Cosmet.

Sci., 57, 153-169 (March/April 2006)

Principlesof emulsionstabilizationwith specialreference

to polymericsurfactants

THARWAT TADROS, $9 Nash GroveLane, Workingham,

BerkshireRG40 4HE, U.K.

Accepted
for publication
November
17, 2005.

Synopsis
This overviewsummarizesthe basicprinciplesof emulsionstabilizationwith particularreferenceto poly-
mericsurfactants.The main breakdownprocesses in emulsionsarebrieflydescribed.A sectionis devotedto
the structureof polymericsurfactantsand their conformationat the i•nterface.
Particularattention3
is given
to two polymericsurfactantsthat aresuitablefor oil-in-water (O/W) andwater-in-oil (W/O) emulsions.For
O/W emulsions,a hydrophobically modifiedinulin (HMI), obtainedby graftingseveralalkyl groupson the
backboneof the inulin (polyfructose) chain, is the most suitable.For W/O emulsions,an A-B-A block
copolymerof polydroxystearic acid(PHS), the A chains,and polyethyleneoxide(PEO), the B chain,is the
mostsuitable.The conformation of bothpolymericsurfactants at the O/W andW/O interfacesis described.
A sectionis devotedto the interactionbetweenemulsiondropletscontainingadsorbedpolymersurfactant
molecules.This interaction is referredto as steric stabilization, and it is a combination of two main effects,
namely, unfavorablemixing of the A chains,referredto as the mixing interaction,G..... and lossof
configurational
entropyon significantoverlapof the stabilizingchains,referredto aselasticinteraction,G•.
The criteria for effective steric stabilization are summarized. O/W emulsions basedon HMI are described,
and their stability in water and in aqueouselectrolytesolutionsis investigatedusingoptical microscopy.
Very stableemulsionscan be producedboth at room temperatureand at 50øC. The reasonfor this high
stabilityis describedin termsof the multipoint anchoringof the polymericsurfactant(by severalalkyl
groups),the stronghydrationof the inulin (polyfructose)chains,andthe high concentrationof inulin in the
adsorbedlayer. W/O emulsionsusing PHS-PEO-PHS block copolymercan be preparedat a high volume
fractionof water, q>,and theseemulsionsremain fluid up to high q>values(>0.6). Theseemulsionsalso
remainstablefor severalmonthsat room temperatureand at 50øC.
The last two sectionsare concernedwith the problemsof creamingor sedimentationand phaseinversion.
Creamingor sedimentationcan be preventedby the use of "thickeners"in the continuousphase.These
moleculesproducenon-Newtoniansystemsthat will havea very high residualor zeroshearviscosity.The
latter, which may exceed1000 Pus,canpreventany creamingor sedimentation. Syneresisof the e•ulsions
can alsobe preventedby control of the bulk (or elastic)modulusof the system.Phaseinversionin O/W
emulsionscanalsobe preventedusingHMI, sincethis polymericsurfactantis not solublein the oil phase.
As long ascoalescence and Ostwaldripeningare prevented,the emulsionscan remainstablefor very long
times both at room temperatureand at 50øC.

INTRODUCTION

Many personalcare and cosmeticproductsare formulated as oil-in-water (O/W) or

water-in-oil(W/O) emulsions.
Thesesystemsareonlykineticallystablesincethe energy
153
154 JOURNAL OF COSMETIC SCIENCE

requiredto expandtheinterfaceAA y (whereAA is theincrease

in surface
areawhenthe
bulk oil is subdividedinto small dropletsand y is the interfacialtension),which is
positive,is muchhigherthanthe entropyof dispersion T AS (whereT is the absolute
temperature andAS is the increase
in entropydueto the formationof a largenumber
of droplets).From the secondlaw of thermodynamics,
the freeenergyof formationof the
emulsionis given (1):
AG = AA y- T AS (1)
With macroemulsions
AA y >> - T AS, AG is positive,emulsification
is non-
spontaneous (energyis requiredto form the emulsion),and the systemis thermody-
namicallyunstable.This leadsto a numberof breakdownprocesses, as is schematically
illustratedin Figure 1. Creamingand sedimentation may occuras a resultof gravity
whenthe densityof the dropletsis differentfrom that of the mediumand the droplet
size is large (wherebythe Brownianmotion is not sufficientto overcomegravity).
Flocculationmay occurasa resultof insufficientrepulsiveenergybetweenthe droplets.
Ostawaldripeningis due to the differencein solubilitybetweenthe small and large
droplets.Coalescence is the resultof thinning anddisruptionof the liquid film between
the droplets.Phaseinversionmay occurunder conditionswherebythe surfactantbe-
comessolublein the oil phase,and hencea W/O emulsionis produced.
In orderto overcomethe above-mentioned breakdownprocesses,a numberof stabili-
zation mechanismsare necessarysuch that the emulsionremainsstable over a long

Figure 1. Schematicrepresentation
of the breakdownprocesses
of emulsions.
 EMULSION STABILIZATION 15 5

period (usually 2-3 yearsat varioustemperatures).This paper, discusses the various

stabilizationmechanisms that are requiredfor preventionof strongfiocculation,coales-
cence,and Ostwaldripening.This is bestachievedusingpolymericsurfactants, which
is the main objectiveof the presentpaper.A summarywill alsobe givenfor the methods
that can be applied to preventcreamingor sedimentationand phaseinversionof the
emulsion.

