Epoxy adhesives Primers

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. 

Generally, systems developed in the USA favour a combination of polyethylene with either butyl-rubber or hot-applied mastic adhesives, the latter consisting of a blend of rubber, asphalt and high molecular weight resins. In European and Far East coating plants, epoxy type primers and hard ethylene copolymer adhesives have been successfully employed. 

Materials. The adhesives and primers used in this study were model and commercial materials that were cured according to conditions appropriate for the specific adhesive chemistry. Adhesives A and B were conventional epoxy/Versamid and epoxy/dlcyandiamlde adhesives, respectively. Adhesives C and D were commercial urethane and epoxy/polyamlde adhesives, respectively. Adhesive E was a conventional two-part epoxy/amldoamlne adhesive. Adhesive F was a vinyl plastlsol adhesive. The adhesive primers used in this study were a urethane crosslinked epoxy electrocoat primer and spray primers based on tall oil modified epoxy ester, and polyesterpolyol/isocyan-ate chemistry. Dicyandlamlde was obtained from Aldrich Chemical Company. Epon 828 was obtained from Shell Chemical Company. 

Table IV. Effect of Primer Chemistry on Bond Strength of SMC/Primed Steel Epoxy Adhesive Bonds...

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. 

Primer Epoxy vs. Nitrile-Modified Epoxy. The compatibility of the epoxy-polyamide primer with the nitrile-modified epoxy adhesive facsimile and the aluminum oxide surface was also evaluated by the wedge test, since earlier tests using the primer as the adhesive had failed immediately. As shown in Fig. 8, the addition of the primer directly to the prepared... 

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. 

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. 

The effect of a multicomponent silane primer on the interphase structure of aluminum/epoxy adhesive joints... 

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. 

The primer chosen for this investigation consisted of an equimolar mixture of phenyl- and amino-functional silanes, suggested as a potential superior primer for aluminum/epoxy adhesive joints [7], The amino-functional silane is known to be effective as an adhesion promoter for fiber-reinforced composite materials [1, 2] as well as for epoxy/metal adhesive joints [8, 9] and provides for strong chemical interaction between the adhesive and primer, while the phenyl functional silane should reduce the overall concentration of polar, hydrophilic functional groups in the interphase region and at the same time maintain or improve the ability of the resin and primer to interpenetrate due to its structural similarity to the adhesive resin. 

The two aluminum alkoxide primers on mild steel showed improved adhesion and better resistance to crack propagation with both the thermoplastic polyether-sulfone (PES) and the FM 300U thermoset epoxy adhesive. The titanium alkoxide exhibited the poorest resistance to crack growth, while tetrabutyl orthosilicate showed intermediate behavior between the two aluminum alkoxides and the titanium alkoxide. 

Epoxy-based primers are commonly used in the aerospace and automotive industries. These primers have good chemical resistance and provide corrosion resistance to aluminum and other common metals. Primer base resins, curing agents, and additives are much like adhesive or sealant formulations except for the addition of solvents or low-viscosity resins to provide a high degree of flow. 

Representative data are shown in Fig. 10.5 for aluminum joints bonded with an epoxy film adhesive and a standard chromate-containing primer. Up until recently, standard corrosion-resistant primers contained high levels of solvent, contributing to high levels of volatile organic compounds (VOCs) and chromium compounds, which are considered to be carcinogens. As a result, development programs have been conducted on waterborne adhesive primers that contain low VOC levels and little or no chrome. Data are presented on several of these primers in Tables 10.8 and 10.9. 

The usual approach to good bonding practice is to prepare the aluminum surface as thoroughly as possible, then wet it with the adhesive as soon afterward as practical. In any event, aluminum parts should ordinarily be bonded within 48 h after surface preparation. However, in certain applications this may not be practical, and primers are used to protect the surface between the time of treatment and the time of bonding. Primers are also applied as a low-viscosity solution which wets a metal surface more effectively than more viscous, higher-solids-content adhesives. Corrosion-resistant epoxy primers are often used to protect the etched surface during assembly operations. Primers for epoxy adhesive systems are described in Chap. 10. 

To obtain a usable adhesive bond with polyolefins, the surface must be treated. A number of surface preparation methods, including flame, chemical, plasma, and primer treatments, are in use. Figure 16.4 illustrates the epoxy adhesive strength improvements that can be made by using various prebond surface treatments to change the critical surface tension of polyethylene. 

Polyamide (nylon) Acetone, methyl ethyl ketone 1. Abrasion. Grit or vapor blast or abrade with 100-grit emery cloth followed by solvent degreasing. 2. Prime with a spreading dough based on the type of rubber to be bonded in an admixture with isocyanate. 3. Prime with resorcinol formaldehyde adhesives. Sand or steel shot is suitable abrasive Suitable for bonding polyamide textiles to natural and synthetic rubbers Good adhesion to primer coat with epoxy adhesives in metal-to-plastic joints... 

The (physically wetting) polyaniline primer CORRPASSIV was compared with a fast-drying two-component epoxy resin primer (Messrs. Finalin, Type 144) and a metal-reactive two-component primer with adhesion-promoting properties (Type 918). All three primers were coated with a two-component polyurethane paint (B412). CORRPASSIV, both with and without top coat, exhibited no rust formation beneath the primer. The slight undermining receded after the test, and even within the cross and scratch injuries, it was virtually impossible to detect any corrosion. 

The hyperbranched HA-1300 contains hydroxyl end groups thus the cross-linking with epoxy and PU is very hmited and the wetting is inhibited. It is used as a primer. Mechanical results show that at optimal concentration (0.5 wt.%) of HA-1300 the adhesion strength is increased by only 20-33% for the epoxy adhesive (Epon 815C/Versamide 140) and not at aU for PU adhesive (Table 15.3). 

Table 15.7 presents the single lap shear strength of Al adherends primed with G3 and G4 dendrimers bonded with epoxy adhesive. On anodized Al, results show improvement of 33-53% in lap shear strength and in failure mode using dendrimers as a primer. 

Epoxy adhesive showed better improvement with all HB polymer and dendri-mer primers. 

L. Moshinsky, S. Kenig, H. Dodiuk-Ke-nig, A. Buchman, Epoxy Adhesives and Primers Based on Hyperbranched Poly-amidoamines . Meeting of the Adhesion Society, Williamsburg, VA, Eeb. 2000. 

In his test, a thin film of adhesive on a glass microscope slide or a metal coupon is cured and soaked in hot water until the film can be loosened with a razor blade. There is usually a sharp transition between samples that exhibited cohesive failure in the polymer and those which exhibited more of an interfacial failure. Since the diffusion of water into the interface is very rapid in this test, the time to failure is dependent only on interfacial properties and may differ dramatically between unmodified epoxy bonds and epoxy bonds primed with an appropriate silane coupling agent. The time to debond in the hot water for various silane primers differed by several thousandfold when used with a given epoxy. In parallel tests, a thick film of epoxy adhesive on nonsilaned aluminum coupon showed about the same degree of failure after 2h in 70°C water as a silaned joint exhibited after more than 150 days (3600 h) under the same conditions. 

Formation of durable chemical bonds is an obvious means to stabilize the interface and has been demonstrated for phenolic/alumina joints [25] and for silane coupling agents [26,27]. However, for most structural joints using epoxy adhesives and metallic adherends, moisture-resistant chemical bonds are not formed and mechanical interlocking on a microscopic scale is needed between the adhesive/primer and adherend for good durability. In these cases, even if moisture disrupts interfacial chemical bonds, a crack cannot follow the convoluted interface between the polymer and oxide and the joint remains intact unless this interface or the polymer itself is destroyed. 

Chem. Descrip. Bisphenol A epoxy sol n. resin in MEK Uses Epoxy for fhermoset or thermoplaslic applies, such as high flexibility coatings or as adhesive primers, often formulated with zinc to form corrosion-resisf. primers... 

Chem. Descrip. Solv. cut of epoxy resin in MEK/EGMEA/cyclohexanone Uses Film-former for coil coatings, industrial maintenance coatings, primers, and traffic paint modifier for epoxy adhesives and laminates Features Ultra high m.w. exc. flexibility and adhesion Properties Gardner 3 liq. sp.gr. 0.96 dens. 8.0 Ib/gal vise. 1250 cps EEW 5500 40% solids Epotut 38-531 [Reichhold]... 

---