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).     

Improvement of the Durability of Zinc-Coated Steel/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and hot-dipped galvanized (G2F) or electroplated-phosphated (EZ2) steel have been investigated. The degradation mechanisms have been studied after three accelerated ageing tests: the “cataplasme humide” (“C.H.T.”), immersion (“I.T.”), and salt spray (“S.S.T.”) tests. X-ray photoelectron spectroscopy (XPS) analysis of fracture surfaces after ageing have shown that anodic dissolution of the zinc-coating is responsible for debonding in all cases and that intergranular corrosion phenomena account for poorer performances of the hot-dipped galvanized substrate during “C.H.T.” and “I.T.” Silane coupling agents were successfully used as primers on both substrates to increase the hydrolytic stability of the metal/adhesive interface. XPS results indicate that both the interfacial dissolution of the phosphate coating of EZ2 and intergranular corrosion of G2F are delayed for silane-primed specimens. The observed improvements do not appear to depend on the nature of the silane coupling agents. Alkylsilanes have been found to perform as well as silanes having a group capable of reacting with the epoxy/dicyandiamide system.

Additional tests were carried out in view of the possible application of organosilane reagents as additives in corrosion-protective oils. Good durability properties have been obtained by priming the metal coupons with a standard oil/silane mixture prior to bonding.

When corrosion was the controlling degradation mechanism as is the case during the salt spray test, silane treated specimens did not generally perform better than control specimens.     

Improvement of the Durability of Zinc-Coated Steel/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and hot-dipped galvanized (G2F) or electroplated-phosphated (EZ2) steel have been investigated. The degradation mechanisms have been studied after three accelerated ageing tests: the “cataplasme humide” (“C.H.T.”), immersion (“I.T.”), and salt spray (“S.S.T.”) tests. X-ray photoelectron spectroscopy (XPS) analysis of fracture surfaces after ageing have shown that anodic dissolution of the zinc-coating is responsible for debonding in all cases and that intergranular corrosion phenomena account for poorer performances of the hot-dipped galvanized substrate during “C.H.T.” and “I.T.” Silane coupling agents were successfully used as primers on both substrates to increase the hydrolytic stability of the metal/adhesive interface. XPS results indicate that both the interfacial dissolution of the phosphate coating of EZ2 and intergranular corrosion of G2F are delayed for silane-primed specimens. The observed improvements do not appear to depend on the nature of the silane coupling agents. Alkylsilanes have been found to perform as well as silanes having a group capable of reacting with the epoxy/dicyandiamide system.

Additional tests were carried out in view of the possible application of organosilane reagents as additives in corrosion-protective oils. Good durability properties have been obtained by priming the metal coupons with a standard oil/silane mixture prior to bonding.

When corrosion was the controlling degradation mechanism as is the case during the salt spray test, silane treated specimens did not generally perform better than control specimens.     

Effect of moisture content in uncured adhesive on static strength of bonded galvanized DP600 steel joints

Experiments to characterize the effect of moisture content in uncured adhesive on static strength of bonded galvanized DP600 steel joints were conducted. Prior to adhesive curing, the adhesive and galvanized steel coupons were pre-exposed to 96% relative humidity at 40 °C (i.e., open-faced exposure). It was found that the exposure of adhesive and steel sheets in hot humid environment decreases the quasi-static strength of adhesive-bonded galvanized DP600 steel joints by as much as 96% after 1008 h of exposure. Optical microscopy and scanning electron microscopy of quasi-static tensile tested specimens and moisture absorption testing of bulk adhesive revealed that static strength degradation is mainly due to the plasticization and micro-cracking of adhesive and zinc oxidation by the water vapor.     

