Substrate surface, adhesion

Thus, the adhesive contacts the substrate via a layer of substances that frequently differ from the adhesive in composition. If the cohesion strength of these substances is less than that of the adhesive, this will determine the failure stress of the adhesive-bonded joint. The adhesive, which has the same composition as that of the adhesive in bulk, can form a weak zone in the substrate surface. Adhesives are polymers and the particular nature of a polymer must have effects at all stages of formation and operation of an adhesive-bonded joint. 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

Film Adhesion. The adhesion of an inorganic thin film to a surface depends on the deformation and fracture modes associated with the failure (4). The strength of the adhesion depends on the mechanical properties of the substrate surface, fracture toughness of the interfacial material, and the appHed stress. Adhesion failure can occur owiag to mechanical stressing, corrosion, or diffusion of interfacial species away from the interface. The failure can be exacerbated by residual stresses in the film, a low fracture toughness of the interfacial material, or the chemical and thermal environment or species in the substrate, such as gases, that can diffuse to the interface. 

Poor preparation of the substrate can result in loss of adhesion, pitting, roughness, lower corrosion resistance, smears, and stains. Because electroplating takes place at the exact molecular surface of a work, it is important that the substrate surface be absolutely clean and receptive to the plating. In the effort to get the substrate into this condition, several separate steps may be required, and it is in these cleaning steps that most of the problems associated with plating arise. 

Surface analysis has made enormous contributions to the field of adhesion science. It enabled investigators to probe fundamental aspects of adhesion such as the composition of anodic oxides on metals, the surface composition of polymers that have been pretreated by etching, the nature of reactions occurring at the interface between a primer and a substrate or between a primer and an adhesive, and the orientation of molecules adsorbed onto substrates. Surface analysis has also enabled adhesion scientists to determine the mechanisms responsible for failure of adhesive bonds, especially after exposure to aggressive environments. The objective of this chapter is to review the principals of surface analysis techniques including attenuated total reflection (ATR) and reflection-absorption (RAIR) infrared spectroscopy. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) and to present examples of the application of each technique to important problems in adhesion science. 

One of the most common rubber adhesives are the contact adhesives. These adhesives are bonded by a diffusion process in which the adhesive is applied to both surfaces to be joined. To achieve optimum diffusion of polymer chains, two requirements are necessary (1) a high wettability of the adhesive by the smooth or rough substrate surfaces (2) adequate viscosity (in general rheological properties) of the adhesive to penetrate into the voids and roughness of the substrate surfaces. Both requirements can be easily achieved in liquid adhesives. Once the adhesive solution is applied on the surface of the substrate, spontaneous or forced evaporation of the solvent or water must be produced to obtain a dry adhesive film. In most cases, the dry-contact adhesive film contains residual solvent (about 5-10 wt%), which usually acts as a plasticizer. The time necessary... 

Wide range of substrates. CR adhesives bond to almost any high-polar surface, as well as many low-polar surfaces (including polyolefins). 

The energy release rate (G) represents adherence and is attributed to a multiplicative combination of interfacial and bulk effects. The interface contributions to the overall adherence are captured by the adhesion energy (Go), which is assumed to be rate-independent and equal to the thermodynamic work of adhesion (IVa)-Additional dissipation occurring within the elastomer is contained in the bulk viscoelastic loss function 0, which is dependent on the crack growth velocity (v) and on temperature (T). The function 0 is therefore substrate surface independent, but test geometry dependent. 

The chemical bonding theory of adhesion applied to silicones involves the formation of covalent bonds across an interface. This mechanism strongly depends on both the reactivity of the selected silicone cure system and the presence of reactive groups on the surface of the substrate. Some of the reactive groups that can be present in a silicone system have been discussed in Section 3.1. The silicone adhesive can be formulated so that there is an excess of these reactive groups, which can react with the substrate to form covalent bonds. It is also possible to enhance chemical bonding through the use of adhesion promoters or chemical modification of the substrate surface. 

The mechanism by which the primers are thought to work is relatively straightforward. The primer first diffuses into the polyolefin surface, and subsequently becomes entangled in the polyolefin. The primer molecule can then act as an anchor in the substrate surface for the adhesive polymer, which forms after the primer initiates polymerization of the alkyl cyanoacrylate monomer [37]. 

Absorption and wetting. Generally, it is necessary for the adhesive resin to wet the substrate surfaces. The surface energy of the composite substrate must be greater than the surface energy or surface tension of the resin in order for effective wetting to occur. 

Endoh, M., Influence of Surface Roughness of Mild Steel Substrate on Adhesive Strength of Zinc Sprayed Coatings . Proc. 8th Int. Thermal Spray. Conf., American Welding Society, pp. 492-502 (1976)... 

As mentioned previously, a CVD reaction may occur in the gas phase instead of at the substrate surface if the supersaturation of the reactive gases and the temperature are sufficiently high. This is generally detrimental because gas-phase precipitated particles, in the form of soot, become incorporated in the deposit, causing nonuniformity in the structure, surface roughness, and poor adhesion. In some cases, gas-phase precipitation is used purposely, such as in the production of extremely fine powders (see Ch. 19). 

The technique used to study dewetting dynamics on materials consists of making a flat, smooth elastomer surface. A hquid puddle is deposited within a 50-mm-diameter ring of 0.1-mm-thick plasticized adhesive paper adhering to the substrate. The adhesive paper acts as a spacer. A microscope slide is drawn over the liquid to obtain a liquid film of ca. 0.1-mm thickness. At this thickness, the liquid film is unstable, being much less than the equilibrium value, of ca. 1.5 mm calculated from Eq. (29). Nucleation of dry patches... 

Polyelectrolytes form the basis of those modern cements which are distinguished by their ability to adhere to reactive surfaces. At present the main use of such cements lies in the medical field, principally in dental surgery. They adhere permanently to biological surfaces where they have to withstand adverse conditions of wetness, chemical attack, the stress of biological activity, and chemical and biological changes within the substrate. Nevertheless, adhesive bonds are maintained. 

Wilson (1974) emphasized the importance of wetting the substrate surface. Later, as the reaction proceeded, these hydrogen bonds would be replaced by ionic salt bridges. Wilson stressed the importance of the polymeric nature of these cements in adhesion. Their polymeric nature allowed interfacial gaps between cement and substrate to be bridged and also provided a multiplicity of bonds. Under oral conditions, where the substrate is subject to change, adhesive bonds will be broken, but if there are a multiplicity of these, attachment of the cement to the substrate will endure and allow broken bonds to be re-established. It is significant that... 

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