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Micromechanical deformation processes responsible for toughening mechanisms in ultrafine monospherical inorganic particle-filled polyethylene were investigated in situ by a field-emission gun-environmental scanning electron microscope (FEG-ESEM) with low-voltage techniques. In general, the ultimate properties of polymer composites are largely dependent on the degree of dispersion of filler particles into the matrix. Very often, the agglomeration is one of inevitable occurrences in polymer composites, mixed with ultrafine filler particles. In the present work, the effects of agglomerates, consisting of ultrafine monospherical filler particles, were reexamined in polymer composites on the toughening mechanism. The results show that the dominant micromechanical deformation processes are the multiple debonding processes inside agglomerates, in which the ratio of the matrix strand and the size of agglomerate plays a great role of matrix yielding. In the specimen, where the agglomerates are isolated in the matrix, deformation begins at the equatorial region of agglomerates and propagates through them. However, in the case of closely placed agglomerates, deformation occurs homogeneously within the whole area inside the agglomerates. In both cases, in conjunction with the multiple debonding processes, the major part of energy during the deformation dissipates through the shear-flow processes of the matrix material. In particular, the micromechanical deformation processes observed in this work confirm that the agglomerates do not always have negative effects on the mechanical properties-at least, in the shear deformable semicrystalline polymer matrices. The agglomerates may be effectively used for the improvement of toughness. Furthermore, the FEG-ESEM with low-voltage techniques offers an extremely promising and efficient alternative method to study the morphology as well as in situ micromechanical deformation processes in nonconducting polymer systems.

A theory of crack healing in polymers is presented in terms of the stages of crack healing, namely, (a) surface rearrangement, (b) surface approach, (c) wetting, (d) diffusion, and (e) randomization. The recovery ratio R of mechanical properties with time was determined as a convolution product, R = Rh (t)*φ(t), where Rh (t) is an intrinsic healing function, and φ(t) is a wetting distribution function for the crack interface or plane in the material. The reptation model of a chain in a tube was used to describe self-diffusion of interpenetrating random coil chains which formed a basis for Rh (t). Applications of the theory are described, including crack healing in amorphous polymers and melt processing of polymer resins by injection or compression molding. Relations are developed for fracture stress σ, strain ε, and energy E as a function of time t, temperature T, pressure P, and molecular weight M. Results include (i) during healing or processing at t<t∞, σ,ε∼t1/4, E∼t1/2; (ii) at constant t<t∞, σ,ε∼M−1/4, E∼M−1/2; (iii) in the fully interpenetrated healed state at t = t∞, σ,ε∼M1/2, E∼M; (iv) the time to achieve complete healing, t∞ ∼M3, ∼exp P, ∼exp 1/T. Chain fracture, creep, and stress relaxation are also discussed. New concepts for strength predictions are introduced.

Crack healing in polymers has several stages, namely, surface rearrangement, surface approach, wetting, diffusion, and randomization. We present a microscopic theory of the diffusion and randomization stages based on the reptation model of chain dynamics by de Gennes. The theory analyzes motion of chains at the interface and calculates the average interpenetration distance of polymer segments as a function of time t and molecular weight M. The theory predicts that, when fracture stress is proportional to , (i) / " ~t1/4Ai~3/4 for t < Tr, where T, is the tube renewal time of the reptation model and " is the virgin fracture stress, and (ii) the t1/4 dependence persists for a wide range of M and also for time t until t becomes comparable to Tv These results are in agreement with healing experiments.

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