Inorganic primers in bonded joints

An amorphous aluminium oxide coating, generated from aluminium chelate or alkoxide compounds, has been investigated as a primer for adhesively bonded phosphoric acid anodized 2024 aluminium adherends. Tensile lap shear and T-peel specimens were used to evaluate the effect of the alumina-coated surfaces on the mechanical properties of the bonded joints. Equivalent wet and dry tensile lap shear and T-peel bond strenghts were obtained when the inorganic coating was substituted for the normally used organic primer. Transmission and scanning electron microscopy of the alumina-primed surfaces showed that the oxide honeycomb/protrusion morphology resulting from phosphoric acid anodizing was infiltrated by the solution-deposited inorganic primer to produce a low profile bonding surface.     

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.     

The Fatigue and Durability Behaviour of Automotive Adhesives. Part II: Failure Mechanisms

In part I [1] a fracture mechanics approach has been successfully used to examine the cyclic fatigue behaviour of adhesively-bonded joints, which consisted of aluminium-alloy or electro-galvanised (EG) steel substrates bonded using toughened-epoxy structural paste-adhesives. The adhesive systems are typical of those being considered for use, or in use, for bonding load-bearing components in the automobile industry. The cyclic fatigue tests were conducted in a relatively dry environment, of 23°C and 55% RH, and in a “wet” environment, namely immersion in distilled water at 28°C. The “wet” fatigue tests clearly revealed the significant effect an aggressive, hostile environment may have upon the mechanical performance of adhesive joints, and highlighted the important influence that the surface pretreatment, used for the substrates prior to bonding, has upon joint durability. The present paper, Part II, discusses the modes and mechanisms of failure for the two adhesive systems in both the “dry” and “wet” environments. The failure surfaces of the joints tested in Part I have been examined using a variety of analytical techniques and the surface chemistry and morphology compared with that of the “as prepared” (i.e. non-bonded) metal surfaces and cured adhesive. In the present investigation use has been made of an elemental mapping form of X-ray photoelectron spectroscopy (EM-XPS) along with conventional XPS. The surface topography has been examined using scanning electron microscopy and atomic force microscopy. Also, cross-sections of the joints have been studied using the transmission electron microscope. The results reveal that for both the aluminium alloy and EG steel joints that the failure path is complex, and is associated with electrochemical activity (i.e. corrosion) in the case of the latter joints when tested in the “wet” environment. In part III [2], the results presented in the earlier papers will be used to predict the lifetime of single-overlap joints subjected to cyclic fatigue loading.     

Adhesive Bonding to Galvanized Steel: II. Substrate Chemistry, Morphology and Bond Failure Analysis

Galvanized substrate morphology, oxide layer chemistry, bond failure modes, failure loci, and bondline corrosion have been investigated for adhesive bonds to galvanized steel. Significant differences in surface morphology were observed between the relatively smooth surfaces of “hot-dipped” substrates and the considerably rougher texture of “electroplated” substrates. The hot-dipped substrates were also chemically heterogeneous, with significant amounts of Al, Mg, Ca, and Pb, in addition to Zn, constituting the surface layer. For electroplated substrates, on the other hand, Zn was the major constituent. It was concluded that, for a given adhesive, low strengths and poor bond durability generally correlated with the minimum surface roughness and maximum chemical heterogeneity of the hot-dipped substrates. Higher strengths, and better durability, on the other hand, were observed for electroplated substrates, which showed the greater roughness, as well as chemically the more uniform surface.

Significantly, ESCA spectroscopy of fracture surfaces of unaged samples established that failure loci for both one and two-part epoxy adhesives included the oxide layer of the substrate. This was true for both hot-dipped, as well as electroplated substrates. For aged samples, scanning electron microscopy and X-ray diffraction analysis of failure surface identified zinc-based corrosion products present in the original bond area.     

The Adhesively Bonded Aluminium Joint: The Effect of Pretreatment on Durability

The interface in aluminium bonded structures can be revealed by ultramicrotomy and subsequently studied by transmission electron microscopy. By these means, the more usual surface pretreatments encountered, have been characterised in depth.

