Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks
Abstract
Solid state nuclear magnetic resonance (NMR) spectroscopy and small-to wide-angle X-ray scattering (SWAXS) methods were used to characterize the heterogeneous dynamics and polymer domain structure in rubber modified thermoset materials containing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin and a mixture of Jeffamine reactive rubber and 4,4-diaminodicyclohexylmethane (PACM) amine curing agent. The polymer chain dynamics and morphologies as a function of the PACM/Jeffamine ratio were determined. Using dipolar-filtered NMR experiments, the resulting networks are shown to be composed of mobile and rigid regions that are separated on nanometer length scales, along with a dynamically immobilized interface region. Proton NMR spin diffusion experiments measured the dimensions of the mobile phase to range between 9 and 66 nm and varied with the relative PACM concentration. Solid state 13C magic angle spinning NMR experiments show that the highly mobile phase is composed entirely of the dynamically flexible polyether chains of the Jeffamine rubber, the immobilized interface region is a mixture of DGEBA, PACM, and the Jeffamine rubber, with the PACM cross-linked to DGEBA predominantly residing in the rigid phase. The SWAXS results showed compositional nanophase separation spanning the 11–77 nm range. These measurements of the nanoscale compositional and dynamic heterogeneity providemore »
- Authors:
-
[1];
[2];
[3]
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); ACC Consulting New Mexico, Cedar Crest, NM (United States)
- Rensselaer Polytechnic Inst., Troy, NY (United States)
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1872002
- Report Number(s):
- SAND2022-6503J
Journal ID: ISSN 0142-9418; 706061
- Grant/Contract Number:
- NA0003525; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Polymer Testing
- Additional Journal Information:
- Journal Volume: 112; Journal ID: ISSN 0142-9418
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; polymerization-induced phase separation; glass transition; microstructure; dynamic heterogeneity; spin diffusion
Citation Formats
Alam, Todd M., Ahn, Juhong, Lee, Sangwoo, Leguizamon, Samuel C., and Jones, Brad H. Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks. United States: N. p., 2022.
Web. doi:10.1016/j.polymertesting.2022.107616.
Alam, Todd M., Ahn, Juhong, Lee, Sangwoo, Leguizamon, Samuel C., & Jones, Brad H. Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks. United States. https://doi.org/10.1016/j.polymertesting.2022.107616
Alam, Todd M., Ahn, Juhong, Lee, Sangwoo, Leguizamon, Samuel C., and Jones, Brad H. Fri .
"Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks". United States. https://doi.org/10.1016/j.polymertesting.2022.107616. https://www.osti.gov/servlets/purl/1872002.
@article{osti_1872002,
title = {Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks},
author = {Alam, Todd M. and Ahn, Juhong and Lee, Sangwoo and Leguizamon, Samuel C. and Jones, Brad H.},
abstractNote = {Solid state nuclear magnetic resonance (NMR) spectroscopy and small-to wide-angle X-ray scattering (SWAXS) methods were used to characterize the heterogeneous dynamics and polymer domain structure in rubber modified thermoset materials containing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin and a mixture of Jeffamine reactive rubber and 4,4-diaminodicyclohexylmethane (PACM) amine curing agent. The polymer chain dynamics and morphologies as a function of the PACM/Jeffamine ratio were determined. Using dipolar-filtered NMR experiments, the resulting networks are shown to be composed of mobile and rigid regions that are separated on nanometer length scales, along with a dynamically immobilized interface region. Proton NMR spin diffusion experiments measured the dimensions of the mobile phase to range between 9 and 66 nm and varied with the relative PACM concentration. Solid state 13C magic angle spinning NMR experiments show that the highly mobile phase is composed entirely of the dynamically flexible polyether chains of the Jeffamine rubber, the immobilized interface region is a mixture of DGEBA, PACM, and the Jeffamine rubber, with the PACM cross-linked to DGEBA predominantly residing in the rigid phase. The SWAXS results showed compositional nanophase separation spanning the 11–77 nm range. These measurements of the nanoscale compositional and dynamic heterogeneity provide molecular level insight into the very broad and controllable glass transition temperature distributions observed for these highly cross-linked polymer networks.},
doi = {10.1016/j.polymertesting.2022.107616},
journal = {Polymer Testing},
number = ,
volume = 112,
place = {United States},
year = {Fri May 06 00:00:00 EDT 2022},
month = {Fri May 06 00:00:00 EDT 2022}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
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:
Micellar structure and mechanical properties of block copolymer-modified epoxies
journal, January 2001
- Dean, J. M.; Lipic, P. M.; Grubbs, R. B.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 23
Tuning Mesoporosity in Cross-Linked Nanostructured Thermosets via Polymerization-Induced Microphase Separation
journal, January 2017
- Schulze, Morgan W.; Hillmyer, Marc A.
