Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Effect of hydration on morphology of thin phosphonate block copolymer electrolyte membranes studied by electron tomography

Abstract

The morphological changes of phosphonate polypeptoid electrolyte membranes, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNehm-b-pNpmn), in hydrated and dry states were characterized by cryogenic transmission electron microscopy (cryo-TEM) and cryogenic electron tomography (cryo-ET). The analysis of 3D tomograms revealed that the pNeh9-b-pNpm9 thin films absorbed a large amount of water, resulting in the formation of membranes that were nearly flat and giant multicompartment vesicles dispersed in the water phase. A simple lamellar phase appeared when the films were dried. In contrast, pNeh18-b-pNpm18 thin films absorbed little water and formed small highly curved unilamellar and multilamellar vesicles. Water was located mainly outside the closely-packed vesicles. When water was removed by drying, the walls of adjacent vesicles collapsed to form honeycomb-like capsules. Here, the changes in domain size reflected changes in chain conformations. The pNpm9 blocks were saturated by water and fully extended, while pNpm18 blocks were neither saturated by water nor fully extended. In addition, the thicknesses of hydrophobic blocks in the hydrated films of both pNeh9-b-pNpm9 and pNeh18-b-pNpm18 were smaller than those in the dry films, reflecting an increase of the average distance between the neighboring junctions of polypeptoid molecules.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Qingdao Univ. of Science and Technology (China)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1826550
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Polymer Engineering and Science
Additional Journal Information:
Journal Volume: 61; Journal Issue: 4; Journal ID: ISSN 0032-3888
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; cryogenic; electron tomography; low-dose; polymer electrolyte membrane; polypeptoid; transmission electron microscopy

Citation Formats

Jiang, Xi, Sun, Jing, Zuckermann, Ronald N., and Balsara, Nitash P. Effect of hydration on morphology of thin phosphonate block copolymer electrolyte membranes studied by electron tomography. United States: N. p., 2021. Web. doi:10.1002/pen.25646.
Copy to clipboard
Jiang, Xi, Sun, Jing, Zuckermann, Ronald N., & Balsara, Nitash P. Effect of hydration on morphology of thin phosphonate block copolymer electrolyte membranes studied by electron tomography. United States. https://doi.org/10.1002/pen.25646
Copy to clipboard
Jiang, Xi, Sun, Jing, Zuckermann, Ronald N., and Balsara, Nitash P. Wed . "Effect of hydration on morphology of thin phosphonate block copolymer electrolyte membranes studied by electron tomography". United States. https://doi.org/10.1002/pen.25646. https://www.osti.gov/servlets/purl/1826550.
Copy to clipboard
@article{osti_1826550,
title = {Effect of hydration on morphology of thin phosphonate block copolymer electrolyte membranes studied by electron tomography},
author = {Jiang, Xi and Sun, Jing and Zuckermann, Ronald N. and Balsara, Nitash P.},
abstractNote = {The morphological changes of phosphonate polypeptoid electrolyte membranes, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNehm-b-pNpmn), in hydrated and dry states were characterized by cryogenic transmission electron microscopy (cryo-TEM) and cryogenic electron tomography (cryo-ET). The analysis of 3D tomograms revealed that the pNeh9-b-pNpm9 thin films absorbed a large amount of water, resulting in the formation of membranes that were nearly flat and giant multicompartment vesicles dispersed in the water phase. A simple lamellar phase appeared when the films were dried. In contrast, pNeh18-b-pNpm18 thin films absorbed little water and formed small highly curved unilamellar and multilamellar vesicles. Water was located mainly outside the closely-packed vesicles. When water was removed by drying, the walls of adjacent vesicles collapsed to form honeycomb-like capsules. Here, the changes in domain size reflected changes in chain conformations. The pNpm9 blocks were saturated by water and fully extended, while pNpm18 blocks were neither saturated by water nor fully extended. In addition, the thicknesses of hydrophobic blocks in the hydrated films of both pNeh9-b-pNpm9 and pNeh18-b-pNpm18 were smaller than those in the dry films, reflecting an increase of the average distance between the neighboring junctions of polypeptoid molecules.},
doi = {10.1002/pen.25646},
journal = {Polymer Engineering and Science},
number = 4,
volume = 61,
place = {United States},
year = {Wed Jan 27 00:00:00 EST 2021},
month = {Wed Jan 27 00:00:00 EST 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/pen.25646
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Formation of Block Copolymer-Protected Nanoparticles via Reactive Impingement Mixing
journal, September 2007