STRUCTURE OF POLYMERIC SURFACTANTS AND THEIR CONFORMATION

AT INTERFACES

The simplesttype of a polymericsurfactantis a homopolymer,which is formedfrom the

samerepeatingunits: poly(ethyleneoxide) (PEO) and poly(vinylpyrrolidone) (PVP).
Homopolymershave little surfaceactivity at the oil/water (O/W) interface.In general,
homopolymersare not the most suitableemulsifiers.
A smallvariantis to usepolymersthat containspecificgroupsthat havehigh affinity to
the surface,e.g., partially hydrolyxedpoly(vinylacetate)(PVAc), technicallyreferredto
as poly(vinylalcohol)(PVA). CommerciallyavailablePVA moleculescontain4-12%
acetategroups.The acetategroupsgive the molecule its amphipathic character;on a
hydrophobicsurface(suchasoil droplets),the polymeradsorbswith preferentialattach-
ment of the acetategroupson the surface,leavingthe more hydrophilicvinyl alcohol
segments danglingin the aqueous medium.PartiallyhydrolyzedPVA moleculesexhibit
surfaceactivity at the O/W interface.
Polymericsurfactantsof the block (A-B or A-B-A) or graft (BA•) type are essential
materialsfor the preparationof many emulsionsystems,particularlyin personalcare
products.A block copolymeris a linear arrangementof blocksof varyingcomposition
(2):

Diblock - poly A - blockpoly B

Triblock- poly A - blockpolyB - poly A -•A .B A.
A graft copolymeris a non-lineararrayof oneB block on which severalA polymersare
grafted:
B

AA A A A

Most blockand graft copolymers havelow criticalmicelieconcentrations (cmc),and in

manycases it is not easyto measurethe cmcfor theseblockandgraft copolymers. Several
examplesof block and graft copolymers may be cited: triblockpolymericsurfactants;
"Pluronics"(BASF)or "Synperonic PE" (ICI); and two poly-A blocksof PEO and one
blockpoly-B of polypropylene oxide(PPO). Severalchainlengthsof PEO and PPO are
available.Triblocksof PPO-PEO-PEO(inverse"Pluronics") arealsoavailable.Polymeric
triblocksurfactants canbe appliedasemulsifiers anddispersants. The hydrophobic PPO
chain residesat the hydrophobicsurface,leavingthe two PEO chainsdangling in
aqueoussolution(providingstericstabilization).
The above-mentionedtriblocks are not the most efficient emulsifiers, and the PPO chain
is not sufficientlyhydrophobic
to providea strong"anchor"to an oil droplet.The reason
156 JOURNAL OF COSMETIC SCIENCE

for the surfaceactivityof the PEO-PPO-PEO triblock at the O/W interfaceis probably
"rejection"anchoring.The PPO chainis not solublein water or most oils.
Severalotherdi- andtri-blockcopolymershavebeensynthesized: diblocksof polystyrene
block-polyvinylalcohol;triblocksof poly(methylmethacrylate)-block
polyethyleneox-
ide-poly(methyl methacrylate);
diblocksof polystyrene-polyethylene
oxide;andtriblocks
of polyethyleneoxide-polystyrene-polyethylene
oxide.
An alternative(andperhapsmoreefficient)polymericsurfactantis the amphipathicgraft
copolymerconsistingof a polymericbackboneB (polystyrene or polymethylmethacry-
late) and severalA chains("teeth")suchaspolyethyleneoxide.The graft copolymeris
referredto asa "comb"stabilizer,andthe polymerformsa "brush"at the O/W interface.
The copolymeris usually preparedby grafting a macromonomersuch as methoxy
polyethyleneoxidemethacrylatewith polymethylmethacrylate.Typical commercially
availablegraft copolymers are Atlox 4913 and HypermerCG-6 suppliedby ICI. The
"grafting into" techniquehas also been used to synthesizepolystyrene-polyethylene
oxidegraftcopolymers. Thesemolecules arenot commercially
available,andtheyarenot
approvedfor usein personalcareand cosmeticpreparations.
Recentlya novelgraft copolymerbasedon a naturallyoccurringpolysaccharide, inulin
(polyfructose),
hasbeensynthesized (3). Inulin is a polydisperse
polysaccharide
consist-
ing mainly,if not exclusively,
of [3(2->1) fructosylfructoseunits (Fro)with normally,
but not necessarily,
oneglucopyranose unit at the reducingend(GFn)(4,5). To produce
the amphipathicgra• copolymer,the chainswere modifiedby introductionof alkyl
groups(C4 - ClS) on the polyfructose backbone. The structureof the molecule(hydro-
ponicallymodified inulin, HMI) is illustratedin Figure 2.
In this structure,the alkyl groupsrepresentthe B chains(that are randomlydistributed
on the sugarbackboneon primaryhydroxylfunctionsaswell ason the secondary ones),
whichbecomestronglyadsorbed on an oil droplet.The sugarchainformsthe stabilizing
chain,asthisis highlywater-soluble. Thesegraftcopolymers aresurface-active,
andthey
lower the surface tension of water and the interfacial tension at the oil/water interface.

