Monte Carlo simulation and mean field analysis of two-dimensional random copolymer/homopolymer blends

Vliet, J.H. van; Brinke, G. ten

doi:10.1021/ma00202a040

Cited by 5 publications

(2 citation statements)

References 9 publications

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“…leading to a higher number of contacts between unlike chains for favorable interaction energies, as was demonstrated by van Vliet and ten Brinke. 18 Alternatively, unfavorable interactions may lead to deviations from random mixing and to local aggregation of chains of the same components, even before macroscopic phase separation takes place; these arguments are similar to those used to describe deviations of random mixing on the segmental level due to enthalpic interactions.lg…”

Section: Introductionmentioning

confidence: 94%

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Thin-film behavior of poly(methyl methacrylates). 6. Monolayer phase behavior in relation to stereocomplexation in mixed monolayers of i- and s-PMMA

Brinkhuis¹,

Schouten²

1993

Macromolecules

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The stereocomplexation process in mixed monolayers of isotactic and syndiotactic poly(methy1 methacrylate) is efficient only when low molecular weight samples are used. This phenomenon can be explained by an increasing tendency for phase separation in the monolayer upon using higher molecular weight samples, leading to larger domain sizes and a limited mutual accessibility: especially the use of high molecular weight syndiotactic PMMA appears to result in strong aggregation processes of these chains caused by the strong cohesive intersegment interactions at the air-water interface. This hypothesis is corroborated by the observation that addition of stereoblock PMMA strongly enhances the efficiency of the stereocomplexation process, thus acting as a compatibilizer, dispersing the s-PMMA chains in the monolayer. IntroductionIn previous publications,lt2 we discussed stereocomplexation processes that can take place in monolayers of mixtures of isotactic and syndiotactic PMMA. Upon compression, the monolayers exhibit an isotherm transition that can be correlated to the formation of double helical stereocomplex structures of both components, similar to the formation of such complexes in solution and melt mixtures of these materials. Indications for stereocomplexation were inferred from, e.g., the stoichiometry, the tacticity dependence, the surface potential behavior, and IR measurements of transferred monolayers. The monolayer stereocomplexation was most effectively conducted at elevated temperatures, lower temperatures leading to incomplete conversions.2 In this paper, we will focus on the relation between this stereocomplexation process and the phase behavior in the monolayer blends.The behavior of monolayers of polymer mixtures has been the subject of many reports in the literature. Especially the group of Gabrielli dedicated much effort to studying mixed monolayer^;^^ Kawaguchi recently also addressed the monolayer behavior of a series of polymer mixtures: and many other authors reported on the miscibility behavior of specific polymers in monolayers. Most of these studies assess the miscibility of two components on the basis of deviations from addivity of the specific areas or the compressibility or on the basis of the collapse behavior of the mixed monolayers. The first approach may not be very sensitive in many cases, since often the effects are quite small; the latter approach gives information only about the collapse regime, with very high segment concentrations and strongly deformed conformations, and the results are not always unambiguous. In most cases, the mixtures are either classified as miscible or nonmiscible; more detailed information is usually not extracted. Phenomena such as the extent of segregation of the individual coils, limited interpenetration, and molecular weight effects have not been addressed in detail in these experimental studies; a direct correlation with theoretical results on the behavior of two-dimensional polymer mixtures is not often given.Langmuir-Blodgett monolayers o...

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Section: Introductionmentioning

confidence: 94%

“…Unfavorable segment-segment energies that can be tolerated before phase separation occurs, will scale as N-1/2. 18 Mixtures of long chains will therefore exhibit a stronger tendency for phase separation (beyond the segregation of the individual chains) than mixtures of short chains.…”

Section: Introductionmentioning

confidence: 99%

Thin-film behavior of poly(methyl methacrylates). 6. Monolayer phase behavior in relation to stereocomplexation in mixed monolayers of i- and s-PMMA

Brinkhuis¹,

Schouten²

1993

Macromolecules

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Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

Shi

Wen

Jiang

et al. 2003

European Polymer Journal

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Comparison of the stability of blends of chemically identical and different homopolymers in the bulk and in a film

Kosmas

Vlahos

2003

The Journal of Chemical Physics

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We present a criterion of the stability of a polymeric blend of two species in terms of the three different interaction parameters between the same or different monomeric units. Long chain correlations among different chains are taken into account by including the contribution from all configurations having one loop. The special cases of chemically identical polymers of different size where all three interaction parameters become the same can be deduced and compared with that of different polymers. The stability limits of the system is analyzed in the three dimensional (3D) and in the two dimensional (2D) space in order to describe the behavior of a blend in the bulk and in a thin film where the 2D character of the chains is increased. Going from the 3D to the 2D case while the stability of a system of chemically identical homopolymers of different size decreases that of two different homopolymers increases but may decrease too.

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Monte Carlo simulation and mean field analysis of two-dimensional random copolymer/homopolymer blends

Cited by 5 publications

References 9 publications

Thin-film behavior of poly(methyl methacrylates). 6. Monolayer phase behavior in relation to stereocomplexation in mixed monolayers of i- and s-PMMA

Thin-film behavior of poly(methyl methacrylates). 6. Monolayer phase behavior in relation to stereocomplexation in mixed monolayers of i- and s-PMMA

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

Comparison of the stability of blends of chemically identical and different homopolymers in the bulk and in a film

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