Epoxies/adhesives

Epoxy-based adhesives were first introduced in the 1950 s. Since then they have become widely used, particularly in the aerospace, vehicie and boat buiiding industries, for applications requiring high strength and endurance. 

Epoxy adhesives may have a variety of cure temperatures, from room temperature (RT) up to 175°C, and are available as pastes (one or two-part) or films. Two-part, RT curing varieties are widely available for domestic use. 

In the unhardened state, the chemical structure for an epoxy resin is characterized by the epoxide group, shown in Fig. 8.1. 

AU epoxy compounds contain two or more of these groups. Epoxy resins may vary from low-viscosity liquids to high-melting point solids. More than two dozen types are known. Tens of curing agents, including commonly available compounds such as amines, primary and secondary amines, and anhydrides, are used. Only a few of these are used widely in adhesive formulations. 

Of all the thermosetting plastics, epoxies are more widely used than any other plastic, in a variety of applications. There are resin/hardener systems (two-part) that cure at room temperature, as well as one-part systems that require extreme heat cures to develop optimum properties (e.g., 121 °C and 

One-part epoxy adhesives include solvent-free liquid resins, solutions in solvent, liquid resin pastes, fusible powders, sticks, pellets and paste, supported and unsupported films, and preformed shapes to fit a particular joint. Two-part epoxy adhesives are usually composed of the resin and the curing agent, which are mixed just prior to use. The components may be liquids, putties, or liquid and hardener powder. They may also contain plasticizers, reactive diluents, fillers, and resinous modifiers. The processing conditions are determined by the curing agent employed. In general, two-part systems are mixed, applied within the recommended pot life (a few minutes to several hours), and cured at room temperature for up to 24 h or at elevated temperatures to reduce the cure time. Typical cure conditions range from 3 h at 60 °C to 20 min at 100 °C.  

With an aliphatic amine (e.g., diethylenetriamine) as curing agent at room temperature, the resin is cured in 4—12 h to an extent sufficient to permit handling of the bonded assembly. Full strength develops over several days. A compromise between 

Epoxy resins were invented by the Swiss chemist Dr Pierre Castan and patented in 1939. The Swiss company Ciba Geigy (the epoxy division is now part of Huntsman) and Shell Chemical (the epoxy division is now part of Hexion) carried out the commercial development of epoxy adhesives in the 1940s and 1950s. 

There are two main categories of epoxy resins glycidyl epoxy, and non-glycidyl epoxy. The former are further classified as glycidyl-ether, glycidyl-ester and glycidyl-amine. 

Glycidyl epoxies are prepared via a condensation reaction of a dihydroxy compound, dibasic acid or a diamine and epichlorohydrin. 

Non-glycidyl epoxies are aliphatic or cycloaliphatic epoxy resins. They are made by peroxidation of an olefinic double bond. Cycloaliphatic epoxies have recently become important for the preparation of UV-cured adhesives and coatings (see Section 2.4). 

The most often used epoxies in adhesives are based on the diglycidyl ether of bisphenol-A (DGEBA) as seen in Equation 2.9  

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Tetrahydrofurfuryl alcohol is used in elastomer production. As a solvent for the polymerization initiator, it finds appHcation in the manufacture of chlorohydrin mbber. Additionally, tetrahydrofurfuryl alcohol is used as a catalyst solvent-activator and reactive diluent in epoxy formulations for a variety of apphcations. Where exceptional moisture resistance is needed, as for outdoor appHcations, furfuryl alcohol is used jointly with tetrahydrofurfuryl alcohol in epoxy adhesive formulations. 

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. 

The two-part epoxy adhesive, readily available in hardware stores or other consumer outlets, comes in two tubes. One tube contains the epoxy resin, the other contains an amine hardener. Common diamine room temperature epoxy curing agents are materials such as the polyamides, available under the trade name Versamid. These polyamides are the reaction products of dimer acids and aUphatic diamines such as diethylenetriamine [111-40-0] ... 

A.dhesiveslCements Sealants j Coatings. Excellent adhesives of high strength and high oil resistance can be prepared using nitnle mbber (25). Many references have discussed the use of nitnle mbber—phenoHc and nitnle mbber—epoxy adhesives for printed circuit boards. 

The commercial possibiUties for epoxy resins were first recognized by DeTrey Emres in Switzerland and DeVoe and Raynolds in the United States (1,2). In 1936, DeTrey Emres produced a low melting bisphenol A-based epoxy resin that gave a thermoset composition with phthaUc anhydride. Apphcation of the hardened composition was foreseen in dental products, but initial attempts to market the resin were unsuccessful. The patents were hcensed to CIBA AG of Basel, Switzerland (now CIBA-GEIGY), and in 1946 the first epoxy adhesive was shown at the Swiss Industries Eair and samples of casting resin were offered to the electrical industry. 