OH

(GFn)
Figure 2. Structureof hydrophobically
midfield inulin (HMI).
 EMULSION STABILIZATION 157

They will also adsorbon the oil dropletswith the alkyl groups strongly attached
(multipoint anchoring),leavingthe polyfructosechainsdangling in solutionand prob-
ablyforminglargeloops.As we will seelater, thesegraft copolymerscanproducehighly
stableemulsions,in particularat high electrolyteconcentrations.
An exampleof com-
merciallyavailableHMI is INUTEC © SP1 (producedby Orafti, Belgium).
AnotherA-B-A blockcopolymerfor stabilizationof W/O emulsionshasbeendeveloped
by Uniqema(ICI), namelyArlacelP135 (6). The A chainsarepoly(12-hydroxystearic
acid) (PHS), whereasthe B chain is poly(ethyleneoxide (PEO), i.e., PHS-PEO-PHS. A
schematicrepresentation of the structureof the polymeris given in Figure 3.
The polymerhas a weight averagemolecularweight, Mw, of 6809 and an average
molecularweight, M•, of 3499 (polydispersity of 1.94). It hasan HLB numberof 5-6,
which makesit suitablefor W/O emulsions.The PHS chains(the stabilizingchains)are
highly solublein mosthydrocarbonsolventsand stronglysolvatedby their molecules.
Thesechainsextendin the oil, giving a layerthicknessof the orderof 10 nm. This makes
the molecule ideal for steric stabilization (see below). The PEO chain (the "anchor
chain")is highly solublein water and in moderateelectrolytesolutions,and this gives
very strongadsorptionat the W/O interface.
Understandingthe adsorptionand conformationof polymericsurfactantsat interfacesis
key to knowinghow thesemoleculesact as stabilizers.Most basicideason adsorption
andconformation of polymershavebeendeveloped for the solid/liquidinterface(7). The
sameconceptsmay be appliedto the liquid/liquid interface,with somemodification
wherebysomepartsof the moleculemay residewithin the oil phase,ratherthansimply
stayingat the interface.Suchmodificationdoesnot alter the basicconcepts,particularly
when one dealswith stabilizationby thesemolecules.
The processof polymer adsorptioninvolvesa number of interactionsthat must be
separatelyconsidered.
Three main interactionsmust be taken into account,namely,the
interaction of the solvent moleculeswith the oil in the caseof O/W emulsions,which
needto be displacedfor the polymer segmentsto adsorb,the interactionbetweenthe
chainsand the solvent,and the interactionbetweenthe polymerand the surface.Apart
from knowing theseinteractions,one of the most fundamentalconsiderations is the
conformationof the polymermoleculeat the interface.Thesemoleculesadoptvarious
conformations,dependingon their structure.A schematicrepresentationof the confor-

• PH• i,

PE•
Figure 3. Schematicrepresentation
of the structureof PHS-PEO-PHSblockcopolymer.
158 JOURNAL OF COSMETIC SCIENCE

Figure 4. Conformation of hydrophobicallymodifiedinulin (HMI) at the O/W interSPace.

The alkyl chains
are solublein the oil, and the polyfructose
loopsextendinto the aqueousphase.

marionof HMI at the O/W interfaceis given in Figure4, whereasthat of PHS-PEO at

the W/O interfaceis given in Figure 5.
It is clearfrom the abovedescriptionof polymerconfigurationsthat for full character-
izationof the process of adsorption,it is necessary
to know the followingparameters,
namely, theamount ofpolymer
adsorbedperunitareaofthesurface,
17(molem 2ormg
m--2),thefraction
ofsegments
in close
contact
withthesurf•tce,
p, andthedistribution
of polymersegments,p(z), from the surfacetowardsthe bulk solution.It is essentialto
know how far the segmentsextendinto the solution,i.e., the thicknessof the adsorbed
layer. It is important to know how theseparameterschangewith polymer overage
(concentration),the structureof the polymer,and its molecularweight. It is alsoessen-

Figure 5. Conformationof PHS-PEO-PHS block copolymerat the W/O interface.The PEO chainsare
solublein the waterdroplets,and the PHS chainsextendinto the oil phase.
 EMULSION STABILIZATION 159

tial to know how theseparameterschangewith the environment,in suchaspectsas

solvencyof the medium for the chainsand temperature.

INTERACTION BETWEEN DROPLETS CONTAINING ADSORBED POLYMER

LAYERS (STERIC STABILIZATION)

When two dropletscontainingadsorbed polymerlayers(with an adsorbed layerthick-

ness,8) approach
a distanceof separation,
h, wherebytheselayersbeginto overlap,i.e.,
whenh < 28, repulsionoccursasa resultof twomaineffects(8). The firstrepulsive
force
arisesfrom the unfavorablemixing of the polymer layerswhen theseare presentin a
goodsolvent(i.e., the chainsare stronglysolvatedby the medium).The unfavorable
mixing of polymersolutionsin goodsolventconditionswasconsidered by Flory (9),
whosetheorywasappliedto the presentcaseof interparticleinteraction.A schematic
representation of the mixingof polymerlayerson closeapproach is shownin Figure6,
whichshowsthe situationwhentwo dropletswith polymerlayersareforcedto approach
a distance,h, that is lessthan28, formingan overlapregionwith a volumeelement,dV.
Beforeoverlap,the chainshavea volumefraction,cp2,and the solventhasa chemical
potential,pl•. In theoverlap
region,thevolumefractionof thechainsis cp2',whichis
higher
thancp2,
andthesolvent
hasa chemical
potential,
p•6,which
islowerthanpl•.
This is equivalentto an increasein the osmoticpressurein the overlapregion.As a
result, solventdiffusesfrom the bulk to the overlapregion and the two particlesor
dropletsare separated, i.e. this resultsin strongrepulsion.The latter is referredto as
mixing or osmoticrepulsion.
UsingtheFlory-Krigbaumtheory(9), onecancalculatethe freeenergyof mixing,Gmix,
due to this unfavorableoverlap,i.e.,

