Adhesion practical

The usual practical situation is that in which two solids are bonded by means of some kind of glue or cement. A relatively complex joint is illustrated in Fig. XII-14. The strength of a joint may be measured in various ways. A common standard method is the peel test in which the normal force to separate the joint 

Returning to more surface chemical considerations, most literature discussions that relate adhesion to work of adhesion or to contact angle deal with surface free energy quantities. It has been pointed out that structural distortions are generally present in adsorbed layers and must be present if bulk liquid adsorbate forms a finite contact angle with the substrate (see Ref. 115). Thus both the entropy and the energy of adsorption are important (relative to bulk liquid). The 

The coefficient of friction for copper on copper is about 0.9. Assuming that asperities or junctions can be represented by cones of base and height each about 5 x 10 cm, and taking the yield pressure of copper to be 30 kg/mm, calculate the local temperature that should be produced. Suppose the frictional heat to be confined to the asperity, and take the sliding speed to be 10 cm/sec and the load to be 20 kg. 

The resistance due to a circular junction is given by / = /2ak, where a is the radius of the junction and k is specific conductivity of the metal. For the case of two steel plates, the measured resistance is 5 x 10 Q for a load of 50 kg the yield pressure of steel is 60 kg/mm, and the specific resistance is 5x 10 Q/cm. Calculate the number of junctions, assuming that it is their combined resistance that is giving the measured value. 

Deduce from Fig. XII-5, using the data for Hs, how the contact area appears to be varying with load, and plot A versus IV. 

The brief analysis of ideal adhesion given above indicates that, under the best of circumstances, one might expect to be able to attain very strong adhesive 

FIGURE 19.2. Since aU surfaces have a certain degree of roughness, it is common that an adhesive apphed to such surfaces wiU entrap air bubbles, reducing the area of contact of adhesive with the surfaces and reducing the effectiveness of the bond or weld. 

FIGURE 19.3. In what is generally classified as adhesive failure, breakage may occur at various locations including entrapped bubbles (a), at the interface ( true adhesive failure) (b), in the substrate (cohesive failure) (c), or in the adhesive (also cohesive failure) d). 

The fracture of practical adhesive joints involves two primary processes— cohesive or adhesive failure at or near the joint and work (reversible and irreversible) involved in plastic, elastic, or viscoelastic deformation of one or all of the components of the joint—one of the two solid surfaces or the adhesive (Fig. 19.4). As indicated in the preceding chapter on friction, cohesive failure of the weaker of two solids in contact is common. The same can be said for normal adhesive joints, in that actual adhesive failure (i.e., exactly at the interface) is less common that cohesive failure, of, for example, the adhesive material, near the interface. What, then, are the necessary conditions for obtaining good adhesion between two surfaces  

FIGURE 19.4. When a tension or shear strain is placed on a joint, the energy may be dissipated by several mechanisms including adhesive and cohesive failure at various points, as already mentioned, but also by the plastic, elastic, or viscoelastic stretching of the adhesive and/or one or both substrates. 

---

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. 

The relationship between practical adhesion and the work of adhesion,... 

Assuming the work of adhesion to be measurable, one must next ask if it can be related to practical adhesion. If so, it may be a useful predictor of adhesion. The prospect at first looks bleak. The perfect disjoining of phases contemplated by Eq. 1 almost never occurs, and it takes no account of the existence of an interphase , as discussed earlier. Nonetheless, modeling the complex real interphase as a true mathematical interface has led to quantitative relationships between mechanical quantities and the work of adhesion. For example, Cox [22] suggested a linear relationship between Wa and the interfacial shear strength, r, in a fiber-matrix composite as follows ... 

The most-often cited theoretical underpinning for a relationship between practical adhesion energy and the work of adhesion is the generalized fracture mechanics theory of Gent and coworkers [23-25] and contributed to by Andrews and Kinloch [26-29]. This defines a linear relationship between the mechanical work of separation, kj, , and the thermodynamic work of adhesion ... 

Combination of Eq. 7 or Eq. 8 with the Young-Dupre equation, Eq. 3, suggests that the mechanical work of separation (and perhaps also the mechanical adhesive interface strength) should be proportional to (I -fcos6l) in any series of tests where other factors are kept constant, and in which the contact angle is finite. This has indeed often been found to be the case, as documented in an extensive review by Mittal [31], from which a few results are shown in Fig. 5. Other important studies have also shown a direct relationship between practical and thermodynamic adhesion, but a discussion of these will be deferred until later. It would appear that a useful criterion for maximizing practical adhesion would be the maximization of the thermodynamic work of adhesion, but this turns out to be a serious over-simplification. There are numerous instances in which practical adhesion is found not to correlate with the work of adhesion at ail, and sometimes to correlate inversely with it. There are various explanations for such discrepancies, as discussed below. 

The practical adhesion, for example fracture energy T, will comprise a surface energy term Fq (VTa or VTcoh) lo vvhich must be added a term xf representing other... 

Surface energies are again important in determining the practical adhesion, F, in the breaking of an adhesive bond. Eqs. 7 to 10 show how the two are related. Emphasis was placed on the important contribution to fracture energy of which represents energy absorbing processes other than those (VTa and Wcoh) directly associated with the actual formation of new surfaces. It must be remembered that... 