  • Zhu, Zhengxi; Anacker, Jessica L.; Ji, Shengxiang
  • Langmuir, Vol. 23, Issue 21
  • DOI: 10.1021/la701420z

Synthesis and characterization of chemically stable sulfonated copoly(triazole imide)s with high proton conductivity
journal, September 2019

  • Singh, Asheesh; Kumar, Anaparthi G.; Saha, Sayantani
  • Polymer Engineering & Science, Vol. 59, Issue 11
  • DOI: 10.1002/pen.25231

Preparation of giant vesicles by external AC electric fields. Kinetics and applications
book, January 2007

  • Angelova, M. I.; Soleau, S.; Meleard, Ph.
  • Progress in Colloid & Polymer Science
  • DOI: 10.1007/BFb0116295

Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers
journal, April 2016

Direct Imaging of Nanoscale Acidic Clusters in a Polymer Electrolyte Membrane
journal, December 2011

  • Yakovlev, Sergey; Wang, Xin; Ercius, Peter
  • Journal of the American Chemical Society, Vol. 133, Issue 51
  • DOI: 10.1021/ja209240d

Spatial and temporal resolution in cryo-electron microscopy—A scope for nano-chemistry
journal, December 2005

Charged Polypeptide Vesicles with Controllable Diameter
journal, September 2005

  • Holowka, Eric P.; Pochan, Darrin J.; Deming, Timothy J.
  • Journal of the American Chemical Society, Vol. 127, Issue 35
  • DOI: 10.1021/ja053557t

Quantitative Analysis of Electron Beam Damage in Organic Thin Films
journal, May 2017

  • Leijten, Zino J. W. A.; Keizer, Arthur D. A.; de With, Gijsbertus
  • The Journal of Physical Chemistry C, Vol. 121, Issue 19
  • DOI: 10.1021/acs.jpcc.7b01749

Universal Relationship between Molecular Structure and Crystal Structure in Peptoid Polymers and Prevalence of the cis Backbone Conformation
journal, January 2018

  • Greer, Douglas R.; Stolberg, Michael A.; Kundu, Joyjit
  • Journal of the American Chemical Society, Vol. 140, Issue 2
  • DOI: 10.1021/jacs.7b11891

Probing nanoscale membrane degradation in fuel cells through electron tomography
journal, October 2017

Quantitative Morphology Study of Cu-Neutralized Poly(styrene- ran -methacrylic acid) Ionomers:  STEM Imaging, X-ray Scattering, and Real-Space Structural Modeling
journal, February 2007

  • Benetatos, Nicholas M.; Chan, Christopher D.; Winey, Karen I.
  • Macromolecules, Vol. 40, Issue 4
  • DOI: 10.1021/ma0621371

X-ray computed tomography reconstruction and analysis of polymer electrolyte membrane fuel cell porous transport layers
journal, December 2012

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013

  • Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid
  • Nature Materials, Vol. 12, Issue 5
  • DOI: 10.1038/nmat3602

Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers
journal, November 2018

Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes
journal, January 2013

  • Yuan, Rodger; Teran, Alexander A.; Gurevitch, Inna
  • Macromolecules, Vol. 46, Issue 3
  • DOI: 10.1021/ma3024552

Polymersomes for drug delivery: Design, formation and characterization
journal, July 2012

Block Copolymers for Fuel Cells
journal, January 2011

  • Elabd, Yossef A.; Hickner, Michael A.
  • Macromolecules, Vol. 44, Issue 1
  • DOI: 10.1021/ma101247c

