Adhesion, interfacial

Matrix-rubber particle adhesion is an important parameter for rubber toughening. For effective rubber toughening, rubber particles must be well bonded to the thermoset matrix. The poor intrinsic adhesion across the particle-matrix interface causes premature debonding of particles, leading to catastrophic failure of the materials. Nearly all the studies [9, 193, 2-10] have been concerned with reactive rubbers as toughening agents, and showed that dispersed particles have interfacial chemical bonds as a consequence of chemical reactivity. 

Some authors have refused to accept the role of interfacial adhesion on the toughening of thermoset resins. Lavita and co-workers [190] reported that non-reactive rubber can toughen BPA-modified epoxy, but the mechanism was not fully discussed. Huang and co-workers [194] showed that when the second phase consists of micron-size rubber particles, the interfacial bonding has only a modest effect on the fracture properties of blends. 

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Mangipudi V S ef a/1996 Measurement of interfacial adhesion between glassy polymers using the JKR method Macromoi. Symp. 102 131-43... 

By employing additives to improve interfacial adhesion and the cohesive strength of the mbber phase, natural mbber can compete with ethylene—propylene mbbers as an impact modifier for polypropylene. These hard grades, containing between 15 and 25% natural mbber, have the potential for use in the automotive and domestic markets, eg, in bumpers, spoilers, grilles, electrical connectors, and floor tiles. 

Wear. Ceramics generally exhibit excellent wear properties. Wear is deterrnined by a ceramic s friction and adhesion behavior, and occurs by two mechanisms adhesive wear and abrasive wear (43). Adhesive wear occurs when interfacial adhesion produces a localized Kj when the body on one side of the interface is moved relative to the other. If the strength of either of the materials is lower than the interfacial shear strength, fracture occurs. Lubricants (see Lubricants and lubrication) minimize adhesion between adj acent surfaces by providing an interlayer that shears easily. Abrasive wear occurs when one material is softer than the other. Particles originating in the harder material are introduced into the interface between the two materials and plow into and remove material from the softer material (52). Hard particles from extrinsic sources can also cause abrasive wear, and wear may occur in both of the materials depending on the hardness of the particle. 

Contact mechanics, in the classical sense, describes the behavior of solids in contact under the action of an external load. The first studies in the area of contact mechanics date back to the seminal publication "On the contact of elastic solids of Heinrich Hertz in 1882 [ 1 ]. The original Hertz theory was applied to frictionless non-adhering surfaces of perfectly elastic solids. Lee and Radok [2], Graham [3], and Yang [4] developed the theories of contact mechanics of viscoelastic solids. None of these treatments, however, accounted for the role of interfacial adhesive interactions. 

As mentioned earlier, the contact-mechanics-based experimental studies of interfacial adhesion primarily include (1) direct measurements of surface and interfacial energies of polymers and self-assembled monolayers (2) quantitative studies on the role of interfacial coupling agents in the adhesion of elastomers (3) adhesion of microparticles on surfaces and (4) adhesion of viscoelastic polymer particles. In these studies, a variety of experimental tools have been employed by different researchers. Each one of these tools offers certain advantages over the others. These experimental studies are reviewed in Section 4. 

As mentioned earlier, the contact-mechanics-based experimental studies on interfacial adhesion primarily include ... 

In the JKR experiments, a macroscopic spherical cap of a soft, elastic material is in contact with a planar surface. In these experiments, the contact radius is measured as a function of the applied load (a versus P) using an optical microscope, and the interfacial adhesion (W) is determined using Eqs. 11 and 16. In their original work, Johnson et al. [6] measured a versus P between a rubber-rubber interface, and the interface between crosslinked silicone rubber sphere and poly(methyl methacrylate) flat. The apparatus used for these measurements was fairly simple. The contact radius was measured using a simple optical microscope. This type of measurement is particularly suitable for soft elastic materials. 

Israelachvili and coworkers [64,69], Tirrell and coworkers [61-63,70], and other researchers employed the SFA to measure molecular level adhesion and deformation of self-assembled monolayers and polymers. The pull-off force (FJ, and the contact radius (a versus P) are measured. The contact radius, the local radius of curvature, and the distance between the surfaces are measured using the optical interferometer in the SFA. The primary advantage of using the SFA is its ability to study the interfacial adhesion between thin films of relatively high... 

Given the importance of surface and interfacial energies in determining the interfacial adhesion between materials, and the unreliability of the contact angle methods to predict the surface energetics of solids, it has become necessary to develop a new class of theoretical and experimental tools to measure the surface and interfacial energetics of solids. Thia new class of methods is based on the recent developments in the theories of contact mechanics, particularly the JKR theory. 

