skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on April 19, 2020

Title: NMR spin diffusion measurements in disordered polymers: Insights and limitations

Abstract

Nuclear magnetic resonance (NMR) spin diffusion measurements have been widely used to estimate domain sizes in a variety of polymer materials. In cases where the domains are well-described as regular, repeating structures (e.g., lamellar, cylindrical channels, monodispersed spherical domains), the domain sizes estimated from NMR spin diffusion experiments agree with the characteristic length scales obtained from small-angle x-ray scattering and microscopy. In our laboratory, recent NMR spin diffusion experiments for hydrated sulfonated Diels Alder poly(phenylene) (SDAPP) polymer membranes have revealed that assuming a simple structural model can often misrepresent or overestimate the domain size in situations where more complex and disordered morphologies exist. Molecular dynamics simulations of the SDAPP membranes predict a complex heterogeneous hydrophilic domain structure that varies with the degree of sulfonation and hydration and is not readily represented by a simple repeating domain structure. This heterogeneous morphology results in NMR-measured domain sizes that disagree with length scales estimated from the ionomer peak in scattering experiments. Here we present numerical NMR spin diffusion simulations that show how structural disorder in the form of domain size distributions or domain clustering can significantly impact the spin diffusion analysis and estimated domain sizes. As a result, simulations of NMR spin diffusionmore » with differing domain size distributions and domain clustering are used to identify the impact of the heterogeneous domain structure and highlight the limitations of using NMR spin diffusion techniques for irregular structures.« less

Authors:
 [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1515218
Alternate Identifier(s):
OSTI ID: 1507807
Report Number(s):
SAND-2019-3668J
Journal ID: ISSN 2475-9953; PRMHAR; 674282
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sorte, Eric Glenn, Frischknecht, Amalie L., and Alam, Todd M. NMR spin diffusion measurements in disordered polymers: Insights and limitations. United States: N. p., 2019. Web. doi:10.1103/PhysRevMaterials.3.045602.
Sorte, Eric Glenn, Frischknecht, Amalie L., & Alam, Todd M. NMR spin diffusion measurements in disordered polymers: Insights and limitations. United States. doi:10.1103/PhysRevMaterials.3.045602.
Sorte, Eric Glenn, Frischknecht, Amalie L., and Alam, Todd M. Fri . "NMR spin diffusion measurements in disordered polymers: Insights and limitations". United States. doi:10.1103/PhysRevMaterials.3.045602.
@article{osti_1515218,
title = {NMR spin diffusion measurements in disordered polymers: Insights and limitations},
author = {Sorte, Eric Glenn and Frischknecht, Amalie L. and Alam, Todd M.},
abstractNote = {Nuclear magnetic resonance (NMR) spin diffusion measurements have been widely used to estimate domain sizes in a variety of polymer materials. In cases where the domains are well-described as regular, repeating structures (e.g., lamellar, cylindrical channels, monodispersed spherical domains), the domain sizes estimated from NMR spin diffusion experiments agree with the characteristic length scales obtained from small-angle x-ray scattering and microscopy. In our laboratory, recent NMR spin diffusion experiments for hydrated sulfonated Diels Alder poly(phenylene) (SDAPP) polymer membranes have revealed that assuming a simple structural model can often misrepresent or overestimate the domain size in situations where more complex and disordered morphologies exist. Molecular dynamics simulations of the SDAPP membranes predict a complex heterogeneous hydrophilic domain structure that varies with the degree of sulfonation and hydration and is not readily represented by a simple repeating domain structure. This heterogeneous morphology results in NMR-measured domain sizes that disagree with length scales estimated from the ionomer peak in scattering experiments. Here we present numerical NMR spin diffusion simulations that show how structural disorder in the form of domain size distributions or domain clustering can significantly impact the spin diffusion analysis and estimated domain sizes. As a result, simulations of NMR spin diffusion with differing domain size distributions and domain clustering are used to identify the impact of the heterogeneous domain structure and highlight the limitations of using NMR spin diffusion techniques for irregular structures.},
doi = {10.1103/PhysRevMaterials.3.045602},
journal = {Physical Review Materials},
number = 4,
volume = 3,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on April 19, 2020
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Spin diffusion in block copolymers as studied by pulsed NMR
journal, January 1986