(2)

Figure 6. Schematic
representation
of the overlapof two polymerlayers.
160 JOURNAL OF COSMETIC SCIENCE

where k is the Boltzmannconstant,T is the absolutetemperature,V• is the molar

volumeof the solvent,andN•v is the Avogadros's
constant.X is a dimensionless
quantity
that gives a measureof the polymer-solventinteraction,i.e., the solvationof the A
chainsby the moleculesof the medium. It is referredto as the Floury-Hugginsinter-
action parameter.
It is clearfrom equation2 that whenthe Flory-Hugginsinteractionparameter,X, is less
than 0.5, the chainsarein goodsolventconditions,Ginix is positive,and the interaction
is repulsiveand increasesvery rapidlywith decreasing
h, when the latter is lower than
28. This explainswhy the hydrophobicallymodifiedinulin (HMI) polymericsurfactant
is ideal for stabilizingO/W emulsions.
In this casethe polyfructose
loopsare strongly
hydratedby watermolecules.For stabilizationof W/O emulsions,the stabilizingchains
haveto be solublein the oil phase(normallya hydrocarbon).In this case,poly(hydroxy-
stearicacid) (PHS) chainsare ideal. A polymericsurfactantof PHS-PEO-PHS (Arlacel
P135) is an ideal W/O emulsifier.
Equation2 alsoshowsthat whenX > 0.5, i.e., when the solvencyof the mediumfor the
chainsbecomespoor, Ginix is negativeand the interactionbecomesattractive.The
conditionX -- 0.5 is referredto asO-solvent,in which casemixing of the chainswith the
solventdoesnot lead to an increaseor decreaseof the free energyof the system(i.e.,
polymer mixing behavesas ideal). The O-conditiondenotesthe onsetof changeof
repulsionto attraction.Thus, to ensurestericstabilizationby the abovemechanism,one
hasto ensurethat the chainsare kept in better than a O-solvent.
The secondrepulsiveforcearisesfrom the lossof configurationalentropywhen the
chainsoverlap.This is schematically illustratedin Figure 7, wherebythe polymerchain
is representedby a simplerod with oneattachmentpoint to the surface.When the two
surfacesare separated at infinite distance,eachchainwill havea numberof configura-
tions,12o•,that aredetermined by thevolumeof thehemisphere sweptby the rod.When
the two surfaces approach a distance,h, that is smallerthanthe radiusof the hemisphere
sweptby the rod, the volumeavailableto the chainsbecomes smallerandthis resultsin
a reductionin the configurational entropyto a value,12 (whichis lessthan12•). This
resultsin strongrepulsion,and the effectis referredto asentropic,volumerestrictionor
elasticrepulsion,and is given by the followingexpression (8):

Od=2vIn12--• (3)

Volume los{

no. of configuration

Figure 7. Schematicrepresentation
of the entropic,volumerestrictionor elasticinteraction.
 EMULSION STABILIZATION 161

wherev is the numberof polymerchainsper unit area of the surface.It shouldbe

mentionedthat Gd is alwaysrepulsiveandbecomes
veryhigh on considerable overlap
of the polymer chains.
Plotsof Gmix and Gd versush areillustratedin Figure8. This figureshowsthat G....
increasesveryrapidlywith a decreasein h assoonash becomes smallerthan28 (andX
< 0.5). Gd alsoincreasesveryrapidlywith a decrease in h on furtheroverlap.Combi-
nationof G.... Gd, and GA (thevan der Waalsattraction)resultsin the total GT - h
curveshownin Figure8. This curveshowsa minimum (Groin)at h - 28, but whenh
< 28, G.r increases
veryrapidlywith a furtherdecrease
in h. The depthof the minimum,
Gmin,depends on the adsorbedlayerthickness. With an increase of 8, Ginin decreases,
and at sufficientlyhigh valuesof 8 (of the orderof 5-10 nm), it reachessmallvalues
(fractionof kT units). This showsthat with stericallystabilizeddispersions,
thereis only
weak attractionat relativelylong distancesof separation,which in most casesis over-
comeby BrownJandiffusion.Thus, onecansaythat the net interactionis repulsive,and
this ensuresthe long-term stability of the emulsion.
From the above discussion one can summarize the main criteria for effective steric
stabilization.First, thereshouldbe enoughpolymerto ensurecompletecoverage of the
surfaceby the chains.This will preventany attractionbetweenthe barepatchesor
bridgingby the polymerchains(whichcan adsorbsimultaneously on more than one
particle).Secondly,the chainsmust be stronglyadsorbed ("anchored") to the surface.
This preventsany displacement on closeapproach.In this respect,block and graft
copolymers containingan anchoringchain(suchas the alkyl groupsof HMI) for oil
dropletsarethe beststabilizers. The third criteriafor effectivestericstabilization
is to
ensurethat the stabilizingA chainremainsin goodsolventconditionat all times and

