Morphological Consequences of Frustration in ABC Triblock Polymers

Radlauer, Madalyn R.; Sinturel, Christophe; Asai, Yusuke; Arora, Akash; Bates, Frank S.; Dorfman, Kevin D.; Hillmyer, Marc A.

doi:10.1021/acs.macromol.6b02112

Morphological Consequences of Frustration in ABC Triblock Polymers

Journal Article · Sun Dec 18 23:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b02112· OSTI ID:1343138

^[1]; Sinturel, Christophe ^[2]; Asai, Yusuke ^[3]; Arora, Akash ^[1]; ^[1]; Dorfman, Kevin D. ^[1]; ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. d’Orléans (France)
Nagoya Univ. (Japan)

In this work, three poly(styrene)-block-poly(isoprene)-block-poly(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core–shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); Camille and Henry Dreyfus Foundation; Ministry of Education, Culture, Sports, Science and Technology (MEXT); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1343138

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 1 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (80)

Conformationally asymmetric block copolymers Matsen, M. W.; Bates, F. S. Journal of Polymer Science Part B: Polymer Physics, Vol. 35, Issue 6, p. 945-952 https://doi.org/10.1002/(SICI)1099-0488(19970430)35:6<945::AID-POLB9>3.0.CO;2-G	journal	April 1997
Nanoporous Membranes with Ultrahigh Selectivity and Flux for the Filtration of Viruses Yang, S. Y.; Ryu, I.; Kim, H. Y. Advanced Materials, Vol. 18, Issue 6 https://doi.org/10.1002/adma.200501500	journal	March 2006
Fluctuations, Order, and Disorder in Short Diblock Copolymers Lee, Sangwoo; Gillard, Timothy M.; Bates, Frank S. AIChE Journal, Vol. 59, Issue 9 https://doi.org/10.1002/aic.14023	journal	February 2013
Cylindrical morphologies in asymmetric ABC triblock copolymers Breiner, Ulrike; Krappe, Udo; Abetz, Volker Macromolecular Chemistry and Physics, Vol. 198, Issue 4 https://doi.org/10.1002/macp.1997.021980411	journal	April 1997
Evolution of the “knitting pattern” morphology in ABC triblock copolymers Breiner, Ulrike; Krappe, Udo; Stadler, Reimund Macromolecular Rapid Communications, Vol. 17, Issue 8 https://doi.org/10.1002/marc.1996.030170810	journal	August 1996
Towards Nanoporous Membranes based on ABC Triblock Terpolymers Sperschneider, Alexandra; Schacher, Felix; Gawenda, Marcel Small, Vol. 3, Issue 6 https://doi.org/10.1002/smll.200600579	journal	June 2007
Phase Behaviour and Morphologies of Block Copolymers Abetz, Volker; Simon, Peter F. W. Block Copolymers I https://doi.org/10.1007/12_004	book	January 2005
Nanopattern Evolution in Block Copolymer Films: Experiment, Simulations and Challenges Tsarkova, Larisa; Sevink, G. J. Agur; Krausch, Georg Complex Macromolecular Systems I https://doi.org/10.1007/12_2010_54	book	January 2010
Thermodynamics of Polymer Blends Eitouni, Hany B.; Balsara, Nitash P. Physical Properties of Polymers Handbook https://doi.org/10.1007/978-0-387-69002-5_19	book	January 2007
Triblock copolymers: the role of interfacial tension coefficients at two interfaces Lyatskaya, Yu. V.; Birshtein, T. M. Polymer, Vol. 36, Issue 5 https://doi.org/10.1016/0032-3861(95)93597-F	journal	March 1995
Effect of surface roughness of carbon support films on high-resolution electron diffraction of two-dimensional protein crystals Butt, H. -J.; Wang, D. N.; Hansma, P. K. Ultramicroscopy, Vol. 36, Issue 4 https://doi.org/10.1016/0304-3991(91)90123-N	journal	September 1991
Surface induced self assembly in thin polymer films Krausch, G. Materials Science and Engineering: R: Reports, Vol. 14, Issue 1-2 https://doi.org/10.1016/0927-796X(94)00173-1	journal	March 1995
Influence of the block sequence on the morphological behavior of ABC triblock copolymers Hückstädt, H.; Göpfert, A.; Abetz, V. Polymer, Vol. 41, Issue 26 https://doi.org/10.1016/S0032-3861(00)00290-1	journal	December 2000