New Insights into Perfluorinated Sulfonic-Acid Ionomers
journal, January 2017


Transport in Proton Conductors for Fuel-Cell Applications:  Simulations, Elementary Reactions, and Phenomenology
journal, October 2004

  • Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020715f

Hybrid materials for polymer electrolyte membrane fuel cells: Water uptake, mechanical and transport properties
journal, November 2007


Sulfophenylated Terphenylene Copolymer Membranes and Ionomers
journal, November 2018

  • Skalski, Thomas J. G.; Adamski, Michael; Britton, Benjamin
  • ChemSusChem, Vol. 11, Issue 23
  • DOI: 10.1002/cssc.201801965

A Generalization of the Half-Normal Distribution with Applications to Lifetime Data
journal, March 2008

  • Cooray, Kahadawala; Ananda, Malwane M. A.
  • Communications in Statistics - Theory and Methods, Vol. 37, Issue 9
  • DOI: 10.1080/03610920701826088

Measuring Domain Sizes and Compositional Heterogeneities in P3HT-PCBM Bulk Heterojunction Thin Films with 1H Spin Diffusion NMR Spectroscopy
journal, January 2012

  • Nieuwendaal, Ryan C.; Ro, Hyun Wook; Germack, David S.
  • Advanced Functional Materials, Vol. 22, Issue 6
  • DOI: 10.1002/adfm.201102138

Nanoscale Structure and Morphology of Sulfonated Polyphenylenes via Atomistic Simulations
journal, January 2017


Direct Observation of Interphase Composition in Block Copolymers
journal, December 2008

  • Saalwächter, Kay; Thomann, Yi; Hasenhindl, Alfred
  • Macromolecules, Vol. 41, Issue 23
  • DOI: 10.1021/ma802094h

Some perspectives on the interpretation of proton NMR spin diffusion data in terms of polymer morphologies
journal, August 1996


Multiple‐quantum NMR in solids
journal, March 1983

  • Yen, Yu‐Sze; Pines, A.
  • The Journal of Chemical Physics, Vol. 78, Issue 6
  • DOI: 10.1063/1.445185

Tuned Polymer Electrolyte Membranes Based on Aromatic Polyethers for Fuel Cell Applications
journal, April 2007

  • Miyatake, Kenji; Chikashige, Yohei; Higuchi, Eiji
  • Journal of the American Chemical Society, Vol. 129, Issue 13
  • DOI: 10.1021/ja0672526

Complex Morphology of Melt-Spun Nylon-6 Fibres Investigated by1H Double-Quantum-Filtered NMR Spin-Diffusion Experiments
journal, June 2004


NMR study of interphase structure in layered polymer morphologies with mobility contrast: disorder and confinement effects vs. dynamic heterogeneities
journal, July 2014

  • Roos, Matthias; Schäler, Kerstin; Seidlitz, Anne
  • Colloid and Polymer Science, Vol. 292, Issue 8
  • DOI: 10.1007/s00396-014-3218-8

Proton spin diffusion for spatial heterogeneity and morphology investigations of polymers
journal, January 1995

  • Demco, Dan E.; Johansson, Anna; Tegenfeldt, Jörgen
  • Solid State Nuclear Magnetic Resonance, Vol. 4, Issue 1
  • DOI: 10.1016/0926-2040(94)00036-C

Spin-diffusion NMR at low field for the study of multiphase solids
journal, July 2008


Phase Structure of Polymers by Dipolar-Induced Spin Diffusion: Model Spin Diffusion Calculations
journal, November 1997


Large-Sample Inference for the General Half-Normal Distribution
journal, July 2002

  • Pewsey, Arthur
  • Communications in Statistics - Theory and Methods, Vol. 31, Issue 7
  • DOI: 10.1081/STA-120004901

Impact of Hydration and Sulfonation on the Morphology and Ionic Conductivity of Sulfonated Poly(phenylene) Proton Exchange Membranes
journal, January 2019


Residual dipolar couplings by 1H dipolar-encoded longitudinal magnetization, double- and triple-quantum nuclear magnetic resonance in cross-linked elastomers
journal, July 1999

  • Schneider, M.; Gasper, L.; Demco, D. E.
  • The Journal of Chemical Physics, Vol. 111, Issue 1
  • DOI: 10.1063/1.479291

Sulfonated poly(arylene ether sulfone) copolymer proton exchange membranes: composition and morphology effects on the methanol permeability
journal, November 2004


