Emulsions, Microemulsions and Foams

354 Pages·2021·12.599 MB·English

by  Dominique Langevin

Soft and Biological Matter
Dominique Langevin
Emulsions,
Microemulsions
and Foams
Soft and Biological Matter
SeriesEditors
DavidAndelman,SchoolofPhysicsandAstronomy,TelAvivUniversity,
TelAviv,Israel
Wenbing Hu, School of Chemistry and Chemical Engineering, Department of
PolymerScienceandEngineering,NanjingUniversity,Nanjing,China
Shigeyuki Komura, Department of Chemistry, Graduate School of Science and
Engineering,TokyoMetropolitanUniversity,Tokyo,Japan
RolandNetz,DepartmentofPhysics,FreeUniversityofBerlin,Berlin,Germany
RobertoPiazza,DepartmentofChemistry,MaterialsScience,andChemical
Engineering"G.Natta",PolytechnicUniversityofMilan,Milan,Italy
PeterSchall,VanderWaals-ZeemanInstitute,UniversityofAmsterdam,
Amsterdam,TheNetherlands
Gerard Wong, Department of Bioengineering, California NanoSystems Institute,
UCLA,LosAngeles,CA,USA
“SoftandBiologicalMatter”isaseriesofauthoritativebookscoveringestablished
andemergentareasintherealmofsoftmatterscience,includingbiologicalsystems
spanning all relevant length scales from the molecular to the mesoscale. It aims to
serve a broad interdisciplinary community of students and researchers in physics,
chemistry,biophysicsandmaterialsscience.
Pure research monographs in the series, as well as those of more pedagogical
nature, will emphasize topics in fundamental physics, synthesis and design,
characterization and new prospective applications of soft and biological matter
systems. The series will encompass experimental, theoretical and computational
approaches. Topics in the scope of this series include but are not limited to:
polymers, biopolymers, polyelectrolytes, liquids, glasses, water, solutions, emul-
sions, foams, gels, ionic liquids, liquid crystals, colloids, granular matter, complex
fluids, microfluidics, nanofluidics, membranes and interfaces, active matter, cell
mechanicsandbiophysics.
Bothauthoredandeditedvolumeswillbeconsidered.
Moreinformationaboutthisseriesathttp://www.springer.com/series/10783
Dominique Langevin
Emulsions, Microemulsions
and Foams
DominiqueLangevin
LaboratoiredePhysiquedesSolides
UniversiteParisSaclay
ORSAY,France
ISSN2213-1736 ISSN2213-1744 (electronic)
SoftandBiologicalMatter
ISBN978-3-030-55680-8 ISBN978-3-030-55681-5 (eBook)
https://doi.org/10.1007/978-3-030-55681-5
©SpringerNatureSwitzerlandAG2020
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor
informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodologynowknownorhereafterdeveloped.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt
fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
Thepublisher,theauthors,andtheeditorsaresafetoassumethattheadviceandinformationinthisbook
arebelievedtobetrueandaccurateatthedateofpublication.Neitherthepublishernortheauthorsorthe
editorsgiveawarranty,expressedorimplied,withrespecttothematerialcontainedhereinorforany
errorsoromissionsthatmayhavebeenmade.Thepublisherremainsneutralwithregardtojurisdictional
claimsinpublishedmapsandinstitutionalaffiliations.
ThisSpringerimprintispublishedbytheregisteredcompanySpringerNatureSwitzerlandAG
Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland
Preface
Emulsions, microemulsions, and foams are dispersions of two immiscible fluids
stabilizedbysurface-activespecies.Emulsionsandmicroemulsionsaredispersions
usuallymadewithwaterandanorganicliquid,calledoil,andfoamsaremadewith
gas and liquid, frequently water, but sometimes oil. These dispersions have very
differentaspects:microemulsionsaretransparentbecausethedisperseddropletsare
very small (nanometric), emulsions are milky because droplets are larger
(micrometric), and foams are made of bubbles that can frequently been seen by
eye(millimetric).Their stabilityisalso verydifferent: microemulsionsarethermo-
dynamicallystableanddonotevolvewithtime, emulsionsandfoamsaremetasta-
ble,butemulsionslivelongerthanfoamsingeneral.Acommonpointbetweenthese
dispersionsistheexistenceofsurface-activespeciesadsorbedatinterfacesbetween
oilandwaterorgasandwater.Thesespeciesforminterfaciallayersthatcontrolmost
ofthedispersionproperties.
Solidfoams,whicharedispersionsofgasintosolids,arebecomingincreasingly
importantforapplications.Similarly,emulsionsarenowusedasscaffoldstoobtain
porousmaterials,amongwhicharemetamaterials.Theseaspectsarenotincludedin
thisbookwiththeexceptionofgeldispersions,whichwillbebrieflydiscussed.Gels,
despitebeingsolid,canflowifrelativelysmallmechanicalstressesareapplied.
Inthisbook,thepropertiesofinterfaciallayersaredescribedinChapter1,those
ofthinliquidfilmsformingbetweendropsorbubblesinChapter2,andthoseofthe
bulk fluids used in the elaboration of the various dispersions in Chapter 3.
