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

Title: Nanoscale Critical Phenomena in a Complex Fluid Studied by X-ray Photon Correlation Spectroscopy.

Abstract

The advent of high-speed x-ray photon correlation spectroscopy now allows the study of critical phenomena in fluids to much smaller length scales and over a wider range of temperatures than is possible with dynamic light scattering. We present an x-ray photon correlation spectroscopy study of critical fluctuation dynamics in a complex fluid typical of those used in liquid-liquid extraction (LLE) of ions,dodecane-DMDBTDMA with extracted aqueous Ce(NO3)3. We observe good agreement with both staticand dynamic scaling without the need for significant noncritical background corrections. Critical exponents agree with 3D Ising values, and the fluctuation dynamics are described by simple exponential relaxation.The form of the dynamic master curve deviates somewhat from the Kawasaki result, with a more abrupt transition between the critical and noncritical asymptotic behavior. The concepts of critical phenomena thus provide a quantitative framework for understanding the structure and dynamics of LLE systems and a path forward to new LLE processes.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [1];  [3];  [4];  [4];  [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States) ; Univ. of Illinois, Chicago, IL (United States)
  4. AGH - Univ. of Science and Technology, Krakow (Poland)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1661857
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 125; Journal Issue: 12; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Critical exponents; Critical phenomena; Liquids; X-ray photon correlation spectroscopy

Citation Formats

Sheyfer, D., Zhang, Q., Lal, J., Loeffler, T., Dufresne, E. M., Sandy, A. R., Narayanan, S., Sankaranarayanan, S. K.R.S., Szczygiel, R., Maj, P., Soderholm, L., Antonio, M. R., and Stephenson, G. B. Nanoscale Critical Phenomena in a Complex Fluid Studied by X-ray Photon Correlation Spectroscopy.. United States: N. p., 2020. Web. doi:10.1103/PhysRevLett.125.125504.
Sheyfer, D., Zhang, Q., Lal, J., Loeffler, T., Dufresne, E. M., Sandy, A. R., Narayanan, S., Sankaranarayanan, S. K.R.S., Szczygiel, R., Maj, P., Soderholm, L., Antonio, M. R., & Stephenson, G. B. Nanoscale Critical Phenomena in a Complex Fluid Studied by X-ray Photon Correlation Spectroscopy.. United States. https://doi.org/10.1103/PhysRevLett.125.125504
Sheyfer, D., Zhang, Q., Lal, J., Loeffler, T., Dufresne, E. M., Sandy, A. R., Narayanan, S., Sankaranarayanan, S. K.R.S., Szczygiel, R., Maj, P., Soderholm, L., Antonio, M. R., and Stephenson, G. B. Fri . "Nanoscale Critical Phenomena in a Complex Fluid Studied by X-ray Photon Correlation Spectroscopy.". United States. https://doi.org/10.1103/PhysRevLett.125.125504. https://www.osti.gov/servlets/purl/1661857.
@article{osti_1661857,
title = {Nanoscale Critical Phenomena in a Complex Fluid Studied by X-ray Photon Correlation Spectroscopy.},
author = {Sheyfer, D. and Zhang, Q. and Lal, J. and Loeffler, T. and Dufresne, E. M. and Sandy, A. R. and Narayanan, S. and Sankaranarayanan, S. K.R.S. and Szczygiel, R. and Maj, P. and Soderholm, L. and Antonio, M. R. and Stephenson, G. B.},
abstractNote = {The advent of high-speed x-ray photon correlation spectroscopy now allows the study of critical phenomena in fluids to much smaller length scales and over a wider range of temperatures than is possible with dynamic light scattering. We present an x-ray photon correlation spectroscopy study of critical fluctuation dynamics in a complex fluid typical of those used in liquid-liquid extraction (LLE) of ions,dodecane-DMDBTDMA with extracted aqueous Ce(NO3)3. We observe good agreement with both staticand dynamic scaling without the need for significant noncritical background corrections. Critical exponents agree with 3D Ising values, and the fluctuation dynamics are described by simple exponential relaxation.The form of the dynamic master curve deviates somewhat from the Kawasaki result, with a more abrupt transition between the critical and noncritical asymptotic behavior. The concepts of critical phenomena thus provide a quantitative framework for understanding the structure and dynamics of LLE systems and a path forward to new LLE processes.},
doi = {10.1103/PhysRevLett.125.125504},
journal = {Physical Review Letters},
number = 12,
volume = 125,
place = {United States},
year = {Fri Sep 18 00:00:00 EDT 2020},
month = {Fri Sep 18 00:00:00 EDT 2020}
}

