Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane

Abstract

Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxylterminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxylterminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxy alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. Finally, the effective length of the linear-associated chains was estimated from the rheological measurements.

Authors:
 [1];  [1];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States); Technische Univ. Dortmund, Dortmund (Germany)
  4. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1342694
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 8; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; hydrogen bonds; associating polymers; Debye process; dielectric spectroscopy; rheology

Citation Formats

Xing, Kunyue, Chatterjee, Sabornie, Saito, Tomonori, Gainaru, Catalin P., and Sokolov, Alexei P. Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b00262.
Copy to clipboard
Xing, Kunyue, Chatterjee, Sabornie, Saito, Tomonori, Gainaru, Catalin P., & Sokolov, Alexei P. Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane. United States. https://doi.org/10.1021/acs.macromol.6b00262
Copy to clipboard
Xing, Kunyue, Chatterjee, Sabornie, Saito, Tomonori, Gainaru, Catalin P., and Sokolov, Alexei P. Wed . "Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane". United States. https://doi.org/10.1021/acs.macromol.6b00262. https://www.osti.gov/servlets/purl/1342694.
Copy to clipboard
@article{osti_1342694,
title = {Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane},
author = {Xing, Kunyue and Chatterjee, Sabornie and Saito, Tomonori and Gainaru, Catalin P. and Sokolov, Alexei P.},
abstractNote = {Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxylterminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxylterminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxy alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. Finally, the effective length of the linear-associated chains was estimated from the rheological measurements.},
doi = {10.1021/acs.macromol.6b00262},
journal = {Macromolecules},
number = 8,
volume = 49,
place = {United States},
year = {Wed Apr 06 00:00:00 EDT 2016},
month = {Wed Apr 06 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.macromol.6b00262
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 48 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
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:

Supramolecular Polymers
journal, December 2001

  • Brunsveld, L.; Folmer, B. J. B.; Meijer, E. W.
  • Chemical Reviews, Vol. 101, Issue 12
  • DOI: 10.1021/cr990125q

Supramolecular Polymerization
journal, November 2009

  • De Greef, Tom F. A.; Smulders, Maarten M. J.; Wolffs, Martin
  • Chemical Reviews, Vol. 109, Issue 11
  • DOI: 10.1021/cr900181u

Advanced supramolecular polymers constructed by orthogonal self-assembly
journal, January 2012

  • Li, Shao-Lu; Xiao, Tangxin; Lin, Chen
  • Chemical Society Reviews, Vol. 41, Issue 18
  • DOI: 10.1039/c2cs35099h

Supramolecular Polymers: Historical Development, Preparation, Characterization, and Functions
journal, March 2015

  • Yang, Liulin; Tan, Xinxin; Wang, Zhiqiang
  • Chemical Reviews, Vol. 115, Issue 15
  • DOI: 10.1021/cr500633b

Understanding Cooperativity in Hydrogen-Bond-Induced Supramolecular Polymerization: A Density Functional Theory Study
journal, November 2010

  • Filot, Ivo A. W.; Palmans, Anja R. A.; Hilbers, Peter A. J.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 43
  • DOI: 10.1021/jp1072928

New triply hydrogen bonded complexes with highly variable stabilities
journal, May 1992

  • Murray, Thomas J.; Zimmerman, Steven C.
  • Journal of the American Chemical Society, Vol. 114, Issue 10
  • DOI: 10.1021/ja00036a079

Hydrogen bonded complexes with the AA·DD, AA·DDD, and AAA·DD motifs: The role of three centered (bifurcated) hydrogen bonding
journal, June 1994

Synthesis of heterocyclic compounds containing three contiguous hydrogen bonding sites in all possible arrangements
journal, January 1995

Reversible Polymers Formed from Self-Complementary Monomers Using Quadruple Hydrogen Bonding
journal, November 1997

Quadruple hydrogen bonded systems
journal, August 2002

  • Sijbesma, Rint P.; Meijer, E. W.
  • Chemical Communications, Issue 1
  • DOI: 10.1039/b205873c

Self-Association without Regard to Prototropy. A Heterocycle That Forms Extremely Stable Quadruply Hydrogen-Bonded Dimers
journal, September 1998

  • Corbin, Perry S.; Zimmerman, Steven C.
  • Journal of the American Chemical Society, Vol. 120, Issue 37
  • DOI: 10.1021/ja981884d

