Toughening mechanisms in composites of miscible polymer blends with rigid filler particles

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2006.Vita.Includes bibliographical references (leaves 97-98).Fillers are often added to polymers improve stiffness at the cost of reduced toughness, but this tradeoff is not universal. Well-dispersed microscopic particles have been shown to improve toughness and stiffness simultaneously in some cases. The effect depends on interparticle distance as well as interfacial adhesion. This type of toughening has been more successful in semicrystalline than in amorphous systems. An amorphous polymer blend was chosen to elucidate the effect of matrix properties on the toughening mechanism. The ternary blend of PMMA, PVC, and DOP (a common plasticizer) was characterized using TEM, and was found to be miscible over much of the PVC-rich domain. The blend Tg's fit well to an empirical model, which was used to predict a constant-Tg ([approx.] 40°C) blend series. Mechanical testing showed a wide, systematic variation in properties among these blends, although all were brittle in tension. The blend 90% PVC / 10% DOP was mixed with barium sulfate filler and evaluated for toughness in slow tension. In general, the composites showed decreasing toughness with increasing filler content. However, several specimens at 5 vol% filler exhibited a large increase in ductility and toughness ([approx.] 19-fold).(cont.) SEM examination of tough specimens revealed several important findings: (1) Filler is present both as micron-scale agglomerates and as well dispersed particles. (2) Well-dispersed particles remain bonded to the matrix even for large deformations. (3) Filler agglomerates are prone to debonding and internal fracture, creating void space and enabling deformation. Base blend properties significantly affect the response to filler. The blend 8% PMMA / 80% PVC / 12% DOP showed small increases in ductility for 5 and 10 vol% filler, with the best result being a 10 vol% specimen showing a 6-fold toughness increase over the neat-blend average. This specimen showed similar microscopic behavior to the 90/10 blend, i.e. agglomerate debonding and fracture, but to a lesser degree. The blend 16% PMMA / 70% PVC / 14% DOP, showed no significant toughening. Also investigated were high-Tg ([approx.] 70°C) blends, which were brittle and became weaker with filler, and low-Tg ([approx.] 30°C) blends, which were intrinsically ductile and were not toughened by filler.by Roger Lockwood Aronow.Ph.D