- Macromolecules, Vol. 50, Issue 3
Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)-block-poly(dimethylsiloxane) diblock copolymer
journal, January 2006
- Guo, Qipeng; Chen, Fei; Wang, Ke
- Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 21
Investigating Chain Dynamics in Highly Crosslinked Polymers using Solid‐State 1 H NMR Spectroscopy
journal, July 2019
- Alam, Todd M.; Jones, Brad H.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 17
Versatility of the dipolar filter selection: From 1H nuclear spin diffusion experiment to the measurement of nuclear Overhauser effect in homopolymer melts
journal, September 2005
- Gaborieau, Marianne; Graf, Robert; Spiess, Hans Wolfgang
- Solid State Nuclear Magnetic Resonance, Vol. 28, Issue 2-4
Influence of nano-scale morphology on impact toughness of epoxy blends
journal, October 2016
- Masser, Kevin A.; Bain, Erich D.; Beyer, Frederick L.
- Polymer, Vol. 103
Structure of Atactic Polystyrene: A Molecular Dynamics Simulation Study
journal, August 2000
- Ayyagari, Chakravarthy; Bedrov, Dmitry; Smith, Grant D.
- Macromolecules, Vol. 33, Issue 16
Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994
- Fetters, L. J.; Lohse, D. J.; Richter, D.
- Macromolecules, Vol. 27, Issue 17
Toughening of epoxy resins
journal, January 2006
- Unnikrishnan, K. P.; Thachil, Eby Thomas
- Designed Monomers and Polymers, Vol. 9, Issue 2
Solid-State Proton NMR Characterization of Ethylene Oxide and Propylene Oxide Random and Block Copolymer Composites with Poly(methyl silsesquioxanes)
journal, November 2001
- Mirau, Peter A.; Yang, Shu
- Chemistry of Materials, Vol. 14, Issue 1
Multiphase structure of a segmented polyurethane: effects of temperature and annealing
journal, December 1992
- Li, Yingjie; Gao, Tong; Liu, Jian
- Macromolecules, Vol. 25, Issue 26
Controlling Nanodomain Morphology of Epoxy Thermosets Modified with Reactive Amine-Containing Epoxidized Poly(styrene-b-isoprene-b-styrene) Block Copolymer
journal, October 2014
- Garate, Hernan; Goyanes, Silvia; D’Accorso, Norma B.
- Macromolecules, Vol. 47, Issue 21
Uniquely Broad Glass Transition Temperatures of Gradient Copolymers Relative to Random and Block Copolymers Containing Repulsive Comonomers
journal, September 2006
- Kim, Jungki; Mok, Michelle M.; Sandoval, Robert W.
- Macromolecules, Vol. 39, Issue 18
Direct Measurement of the Local Glass Transition in Self-Assembled Copolymers with Nanometer Resolution
journal, February 2018
- Christie, Dane; Register, Richard A.; Priestley, Rodney D.
- ACS Central Science, Vol. 4, Issue 4
A Study on Polymerization-Induced Phase Separation (PIPS) of Epoxy Solution in Oligoethylene Glycol Aiming at Controlling the Characteristic Length
journal, January 2016
- Kanaya, Toshiji; Ogino, Yoshiko; Mizuike, Atsuko
- Journal of Fiber Science and Technology, Vol. 72, Issue 6
Influence of cure schedule and stoichiometry on the dynamic mechanical behaviour of tetrafunctional epoxy resins cured with anhydrides
journal, May 1996
- Guerrero, P.; De la Caba, K.; Valea, A.
