Problems in Adhesion

Most polymeric adhesive systems undergo some degree of shrinkage during the process of crosslinking and this will create stresses within the adhesive/substrate interface. Adhesives with filler content have a lower shrinkage and thus lower stresses. 

The presence of water at the interface will cause interference with the establishment of a good bond. Some materials occurring as the substrate are hydrophilic in nature and will always attempt to achieve a monomolecular water film on their surfaces. This can occur, after the substrate has been cleaned and before the adhesive has been applied, from the atmosphere direct to the substrate surface, or later after the bond has been established, by diffusion. The presence of a water film at the interface can result in leaching of materials from the substrate which then can cause corrosion of the substrate, with resultant progressive loss of adhesion as corrosion spreads under the adhesive. 

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Applications of ISS to polymer analysis can provide some extremely useful and unique information that cannot be obtained by other means. This makes it extremely complementary to use ISS with other techniques, such as XPS and static SIMS. Some particularly important applications include the analysis of oxidation or degradation of polymers, adhesive failures, delaminations, silicone contamination, discolorations, and contamination by both organic or inorganic materials within the very outer layers of a sample. XPS and static SIMS are extremely comple-mentar when used in these studies, although these contaminants often are undetected by XPS and too complex because of interferences in SIMS. The concentration, and especially the thickness, of these thin surfiice layers has been found to have profound affects on adhesion. Besides problems in adhesion, ISS has proven very useful in studies related to printing operations, which are extremely sensitive to surface chemistry in the very outer layers. 

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. 

Many applications of XPS to problems in adhesion science have been reported in the literature. One interesting example is provided by the work of Tsai et al. on the use of XPS to investigate reactions between model rubber compound and plasma polymerized acetylene films that was discussed above [22,23], Consideration of that system permits some interesting comparisons to be made regarding the type of information that can be obtained from RAIR and XPS. 

Other problems in adhesion may be tackled by studying the surface of the material after fracture. Mass spectroscopic methods like SIMS may reveal transfer of molecular fragments from the one component towards the other one. 

It can be expected, then, that one of the major problems in adhesives technology is the development of adhesives that must withstand both elevated temperatures as well as periodic excursions to low temperatures. Several solutions have been developed. Certain adhesive systems, notably blends of epoxy resin with more elastic resins, have been formulated with a very broad glass transition temperature range or with multiple glass transitions at both high and low temperatures. These have found some success in the applications discussed in this chapter. 

The following unsolved problems in adhesive technology are considered risks that are slowing down the increased use of adhesives and related technologies ... 

We then discussed several examples of how these surface-sensitive techniques can be used to solve problems in adhesion science. The studies chosen were designed to illustrate the methodology involved, the interplay among different techniques, and the usefulness of different forms of data analysis. 

As stated above, MD simulations and QM calculations show enormous capacity in handling problems in adhesion. However, in many cases, current force fields used in MD as well as MM simulations are not sufficiently accurate to reproduce the dynamics of molecular systems. At... 

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