A similar examination has been effected following exposure of bonded joints (floating roller peel specimens) to 85% relative humidity at 70°C. Although a drop in peel performance is noted over the exposure time, interfacial examination reveals little damage to the adhesive or adherend. Possible mechanisms for bond strength reduction are discussed: subtle undermining of the alumina film and disruption of physico-chemical bonds across the interface. Both are initiated by moisture reaching the alumina film, either passing along the interface itself or travelling through the adhesive matrix. Also considered are the effects of surface pretreatment and “oxide” penetration, by the adhesive, on durability.

The effect of priming the adherend surface prior to bonding, using a heavily strontium chromate filled adhesive primer, is mentioned and its possible influence on durability is briefly discussed.     

Moisture durability of four moisture cure urethane adhesives

Moisture durability of four low modulus adhesives was examined. The four low modulus adhesives all had the same basic moisture cure polymer but contained different fillers and additives. Hot-dipped galvanized steel was bonded to random fiber-reinforced unsaturated polyester and aged in two moisture environments for various durations. Adherend surface wipes included acetone, isopropyl alcohol and a typical surface contamination for galvanized steel (an organic lubricant). Diffusion coefficients, moisture uptake and modulus changes due to moisture environment were determined for the adhesives and the fiber-reinforced plastic (FRP). The moisture cure adhesive with clay and poly(vinyl chloride) (PVC) as fillers (adhesive 252) had the highest retained lap joint strengths. Initially, adhesive 252 had single lap joint strengths of 1.47 ± 0.08 MPa for acetone-wiped joints and 1.39 ± 0.33 MPa for organic lubricant-wiped joints. After accelerated aging in a cataplasma environment for 9 weeks, lap joint strengths fell to 0.61 ± 0.08 MPa for acetone-wiped joints and to 0.65 ± 0.11 MPa for organic lubricant-wiped joints. Environmental scanning electron microscopy (ESEM) and energy-dispersive spectrometry (EDS) showed that the actual failure locus was through a corroded zinc layer and between the adhesive and the zinc surface after aging. Dynamic mechanical analysis (DMA) showed that the modulus for adhesive 252 dropped from 21.7 to 13.9 MPa after cataplasma aging. From finite element analysis (FEA), this modulus drop corresponded to a drop in normal stress concentration from 0.75 to 0.57, and a drop in shear stress concentration from 1.41 to 1.36 at a point 0.5 mm from the end of the single lap joint overlap.     

Adhesive Bonding to Galvanized Steel: II. Substrate Chemistry,Morphology and Bond Failure Analysis

Galvanized substrate morphology, oxide layer chemistry, bond failure modes, failure loci, and bondline corrosion have been investigated for adhesive bonds to galvanized steel. Significant differences in surface morphology were observed between the relatively smooth surfaces of “hot-dipped” substrates and the considerably rougher texture of “electroplated” substrates. The hot-dipped substrates were also chemically heterogeneous, with significant amounts of Al, Mg, Ca, and Pb, in addition to Zn, constituting the surface layer. For electroplated substrates, on the other hand, Zn was the major constituent. It was concluded that, for a given adhesive, low strengths and poor bond durability generally correlated with the minimum surface roughness and maximum chemical heterogeneity of the hot-dipped substrates. Higher strengths, and better durability, on the other hand, were observed for electroplated substrates, which showed the greater roughness, as well as chemically the more uniform surface.

Significantly, ESCA spectroscopy of fracture surfaces of unaged samples established that failure loci for both one and two-part epoxy adhesives included the oxide layer of the substrate. This was true for both hot-dipped, as well as electroplated substrates. For aged samples, scanning electron microscopy and X-ray diffraction analysis of failure surface identified zinc-based corrosion products present in the original bond area.     