Block copolymers and conventional lithography Stoykovich, Mark P.; Nealey, Paul F. Materials Today, Vol. 9, Issue 9, p. 20-29 https://doi.org/10.1016/S1369-7021(06)71619-4	journal	September 2006
Synthesis, characterization, and bulk crosslinking of polybutadiene-block-poly(2-vinyl pyridine)-block-poly(tert-butyl methacrylate) block terpolymers Schacher, Felix; Yuan, Jiayin; Schoberth, Heiko G. Polymer, Vol. 51, Issue 9 https://doi.org/10.1016/j.polymer.2010.02.046	journal	April 2010
Polydispersity and block copolymer self-assembly Lynd, Nathaniel A.; Meuler, Adam J.; Hillmyer, Marc A. Progress in Polymer Science, Vol. 33, Issue 9 https://doi.org/10.1016/j.progpolymsci.2008.07.003	journal	September 2008
Surface-treatment effects on organic thin-film transistors Lim, Sang Chul; Kim, Seong Hyun; Lee, Jung Hun Synthetic Metals, Vol. 148, Issue 1 https://doi.org/10.1016/j.synthmet.2004.08.034	journal	January 2005
Novel lift-off technique for Transmission Electron Microscopy imaging of block copolymer films Roache, Fergus J. M.; Radjainia, Mazdak; Williams, David E. Ultramicroscopy, Vol. 150 https://doi.org/10.1016/j.ultramic.2014.12.004	journal	March 2015
Fluctuations, Phase Transitions, and Latent Heat in Short Diblock Copolymers: Comparison of Experiment, Simulation, and Theory Gillard, Timothy M.; Medapuram, Pavani; Morse, David C. Macromolecules, Vol. 48, Issue 8 https://doi.org/10.1021/acs.macromol.5b00277	journal	April 2015
Mapping Substrate Surface Field Propagation in Block Polymer Thin Films Shelton, Cameron K.; Epps, Thomas H. Macromolecules, Vol. 49, Issue 2 https://doi.org/10.1021/acs.macromol.5b02141	journal	January 2016
Broadly Accessible Self-Consistent Field Theory for Block Polymer Materials Discovery Arora, Akash; Qin, Jian; Morse, David C. Macromolecules, Vol. 49, Issue 13 https://doi.org/10.1021/acs.macromol.6b00107	journal	June 2016
Stabilizing the Frank-Kasper Phases via Binary Blends of AB Diblock Copolymers Liu, Meijiao; Qiang, Yicheng; Li, Weihua ACS Macro Letters, Vol. 5, Issue 10 https://doi.org/10.1021/acsmacrolett.6b00685	journal	September 2016
Cornucopia of Nanoscale Ordered Phases in Sphere-Forming Tetrablock Terpolymers Chanpuriya, Siddharth; Kim, Kyungtae; Zhang, Jingwen ACS Nano, Vol. 10, Issue 5 https://doi.org/10.1021/acsnano.6b00495	journal	April 2016
Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes Phillip, William A.; O’Neill, Brandon; Rodwogin, Marc ACS Applied Materials & Interfaces, Vol. 2, Issue 3 https://doi.org/10.1021/am900882t	journal	February 2010
Nanopore and Nanobushing Arrays from ABC Triblock Thin Films Containing Two Etchable Blocks Guo, Shouwu; Rzayev, Javid; Bailey, Travis S. Chemistry of Materials, Vol. 18, Issue 7 https://doi.org/10.1021/cm052694m	journal	March 2006
Core−Shell Gyroid Morphology in a Poly(isoprene- block -styrene- block -dimethylsiloxane) Triblock Copolymer Shefelbine, T. A.; Vigild, M. E.; Matsen, M. W. Journal of the American Chemical Society, Vol. 121, Issue 37 https://doi.org/10.1021/ja991442h	journal	September 1999
Effect of Polydispersity on the Phase Diagrams of Linear ABC Triblock Copolymers in Two Dimensions Jiang, Ying; Yan, Xiaoyan; Liang, Haojun The Journal of Physical Chemistry B, Vol. 109, Issue 44 https://doi.org/10.1021/jp052902y	journal	November 2005
Morphologies of ABC Triblock Terpolymer Melts Containing Poly(Cyclohexadiene): Effects of Conformational Asymmetry Kumar, Rajeev; Sides, Scott W.; Goswami, Monojoy Langmuir, Vol. 29, Issue 6 https://doi.org/10.1021/la304576c	journal	January 2013
Interfacial Manipulations: Controlling Nanoscale Assembly in Bulk, Thin Film, and Solution Block Copolymer Systems Mastroianni, Sarah E.; Epps, Thomas H. Langmuir, Vol. 29, Issue 12 https://doi.org/10.1021/la304800t	journal	February 2013