Molecular recognition of biologically interesting substrates: synthesis of an artificial receptor for barbiturates employing six hydrogen bonds
journal, February 1988

  • Chang, Suk Kyu.; Hamilton, Andrew D.
  • Journal of the American Chemical Society, Vol. 110, Issue 4
  • DOI: 10.1021/ja00212a065

Structure and dynamics of monohydroxy alcohols—Milestones towards their microscopic understanding, 100 years after Debye
journal, December 2014

Associating polymers: Equilibrium and linear viscoelasticity
journal, July 1995

  • Semenov, A. N.; Joanny, J. -F.; Khokhlov, A. R.
  • Macromolecules, Vol. 28, Issue 4
  • DOI: 10.1021/ma00108a038

Supramolecular Polymers from Linear Telechelic Siloxanes with Quadruple-Hydrogen-Bonded Units
journal, April 1999

  • Hirschberg, J. H. K. Ky; Beijer, Felix H.; van Aert, Huub A.
  • Macromolecules, Vol. 32, Issue 8
  • DOI: 10.1021/ma981950w

Dielectric Relaxation and Rheological Behavior of Supramolecular Polymeric Liquid
journal, April 2013

  • Lou, Nan; Wang, Yangyang; Li, Xiaopeng
  • Macromolecules, Vol. 46, Issue 8
  • DOI: 10.1021/ma400088w

Equilibrium and Non-Equilibrium Type β-Relaxations:  d -Sorbitol versus o -Terphenyl
journal, May 1999

  • Wagner, Hermann; Richert, Ranko
  • The Journal of Physical Chemistry B, Vol. 103, Issue 20
  • DOI: 10.1021/jp9838947

Ionic Transport, Microphase Separation, and Polymer Relaxation in Poly(propylene glycol) and Lithium Perchlorate Mixtures
journal, November 2013

  • Fan, Fei; Wang, Yangyang; Sokolov, Alexei P.
  • Macromolecules, Vol. 46, Issue 23
  • DOI: 10.1021/ma401238k

Molecular Weight Dependence of Glassy Dynamics in Linear Polymers Revisited
journal, December 2008

  • Hintermeyer, J.; Herrmann, A.; Kahlau, R.
  • Macromolecules, Vol. 41, Issue 23
  • DOI: 10.1021/ma8016794

Dielectric Relaxation in Glycerine
journal, October 1950

  • Davidson, D. W.; Cole, R. H.
  • The Journal of Chemical Physics, Vol. 18, Issue 10
  • DOI: 10.1063/1.1747496

Dynamic Shear Modulus of Tricresyl Phosphate and Squalane
journal, May 1999

  • Deegan, Robert D.; Leheny, Robert L.; Menon, Narayanan
  • The Journal of Physical Chemistry B, Vol. 103, Issue 20
  • DOI: 10.1021/jp983832g

Supercooled Liquid Dynamics Studied via Shear-Mechanical Spectroscopy
journal, December 2008

  • Maggi, Claudio; Jakobsen, Bo; Christensen, Tage
  • The Journal of Physical Chemistry B, Vol. 112, Issue 51
  • DOI: 10.1021/jp805097r

Molecular motions in poly(dimethyl siloxane) oligomers and polymers
journal, September 1973

Molecular dynamics of cyclic and linear poly(dimethylsiloxanes)
journal, November 1994

  • Kirst, K. U.; Kremer, F.; Pakula, T.
  • Colloid & Polymer Science, Vol. 272, Issue 11
  • DOI: 10.1007/BF00654172

Nonexponential relaxations in strong and fragile glass formers
journal, September 1993

  • Böhmer, R.; Ngai, K. L.; Angell, C. A.
  • The Journal of Chemical Physics, Vol. 99, Issue 5
  • DOI: 10.1063/1.466117

Role of Chemical Structure in Fragility of Polymers: A Qualitative Picture
journal, October 2008

  • Kunal, Kumar; Robertson, Christopher G.; Pawlus, Sebastian
  • Macromolecules, Vol. 41, Issue 19, p. 7232-7238
  • DOI: 10.1021/ma801155c

Fragility of Glass-Forming Polymer Liquids †
journal, November 2005

  • Dudowicz, Jacek; Freed, Karl F.; Douglas, Jack F.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 45
  • DOI: 10.1021/jp053693k