Influence of Chemical Pretreatments on Surface Morphology and Bondability of Aluminium

Wettability combined with a strong oxide layer are needed for adhesive bonding and these properties can only be examined by making joints with an adhesive and testing them. The best test for this purpose is the climbing drum peel test. Surfaces must be pickled and anodized. The acids used for pickling influence the anodized structure and chromic-sulphuric acid mixture followed by anodizing in chromic acid gives optimum results. Metal pickled in sulphuric acid shows lower peel strength on bonding. Electron-micrographs show a clear relation between surface morphology and bondability and a fine etchpit structure within coarser etchpits gives the most desirable structure. Low strengths are associated with either weak oxide or a weakened aluminium surface.     

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.     

The Durability of Adhesively-bonded Ti-6Al-4V

The durability of chromic acid-anodized Ti-6Al-4V alloy, adhesively-bonded with FM-5 supported polyimide adhesive has been studied. The performance tests compared titanium samples that had been thermally treated and bonded, and samples that were bonded and thermally treated. Following the thermal treatment, the durability was examined (1) by immersing wedge-type specimens in boiling water and measuring the crack growth and (2) by measuring the lap shear strength for single lap specimens. In the wedge tests, failure occurs within the adhesive for specimens treated at temperatures below 371°C for less than one hour. For treatments at higher temperatures and for longer periods of time, failure occurs within the anodic oxide. From the lap shear tests, the principal finding is that the lap strength decreases with increasing treatment time at constant temperature and with increasing temperature at a fixed time. For the lap specimens, failure occurs to a greater extent within the oxide as the treatment time and temperature increase. Surface analysis results indicate the formation of an aluminum fluoride species. It is reasoned that the formation of fluorine-containing materials weakens the oxide and promotes failure within the anodic oxide.     

J-133胶黏剂铝合金胶接接头湿热老化性能的研究

选取J-133环氧结构胶黏剂,制备铝合金胶接接头。通过在湿热条件下对试样进行环境试验,对结构胶黏剂和胶接接头的耐久性进行了评价。采用TG、IR和光学显微镜分别对胶黏剂样品变化和胶接接头破坏面形貌进行分析。分析结果表明:该胶黏剂在55℃和80℃,2200h湿热老化后剪切强度下降分别超过5%和7%;胶黏剂热失重峰温度下降,发生了断链分解;断链反应发生在固化生成的新官能团部位;胶接界面层和胶黏剂层都受到了水分的影响。     

A Surface Treatment for Ti-6AI-4V

A simple nonchromate surface treatment that was developed for aluminum alloys (STAB (3)) has been found to provide Ti-6A1-4V, bonded with epoxy adhesives, with good hydrothermal endurance. The simplest form of the treatment is to degrease, dip in caustic soda, hard [i. e., forceful) spray-rinse and dry. Although STAB (3) for aluminum was satisfactory with a room temperature dip in caustic soda, the solution temperature should be greater than 40°C for Ti-6A1-4V. A steel wool scrub prior to the NaOH dip enhances durability. Surface property measurements following the surface treatment indicate that a porous oxide layer is formed on top of a 300A barrier layer. The durability of this treatment is attributed to mechanical interlocking between the adhesive and the porous oxide (hydroxide) and to the chemical stability of the oxide (hydroxide) under hydrothermal stress.     

Ageing of adhesively bonded joints—fracture and failure analysis using video imaging techniques

An investigation into the durability of adhesively bonded joints has been undertaken to help improve the prediction of joint lifetimes. Polymethylmethacrylate (PMMA) substrates have been bonded with a two-part acrylic adhesive to make single lap-shear joints. Joints have been aged in a hot/wet environment (40°C and 95% humidity) with no applied stress for up to 4000 h and were tested in tension. The novel aspect of the research has been the development of a video imaging analysis technique which allows damage initiation and propagation within the joint to be detected as load is applied to the joint. Images of fracture initiation and damage propagation have been correlated with stress/displacement data for joints under tensile loading. The data from aged samples is compared with data from un-aged samples. Both the stresses at which damage is seen to initiate and the final failure stress of the joints decrease as the ageing time increases. The failure mode changes from cohesive failure within the PMMA substrate to failure within the adhesive, near the PMMA/acrylic adhesive interface.     

