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.     

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     

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.     

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.     

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.     

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.     

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.     

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.     

Enhanced mechanical,thermal and adhesion properties of polysilsesquioxane spheres reinforced epoxy nanocomposite adhesives

ABSTRACT

Epoxy-based systems serve as excellent adhesives to join a wide range of substrates such as metal, ceramics, plastics, etc. The mechanical properties of such systems can be improved considerably by the addition of filler to the epoxy matrix. Herein, polymethylsilsesquioxane (PMS) and poly(methyl/vinyl)silsesquioxane (PMVS) nanosphere were synthesised by hydrolytic condensation of oraganosilane as a precursor in aqueous phase. The epoxy nanocomposite adhesives were prepared by adding different weight percentages (1–4 wt%) of the PS nanospheres. Tensile and compressive strength of the adhesive formulations were studied using the universal testing machine (UTM) and it was observed that the mechanical properties of the composites showed an increasing trend on increasing the filler loading. Adhesive strength of the epoxy composites on mild steel substrate was studied by conducting the lap shear test and EPV-4 exhibited a 31% increase in adhesive strength on the mild steel compared to the neat epoxy. Surface morphology of the epoxy composites were visualised from the SEM images and the composites also showed enhanced thermal conductivity. Higher mechanical and adhesive strength indicates the potential of the prepared nanocomposites to be used as an effective formulation in adhesive-based systems.     

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.     

Characterization of canola oil based polyurethane wood adhesives

A novel bio-based poly (ether ester) polyol containing both primary and secondary functional groups was synthesized from canola oil using a low cost and efficient procedure. In this work, use of the new canola oil derived polyol for the production of polyurethane (PU) adhesives was demonstrated. The canola oil based PU adhesives had similar or better adhesive properties in terms of lap shear strength than three commercial PU adhesives. The effect of NCO/OH ratio and temperature on adhesive characteristics on wood bonding was also evaluated by lap shear tests. It was found that the use of an elevated curing temperature (i.e. 100 °C), as well as optimized NCO/OH molar ratio (higher than 1.5/1.0), improved the wood adhesive properties. The overall chemical resistance of bio-based PU adhesives to cold water, acid and alkali was comparable to that of commercial PU adhesives whilst its resistance to hot water was superior.     

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.     

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.     

Adhesive Bonding of Clean and Oil-Contaminated Electrogalvanized Steel Substrates

The performance of two-part, amidoamine-cured epoxy adhesives on clean and oil-contaminated electrogalvanized steel (EGS) was studied using screening and lap shear tests. On exposure to boiling water, the cured epoxy adhesives with amidoamines having higher amine value delaminated from the clean and oil-contaminated EGS surfaces before those cured with amidoamines having low amine value. The results of X-ray photoelectron spectroscopy (XPS) showed that the adhesives cured with amidoamines having high amine value were unable to displace the oil from the EGS substrate. However, the durability and the strength of the adhesive bonds on the oiled EGS could be improved by adding proper amounts of silane or wetting agent to the adhesive. The preferential adsorption of amino curing agents occurred on the clean EGS surface, confirmed by XPS and reflection absorption infrared spectroscopy, and this decreased the durability of the bonds in boiling water. In addition, from XPS analyses of various specimens, different amounts of cured resins were detected in the adhesive/EGS interfacial regions which affecting the durability of the adhesive bonds. In addition, the amidoamine curing agents may form complexes on the EGS surface.     

Strength and Durability of Epoxy-Aluminum Joints

The adhesive strength and durability of adhesively-bonded aluminum joints in wet environments was analyzed. A2024-T4 alloy was subjected to two different surface treatments based on etching with chromic-sulfuric acid (FPL) and with sulfuric acid-ferric sulfate (P2). Small differences were observed in the lap shear strength as a function of the applied surface treatment. However, durability in humid environments was higher for the joints whose adherends were treated with P2.

Although the amount of water absorbed by the epoxy adhesive is lower in saline environments, the effects on the glass transition temperature of the epoxy adhesive and on the lap shear strength of the joints are more marked than the effects caused by aging with distilled water.

Finally, a new epoxy adhesive with a siloxanic hardener was tested, obtaining good mechanical properties, high glass transition temperature, moderate values of lap shear strength, and high durability in wet environments.     

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.     

Preparation and performance of urethane-modified polytriazole adhesives

Polytriazole adhesives are a new type of adhesives with excellent heat resistance, but the lap shear strength at room temperature is not ideal, which is about 15 MPa. In order to improve its adhesion performance at room temperature, a series of urethane-modified polytriazole (UPTA) adhesives were successfully synthesized via 1, 3-dipolar cycloaddition reaction between azides, and alkynes. Firstly, an alkynyl-terminated urethane monomer di(but-3-yn-1-yl) (1,3-phenylenebis(methylene)) dicarbamate (DBPMD) was synthesized and characterized. Then DBPMD was reacted with biphenyl dibenzyl azide (BPDBA) and N′,N′,N′,N′-tetrapropargyl-p,p′-diaminodiphenyl methane (TPDDM) to prepare UPTA adhesives. Curing behavior, thermal properties, bonding performance, and resistance to damp heat aging of UPTA adhesives were studied. The results show that the introduction of urethane group has almost no effect on the curing behavior. The glass transition temperature (T_g) and the 5% thermal weight loss temperature (T_d5) gradually decreased with the increased proportion of DBPMD added. T_g of UPTA adhesives ranged from 185 to 215°C and T_d5 of UPTA adhesives were all above 300°C, which indicated its outstanding thermal stability. The lap shear strength at room temperature of UPTA adhesives increased first and then decreased with the increasing amount of DBPMD, which ranged from 13.9 to 19.9 MPa. The highest lap shear strength of UPTA adhesives can reach 19.9 MPa, which was 31.8% higher than PTA adhesive. The lap shear strength retention rate of UPTA adhesives at 180°C was all over 75%. Lap shear strength retention rate of UPTA adhesives under 168 h damp heat aging time was all over 80%. UPTA adhesives have good bonding performance, heat resistance, and damp heat aging resistance, which can meet many complex construction requirements.     

Durability of adhesives based on different epoxy/aliphatic amine networks

The mechanical and adhesives properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact tests were used to determine the impact energy. The adhesive properties have been evaluated in terms single lap shear using steel adherends. Its durability in water at ambient temperature (24 °C) and at 80 °C has also been analyzed. The fracture mechanisms were determined by optical microscopy. It was observed a strong participation of the cohesive fracture mechanisms in all epoxy system studied. The 1-(2-aminoethyl)piperazine epoxy adhesive and piperidine epoxy adhesive presents the best adhesive strength and the largest impact energy. The durability in water causes less damage to piperidine epoxy networks. This behavior appears to be associated with the lower water uptake tendency of homopolymerised resins due to its lower hydroxyl group concentration.     

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.