Self microdomains

It is well known that block copolymers and graft copolymers composed of incompatible sequences form the self-assemblies (the microphase separations). These morphologies of the microphase separation are governed by Molau s law [1] in the solid state. Nowadays, not only the three basic morphologies but also novel morphologies, such as ordered bicontinuous double diamond structure, are reported [2-6]. The applications of the microphase separation are also investigated [7-12]. As one of the applications of the microphase separation of AB diblock copolymers, it is possible to synthesize coreshell type polymer microspheres upon crosslinking the spherical microdomains [13-16]. 

Morishima etal. [29 — 31] prepared amphiphilic copolymers of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) with various hydrophobic comonomers, and studied the tendency of their self-aggregation and the nature of the hydrophobic microdomains thus formed in aqueous solution. Chart 1 shows some of these amphiphilic copolymers. Here, the value of x indicates the mol% content of hydrophobic comonomer units. 

The ability of block copolymers to self-assemble into organized microdomain (MD) structures when the thermodynamic repulsion between the constituents is high enough seems to be fairly well understood. This is particularly true in the case of amorphous diblock copolymers where phase diagrams for particular systems have been successfully predicted and experimentally proven [1-5]. 

Self-Assembled Microdomain Patterns from Block Copolymers. 186... 

Abstract This article is a review of the chemical and physical nature of patternable block copolymers and their use as templates for functional nanostructures. The patternability of block copolymers, that is, the ability to make complex, arbitrarily shaped submicron structures in block copolymer films, results from both their ability to self-assemble into microdomains, the bottom-up approach, and the manipulation of these patterns by a variety of physical and chemical means including top-down lithographic techniques. Procedures for achieving long-range control of microdomain pattern orientation as well... 

The self-assembly of block polymers, in the bulk, thin film and solution states, produces uniformly sized nanostructured patterns that are very useful for nanofabrication. Optimal utilization of these nanoscopic patterns requires complete spatial and orientational control of the microdomains. However, the microdomains in the bulk state normally have grain sizes in the submicron range and have random orientations. In block copolymer thin films, the natural domain orientations are generally not desirable for nanofabrication. In particular, for composition-asymmetric cylindrical thin films, experimental... 

The formation of bottom-up block copolymer patterns within or on top-down substrate patterns is the basis for so-called templated self-assembly processes, in which long-range order and orientation of microdomain patterns can be imposed by a template or guide . These top-down templates can take a variety of forms including periodic thickness profiles and chemically patterned surfaces. 

A mean field approach was applied to determine homopolymer distributions in the lamellar phase of a blend of AB diblock and A homopolymer by Shull and Winey (1992). In the strong segregation limit, complete segregation of the A homopolymer into the A microdomain was predicted. Furthermore, in this limit, the diblocks were treated as brushes , wetted by homopolymer in the A domain. Composition profiles showing the distribution of homopolymer and copolymer were determined by numerical solution of the self-consistent field equations. 

Heteropolymers can self-assemble into highly ordered patterns of microstructures, both in solution and in bulk. This subject has been reviewed extensively [1,123-127]. The driving force for structure formation in such systems is competing interactions, i.e., the attraction between one of the monomer species and the repulsion between the others, on the one hand, and covalent bonding of units within the same macromolecule, on the other hand. The latter factor prevents the separation of the system into homogeneous macroscopic phases, which can, under specific conditions, stabilize some types of microdomain structures. Usually, such a phenomenon is treated as microphase separation transition, MIST, or order-disorder transition, ODT. 

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