Abstract:Dynamic lattice Monte Carlo simulations on a simple cubic lattice were used to study the association behavior of heteroarm star copolymers with two types of chemically different arms (miktoarm star). The effect of architecture and composition (number and length of arms) on self‐assembly was investigated. Simulations revealed substantial differences between associates formed by linear diblock copolymers and by star copolymers. It was also observed that the length of arms considerably influences the association … Show more
“…In our earlier paper,49 we developed an improved recognition criterion that discerns better between the real and random associates: a group of copolymer heteroarm chains (we actually studied heteroarm copolymer stars) is considered to be an associate only if there are more inter‐chain contacts between insoluble blocks than in a random homopolymer cluster formed under identical conditions. Although this criterion is relatively simple (it is based on one parameter only), it corrects and improves the distribution of association numbers significantly in favor of the closed association scheme and works well for identifying micellar aggregates with well‐segregated domains formed by block copolymers 56–58. As will be show later, this criterion is not very proper for gradient copolymer in selective solvents where aggregates with relatively thick diffusive interface between core and shell and/or thin bridges between cores may exist (simulation snapshots are available upon request).…”
We present a computer study of the association behavior of copolymer chains with a gradient part and soluble tail of variable length. As a simulation method we use dynamic Monte Carlo simulation on a simple cubic lattice with pair interaction parameters. The solvent quality and selectivity is modeled by the variation of pair interaction parameters between nearest neighbors on the lattice. The role of the length of soluble part in the self‐assembly and its effect on the structure of aggregates was the main goal of this work. The size and structure of aggregates were analyzed using an improved topological classification method which has been developed and tested in the present study. The structure and association numbers of aggregates were compared with those of linear diblock copolymers.
“…In our earlier paper,49 we developed an improved recognition criterion that discerns better between the real and random associates: a group of copolymer heteroarm chains (we actually studied heteroarm copolymer stars) is considered to be an associate only if there are more inter‐chain contacts between insoluble blocks than in a random homopolymer cluster formed under identical conditions. Although this criterion is relatively simple (it is based on one parameter only), it corrects and improves the distribution of association numbers significantly in favor of the closed association scheme and works well for identifying micellar aggregates with well‐segregated domains formed by block copolymers 56–58. As will be show later, this criterion is not very proper for gradient copolymer in selective solvents where aggregates with relatively thick diffusive interface between core and shell and/or thin bridges between cores may exist (simulation snapshots are available upon request).…”
We present a computer study of the association behavior of copolymer chains with a gradient part and soluble tail of variable length. As a simulation method we use dynamic Monte Carlo simulation on a simple cubic lattice with pair interaction parameters. The solvent quality and selectivity is modeled by the variation of pair interaction parameters between nearest neighbors on the lattice. The role of the length of soluble part in the self‐assembly and its effect on the structure of aggregates was the main goal of this work. The size and structure of aggregates were analyzed using an improved topological classification method which has been developed and tested in the present study. The structure and association numbers of aggregates were compared with those of linear diblock copolymers.
“…Apart from experimental characterization, numerical investigations of model chains are the most direct approach to study these systems. Therefore, a lot of effort has been put into the investigation of block copolymer and miktoarm stars based on lattice Monte Carlo algorithms [5][6][7][8][9][10][11][12][13][14][15][16] as well as molecular dynamics, [17][18][19][20][21][22] in many cases focusing the attention to a quantitative description or the graphical presentation of microdomains.…”
Characteristic properties of linear (F = 2) and star‐branched copolymers with F = 3 to 12 arms in common good, common theta and in selective solvents are summarized. Based on ensembles of chains or stars with chain lengths up to ≈50 000 segments, exponents of scaling laws of mean square dimensions of the whole star and of individual blocks and arms may be reduced to five cases. Several ratios which compare stars to linear chains (so‐called g factors) and shape‐parameters in the limit of infinite chain lengths are deduced from the prefactors of scaling laws and by proper extrapolation, respectively. Shape parameters give evidence for some orientation effects which in addition are directly demonstrated.
“…There is evidence that polymeric architecture and composition have a direct influence on micelle formation and its corresponding solution properties, such as aggregation number, size, and morphology. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Considerable experimental 16,17,[20][21][22][23][24] and theoretical [25][26][27] work has been devoted to the study of micellization of complex architectures in selective organic solvents. The micellization process was found to be driven by enthalpy gains that are Additional Supporting Information may be found in the online version of this article.…”
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