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

This content will become publicly available on June 14, 2020

Title: Elasticity and yielding of mesophases of block copolymers in water–oil mixtures

Abstract

Here, amphiphilic block copolymers self-assemble at the water/oil interface to form different mesomorphic structures, such as lamellar, micellar cubic, normal hexagonal, and reverse hexagonal structures. Usually, these structures are polycrystalline and the value of their elastic modulus depends on the average orientation of their constituent's single crystals. We introduce a model to predict the elastic modulus and yielding of mesophases from their characteristic length and intermicellar interactions. Shear modulus of each structure is measured as a function of deformation (strain). Zero-shear modulus, G 0, depends on the inverse of the intermicellar distance with a power law model. The power law index for each structure is approximately n + 2 where n is the degree of confinement in the mesophase: 1 for lamellar, 2 for both normal and reverse hexagonal, and 3 for micellar cubic structures. Rheological properties of different mesophases of Pluronic P84 in the presence of water and p-xylene are used as a case study. The model is found to be in good agreement with experimental data in the linear viscoelastic region. When compared to experimental data, the yield strain value obtained from the model is one order of magnitude higher than the limit of the linear viscoelastic regimemore » and close to the strain at the cross-over point of storage and loss moduli. Frequency sweep measurements are done to characterize the relaxation and cooperative model behaviors of each mesophase structure.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. New Mexico State Univ., Las Cruces, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1544743
Alternate Identifier(s):
OSTI ID: 1529680
Report Number(s):
LA-UR-19-23927
Journal ID: ISSN 1744-683X; SMOABF
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Soft Matter
Additional Journal Information:
Journal Volume: 15; Journal Issue: 28; Journal ID: ISSN 1744-683X
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Qavi, Sahar, Firestone, Millicent A., and Foudazi, Reza. Elasticity and yielding of mesophases of block copolymers in water–oil mixtures. United States: N. p., 2019. Web. doi:10.1039/C8SM02336K.
Qavi, Sahar, Firestone, Millicent A., & Foudazi, Reza. Elasticity and yielding of mesophases of block copolymers in water–oil mixtures. United States. doi:10.1039/C8SM02336K.
Qavi, Sahar, Firestone, Millicent A., and Foudazi, Reza. Fri . "Elasticity and yielding of mesophases of block copolymers in water–oil mixtures". United States. doi:10.1039/C8SM02336K.
@article{osti_1544743,
title = {Elasticity and yielding of mesophases of block copolymers in water–oil mixtures},
author = {Qavi, Sahar and Firestone, Millicent A. and Foudazi, Reza},
abstractNote = {Here, amphiphilic block copolymers self-assemble at the water/oil interface to form different mesomorphic structures, such as lamellar, micellar cubic, normal hexagonal, and reverse hexagonal structures. Usually, these structures are polycrystalline and the value of their elastic modulus depends on the average orientation of their constituent's single crystals. We introduce a model to predict the elastic modulus and yielding of mesophases from their characteristic length and intermicellar interactions. Shear modulus of each structure is measured as a function of deformation (strain). Zero-shear modulus, G0, depends on the inverse of the intermicellar distance with a power law model. The power law index for each structure is approximately n + 2 where n is the degree of confinement in the mesophase: 1 for lamellar, 2 for both normal and reverse hexagonal, and 3 for micellar cubic structures. Rheological properties of different mesophases of Pluronic P84 in the presence of water and p-xylene are used as a case study. The model is found to be in good agreement with experimental data in the linear viscoelastic region. When compared to experimental data, the yield strain value obtained from the model is one order of magnitude higher than the limit of the linear viscoelastic regime and close to the strain at the cross-over point of storage and loss moduli. Frequency sweep measurements are done to characterize the relaxation and cooperative model behaviors of each mesophase structure.},
doi = {10.1039/C8SM02336K},
journal = {Soft Matter},
number = 28,
volume = 15,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 14, 2020
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Advances and challenges in smart and functional polymer vesicles
journal, January 2009

  • Du, Jianzhong; O'Reilly, Rachel K.
  • Soft Matter, Vol. 5, Issue 19
  • DOI: 10.1039/b905635a

