Durability epoxy adhesives

Epoxy resins are also used in special appHcations, such as an overlaying procedure requiring a durable, heat-resistant bond of a difficult-to-bond overlay on a wood-base panel substrate. Metal sheets used as overlays, for example, often require an epoxy adhesive. 

Primers are required to be resistant to all of the same fluids and environments as the adhesive, and are in addition expected to be compatible with secondary finishes such as corrosion and fluid resistant primers applied to cured bond assemblies. The most commonly used primers for 250°F cured epoxy adhesives also have active corrosion inhibitors themselves to combat corrosion at bondlines. This last requirement is somewhat dated, evolving from the severe corrosion and delamination problems experienced before U.S. airframe manufacturers adopted durable surface treatments. 

Adhesives and sealers can be an important part of a total corrosion protection system. Structural bonding procedures and adhesives for aluminum, polymer composites, and titanium are well established in the aerospace industry. Structural bonding of steel is gaining increasing prominence in the appliance and automotive industries. The durability of adhesive bonds has been discussed by a number of authors (see, e.g., 85). The effects of aggressive environments on adhesive bonds are of particular concern. Minford ( ) has presented a comparative evaluation of aluminum joints in salt water exposure Smith ( ) has discussed steel-epoxy bond endurance under hydrothermal stress Drain et al. (8 ) and Dodiuk et al. (8 ) have presented results on the effects of water on performance of various adhesive/substrate combinations. In this volume, the durability of adhesive bonds in the presence of water and in corrosive environments is discussed by Matienzo et al., Gosselin, and Holubka et al. The effects of aggressive environments on adhesively bonded steel structures have a number of features in common with their effects on coated steel, but the mechanical requirements placed on adhesive bonds add an additional level of complication. 

Wedge Test. The adhesive bond durabilities of the Inhibitor-treated 7075-T6 surfaces were evaluated by wedge tests (ASTM D-3762) on bonded specimens using the FM 123-2 epoxy adhesive to simulate the epoxy primer. The specimens were placed In a humidity chamber at 65°C and 95% relative humidity and removed at specified time Intervals to record the crack tip locations after each examination, they were returned to the humidity chamber. 

The corrosion resistance and polymer-bonding compatibilities of the lonizable organophosphonates and the neutral organo-silanes are directly related to their inherent chemical properties. Specifically, NTMP inhibits the hydration of AI2O2 and maintains or Improves bond durability with a nitrile-modified epoxy adhesive which is cured at an elevated temperature. The mercaptopropyl silane, in addition to these properties, is compatible with a room temperature-cured epoxy-polyamide primer and also exhibits resistance to localized environmental corrosion. These results, in conjunction with the adsorbed Inhibitor films and the metal substrate surfaces, are subsequently discussed. 

The ionic phosphonates like NTMP are effective hydration inhibitors because they can form an insoluble complex with the oxide surface. They are useful as epoxy adhesive couplers in cases where the adhesive and its curing cycle are compatible with the adsorbed phosphonate molecule. (14) Wedge test results indicate that in two epoxy-aluminum systems studied, certain organosilanes tend to both increase the epoxy-metal bond durability and maintain hydration resistance. The results of anodic polarization experiments further suggest that these silane films are effective against localized pitting. 

Adsorbed NTMP exhibits a pH-dependent surface coverage on anodized aluminum, which Includes a region characterized by a multilayer of hydrogen-bonded phosphonate molecules. These thick layers are weak and fall to provide good bond durability in a humid environment. NTMP monolayers are protective against hydration and are compatible with a nitrile-modified epoxy adhesive, but not with an epoxy-polyamide primer topcoat. 

Aluminum powder, in particular, is frequently employed at relatively high concentrations in high-temperature epoxy adhesive formulations. The filler provides improvement in both tensile strength and heat resistance, and it increases the thermal conductivity of the adhesive. Aluminum powder fillers also reduce undercut corrosion and, hence, improve adhesion and durability of epoxy adhesive between bare steel substrates. It is believed that this is accomplished by the aluminum filler providing a sacrificial electrochemical mechanism.27... 

FIGURE 10.3 Effect of silane adhesion promoter on the durability of a mild steel joint bonded with epoxy adhesives.16... 

Nitrilotrismethylene Epoxy adhesives Single molecular Application in aqueous Improves durability of aluminum... 

De Nicola, A. J., and Bell, J. P., Synthesis and Testing of p-Diketone Coupling Agents for Improved Durability of Epoxy Adhesion to Steel, in Adhesion Aspects of Polymeric Coatings, K. L. Mittal, ed., Plenum Press, New York, 1983, p. 443. 

These low-temperature environmental effects can be significant factors that contribute to an adhesive system s durability and life. This section discusses the characteristics of epoxy adhesive joints exposed to low temperatures and to thermal cycling and suggests formulations for improving the resistance of adhesives and sealants to these conditions. 

Strong chemical bonds between the adhesive and adherend help stabilize the interface and increase joint durability. Aluminum joints formed with phenolic adhesives generally exhibit better durability than those with epoxy adhesives. This is partially attributable to strongly interacting phenolic and aliphatic hydroxyl groups that form stable primary chemical bonds across the interface. 

The outdoor durability of epoxy bonded joints is very dependent on the type of epoxy adhesive, specific formulation, nature of the surface preparation, and specific environmental conditions encountered in service. The data shown in Fig. 15.19, for a two-part room temperature cured polyamide epoxy adhesive with a variety of fillers, illustrates the differences in performance that can occur due to formulation changes. Excellent outdoor durability is provided on aluminum adherends when chromic-sulfuric acid etch or other chemical pretreatments are used. 

The factors that influence the durability of epoxy adhesives in outdoor weathering conditions are... 

It is impossible to avoid a discussion on prebond surface preparation since it is one of the most important factors in the fabrication of a durable and consistent epoxy adhesive joint. Selection of a proper surface preparation is not an easy task, and the actual implementation of the surface treating process in production is equally daunting. 

However, the corrosion resistance of aluminum as well as the durability of joints made with epoxy adhesives is very dependent on the type of aluminum alloy used. Bonds made with relatively corrosion-resistant 6061-T6 aluminum alloy will last about 4 times as long as equivalent joints made with 2024-T3 alloy when exposed to marine environments. 

However, with the proper combination of surface treatment and adhesive, these differences in durability to aggressive environments can be minimized, as shown in Table 16.3. The initial shear strength and permanence depend on the type of alloy and the pretreatment used. Note that the data presented here show only the relative differences in joint strength for one specific epoxy adhesive and are not representative of other adhesive formulations. There was no attempt to maximize any of these values through choice of the adhesive. 

All of the commercial epoxy adhesives presented in App. B bond well to aluminum and to a wide variety of other materials. Sell22 has ranked a number of aluminum adhesives in order of decreasing durability as follows nitrile-phenolics, high-temperature epoxies, elevated-temperature curing epoxies, elevated-temperature curing rubber-modified epoxies, vinyl epoxies, two-part room temperature curing epoxy paste with amine cure, and two-part urethanes. 

Copper substrates are commonly bonded with epoxy adhesives in the microelectronics and marine industries. Compared to aluminum substrates, copper when bonded with epoxy adhesives provides lower initial strength. Depending on the adhesive and the type of test used, this can be as much as 50 percent lower. Similar to aluminum joints, copper joints bonded with epoxy adhesives can show poor durability in moist environments unless the interface is protected. 

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