Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings

Wei, Wei; Kim, Tae-Yi; Balamurugan, A.; Sun, Jian; Chen, Ri; Ghosh, Atanu; Rodolakis Simoes, Fanny; McChesney, Jessica L.; Lakkham, Arunee; Evans, Paul G.; Hur, Su-Mi; Gopalan, Padma

doi:10.1021/acsmacrolett.9b00501

Title: Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings

Abstract

Experimental validation of the predicted melt phase behavior of A/B mixed or binary brush on planar substrate is presented using poly(methyl methacrylate) (A)/ polystyrene (B) (PMMA/PS) with equal number of A/B chains as an example. Specifically, well-defined mixed A/B brushes are synthesized using a single component inimer coating to achieve high grafting density (0.9 chains/ nm²), uniformity of grafting sites, and predictable chain length. The inimer coating is a copolymer ofnitroxide-mediated polymerization (NMP) inimer, atom transfer radical polymerization (ATRP) inimer, styrene, and glycidyl methacrylate (GMA). Cross-linking of the film provides the required stability to probe the melt morphology. Our studies show that even with equal grafting density of the A and B the morphology can be modulated by varying the length of B chains while keeping that of A fixed. We show the very first example of transition of self-assembled structures from disorder to cylinder to ripple phase at sub-30 nm length scale on a planar surface by thermal annealing of mixed brushes. These results are supported by a new phase diagram established through Monte-Carlo simulation using a coarse-grained particle-based model.

Authors:

Wei, Wei ^[1]; Kim, Tae-Yi ^[2]; Balamurugan, A. ^[1]; Sun, Jian ^[1]; Chen, Ri ^[1]; Ghosh, Atanu ^[1]; Rodolakis Simoes, Fanny ^[3]; McChesney, Jessica L. ^[3]; Lakkham, Arunee ^[1]; Evans, Paul G. ^[1]; Hur, Su-Mi ^[2];

^[4]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering
Chonnam National Univ., Gwangju (Republic of Korea)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering and Dept. of Chemistry

Publication Date:: Wed Aug 14 00:00:00 EDT 2019

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: National Science Foundation (NSF); National Research Foundation of Korea (NRF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

OSTI Identifier:: 1599074

Grant/Contract Number:: AC02-06CH11357; DMR-1507409; 2018R1D1A1A02044073; DMR-1720415; DMR-0703406

Resource Type:: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thickness; Coating materials; Thermal annealing; Organic compounds; Radical polymerization

Citation Formats


                    Wei, Wei, Kim, Tae-Yi, Balamurugan, A., Sun, Jian, Chen, Ri, Ghosh, Atanu, Rodolakis Simoes, Fanny, McChesney, Jessica L., Lakkham, Arunee, Evans, Paul G., Hur, Su-Mi, and Gopalan, Padma. Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings.  United States: N. p., 2019. 
Web.  doi:10.1021/acsmacrolett.9b00501.

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                    Wei, Wei, Kim, Tae-Yi, Balamurugan, A., Sun, Jian, Chen, Ri, Ghosh, Atanu, Rodolakis Simoes, Fanny, McChesney, Jessica L., Lakkham, Arunee, Evans, Paul G., Hur, Su-Mi, & Gopalan, Padma. Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings.  United States.  https://doi.org/10.1021/acsmacrolett.9b00501

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                    Wei, Wei, Kim, Tae-Yi, Balamurugan, A., Sun, Jian, Chen, Ri, Ghosh, Atanu, Rodolakis Simoes, Fanny, McChesney, Jessica L., Lakkham, Arunee, Evans, Paul G., Hur, Su-Mi, and Gopalan, Padma. Wed .  
"Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings".  United States.  https://doi.org/10.1021/acsmacrolett.9b00501.  https://www.osti.gov/servlets/purl/1599074.

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@article{osti_1599074,

  title        = {Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings},

  author       = {Wei, Wei and Kim, Tae-Yi and Balamurugan, A. and Sun, Jian and Chen, Ri and Ghosh, Atanu and Rodolakis Simoes, Fanny and McChesney, Jessica L. and Lakkham, Arunee and Evans, Paul G. and Hur, Su-Mi and Gopalan, Padma},

  abstractNote = {Experimental validation of the predicted melt phase behavior of A/B mixed or binary brush on planar substrate is presented using poly(methyl methacrylate) (A)/ polystyrene (B) (PMMA/PS) with equal number of A/B chains as an example. Specifically, well-defined mixed A/B brushes are synthesized using a single component inimer coating to achieve high grafting density (0.9 chains/ nm2), uniformity of grafting sites, and predictable chain length. The inimer coating is a copolymer ofnitroxide-mediated polymerization (NMP) inimer, atom transfer radical polymerization (ATRP) inimer, styrene, and glycidyl methacrylate (GMA). Cross-linking of the film provides the required stability to probe the melt morphology. Our studies show that even with equal grafting density of the A and B the morphology can be modulated by varying the length of B chains while keeping that of A fixed. We show the very first example of transition of self-assembled structures from disorder to cylinder to ripple phase at sub-30 nm length scale on a planar surface by thermal annealing of mixed brushes. These results are supported by a new phase diagram established through Monte-Carlo simulation using a coarse-grained particle-based model.},

  doi          = {10.1021/acsmacrolett.9b00501},

  journal      = {ACS Macro Letters},

  number       = 9,

  volume       = 8,

  place        = {United States},

  year         = {Wed Aug 14 00:00:00 EDT 2019},

  month        = {Wed Aug 14 00:00:00 EDT 2019}

}

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https://doi.org/10.1021/acsmacrolett.9b00501

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Cited by: 8 works

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Figures / Tables:

Figure 1: (a) Illustration of PS chain end group substitution. SEM images of the PMMA/PS mixed brushes (h₁ = 20.3 nm, Δh = 17.4 nm) thermally annealed at 160 °C/3 h with (b) the TEMPO end group, and (c) the N-phenylmaleimide end group. (b) and (c) share the same scalemore »

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