DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nanoscale viscosity of confined polyethylene oxide

Abstract

Complex fluids near interfaces or confined within nanoscale volumes can exhibit substantial shifts in physical properties compared to bulk, including glass transition temperature, phase separation, and crystallization. Because studies of these effects typically use thin film samples with one dimension of confinement, it is generally unclear how more extreme spatial confinement may influence these properties. In this work, we used x-ray photon correlation spectroscopy and gold nanoprobes to characterize polyethylene oxide confined by nanostructured gratings (<100nm width) and measured the viscosity in this nanoconfinement regime to be ~500 times the bulk viscosity. Here, this enhanced viscosity occurs even when the scale of confinement is several times the polymer's radius of gyration, consistent with previous reports of polymer viscosity near flat interfaces.

Authors:
 [1]; ORCiD logo [2];  [1];  [1];  [1];  [1];  [3];  [1];  [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Steven Inst. of Technology, Hoboken, NJ (United States)
  3. Brooklyn College and the Graduate Center of the City University of New York, Brooklyn, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1593244
Report Number(s):
BNL-213558-2020-JAAM
Journal ID: ISSN 2470-0045; PLEEE8; TRN: US2100804
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review E
Additional Journal Information:
Journal Volume: 100; Journal Issue: 6; Journal ID: ISSN 2470-0045
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhang, Zheng, Ding, Junjun, Ocko, Benjamin M., Fluerasu, Andrei, Wiegart, Lutz, Zhang, Yugang, Kobrak, Mark, Tian, Ye, Zhang, Honghu, Lhermitte, Julien, Choi, Chang-Hwan, Fisher, Frank T., Yager, Kevin G., and Black, Charles T. Nanoscale viscosity of confined polyethylene oxide. United States: N. p., 2019. Web. doi:10.1103/PhysRevE.100.062503.
Zhang, Zheng, Ding, Junjun, Ocko, Benjamin M., Fluerasu, Andrei, Wiegart, Lutz, Zhang, Yugang, Kobrak, Mark, Tian, Ye, Zhang, Honghu, Lhermitte, Julien, Choi, Chang-Hwan, Fisher, Frank T., Yager, Kevin G., & Black, Charles T. Nanoscale viscosity of confined polyethylene oxide. United States. https://doi.org/10.1103/PhysRevE.100.062503
Zhang, Zheng, Ding, Junjun, Ocko, Benjamin M., Fluerasu, Andrei, Wiegart, Lutz, Zhang, Yugang, Kobrak, Mark, Tian, Ye, Zhang, Honghu, Lhermitte, Julien, Choi, Chang-Hwan, Fisher, Frank T., Yager, Kevin G., and Black, Charles T. Thu . "Nanoscale viscosity of confined polyethylene oxide". United States. https://doi.org/10.1103/PhysRevE.100.062503. https://www.osti.gov/servlets/purl/1593244.
@article{osti_1593244,
title = {Nanoscale viscosity of confined polyethylene oxide},
author = {Zhang, Zheng and Ding, Junjun and Ocko, Benjamin M. and Fluerasu, Andrei and Wiegart, Lutz and Zhang, Yugang and Kobrak, Mark and Tian, Ye and Zhang, Honghu and Lhermitte, Julien and Choi, Chang-Hwan and Fisher, Frank T. and Yager, Kevin G. and Black, Charles T.},
abstractNote = {Complex fluids near interfaces or confined within nanoscale volumes can exhibit substantial shifts in physical properties compared to bulk, including glass transition temperature, phase separation, and crystallization. Because studies of these effects typically use thin film samples with one dimension of confinement, it is generally unclear how more extreme spatial confinement may influence these properties. In this work, we used x-ray photon correlation spectroscopy and gold nanoprobes to characterize polyethylene oxide confined by nanostructured gratings (<100nm width) and measured the viscosity in this nanoconfinement regime to be ~500 times the bulk viscosity. Here, this enhanced viscosity occurs even when the scale of confinement is several times the polymer's radius of gyration, consistent with previous reports of polymer viscosity near flat interfaces.},
doi = {10.1103/PhysRevE.100.062503},
journal = {Physical Review E},
number = 6,
volume = 100,
place = {United States},
year = {2019},
month = {12}
}