h h

Figure 8. Schematicrepresentation
of the variationof G.... Gd, G^, and G•. with h.
162 JOURNAL OF COSMETIC SCIENCE

under all conditions.As discussedabove,for systemswhere water is the continuous

medium,polyfructose (inulin) is the mostsuitableA chain.This polymerchainis highly
soluble in water and remainssolvatedup to high temperatures.It can also tolerate
reasonableamountsof electrolyte.For dispersions, where the continuousmedium is a
hydrocarbon oil (e.g.,W/O emulsions) poly(hydroxystearic acid)is the mostsuitableA
chain(s).The lastcriterionfor effectivestearicstabilizationis to havea sufficientlythick
adsorbedlayer to avoidany weak flocculation.This is particularlyimportantfor con-
centratedemulsions.A value of • of the orderof 5-10 nm is usuallysufficient.

O/W EMULSION STABILIZATION USING HYDROPHOBICALLY MODIFIED

INULIN (HMI) BASED POLYMERIC SURFACTANT

As mentionedabove,the graft copolymerbasedon inulin (hydrophilicpolyfructose

chain)on whichseveralalkyl groupshavebeengrafted(INUTEC © SP1) wasrecently
evaluatedas an effectivestabilizerfor O/W emulsions.This polymericsurfactantwas
prepared usinginulin(INUTEC© N25) with a degreeofpolymerization greaterthan23.
The inulin chainswerehydrophobically modifiedby graftingseveralalkyl chainson the
inulin backbone.Two oils, IsoparM (suppliedby Exxon)and cyclomethicone (supplied
by Dow Corning) were used to prepare the O/W emulsions(10). Most emulsions
consistedof 50/50 (v/v) ratio oil in water,and the polymericsurfactantconcentration
was
changedfrom 0.25 (w/v)% to 2 (w/v)%. The emulsionswere preparedusing a high-
speedstirrer,anUltra-Turrax(CAT X620). The emulsionqualitywasassessed by optical
microscopy. Samplesof the emulsionswerestoredat roomtemperatureandat 50øC,and
the droplet size was qualitativelyassessed by taking optical micrographsat various
intervals of time.

Figure 9 showstypical micrographs of diluted 50/50 IsoparM/water emulsionscon-

taining2 (w/v)% INUTEC © surfactant that werestoredforperiodsof 1.5 and 14 weeks
at 50øC.As canbe seen,thereis no apparentincreasein dropletsizeduring this storage
time, and this wastakenasan indexof stability againstcoalescence.
Similar resultswere

A B
Figure9. Opticalmicrographs
of diluted50/50IspoarM/wateremulsions
containing
2(w/v)%INUTEC©
SP1 that were stored at 50øC for 1.5 (A) and 14 (B) weeks.
 EMULSION STABILIZATION 163

alsoobtainedfor ennuisions storedat roomtemperature.No oil separation

wasdetected
after this period at RT and 50øC.

In order to evaluatethe minimum polymericsurfactantthat is requiredto preparea

stableennuision, systems(50/50 O/W) werepreparedat 0.25, 0.3, 0.4, 0.5, 1, 1.5, and
2%. All the sampleswereassessed for stabilityusingthe proceduredescribedabove.All
ennuisions containing>0.5 (w/v)% polymericsurfactantremainedstableboth at room
temperatureand 50øC. Thesesamplesdid not showany apparentoil separationeven
after storagefor 10 monthsat 50øC. Basedon theseresults,it was shownthat for 50/50
(v/v) O/W emulsions,an emulsifierconcentrationin the region of 0.5 (w/v)% is suffi-
cient for stabilization.This is aboutan orderof magnitudelowerthan the concentration
usedwith conventionalsurfactants(suchas alcoholethoxylates).

Emulsions wereprepared
at 0.5, 1.0,and2 moldm-3 NaC1,aswellasin thepresence
of0.5, 1.0,1.5,and2 moldm-3 MgSO 4.All ennuisions
containing
NaC1didnotshow
any coalescence
up to 50øCfor almostoneyearof storage.With MgSO4, the ennuisions
werealsostableup to 1.0 moldm--•.
The above-mentioned stability in high electrolyteconcentrations
is not observedwith
polymericsurfactants containingpoly(ethyleneoxide)(PEO) as the stabilizingchain.
The differencebetweenthe inulin- and PEO-containingchainscanbe understoodif one
considersthe repulsiveenergyobtainedusingthesepolymericsurfactants. As discussed
previously,the mixing freeenergy,Gmix,for two dropletsstabilizedby A chainswith
thickness
8 depends
on the valueof (1/2 - X) (seeequation2). As discussed
previously,
when (1/2 - X) is positive,i.e., X < 1/2, Ginix is positiveand the net interactionis
repulsive.If X > 1/2, Ginix is negative,and this leadsto incipient fiocculationthat is
normally accompanied by coalescence of the emulsion.

