Epoxy adhesive product

The epoxy raw materials can be harmful and hazardous. These materials could be toxic, flammable, and irritating to skin. It is generally the duty of the formulator to make sure that these materials are worked within a safe environment. Once they are formulated, the end user also has responsibilities with regard to safe handling of epoxy adhesive products. 

TABLE 18.3 Exposure Potential of Epoxy Adhesive Production and Application Processes... 

The base resin in epoxy adhesive products can be readily identified by IR and NMR spectrometry. The most commonly employed resin in these products (both one-part and two-part) is that based on the diglycidyl ether of bisphenol A (bisphenol A epoxy resin). Other resins of importance include the cycloaliphatic epoxies and phenolic epoxy novolaks. 

A research project to de-bond structural adhesive joints upon command has been described, and the results of tests on different epoxy adhesive products in combination with various surface treatments to assess the versatility of the process on this type of... 

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. 

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] ... 

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. 

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). 

Many epoxy adhesives are capable of being B-staged. A B-staged resin is one in which a limited reaction between the resin and hardener has taken place so that the product is in a semicured but solid state. In the B-staged state, the polymeric adhesive is still fusible and soluble. On additional heat curing, the adhesive will progress from the B stage to a completely cured state. This will usually be accompanied by moderate flow. 

Formulators in the adhesives industry do not normally manufacture epoxy resins. Generally, formulators buy epoxy resins, modify them with other materials, do similar compounding to the curative, and then package the product as a complete adhesive system ready for the end user. There are many excellent textbooks6-8 available giving information about the preparation, chemistry, and use of epoxy resins in general applications. It is not the intention here to go into such detail but to focus only on epoxy adhesive systems. 

Despite epoxy adhesives finding use in many fragmented markets, actual consumption in volume is surprisingly concentrated in a few specific end-use market segments. For example, automotive assembly applications account for nearly 50 percent of the total volume of epoxy adhesives consumed in the United States. The highest-value market areas include structural automotive, aircraft, and many specialty product assembly applications. These market areas are also expected to enjoy the highest growth rates. 

An ingredient added to an adhesive to reduce the concentration of base resin or binder is called a diluent. Diluents are principally used to lower the viscosity and modify the processing conditions of some adhesives. The degree of viscosity reduction caused by various diluent additions to a conventional epoxy adhesive is shown in Fig. 1.5. Diluents do not evaporate as does a solvent, but they become part of the final adhesive. Reactive diluents react with the resin base during cure, so that the final adhesive characteristics are determined by the reaction product of the binder and diluent. Nonreactive diluents do not react with the resin or curing agent and, therefore, more seriously weaken the final properties. Coal and pine tar are common nonreactive diluents. 

The vapor pressure of an epoxy resin system will have an indirect effect on the final properties of the cured adhesive. However, vapor pressure of the epoxy adhesive and its components may have a direct effect on the health and safety of those who manufacture or apply these products. 

Solid epoxy resins are usually formulated as solvent solutions and blends with lower-MW resins for the production of liquid adhesive systems. However, solid epoxy resins are also often employed in the manufacture of adhesive systems having solid form. There are several forms of solid epoxy adhesives that find application. The most common are supported or unsupported film, powder, and solder stick. Formulations for these adhesives are detailed in Chap. 13. 

Two curing agents that have found their way into many epoxy adhesive formulations are the polyamides and amidoamines. These are commonly used in the hardware store variety two-part epoxy resins that cure at room temperature. Both are reaction products of aliphatic amines, such as diethylenetriamine, and should be included under the subclassification of modified amines. However, these products have such widespread and popular use, they are addressed here as a separate classification. 

The choice of solvent or diluent is made with regard to the solubility of individual components and to the viscosity, drying times, and wetting characteristics required of the final product. All these properties affect the bond performance of the resulting epoxy adhesive formulation. 

Reactive diluents enter into the polymerization reaction of the epoxy resin and the curing agent. In this way the final adhesive characteristics are determined by the reaction product of the binder and the diluent. The most common reactive diluents used for epoxy adhesive formulations are shown in Table 6.2. 

One of the disadvantages of CTBN-epoxy adhesives has been their high viscosity, which limits additional formulation options. Recently new adducts, such as EPON 58003 and RSM-2577 from Resolution Performance Products LLC, have been introduced which have significantly lower viscosities.19 In addition, lower concentrations of these new CBTN-epoxy adducts are generally required to achieve equivalent adhesive performance. 

Technical Bulletin, Hycar CTBN Modified Epoxy Adhesives, B. F. Goodrich Company, AB-8, Cleveland, OH, 1990. (Hycar products now manufactured by Noveon, Inc.)... 

Selecting a flame retardant for an adhesive system has many ramifications, depending on the formulation being modified, the end use, how it will be processed, and the cost/performance ratio. When one is choosing a flame retardant, characteristics such as water extraction, particle size, viscosity, toxicity, dusting, uniformity, as well as economics must be considered. The materials chosen to perform the function of flame retardation must not interfere with the final product s performance. The major problem with incorporating flame retardants in adhesives is that very often a significant amount is required, and they interfere with the other properties of the adhesive and contribute to the cost. This is why bromo bisphenol epoxy resins are often employed in flame-retardant epoxy adhesives. 

Room temperature curing epoxy adhesives provide widely varying application and performance properties depending on the formulation employed. The following sections highlight certain formulations and commercial products that fall under this popular classification of epoxy adhesives. 

In one-component epoxy adhesives, the curing agent and resin are compounded together as a single product by the adhesive formulator. The curing agent system is chosen so that it does not react with the resin until the appropriate processing conditions are applied. 

Amines have also been microencapsulated within small cellulosic or polyelectrolyte capsules. This is a method for keeping the amine separate from the epoxy resin during storage. When the user decides to initiate cure, the capsules are broken, usually in the application process, and the amine is free to react with the epoxy resin. A successful example of this type of product is an epoxy adhesive that can be preapplied to machine screw threads. When the screw is ultimately threaded into place, the shearing action causes the capsule to break. Bond strengths are generally low for this type of adhesive, but this may not be important in certain applications. 

Epoxy adhesives are most commonly used as liquids or pastes. However, certain types of epoxies can be employed in the form of a solid. The components in these adhesives are mixed and processed to a stage where the resulting adhesive product is in a solid but still fusible (uncrosslinked) state. When the applied solid adhesive is heated, it melts, flows, and wets the substrate. Additional heating time then causes the adhesive to cure completely into a strong, thermosetting structure. 

Tape and film are the most common forms of solid epoxy adhesives. Tape and film are terms that are used rather loosely for adhesives in a thin sheet form. The term tape generally refers to an adhesive that is supported on a web of paper or nonwoven fabric, or on an open-weave scrim of glass, cotton, or nylon. Films, on the other hand, are free of supporting material and consist only of the adhesive. Both tape and film products may be accompanied with a release liner depending on the tack or blocking characteristics of the adhesive. 

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