Works referenced in this record:

Entropic competition in polymeric systems under geometrical confinement
journal, June 2015


Nanoscopic-Confinement Effects on Local Dynamics
journal, January 2000


Interfacial Energy and Glass Temperature of Polymers Confined to Nanoporous Alumina
journal, September 2016


Ionic-Liquid-Nanoparticle Hybrid Electrolytes: Applications in Lithium Metal Batteries
journal, November 2013

  • Lu, Yingying; Korf, Kevin; Kambe, Yu
  • Angewandte Chemie International Edition, Vol. 53, Issue 2
  • DOI: 10.1002/anie.201307137

External normal pressure prevents preferential wetting of PS/PMMA blend thin films
journal, August 2014


Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Size Effect of Nanoparticle Diffusion in a Polymer Melt
journal, October 2014

  • Grabowski, Christopher A.; Mukhopadhyay, Ashis
  • Macromolecules, Vol. 47, Issue 20
  • DOI: 10.1021/ma501670u

Viscoelastic Dynamics of Confined Polymer Melts
journal, November 1992


Suppression of Capillary Instability of a Polymeric Thread via Parallel Plate Confinement
journal, July 2003

  • Son, Younggon; Martys, Nicos S.; Hagedorn, John G.
  • Macromolecules, Vol. 36, Issue 15
  • DOI: 10.1021/ma0343986

Directing the self-assembly of block copolymers
journal, October 2007


Influences of Substrate Adhesion and Particle Size on the Shape Memory Effect of Polystyrene Particles
journal, April 2016


Morphing Metal-Polymer Janus Particles
journal, October 2013

  • Cox, Lewis M.; Killgore, Jason P.; Li, Zhengwei
  • Advanced Materials, Vol. 26, Issue 6
  • DOI: 10.1002/adma.201304079

Effect of Spatial Confinement on the Glass-Transition Temperature of Patterned Polymer Nanostructures
journal, March 2007

  • Mundra, Manish K.; Donthu, Suresh K.; Dravid, Vinayak P.
  • Nano Letters, Vol. 7, Issue 3
  • DOI: 10.1021/nl062894c

Entanglement Reduction and Anisotropic Chain and Primitive Path Conformations in Polymer Melts under Thin Film and Cylindrical Confinement
journal, September 2014

  • Sussman, Daniel M.; Tung, Wei-Shao; Winey, Karen I.
  • Macromolecules, Vol. 47, Issue 18
  • DOI: 10.1021/ma501193f

Confined crystallization of polymeric materials
journal, March 2016


Effect of Confinement on Stiffness and Fracture of Thin Amorphous Polymer Films
journal, November 2011

  • Lee, Jung-Hyun; Chung, Jun Young; Stafford, Christopher M.
  • ACS Macro Letters, Vol. 1, Issue 1
  • DOI: 10.1021/mz200090a

Molecular Confinement Accelerates Deformation of Entangled Polymers During Squeeze Flow
journal, October 2008


Ultrathin Polymer Films: Rubbery Stiffening, Fragility, and T g Reduction
journal, August 2015


Reduced Viscosity of the Free Surface in Entangled Polymer Melt Films
journal, February 2010


Simulating X-ray diffraction of textured films
journal, March 2008

  • Breiby, Dag W.; Bunk, Oliver; Andreasen, Jens W.
  • Journal of Applied Crystallography, Vol. 41, Issue 2
  • DOI: 10.1107/S0021889808001064

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013

  • Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid
  • Nature Materials, Vol. 12, Issue 5
  • DOI: 10.1038/nmat3602

Unperturbed dimensions of poly(ethylene oxide)
journal, March 1969


The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces
journal, January 2005