The Flory-HugginsinteractionparameterX is relatedto the solvencyof the mediumfor

the chains.In water,both inulin and PEO arestronglyhydratedby the watermolecules,
and henceX < 1/2 under theseconditions.On increasingthe temperature,H-bonds
betweenthe chainsand water moleculeswill be brokenand the X parameterwill
increase.However,with both inulin and PEO, this will happenat much higher tem-
peraturesthan thoseexperiencedon storage(usuallythe X parameteris lessthan 1/2
below80øC).With inulin, it doesnot showany dehydrationup to 100øC.

On additionof electrolytes,
dehydration of the chainsmaytakeplace(salting-outeffect),
andat a givenelectrolyteconcentration (andtype) andtemperature,X will changevalue
from < 1/2 to > 1/2 andGinix will changesignfrom positiveto negative.It seenns that
the inulin-stabilizingchaincanretain its hydrationto much higher temperatures and
electrolyteconcentrationswhencomparedto PEO chains,andthis is probablythe reason
for the higherstabilityobtainedwhenusingthe hydrophobically modifiedinulin asan
emulsion stabilizer.

To confirmthe above-mentionedeffects,we havecarriedout cloudpoint measurements

for PEO with 4000 molecularweightin the presenceof variousconcentrations
of NaC1
and MgSO4. Someresultswere alsoobtainedfor a PEO with a molecularweight of
20000 in the presenceof NaC1. For comparison,resultswere alsoobtainedfor inulin
(INUTEC© N25) in the presence
of NaCI andMgSO4.
164 JOURNAL OF COSMETIC SCIENCE

PEG 4000 - Cloud point (øC) PEG 4000 - Cloud Point (øC)

120

C 0 M NaCI
IO0
-*- 2M NaCI
- 3M NaCI

OOM
MgSO
• 4M NaCI [] 0.5M MgSO4
-•- 1M MgSO4
• 4.5M NaCI
:)1( 2M MgSO4
O 5M NaCI

I 6M NaCl 2O

0
ß .

2 4
2 4
% PEG 4000
% PEG 4000

A B
Figure 10. Cloudpointsof PEO 4000 at variousNaC1(A) andMgSO4 (B) concentrations
asa functionof
PEO concentrations.
Cloud points of 100øC mean that no cloud point could be noticedup to this
temperature.

Figures10A and 10B showthe resultsfor the cloudpointsof PEO 4000 at various
concentrations
of NaC1 and MgSO4, whereasFigure 11 showsthe resultsfor PEO
20000. The resultsfor inulin (INUTEC © N25) are shownin Figure 12.
It canbe seenfromthe resultsof Figure10 that for PEO 4000 in water,the cloudpoint
is around 100øC and it showsvery little dependenceon concentration(in the range
1-5 %). On addition of NaC1, there is a systematicreductionin the cloudpoint with an
increasein NaC1 concentration.Also, the cloudpoint showsa reductionwith an increase
in PEO concentration from 1% to 5%. The results for PEO 20000 showed lower cloud
point valueswhencomparedwith the valuesobtainedwith PEO 4000. However,the
results
forinulin(Figure12)showed
nocloudpointupto4 moldm-• NaC1,indicating
an absenceof dehydrationby this electrolyte.With MgSIO4, a cloudpoint could only
bemeasured
at 1.5and2 moldm-• MgSO4,reaching
values
belowroomtemperature.
Generallyspeaking,the cloudpoint is relatedto the X parameter.When X is < 1/2, the
chainsshouldremainsolratedby the moleculesof the mediumandthe solutionis clear;
when X > 1/2, dehydrationof the chainswill occurand chain-chaininteractiontakes

PEG 20000. Cloud points (øC)

120 " 0 M NaCI
[] 1M NaCI
100
.". 2M NaCI
8O
'•' 4M NaCI
o 6M NaCI

4o
2O
0 ! !

0 2 4 6

% PEG 20000

Figure 11. Cloudpointsof PEO 20000 at variousNaC1concentrations

asa functionof PEO concentration.
 EMULSION STABILIZATION 165

INUTEC©N 25 - Cloud points (øC) INUTEC©N 25 - Cloud points (øC)

-,_ _-, = •0 MNaCI

•IM NaCl 0 OM MgS04
---• 2MNaCI • 1M MgS04
•3M NaCI
---)K---
4MNaCl •, 1.5M MgS04
•5M NaCI • 2M MgS04
•6M NaC

0 2 4 6

% INUTEC•125
% INUTEC•125

A B
Figure 12. Cloud pointsof INUTEC© N25 at variousNaC1 (A) and MgSO• (B) concentrations
as a
function of INUTEC © N25 concentrations.

