Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks

Alam, Todd M.; Ahn, Juhong; Lee, Sangwoo; Leguizamon, Samuel C.; Jones, Brad H.

doi:10.1016/j.polymertesting.2022.107616

Title: Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks

Journal Article · Fri May 06 00:00:00 EDT 2022 · Polymer Testing

DOI:https://doi.org/10.1016/j.polymertesting.2022.107616· OSTI ID:1872002

^[1];

^[2]; Lee, Sangwoo ^[2]; Leguizamon, Samuel C. ^[3];

^[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)

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.

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Research Organization:: 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 Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: NA0003525; SC0012704

OSTI ID:: 1872002

Report Number(s):: SAND2022-6503J; 706061

Journal Information:: Polymer Testing, Vol. 112; ISSN 0142-9418

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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