Surface-directed spinodal decomposition modified by a surface active copolymer

Rysz, Jakub; Bernasik, Andrzej; Ermer, Hubert; Budkowski, Andrzej; Brenn, R.; Hashimoto, Takeji; Jedliński, J.

doi:10.1209/epl/i1997-00495-1

Cited by 17 publications

(38 citation statements)

References 25 publications

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“…by changing the chemical nature of the substrate [9,11] Approaches using mixed SAMs [67] or end-grafted random copolymer brushes [68], both with variable composition, were used to tune the effective interactions between polymers and the substrate. A controlled variation of both effective surface fields was achieved by adding surface-active copolymers to the mixtures [10,12,69]. The co-polymers segregate predominantly to both surfaces of the blend film and reduce the fraction of the surface area exerting ordering interactions.…”

Section: A Surface/polymers Interactions Tuned By Surface-active DImentioning

confidence: 99%

“…The co-polymers segregate predominantly to both surfaces of the blend film and reduce the fraction of the surface area exerting ordering interactions. Here we will discuss briefly this versatile approach to control the self-stratification process [10,12].…”

Section: A Surface/polymers Interactions Tuned By Surface-active DImentioning

confidence: 99%

“…In our studies [10,12] polyisoprene-polystyrene PI-PS (PI-hPS and PI-dPS) diblock copolymers were used, added to two different critical mixtures: hPS 1 /dPS 1 and dPS 2 /PBrS 1 (hPS 2 /PBrS 1 ). Isotopic polymer counterparts were used to provide the contrast necessary for the depth profiling techniques.…”

Section: A Surface/polymers Interactions Tuned By Surface-active DImentioning

confidence: 99%

“…1a). Self-stratification of thin films with initial compositional homogeneity, leading to a multilayer ordering, is the first [4,[10][11][12][13] of two main problems considered in the present paper. Phase separation in polymer mixtures is also altered by the presence of a pre-structured substrate with lateral pattern of surface energy [7,[14][15][16][17][18][19][20][21] (Fig.…”

Section: Introductionmentioning

confidence: 99%

“…the alignment of phase domains with respect to the patterned substrate (accompanied by free surface undulations), is the second main issue [19] discussed here. Selfassembly of polymer blends, cast as thin films on both homogeneous as well as patterned substrates, is a consequence of surface-directed phase separation [1,3,4,[9][10][11][12][13][23][24][25][26][27][28][29][30][31][32], discovered [23,27] only 10 years ago and described shortly below. Molecular mobility in the phase-separating films is promoted by the temperature elevated above glass transition (temperature quench applied for partly miscible or immiscible mixtures) or a common solvent added to the polymer blend (solvent quench encountered commonly for immiscible blends).…”

Section: Introductionmentioning

confidence: 99%

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Surface-directed phase separation in nanometer polymer films: self-stratification and pattern replication

et al. 2002

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Phase separation occurs in thin films of polymer blends when molecular mobility is promoted by a temperature above the glass transition but inside the twophase region (temperature quench), or a common solvent added to the polymers (solvent quench). This phenomenon can be altered by a homogeneous surface or pre-patterned substrate, resulting, e.g., in self-stratification or pattern replication, respectively. Such self-organisation processes ordering polymer phases were observed for model polymer blends (deuterated/hydrogenated polystyrene, dPS/hPS, and deuterated/partially brominated PS, dPS/PBrS, both with hPSpolyisoprene diblocks added; dPS/poly(vinylpyridine) and PBrS/PVP) with highresolution ion beam techniques (Nuclear Reaction Analysis, profiling and mapping mode of dynamic Secondary Ion Mass Spectrometry) and Atomic Force Microscopy. The self-stratification process is strongly affected by both the range as well as the strength of the surface/polymer interactions. This is illustrated for the temperature-quenched blends with surface-active copolymer additives tuning the interactions exerted by both external surfaces. The pattern transfer from the substrate to the films is demonstrated for the solvent-quenched blends. Patterndirected composition variations (SIMS maps) coincide with free surface undulations (AFM images). The most effective pattern replication is achieved for the length scale of phase domain morphology comparable with the pattern periodicity and for carefully adjusted polymer/substrate interactions.

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Section: A Surface/polymers Interactions Tuned By Surface-active DImentioning

confidence: 99%

Section: A Surface/polymers Interactions Tuned By Surface-active DImentioning

confidence: 99%

Section: A Surface/polymers Interactions Tuned By Surface-active DImentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Surface-directed phase separation in nanometer polymer films: self-stratification and pattern replication

et al. 2002

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Surface‐directed morphology evolution in ternary blends of polyethylene, polypropylene, and ethylene–propylene copolymer: A study by laser scanning confocal fluorescence microscopy

Moffitt¹,

Rharbi²,

Tong³

et al. 2003

J Polym Sci B Polym Phys

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With laser scanning confocal fluorescence microscopy, we demonstrate a novel type of morphology evolution in moderately thick films (70 -100 m) of ternary blends of polypropylene (PP), polyethylene (PE), and ethylene-propylene rubber (EPR), in which EPR is labeled with a benzothioxanthene dye (HY-EPR). The blends are prepared by solution blending, and the phase morphology evolves during the annealing of the blend films in a stainless steel mold. Our results indicate that wetting of the mold surface is a driving force in morphology evolution for the two blend compositions investigated. For 81/14/5 PP/PE/HY-EPR, phase evolution within the mold results in a laminar structure and hydrodynamic channels, features which have previously been found in thin films of polymer blends as a result of surface-directed spinodal decomposition. In a blend with a lower weight fraction of the dispersed phase (92/7/1 PP/PE/ HY-EPR), we find that the PE/HY-EPR domains are larger and more polydisperse closer to the surface because of wetting of the mold wall. We also show that the phase morphology in these films can be controlled by the nature of one or both of the surfaces being varied. When one of the mold surfaces is replaced with a thin film of PP homopolymer, we observe draining of PE/HY-EPR from the PP to the mold surface, which results in a bilayer structure. A trilayer morphology is likewise obtained by the replacement of both mold surfaces with PP. We also carry out three-dimensional image reconstruction on a single PE/HY-EPR particle within the 81/14/5 PP/PE/HY-EPR blend to obtain detailed information on the interphase structure. We find that HY-EPR of this composition (30/70 ethylene/propylene) fully coats the PE dispersed phase and partially penetrates the PE droplets. This result falls between the interphase structures found for previously investigated EPR compositions (40/60 and 80/20 ethylene/ propylene).

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Interfacial Phenomena in Thin Polymer Films: Phase Coexistence and Segregation

Budkowski

Interfaces Crystallization Viscoelasticity

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Surface-directed spinodal decomposition modified by a surface active copolymer

Cited by 17 publications

References 25 publications

Surface-directed phase separation in nanometer polymer films: self-stratification and pattern replication

Surface-directed phase separation in nanometer polymer films: self-stratification and pattern replication

Surface‐directed morphology evolution in ternary blends of polyethylene, polypropylene, and ethylene–propylene copolymer: A study by laser scanning confocal fluorescence microscopy

Interfacial Phenomena in Thin Polymer Films: Phase Coexistence and Segregation

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