placeresultingin cloudiness.The cloudpoint dependsboth on polymer concentration

as well as the molecularweight; with increasein molecularweight and concentration,
the cloudpoint generallydecreases, and this can be illustratedt•}omthe resultsshown
in Figures
10and11.With PEOat 2 tooldin-.3NaC1,thecloudpointisabout60øC,
andif thepolymerconcentration
will reach,for example,20%, the cloudpoint couldbe
lower than 50øC. Thus, for emulsion stabilizersbasedon PEO, stability cannot be
maintainedat 2 tooldin-.3NaC1.With MgSO4,thesituation
is evenworse,
asshown
in Figure10:at 5% PEO4000,thecloudpointislowerthanRT at 1 moldm _3, and
henceinstabilitywill be moreseriouswith this electrolyte.However,for inulin the cloud
pointcanbemaintained
at about100øCupto4 tooldin-• NaC1,andhence
onewould
expectstableemulsionsat temperaturesexceeding50øC up to this electrolyteconcen-
tration. With MgSO4 stability can be maintainedat high temperaturesup to 1 tool
dm-3. Thus,thesecloud-point
measurements
giveconclusive
evidence
of the unique
behaviorof polymericsurfactantsbasedon inulin. The polyfructosechain remainshy-
drated up to high temperaturesand in the presenceof high electrolyteconcentrations.
This makesthis polymericsurfactanta very usefulcandidatefor the stabilizationof
emulsionsin high electrolyteconcentrationswhen comparedwith emulsionsprepared
usingpolymericsurfactantsbasedon PEO.

Similar resultswere alsoobtainedwhen using cyclomethicone

as the oil: 50/50 O/W
emulsions
preparedusing2 (w/v)% INUTEC © surfactant
showedstabilityat RT and
50øCformorethanoneyear.Emulsions
prepared
in thepresence
of 1 tooldm-3 NaC1
and MgSO4 were alsostableup to 50øC for more than eight months.

From the abovediscussion, it is clear that using HMI as an emulsionstabilizerwill

eliminateany strongfiocculationor coalescence of the emulsionboth in water and in
high electrolyteconcentrations.This can be attributed to a number of effects:(i) the
multipoint attachmentof the polymerby the severalalkyl chainsthat aregraftedon the
backbone,ensuringstrongadsorption("anchoring")at the O/W interface;(ii) strong
hydration of the polyfructose"loops"(in between the alkyl chains) that dangle in
solution,ensuringa X < 0.5 both in water and high electrolyteconcentrations; fiji)
high-volumefraction(concentration)of the loopsat the interface,recentresultsusing
polystyrenelatex dispersions
(11) showingan adsorbed-layer thicknessin the regionof
166 JOURNAL OF COSMETIC SCIENCE

4 nm (and,therefore,
theconcentration
of thepolyfructose
in thislayeris highandthis
increases
the freeenergyox mixing accordingto equation2); and (iv) enhanced
steric
stabilization
assuggestedby Napper(8) for polymers
with multi-attachment points.
The hydrophobically modifiedinulinsurfactant canalsostabilizetheemulsions against
Ostwaldripening.The latter arisesfrom the difference in solubilitybetweenthe small
andlargedroplets. Duringstorage, oil moleculeswill diffusefromthesmallerdroplets
(whichhavehighersolubilitydueto theirhighercurvature) to thelargerdroplets(with
lowersolubilitydueto the smallercurvature). Thisprocess canbeprevented by using
polymersthat adsorbverystronglyat the O/W interface. As discussed by Walstra(12),
thisstrongadsorption resultsin an increase
in dilatationalelasticity,thusreducingthe
processof diffusionfromthe smallto the largedroplets.

W/O EMULSIONS STABILIZED WITH PHS-PEO-PHS BLOCK POLYMER

W/O emulsions(with the oil beingIsoparM) canbe preparedusingPHS-PEO-PHS

block copolymerat a very high watervolumefraction(>0.7). Theseemulsionshavea
narrowdropletsizedistribution, with anaverage radius,R, of 183 nm.Theyalsoremain
fluid up to high-volume fraction(>0.6), asis illustratedin Figure13, whichshowsthe
viscosity-volume fractioncurvesfor the emulsion(13). The effectivevolume fraction,
q%ff,
wascalculated
fromtherelativeviscosity,
Xlr, usingtheDouherty-Krieger
equation
(14):

15o

0.4 0.5 0.6 0.7 0.8 0.9

volume fraction

Figure 13. Viscosity-volumefraction curvesfor W/O emulsionsstabilizedwith PHS-PEO-PHS block

copolymer.
o, experimental
points;I, calculated
usingequation4.
 EMULSION STABILIZATION 167

- %? (4)
whereIxI] is theintrinsicviscosity
thatis equalto 2.5 forhard-spheres
andqop
is the
maximumpackingfractionthat wasfoundto be 0.84 (which is a reasonable
valuefor a
polydispersesystem).
From q%ffand qo,the adsorbed
layerthickness,8, wascalculatedusingequation5:

where 8 was found to be -10 nm at qo= 0.4 and decreased with an increasein qoas a
result of the possibleinterpenetrationand/or compression
of the PHS chains.
The emulsionsremainedstableboth at room temperatureand 50øC for severalmonths,
and there was no evidenceof flocculationand/or coalescence,
as assessed by using
rheologicalmeasurementsfor concentratedW/O emulsions.This stability is expected
sincethe anchorchain(PEO) is solublein water and insolublein oil, thus ensuringlack
of displacementof the polymermolecules. The PHS chainsremainedstronglysolvated
by the oil moleculesboth at room temperatureand at 50øC, and this ensuredeffective
steric stabilization.