Self-assembly in the synthesis of ceramic materials and composites
journal, December 1996


Self-Assembly of Amphiphilic Block Copolymers: The (EO)13(PO)30(EO)13-Water-p-Xylene System
journal, November 1995

  • Alexandridis, Paschalis; Olsson, Ulf; Lindman, Bjoern
  • Macromolecules, Vol. 28, Issue 23
  • DOI: 10.1021/ma00127a016

Physicochemical aspects of drug delivery and release from polymer-based colloids
journal, March 2000


Molecularly Imprinted Microrods via Mesophase Polymerization
journal, December 2017


Thermoresponsive self-assembled polymer colloids in water
journal, January 2013


Cross-Linking of Reactive Lyotropic Liquid Crystals for Nanostructure Retention
journal, March 2009

  • Sievens-Figueroa, Lucas; Guymon, C. Allan
  • Chemistry of Materials, Vol. 21, Issue 6
  • DOI: 10.1021/cm803383d

Photopolymerization in Pluronic Lyotropic Liquid Crystals:  Induced Mesophase Thermal Stability
journal, August 2003

  • McCormick, Demetrius T.; Stovall, Kalena D.; Guymon, C. Allan
  • Macromolecules, Vol. 36, Issue 17
  • DOI: 10.1021/ma030037e

Influence of Polymerization Conditions on Nanostructure and Properties of Polyacrylamide Hydrogels Templated from Lyotropic Liquid Crystals
journal, November 2006

  • DePierro, Michael A.; Carpenter, Kyle G.; Guymon, C. Allan
  • Chemistry of Materials, Vol. 18, Issue 23
  • DOI: 10.1021/cm061969a

New Type of Membrane Material for Water Desalination Based on a Cross-Linked Bicontinuous Cubic Lyotropic Liquid Crystal Assembly
journal, August 2007

  • Zhou, Meijuan; Nemade, Parag R.; Lu, Xiaoyun
  • Journal of the American Chemical Society, Vol. 129, Issue 31
  • DOI: 10.1021/ja073067w

Scalable Fabrication of Polymer Membranes with Vertically Aligned 1 nm Pores by Magnetic Field Directed Self-Assembly
journal, November 2014

  • Feng, Xunda; Tousley, Marissa E.; Cowan, Matthew G.
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505037b

Polymerization of and within self-organized media
journal, June 2003


Ultrafiltration membranes from polymerization of self-assembled Pluronic block copolymer mesophases
journal, June 2019


X-ray Structural Modeling and Gas Adsorption Analysis of Cagelike SBA-16 Silica Mesophases Prepared in a F127/Butanol/H 2 O System
journal, October 2006

  • Kleitz, Freddy; Czuryszkiewicz, Teresa; Solovyov, Leonid A.
  • Chemistry of Materials, Vol. 18, Issue 21
  • DOI: 10.1021/cm061534n

Linear Viscoelasticity of Disordered Polystyrene−Polyisoprene Block Copolymer Based Layered-Silicate Nanocomposites
journal, May 2000

  • Ren, Jiaxiang; Silva, Adriana S.; Krishnamoorti, Ramanan
  • Macromolecules, Vol. 33, Issue 10
  • DOI: 10.1021/ma992091u

Viscoelastic behavior of cubic phases in block copolymer melts
journal, January 1999

  • Kossuth, M. B.; Morse, D. C.; Bates, F. S.
  • Journal of Rheology, Vol. 43, Issue 1
  • DOI: 10.1122/1.550981

Wormlike reverse micelles
journal, January 2013


Structure and Rheology of Wormlike Micelles Formed by Fluorocarbon–Hydrocarbon-Type Hybrid Gemini Surfactant in Aqueous Solution
journal, June 2017


Rheological Properties of the L Phase and the Hexagonal, Lamellar, and Cubic Liquid Crystals of the CTAB/Benzyl Alcohol/Water System
journal, January 1996

  • Montalvo, Gemma; Valiente, Mercedes; Rodenas, Elvira
  • Langmuir, Vol. 12, Issue 21
  • DOI: 10.1021/la9515682

Structural changes in CTAB/H2O mixtures using a rheological approach
journal, January 2004

