhesive shear strength of the LJ exposed to dry air at 100°C for 24 h. In addition, the percentage of delamination length under outdoor exposure test for three months (outdoor-resistance) of the LT showed a trend with the adhesive shear strength of the LJ exposed to dry air at 100°C for 24 h, as well as with the adhesive shear strength of the LJ immersed in water at 60°C for 3 h. These trends pointed out that the thermal stability of the adhesive from ?20°C for 16 h up to 50°C for 8 h was an important parameter in order to improve adhesive durability for the LT.     

Mechanical and thermal behavior of modified epoxy–novolak film adhesives

Modified epoxy-based film adhesives were developed for bonding structural joints. Film adhesives with different compositions were prepared by hot pressing the molten resins. Peel and shear tests were carried out to evaluate the adhesion properties. Dynamic mechanical thermal analyses were conducted to follow the changes in the adhesive structure and also the trend of impact strength. Incorporation of thermoplastic poly(vinyl butyral) (PVB) into an epoxy- novolak combination resulted in higher cohesive strength, better film-forming ability, enhanced adhesive shear and peel strengths, but decreased thermostability. However, due to the lower chemical functionality of PVB, a lower crosslink density was achieved. Incorporation of a small amount of ethylene glycol dimethacrylate (EGDM) as a flexibilizer led to improved mechanical properties, easy handling and facile application. Finally, good shear strength retention up to 200 °C for 1 h was observed in the case of EGDM-modified adhesives.     

The Effect of Moisture Content in Epoxy Film Adhesives on their Performance. III: Bulk Properties

Humidity absorbed by epoxy film adhesives during low temperature storage or exposure to atmosphere may result in reversible changes and irreversible modifications. Vacuum treatment may partially remedy the reversible changes. The consequences of vacuum drying are manifested in enhancement of both the peel and shear properties of bonded joints (Part I and Part II of this series of papers) and the thermal, physical and mechanical properties of the bulk adhesive, characterized in the present study.

Experimental results have shown that the bulk properties of structural epoxy based adhesives are highly correlated with the aging processes caused by water absorption in the prepolymerized adhesive. Applying the vacuum process is harmful to fresh unaged adhesive due to devolatization of low molecular species of the film adhesive.

The characterization of bulk properties for the purpose of following the aging and recovery processes is advantageous, since the bulk is independent of geometrical and interfacial effects which dominate in the case of property evaluation of the adhesive in a bonded joint.     

Torque Transmission Capabilities of Bonded Polygonal Lap Joints for Carbon Fiber Epoxy Composites

Although carbon fiber epoxy composite materials have excellent properties for structures, the joint in composite materials often reduces the efficiency of the composite structure because the joint is often the weakest area in the composite structure.

In this paper, the effects of the adhesive thickness and the adherend surface roughness on the static and fatigue strengths of adhesively-bonded tubular polygonal lap joints have been investigated by experimental methods. The dependencies of the static and fatigue strengths on the stacking sequences of the composite adherends were observed.

From the experimental investigations, it was found that the fatigue strength of the circular adhesively-bounded joints was quite dependent on the surface roughness of the adherends and that polygonal adhesively-bonded joints had better fatigue strength characteristics than circular adhesively-bonded joints.     

Synergistic effect of graphene and carbon nanotube on lap shear strength and electrical conductivity of epoxy adhesives

In this study, synergy between graphene platelets (GnPs) and carbon nanotubes (CNTs) in improving lap shear strength and electrical conductivity of epoxy composite adhesives is demonstrated. Adding two-dimensional GnPs with one-dimensional CNTs into epoxy matrix helped to form global three-dimensional network of both GnPs and CNTs, which provide large contact surface area between the fillers and the matrix. This has been evidenced by comparing the mechanical properties and electrical conductivity of epoxy/GnP, epoxy/CNT, and epoxy/GnP-CNT composites. Scanning electron microscopic images of lap shear fracture surfaces of the composite adhesives showed that GnP-CNT hybrid nanofillers demonstrated better interaction to the epoxy matrix than individual GnP and CNT. The lap shear strength of epoxy/GnP-CNT composite adhesive was 89% higher than that of the neat epoxy adhesive, compared with only 44 and 30% increase in the case of epoxy/GnP and epoxy/CNT composite adhesives, respectively. Electrical percolation threshold of epoxy/GnP-CNT composite adhesive is recorded at 0.41 vol %, which is lower than epoxy/GnP composite adhesive (0.58 vol %) and epoxy/CNT composite adhesive (0.53 vol %), respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48056.     

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.