Direct Comparisons of X-ray Scattering and Atomistic Molecular Dynamics Simulations for Precise Acid Copolymers and Ionomers
journal, January 2015

  • Buitrago, C. Francisco; Bolintineanu, Dan S.; Seitz, Michelle E.
  • Macromolecules, Vol. 48, Issue 4
  • DOI: 10.1021/ma5022117

The hydration of paper studied with solid-state magnetisation-exchange 1H NMR spectroscopy
journal, July 2006

  • Garvey, Christopher J.; Parker, Ian H.; Simon, George P.
  • Holzforschung, Vol. 60, Issue 4
  • DOI: 10.1515/HF.2006.064

Synthesis and characterization of sulfonated poly(phthalazinone ether phosphine oxide)s by direct polycondensation for proton exchange membranes
journal, January 2008

  • Ma, Xuhui; Zhang, Chunjie; Xiao, Guyu
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 46, Issue 5
  • DOI: 10.1002/pola.22519

Domain sizes in heterogeneous polymers by spin diffusion using single-quantum and double-quantum dipolar filters
journal, August 2003


Membrane Protein Topology Probed by 1 H Spin Diffusion from Lipids Using Solid-State NMR Spectroscopy
journal, February 2002

  • Huster, Daniel; Yao, Xiaolan; Hong, Mei
  • Journal of the American Chemical Society, Vol. 124, Issue 5
  • DOI: 10.1021/ja017001r

Dipolar recoupling in fast-MAS solid-state NMR spectroscopy
journal, September 2004


Basic principles of static proton low-resolution spin diffusion NMR in nanophase-separated materials with mobility contrast
journal, November 2015


Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability
journal, March 2017


Hydrophilic domain structure in polymer exchange membranes: Simulations of NMR spin diffusion experiments to address ability for model discrimination
journal, September 2017

  • Sorte, Eric G.; Abbott, Lauren J.; Frischknecht, Amalie L.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 1
  • DOI: 10.1002/polb.24439

Effects of Disorder in Polymer Morphology on Spin Diffusion
journal, November 1999

  • Cheung, T. T. P.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 44
  • DOI: 10.1021/jp9906684

Effect of the Hydrophobic Component on the Properties of Sulfonated Poly(arylene ether sulfone)s
journal, March 2009

  • Bae, Byungchan; Miyatake, Kenji; Watanabe, Masahiro
  • Macromolecules, Vol. 42, Issue 6
  • DOI: 10.1021/ma8026518

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

Morphology of poly(ethylene terephthalate) fibers as studied by multiple-pulse proton NMR
journal, September 1985

  • Havens, John R.; VanderHart, David L.
  • Macromolecules, Vol. 18, Issue 9
  • DOI: 10.1021/ma00151a005

High resolution 1 H solid state NMR studies of polyethyleneterephthalate
journal, December 1980

  • Cheung, T. T. P.; Gerstein, B. C.; Ryan, L. M.
  • The Journal of Chemical Physics, Vol. 73, Issue 12
  • DOI: 10.1063/1.440141

Spin diffusion and spin-lattice relaxation in multiphase polymers
journal, July 1997

  • Wang, Jiahu; Jack, Kevin S.; Natansohn, Almeria L.
  • The Journal of Chemical Physics, Vol. 107, Issue 3
  • DOI: 10.1063/1.474430

Oriented Morphology and Anisotropic Transport in Uniaxially Stretched Perfluorosulfonate Ionomer Membranes
journal, July 2011

  • Park, Jong Keun; Li, Jing; Divoux, Gilles M.
  • Macromolecules, Vol. 44, Issue 14
  • DOI: 10.1021/ma200865p

General Analytical Description of Spin-Diffusion for a Three-Domain Morphology. Application to Melt-Spun Nylon 6 Fibers
journal, June 2003

  • Buda, A.; Demco, D. E.; Bertmer, M.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 22
  • DOI: 10.1021/jp021684v

Determination of Domain Sizes in Compatibilized Polystyrene−(Ethylene-Propylene Rubber) Blends by Measurements of 1 H Spin Diffusion
journal, May 1998

  • Jack, Kevin S.; Natansohn, Almeria; Wang, Jiahu
  • Chemistry of Materials, Vol. 10, Issue 5
  • DOI: 10.1021/cm970670c

Multispin moments edited by multiple-quantum NMR: application to elastomers
journal, January 2005