Weak boundary layers , adhesion

Weak boundary layer Adhesion can be prevented if there is a weak boundary layer between the adhesive and the substrate. Weak boundary layers can be corrosion, contamination, moisture, etc. In these cases, faUine occins within the boundary layer and not the adhesive. 

Another factor that can contribute to the low release force provided by a release material is the presence of a mechanically weak boundary layer at the surface of the release coating [40,41]. Upon peeling the PSA from the release coating, the locus of failure is within this mechanically weak layer, resulting in transfer of material to the adhesive and a subsequent loss in adhesion of the PSA. Although the use of a weak boundary layer may not be the preferred method of achieving low adhesion for PSA release coatings, it can be useful if the amount of transfer is consistent and kept to a minimum [42]. However, in many cases the unintentional or uncontrolled transfer of a weak boundary layer to a PSA results in an undesirable loss in readhesion. 

A word should be said about the weak boundary layer effect and silicone release [40,41]. Studies have shown that having loose silicone oil that can transfer to the PSA will lower release, however subsequent adhesion will likely suffer as well. In most commercial instances using silicone liners, a weak boundary layer is not intentionally employed. Additionally, many low transfer silicone liners are commercially available which provide premium release and show low to no PDMS transfer to PSAs, indicating that PDMS transfer is not a necessary condition for easy release. 

Loss of adhesion occurs at the silicone substrate interface and two main mechanisms can be outlined the formation of a weak boundary layer (WBL) and the breaking of adhesive bonds. 

Weak boundary layer. WBL theory proposes that a cohesively weak region is present at the adhesive-substrate interface, which leads to poor adhesion. This layer can prevent the formation of adhesive bonds, or the adhesive can preferentially form bonds with the boundary layer rather that the surface it was intended for. Typically, the locus of failure is interfacial or in close proximity to the silicone-substrate interface. One of the most common causes of a WBL being formed is the presence of contaminants on the surface of the substrate. The formation of a WBL can also result from migration of additives from the bulk of the substrate, to the silicone-substrate interface. Alternatively, molecular... 

A WBL can also be formed within the silicone phase but near the surface and caused by insufficiently crosslinked adhesive. This may result from an interference of the cure chemistry by species on the surface of substrate. An example where incompatibility between the substrate and the cure system can exist is the moisture cure condensation system. Acetic acid is released during the cure, and for substrates like concrete, the acid may form water-soluble salts at the interface. These salts create a weak boundary layer that will induce failure on exposure to rain. The CDT of polyolefins illustrates the direct effect of surface pretreatment and subsequent formation of a WBL by degradation of the polymer surface [72,73]. 

This difference in reactivity between the different classes of amines explains the difference in the primer performance on polyolefin substrates with ethyl cyanoacrylate-based adhesives [37J. Since primary and secondary amines form low molecular weight species, a weak boundary layer would form first, instead of high molecular weight polymer. Also, the polymer, which does ultimately form, has a lower molecular weight, which would lower adhesives strength [8,9]. 

On the other hand, if the mbber contains paraffin wax, the surface treatment with sulfuric acid promotes its migration to the surface creating a weak boundary layer able to produce poor adhesion. Solvent wiping with petroleum ether after surface treatment removes this antiadherent moiety but a progressive migration from the bulk to the mbber surface with time occurs. 

Pastor-Bias M.M. and Martm-Martfnez J.M., 1995, Mechanisms of formation of weak boundary layers in styrene-butadiene rubber, in Proceedings of The International Adhesion Symposium, H. Mizumachi (Ed.), Gordon and Breach Science Publishers, Melbourne, 215-233. 

The interfacial chemistry of corrosion-induced failure on galvanized steel has been investigated (2) adhesion of a polyurethane coating was not found to involve chemical transformations detectable by XPS, but exposure to Kesternich aging caused zinc diffusion into the coating. Similar results were obtained with an alkyd coating. Adhesion loss was proposed to be due to formation of a weak boundary layer of zinc soaps or water-soluble zinc corrosion products at the paint metal Interface. 

Moisture acts as a debonding agent through one of or a combination of the following mechanisms 1) attack of the metallic surface to form a weak, hydrated oxide interface, 2) moisture assisted chemical bond breakdown, or 3) attack of the adhesive. (2 ) A primary drawback to good durability of metal/adhesive bonds in wet environments is the ever present substrate surface oxide. Under normal circumstances, the oxide layer can be altered, but not entirely removed. Since both metal oxides and water are relatively polar, water will preferentially adsorb onto the oxide surface, and so create a weak boundary layer at the adhesive/metal interface. For the purposes of this work, the detrimental effects of moisture upon the adhesive itself will be neglected. The nitrile rubber modified adhesive used here contains few hydrolyzable ester linkages and therefore will be considered to remain essentially stable. 

The two predominant mechanisms of failure in adhesively bonded joints are adhesive failure or cohesive failure. Adhesive failure is the interfacial failure between the adhesive and one of the adherends. It indicates a weak boundary layer, often caused by improper surface preparation or adhesive choice. Cohesive failure is the internal failure of either the adhesive or, rarely, one of the adherends. 

