Abstract
This discussion has outlined a series of considerations which begin with engineering definitions of system response of adhesive joints and end with propositions involving molecular interactions at interfaces. Connecting these extreme aspects of the argument is the central subject of the micromechanics of bonding and fracture. Cavitation theory, as simply described by Equations (6a) and (7), illustrates the scale of microresponse in which both the thermodynamic and rheological aspects of adhesion phenomena achieve a parity when applied to cavities of radius r=0.1 to 10 μ. The discussion of the micromechanics of polymer fracture provides ample evidence that pure materials, polymer composites, and adhesive joints, need to be described in terms of their microdefects. The several mathematical models for crack propagation which are imposed upon fracture mechanics data tend to oversimplify the visualization of the true micromechanisms of fracture. The fuller development of micromechanics theory and experimental analysis promises to be an important area of current developments in the better understanding of macroscopic response of filled systems, fiber reinforced composites, and adhesively bonded structures. Recent developments in the several theories of intermolecular forces and the physical chemistry of bonding provide new impetus to the chemist to design optimized polymeric materials with finely adjusted balances of surface and bulk properties. The fuller visualization of adsorption-interdiffusion bonding as a process involving both the two-dimensional interface and the three-dimensional interphase defines bonding as both a thermodynamical and a rheological process. The microstages of bond formation are somewhat the reverse of the stages of microfracture listed earlier. The microdefects that commonly exist in polymeric materials and polymer composites tend to indicate that the viscoelastic constraints typical of polymer chains and networks play an important role in preventing equilibrium bonding in the simple thermodynamic sense as expressed by idealized liquid—liquid or liquid—solid interactions. The current development and application of a refined thermodynamical and rheological argument to both bonding and fracture processes stands as a central issue in directly correlating the molecular criteria of adhesion and performance of bonded systems. Any of the simple mathematical relations introduced in this discussion may be expressed with greater detail and precision by incorporating detailed statements concerning chemical composition, macromolecular structure, and free volume state of the polymeric adhesive.