- Polymer, Vol. 37, Issue 11
Development of low field NMR technique for analyzing segmental mobility of crosslinked polymers
journal, February 2018
- Patel, Jigneshkumar P.; Hsu, Shaw Ling
- Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 8
Effect of Temperature and Annealing on the Phase Composition, Molecular Mobility, and the Thickness of Domains in Isotactic Polypropylene Studied by Proton Solid-State NMR, SAXS, and DSC
journal, May 2007
- Hedesiu, C.; Demco, D. E.; Kleppinger, R.
- Macromolecules, Vol. 40, Issue 11
Exploiting heterogeneous time scale of dynamics to enhance 2D HETCOR solid-state NMR sensitivity
journal, December 2019
- Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy
- Journal of Magnetic Resonance, Vol. 309
Glass Transition Breadths and Composition Profiles of Weakly, Moderately, and Strongly Segregating Gradient Copolymers: Experimental Results and Calculations from Self-Consistent Mean-Field Theory
journal, October 2009
- Mok, Michelle M.; Kim, Jungki; Wong, Christopher L. H.
- Macromolecules, Vol. 42, Issue 20
Investigation of Domain Size in Polymer Membranes Using Double-Quantum-Filtered Spin Diffusion Magic Angle Spinning NMR
journal, January 2005
- Cherry, B. R.; Fujimoto, C. H.; Cornelius, C. J.
- Macromolecules, Vol. 38, Issue 4
Characterization of interphases in core—shell latexes by solid-state NMR
journal, September 1998
- Landfester, K.; Spiess, H. W.
- Acta Polymerica, Vol. 49, Issue 9
Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra
journal, July 2020
- Alam, Todd M.; Allers, Joshua P.; Jones, Brad H.
- International Journal of Molecular Sciences, Vol. 21, Issue 15
Epoxy resin curing reaction studied by proton multiple-quantum NMR
journal, June 2015
- Martin-Gallego, Mario; González-Jiménez, Antonio; Verdejo, Raquel
- Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 18
Simulation of polymerization induced phase separation in model thermosets
journal, August 2021
- Stevens, Mark J.
- The Journal of Chemical Physics, Vol. 155, Issue 5
Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications
journal, August 2020
- Xie, Shuyi; Zhang, Bo; Mao, Yimin
- Macromolecules, Vol. 53, Issue 16
Reactive Block Copolymers for Modification of Thermosetting Epoxy
journal, December 2000
- Grubbs, Robert B.; Dean, Jennifer M.; Broz, Margaret E.
- Macromolecules, Vol. 33, Issue 26
Local glass transition temperature T g ( z ) of polystyrene next to different polymers: Hard vs. soft confinement
journal, May 2017
- Baglay, Roman R.; Roth, Connie B.
- The Journal of Chemical Physics, Vol. 146, Issue 20
Nanostructured Thermosets from Self-Assembled Amphiphilic Block Copolymer/Epoxy Resin Mixtures
journal, September 1998
- Lipic, Paul M.; Bates, Frank S.; Hillmyer, Marc A.
- Journal of the American Chemical Society, Vol. 120, Issue 35
Small angle X-ray scattering from amorphous polymers arising from heterogeneities
journal, November 1973
- Wendorff, J. H.; Fischer, E. W.
- Kolloid-Zeitschrift und Zeitschrift für Polymere, Vol. 251, Issue 11
Mechanical characterization of copolymers based on benzoxazine and epoxy
journal, September 1996
- Ishida, Hatsuo; Allen, Douglas J.
- Polymer, Vol. 37, Issue 20
Reversible Cross-Linking, Microdomain Structure, and Heterogeneous Dynamics in Thermally Reversible Cross-Linked Polyurethane as Revealed by Solid-State NMR
journal, January 2014
- Zhang, Rongchun; Yu, Shen; Chen, Shengli
- The Journal of Physical Chemistry B, Vol. 118, Issue 4
Heteronuclear decoupling in rotating solids
journal, October 1995
- Bennett, Andrew E.; Rienstra, Chad M.; Auger, Michèle
- The Journal of Chemical Physics, Vol. 103, Issue 16
Beyond the ring flip: A molecular signature of the glass–rubber transition in tetrafunctional epoxy resins
journal, October 2020
- Vuković, Filip; Swan, Sam R.; Reyes, Larry Q.
- Polymer, Vol. 206
Gradient copolymers with broad glass transition temperature regions: Design of purely interphase compositions for damping applications
journal, January 2007
- Mok, Michelle M.; Kim, Jungki; Torkelson, John M.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 46, Issue 1
Solid state NMR investigation of cationic polymerized epoxy resins
journal, January 1992
- Egger, N.; Schmidt-Rohr, K.; Blümich, B.
- Journal of Applied Polymer Science, Vol. 44, Issue 2
Direct Observation of Interphase Composition in Block Copolymers
journal, December 2008
- Saalwächter, Kay; Thomann, Yi; Hasenhindl, Alfred
- Macromolecules, Vol. 41, Issue 23
A theoretical basis for viscoelastic relaxation of elastomers in the long-time limit
journal, April 1983
- Curro, John G.; Pincus, Philip
- Macromolecules, Vol. 16, Issue 4
Effect of PEO molecular weight on the miscibility and dynamics in epoxy/PEO blends
journal, November 2015
- Lu, Shoudong; Zhang, Rongchun; Wang, Xiaoliang
- The European Physical Journal E, Vol. 38, Issue 11
Polymerization-induced phase separation and resulting thermomechanical properties of thermosetting/reactive nonlinear polymer blends: A review
journal, November 2012
- Liu, Yuhong
- Journal of Applied Polymer Science, Vol. 127, Issue 5
Effect of the crosslinking density of epoxide polymers on their relaxation and strain characteristics
journal, January 1980
- Yurechko, N. A.; Lipskaya, V. A.; Nesolenaya, L. G.
- Polymer Science U.S.S.R., Vol. 22, Issue 1
Calibration of 1 H NMR Spin Diffusion Coefficients for Mobile Polymers through Transverse Relaxation Measurements
journal, July 1999
- Mellinger, F.; Wilhelm, M.; Spiess, H. W.
- Macromolecules, Vol. 32, Issue 14
Binder and Interphase Microstructure in a Composite Material Characterized by Scanning Electron Microscopy and NMR Spin Diffusion Experiments
journal, December 2019
- Parisse, Silène; Petit, Jean‐Fabien; Forzy, Alexandre
- Macromolecular Chemistry and Physics, Vol. 221, Issue 2
Polymerization-Induced Phase Separation in Rubber-Toughened Amine-Cured Epoxy Resins: Tuning Morphology from the Nano- to Macro-scale
journal, August 2021
- Leguizamon, Samuel C.; Powers, Jackson; Ahn, Juhong
- Macromolecules, Vol. 54, Issue 17
Reactive Tetrablock Copolymers Containing Glycidyl Methacrylate. Synthesis and Morphology Control in Epoxy−Amine Networks
journal, November 2003
- Rebizant, Valéry; Abetz, Volker; Tournilhac, François
- Macromolecules, Vol. 36, Issue 26
Novel thermoplastic polyhydroxyurethane elastomers as effective damping materials over broad temperature ranges
journal, November 2016
- Beniah, Goliath; Liu, Kun; Heath, William H.
- European Polymer Journal, Vol. 84
Impact of Hydration and Sulfonation on the Morphology and Ionic Conductivity of Sulfonated Poly(phenylene) Proton Exchange Membranes
journal, January 2019
- Sorte, Eric G.; Paren, Benjamin A.; Rodriguez, Christina G.
- Macromolecules, Vol. 52, Issue 3
Complex Morphology of the Intermediate Phase in Block Copolymers and Semicrystalline Polymers As Revealed by 1 H NMR Spin Diffusion Experiments
journal, November 2017
- Schneider, Horst; Saalwächter, Kay; Roos, Matthias
- Macromolecules, Vol. 50, Issue 21
Polymers under nanoconfinement: where are we now in understanding local property changes?
journal, January 2021
- Roth, Connie B.
- Chemical Society Reviews, Vol. 50, Issue 14
Scaling of Star Polymers with 1−80 Arms
journal, May 2004
- Hsu, Hsiao-Ping; Nadler, Walter; Grassberger, Peter
- Macromolecules, Vol. 37, Issue 12
Ultimate properties of epoxy resins modified with a polysiloxane–polycaprolactone block copolymer
journal, November 1994
- Könczöl, L.; Döll, W.; Buchholz, U.
- Journal of Applied Polymer Science, Vol. 54, Issue 6
Dynamic heterogeneity in epoxy networks for protection applications
journal, March 2016
- Masser, Kevin A.; Knorr, Daniel B.; Yu, Jian H.
- Journal of Applied Polymer Science, Vol. 133, Issue 45
Domain sizes in heterogeneous polymers by spin diffusion using single-quantum and double-quantum dipolar filters
journal, August 2003
- Buda, A.; Demco, D. E.; Bertmer, M.
- Solid State Nuclear Magnetic Resonance, Vol. 24, Issue 1
Breadth of glass transition temperature in styrene/acrylic acid block, random, and gradient copolymers: Unusual sequence distribution effects: Breadth of T g in S/AA Copolymers
journal, August 2007
- Wong, Christopher L. H.; Kim, Jungki; Torkelson, John M.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 20
Pulsed NMR Study of the Curing Process of Epoxy Resin
journal, January 2008
- Kimoto, Hiroki; Tanaka, Chikako; Yaginuma, Michiko
- Analytical Sciences, Vol. 24, Issue 7
Mobility, Miscibility, and Microdomain Structure in Nanostructured Thermoset Blends of Epoxy Resin and Amphiphilic Poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) Triblock Copolymers Characterized by Solid-State NMR
journal, May 2005
- Sun, Pingchuan; Dang, Qinqin; Li, Baohui
- Macromolecules, Vol. 38, Issue 13
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
Communication: Experimentally determined profile of local glass transition temperature across a glassy-rubbery polymer interface with a T g difference of 80 K
journal, September 2015
- Baglay, Roman R.; Roth, Connie B.
- The Journal of Chemical Physics, Vol. 143, Issue 11
Heterogeneous Dynamics and Microdomain Structure of High-Performance Chitosan Film as Revealed by Solid-State NMR
journal, June 2021
- Wang, Fenfen; Deng, Zhou; Yang, Zhijun
- The Journal of Physical Chemistry C, Vol. 125, Issue 24
Unique Interphase and Cross-Linked Network Controlled by Different Miscible Blocks in Nanostructured Epoxy/Block Copolymer Blends Characterized by Solid-State NMR
journal, June 2014
- He, Xin; Liu, Yuan; Zhang, Rongchun
- The Journal of Physical Chemistry C, Vol. 118, Issue 24
Proton multiple-quantum NMR for the study of chain dynamics and structural constraints in polymeric soft materials
journal, August 2007
- Saalwachter, K.
- Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 51, Issue 1
Effect of nanoscale confinement on glass transition of polystyrene domains from self-assembly of block copolymers
journal, March 2010
- Robertson, C. G.; Hogan, T. E.; Rackaitis, M.
- The Journal of Chemical Physics, Vol. 132, Issue 10
Signal intensities in 1H–13C CP and INEPT MAS NMR of liquid crystals
journal, May 2013
- Nowacka, A.; Bongartz, N. A.; Ollila, O. H. S.
- Journal of Magnetic Resonance, Vol. 230
1
H-19
F REDOR-filtered NMR spin diffusion measurements of domain size in heterogeneous polymers
journal, July 2017
- Sorte, Eric G.; Alam, Todd M.
- Magnetic Resonance in Chemistry, Vol. 55, Issue 11
Quantification of the amount of mobile components in intact stratum corneum with natural-abundance13C solid-state NMR
journal, January 2020
- Pham, Quoc Dat; Carlström, Göran; Lafon, Olivier
- Physical Chemistry Chemical Physics, Vol. 22, Issue 12
Functionalization of hydroxyl groups in segmented polyhydroxyurethane eliminates nanophase separation
journal, July 2017
- Beniah, Goliath; Heath, William H.; Torkelson, John M.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 20
Reticulated Nanoporous Polymers by Controlled Polymerization-Induced Microphase Separation
journal, June 2012
- Seo, M.; Hillmyer, M. A.
- Science, Vol. 336, Issue 6087
An Emerging Unified View of Dynamic Interphases in Polymers
journal, December 2015
- Simmons, David S.
- Macromolecular Chemistry and Physics, Vol. 217, Issue 2