Rheology of Block Copolymers

Abstract

Abstract Block copolymer consists of two or more long blocks with dissimilar chemical structures which are chemically connected. There are different architectures of block copolymers, namely, AB-type diblock, ABA-type triblock, ABC-type triblock, and AmBn radial or star-shaped block copolymers, as shown schematically in Figure 8.1. The majority of block copolymers has long been synthesized by sequential anionic polymerization, which gives rise to narrow molecular weight distribution, although other synthesis methods (e.g., cationic polymerization, atom transfer radical polymerization) have also been developed in the more recent past. Owing to immiscibility between the constituent blocks, block copolymers above a certain threshold molecular weight form microdomains (10–50 nm in size), the structure of which depends primarily on block composition (or block length ratio). The presence of microdomains confers unique mechanical properties to block copolymers. There are many papers that have dealt with the synthesis and physical/mechanical properties of block copolymers, too many to cite them all here. There are monographs describing the synthesis and physical properties of block copolymers (Aggarwal 1970; Burke and Weiss 1973; Hamley 1998; Holden et al. 1996; Hsieh and Quirk 1996; Noshay and McGrath 1977). Figure 8.2 shows schematically four types of equilibrium microdomain structures observed in block copolymers. Referring to Figure 8.2, it is well established (Helfand and Wasserman 1982; Leibler 1980) that in microphase-separated block copolymers, spherical microdomains are observed when the volume fraction f of one of the blocks is less than approximately 0.15, hexagonally packed cylindrical microdomains are observed when the value of f is between approximately 0.15 and 0.44, and lamellar microdomains are observed when the value of f is between approximately 0.44 and 0.50. Some investigators have observed ordered bicontinuous double-diamonds (OBDD) (Thomas et al. 1986; Hasegawa et al. 1987) or bicontinuous gyroids (Hajduk et al. 1994) at a very narrow range of f (say, between approximately 0.35 and 0.40) for certain block copolymers. Figure 8.2 shows only one half of the symmetricity about f = 0.5. Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) have long been used to investigate the types of microdomain structures in block copolymers.