  • Coppola, Luigi; Gianferri, Raffaella; Nicotera, Isabella
  • Physical Chemistry Chemical Physics, Vol. 6, Issue 9
  • DOI: 10.1039/b316621j

Concentration, salt and temperature dependence of strain hardening of step shear in CTAB/NaSal surfactant solutions
journal, September 2017

  • Adams, Abdulrazaq A.; Solomon, Michael J.; Larson, Ronald G.
  • Journal of Rheology, Vol. 61, Issue 5
  • DOI: 10.1122/1.4996008

Rheological analysis of core-stabilized Pluronic F127 by semi-interpenetrating network (sIPN) in aqueous solution
journal, January 2018

  • Li, Xiaolei; Park, Eun-kyoung; Hyun, Kyu
  • Journal of Rheology, Vol. 62, Issue 1
  • DOI: 10.1122/1.5009202

The effect of shear on ordered block copolymer solutions
journal, November 2000


Shear effects on solvated block copolymer lamellae: Polystyrene-polyisoprene in dioctyl phthalate
journal, January 1994


Influence of Shear on Solvated Amphiphilic Block Copolymers with Lamellar Morphology
journal, May 2002

  • Zipfel, Johannes; Berghausen, Jörg; Schmidt, Gudrun
  • Macromolecules, Vol. 35, Issue 10
  • DOI: 10.1021/ma0116912

Shear induced structures in lamellar phases of amphiphilic block copolymers
journal, January 1999

  • Zipfel, Johannes; Berghausen, Jörg; Schmidt, Gudrun
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 17
  • DOI: 10.1039/a904014e

Non-linear viscoelastic properties of ordered phases of a poly(ethylene oxide)-poly(propylene oxide) triblock copolymer
journal, June 2008


Local elastic constants in thin films of an fcc crystal
journal, March 2003


Measuring liquid crystal elastic constants with free energy perturbations
journal, January 2014

  • Joshi, Abhijeet A.; Whitmer, Jonathan K.; Guzmán, Orlando
  • Soft Matter, Vol. 10, Issue 6
  • DOI: 10.1039/C3SM51919H

Averaging of elastic constants for polycrystals
journal, October 2017

  • Blaschke, Daniel N.
  • Journal of Applied Physics, Vol. 122, Issue 14
  • DOI: 10.1063/1.4993443

Relation between Third‐Order Elastic Constants of Single Crystals and Polycrystals
journal, July 1968


The relation between single crystal elasticity and the effective elastic behaviour of polycrystalline materials: theory, measurement and computation
journal, November 1999

  • Toonder, J. M. J. den; Dommelen, J. A. W. van; Baaijens, F. P. T.
  • Modelling and Simulation in Materials Science and Engineering, Vol. 7, Issue 6
  • DOI: 10.1088/0965-0393/7/6/301

Phase Behavior and Rheological Analysis of Reverse Liquid Crystals and W/I 2 and W/H 2 Gel Emulsions Using an Amphiphilic Block Copolymer
journal, March 2011

  • May, Anna; Aramaki, Kenji; Gutiérrez, José María
  • Langmuir, Vol. 27, Issue 6
  • DOI: 10.1021/la104539q

Shear Rheology of Lyotropic Liquid Crystals: A Case Study
journal, April 2005

  • Mezzenga, Raffaele; Meyer, Cedric; Servais, Colin
  • Langmuir, Vol. 21, Issue 8
  • DOI: 10.1021/la046964b

Investigating reversed liquid crystalline mesophases
journal, October 2006

  • Sagalowicz, Laurent; Mezzenga, Raffaele; Leser, Martin E.
  • Current Opinion in Colloid & Interface Science, Vol. 11, Issue 4
  • DOI: 10.1016/j.cocis.2006.07.002

Ueber die Beziehung zwischen den beiden Elasticitätsconstanten isotroper Körper
journal, January 1889


Computer simulations of bilayer membranes: Self-assembly and interfacial tension
journal, May 1998

  • Goetz, Rüdiger; Lipowsky, Reinhard
  • The Journal of Chemical Physics, Vol. 108, Issue 17
  • DOI: 10.1063/1.476160

