High-Temperature Epoxy Adhesive Formulations

Temperature-resistant two-part, elevated-temperature curing epoxy adhesives can be formulated with aromatic amines, such as metaphenylenediamine (MPDA), methylene dianiline (MDA), or a eutectic blend of the two. These adhesives will provide relatively high temperature strength, but they are generally brittle. When mixed with epoxy resin at concentrations of about 15 pph for MPDA and 26 pph for MDA, they provide complete cure in about 30 min at 175°C. The aromatic amines also provide a working life of several hours at room temperature. Starting formulations for aromatic amine cured epoxy adhesives are shown in Table 12.4. 

Advantages of epoxy-based high-temperature adhesives relative to other adhesive types include relatively low cure temperatures, no volatiles formed during cure, low cost, and a variety of available formulating and application possibilities. The higher-temperature aromatic... 

Structural adhesives are formulated from epoxy resins, phenolic resins, acrylic monomers and resins, high temperature-resistant resins (e.g., polyimidcs), and urethanes. Structural adhesive resins arc often modified by elastomers. 

Over the past several decades, significant advances have been made in developing epoxy-based adhesives having improved performance over these early adhesive systems. These improvements were made possible by (1) the incorporation of toughening additives into epoxy resin formulations and (2) the use of multifunctional epoxy resins primarily for high-temperature applications. These innovations are discussed in later chapters. 

Since epoxy formulations are generally good thermal insulators, the exotherm will depend on the mass of the system. A high rate of exotherm is needed with some epoxy adhesive systems to achieve practical curing rates. However, excessively high exothermic temperatures can result in bubble formation, thermal degradation, and even a potentially hazardous situation. Control of the exotherm is, therefore, a very important factor in formulating epoxy adhesives. 

Glycidyl amine epoxy resins are reaction products of aromatic amines and epichlorohy-drin. They have high modulus and high glass transition temperature. These resins find use in aerospace composites and high-temperature adhesive formulations. 

DADS melts at 135°C and is employed stoichiometrically with DGEBA at 33.5 pph. Fortunately, it is relatively unreactive so it can be mixed with epoxy resin at elevated temperatures. It can also be used in epoxy solutions to provide an adhesive formulation for manufacturing supported or unsupported film with long shelf life. Because of the low reactivity of the system, DADS is generally employed at a concentration that is about 10 percent greater than stoichiometry, or an accelerator, such as BF3-MEA, is employed at about 0.5 to 2 pph. When DADS is mixed with liquid DGEBA resin, it provides a pot life of 3 h at 100°C and requires a rather extended high-temperature cure to achieve optimal physical properties. 

Anhydrides are sometimes used in epoxy adhesives to provide specific properties or to provide improvements in handling strengths. The most important anhydride in epoxy adhesive formulations is pyromellitic dianhydride (PMDA), which provides very high temperature properties. 

Benzyldimethylamine (BDMA) is another tertiary amine that can be used as either a sole catalyst or an accelerator with other curing agents. It is used with DGEBA epoxy resins at 6 to 10 pph. The pot life is generally 1 to 4 h, and the cure will be complete in about 6 days at room temperature. When used by itself, BDMA can provide epoxy adhesive formulations with high-temperature resistance (Chap. 15). However, BDMA is mostly used as an accelerator for anhydride and dicyandiamide cured epoxy resins. 

In general, the elastomer must be prereacted (adducted) with the epoxy for the toughening effect to take place. Adducts reduce the likelihood of early phase separation and maintain the solubility of the elastomer in the uncured resin system. For CTBN the reaction is carried out at high temperatures (150 to 160°C) and usually in the presence of a catalyst, such as tris-dimethylamino phenol or piperidine. The resulting epoxy-CTBN adducts are available from several suppliers, and they can be easily formulated into epoxy adhesives. 

Compared to the carboxylated nitrile elastomer additives, the use of thermoplastics has primarily been focused on the aerospace industry. On a cost per pound basis, the two-phase nitrile additives offer the best combination of property improvement without negative impact. The thermoplastic additives, however, may offer better high-temperature performance, but they are more difficult to formulate and to process as adhesives. As a result, the cost of these adhesives is generally much higher than that of other toughened epoxy mechanisms. 

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... 

There are several ways by which the formulator can moderately improve the heat or chemical resistance of room temperature curing epoxy adhesives. Using an elevated-temperature cure or a postcure will, of course, improve the temperature resistance by virtue of improved crosslink density. However, this section describes formulations that have been developed for moderately improved heat resistance after only a cure at room temperature. Optimal (heat-curing) high-temperature and chemically resistant epoxy adhesives are discussed in Chap. 15. 

Benzoquinone tetracarboxylic acid dianhydride (BTDA) has been found to provide epoxy adhesives with excellent high-temperature properties, in both the short and long terms. The formulation described in Table 12.12 provides good resistance to 260°C. This two-part adhesive can be cured 2 h at 200°C. The disadvantage of BTDA is that relatively high cure temperatures are required that result in a high degree of internal stress within the bond line. 

PMDA or trimellitic anhydride has also been shown to provide epoxy adhesive formulations with high-temperature properties. Table 12.13 shows the elevated-temperature tensile shear strength of an epoxy adhesive cured with 4 pph of PMDA. Another specialized formulation employing PMDA was found to provide high shear strength when tested at 260°C even after aging 1000 h at 260°C.15... 

Epoxy-phenolic adhesive was the first true high-temperature adhesive. It was developed in the early 1950s as a high-temperature aircraft adhesive. An example formulation is provided in Table 13.4, but these adhesives are discussed predominantly in Chap. 15. 

Pyrolysis is simple thermal destruction of the molecular chain of the base polymer in the adhesive or sealant formulation. Pyrolysis causes chain scission and decreased molecular weight of the bulk polymer. This results in reduced cohesive strength and increased brittleness. Resistance to pyrolysis is predominantly a function of the intrinsic heat resistance of the polymers used in the adhesive formulation. As a result, many of the aromatic and multifunctional epoxy resins that are used as base resins in high-temperature adhesives are rigidly crosslinked or are made of a molecular backbone referred to as a ladder structure, as shown in Fig. 15.4. 

The high-temperature resins described above provide the main elements in the adhesive formulator s recipe. However, there are also additives, fillers, etc., that can further enhance the thermal properties of more conventional epoxy adhesives. These additional components improve thermal resistance by providing oxidation resistance, toughening, and control of bond line stress. 

A typical formulation for a metal-to-metal adhesive-sealant that is cured with a combination of phthalic anhydride and pyromellitic anhydride is shown in Table 12.6. Table 15.9 shows the high-temperature properties of another epoxy formulation cured with pyromellitic dianhydride. Epoxy formulations cured with pyromellitic dianhydride (PMDA) show good short-term thermal stability in the temperature range of 150 to 230°C. 

The BTDA-epoxy blends are relatively easy to formulate, and several high-temperature epoxy adhesive formulations have been developed aimed at specific end properties. 

Flexibilized epoxy adhesives have moderate strength on flame and corona treated polyolefin substrates. Elevated cure temperature results in better adhesion because of more efficient wetting of the substrate surface. Table 16.13 shows a starting formulation for an epoxy adhesive that develops high peel strength to many difficult-to-bond substrates such as polyethylene, thermoplastic rubber, and polyester film. 

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