Preparation and morphology of triblock copolymers of the ABC type Mogi, Yasuhiro; Kotsuji, Hiroyuki; Kaneko, Yuji Macromolecules, Vol. 25, Issue 20 https://doi.org/10.1021/ma00046a043	journal	September 1992
Correlation of binary polyolefin phase behavior with statistical segment length asymmetry Bates, Frank S.; Schulz, Mark F.; Rosedale, Jeffrey H. Macromolecules, Vol. 25, Issue 20 https://doi.org/10.1021/ma00046a070	journal	September 1992
New ordered morphologies in ABC triblock copolymers Auschra, Clemens; Stadler, Reimund Macromolecules, Vol. 26, Issue 9 https://doi.org/10.1021/ma00061a005	journal	April 1993
Observation of a non-constant mean curvature interface in an ABC triblock copolymer Gido, Samuel P.; Schwark, Dwight W.; Thomas, Edwin L. Macromolecules, Vol. 26, Issue 10 https://doi.org/10.1021/ma00062a040	journal	May 1993
Tricontinuous Double-Diamond Structure Formed by a Styrene-Isoprene-2-Vinylpyridine Triblock Copolymer Matsushita, Yushu; Tamura, Masaki; Noda, Ichiro Macromolecules, Vol. 27, Issue 13 https://doi.org/10.1021/ma00091a036	journal	June 1994
Microphases of a Diblock Copolymer with Conformational Asymmetry Matsen, M. W.; Schick, M. Macromolecules, Vol. 27, Issue 14 https://doi.org/10.1021/ma00092a049	journal	July 1994
Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties Fetters, L. J.; Lohse, D. J.; Richter, D. Macromolecules, Vol. 27, Issue 17 https://doi.org/10.1021/ma00095a001	journal	August 1994
Morphology and Thermodynamics of Symmetric Poly(A-block-B-block-C) Triblock Copolymers Stadler, Reimund; Auschra, Clemens; Beckmann, Joerg Macromolecules, Vol. 28, Issue 9 https://doi.org/10.1021/ma00113a010	journal	April 1995
Chiral Assembly in Amorphous ABC Triblock Copolymers. Formation of a Helical Morphology in Polystyrene-block-polybutadiene-block-poly(methyl methacrylate) Block Copolymers Krappe, Udo; Stadler, Reimund; Voigt-Martin, Ingrid Macromolecules, Vol. 28, Issue 13 https://doi.org/10.1021/ma00117a027	journal	June 1995
Morphology of ABC Triblock Copolymers Zheng, Wei; Wang, Zhen-Gang Macromolecules, Vol. 28, Issue 21 https://doi.org/10.1021/ma00125a026	journal	October 1995
Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition Khandpur, Ashish K.; Foerster, Stephan; Bates, Frank S. Macromolecules, Vol. 28, Issue 26 https://doi.org/10.1021/ma00130a012	journal	December 1995
Morphological Behavior Bridging the Symmetric AB and ABC States in the Poly(styrene- b -isoprene- b -ethylene oxide) Triblock Copolymer System Bailey, Travis S.; Pham, Hoai D.; Bates, Frank S. Macromolecules, Vol. 34, Issue 20 https://doi.org/10.1021/ma0103371	journal	September 2001
Antiferromagnetic Ordering in a Helical Triblock Copolymer Mesostructure Elbs, Hubert; Abetz, Volker; Hadziioannou, Georges Macromolecules, Vol. 34, Issue 23 https://doi.org/10.1021/ma011123m	journal	October 2001
Field-Theoretic Computer Simulation Methods for Polymers and Complex Fluids Fredrickson, Glenn H.; Ganesan, Venkat; Drolet, François Macromolecules, Vol. 35, Issue 1 https://doi.org/10.1021/ma011515t	journal	January 2002
A Noncubic Triply Periodic Network Morphology in Poly(isoprene- b -styrene- b -ethylene oxide) Triblock Copolymers Bailey, Travis S.; Hardy, Cordell M.; Epps, Thomas H. Macromolecules, Vol. 35, Issue 18 https://doi.org/10.1021/ma011716x	journal	August 2002
Thin Film Morphologies of ABC Triblock Copolymers Prepared from Solution Elbs, Hubert; Drummer, Clarissa; Abetz, Volker Macromolecules, Vol. 35, Issue 14 https://doi.org/10.1021/ma011734e	journal	July 2002
Influence of Conformational Asymmetry on Polymer−Polymer Interactions: An Entropic or Enthalpic Effect? Almdal, Kristoffer; Hillmyer, Marc A.; Bates, Frank S. Macromolecules, Vol. 35, Issue 20 https://doi.org/10.1021/ma020148y	journal	September 2002