If contact with a rough surface is poor, whether as a result of thermodynamic or kinetic factors, voids at the interface are likely to mean that practical adhesion is low. Voids can act as stress concentrators which, especially with a brittle adhesive, lead to low energy dissipation, i/f, and low fracture energy, F. However, it must be recognised that there are circumstances where the stress concentrations resulting from interfacial voids can lead to enhanced plastic deformation of a ductile adhesive and increase fracture energy by an increase in [44]. 

As the scale of roughness becomes finer, the effective increase in A can become enormous. Consequently Fg may be raised to very high value. Indeed, as many engineering surfaces are fractal in nature [36], we can only retain the concept of area at all, if we accept that it can be considered as indefinitely large. The practical adhesion does not become infinite, because the joint with a strong interfacial region will fail (cohesively) in some other region where Fg is smaller [89],... 

The surface of the substrate, the silicone/substrate interface, and the bulk properties of silicones all play significant and influential roles that affect practical adhesion and performance of the silicone. The design of silicone adhesives, sealants, coatings, encapsulants or any products where adhesion property is needed requires the development chemist to have a thorough understanding of both silicone chemistry and adhesion phenomena. 

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. 

There is no unify ing theory of adhesion describing the relationship between practical adhesion and the basic intermolecular and interatomic interactions which take place between the adhesive and die adherend either at die interface or within the interphase. The existing adhesion theories are, for the most part, rationalizations of observed phenomena, although in some cases, predictions regarding the relative ranking of practical adhesion can actually be made. 

Mechanical Interlocking Theory. A practical adhesion can be enhanced if the adhesive is applied to a surface which is microscopically rough. 

Throughout the paper the term bond strength rather than adhesion has been used as it is the author s view that all adhesion values are in fact cohesion values [13], as paints and adhesives fail cohesively, while frequently appearing, especially under water-soaked conditions, to fail cleanly from the substrate. For all practical purposes these failures may be regarded as adhesional failures, and represent practical adhesion failures [ 14]. 

These are essential considerations for a practical adhesive system. The adhesive composition must have sufficient reactivity to cure under conditions that are convenient and practical to the end user. It must have viscosity that allows easy mixing and application. Once on the substrate, the adhesive must be able to flow over the substrate and come into intimate contact with it—a process called wetting. 

The chemical structures of important amines for curing epoxy resins in adhesive systems are identified in Fig. 5.1. Diethylenetriamine (DETA), triethylenetetramine (TETA), ra-aminoethylpiperazine (AEP), diethylaminopropylamine (DEAPA), ra-phenylenediamine (MPDA), and diaminodiphenyl sulfone (DDS) are the most commonly used members of this class. They are all primary amines. They give room or elevated temperature cure at near stoichiometric ratios. Ethylenediamine is too reactive to be used in most practical adhesive formulations. Polyoxypropyleneamines (amine-terminated polypropylene glycols) impart superior flexibility and adhesion. 

Polysulfides can be cured by themselves with an oxidizing agent as a catalyst. They can also be used to cure epoxy resins (see Chap. 5) however, the rate of cure is very slow for a practical adhesive. Thus, polysulfide resins are generally added into epoxy formulations as a modifier to increase flexibility. In applications where maximum flexibility is required, the level of polysulfide may be greater than the epoxy resin present in the formulation. 

Life prediction methodology embraces all aspects of the numerous processes that could affect the function of the element—in this case the bulk adhesive. The first step is to define the function of the adhesive clearly enough for a failure criterion to be derived. This failure criterion may be an unacceptable reduction in tensile strength, time to creep failure under a given stress, reduction in modulus due to moisture ingression, increase in modulus due to oxidation, unacceptable crack depth, or a variety of other possible criteria. It is also important that the criteria be related to practical adhesive joint performance. This is where it is difficult, and one must presume, at least for this limited analysis, that the adhesive will fail via a bulk (cohesive) property. 

An adhesive is a material capable of holding together solid materials by means of surface attachment. Adhesion is the physical attraction of the surface of one material for the surface of another. An adherend is the solid material to which the adhesive adheres and the adhesive bond or adhesive joint is the assembly made by joining adlierends together by means of an adhesive. Practical adhesion is the physical strength of an adhesive bond It primarily depends on the forces of adhesion, but its magnitude is determined by the physical properties of the adhesive and the adherend, as well as the engineering of the adhesive bond. 

The most important inference is that Chemisorption is a direct response to carboxyl group concentration indicated by the XPS photopeak component at 288.7 eV. It seems likely that weak add functionality is of minor import to applications for surface treatments, while interfacial phenomena such as practical adhesion may be sensitive to small concentrations of very high site energies. Interphase modification in epoxy resins, for example, can occur by direct reaction of epoxide groups with surface carboxyls (17), or by accelerated cure chemistry near the surface (39). Carboxyl groups on carbon surfaces may interact with basic moieties in polymers such as polycarbonate or poly(ethylene)oxide (40=42), or promote interfacial crystallinity that improves impact strength and other aspects of composite performance (43, M)-... 

---