Works referenced in this record:

Critical‐point universality and fluids
journal, December 1977

  • Sengers, Anneke Levelt; Hocken, Robert; Sengers, Jan V.
  • Physics Today, Vol. 30, Issue 12
  • DOI: 10.1063/1.3037826

Recycling metals by controlled transfer of ionic species between complex fluids: en route to “ienaics”
journal, November 2014

  • Zemb, Thomas; Bauer, Caroline; Bauduin, Pierre
  • Colloid and Polymer Science, Vol. 293, Issue 1
  • DOI: 10.1007/s00396-014-3447-x

Decoupled-Mode Dynamical Scaling Theory of the Binary-Liquid Phase Transition
journal, May 1970


Seven chemical separations to change the world
journal, April 2016

  • Sholl, David S.; Lively, Ryan P.
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/532435a

Coordination Structures and Supramolecular Architectures in a Cerium(III)–Malonamide Solvent Extraction System
journal, March 2012

  • Ellis, Ross J.; Antonio, Mark R.
  • Langmuir, Vol. 28, Issue 14
  • DOI: 10.1021/la3002916

Salt-induced microheterogeneities in binary liquid mixtures
journal, August 2017


Dynamic Critical Phenomena in Aqueous Protein Solutions
journal, January 1995


Amphiphile-Based Complex Fluids: The Self-Assembly Ensemble as Protagonist
journal, December 2018


Reverse aggregate nucleation induced by acids in liquid–liquid extraction processes
journal, January 2014

  • Déjugnat, Christophe; Dourdain, Sandrine; Dubois, Véronique
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 16
  • DOI: 10.1039/c4cp00073k

Concentration fluctuations in the binary mixture hexane-nitrobenzene with static and dynamic x-ray scattering
journal, June 2002


Universality of critical phenomena in complex fluids
journal, March 1994

  • Chen, S. H.; Rouch, J.; Tartaglia, P.
  • Physica A: Statistical Mechanics and its Applications, Vol. 204, Issue 1-4
  • DOI: 10.1016/0378-4371(94)90422-7

Observation of 3D-Ising exponents in micellar solutions
journal, May 1988


Static and dynamic properties of water-in-oil microemulsions near the critical and percolation points
journal, December 1994


Static and dynamic light scattering studies of water‐in‐oil microemulsions in the critical region. Evidence of a crossover effect
journal, April 1989

  • Rouch, J.; Safouane, A.; Tartaglia, P.
  • The Journal of Chemical Physics, Vol. 90, Issue 7
  • DOI: 10.1063/1.455834

Scaling behaviour of concentration fluctuations in a ternary liquid mixture: a dynamic light-scattering study
journal, November 1990


Hard X-Ray Photon Correlation Spectroscopy Methods for Materials Studies
journal, July 2018


Combined supramolecular and mesoscale modelling of liquid–liquid extraction of rare earth salts
journal, October 2018

  • Karmakar, Anwesa; Duvail, Magali; Bley, Michael
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 555
  • DOI: 10.1016/j.colsurfa.2018.07.013

XPCS: Nanoscale motion and rheology
journal, February 2012


Self-assembling properties of malonamide extractants used in separation processes
journal, January 2008

  • Testard, Fabienne; Bauduin, Pierre; Martinet, L.
  • Radiochimica Acta, Vol. 96, Issue 4-5
  • DOI: 10.1524/ract.2008.1487

Static and dynamic light-scattering study of a critical ternary mixture: Renormalization of the critical exponents
journal, June 1988


Structure and Nanostructure in Ionic Liquids
journal, June 2015

  • Hayes, Robert; Warr, Gregory G.; Atkin, Rob
  • Chemical Reviews, Vol. 115, Issue 13
  • DOI: 10.1021/cr500411q

Kinetic equations and time correlation functions of critical fluctuations
journal, November 1970


Crossover from mean field to three-dimensional Ising critical behavior in a three-component microemulsion system
journal, July 1996


Decay rate of critical concentration fluctuations in a binary liquid
journal, January 1982


Theory of dynamic critical phenomena
journal, July 1977


Small-Angle X-ray Scattering Using Coherent Undulator Radiation at the ESRF
journal, January 1998


Dynamics of Fluids near the Critical Point: Decay Rate of Order-Parameter Fluctuations
journal, November 1973


Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions
journal, February 2018


Dynamic scaling function for critical fluctuations in classical fluids
journal, September 1983

  • Burstyn, H. C.; Sengers, J. V.; Bhattacharjee, J. K.
  • Physical Review A, Vol. 28, Issue 3
  • DOI: 10.1103/PhysRevA.28.1567

Relaxation rate and scaling function of the critical system 3-methylpentane-nitroethane-cyclohexane
journal, August 2008

  • Iwanowski, I.; Mirzaev, S. Z.; Kaatze, U.
  • The Journal of Chemical Physics, Vol. 129, Issue 6
  • DOI: 10.1063/1.2965521

Attractive Interactions between Reverse Aggregates and Phase Separation in Concentrated Malonamide Extractant Solutions
journal, March 1999

  • Erlinger, C.; Belloni, L.; Zemb, Th.
  • Langmuir, Vol. 15, Issue 7
  • DOI: 10.1021/la980313w

Noise on photon correlation data. I. Autocorrelation functions
journal, August 1990

  • Schatzel, K.
  • Quantum Optics: Journal of the European Optical Society Part B, Vol. 2, Issue 4
  • DOI: 10.1088/0954-8998/2/4/002

A Telescoping View of Solute Architectures in a Complex Fluid System
journal, December 2018


Experimental evidence of nonexponential relaxation near the critical point of a supramolecular liquid mixture
journal, September 1993


Liquid/liquid metal extraction: Phase diagram topology resulting from molecular interactions between extractant, ion, oil and water
journal, November 2012

  • Bauer, C.; Bauduin, P.; Dufrêche, J. F.
  • The European Physical Journal Special Topics, Vol. 213, Issue 1
  • DOI: 10.1140/epjst/e2012-01673-4

Reexamination of the static and dynamic critical phenomena in water-amphiphile micellar solutions
journal, August 1989


Critical Exponents for Solvent Extraction Resolved Using SAXS
journal, December 2013

  • Ellis, Ross J.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 1
  • DOI: 10.1021/jp408078v

Double-exponential relaxation near the critical point of an ionic micellar system
journal, November 1996


Distributed X-ray photon correlation spectroscopy data reduction using Hadoop MapReduce
journal, June 2018

  • Khan, Faisal; Narayanan, Suresh; Sersted, Roger
  • Journal of Synchrotron Radiation, Vol. 25, Issue 4
  • DOI: 10.1107/S160057751800601X

Critical dynamics of supramolecular mixtures. Application to microemulsion systems and to nonionic amphiphile-water micellar solutions
journal, September 1996

  • Hamano, K.; Ducros, E.; Louisor, E.
  • Physica A: Statistical Mechanics and its Applications, Vol. 231, Issue 1-3
  • DOI: 10.1016/0378-4371(96)00084-2

Experimental Critical-Exponent Values for Fluids
journal, October 2009


Critical fluctuations of the micellar triethylene glycol monoheptyl ether-water system
journal, March 2006

  • Haller, J.; Behrends, R.; Kaatze, U.
  • The Journal of Chemical Physics, Vol. 124, Issue 12
  • DOI: 10.1063/1.2179424

Dynamic critical phenomena in water-butoxyethanol mixtures studied by viscosity and light-scattering measurements
journal, February 1994


Low Dose X-Ray Speckle Visibility Spectroscopy Reveals Nanoscale Dynamics in Radiation Sensitive Ionic Liquids
journal, April 2018