The Fatigue and Durability Behaviour of Automotive Adhesives. Part I: Fracture Mechanics Tests

A fracture mechanics approach has been successfully used to examine the cyclic fatigue behaviour of adhesively-bonded joints, which consisted of aluminium-alloy or electro-galvanised (EG) steel substrates bonded using toughened-epoxy structural paste-adhesives. The adhesive systems are typical of those being considered for use, or in use, for bonding load-bearing components in the automobile industry. The results were plotted in the form of the rate of crack growth per cycle, da/dN, versus the maximum strain-energy release rate, G_max, applied in the fatigue cycle, using logarithmic axes. Of particular interest was the presence of a threshold value of the strain-energy release rate, G_th, applied in the fatigue cycle, below which fatigue crack growth was not observed to occur. The cyclic fatigue tests conducted in a relatively dry environment of 23°C, and 55%; RH were shown to cause crack propagation at far lower values of G_max compared with the value of the adhesive fracture energies, G_c, which were determined from monotonically-loaded fracture tests. Cyclic fatigue tests were also conducted in a “wet” environment, namely immersion in distilled water at 28 C. The “wet” fatigue tests clearly revealed the further significant effect an aggressive, hostile environment may have upon the mechanical performance of adhesive joints, and highlighted the important influence that the surface pretreatment, used for the substrates prior to bonding, has upon joint durability. The development and standardisation of “wet” fatigue tests may provide the basis for a very effective accelerated-ageing test.     

A design of experiments assessment of moisture content in uncured adhesive on static strength of adhesive-bonded galvanized SAE1006 steel

As part of a cooperative research program to develop and implement crash-resistant toughened adhesives targeted for future vehicles, this paper summarizes a study of the influence of pre-exposure of uncured adhesive and steel sheets in a humid and elevated temperature environment on quasi-static strength of bonded hot dipped galvanized SAE1006 steel joints.In this study, we use a DOE (design-of-experiment) program called DEXPERT to design the experiment and to analyze the effects of exposure temperature, exposure time, curing temperature and curing time on joint strength of adhesive-bonded galvanized SAE1006 steel. Prior to adhesive curing, the adhesive and galvanized steel coupons were pre-exposed to various relative humidity levels and temperatures. The experimental results were then analyzed by DEXPERT and the relative contributions of each factor on variance in joint strength were calculated. It was found that curing temperature is the most influential factor affecting the strength of adhesive-bonded galvanized SAE1006 steel joints. The curing of a joint at 180 °C can increase the robustness of the process and provides the greatest strength regardless of the variation of other factors. The joint strength curing at 150 °C shows a strong sensitivity to the curing time, while the adhesive cannot cure at 130 °C at all under all conditions. It has also been found that the pre-exposure of adhesive and steel for an hour can slightly decrease the joint strength at high temperature and humidity. Therefore, the effect of long time exposure of the uncured adhesive and steel still needs to be further investigated.     

Effect of Flaws in the Adhering Interface on the Strength of Adhesive-bonded Butt Joints

This paper presents the strength of metal-to-metal bonded joints with a flaw in the interface between the adhesive layer and the adhering surface of adherend. The test specimens of butt joints are prepared by bonding two thin-wall metal tubes. The materials are carbon steel, aluminum alloy, brass and copper. The adhesive is epoxy resin. The tensile and shear strength of the joints are experimentally determined by subjecting the specimens to axial load and torsion for various flaw sizes and thickness of adhesive layers. Linear elastic fracture mechanics is applied to the experimental results. The stress intensity factors for a layered composite with a flaw in the interface are numerically calculated in terms of flaw size and loading by using Erdogan's formulas. The fracture stresses of joints with a flaw are predicted at the critical values of the stress intensity factors. The strength of joints without a flaw is also correlated with the stress intensity factors by use of a concept of “effective flaw size”.