Water can reduce adhesion strength by reducing the strength of the metal oxide layer via hydration52,81 . Hydration of the oxide layer is detrimental because the resulting aluminum-, iron-, or other metal-hydrates generally exhibit very poor adhesion to their base metals 52 Therefore, the produced layer of hydrates will effectively act as a weak boundary layer in the system and decrease adhesion strength. Since the hydration reaction has been most heavily studied on aluminum oxides, the authors have chosen to base the discussion of the hydration mechanism on this case. 

Failure can occur in metal/epoxy adhesion systems in any one or more of a number of different regions. The fracture may propagate through the bulk metal or epoxy, the metal oxide layer, the metal oxide/epoxy or metal/metal oxide interfaces, or through weak boundary layers (WBL s) very near the interfaces. Some workers -78,153) be]ieve that most failures that have been claimed to be interfacial have actually... 

With time (under increased temperature and humidity) the crack tip continues to a weaker region which for this surface treatment appears to be near the oxide/alloy interface. Figure 11 summarizes the analysis of the bond failure for this particular surface treatment. The important aspect here is that under identical conditions, different surface preparations show different modes of failure. Weak boundary layers are not developed using some treatment/bonding combinations. Processes have been developed in which the locus of failure remains in the adhesive ("a cohesive failure") and it is necessary to use a mechanical test in which even more stress is placed on the interfacial region (19). 

The viscosity increase in a epoxy resin-curing agent system could result in poor wetting of the substrate surface, resulting in suboptimal adhesion. Several reaction mechanisms can also occur to an epoxy adhesive once it is mixed and applied to a substrate but before the substrates are mated. These mechanisms can result in a weak boundary layer, which will prevent optimal wetting and reduce the strength of the adhesive. 

For example, elevated-temperature exposure could cause oxidation or pyrolysis and change the rheological characteristics of the adhesive. Thus, not only is the cohesive strength of the adhesive weakened, but also its ability to absorb stresses due to thermal expansion or impact is degraded. Chemical environments may affect the physical properties of the adhesive and also cause corrosion at the interface however, the adhesive may actually become more flexible and be better able to withstand cyclic stress. Exposure to a chemical environment may also result in unexpected elements from the environment replacing the adhesive at the interface and creating a weak boundary layer. These effects are dependent not only on the type and degree of environment but also on the specific epoxy adhesive formulation. 

Another way moisture can degrade the strength of adhesive joints is through hydration or corrosion of the metal oxide layer at the interface. Common metal oxides, such as aluminum and iron, can undergo hydration. The resulting metal hydrates become gelatinous, and they act as a weak boundary layer because they exhibit very inadequate bonding to their base metals. Thus, the adhesive or sealant used for these materials must be compatible with the firmly bound layer of water attached to the surface of the metal oxide layer. 

Some primers will improve the durability of the joint by protecting the substrate surface area from hydration and corrosion. These primers suppress the formation of weak boundary layers that could develop during exposure to wet environments. Primers that contain film-forming resins are sometimes considered interfacial water barriers. They keep water out of the joint interface area and prevent corrosion of the metal surfaces. By establishing a strong, moisture-resistant bond, the primer protects the adhesive-adherend interface and lengthens the service life of the bonded joint. 

Chemical Surface Modification. In considering the interface, one must contemplate not only the possibility of moisture disrupting the bond but also the possibility of corrosion of the substrate. Corrosion can quickly deteriorate the bond by providing a weak boundary layer before the adhesive or sealant is applied. Corrosion can also occur after the joint is made and, thereby, affect its durability. Mechanical abrasion or solvent cleaning can provide adhesive joints that are strong in the dry condition. However, this is not always the case when joints are exposed to water or water vapor. Resistance to water is much improved if metal surfaces can be treated with a protective coating before being bonded. 

For most adhesive bonded metal joints that must see outdoor service, corrosive environments are a more serious problem than the influence of moisture. The degradation mechanism is corrosion of the metal interface, resulting in a weak boundary layer. Surface preparation methods and primers that make the adherend less corrosive are commonly employed to retard the degradation of adhesive joints in these environments. 

Various substrate surface treatments suggested for use with a common epoxy-substrate joint and service environment combinations are discussed in this chapter. Surface preparation processes for a range of specific substrates and detailed process specifications are provided in App. F. The reader is also directed to several excellent texts that provide prebond surface treatment recipes and discuss the basics of surface preparation, the importance of contamination or weak boundary layers, and specific processes for adhesive systems other than epoxy.1,2,3... 

One of the benefits of surface treatment prior to adhesive bonding is that it not only removes weak boundary layers such as contamination, but also provides a more consistent surface to which the adhesive can bond. Common surface treatments used for metal substrates are characterized generally in Table 16.2. 

The plastic surface, at the time of bonding, may be well suited to the adhesive process. However, after aging, undesirable surface conditions may present themselves at the interface, displace the adhesive, and result in bond failure. These weak boundary layers could come from the environment or from within the plastic substrate itself. Plasticizer migration and degradation of the interface through uv radiation are common examples of weak boundary layers that can develop with time at the interface. 

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