A Dielectric Study of Oligo- and Poly(propylene glycol)
journal, February 2010

  • Gainaru, Catalin; Hiller, Wolf; Böhmer, Roland
  • Macromolecules, Vol. 43, Issue 4
  • DOI: 10.1021/ma9026383

Chain-Length-Dependent Relaxation Scenarios in an Oligomeric Glass-Forming System: From Merged to Well-Separated α and β Loss Peaks
journal, February 2003

Dielectric normal mode relaxation
journal, January 1993

Dielectric Properties of Alkyl Amides. II. Liquid Dielectric Constant and Loss
journal, March 1964

  • Bass, S. J.; Nathan, W. I.; Meighan, R. M.
  • The Journal of Physical Chemistry, Vol. 68, Issue 3
  • DOI: 10.1021/j100785a011

Dynamics in Supercooled Secondary Amide Mixtures: Dielectric and Hydrogen Bond Specific Spectroscopies
journal, December 2015

  • Gainaru, C.; Bauer, S.; Vynokur, E.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 51
  • DOI: 10.1021/acs.jpcb.5b10034

Communication: Synperiplanar to antiperiplanar conformation changes as underlying the mechanism of Debye process in supercooled ibuprofen
journal, September 2013

  • Adrjanowicz, K.; Kaminski, K.; Dulski, M.
  • The Journal of Chemical Physics, Vol. 139, Issue 11
  • DOI: 10.1063/1.4820492

Evidence of slow Debye-like relaxation in the anti-inflammatory agent etoricoxib
journal, August 2015

Observation of the slow, Debye-like relaxation in hydrogen-bonded liquids by dynamic light scattering
journal, March 2014

  • Wang, Yangyang; Griffin, Philip J.; Holt, Adam
  • The Journal of Chemical Physics, Vol. 140, Issue 10
  • DOI: 10.1063/1.4867913

Proton Transport in Imidazoles: Unraveling the Role of Supramolecular Structure
journal, September 2015

  • Cosby, Tyler; Holt, Adam; Griffin, Philip J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 19
  • DOI: 10.1021/acs.jpclett.5b01887

Structures of Neat and Hydrated 1-Octanol from Computer Simulations
journal, December 2002

  • MacCallum, Justin L.; Tieleman, D. Peter
  • Journal of the American Chemical Society, Vol. 124, Issue 50
  • DOI: 10.1021/ja027422o

Association effects in pure methanol via Monte Carlo simulations. I. Structure
journal, January 2013

  • Gómez-Álvarez, Paula; Romaní, Luis; González-Salgado, Diego
  • The Journal of Chemical Physics, Vol. 138, Issue 4
  • DOI: 10.1063/1.4778596

Microstructure of neat alcohols: A molecular dynamics study
journal, July 2007

  • Zoranić, Larisa; Sokolić, Franjo; Perera, Aurélien
  • The Journal of Chemical Physics, Vol. 127, Issue 2
  • DOI: 10.1063/1.2753482

Structural Properties of Pure Simple Alcohols from Ethanol, Propanol, Butanol, Pentanol, to Hexanol:  Comparing Monte Carlo Simulations with Experimental SAXS Data
journal, February 2007

  • Tomšič, Matija; Jamnik, Andrej; Fritz-Popovski, Gerhard
  • The Journal of Physical Chemistry B, Vol. 111, Issue 7
  • DOI: 10.1021/jp066139z

A statistical model of hydrogen bond networks in liquid alcohols
journal, March 2012

  • Sillrén, Per; Bielecki, Johan; Mattsson, Johan
  • The Journal of Chemical Physics, Vol. 136, Issue 9
  • DOI: 10.1063/1.3690137

X-Ray Diffraction in Liquids: Primary Normal Alcohols
journal, September 1927

Molecular Organization of Liquid n-Octanol: An X-ray Diffraction Analysis
journal, May 1993

  • Franks, N. P.; Abraham, M. H.; Lieb, W. R.
  • Journal of Pharmaceutical Sciences, Vol. 82, Issue 5
  • DOI: 10.1002/jps.2600820507

Determination of Liquid Structures of the Primary Alcohols Methanol, Ethanol, 1-Propanol, 1-Butanol and 1-Octanol by X-ray Scattering
journal, April 1995