Microemulsions,whicharethermodynamicallystabledispersions,arealsodescribed
inChapter3.Emulsionsandfoamsarenotthermodynamicallystableandrequirea
differenttypeofdescription,whichisprovidedinChapter4.Theirpropertiesarenot
fullyunderstoodyet,inparticularemulsionandfoamstability,andthestateoftheart
of existing knowledge is presented. Comparisons between studies performed with
emulsionsandfoamsarepresented,showinghowparallelstudieshelptoachievea
betterunderstandingoftheirbehavior.
v
Acknowledgements
My knowledge on the topics of this book benefited from numerous collaborations
with colleagues and students, to whom I am greatly indebted. I want to thank first
Marie Anne Bouchiat and Jacques Meunier, with whom I started the adventure of
Surface Light Scattering, and Lisbeth Ter Minassian, who kindly taught me the
subtleties of monolayers at the surface of water. I continued my early work on
monolayers thanks to enjoyable collaborations with Francisco Monroy, Hernan
Ritacco, Gabriel Espinosa, and Anniina Salonen. I am indebted to Lay-Theng Lee
whointroducedmetothetopicofneutronreflectivity,agreattoolformonolayers.
Ibeganmicroemulsionstudieswithmodelsystemschosenthankstoenlightened
advice by Pierre Lalanne and Anne-Marie Bellocq,and laterby Manfred Kahlweit
andReinhardStrey.RaymondOberandChristianeTaupinrevealedtomethesecrets
ofmicroemulsiondilution,astepthatwasessentialtotheelucidationoftheoriginof
the ultralow interfacial tensions in microemulsion systems. I benefited from many
illuminatingdiscussionsonmicroemulsiontheorieswith SamSafran,BenWidom,
and Kenneth Dawson. Ben Widom wisely suggested the wetting experiment
described in section 3.3.7, which, together with his theory in 1982, threw light on
the unusual behavior of microemulsion interfaces. I also benefited from fruitful
discussions with Barry Ninham and Jacob Israelachvili about surfactant behavior
and who introduced me to the exciting world of surface forces. I greatly enjoyed
workingwithAnne-MarieCazabat,AlainPouchelon,DidierChatenay,RaoulZana,
HeinzHoffmann,andMichaelGradzielski.
Aftermicroemulsions,Iturnedtoemulsionstudiesandenjoyedfruitfulcollabo-
rations with Jean-François Argillier, Eric Perez, Wladimir Urbach, Véronique
Schmitt, Fernando LealCalderon, Jean Louis Salager, andRonaldMarquez. Ialso
enjoyed memorable discussions with Ivan Ivanov, Peter Kralchevsky, and Nikolai
Denkov.Aimingtounderstandbubblesanddropscoalescenceledmetobeginthin
film studies with Andrei Sonin and Vance Bergeron, and to pursue the work with
Annie Colin, Joanna Kahn, Thomas Zemb, Arnaud Saint Jalmes, Cosima
Stubenrauch, and Regine von Klitzing. Their help was invaluable and is gratefully
acknowledged. I am also grateful to Denis Weaire, who introduced me to the
vii
viii Acknowledgements
problemoffoamdrainageandarousedmyinterestonfoams.Iwashappytobeable
to continue the foam work with Emmanuelle Rio, Wiebke Drenckhan, Anniina
Salonen,AmirMaldonado,andBernieBinks.Ibenefitedfromalongcollaboration
withAlainCagna,thankstowhomIcouldhaveaccesstoinnovativeinstrumentation
andsolveanumberofemulsionandfoamproblems.
Thislonglistisbynomeancomplete.IespeciallyenjoyedworkingwithPhDand
postdoctoral students and I kept many nice memories of the time spent with them.
They are too numerous to be cited here, but they all know how much I value their
inputs.
IcannotendwithoutsayinghowmuchIamindebtedtoPierreGillesdeGennes
for constant inspiration. He used to prefer polymers to surfactants that were not
amenable to scaling laws and much more prone to specific behavior. He made
however a few exceptions, a notable one with soap films, for which he kept a
constant interest. His great work clarified an endless number of open questions in
theareacoveredbythisbook.
Inowwanttoexpressmysincerethankstocolleagueswhotookthetimetoread
parts of the book and who made very useful suggestions, Wiebke Drenckhan,
Reinhard Höhler, and Bernie Binks. I also thank Siegfried Dietrich, Roland Netz,
Véronique Schmitt, Jean-Marie Aubry, and Nikolai Denkov who kindly clarified a
number of my questions. Francisco Monroy, Samuel Guillot, Michael Gradzielski,
ArnaudSaintJalmes,WiebkeDrenckhan,EmmanuelleRio,andMaximeSchneider
helped me with the figures, they are gratefully acknowledged. I am also happy to
thankthestaffatSpringer,especiallyMariaBellantonewhoencouragedmetowrite
thisbookandDavidPackerandBarbaraAmoresewhokindlyhelpedmeduringits
preparation.
And last but certainly not least, I want to thank my husband, Michel, for his
forbearanceduringthelongwritingofthebook.