High-Resolution Imaging of Polymer Electrolyte Membrane Fuel Cell Cathode Layers by Soft X-ray Spectro-Ptychography
journal, May 2018

  • Wu, Juan; Zhu, Xiaohui; West, Marcia M.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 22
  • DOI: 10.1021/acs.jpcc.8b02933

Advances in cryogenic transmission electron microscopy for the characterization of dynamic self-assembling nanostructures
journal, December 2012

  • Newcomb, Christina J.; Moyer, Tyson J.; Lee, Sungsoo S.
  • Current Opinion in Colloid & Interface Science, Vol. 17, Issue 6
  • DOI: 10.1016/j.cocis.2012.09.004

The morphology in nafion perfluorinated membrane products, as determined by wide- and small-angle x-ray studies
journal, November 1981

  • Gierke, T. D.; Munn, G. E.; Wilson, F. C.
  • Journal of Polymer Science: Polymer Physics Edition, Vol. 19, Issue 11
  • DOI: 10.1002/pol.1981.180191103

Surface Structure of Nafion in Vapor and Liquid
journal, March 2010

  • Bass, Maria; Berman, Amir; Singh, Amarjeet
  • The Journal of Physical Chemistry B, Vol. 114, Issue 11
  • DOI: 10.1021/jp9113128

Assessing internal structure of polymer assemblies from 2D to 3D CryoTEM: Bicontinuous micelles
journal, December 2012

  • McKenzie, Beulah E.; Holder, Simon J.; Sommerdijk, Nico A. J. M.
  • Current Opinion in Colloid & Interface Science, Vol. 17, Issue 6
  • DOI: 10.1016/j.cocis.2012.09.002

Dynamic Behavior of Water within a Polymer Electrolyte Fuel Cell Membrane at Low Hydration Levels
journal, January 2005

  • Pivovar, Adam M.; Pivovar, Bryan S.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 2
  • DOI: 10.1021/jp046029x

Consequences of Nonergodicity in Aqueous Binary PEO−PB Micellar Dispersions
journal, February 2004

  • Jain, Sumeet; Bates, Frank S.
  • Macromolecules, Vol. 37, Issue 4
  • DOI: 10.1021/ma035467j

Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes
journal, October 2018

  • Chen, X. Chelsea; Jiang, Xi; Balsara, Nitash P.
  • The Journal of Chemical Physics, Vol. 149, Issue 16
  • DOI: 10.1063/1.5029452

MotionCor2: anisotropic correction of beam-induced motion for improved cryo-electron microscopy
journal, February 2017

  • Zheng, Shawn Q.; Palovcak, Eugene; Armache, Jean-Paul
  • Nature Methods, Vol. 14, Issue 4
  • DOI: 10.1038/nmeth.4193

Self-Assembly and Transport Limitations in Confined Nafion Films
journal, January 2013

  • Modestino, Miguel A.; Paul, Devproshad K.; Dishari, Shudipto
  • Macromolecules, Vol. 46, Issue 3, p. 867-873
  • DOI: 10.1021/ma301999a

Stretching Effect on Nafion Fibrillar Nanostructure
journal, December 2007

  • Rubatat, Laurent; Diat, Olivier
  • Macromolecules, Vol. 40, Issue 26
  • DOI: 10.1021/ma070362s

Mesoscale modeling of hydrated morphologies of sulfonated polysulfone ionomers
journal, January 2014

Ion Transport in Nanostructured Phosphonated Block Copolymers Containing Ionic Liquids
journal, April 2016

  • Jung, Ha Young; Kim, Onnuri; Park, Moon Jeong
  • Macromolecular Rapid Communications, Vol. 37, Issue 14
  • DOI: 10.1002/marc.201600036

Cryogenic Transmission Electron Microscopy Imaging of Vesicles Formed by a Polystyrene−Polyisoprene Diblock Copolymer
journal, August 2005