Combinatorial Mapping of the Phase Behavior of ABC Triblock Terpolymers in Thin Films: Experiments Ludwigs, S.; Schmidt, K.; Stafford, C. M. Macromolecules, Vol. 38, Issue 5 https://doi.org/10.1021/ma049048d	journal	February 2005
Routes to Alkene and Epoxide Functionalized Nanoporous Materials from Poly(styrene- b -isoprene- b -lactide) Triblock Copolymers Bailey, Travis S.; Rzayev, Javid; Hillmyer, Marc A. Macromolecules, Vol. 39, Issue 25 https://doi.org/10.1021/ma061892b	journal	December 2006
Guanidine and Amidine Organocatalysts for Ring-Opening Polymerization of Cyclic Esters Lohmeijer, Bas G. G.; Pratt, Russell C.; Leibfarth, Frank Macromolecules, Vol. 39, Issue 25 https://doi.org/10.1021/ma0619381	journal	December 2006
Phase Behavior of Nonfrustrated ABC Triblock Copolymers: Weak and Intermediate Segregation Qin, Jian; Bates, Frank S.; Morse, David C. Macromolecules, Vol. 43, Issue 11 https://doi.org/10.1021/ma100400q	journal	June 2010
Morphologies of Linear Triblock Copolymers from Monte Carlo Simulations Nagpal, Umang; Detcheverry, François A.; Nealey, Paul F. Macromolecules, Vol. 44, Issue 13 https://doi.org/10.1021/ma200330f	journal	June 2011
Emergence and Stability of Helical Superstructures in ABC Triblock Copolymers Li, Weihua; Qiu, Feng; Shi, An-Chang Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma2023952	journal	December 2011
Self-Consistent Field Theory for Melts of Low-Molecular-Weight Diblock Copolymer Matsen, M. W. Macromolecules, Vol. 45, Issue 20 https://doi.org/10.1021/ma301788q	journal	October 2012
Theoretical Study of Phase Behavior of Frustrated ABC Linear Triblock Copolymers Liu, Meijiao; Li, Weihua; Qiu, Feng Macromolecules, Vol. 45, Issue 23 https://doi.org/10.1021/ma302060m	journal	November 2012
Block Copolymer Lithography Bates, Christopher M.; Maher, Michael J.; Janes, Dustin W. Macromolecules, Vol. 47, Issue 1, p. 2-12 https://doi.org/10.1021/ma401762n	journal	November 2013
Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)- block -poly(methyl methacrylate) Block Polymers for Lithography Kennemur, Justin G.; Yao, Li; Bates, Frank S. Macromolecules, Vol. 47, Issue 4 https://doi.org/10.1021/ma4020164	journal	February 2014
Origins of Complex Self-Assembly in Block Copolymers Matsen, M. W.; Bates, F. S. Macromolecules, Vol. 29, Issue 23 https://doi.org/10.1021/ma960744q	journal	January 1996
Reversible Kinetics and Thermodynamics of the Homopolymerization of l -Lactide with 2-Ethylhexanoic Acid Tin(II) Salt Witzke, David R.; Narayan, Ramani; Kolstad, Jeffrey J. Macromolecules, Vol. 30, Issue 23 https://doi.org/10.1021/ma970631m	journal	November 1997
σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers Xie, Nan; Li, Weihua; Qiu, Feng ACS Macro Letters, Vol. 3, Issue 9 https://doi.org/10.1021/mz500445v	journal	August 2014
Safe and Convenient Procedure for Solvent Purification Pangborn, Amy B.; Giardello, Michael A.; Grubbs, Robert H. Organometallics, Vol. 15, Issue 5, p. 1518-1520 https://doi.org/10.1021/om9503712	journal	January 1996
Asymmetric superstructure formed in a block copolymer via phase separation Peinemann, Klaus-Viktor; Abetz, Volker; Simon, Peter F. W. Nature Materials, Vol. 6, Issue 12 https://doi.org/10.1038/nmat2038	journal	November 2007
Self-assembly of functional nanostructures from ABC triblock copolymers Ludwigs, Sabine; Böker, Alexander; Voronov, Andrej Nature Materials, Vol. 2, Issue 11 https://doi.org/10.1038/nmat997	journal	October 2003
A double helical structure formed from an amorphous, achiral ABC triblock terpolymer Jinnai, Hiroshi; Kaneko, Takeshi; Matsunaga, Kazuyuki Soft Matter, Vol. 5, Issue 10 https://doi.org/10.1039/b901008d	journal	January 2009
