Functional Macromolecular Systems: Kinetic Pathways to Obtain Tailored Structures

Abstract

This article aims to stimulate research on non‐equilibrium macromolecular systems, as nowadays a large toolbox to synthesize tailored macromolecules is available. A large variety of characterization methods covering a broad spectrum of length and timescales allows researchers to follow and also manipulate macromolecular systems on their paths toward equilibrium. These possibilities are paralleled by the development of new concepts of the statistical physics of non‐equilibrium phenomena in macromolecular systems as well as new models and algorithms for computer simulation.

Quo Vadis, Macromolecular Science? Reflections by the IUPAC Polymer Division on the Occasion of the Staudinger Centenary

“…confinement effects in semiconductors leading to spectroscopic shifts), physical properties in polymers depend on the state of stress, which may be even inhomogeneously distributed within the material. The increasing possibilities in computer and in time‐resolved characterization and manipulation of materials may lead to materials with new properties, if processing can be directed along the free energy landscape of the polymer following prediction of theory and simulation …”

“…The increasing possibilities in computer and in time-resolved characterization and manipulation of materials may lead to materials with new properties, if processing can be directed along the free energy landscape of the polymer following prediction of theory and simulation. [19] These are just some examples of ways in which macromolecular science stands distinct from the other fields of chemistry, even if there is obviously overlap with each of them. This overlap is obviously important in terms of future developments in macromolecular science and technology, because often such developments flow from advancements in other disciplines.…”

Planet‐Like Nanostructures Formed by an ABC Triblock Terpolymer

“…Morphological transitions can also be induced by pathway‐dependent ordering and kinetic control. The advantage of this kind of methods is the possibility to obtain distinct self‐assembled nanostructures of block copolymers without having to change their chemistry or to blend them with other components . Thermally induced morphological transitions are one example of pathway‐dependent ordering and can often be kinetically controlled.…”

“…In that study, the question if the transition is reversible or not could not be answered due to the proximity of the glass transition of the PS block. Block copolymers as a nice class of soft matter may display many local minima in their free energy landscape, where they can be trapped in non‐equilibrium states, if processed in the “right way.” This can happen especially if a block copolymer is close to a morphological transition line or plane in a multidimensional phase diagram and self‐assembles under the influence of an external field (e.g., electrical field, or it is cast from a selective solvent in a sufficiently fast way. In such a scenario, a sequential microphase separation may occur, where first one block segregates from the solution and defines the microphase structure, before further removal of the solvent, when the other blocks also separate from each other within the predefined structure .…”

“…The advantage of this kind of methods is the possibility to obtain distinct selfassembled nanostructures of block copolymers without having to change their chemistry or to blend them with other components. [43,44] Thermally induced morphological transitions are one example of pathway-dependent ordering and can often be kinetically controlled. For example, thermoreversible morphological transitions between cylinders and spheres of a polystyrene-blockpolyisoprene) (SI) diblock copolymer in melt [45,46] and in dioctyl phthalate solutions [47] were observed by Sakurai et al Not only neat block copolymers, but also block copolymer blends can experience a morphological transition by thermal treatment, as it was studied for a blend of SI diblock copolymers transforming from a lamellar to a gyroid phase upon heating.…”