Tube Renewal versus Reptation: Polymer Diffusion in Molten Poly(Propylene Oxide)
journal, January 1984


Crystallization of polyethylene oxide under shear
journal, June 1974

  • Fritzsche, A. K.; Price, F. P.
  • Polymer Engineering and Science, Vol. 14, Issue 6
  • DOI: 10.1002/pen.760140602

The Reflection of X-rays by Crystals
journal, July 1913

  • Bragg, W. H.; Bragg, W. L.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 88, Issue 605
  • DOI: 10.1098/rspa.1913.0040

Phase Behavior of Amphiphilic Block Copolymers in Water−Oil Mixtures:  The Pluronic 25R4−Water− p -Xylene System
journal, January 1996

  • Alexandridis, Paschalis; Olsson, Ulf; Lindman, Björn
  • The Journal of Physical Chemistry, Vol. 100, Issue 1
  • DOI: 10.1021/jp951626s

Shear orientation of a lamellar lyotropic liquid crystal
journal, January 1995

  • Lauger, J�rg; Linemann, Reinhard; Richtering, Walter
  • Rheologica Acta, Vol. 34, Issue 2
  • DOI: 10.1007/BF00398432

Shear-Induced Alignment of a Hexagonal Lyotropic Liquid Crystal as Studied by Rheo-NMR
journal, September 1995

  • Lukaschek, Michail; Grabowski, David A.; Schmidt, Claudia
  • Langmuir, Vol. 11, Issue 9
  • DOI: 10.1021/la00009a050

Non-linear rheology of a face-centred cubic phase in a diblock copolymer gel
journal, January 2001

  • Daniel, Christophe; Hamley, Ian W.; Mingvanish, Withawat
  • Rheologica Acta, Vol. 40, Issue 1
  • DOI: 10.1007/s003970000124

Structure and rheology of direct and reverse liquid-crystal phases in a block copolymer/water/oil system
journal, November 2005

  • Rodriguez-Abreu, Carlos; Acharya, Durga P.; Aramaki, Kenji
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 269, Issue 1-3
  • DOI: 10.1016/j.colsurfa.2005.06.061

Physical chemistry of highly concentrated emulsions
journal, June 2015

  • Foudazi, Reza; Qavi, Sahar; Masalova, Irina
  • Advances in Colloid and Interface Science, Vol. 220
  • DOI: 10.1016/j.cis.2015.03.002

The rheology of binary mixtures of highly concentrated emulsions: Effect of droplet size ratio
journal, September 2012

  • Foudazi, R.; Masalova, I.; Malkin, A. Ya.
  • Journal of Rheology, Vol. 56, Issue 5
  • DOI: 10.1122/1.4736556

Large amplitude oscillatory shear as a way to classify the complex fluids
journal, December 2002


Oscillatory and simple shear flows of a flour-water dough: a constitutive model
journal, January 1997

  • Phan-Thien, Nhan; Safari-Ardi, Mohsen; Morales-Pati�o, Alexandro
  • Rheologica Acta, Vol. 36, Issue 1
  • DOI: 10.1007/BF00366722

Elasticity of Compressed Emulsions
journal, September 1995


Linear Viscoelasticity of Colloidal Hard Sphere Suspensions near the Glass Transition
journal, October 1995


Rheology of concentrated microgel solutions
journal, September 1988

  • Ketz, R. J.; Prud'homme, R. K.; Graessley, W. W.
  • Rheologica Acta, Vol. 27, Issue 5
  • DOI: 10.1007/BF01329353

Structure, dynamics, and rheology of colloid-polymer mixtures: From liquids to gels
journal, April 2009

  • Laurati, M.; Petekidis, G.; Koumakis, N.
  • The Journal of Chemical Physics, Vol. 130, Issue 13
  • DOI: 10.1063/1.3103889

Rheological constitutive equation for a model of soft glassy materials
journal, July 1998


A theory of flow as a cooperative phenomenon
journal, April 1980


A weak gel model for foods
journal, March 2001

  • Gabriele, Domenico; de Cindio, Bruno; D'Antona, Paolo
  • Rheologica Acta, Vol. 40, Issue 2
  • DOI: 10.1007/s003970000139