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Title: Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers

Abstract

Here, incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE–PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ~ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, R g. Over the temperature range 30–90 °C, the values of χ were determined to be very large (~2–2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE–PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ~ 2 nm -1) for relatively small polymer chains. Finally, our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [2];  [3];  [5];  [6]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  4. Adam Mickiewicz Univ. in Poznań (Poland). Faculty of Physics. NanoBioMedical Centre
  5. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemical and Biomolecular Engineering
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Environmental Energy Technologies Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
State Univ. of New York (SUNY), Syracuse, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1597269
Alternate Identifier(s):
OSTI ID: 1474994
Grant/Contract Number:  
SC0012673; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Soft Matter
Additional Journal Information:
Journal Volume: 13; Journal Issue: 22; Journal ID: ISSN 1744-683X
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Wide angle X-ray scattering; Thermodynamics; Perfluoropolyether

Citation Formats

Chintapalli, Mahati, Timachova, Ksenia, Olson, Kevin R., Banaszak, Michał, Thelen, Jacob L., Mecham, Sue J., DeSimone, Joseph M., and Balsara, Nitash P. Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers. United States: N. p., 2017. Web. doi:10.1039/C7SM00738H.
Chintapalli, Mahati, Timachova, Ksenia, Olson, Kevin R., Banaszak, Michał, Thelen, Jacob L., Mecham, Sue J., DeSimone, Joseph M., & Balsara, Nitash P. Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers. United States. doi:10.1039/C7SM00738H.
Chintapalli, Mahati, Timachova, Ksenia, Olson, Kevin R., Banaszak, Michał, Thelen, Jacob L., Mecham, Sue J., DeSimone, Joseph M., and Balsara, Nitash P. Thu . "Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers". United States. doi:10.1039/C7SM00738H. https://www.osti.gov/servlets/purl/1597269.
@article{osti_1597269,
title = {Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers},
author = {Chintapalli, Mahati and Timachova, Ksenia and Olson, Kevin R. and Banaszak, Michał and Thelen, Jacob L. and Mecham, Sue J. and DeSimone, Joseph M. and Balsara, Nitash P.},
abstractNote = {Here, incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE–PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ~ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, Rg. Over the temperature range 30–90 °C, the values of χ were determined to be very large (~2–2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE–PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ~ 2 nm-1) for relatively small polymer chains. Finally, our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.},
doi = {10.1039/C7SM00738H},
journal = {Soft Matter},
issn = {1744-683X},
number = 22,
volume = 13,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Nika : software for two-dimensional data reduction
journal, March 2012


Water-in-Carbon Dioxide Microemulsions: An Environment for Hydrophiles Including Proteins
journal, February 1996


Some physicochemical properties of perfluoropolyether surfactants
journal, March 1984


Effects of compositional asymmetry in phase behavior of ABA triblock copolymer melts from Monte Carlo simulation
journal, December 2010


Synthesis and self-assembly of highly incompatible polybutadiene-poly(hexafluoropropylene oxide) diblock copolymers
journal, December 2005

  • Zhu, Shixiong; Edmonds, William F.; Hillmyer, Marc A.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 24
  • DOI: 10.1002/polb.20621

Phase Behavior of Deuterated Polystyrene- b lock -poly( n -pentyl methacrylate) Copolymers
journal, April 2003

  • Ryu, Du Yeol; Jeong, Unyong; Lee, Dong Hyun
  • Macromolecules, Vol. 36, Issue 8
  • DOI: 10.1021/ma026002g

Effect of Selective Perfluoroalkylation on the Segregation Strength of Polystyrene−1,2-Polybutadiene Block Copolymers
journal, May 2002

  • Ren, Yu; Lodge, Timothy P.; Hillmyer, Marc A.
  • Macromolecules, Vol. 35, Issue 10
  • DOI: 10.1021/ma011958x

Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987

  • Fredrickson, Glenn H.; Helfand, Eugene
  • The Journal of Chemical Physics, Vol. 87, Issue 1
  • DOI: 10.1063/1.453566

Photochemically Cross-Linked Perfluoropolyether-Based Elastomers: Synthesis, Physical Characterization, and Biofouling Evaluation
journal, September 2009

  • Hu, Zhaokang; Finlay, John A.; Chen, Liang
  • Macromolecules, Vol. 42, Issue 18, p. 6999-7007
  • DOI: 10.1021/ma901227k

Block copolymers near the microphase separation transition. 3. Small-angle neutron scattering study of the homogeneous melt state
journal, December 1985


Protein antifouling and fouling-release in perfluoropolyether surfaces
journal, August 2014


Nonflammable perfluoropolyether-based electrolytes for lithium batteries
journal, February 2014

  • Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 9
  • DOI: 10.1073/pnas.1314615111

Small-angle x-ray diffraction study of thermal transition in styrene-butadiene block copolymers
journal, July 1981

  • Roe, Ryong-Joon; Fishkis, M.; Chang, J. C.
  • Macromolecules, Vol. 14, Issue 4
  • DOI: 10.1021/ma50005a040

Synthesis and Self-Assembly of Discrete Dimethylsiloxane–Lactic Acid Diblock Co-oligomers: The Dononacontamer and Its Shorter Homologues
journal, March 2016

