skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants

Abstract

Bicontinuous jammed emulsions (or bijels) are tortuous, interconnected structures of two immiscible liquids, kinetically trapped by colloidal particles that are irreversibly bound to the oil-water interface. A wealth of applications has been proposed for bijels in catalysis, energy storage and molecular encapsulation, but large domain sizes (on the order of 5 μm or larger) and difficulty in fabrication pose major barriers to their use. Here, we show that bijels with sub-micrometre domains can be formed via homogenization, rather than spinodal decomposition. We achieve this by using nanoparticle surfactants: polymers and nanoparticles of complementary functionality (for example, ion-pairing) that bind to one another at the oil-water interface. This allows the stabilization of the bijel far from the demixing point of the liquids, with interfacial tensions on the order of 20 mN m-1. Furthermore, our strategy is extremely versatile, as solvent, nanoparticle and ligand can all be varied.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [6]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of Massachusetts, Amherst, MA (United States). Polymer Science and Engineering Dept.; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Science Directorate
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Science Directorate
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. The Molecular Foundry
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of Massachusetts, Amherst, MA (United States). Polymer Science and Engineering Dept.; Beijing Univ. of Chemical Technology (China). Beijing Advanced Innovation Center for Soft Matter Science and Engineering; Tohoku Univ., Sendai (Japan). WPI-Advanced Inst. for Materials Research (WPI-AIMR)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1423059
Alternate Identifier(s):
OSTI ID: 1468343
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 12; Journal Issue: 11; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; composites; materials for energy and catalysis; nanoparticles; other nanotechnology

Citation Formats

Huang, Caili, Forth, Joe, Wang, Weiyu, Hong, Kunlun, Smith, Gregory S., Helms, Brett A., and Russell, Thomas P.. Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants. United States: N. p., 2017. Web. https://doi.org/10.1038/NNANO.2017.182.
Huang, Caili, Forth, Joe, Wang, Weiyu, Hong, Kunlun, Smith, Gregory S., Helms, Brett A., & Russell, Thomas P.. Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants. United States. https://doi.org/10.1038/NNANO.2017.182
Huang, Caili, Forth, Joe, Wang, Weiyu, Hong, Kunlun, Smith, Gregory S., Helms, Brett A., and Russell, Thomas P.. Mon . "Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants". United States. https://doi.org/10.1038/NNANO.2017.182. https://www.osti.gov/servlets/purl/1423059.
@article{osti_1423059,
title = {Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants},
author = {Huang, Caili and Forth, Joe and Wang, Weiyu and Hong, Kunlun and Smith, Gregory S. and Helms, Brett A. and Russell, Thomas P.},
abstractNote = {Bicontinuous jammed emulsions (or bijels) are tortuous, interconnected structures of two immiscible liquids, kinetically trapped by colloidal particles that are irreversibly bound to the oil-water interface. A wealth of applications has been proposed for bijels in catalysis, energy storage and molecular encapsulation, but large domain sizes (on the order of 5 μm or larger) and difficulty in fabrication pose major barriers to their use. Here, we show that bijels with sub-micrometre domains can be formed via homogenization, rather than spinodal decomposition. We achieve this by using nanoparticle surfactants: polymers and nanoparticles of complementary functionality (for example, ion-pairing) that bind to one another at the oil-water interface. This allows the stabilization of the bijel far from the demixing point of the liquids, with interfacial tensions on the order of 20 mN m-1. Furthermore, our strategy is extremely versatile, as solvent, nanoparticle and ligand can all be varied.},
doi = {10.1038/NNANO.2017.182},
journal = {Nature Nanotechnology},
number = 11,
volume = 12,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Comparison of solid particles, globular proteins and surfactants as emulsifiers
journal, January 2008

  • Tcholakova, S.; Denkov, N. D.; Lips, A.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 12
  • DOI: 10.1039/b715933c

Making a Robust Interfacial Scaffold: Bijel Rheology and its Link to Processability
journal, September 2012

  • Lee, Matthew N.; Thijssen, Job H. J.; Witt, Jessica A.
  • Advanced Functional Materials, Vol. 23, Issue 4
  • DOI: 10.1002/adfm.201201090

