Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents

Andrey A. Rudov, Elena S. Patyukova, Irina V. Neratova, Pavel G. Khalatur, Dorthe Posselt, Christine Maria Papadakis, Igor I. Potemkin

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

Using dissipative particle dynamics simulations, we study the
swelling of lamellae-forming diblock copolymer films in a nonselective solvent.
Both the parallel and the perpendicular orientations of lamellae in the film are
studied. The swelling of the film with parallel lamellae is accompanied by an
increase of their number. In doing so, the lamellar thickness reveals
nonmonotonous behavior: affine growth (low degree of solvent uptake) is
succeeded by a decrease in thickness (high degree of solvent uptake). Whereas
the first regime reflects a finite size (film thickness) effect, the decrease is a
more common effect, which is also valid for perpendicular lamellae, and is due
to shrinkage of the diblock copolymers due to the shielding of unfavorable AB
contacts by the solvent molecules. The film swelling leads to an increase of the
number of perpendicular lamellae as well. However, such an increase is only
possible if the film at first is dissolved and then condensed absorbing a certain
amount of solvent. Otherwise, splitting of the lamellae requires a large-scale
mass transport which is realizable neither in modeling nor in experiment.
Instead of splitting, the perpendicular lamellae can tilt upon swelling. This
process is much faster and satisfies the space-filling condition at the thinning of
the lamellae. That is why tilted lamellae are often observed in experiments and computer simulations. We demonstrate also that
the distribution of the absorbed solvent in the film is inhomogeneous with a maximum at the AB interfaces. The kinetics of the
parallel lamellae swelling is compared with experimental data.
OriginalsprogEngelsk
TidsskriftMacromolecules
Vol/bind46
Udgave nummer14
Sider (fra-til)5786–5795
Antal sider10
ISSN0024-9297
DOI
StatusUdgivet - 2013

Citer dette

Rudov, A. A., Patyukova, E. S., Neratova, I. V., Khalatur, P. G., Posselt, D., Papadakis, C. M., & Potemkin, I. I. (2013). Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents. Macromolecules, 46(14), 5786–5795. https://doi.org/10.1021/ma400810u
Rudov, Andrey A. ; Patyukova, Elena S. ; Neratova, Irina V. ; Khalatur, Pavel G. ; Posselt, Dorthe ; Papadakis, Christine Maria ; Potemkin, Igor I. . / Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents. I: Macromolecules. 2013 ; Bind 46, Nr. 14. s. 5786–5795.
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title = "Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents",
abstract = "Using dissipative particle dynamics simulations, we study the swelling of lamellae-forming diblock copolymer films in a nonselective solvent. Both the parallel and the perpendicular orientations of lamellae in the film are studied. The swelling of the film with parallel lamellae is accompanied by an increase of their number. In doing so, the lamellar thickness reveals nonmonotonous behavior: affine growth (low degree of solvent uptake) is succeeded by a decrease in thickness (high degree of solvent uptake). Whereas the first regime reflects a finite size (film thickness) effect, the decrease is a more common effect, which is also valid for perpendicular lamellae, and is due to shrinkage of the diblock copolymers due to the shielding of unfavorable AB contacts by the solvent molecules. The film swelling leads to an increase of the number of perpendicular lamellae as well. However, such an increase is only possible if the film at first is dissolved and then condensed absorbing a certain amount of solvent. Otherwise, splitting of the lamellae requires a large-scale mass transport which is realizable neither in modeling nor in experiment. Instead of splitting, the perpendicular lamellae can tilt upon swelling. This process is much faster and satisfies the space-filling condition at the thinning of the lamellae. That is why tilted lamellae are often observed in experiments and computer simulations. We demonstrate also that the distribution of the absorbed solvent in the film is inhomogeneous with a maximum at the AB interfaces. The kinetics of the parallel lamellae swelling is compared with experimental data.",
author = "Rudov, {Andrey A.} and Patyukova, {Elena S.} and Neratova, {Irina V.} and Khalatur, {Pavel G.} and Dorthe Posselt and Papadakis, {Christine Maria} and Potemkin, {Igor I.}",
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Rudov, AA, Patyukova, ES, Neratova, IV, Khalatur, PG, Posselt, D, Papadakis, CM & Potemkin, II 2013, 'Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents', Macromolecules, bind 46, nr. 14, s. 5786–5795. https://doi.org/10.1021/ma400810u

Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents. / Rudov, Andrey A. ; Patyukova, Elena S. ; Neratova, Irina V. ; Khalatur, Pavel G. ; Posselt, Dorthe; Papadakis, Christine Maria; Potemkin, Igor I. .

I: Macromolecules, Bind 46, Nr. 14, 2013, s. 5786–5795.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents

AU - Rudov, Andrey A.

AU - Patyukova, Elena S.

AU - Neratova, Irina V.

AU - Khalatur, Pavel G.

AU - Posselt, Dorthe

AU - Papadakis, Christine Maria

AU - Potemkin, Igor I.

PY - 2013

Y1 - 2013

N2 - Using dissipative particle dynamics simulations, we study the swelling of lamellae-forming diblock copolymer films in a nonselective solvent. Both the parallel and the perpendicular orientations of lamellae in the film are studied. The swelling of the film with parallel lamellae is accompanied by an increase of their number. In doing so, the lamellar thickness reveals nonmonotonous behavior: affine growth (low degree of solvent uptake) is succeeded by a decrease in thickness (high degree of solvent uptake). Whereas the first regime reflects a finite size (film thickness) effect, the decrease is a more common effect, which is also valid for perpendicular lamellae, and is due to shrinkage of the diblock copolymers due to the shielding of unfavorable AB contacts by the solvent molecules. The film swelling leads to an increase of the number of perpendicular lamellae as well. However, such an increase is only possible if the film at first is dissolved and then condensed absorbing a certain amount of solvent. Otherwise, splitting of the lamellae requires a large-scale mass transport which is realizable neither in modeling nor in experiment. Instead of splitting, the perpendicular lamellae can tilt upon swelling. This process is much faster and satisfies the space-filling condition at the thinning of the lamellae. That is why tilted lamellae are often observed in experiments and computer simulations. We demonstrate also that the distribution of the absorbed solvent in the film is inhomogeneous with a maximum at the AB interfaces. The kinetics of the parallel lamellae swelling is compared with experimental data.

AB - Using dissipative particle dynamics simulations, we study the swelling of lamellae-forming diblock copolymer films in a nonselective solvent. Both the parallel and the perpendicular orientations of lamellae in the film are studied. The swelling of the film with parallel lamellae is accompanied by an increase of their number. In doing so, the lamellar thickness reveals nonmonotonous behavior: affine growth (low degree of solvent uptake) is succeeded by a decrease in thickness (high degree of solvent uptake). Whereas the first regime reflects a finite size (film thickness) effect, the decrease is a more common effect, which is also valid for perpendicular lamellae, and is due to shrinkage of the diblock copolymers due to the shielding of unfavorable AB contacts by the solvent molecules. The film swelling leads to an increase of the number of perpendicular lamellae as well. However, such an increase is only possible if the film at first is dissolved and then condensed absorbing a certain amount of solvent. Otherwise, splitting of the lamellae requires a large-scale mass transport which is realizable neither in modeling nor in experiment. Instead of splitting, the perpendicular lamellae can tilt upon swelling. This process is much faster and satisfies the space-filling condition at the thinning of the lamellae. That is why tilted lamellae are often observed in experiments and computer simulations. We demonstrate also that the distribution of the absorbed solvent in the film is inhomogeneous with a maximum at the AB interfaces. The kinetics of the parallel lamellae swelling is compared with experimental data.

U2 - 10.1021/ma400810u

DO - 10.1021/ma400810u

M3 - Journal article

VL - 46

SP - 5786

EP - 5795

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 14

ER -