  • van Genabeek, Bas; de Waal, Bas F. M.; Gosens, Mark M. J.
  • Journal of the American Chemical Society, Vol. 138, Issue 12
  • DOI: 10.1021/jacs.6b00629

Theory of Microphase Separation in Block Copolymers
journal, November 1980


Investigation of non-ideal two-phase polymer structures by small-angle X-ray scattering
journal, April 1973


Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications
journal, September 2016


Theoretical study of interactions of a Li + (CF 3 SO 2 ) 2 N ion pair with CR 3 (OCR 2 CR 2 ) n OCR 3 (R = H or F)
journal, January 2016

  • Abroshan, Hadi; Dhumal, Nilesh R.; Shim, Youngseon
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 9
  • DOI: 10.1039/C6CP00139D

Glassy Carbon as an Absolute Intensity Calibration Standard for Small-Angle Scattering
journal, August 2009

  • Zhang, Fan; Ilavsky, Jan; Long, Gabrielle G.
  • Metallurgical and Materials Transactions A, Vol. 41, Issue 5
  • DOI: 10.1007/s11661-009-9950-x

Morphological behavior of model poly(ethylene-alt-propylene)-b-polylactide diblock copolymers
journal, September 2002

  • Schmidt, Scott C.; Hillmyer, Marc A.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 20
  • DOI: 10.1002/polb.10291

Perfluoropolyether—a Vacuum Pump Fluid resistant to Electron Induced Polymerization
journal, July 1972

  • Holland, L.; Laurenson, L.; Baker, P. N.
  • Nature, Vol. 238, Issue 5358
  • DOI: 10.1038/238036b0

Contact Angle Analysis, Surface Dynamics, and Biofouling Characteristics of Cross-Linkable, Random Perfluoropolyether-Based Graft Terpolymers
journal, April 2006

  • Yarbrough, Jason C.; Rolland, Jason P.; DeSimone, Joseph M.
  • Macromolecules, Vol. 39, Issue 7
  • DOI: 10.1021/ma0524777

Search for a model polymer blend
journal, November 1998

  • Balsara, N. P.; Lefebvre, A. A.; Lee, J. H.
  • AIChE Journal, Vol. 44, Issue 11
  • DOI: 10.1002/aic.690441118

Design of ABC Triblock Copolymers near the ODT with the Random Phase Approximation
journal, February 2003

  • Cochran, Eric W.; Morse, David C.; Bates, Frank S.
  • Macromolecules, Vol. 36, Issue 3
  • DOI: 10.1021/ma020651a

Nanoscale Phase Separation in Sequence-Defined Peptoid Diblock Copolymers
journal, September 2013

  • Sun, Jing; Teran, Alexander A.; Liao, Xunxun
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja404233d

End Group Effects on the Phase Behavior of Polymer Blends:  Poly(dimethylsiloxane) and Poly(methylphenylsiloxane) Blend
journal, January 1996

  • Qian, Caibao; Grigoras, Stelian; Kennan, Linda D.
  • Macromolecules, Vol. 29, Issue 4
  • DOI: 10.1021/ma951018a

Fluctuations, Order, and Disorder in Short Diblock Copolymers
journal, February 2013

  • Lee, Sangwoo; Gillard, Timothy M.; Bates, Frank S.
  • AIChE Journal, Vol. 59, Issue 9
  • DOI: 10.1002/aic.14023

Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990


Effect of Molecular Structure on the Thermodynamics of Block Copolymer Melts
journal, December 1994

  • Lin, C. C.; Jonnalagadda, S. V.; Kesani, P. K.
  • Macromolecules, Vol. 27, Issue 26
  • DOI: 10.1021/ma00104a035

Can a single function for χ account for block copolymer and homopolymer blend phase behavior?
journal, February 1998

  • Maurer, Wayne W.; Bates, Frank S.; Lodge, Timothy P.
  • The Journal of Chemical Physics, Vol. 108, Issue 7
  • DOI: 10.1063/1.475704

Lattice theory of polymer solutions with endgroup effects
journal, July 1997

  • Ryu, Jong-Hoon; Gujrati, P. D.
  • The Journal of Chemical Physics, Vol. 107, Issue 4
  • DOI: 10.1063/1.474137

Phase Behavior and Electrochemical Characterization of Blends of Perfluoropolyether, Poly(ethylene glycol), and a Lithium Salt
journal, January 2015

  • Wong, Dominica H. C.; Vitale, Alessandra; Devaux, Didier
  • Chemistry of Materials, Vol. 27, Issue 2
  • DOI: 10.1021/cm504228a

Solution Properties of a Group of Perfluoropolyethers: Comparison of Unperturbed Dimensions
journal, October 1994


Synthesis and self-assembly of fluorinated block copolymers
journal, November 2001

  • Hillmyer, Marc A.; Lodge, Timothy P.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 40, Issue 1
  • DOI: 10.1002/pola.10074

Thermodynamics of Block Copolymers with and without Salt
journal, December 2013

  • Teran, Alexander A.; Balsara, Nitash P.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 1
  • DOI: 10.1021/jp408079z