  • Kesselman, Ellina; Talmon, Yeshayahu; Bang, Joona
  • Macromolecules, Vol. 38, Issue 16
  • DOI: 10.1021/ma0510587

Observation of ionomer in catalyst ink of polymer electrolyte fuel cell using cryogenic transmission electron microscopy
journal, January 2017

Insights on the Study of Nafion Nanoscale Morphology by Transmission Electron Microscopy
journal, December 2013

Stimuli-Responsive Polymersomes as Nanocarriers for Drug and Gene Delivery: Stimuli-Responsive Polymersomes as Nanocarriers for …
journal, December 2008

  • Onaca, Ozana; Enea, Ramona; Hughes, David W.
  • Macromolecular Bioscience, Vol. 9, Issue 2
  • DOI: 10.1002/mabi.200800248

Review and critical analysis of the morphology of random ionomers across many length scales
journal, June 2008

  • Grady, Brian P.
  • Polymer Engineering & Science, Vol. 48, Issue 6
  • DOI: 10.1002/pen.21024

Deformation of Oriented Lamellar Block Copolymer Films
journal, August 2000

  • Cohen, Yachin; Albalak, Ramon J.; Dair, Benita J.
  • Macromolecules, Vol. 33, Issue 17
  • DOI: 10.1021/ma000513q

Flash Nanoprecipitation: Particle Structure and Stability
journal, October 2013

  • Pustulka, Kevin M.; Wohl, Adam R.; Lee, Han Seung
  • Molecular Pharmaceutics, Vol. 10, Issue 11
  • DOI: 10.1021/mp400337f

Morphology of Hydrated As-Cast Nafion Revealed through Cryo Electron Tomography
journal, December 2014

  • Allen, Frances I.; Comolli, Luis R.; Kusoglu, Ahmet
  • ACS Macro Letters, Vol. 4, Issue 1, p. 1-5
  • DOI: 10.1021/mz500606h

Critical evaluation of electron microscopy of ionomers
journal, May 1981

  • Handlin, Dale L.; MacKnight, William J.; Thomas, Edwin L.
  • Macromolecules, Vol. 14, Issue 3
  • DOI: 10.1021/ma50004a063

Radiation damage and electron microscopy of organic polymers
journal, October 1974

Phosphonated Polymers with Fine-Tuned Ion Clustering Behavior: Toward Efficient Proton Conductors
journal, January 2018

Resolving the Morphology of Peptoid Vesicles at the 1 nm Length Scale Using Cryogenic Electron Microscopy
journal, January 2019

  • Jiang, Xi; Spencer, Ryan K.; Sun, Jing
  • The Journal of Physical Chemistry B, Vol. 123, Issue 5
  • DOI: 10.1021/acs.jpcb.8b11752

Structural control of mixed ionic and electronic transport in conducting polymers
journal, April 2016

  • Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11287

CryoTEM as an Advanced Analytical Tool for Materials Chemists
journal, June 2017

Materials for fuel-cell technologies
journal, November 2001

  • Steele, Brian C. H.; Heinzel, Angelika
  • Nature, Vol. 414, Issue 6861, p. 345-352
  • DOI: 10.1038/35104620

Proton Conduction Mechanisms at Low Degrees of Hydration in Sulfonic Acid–Based Polymer Electrolyte Membranes
journal, August 2003

Cryogenic Transmission Electron Microscopy (Cryo-TEM) of Micelles and Vesicles Formed in Water by Poly(ethylene oxide)-Based Block Copolymers
journal, April 2002

  • Won, You-Yeon; Brannan, Aaron K.; Davis, H. Ted
  • The Journal of Physical Chemistry B, Vol. 106, Issue 13
  • DOI: 10.1021/jp013639d

Understanding Water Uptake and Transport in Nafion Using X-ray Microtomography
journal, March 2013

  • Hwang, Gi Suk; Parkinson, Dilworth Y.; Kusoglu, Ahmet
  • ACS Macro Letters, Vol. 2, Issue 4
  • DOI: 10.1021/mz300651a