Johnson and coworkers [6], in their original paper on the JKR theory, reported the measurements of surface energies and interfacial adhesion of soft elastomeric materials. Israelachvili and coworkers [68,69], and Tirrell and coworkers [62, 63,70,88-90] used the SFA to measure the surface energies of self-assembled monolayers and polymer films, respectively. Chaudhury and coworkers [47-50] adapted the JKR technique to measure the surface energies and interfacial adhesion between self-assembled monolayers. More recently, Mangipudi and coworkers [55] modified the JKR technique to measure the surface energies of glassy polymers. All these measurements are reviewed in this section. 

Creton, C., Kramer, E.J., Hui, C.-Y. and Brown, H.R., Failure mechanisms of polymer interfaces reinforced with block copolymers. Macromolecules, 25, 3075-3088 (1992). Boucher et al., E., Effects of the formation of copolymer on the interfacial adhesion between semicrystalline polymers. Macromolecules, 29, 774-782 (1996). 

Chemical covalent bonding. The formation of covalent chemical bonds between elements at an interface may be an important factor. Such direct chemical bonding would greatly enhance interfacial adhesion, but specific chemical functional groups are required for the reactions to occur. 

Chemical secondary bonding. Low-energy bonds, dipolar interactions, dispersion may all play an important role in the development of interfacial adhesion. 

Polypropylene block and graft copolymers are efficient blend compatibilizers. These materials allow the formation of alloys, for example, isotactic polypropylene with styrene-acrylonitrile polymer or polyamides, by enhancing the dispersion of incompatible polymers and improving their interfacial adhesion. Polyolefinic materials of such types afford property synergisms such as improved stiffness combined with greater toughness. 

Interfacial adhesion and, thereby, compatibility can be enhanced by the selective crosslinking reaction in polymer blends. Inoue and Suzuki [26] reported the properties of blends dynamically crosslinked PP-EPDM blends. The crosslinking agent was yV,N -/w-phenylene-bismaleimide - poly(2,2,4 - trimethyl - 1,2-dihydroquino -line) system. Increase in interfacial adhesion leads to... 

Elliot [38] has reported that interfacial adhesion in the NR-PP blend can be enhanced by the addition of small amounts of HOPE. Addition of HDPE does give some improvement in the notched Izod impact strength of NR-PP blend (Fig. 7). The effect of HDPE on the impact modification of NR-PP is associated with the improved crystallinity of PP, enhanced by HDPE. During the mill mixing of NR and PP, chain scission may occur to give polymeric radicals that, on reaction with... 

Els and McGill [48] reported the action of maleic anhydride on polypropylene-polyisoprene blends. A graft copolymer was found in situ through the modifier, which later enhanced the overall performance of the blend. Scott and Macosko [49] studied the reactive and nonreactive compatibilization of nylon-ethylene-propylene rubber blends. The nonreactive polyamide-ethylene propylene blends showed poor interfacial adhesion between the phases. The reactive polyamide-ethylene propylene-maleic anhydride modified blends showed excellent adhesion and much smaller dispersed phase domain size. 

The graft polymer formed during melt mixing results in good interfacial adhesion between the phases. The... 

The important factors that affect the rubber toughening are (1) interfacial adhesion, (2) nature of the matrix, (3) concentration of the rubber phase, and (4) shape and size of the rubber particles. In the PS-XNBR blend containing OPS, due to the reaction between oxazoline groups of OPS and carboxylic groups of XNBR, the interfacial adhesion increases and as a result, the minor rubber phase becomes more dispersed. The immiscible blend needs an optimum interfacial adhesion and particle size for maximum impact property. In PS-XNBR, a very small concentration of OPS provides this optimum interfacial adhesion and particle size. The interfacial adhesion beyond this point does not necessarily result in further toughening. 

An important chemical modification method is the chemical coupling method. This method improves the interfacial adhesion. The fiber surface is treated with a compound that forms a bridge of chemical bonds between fiber and matrix. 

After this treatment the surface energy of the fibers is increased to a level much closer to the surface energy of the matrix. Thus, a better wettability and a higher interfacial adhesion are obtained. The polypropylene (PP) chain permits segmental crystallization and cohesive coupling between modified fiber and PP matrix [40]. The graft copolymerization method is effective, but complex. 

The single filament pull out test, sometimes called the microdebond test, has received attention for some years as a way to assess the adhesion between fibers and matrices in fiber composite [90,91]. It provides a direct measure of interfacial adhesion and can be used with both brittle and ductile matrix resins. 

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