| Copolymers provide a route to novel polymeric materials by combining two or more existing monomers and arranging them in new ways. Self-consistent mean field theory (SCFT) is a powerful tool for exploring the many possible sequence distributions for copolymers and predicting their equilibrium behavior. In this thesis, SCFT calculations are used in combination with experiments to learn more about the ordering and interfacial behavior of block, random, and gradient copolymers.; A symmetric diblock copolymer melt undergoes separation into lamellar microphases above a critical order-disorder transition. A symmetric gradient copolymer with a controlled composition gradient along its backbone also forms lamellae, but at a higher degree of incompatibility with broader interfaces and wider periodic spacing. Upon renormalization to their respective critical points, it is seen that the scaling behavior of symmetric diblock and gradient copolymers is universal across a wide range in incompatibility, regardless of the sequence distribution.; The interfacial segregation of diblock, random, and gradient copolymers synthesized by ring-opening metathesis polymerization was measured with forward recoil spectrometry and analyzed using SOFT. The diblock copolymers form an interfacial monolayer with low interfacial tension, and the random copolymers form a wetting layer at the interface. The gradient copolymers exhibit intermediate behavior by forming a low interfacial energy layer that is slightly broader than a monolayer. The nature of the gradient can be altered to create a tailored interfacial copolymer monolayer that has a desired interfacial width.; SCFT studies on a system of asymmetric AB copolymer and A and C homopolymers where B and C have favorable interactions show that the copolymer modifies the interfacial curvature so that swollen micelles, inverse swollen micelles, or bicontinuous microemulsions can form. The calculations also show that nanoparticles can be encapsulated in the center of the swollen micelles. A copolymer synthesis method combining anionic and nitroxide mediated controlled radical polymerizations was developed as a corresponding experimental system. In this system, the A homopolymer is polystyrene, the C homopolymer is poly(2-vinylpyridine), and the AB copolymer is a block-random copolymer where the first block is deuterated polystyrene and the second block is a random copolymer of polystyrene and poly(4-hydroxystyrene). |
