The absorption and desorption of water in two different rubber-toughened epoxy adhesives was measured gravimetrically over a relatively wide range of temperature and relative humidity (RH). The data were fitted to a new diffusion model in which Fick's law was assumed to act in two sequential stages, each with its own diffusion coefficient and saturated water concentration. This “sequential dual Fickian” (SDF) model and a Langmuir-type diffusion model were both able to model the absorption behaviour. The dependence of the five SDF model parameters on temperature and RH was investigated in detail. The two diffusion coefficients were found to be largely independent of RH, while the fractional mass uptake values for each stage increased with RH. The absorption temperature only had a significant effect on the diffusion coefficient of the first stage and the fractional mass uptake of the second stage. Water desorption from the two epoxies was modeled accurately using Fick's law. A significant difference was obs...

Hygrothermal Properties of Highly Toughened Epoxy Adhesives

Cathodic delamination is one of the major modes of failure for anticorrosive coatings subjected to a physical damage and immersed in seawater. The cause of cathodic delamination has been reported to be the result of a chemical attack at the coating–steel interface by free radicals and peroxides formed as intermediates in the cathodic reaction during the corrosion process. In this study, antioxidants (i.e., free radical scavengers and peroxide decomposers) have been incorporated into various generic types of coatings to investigate the effect of antioxidants on the rate of cathodic delamination of epoxy coatings on cold rolled steel. The addition of <5 wt% free radical scavengers to epoxy coatings improved the resistance toward cathodic delamination by up to 50% during seawater immersion, while peroxide decomposers had a limited effect. Testing using substrates prepared from stainless steel, copper, aluminum, galvanized steel, and brass also showed a reduction in the rate of cathodic delamination when the coating was modified with a free radical scavenger. The protective mechanism of free radical scavengers investigated for the primers are similar to that of antioxidants used for protection against photochemical degradation by UV-radiation of top coatings. Both substrate corrosion and degradation of a coating exposed to UV-radiation lead to the formation of free radicals as reactive intermediates.

Reduction of cathodic delamination rates of anticorrosive coatings using free radical scavengers

To obtain experimental data in short time on the degradation of adhesives exposed to moisture, a valuable technique is represented using the open-face configuration. With this technique, a layer of adhesive is first applied on one adherend and exposed to the humid environment; then, the second adherend is bonded and the joint can now undergo mechanical testing. Apart from the acceleration of moisture uptake which is obtained due to the larger area exposed, a further advantage is the uniformity of degradation. A further acceleration can be obtained by adding a hygroscopic contaminant at the adhesive/adherend interface, which speeds up moisture uptake and accentuates the interfacial nature of the failure. The main aim of this work was to evaluate the decay of the mechanical strength in the absence or presence of a contaminating agent. The specimens studied were single lap joints, tested under static shear loading. Two sets of specimens were considered; in the first set, the adhesive was applied in standard way and in the second set, the adhesive/adherend interface was contaminated with droplets of CaCl2 aqueous solution. Both sets were subjected to humid and warm environment (100% relative humidity, 50 °C). After the desired exposure times in the range 1–5 weeks, groups of specimens were dried and bonding of the second adherend was carried out. Then, mechanical testing was performed; the fractured surfaces were examined by scanning electron microscopy. The results show that before degradation the failure type is cohesive, but it changes to interfacial failure as the degradation proceeds. Uncontaminated specimens exhibit gradual degradation during the exposure time; contaminated specimens achieve almost half of the degradation in less than one week; after that, the process continues at lower speed and at the end of the observed period both methods show similar values of failure loads. Additional tests were carried out to assess the moisture absorption in the adhesive layer and relate it to the exposure time.

Moisture degradation of open-faced single lap joints

To obtain experimental data in short time on the degradation of adhesives exposed to moisture, a valuable technique is represented using the open-face configuration. With this technique, a layer of adhesive is first applied on one adherend and exposed to the humid environment; then, the second adherend is bonded and the joint can now undergo mechanical testing. Apart from the acceleration of moisture uptake which is obtained due to the larger area exposed, a further advantage is the uniformity of degradation. A further acceleration can be obtained by adding a hygroscopic contaminant at the adhesive/adherend interface, which speeds up moisture uptake and accentuates the interfacial nature of the failure. The main aim of this work was to evaluate the decay of the mechanical strength in the absence or presence of a contaminating agent. The specimens studied were single lap joints, tested under static shear loading. Two sets of specimens were considered; in the first set, the adhesive was applied in standard ...

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The goal of this work was to evaluate and compare the performance of different surface pre-treatments applied to aluminium single lap joints exposed to warm moisture. Four different processes were considered: 1) degreasing-roughening; 2) degreasing-roughening and phosphoric acid anodising; 3) degreasing-roughening and conditioning with Picklex®20 (a water-based product for metal surface preparation); 4) degreasing-roughening and phosphoric acid anodising and contaminating the adherend surface with CaCl2 to accelerate the tests. After each pre-treatment, lap-shear specimens were prepared with the open face technique. The half-joints were exposed to warm moisture (50°C, 100% RH) for times up to 4 weeks, then they were completed and subjected to mechanical testing. The results show that anodising yields the best durability, as strength remained practically constant over time; all the other groups of specimens exhibited progressive reduction in strength and wider scatter of the results. A large role is played...

Effect of Different Substrate Pre-Treatments on the Resistance of Aluminum Joints to Moist Environments

Water-filled blisters were observed to form during accelerated aging experiments with aluminum adherends and two structural epoxy adhesives. Both closed adhesive joints and open-face specimens were affected. The blisters grew with time, originated both in the adhesive and at the epoxy-aluminum interface, and were found only at 100% relative humidity at both 65°C and 85°C; blisters were never observed at 85% relative humidity or lower. The same water-soluble ionic species were found in the blister liquid, the two adhesives and water that had been in contact with adhesive samples for an extended period. It is proposed that the blisters grew under the influence of osmosis, originating in water clusters at microscopic voids. Contamination of the aluminum adherends by residual etching solution, although not a necessary precondition for blistering, could facilitate this process by lowering the partial pressure at which water condenses and by creating higher osmotic pressures.

Y. Tu

Papers

Blistering as a Form of Degradation in Adhesive Joints