Influence of copolymer architectures on adhesion and compatibilization of polymers at interfaces

Adhesion and compatibilization of immiscible homopolymers by a variety of copolymer architectures were studied. The work is arranged into 5 chapters: In Chapter 1, an introduction to recent studies on improvement of adhesion and compatibilization of polymer blends using copolymers was made including the advantages and shortcomings of interfacial reinforcement by a diblock copolymer architecture. Emphasis is on the novel ways to improve adhesion at polymer interfaces by a variety of copolymer architectures, including physical entanglement and chemical modification and chemical bonding. In Chapter 2, a series of Polystyrene-Poly(methyl methacrylate) (PS-PMMA) graft copolymers were introduced to modify the PS and PMMA homopolymer interface and was found to increase the interfacial fracture toughness to a large extent, depending on the detailed architectural variables such as the graft number per chain, the lengths of the backbone and the grafts, and the total molecular weights of the graft copolymers. It was also found that there was an optimal number of grafts per chain which can be interpreted based on the graft length and inter-branch length of the backbone of the copolymer. Effect of in-situ grafting via a chemical reaction between Polystyrene-Poly(vinyl phenol) (PS-PSOH) and oxazoline containing Styrene-Acrylonitril (SAN) was also discussed compared with the physical grafting of a graft copolymer of different structural parameters. In Chapter 3, hydrogen bonding was utilized to toughen the interface between PS and PAA poly(acrylic acid)) or PMMA using a random copolymer architecture of Polystyrene-Poly(vinyl pyridine) (PS-PVP). It was shown that random copolymer architecture is not only economically feasible due to its low cost of producing but also very effective on adhesion because it not only overcomes the issue of micelle formation which is an unavoidable situation in the diblock and graft cases but the enhancement of adhesion is much higher utilizing a H-bonding mechanism than using a pure physical entanglement. In addition, the graft copolymer is directly in the interfacial region where its effectiveness is optimized. In chapter 4, it was shown that it is possible to improve the adhesive strength of the interface between blends of styrene-co-acrylonitrile (SAN) of differing AN content and polycarbonate. The segregation depends upon AN content and can lead to a component migrating to the interface which provides enhanced adhesive strength. In this way, one may maximize both the mechanical properties and the adhesion of the SAN. In Chapter 5, micromechanical behavior of the interface between polystyrene(PS) and polymethyl methacrylate(PMMA) is investigated experimentally. The interface is formed by adding a properly chosen PS-PMMA copolymer between two homopolymers. It is a very sharp interface due to the polymer chainlike structures. The glass transition temperatures of PS and PMMA differ by only 5% so that residual stresses produced by the bonding process are minimal. The Young's moduli and Poisson's ratios of these two polymers are approximately the same. However, their fracture behaviors are very different. This gives rise to a strong mode mixity effect due to different fracture processes. The interfacial fracture toughness of this material system under tension-dominated load states was measured. Fracture surfaces were examined by scanning electron microscope (SEM). In situ observation on the local failure behavior was performed by utilizing SEM's environmental function. The deformation field at small scale near the interface crack tip is mapped by an experimental micromechanics technique, speckle interferomtry with electron microscopy (SIEM).