Assembly of Acid-Functionalized Single-Walled Carbon Nanotubes at Oil/Water Interfaces
journal, September 2013

  • Feng, Tao; Hoagland, David A.; Russell, Thomas P.
  • Langmuir, Vol. 30, Issue 4
  • DOI: 10.1021/la404543s

Structured Liquids with pH-Triggered Reconfigurability
journal, May 2016


From bijels to Pickering emulsions: A lattice Boltzmann study
journal, April 2011


Novel, Robust, and Versatile Bijels of Nitromethane, Ethanediol, and Colloidal Silica: Capsules, Sub-Ten-Micrometer Domains, and Mechanical Properties
journal, May 2011

  • Tavacoli, Joe W.; Thijssen, Job H. J.; Schofield, Andrew B.
  • Advanced Functional Materials, Vol. 21, Issue 11
  • DOI: 10.1002/adfm.201002562

Compressing a spinodal surface at fixed area: bijels in a centrifuge
journal, January 2016

  • Rumble, Katherine A.; Thijssen, Job H. J.; Schofield, Andrew B.
  • Soft Matter, Vol. 12, Issue 19
  • DOI: 10.1039/C6SM00168H

Emulsification of Partially Miscible Liquids Using Colloidal Particles:  Nonspherical and Extended Domain Structures
journal, May 2007

  • Clegg, Paul S.; Herzig, Eva M.; Schofield, Andrew B.
  • Langmuir, Vol. 23, Issue 11
  • DOI: 10.1021/la063707t

Bijels formed by direct mixing
journal, January 2017

  • Cai, Dongyu; Clegg, Paul S.; Li, Tao
  • Soft Matter, Vol. 13, Issue 28
  • DOI: 10.1039/C7SM00897J

Nanoparticle Adsorption at Liquid–Vapor Surfaces: Influence of Nanoparticle Thermodynamics, Wettability, and Line Tension
journal, August 2011

  • Wi, Haeng Sub; Cingarapu, Sreeram; Klabunde, Ken J.
  • Langmuir, Vol. 27, Issue 16
  • DOI: 10.1021/la201791g

Stabilizing bijels using a mixture of fumed silica nanoparticles
journal, January 2015

  • Cai, Dongyu; Clegg, Paul S.
  • Chemical Communications, Vol. 51, Issue 95
  • DOI: 10.1039/C5CC07346D

Bicontinuous emulsions stabilized solely by colloidal particles
journal, November 2007

  • Herzig, E. M.; White, K. A.; Schofield, A. B.
  • Nature Materials, Vol. 6, Issue 12, p. 966-971
  • DOI: 10.1038/nmat2055

Particle-size effects in the formation of bicontinuous Pickering emulsions
journal, September 2015


Stabilizing Liquid Drops in Nonequilibrium Shapes by the Interfacial Jamming of Nanoparticles
journal, October 2013


Using a Molecular Stopwatch to Study Particle Uptake in Pickering Emulsions
journal, June 2016


Bicontinuous Macroporous Materials from Bijel Templates
journal, September 2010


Experimental techniques in high-vacuum anionic polymerization
journal, January 2005

  • Uhrig, David; Mays, Jimmy W.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 24
  • DOI: 10.1002/pola.21016

Assembly of Graphene Oxide at Water/Oil Interfaces: Tessellated Nanotiles
journal, October 2013

  • Sun, Zhiwei; Feng, Tao; Russell, Thomas P.
  • Langmuir, Vol. 29, Issue 44
  • DOI: 10.1021/la402436w

Pickering Emulsions Stabilized by Monodisperse Latex Particles:  Effects of Particle Size
journal, July 2001


A high-level 3D visualization API for Java and ImageJ
journal, May 2010

  • Schmid, Benjamin; Schindelin, Johannes; Cardona, Albert
  • BMC Bioinformatics, Vol. 11, Issue 1
  • DOI: 10.1186/1471-2105-11-274

Self-Regulated Nanoparticle Assembly at Liquid/Liquid Interfaces: A Route to Adaptive Structuring of Liquids
journal, August 2017