Two wooden beams are butt-jointed using an epoxy adhesive (Fig. A1.3). The adhesive was stirred before application, entraining air bubbles which, under pressure in forming the joint, deform to flat, penny-shaped discs of diameter 2fl = 2 mm. If the beam has the dimensions shown, and epoxy has a fracture toughness of 0.5 MN mT , calculate the maximum load F that the beam can support. Assume K = cT Tra for the disc-shaped bubbles. 

A typical comonomer could be a polydimethylsilane to increase the toughness of the polymerized film, or an amine funetional silane for ehemieal eoupling with an epoxy adhesive. 

Fig. 2. Morphology model of a core-shell, rubber-toughened epoxy adhesive.

The two-component urethane structural adhesives are among the most difficult to characterize, simply because of the widely varying properties that are possible. These adhesives may be rigid plastics similar in modulus to standard epoxy adhesives, with glass transition temperatures of the cured adhesive being approximately 60°C. 

Although the above experiments involved exposure to the environment of unbonded surfaees, the same proeess oeeurs for buried interfaces within an adhesive bond. This was first demonstrated by using electrochemical impedance spectroscopy (EIS) on an adhesive-covered FPL aluminum adherend immersed in hot water for several months [46]. EIS, which is commonly used to study paint degradation and substrate corrosion [47,48], showed absorption of moisture by the epoxy adhesive and subsequent hydration of the underlying aluminum oxide after 100 days (Fig. 10). After 175 days, aluminum hydroxide had erupted through the adhesive. 

Direct bonding. In many high-volume production applications (i.e., the automotive and appliance industries), elaborate surface preparation of steel ad-herends is undesirable or impossible. Thus, there has been widespread interest in bonding directly to steel coil surfaces that contain various protective oils [55,56,113-116], Debski et al. proposed that epoxy adhesives, particularly those curing at high temperatures, could form suitable bonds to oily steel surfaces by two mechanisms (1) thermodynamic displacement of the oil from the steel surface, and (2) absorption of the oil into the bulk adhesives [55,56]. The relative importance of these two mechanisms depends on the polarity of the oil and the surface area/volume ratio of the adhesive (which can be affected by adherend surface roughness). 

Although the acrylate adhesives are readily available and studies have shown that they can produce reasonable bonding properties, they have the disadvantages of having high shrinkage, high fluid absorption, and low service temperatures. Acrylate adhesive applications would be limited. The development of EB-curable epoxy adhesives would have applications in the aerospace and automotive industry and potential wider uses. The most immediate application for these resin systems is composite repair of commercial and military aircraft. 

There has been very little work done on the development of EB-curable epoxy adhesives. When undertaking this development work the authors had two objectives. The first objective was to develop a series of adhesives for bonding aluminum-to-aluminum (Al-Al) and composite-to-composite (C-C) with lap shear strengths of 30 MPa or greater at room temperature. The second objective was that the... 

EB processing and rheological properties of EB-cured epoxy adhesives... 

We have also looked at the lap shear strength of selected EB-ciirable epoxy adhesives. Because the adhesives being developed were being used for both aluminum-to-aluminum and composite-to-composite applications the lap shear strengths for both adherends was measured. Aluminum adherends were T2024 phosphoric acid anodized according to ASTM 3933. The composite adherends... 

Lap shear strengths (MPa) of selected EB-cured epoxy adhesives at various temperatures... 

Effects on lap shear strength of EB-cured epoxy adhesives from different surface preparations on aluminum and composite adherends... 

Materials and additives that are chemically basic in nature have a detrimental effect on the curing of cationic-initiated epoxy systems. These substances can either stop the curing mechanism completely or produce under-cured polymers. Therefore such additives as amines or imides that are known to be adhesion promoters cannot be used in the EB-curable epoxy adhesive formulations. 

Though toughened phenolic adhesives remain in use for specific applications, toughened epoxy adhesives have dominated metallic bonding on civil aircraft since their development in the 1960s. Advances since then have been incremental and mostly revolving around manufacturing issues such as handleability and allowed out-time. 

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. 

Many types of chemical treatment are used in industry. Chromic, permanganic, sulphuric, and chlorosul-phonic acids are often used as the oxidants. It has been shown that the adhesion of polyethylene to substrates, such as cellophane, steel, aluminium, and epoxy adhesives, improves upon pretreatment with any of the etchants mentioned previously. 

Epoxy adhesives are prepared in two steps. S -2 reaction of the disodium salt of bisphenol A with cpichlorohydrin forms a "prepolymer," which is then "cured" by treatment with a triaminc such as I-I2NCH2CH2NHCH2CH2NEI2-... 

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