Contents
1 InterfacesBetweenTwoFluids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 InterfacesBetweenPureFluids. . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 SurfaceTension,ContactAngle,Wetting. . . . . . . . . . . . . 1
1.1.2 GibbsDescriptionoftheSurfaceRegion. . . . . . . . . . . . . . 3
1.1.3 ThermalFluctuations. . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 InsolubleSurfaceLayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.1 SurfacePressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.2 SurfaceRheology(Compression,ShearandBending,
Viscoelasticity). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.3 MonolayersofSmallMolecules. . . . . . . . . . . . . . . . . . . . 19
1.2.4 PolymerMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.2.5 SolubleProteinMonolayers. . . . . . . . . . . . . . . . . . . . . . . 25
1.2.6 AsphalteneMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.2.7 ParticleMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.3 SolubleSurfaceLayers:CaseofSurfactants. . . . . . . . . . . . . . . . . 31
1.3.1 GibbsDescriptionoftheInterfacialRegion. . . . . . . . . . . . 33
1.3.2 AreaperSurfactantMolecule. . . . . . . . . . . . . . . . . . . . . . 37
1.3.3 AqueousSolutionsofSalts. . . . . . . . . . . . . . . . . . . . . . . . 38
1.3.4 EquationsofState,EnergySorptionBarriers. . . . . . . . . . . 39
1.3.5 SolidSurfactantMonolayers. . . . . . . . . . . . . . . . . . . . . . . 42
1.3.6 Non-equilibriumSystems:SorptionandTransfer
Kinetics,“Dynamic”Tension. . . . . . . . . . . . . . . . . . . . . . 43
1.3.7 SurfaceRheology:ResistancetoCompression
andShear,Viscoelasticity. . . . . . .. . . . . . . . . . . . . . . .. . 48
1.4 MonolayersofOtherSurface-ActiveSpecies. . . . . . . . . . . . . . . . 52
1.4.1 PolymerandProteinMonolayers. . . . . . . . . . . . . . . . . . . 52
1.4.2 AsphaltenesandParticleLayers. . . . . . . . . . . . . . . . . . . . 54
1.4.3 MixedLayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
1.5 MeasurementMethods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
1.5.1 SurfaceTension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
ix
x Contents
1.5.2 AdsorptionandDesorptionKinetics. . . . . . . . . . . . . . . . . 63
1.5.3 MeasurementofOtherEquilibriumProperties. . . . . . . . . . 63
1.5.4 SurfaceShearRheology. . . . . . . . . . . . . . . . . . . . . . . . . . 64
1.5.5 SurfaceCompressionRheology. . . . . . . . . . . . . . . . . . . . 66
1.5.6 SolidMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1.5.7 CurvatureElasticity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1.6 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2 ThinLiquidFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.1 FilmFormation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.2 FilmElasticity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.3 FilmThinning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.3.1 VerticalFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.3.2 CurvedFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.3.3 HorizontalFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.4 InteractionBetweenSurfaces(vanderWaals,Electrostatic,
andShortRange),DisjoiningPressure. . . . . . . . . . . . . . . . . . . . . 87
2.4.1 DefinitionoftheDisjoiningPressure. . . . . . . . . . . . . . . . . 87
2.4.2 ContributionstotheDisjoiningPressure. . . . . . . . . . . . . . 89
2.5 OscillatoryForces,FilmStratification. . . . . . . . . . . . . . . . . . . . . 97
2.5.1 Surfactant-StabilizedFilms. . . . . . . . . . . . . . . . . . . . . . . . 97
2.5.2 FilmsMadefromAmphiphilicPolymerSolutions. . . . . . . 102
2.5.3 FilmsMadefromMixedPolymer–SurfactantSolutions. . . 103
2.6 FilmRupture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.6.1 FilmsMadeofPureLiquids. . . . . . . . . . . . . . . . . . . . . . . 105
2.6.2 FilmsMadeofDiluteSurfactantSolutions.Models. . . . . . 110
2.6.3 FilmsMadeofConcentratedSurfactantSolutions.
RuptureDuringThinning. . . . . . . . . . . . . . . . . . . . . . . . . 112
2.6.4 RuptureofEquilibriumFilmsMadeofConcentrated
SurfactantSolutions.Models. . . . . . . . . . . . . . . . . . . . . . 113
2.6.5 FilmsMadeofSurfactantSolutions.Experiments. . . . . . . 115
2.6.6 FilmsMadewithSurfactantsandPolymers,
Proteins,orParticles. . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
2.6.7 OilFilms. .. . . .. . . . .. . . .. . . .. . . .. . . . .. . . .. . . .. 120
2.6.8 OpeningofHoles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2.7 MeasurementMethods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2.7.1 VerticalFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2.7.2 CurvedFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
2.7.3 HorizontalFilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2.8 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3 Self-AssemblyinBulk. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3.1 SurfactantSelf-Assembly. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3.1.1 SphericalSurfactantMicelles. . . . . . . . . . . . . . . . . . . . . . 129
3.1.2 OtherSurfactantAggregates:DiluteSolutions. . . . . . . . . . 136