Integration of self-assembled diblock copolymers for semiconductor capacitor fabrication Black, C. T.; Guarini, K. W.; Milkove, K. R. Applied Physics Letters, Vol. 79, Issue 3, p. 409-411 https://doi.org/10.1063/1.1383805	journal	July 2001
Spontaneous alignment of self-assembled ABC triblock terpolymers for large-area nanolithography Kubo, T.; Wang, R. F.; Olson, D. A. Applied Physics Letters, Vol. 93, Issue 13 https://doi.org/10.1063/1.2975370	journal	September 2008
Can a single function for χ account for block copolymer and homopolymer blend phase behavior? Maurer, Wayne W.; Bates, Frank S.; Lodge, Timothy P. The Journal of Chemical Physics, Vol. 108, Issue 7 https://doi.org/10.1063/1.475704	journal	February 1998
Block Copolymers—Designer Soft Materials Bates, Frank S.; Fredrickson, Glenn H. Physics Today, Vol. 52, Issue 2 https://doi.org/10.1063/1.882522	journal	February 1999
The standard Gaussian model for block copolymer melts Matsen, M. W. Journal of Physics: Condensed Matter, Vol. 14, Issue 2 https://doi.org/10.1088/0953-8984/14/2/201	journal	December 2001
Morphology and phase diagram of complex block copolymers: ABC linear triblock copolymers Tang, Ping; Qiu, Feng; Zhang, Hongdong Physical Review E, Vol. 69, Issue 3 https://doi.org/10.1103/PhysRevE.69.031803	journal	March 2004
Discovering Ordered Phases of Block Copolymers: New Results from a Generic Fourier-Space Approach Guo, Zuojun; Zhang, Guojie; Qiu, Feng Physical Review Letters, Vol. 101, Issue 2 https://doi.org/10.1103/PhysRevLett.101.028301	journal	July 2008
Stable and unstable phases of a diblock copolymer melt Matsen, M. W.; Schick, M. Physical Review Letters, Vol. 72, Issue 16 https://doi.org/10.1103/PhysRevLett.72.2660	journal	April 1994
Combinatorial Screening of Complex Block Copolymer Assembly with Self-Consistent Field Theory Drolet, François; Fredrickson, Glenn H. Physical Review Letters, Vol. 83, Issue 21 https://doi.org/10.1103/PhysRevLett.83.4317	journal	November 1999
Orthorhombic F d d d Network in Triblock and Diblock Copolymer Melts Tyler, Christopher A.; Morse, David C. Physical Review Letters, Vol. 94, Issue 20 https://doi.org/10.1103/PhysRevLett.94.208302	journal	May 2005
Block copolymers as photonic bandgap materials Fink, Y.; Urbas, A. M.; Bawendi, M. G. Journal of Lightwave Technology, Vol. 17, Issue 11, p. 1963-1969 https://doi.org/10.1109/50.802981	journal	November 1999
Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly Ruiz, R.; Kang, H.; Detcheverry, F. A. Science, Vol. 321, Issue 5891 https://doi.org/10.1126/science.1157626	journal	August 2008
Multiblock Polymers: Panacea or Pandora's Box? Bates, F. S.; Hillmyer, M. A.; Lodge, T. P. Science, Vol. 336, Issue 6080 https://doi.org/10.1126/science.1215368	journal	April 2012
Block Copolymer Lithography: Periodic Arrays of 10¹¹ Holes in 1 Square Centimeter Park, Miri; Harrison, Christopher; Chaikin, Paul M. Science, Vol. 276, Issue 5317, p. 1401-1404 https://doi.org/10.1126/science.276.5317.1401	journal	May 1997
Numerical Solution of Polymer Self-Consistent Field Theory Ceniceros, Hector D.; Fredrickson, Glenn H. Multiscale Modeling & Simulation, Vol. 2, Issue 3 https://doi.org/10.1137/030601338	journal	January 2004
Block Copolymer Thin Films: Physics and Applications Fasolka, Michael J.; Mayes, Anne M. Annual Review of Materials Research, Vol. 31, Issue 1, p. 323-355 https://doi.org/10.1146/annurev.matsci.31.1.323	journal	August 2001
Polymer self assembly in semiconductor microelectronics Black, C. T.; Ruiz, R.; Breyta, G. IBM Journal of Research and Development, Vol. 51, Issue 5 https://doi.org/10.1147/rd.515.0605	journal	September 2007

Cited By (1)

Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers Hofman, Anton H.; Terzic, Ivan; Stuart, Marc C. A. ACS Macro Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acsmacrolett.8b00570	journal	September 2018