Some general features of limited coalescence in solid-stabilized emulsions
journal, July 2003


Continuous Fabrication of Hierarchical and Asymmetric Bijel Microparticles, Fibers, and Membranes by Solvent Transfer-Induced Phase Separation (STRIPS)
journal, October 2015

  • Haase, Martin F.; Stebe, Kathleen J.; Lee, Daeyeon
  • Advanced Materials, Vol. 27, Issue 44
  • DOI: 10.1002/adma.201503509

In Situ Mechanical Testing of Nanostructured Bijel Fibers
journal, May 2016


Bijels stabilized using rod-like particles
journal, January 2015

  • Hijnen, Niek; Cai, Dongyu; Clegg, Paul S.
  • Soft Matter, Vol. 11, Issue 22
  • DOI: 10.1039/C5SM00265F

Quantitative morphological characterization of bicontinuous Pickering emulsions via interfacial curvatures
journal, January 2016

  • Reeves, Matthew; Stratford, Kevin; Thijssen, Job H. J.
  • Soft Matter, Vol. 12, Issue 18
  • DOI: 10.1039/C5SM03102H

High Temperature Thermoplastic Elastomers Synthesized by Living Anionic Polymerization in Hydrocarbon Solvent at Room Temperature
journal, March 2016


On the Thermodynamics of Particle-Stabilized Emulsions:  Curvature Effects and Catastrophic Phase Inversion
journal, January 2005

  • Kralchevsky, P. A.; Ivanov, I. B.; Ananthapadmanabhan, K. P.
  • Langmuir, Vol. 21, Issue 1
  • DOI: 10.1021/la047793d

Colloidal Jamming at Interfaces: A Route to Fluid-Bicontinuous Gels
journal, September 2005

  • Stratford, K.; Adhikari, R.; Pagonabarraga, I.
  • Science, Vol. 309, Issue 5744, p. 2198-2201
  • DOI: 10.1126/science.1116589

Bijels: a new class of soft materials
journal, January 2008

  • Cates, Michael E.; Clegg, Paul S.
  • Soft Matter, Vol. 4, Issue 11, p. 2132-2138
  • DOI: 10.1039/b807312k

A high-level 3D visualization API for Java and ImageJ
text, January 2010


    Works referencing / citing this record:

    Nanoparticle Assembly at Liquid-Liquid Interfaces: From the Nanoscale to Mesoscale
    journal, July 2018


    Building Reconfigurable Devices Using Complex Liquid–Fluid Interfaces
    journal, February 2019


    Surfactant Assembly within Pickering Emulsion Droplets for Fabrication of Interior-Structured Mesoporous Carbon Microspheres
    journal, July 2018


    Adaptive Structured Pickering Emulsions and Porous Materials Based on Cellulose Nanocrystal Surfactants
    journal, September 2018


    Interfacial Activity of Amine‐Functionalized Polyhedral Oligomeric Silsesquioxanes (POSS): A Simple Strategy To Structure Liquids
    journal, June 2019


    Self‐Assembly of MXene‐Surfactants at Liquid–Liquid Interfaces: From Structured Liquids to 3D Aerogels
    journal, October 2019


    Surfactant Assembly within Pickering Emulsion Droplets for Fabrication of Interior-Structured Mesoporous Carbon Microspheres
    journal, July 2018

    • Liu, Dawei; Xue, Nan; Wei, Lijuan
    • Angewandte Chemie International Edition, Vol. 57, Issue 34
    • DOI: 10.1002/anie.201805022

    Electrostatic-Driven Dynamic Jamming of 2D Nanoparticles at Interfaces for Controlled Molecular Diffusion
    journal, August 2018

    • Luo, Jianhui; Zeng, Minxiang; Peng, Baoliang
    • Angewandte Chemie International Edition, Vol. 57, Issue 36
    • DOI: 10.1002/anie.201807372

    Adaptive Structured Pickering Emulsions and Porous Materials Based on Cellulose Nanocrystal Surfactants
    journal, September 2018

