Curing structural adhesives crosslinking

In most cases, the allophanate reaction is an undesirable side reaction that can cause problems, such as high-viscosity urethane prepolymers, lower pot lives of curing hot-melt adhesives, or poor shelf lives of certain urethane adhesives. The allophanate reaction may, however, produce some benefits in urethane structural adhesives, e.g., additional crosslinking, additional modulus, and resistance to creep. The same may be said about the biuret reaction, i.e., the reaction product of a substituted urea linkage with isocyanate. The allophanate and biuret linkages are not usually as thermally stable as urethane linkages [8]. 

Abstract—The structure of films formed by a multicomponent silane primer applied to an aluminum adherend and the interactions of this primer with an amine-cured epoxy adhesive were studied using X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, and attenuated total reflectance infrared spectroscopy. The failure in joints prepared from primed adherends occurred extremely close to the adherend surface in a region that contained much interpenetrated primer and epoxy. IR spectra showed evidence of oxidation in the primer. Fracture occurred in a region of interpenetrated primer and adhesive with higher than normal crosslink density. The primer films have a stratified structure that is retained even after curing of the adhesive. 

Keywords Acrylates Crosslinking Dual cure Epoxides Glass laminates Interpenetrating polymer networks Isocyanates Photo initiated cationic polymerisation Photoinitiators Photopolymerisation Pressure sensitive adhesives Release coatings Structural adhesives Thiol/polyene UV radiation curing Vinyl ethers. 

In a recent review of the properties of cured epoxy resins, Kaelble has pointed out that even simple formulations of diepoxide monomer and polyfunctional crosslinking agent reflect in the cured state the separate chemistries and structures of the co-reactants. When the molecular weight of both co-reactants in cured resin are high enough to provide more than four chain atoms between junction points, the resultant network begins to display the properties of a three-dimensional block copolymer. Creation of elastomeric microphases in epoxy structural adhesives has been recently identified with in situ block copolymerization between carboxy terminated nitrile (CTBN) rubber and the diepoxide.The adsorption-interdif-... 

The next major improvement in aerospace adhesives occured in the late 1950s with the introduction of adhesives based on epoxy resins. Since these adhesives crosslink via an addition reaction, no volatiles are released during heat cure. This made low pressure bonding possible and the use of nonperforated honeycomb feasible in sandwich structure. Other improvements followed that resulted in more durable bonded structure. These include the development of corrosion inhibiting adhesive primers in 1968, corrosion resistant aluminum honeycomb in 1969, and the phosphoric acid anodizing process for preparing aluminum for bonding in 1974. 

This was one of the earliest types of structural adhesive used by the aerospace industry. Vi-nyl-phenolics are still in use today because they are reasonably low in price and are excellent for applications involving bonding metal skins to wood. FM 47 adhesive is representative of this type. The major disadvantage of this type is that crosslinking occurs via a condensation reaction. As a consequence the volatiles given off during heat cure result in porous bond lines. This type of adhesive may be stored at room temperature and is cured at 350°F. Service temperature is limited to slightly above 180°F. 

The physical properties of automotive enamels are in large part determined by the crosslink structure developed in the paint films during the baking process. Enamels which are not cured sufficiently (undercured) are generally sensitive to humidity and solvents. In addition, they may be prone to chipping and cold cracking. Faints which have been baked excessively (overcured) exhibit intercoat adhesion failure. That is, subsequent coats... 

Tetraglycidyl ether of tetraphenolethane is an epoxy resin that is noted for high-temperature and high-humidity resistance. It has a functionality of 3.5 and thus exhibits a very dense crosslink structure. It is useful in the preparation of high-temperature adhesives. The resin is commercially available as a solid (e.g., EPON Resin 1031, Resolution Performance Polymers). It can be crosslinked with an aromatic amine or a catalytic curing agent to induce epoxy-to-epoxy homopolymerization. High temperatures are required for these reactions to occur. 

Primary and secondary aliphatic amines react relatively rapidly with epoxy groups at room or lower temperature to form three-dimensional crosslinked structures. The resulting cured epoxies have relatively high moisture resistance and good chemical resistance, particularly to solvents. They also have moderate heat resistance with a heat distortion temperature in the range of 70 to 110°C. Thus, short-term exposures of cured adhesive joints at temperatures up to 100°C can generally be tolerated. 

Polyamide cured DGEBA epoxies provide improved flexibility, moisture resistance, and adhesion over aliphatic amines alone. However, polyamide cured epoxies are generally inferior in thermal resistance and shear strength due to the reduction in crosslink density. Polyamide cured epoxies lose structural strength rapidly with increasing temperatures and... 

Solid epoxy adhesive formulations can be processed to either a thermoplastic or a thermoset state. Solid epoxy resins of exceptionally high molecular weight (e.g., phenoxy) can be used without any degree of cure as a hot-melt type of adhesive. However, fully crosslinked, thermoset systems are generally employed in structural applications. 

One of the most popular uses of radiant curing is the advancement (viscosity increase) or crosslinking of pressure-sensitive adhesives. These applications have been satisfied mostly with acrylate-based adhesive systems. With epoxy-based adhesives, the main applications are electrical and electronic components, the bonding of large aerospace structures such as composites, and the bonding of transparent substrates such as glass and plastic. 

The rate of reversion, or hydrolytic instability, depends on the chemical structure of the base polymer, its degree of crosslinking, and the permeability of the adhesive or sealant. Certain chemical linkages such as ester, urethane, amide, and urea can be hydrolyzed. The rate of attack is fastest for ester-based linkages. Ester linkages are present in certain types of polyurethanes and anhydride cured epoxies. Generally, amine cured epoxies offer better hydrolytic stability than anhydride cured types. 

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