  • Vahvaselkä, K. S.; Serimaa, R.; Torkkeli, M.
  • Journal of Applied Crystallography, Vol. 28, Issue 2
  • DOI: 10.1107/S0021889894010149

Hydrogen bonding in liquid methanol and ethanol determined by x‐ray diffraction
journal, April 1984

  • Narten, A. H.; Habenschuss, A.
  • The Journal of Chemical Physics, Vol. 80, Issue 7
  • DOI: 10.1063/1.447093

Structure and Hydrogen Bonding in Neat N-Methylacetamide:  Classical Molecular Dynamics and Raman Spectroscopy Studies of a Liquid of Peptidic Fragments
journal, November 2005

  • Whitfield, T. W.; Martyna, G. J.; Allison, S.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 8
  • DOI: 10.1021/jp053140+

Vibrational Spectroscopy of N -Methylacetamide Revisited
journal, April 2001

  • Herrebout, W. A.; Clou, K.; Desseyn, H. O.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 20
  • DOI: 10.1021/jp004396c

Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr effect spectroscopy
journal, April 2008

  • Turton, David A.; Wynne, Klaas
  • The Journal of Chemical Physics, Vol. 128, Issue 15
  • DOI: 10.1063/1.2897432

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
  • DOI: 10.1021/ma00095a001

Debye relaxation and 250 K anomaly in glass forming monohydroxy alcohols
journal, March 2013

  • Bauer, S.; Burlafinger, K.; Gainaru, C.
  • The Journal of Chemical Physics, Vol. 138, Issue 9
  • DOI: 10.1063/1.4793469

Supramolecular x-ray signature of susceptibility amplification in hydrogen-bonded liquids
journal, November 2014

Synthesis of Molecular Brushes with Block Copolymer Side Chains Using Atom Transfer Radical Polymerization
journal, June 2001

  • Börner, Hans G.; Beers, Kathryn; Matyjaszewski, Krzysztof
  • Macromolecules, Vol. 34, Issue 13
  • DOI: 10.1021/ma010001r

The Structure of Liquid Methanol
journal, July 2005

Theoretical Determination of the NMR Spectrum of Liquid Ethanol
journal, December 2008

  • Zarzycki, Piotr; Rustad, James R.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 1
  • DOI: 10.1021/jp805737a

Nuclear-Magnetic-Resonance Measurements Reveal the Origin of the Debye Process in Monohydroxy Alcohols
journal, December 2010

Vibrational study of anharmonicity, supramolecular structure, and hydrogen bonding in two octanol isomers
journal, July 2015

Shear-Modulus Investigations of Monohydroxy Alcohols: Evidence for a Short-Chain-Polymer Rheological Response
journal, March 2014

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Viscoelasticity in associating oligomers and polymers: experimental test of the bond lifetime renormalization model
    journal, January 2020

    • Ge, Sirui; Tress, Martin; Xing, Kunyue
    • Soft Matter, Vol. 16, Issue 2
    • DOI: 10.1039/c9sm01930h

    Hydrogen-bond strength changes network dynamics in associating telechelic PDMS
    journal, January 2018

    • Xing, Kunyue; Tress, Martin; Cao, Pengfei
    • Soft Matter, Vol. 14, Issue 7
    • DOI: 10.1039/c7sm01805c

    Mechanism of the formation of microphase separated water clusters in a water-mediated physical network of perfluoropolyether tetraol
    journal, January 2018

    • Deshpande, Ashwini A.; Torris A. T., Arun; Pahari, Swagata
    • Soft Matter, Vol. 14, Issue 12
    • DOI: 10.1039/c7sm02181j

    Linear and nonlinear shear studies reveal supramolecular responses in supercooled monohydroxy alcohols with faint dielectric signatures
    journal, March 2019

    • Bierwirth, S. Peter; Honorio, Gabriel; Gainaru, Catalin
    • The Journal of Chemical Physics, Vol. 150, Issue 10
    • DOI: 10.1063/1.5086529

    Coexistence of two structural relaxation processes in monohydroxy alcohol–alkyl halogen mixtures: Dielectric and rheological studies
    journal, July 2018

    • Bierwirth, S. Peter; Gainaru, Catalin; Böhmer, Roland
    • The Journal of Chemical Physics, Vol. 149, Issue 4
    • DOI: 10.1063/1.5037037

    A Critical Approach to Polymer Dynamics in Supramolecular Polymers
    journal, December 2019

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: