Adherend surface

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

It is only in the context of the systematic variation of the properties of the adhesive and/or the adherend surface in a set of otherwise identical specimens subjected to a given mechanical testing procedure that it is reasonable to think of predicting relative interfacial strength. 

Regardless of which, or which combination, of the above mechanisms is responsible for adhesion in a given case, intimate molecular contact between the adhesive and adherend is required. This means that the contact angle of the liquid adhesive against the adherend surface should be as low as possible, and preferably 0°. For the case of contact adhesion, this is immediately evident, but in cases where mechanical interlocking is the primary mechanism for adhesion it is also the case because the adhesive must first be able to flow or wick into the pores of the... 

In seeking to minimize the contact angle or to promote wetting of the adherend by the adhesive, one must consider the effects both of the chemistry of the components and of the morphology of the adherend surface on the observed contact angle. Finally, comment must be made on the dynamics of the wetting process and the factors upon which it depends. 

In developing criteria for the ranking of adhesive formulations or adherend surface treatments or primers, it is necessary to distinguish between two different situations. In one case (contact adhesion), a true interface is believed to exist across which intermolecular forces are engaged, while in the other, an interphase is formed by diffusive interpenetration or interdigitation between the adhesive and the adherend (diffusion interphase adhesion). Even in the case of contact adhesion, more often than not, an mi vphase of macroscopic thickness forms on... 

Rider and Amott were able to produce notable improvements in bond durability in comparison with simple abrasion pre-treatments. In some cases, the pretreatment improved joint durability to the level observed with the phosphoric acid anodizing process. The development of aluminum platelet structure in the outer film region combined with the hydrolytic stability of adhesive bonds made to the epoxy silane appear to be critical in developing the bond durability observed. XPS was particularly useful in determining the composition of fracture surfaces after failure as a function of boiling-water treatment time. A key feature of the treatment is that the adherend surface prepared in the boiling water be treated by the silane solution directly afterwards. Given the adherend is still wet before immersion in silane solution, the potential for atmospheric contamination is avoided. Rider and Amott have previously shown that such exposure is detrimental to bond durability. 

Wedge test fracture energy (from Eqs. 1 and 2) vs. adherend surface treatment (from ref. [3 )... 

Eqs. 1-5 hold whether failure is interfacial or cohesive within the adhesive. Furthermore, Eq. 5 shows that the reversible work of adhesion directly controls the fracture energy of an adhesive joint, even if failure occurs far from the interface. This is demonstrated in Table 5, which shows the static toughness of a series of wedge test specimens with a range of adherend surface treatments. All of these samples failed cohesively within the resin, yet show a range of static toughness values of over 600%. 

The adhesive or primer must wet the adherend surface (Chapter 10). 

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). 

In-service issues. As mentioned previously, many early service failures of bonded structure were due to adherend surface treatments that were unstable in long-term exposure to water. A majority of these problems were resolved by the adoption of surface treatments such as chromic and phosphoric acid anodize for aluminum details. The remaining few were alleviated by the adoption of phosphoric acid anodized honeycomb core and foaming adhesives resistant to water passage. Other service durability issues such as the cracking of brittle potting compound used to seal honeycomb sandwich assemblies, and subsequent delamination, have been minor in scope. 

The Effect of Adhesive Primers. In practice, adhesive bonds involving metal adherends often use primers as pretreatments of the metal surface prior to bonding. Table IV shows the durability of composite-metal bonds prepared with adhesive C over a series of primers (of varying corrosion resistance) in 240 hour salt spray test. The results indicate that the performance of bonds is directly related to the corrosion resistance of the primer used to prepare the adherend surface. In general, the adhesion of the primer to the steel adherend, rather than the adhesive chemistry. 

Cleaning can be a chemical treatment that includes acid or alkaline etching of the adherend surface. The etching process, especially, removes stubborn oxides (such as on aluminum or iron) and roughens the surface on a microscopic scale. 

The surface chemical groups present on the adherend surfaces consist of species chemically bonded to the surface. A real surface exposed to the environment contains not only the surface chemical groups but also physisorbed water, carbon monoxide and carbon dioxide molecules. The amount adsorbed depends on the surface free energy of the adherend and can range in thickness from portions of a monolayer to multilayers of material. 

In addition to preferential adsorption of epoxy components at fiber or adherend surfaces, chemically different species can be added to the interphase to improve or alter an interfacial property. Among the species, that can be added to the composite, coupling agents have a great effect on the interphase structure and properties. 

Based on the studies of adherend surfaces by Fowkes 12), Parks 13) and Zisman and Shafrin 14), Bolger 15) developed a model (Fig. 1) which depicts the fundamental characteristics of the hydrated oxide surface of any metal, metal oxide or silicate. 

In all adhesive joints, the interfacial region between the adhesive and the substrate plays an important role in the transfer of stress from one adherend to another [8]. The initial strength and stability of the joint depend on the molecular structure of the interphase after processing and environmental exposure, respectively. Characterization of the molecular structure near the interface is essential to model and, subsequently, to maximize the performance of an adhesive system in a given environment. When deposited on a substrate, the silane primers have a finite thickness and constitute separate phases. If there is interaction between the primer and the adherend surface or adhesive, a new interphase region is formed. This interphase has a molecular structure different from the molecular structure of either of the two primary phases from which it is formed. Thus, it is essential to characterize these interphases thoroughly. 

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. 

IR data. Spectroscopic techniques were then employed to determine more about the composition of the fracture surfaces. ATR of the adhesive side of the fracture surfaces showed only slight differences in the composition of the organic phase near the interface as a result of applying primer to the adherend surface before applying the adhesive. The spectrum shown in Fig. 7C (obtained with the 45° KRS-5 reflection element) is the difference between a sample prepared from an unprimed adherend (Fig. 7B) and one prepared from a primed... 

The definition of an adhesion promoter in its most literal sense may be stated as any substance which when placed between two adherends results in a measurable increase in the force required to separate the two materials. This definition does not address the basic mechanism responsible for the increased adhesion nor does it concern itself with the mode by which the promoter is contacted with the adherend surface, i.e. as primer, by in situ incorporation into an adhesive or coating, or by other means. 

Protection of surfaces after treatment (primers can be used to extend the time between preparing the adherend surface and bonding)... 

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