NMR spin diffusion measurements in disordered polymers: Insights and limitations

Sorte, Eric Glenn; Frischknecht, Amalie L.; Alam, Todd M.

doi:10.1103/PhysRevMaterials.3.045602

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 »« less

Authors:

Sorte, Eric Glenn ^[1]; Frischknecht, Amalie L. ^[1]; Alam, Todd M. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Publication Date:: Fri Apr 19 00:00:00 EDT 2019

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.

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                    Sorte, Eric Glenn, Frischknecht, Amalie L., & Alam, Todd M. NMR spin diffusion measurements in disordered polymers: Insights and limitations.  United States.  https://doi.org/10.1103/PhysRevMaterials.3.045602

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                    Sorte, Eric Glenn, Frischknecht, Amalie L., and Alam, Todd M. Fri .  
"NMR spin diffusion measurements in disordered polymers: Insights and limitations".  United States.  https://doi.org/10.1103/PhysRevMaterials.3.045602.  https://www.osti.gov/servlets/purl/1515218.

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@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         = {Fri Apr 19 00:00:00 EDT 2019},

  month        = {Fri Apr 19 00:00:00 EDT 2019}

}

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Works referencing / citing this record:

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journal, September 2019

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

Abstract

Citation Formats

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

Structural influence of hydrophobic diamine in sulfonated poly(sulfide sulfone imide) copolymers on medium temperature PEM fuel cell journal, March 2014

Characterization of the Microdomain Structure in Polystyrene−Polyisoprene Block Copolymers by 1 H Spin Diffusion and Small-Angle X-ray Scattering Methods journal, May 1998

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

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

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

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

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

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

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

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

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

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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

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

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

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

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

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

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

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

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

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

Structural evolution of water swollen perfluorosulfonated ionomers from dry membrane to solution journal, July 2000

Physical and electrochemical behaviors of directly polymerized sulfonated poly(arylene ether ketone sulfone)s proton exchange membranes with different backbone structures journal, April 2009

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

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

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

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

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

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

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

Morphology and proton diffusion in a coarse-grained model of sulfonated poly(phenylenes) journal, September 2019

Spin diffusion in block copolymers as studied by pulsed NMR
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New Insights into Perfluorinated Sulfonic-Acid Ionomers
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Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology
journal, October 2004

Structural influence of hydrophobic diamine in sulfonated poly(sulfide sulfone imide) copolymers on medium temperature PEM fuel cell
journal, March 2014

Characterization of the Microdomain Structure in Polystyrene−Polyisoprene Block Copolymers by ¹ H Spin Diffusion and Small-Angle X-ray Scattering Methods
journal, May 1998

Hybrid materials for polymer electrolyte membrane fuel cells: Water uptake, mechanical and transport properties
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Sulfophenylated Terphenylene Copolymer Membranes and Ionomers
journal, November 2018

A Generalization of the Half-Normal Distribution with Applications to Lifetime Data
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journal, January 2012

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journal, January 2017

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

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

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

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

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

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

Investigation of Domain Size in Polymer Membranes Using Double-Quantum-Filtered Spin Diffusion Magic Angle Spinning NMR
journal, January 2005

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

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

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

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

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

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

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

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

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

Structural evolution of water swollen perfluorosulfonated ionomers from dry membrane to solution
journal, July 2000

Physical and electrochemical behaviors of directly polymerized sulfonated poly(arylene ether ketone sulfone)s proton exchange membranes with different backbone structures
journal, April 2009

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

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

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

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

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

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

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

Morphology and proton diffusion in a coarse-grained model of sulfonated poly(phenylenes)
journal, September 2019