  • Monroe, Charles; Newman, John
  • Journal of The Electrochemical Society, Vol. 152, Issue 2
  • DOI: 10.1149/1.1850854

Mobility of Nonsticky Nanoparticles in Polymer Liquids
journal, October 2011

  • Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael
  • Macromolecules, Vol. 44, Issue 19
  • DOI: 10.1021/ma201583q

Rheo-XPCS
journal, August 2015

  • Leheny, Robert L.; Rogers, Michael C.; Chen, Kui
  • Current Opinion in Colloid & Interface Science, Vol. 20, Issue 4
  • DOI: 10.1016/j.cocis.2015.10.001

Enhanced Hole Mobility in Regioregular Polythiophene Infiltrated in Straight Nanopores
journal, December 2005

  • Coakley, K. M.; Srinivasan, B. S.; Ziebarth, J. M.
  • Advanced Functional Materials, Vol. 15, Issue 12
  • DOI: 10.1002/adfm.200500364

Melt viscosity and thermal properties of poly(ethylene oxide) fractions and blends
journal, July 1978


Confinement-Driven Increase in Ionomer Thin-Film Modulus
journal, April 2014

  • Page, Kirt A.; Kusoglu, Ahmet; Stafford, Christopher M.
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl501233g

Thin Film Rheology and Tribology of Confined Polymer Melts:  Contrasts with Bulk Properties
journal, April 1997

  • Luengo, Gustavo; Schmitt, Franz-Josef; Hill, Robert
  • Macromolecules, Vol. 30, Issue 8
  • DOI: 10.1021/ma9519122

Influence of Substrate Confinement on the Phase-Correlation in the Capillary Breakup of Arrays of Patterned Polymer Stripes
journal, February 2013

  • Zhang, Zheng; Wang, Liang; Ding, Yifu
  • Langmuir, Vol. 29, Issue 9
  • DOI: 10.1021/la304528t

Capillary Wave Dynamics of Thin Polymer Films over Submerged Nanostructures
journal, November 2012


Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures
journal, April 2015


Solvent Retention in Thin Spin-Coated Polystyrene and Poly(methyl methacrylate) Homopolymer Films Studied By Neutron Reflectometry
journal, January 2010

  • Zhang, Xiaohua; Yager, Kevin G.; Kang, Shuhui
  • Macromolecules, Vol. 43, Issue 2
  • DOI: 10.1021/ma902168w

X Ray Photon Correlation Spectroscopy for the study of polymer dynamics
journal, August 2016


Nanorheology of Confined Polymer Melts. 3. Weakly Adsorbing Surfaces
journal, October 1994

  • Peanasky, John; Cai, Lenore L.; Granick, Steve
  • Langmuir, Vol. 10, Issue 10
  • DOI: 10.1021/la00022a078

Nanorheology of Confined Polymer Melts. 1. Linear Shear Response at Strongly Adsorbing Surfaces
journal, October 1994


Molecular Mobility under Nanometer Scale Confinement
journal, May 2010

  • Kim, Taek-Soo; Dauskardt, Reinhold H.
  • Nano Letters, Vol. 10, Issue 5
  • DOI: 10.1021/nl101169s

Nanorheology of Confined Polymer Melts. 2. Nonlinear Shear Response at Strongly Adsorbing Surfaces
journal, October 1994

  • Granick, Steve; Hu, Hsuan-Wei; Carson, George A.
  • Langmuir, Vol. 10, Issue 10
  • DOI: 10.1021/la00022a077

Confinement-Induced Ordering in Dewetting and Phase Separation of Polymer Blend Films
journal, April 2012


Sub-50-nm self-assembled nanotextures for enhanced broadband antireflection in silicon solar cells
journal, January 2015

  • Rahman, Atikur; Ashraf, Ahsan; Xin, Huolin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6963

Grazing-incidence transmission X-ray scattering: surface scattering in the Born approximation
journal, January 2013

  • Lu, Xinhui; Yager, Kevin G.; Johnston, Danvers
  • Journal of Applied Crystallography, Vol. 46, Issue 1
  • DOI: 10.1107/S0021889812047887

Enhanced mobility of confined polymers
journal, October 2007

  • Shin, Kyusoon; Obukhov, Sergei; Chen, Jiun-Tai
  • Nature Materials, Vol. 6, Issue 12
  • DOI: 10.1038/nmat2031

Hopping Diffusion of Nanoparticles in Polymer Matrices
journal, January 2015

  • Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma501608x

Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries
journal, May 2014

  • Khurana, Rachna; Schaefer, Jennifer L.; Archer, Lynden A.
  • Journal of the American Chemical Society, Vol. 136, Issue 20
  • DOI: 10.1021/ja502133j

Transfer patterning of large-area graphene nanomesh via holographic lithography and plasma etching
journal, November 2014

  • Ding, Junjun; Du, Ke; Wathuthanthri, Ishan
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 32, Issue 6
  • DOI: 10.1116/1.4895667

Structure and dynamics of polymers studied by X-ray, neutron, and muon techniques
journal, November 2016


Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering
journal, May 2005

  • Lee, Byeongdu; Park, Insun; Yoon, Jinhwan
  • Macromolecules, Vol. 38, Issue 10
  • DOI: 10.1021/ma047562d

Plasma etch transfer of self-assembled polymer patterns
journal, July 2012


Effect of Free Surfaces on the Glass Transition Temperature of Thin Polymer Films
journal, September 1996


Polymer Nanocomposites
journal, April 2007


Effects of nanostructure geometry on nanoimprinted polymer photovoltaics
journal, January 2014

  • Yang, Yi; Mielczarek, Kamil; Aryal, Mukti
  • Nanoscale, Vol. 6, Issue 13
  • DOI: 10.1039/C4NR01114G

X-Ray Photon Correlation Spectroscopy Study of Brownian Motion of Gold Colloids in Glycerol
journal, July 1995


Microrheology of polymeric solutions using x-ray photon correlation spectroscopy
journal, June 2005

  • Papagiannopoulos, A.; Waigh, T. A.; Fluerasu, A.
  • Journal of Physics: Condensed Matter, Vol. 17, Issue 25
  • DOI: 10.1088/0953-8984/17/25/L06

One-Volt Operation of High-Current Vertical Channel Polymer Semiconductor Field-Effect Transistors
journal, July 2012

  • Johnston, Danvers E.; Yager, Kevin G.; Nam, Chang-Yong
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301759j

Two degrees-of-freedom Lloyd–mirror interferometer for superior pattern coverage area
journal, January 2011

  • Wathuthanthri, Ishan; Mao, Weidong; Choi, Chang-Hwan
  • Optics Letters, Vol. 36, Issue 9
  • DOI: 10.1364/OL.36.001593

Rheology and Microstructure of Entangled Polymer Nanocomposite Melts
journal, November 2009

  • Anderson, Benjamin J.; Zukoski, Charles F.
  • Macromolecules, Vol. 42, Issue 21
  • DOI: 10.1021/ma9011158

Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries
journal, August 2015


Entanglement-Controlled Subdiffusion of Nanoparticles within Concentrated Polymer Solutions
journal, August 2012


Local Polymer Dynamics and Diffusion in Cylindrical Nanoconfinement
journal, March 2015


Nanoscopic Patterned Materials with Tunable Dimensions via Atomic Layer Deposition on Block Copolymers
journal, September 2010

  • Peng, Qing; Tseng, Yu-Chih; Darling, Seth B.
  • Advanced Materials, Vol. 22, Issue 45, p. 5129-5133
  • DOI: 10.1002/adma.201002465

Mobility of Nonsticky Nanoparticles in Polymer Liquids
text, January 2011

  • Sergey, Panyukov,; Michael, Rubinstein,; Li-Heng, Cai,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/9d2w-ss96

Effect of Free Surfaces on the Glass Transition Temperature of Thin Polymer Films
journal, November 1996


Entropic competition in polymeric systems under geometrical confinement
text, January 2014