    • Li, Yanan; Liu, Xubo; Zhang, Zhen
    • Angewandte Chemie International Edition, Vol. 57, Issue 41
    • DOI: 10.1002/anie.201808888

    Interfacial Activity of Amine-Functionalized Polyhedral Oligomeric Silsesquioxanes (POSS): A Simple Strategy To Structure Liquids
    journal, June 2019

    • Hou, Honghao; Li, Jin; Li, Xiangming
    • Angewandte Chemie International Edition, Vol. 58, Issue 30
    • DOI: 10.1002/anie.201903420

    Stabilizing Liquids Using Interfacial Supramolecular Polymerization
    journal, August 2019

    • Gu, Pei‐Yang; Chai, Yu; Hou, Honghao
    • Angewandte Chemie International Edition, Vol. 58, Issue 35
    • DOI: 10.1002/anie.201906339

    Self‐Assembly of MXene‐Surfactants at Liquid–Liquid Interfaces: From Structured Liquids to 3D Aerogels
    journal, December 2019

    • Shi, Shaowei; Qian, Bingqing; Wu, Xinyu
    • Angewandte Chemie International Edition, Vol. 58, Issue 50
    • DOI: 10.1002/anie.201908402

    Self‐Assembly of Nanoparticles in 2D and 3D: Recent Advances and Future Trends
    journal, August 2019

    • Ghosh, Sujit Kumar; Böker, Alexander
    • Macromolecular Chemistry and Physics, Vol. 220, Issue 17
    • DOI: 10.1002/macp.201900196

    Harnessing liquid-in-liquid printing and micropatterned substrates to fabricate 3-dimensional all-liquid fluidic devices
    journal, March 2019


    Advanced emulsions via noncovalent interaction-mediated interfacial self-assembly
    journal, January 2018

    • Han, Songling; An, Huijie; Tao, Hui
    • Chemical Communications, Vol. 54, Issue 25
    • DOI: 10.1039/c8cc00016f

    Tuning thin-film bijels with applied external electric fields
    journal, January 2018

    • Carmack, Joseph M.; Millett, Paul C.
    • Soft Matter, Vol. 14, Issue 21
    • DOI: 10.1039/c8sm00638e

    Curvature dynamics and long-range effects on fluid–fluid interfaces with colloids
    journal, January 2019

    • Tiribocchi, A.; Bonaccorso, F.; Lauricella, M.
    • Soft Matter, Vol. 15, Issue 13
    • DOI: 10.1039/c8sm02396d

    Bi-continuous emulsion using Janus particles
    journal, January 2019

    • Sun, Dayin; Si, Yan; Song, Xi-Ming
    • Chemical Communications, Vol. 55, Issue 32
    • DOI: 10.1039/c9cc01191a

    Emerging aqueous two-phase systems: from fundamentals of interfaces to biomedical applications
    journal, January 2020

    • Chao, Youchuang; Shum, Ho Cheung
    • Chemical Society Reviews, Vol. 49, Issue 1
    • DOI: 10.1039/c9cs00466a

    Designing bijels formed by solvent transfer induced phase separation with functional nanoparticles
    journal, January 2019

    • Boakye-Ansah, Stephen; Schwenger, Matthew S.; Haase, Martin F.
    • Soft Matter, Vol. 15, Issue 16
    • DOI: 10.1039/c9sm00289h

    Charge-driven interfacial gelation of cellulose nanofibrils across the water/oil interface
    journal, January 2020

    • Calabrese, Vincenzo; da Silva, Marcelo A.; Schmitt, Julien
    • Soft Matter, Vol. 16, Issue 2
    • DOI: 10.1039/c9sm01551e

    Rapid Stabilization of Immiscible Fluids using Nanostructured Interfaces via Surfactant Association
    journal, May 2019


    Electrostatic-Driven Dynamic Jamming of 2D Nanoparticles at Interfaces for Controlled Molecular Diffusion
    journal, August 2018

    • Luo, Jianhui; Zeng, Minxiang; Peng, Baoliang
    • Angewandte Chemie, Vol. 130, Issue 36
    • DOI: 10.1002/ange.201807372