Electron Tomography of Nafion Ionomer Coated on Pt/Carbon Black in High Utilization Electrode for PEFCs
journal, July 2006

  • Uchida, Hiroyuki; Song, Jung Min; Suzuki, Shinsuke
  • The Journal of Physical Chemistry B, Vol. 110, Issue 27
  • DOI: 10.1021/jp062678s

Morphology and properties of perfluorosulfonic acid polymer/perfluorocarboxylic acid polymer blend membranes
journal, March 2014

  • Wang, Jing; Wang, Xuejun; Dou, Peng
  • Polymer Engineering & Science, Vol. 55, Issue 1
  • DOI: 10.1002/pen.23879

Polymersomes: nature inspired nanometer sized compartments
journal, January 2009

  • LoPresti, Caterina; Lomas, Hannah; Massignani, Marzia
  • Journal of Materials Chemistry, Vol. 19, Issue 22
  • DOI: 10.1039/b818869f

Parallel cylindrical water nanochannels in Nafion fuel-cell membranes
journal, December 2007

  • Schmidt-Rohr, Klaus; Chen, Qiang
  • Nature Materials, Vol. 7, Issue 1
  • DOI: 10.1038/nmat2074

Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers
journal, December 2000

Radiation damage in the TEM and SEM
journal, August 2004

Control of radiation damage in the TEM
journal, April 2013

Ordered structure of block polymer/homopolymer mixtures, 4. Vesicle formation and macrophase separation
journal, September 1992

  • Koizumi, Satoshi; Hasegawa, Hirokazu; Hashimoto, Takeji
  • Makromolekulare Chemie. Macromolecular Symposia, Vol. 62, Issue 1
  • DOI: 10.1002/masy.19920620109

Direct observation of ionic aggregates in sulphonated polystyrene ionomers
journal, July 1989

Cryo Electron Tomography Reveals Confined Complex Morphologies of Tripeptide-Containing Amphiphilic Double-Comb Diblock Copolymers
journal, November 2008

  • Parry, Alison L.; Bomans, Paul H. H.; Holder, Simon J.
  • Angewandte Chemie International Edition, Vol. 47, Issue 46
  • DOI: 10.1002/anie.200802834

Effect of Morphology of Nanoscale Hydrated Channels on Proton Conductivity in Block Copolymer Electrolyte Membranes
journal, June 2014

  • Chen, X. Chelsea; Wong, David T.; Yakovlev, Sergey
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl501537p

Rodlike Colloidal Structure of Short Pendant Chain Perfluorinated Ionomer Solutions
journal, April 1998

Characterization of Polymer Surfaces with Atomic Force Microscopy
journal, August 1997

Radiation damage relative to transmission electron microscopy of biological specimens at low temperature: a review
journal, January 1978

Computer Visualization of Three-Dimensional Image Data Using IMOD
journal, January 1996

  • Kremer, James R.; Mastronarde, David N.; McIntosh, J. Richard
  • Journal of Structural Biology, Vol. 116, Issue 1
  • DOI: 10.1006/jsbi.1996.0013

Liposomal drug delivery systems: From concept to clinical applications
journal, January 2013

Formation and properties of cell-size lipid bilayer vesicles
journal, December 1983

Structure of Hydrated Na−Nafion Polymer Membranes
journal, December 2005

  • Blake, Nick P.; Petersen, Matt K.; Voth, Gregory A.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 51
  • DOI: 10.1021/jp054687r

Vesicle Membrane Thickness in Aqueous Dispersions of Block Copolymer Blends
journal, October 2008

  • Davis, Kevin P.; Lodge, Timothy P.; Bates, Frank S.
  • Macromolecules, Vol. 41, Issue 22
  • DOI: 10.1021/ma801902z

Cryo-electron microscopy of artificial biological membranes
journal, November 1985

  • Lepault, Jean; Pattus, Franc; Martin, Nadine
  • Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol. 820, Issue 2
  • DOI: 10.1016/0005-2736(85)90126-9
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: