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Title: Tunability of Free Volume and Viscoelastic Damping of Thiol–Ene Networks Deep in the Glassy State

Abstract

Model thiol-click glassy networks with low shrinkage and sharp glass transition temperatures are studied down to cryogenic temperatures to relate viscoelastic damping to changes in microscopic hole volume. Networks synthesized by polymerization of divinyl sulfone with pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), trimethylolpropane tris(3-mercaptopropionate) (TMPTMP), and pentaerythritol tetrakis(2-mercaptoacetate) (PETT) were studied to ~50 K using positron annihilation and thermal analysis methods. Across the glass transition temperature, overall volume expansivity is dominated by expansion of microscopic holes. Beneath T g, holes contract upon cooling and then become static with negligible expansivity at temperatures well above 0 K. A trade off between complete rigidity of static free volume and viscoelastic damping ability below T g is discussed. All samples show moderate damping (tan δ > 0.05), and one sample exhibits a prominent β-transition in its viscoelastic loss spectra. These results indicate the potential for tuning the molecular design of low-temperature glassy networks to optimally incorporate damping with low shrinkage.

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [2];  [3]
  1. Univ. of Rochester, NY (United States)
  2. Grand Valley State University, Allendale, MI (United States)
  3. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
Research Org.:
Univ. of Rochester, NY (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
Contributing Org.:
Grand Valley State University, Allendale, MI (United States)
OSTI Identifier:
1427568
Alternate Identifier(s):
OSTI ID: 1487078
Grant/Contract Number:  
NA0003400
Resource Type:
Journal Article: Published Article
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 7; Related Information: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.8b00037.; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 42 ENGINEERING; viscoelastic damping; free volume; thiol-ene networks

Citation Formats

Anthamatten, Mitchell, O’Neill, Sean W., Liu, Dezhi, Wheler, Tyler M., Vallery, Richard S., and Gidley, David W. Tunability of Free Volume and Viscoelastic Damping of Thiol–Ene Networks Deep in the Glassy State. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.8b00037.
Anthamatten, Mitchell, O’Neill, Sean W., Liu, Dezhi, Wheler, Tyler M., Vallery, Richard S., & Gidley, David W. Tunability of Free Volume and Viscoelastic Damping of Thiol–Ene Networks Deep in the Glassy State. United States. doi:10.1021/acs.macromol.8b00037.
Anthamatten, Mitchell, O’Neill, Sean W., Liu, Dezhi, Wheler, Tyler M., Vallery, Richard S., and Gidley, David W. Wed . "Tunability of Free Volume and Viscoelastic Damping of Thiol–Ene Networks Deep in the Glassy State". United States. doi:10.1021/acs.macromol.8b00037.
@article{osti_1427568,
title = {Tunability of Free Volume and Viscoelastic Damping of Thiol–Ene Networks Deep in the Glassy State},
author = {Anthamatten, Mitchell and O’Neill, Sean W. and Liu, Dezhi and Wheler, Tyler M. and Vallery, Richard S. and Gidley, David W.},
abstractNote = {Model thiol-click glassy networks with low shrinkage and sharp glass transition temperatures are studied down to cryogenic temperatures to relate viscoelastic damping to changes in microscopic hole volume. Networks synthesized by polymerization of divinyl sulfone with pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), trimethylolpropane tris(3-mercaptopropionate) (TMPTMP), and pentaerythritol tetrakis(2-mercaptoacetate) (PETT) were studied to ~50 K using positron annihilation and thermal analysis methods. Across the glass transition temperature, overall volume expansivity is dominated by expansion of microscopic holes. Beneath Tg, holes contract upon cooling and then become static with negligible expansivity at temperatures well above 0 K. A trade off between complete rigidity of static free volume and viscoelastic damping ability below Tg is discussed. All samples show moderate damping (tan δ > 0.05), and one sample exhibits a prominent β-transition in its viscoelastic loss spectra. These results indicate the potential for tuning the molecular design of low-temperature glassy networks to optimally incorporate damping with low shrinkage.},
doi = {10.1021/acs.macromol.8b00037},
journal = {Macromolecules},
issn = {0024-9297},
number = 7,
volume = 51,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.macromol.8b00037

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