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Title: Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends

Abstract

Here, the thin film phase behavior of ternary blends consisting of symmetric poly(styrene) (PS)–b–poly(dimethylsiloxane)(PDMS), PS, and PDMS was investigated using X–ray reflectivity (XRR) and atomic force microscopy (AFM). This system is strongly segregated, and the homopolymers are approximately the same length as the corresponding blocks of the copolymer. The XRR and AFM data are used to quantify changes in domain spacing (L) and morphology evolution with increasing homopolymer content (Φ H). In 100 nm thick films, from Φ H = 0 to 0.20, the system maintains a perfect parallel lamellar structure and domains swell as predicted based on theory; however, from Φ H = 0.30 to 0.50, a morphology transition to a “dot pattern” morphology (tentatively identified as perforated lamellae) and mixed morphologies were observed before macrophase separation. In thicker films, dot patterns were observed for a broad range of Φ H before macrophase separation. The absence of the bicontinuous microemulsion phase reported for bulk blends and thin films of perpendicular lamellae and the presence of dot patterns/perforated lamellae are attributed to preferential migration of the PDMS homopolymer to the wetting layers located at the substrate and free air interfaces, which leads to an asymmetric composition within the film andmore » morphology transition.« less

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [1]
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  1. Tulane Univ., New Orleans, LA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1490075
Alternate Identifier(s):
OSTI ID: 1472190
Grant/Contract Number:  
AC02-06CH11357; DE‐AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part B, Polymer Physics
Additional Journal Information:
Journal Volume: 56; Journal Issue: 21; Journal ID: ISSN 0887-6266
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block copolymer blend; domain spacing; perforated lamellae; thin film morphology

Citation Formats

Uddin, Md Fakar, Jiang, Zhang, Raymond, Andrew, Goodson, Amy D., Lwoya, Baraka S., and Albert, Julie N. L.. Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends. United States: N. p., 2018. Web. https://doi.org/10.1002/polb.24732.
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Uddin, Md Fakar, Jiang, Zhang, Raymond, Andrew, Goodson, Amy D., Lwoya, Baraka S., & Albert, Julie N. L.. Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends. United States. https://doi.org/10.1002/polb.24732
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Uddin, Md Fakar, Jiang, Zhang, Raymond, Andrew, Goodson, Amy D., Lwoya, Baraka S., and Albert, Julie N. L.. Sun . "Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends". United States. https://doi.org/10.1002/polb.24732. https://www.osti.gov/servlets/purl/1490075.
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@article{osti_1490075,
title = {Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends},
author = {Uddin, Md Fakar and Jiang, Zhang and Raymond, Andrew and Goodson, Amy D. and Lwoya, Baraka S. and Albert, Julie N. L.},
abstractNote = {Here, the thin film phase behavior of ternary blends consisting of symmetric poly(styrene) (PS)–b–poly(dimethylsiloxane)(PDMS), PS, and PDMS was investigated using X–ray reflectivity (XRR) and atomic force microscopy (AFM). This system is strongly segregated, and the homopolymers are approximately the same length as the corresponding blocks of the copolymer. The XRR and AFM data are used to quantify changes in domain spacing (L) and morphology evolution with increasing homopolymer content (Φ H). In 100 nm thick films, from Φ H = 0 to 0.20, the system maintains a perfect parallel lamellar structure and domains swell as predicted based on theory; however, from Φ H = 0.30 to 0.50, a morphology transition to a “dot pattern” morphology (tentatively identified as perforated lamellae) and mixed morphologies were observed before macrophase separation. In thicker films, dot patterns were observed for a broad range of Φ H before macrophase separation. The absence of the bicontinuous microemulsion phase reported for bulk blends and thin films of perpendicular lamellae and the presence of dot patterns/perforated lamellae are attributed to preferential migration of the PDMS homopolymer to the wetting layers located at the substrate and free air interfaces, which leads to an asymmetric composition within the film and morphology transition.},
doi = {10.1002/polb.24732},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 21,
volume = 56,
place = {United States},
year = {2018},
month = {9}
}
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Journal Article:
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https://doi.org/10.1002/polb.24732
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Figures / Tables:

Figure 1 Figure 1: X-ray reflectivity (XRR) profiles as a function of $Q$$Z$ (nm -1 ), through-film scattering length density (SLD) profiles used to calculate the reflectivity profile, and AFM height images(scale bar = 10 $μ$m and height color scale = 100 nm) of representative PS-b-PDMS and ternary blend films. On themore » XRR profiles, the open colored circles represent the measured data points and solid lines represent the calculated reflectivity profile. Three morphological regimes are noted: (a) from $Փ$$H$ = 0 to 0.20 (red box), parallel lamellae; (b) from $Փ$$H$ = 0.30 to 0.50 (blue box), morphology transition; (c) from $Փ$$H$ =0.60 to 0.80 (green box), macrophase separated.« less
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    Works referencing / citing this record:

    Nanostructure stability and swelling of ternary block copolymer/homopolymer blends: A direct comparison between dissipative particle dynamics and experiment
    journal, April 2019

    • Goodson, Amy D.; Liu, Guoliang; Rick, Maxwell S.
    • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 12
    • DOI: 10.1002/polb.24834
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      Figures / Tables found in this record:

      Figure 1 (p. 11)figure
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      Figure 3 (p. 15)figure
      Figure 4 (p. 17)figure
      Figure 5 (p. 18)figure
      Table S1 (p. 29)table
      Table S2 (p. 29)table
      Figure S1 (p. 30)figure
      Figure S1 (p. 31)figure
      Figure S1 (p. 32)figure
      Figure S2 (p. 33)figure
      Figure S3 (p. 34)figure
      Figure S4 (p. 35)figure
      Figure S5 (p. 36)figure
      Figure S6 (p. 37)figure
      Table S3 (p. 38)table
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