Diffusion and adhesion

Many of the important results for diffusion and adhesion at interfaces discussed in this chapter are summarized in Table 3. 

Diffusion and adhesion bonding are based on different adhesion mechanisms related to solubility. 

S. Yukioka, K. Nagato, and T. Inoue, Ellipsometric studies of mutual diffusion and adhesion... 

Increasing high resistance to diffusion and adhesive wear... 

Diffusion Theory. The diffusion theory of adhesion is mosdy appHed to polymers. It assumes mutual solubiUty of the adherend and adhesive to form a tme iaterphase. The solubiUty parameter, the square root of the cohesive eaergy deasity of a material, provides a measure of the iatermolecular iateractioas occurring within the material. ThermodyaamicaHy, solutioas of two materials are most likely to occur whea the solubiUty parameter of oae material is equal to that of the other. Thus, the observatioa that "like dissolves like." Ia other words, the adhesioa betweea two polymeric materials, oae an adherend, the other an adhesive, is maximized when the solubiUty parameters of the two are matched ie, the best practical adhesion is obtained when there is mutual solubiUty between adhesive and adherend. The diffusion theory is not appHcable to substantially dissimilar materials, such as polymers on metals, and is normally not appHcable to adhesion between substantially dissimilar polymers. 

In what follows, particular attention is given to semi-empirical strategies for optimizing contact adhesion and diffusion interphase adhesion. The former centers around maximizing the strength of inteimolecular interactions across a true interface, while the latter seeks to maximize thermodynamic compatibility between the phases. 

Whatever the specific system or situation, the key issue in diffusion interphase adhesion is physical compatibility. This is once again, a thermodynamic issue and may be quantified in terms of mutual solubility. Most of the strategies for predicting diffusion interphase adhesion are based on thermodynamic compatibility criteria. Thus it is appropriate to review briefly the relevant issues of solution thermodynamics and to seek quantitative measures of compatibility between the phases to be bonded. 

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... 

We have discussed the positive effects that bacterial displacement and adhesion to substrates exerts on the diffusive mass transfer. Theoretically, direct contact with the substrate could also allow microorganisms to employ other modes of uptake in addition to absorption of water-dissolved molecules. So, which are the physical states for which chemicals can be ingested by microorganisms ... 

In order to establish good electrical contact to the sensitive layer, it was necessary to coat the electrodes with a metal stack of Ti/W (diffusion barrier and adhesion layer) and Pt. The usage of a shadow mask during the metal deposition ensures full compatibility with other MEMS processing steps so that it is possible to fabricate various CMOS-MEMS devices on the same wafer. 

The U.S. market is probably near 12 billion lb of adhesives. The business is very diffuse and is one of the few areas of the chemical industry where a small company can thrive. Over 500 U.S. companies manufacture adhesives and sealants. Industrial use is high (60%), but consumers (20%) and craftspersons (20%) also use them. 

Diffusion Theory. The diffusion theory of adhesion is mostly applied to polymers. It assumes mutual solubility of the adherend and adhesive to form an interphase. 

A critical problem with adhesion layers arises from grain boundary diffusion. Deposited films tend to be polycrystalline and granular. The electrochemistry of the adhesion film is frequently much less desirable than the electrochemistry of the primary film. Moreover, minute contamination of the primary metal film surface by adhesion components can dramatically degrade the electron transfer properties (e.g., electrochemical reversibility, as evidenced by cyclic voltammetric peak potential separation) of the film [58], Thus it is essential that the adhesion layer is not exposed to solution. While the rate of diffusion of adhesion metals through the bulk of the primary layer is quite slow, grain boundary diffusion along the surfaces of grains is much faster. In many cases, the adhesion layer can seriously compromise the performance of the electrode. This is particularly a problem for chromium underlayers. Recently a codeposited Ti/W adhesion layer has been recommended as an alternative to chromium, with reportedly better adhesion and fewer interferences than Cr. A procedure was also described to recondition these electrodes to minimize interference by adhesion layer metals [58]. 

The same theories relevant to adhesion, developed to explain and predict the performance of glues, adhesives, and paints, have also been applied to bioadhesive systems [44], These include the electronic, absorption, wetting, diffusion, and fracture theories. 

Solvents are selected such that some will escape relatively quickly from paint films to prevent excessive flow, while others will escape slowly to provide film leveling and adhesion. With typical alkyd coatings, the first 30% of solvent has been observed to evaporate as quickly as the neat solvents, essentially at a constant rate which is dependent on volatility. Later stage evaporation occurred several times more slowly and was rate-controlled by solvent diffusion to the surface of the paint film. The transition point between this behavior was defined as the resin solids content at which the evaporation rate due to volatility equaled that due to diffusion. Transition points have been observed to typically occur at a resin solids content of 40-50% v/v. Thus alkyd paints, normally formulated at 27-40% v/v resin solids, generally exhibit rapid initial solvent-release driven by volatility while high solids coatings (usually 65-75% v/v resin solids) dry solely by a diffusion-controlled process with negligible influence by solvent volatility (Ellis, 1983). 

---