CONTROL OF CREAMING OR SEDIMENTATION OF EMULSIONS

Creamingor sedimentationcan be controlledby addition of "thickeners"in the con-

tinuousphase.Most of thesethickenersare high-molecular-weight polymerssuchas
hydroxyethylcellulose(or its hydrophobicallymodifiedversion,referredto asassociative
thickeners),
xanthangum, alginates,carbomers (e.g., Carbopol),etc. All thesematerials
producenon-Newtoniansystemsabovea critical concentration.This non-Newtonian
behaviorcan be expressed from plots of shearstress,tr (Pa), as a functionof shearrate,
•/ (s-•),asis illustrated
in Figure14,referred
to aspsudopolastic
flow.

rl/Pa.s

o/Pa

3/s- 5ds-
Figure 14. Shearstressand viscosityas a functionof shearrate for a psudoplastic
system.
168 JOURNAL OF COSMETIC SCIENCE

As discussedbefore(15), thesesystemsproducehigh viscosities

at very low shearrates
or shearstresses
(>100 Pas),and this preventsany creamingor sedimentationof the
emulsion.

Another problemwith many emulsionsystemsthat are weakly fiocculatedor "struc-

tured" to reducecreamingor sedimentationis "syneresis." The "gel network"produced
in the systemmaycontractwith time (asa resultof gravityforces)andsomesupernatant
liquid may be "squeezed out," leavinga clearliquid layerat the top or bottom of the
container.To preventsyneresis, onehasto optimize the bulk modulus(which is related
to the elasticor storagemodulus).The latter canbe measuredusingdynamicor oscil-
latory techniquesthat havebeendescribedpreviously(15).

CONTROL OF PHASE INVERSION

Phaseinversioncanbe of two types:(i) Catastrophicinversioncausedby increasingthe

dispersephasevolume fraction abovea critical value (mostly above the maximum
packingfraction)and (ii) transitionalphaseinversionproducedby changingthe condi-
tions,e.g., an increasein temperaturewith emulsionsstabilizedby ethoxylatedsurfac-
rants.Catastrophic phaseinversioncanbe eliminatedby reducingthe phasevolumeof
the dispersephasein the emulsion.This is usuallynot a problemsincemostemulsion
systemsare preparedat dispersevolume fractionswell below the maximum packing
fraction. Transitional phase inversionhas to be preventedby the proper choiceof
emulsifier.This problemhasbeendiscussed in detail by Shinodaand Saito(16). With
O/W emulsionsbasedon ethoxylatedsurfactants, phaseinversionmay take placeat a
critical temperature(referredto asthe phaseinversiontemperature,PIT). With increas-
ing temperature,the polyethyleneoxide(PEO) chainbecomesdehydrated(asa resultof
the breakdownof the hydrogenbondbetweenEO and H20 ). This resultsin reduction
of the aqueoussolubilityof the surfactant,and at the PIT the surfactantbecomesmore
oil-soluble and hence suitable for formation of a W/O emulsion.

The above-mentioned problemof phaseinversionis eliminatedwhen usingpolymeric

surfactantssuchashydrophobically modifiedinulin (HMI). This polymericsurfactantis
not oil-solubleat any temperature,and henceby increasingthe temperaturethereis no
chanceof inversionto a W/O emulsion.As long as no coalescence or Ostwald ripening
occurs(asdiscussed above),the O/W emulsionremainsstableup to high temperatures
without any phaseinversionoccurring.

CONCLUSIONS

This overviewshowsthe main advantages of polymericsurfactants in the stabilizationof

emulsions for personalcareapplications.For O/W emulsions, a hydrophobically modi-
fied inulin (HMI) graft copolymeris shownto be very effectivefor stabilizationof the
emulsionsboth in water and in high electrolyteconcentrations at high temperatures.
This is attributedto the multipoint anchorof the HMI at the O/W interface.The loops
of polyfructose remainhydratedboth in water and in high electrolytesolutionsup to
high temperatures.For W/O emulsions,an A-B-A block copolymerwas the most
suitable.A is poly(ethyleneoxide)(PEO) (the anchorchainin water droplets),and B is
polyhydroxystaric acid (PHS) (the stabilizingchainsthat are stronglysolvatedby hy-
 EMULSION STABILIZATION 169

drocarbon molecules).Any creamingor sedimentation of the emulsionscanbeprevented

by using"thickeners" (suchashydroxyethylcelluloseor xanthangum) that producehigh
viscosity(> 1000 Pas)at low shearstresses
or shearrates.The HMI polymericsurfactant
alsopreventsphaseinversion,sincethe moleculeis insolublein oil at all temperatures.

ACKNOWLEDGMENT

The authoris gratefulto Orafti BiobasedProductsfor sponsoring

the researchon the use
of INUTEC © SP1 for the stabilization of emulsions. For more information on the
technicalapplications
of INUTEC © SP1 in cosmetic formulations
the readercancontact
Mr Karl Bootenof Orafti: e-mail addresskar/.boote,@orafii.
com.

REFERENCES

(1) Th.F. Tadrosand B. Vincent, in Encyclopedia

of Emulsion
Technology,
P. Becher,Ed. (Marcel Dekker,
New York, 1983).
(2) I. Piirma, PolymericSurfactants,
SurfactantScienceSeries,No. 42 (MarcelDekker, New York, 1992).
(3) C. V. Stevens,A. Meriggi, M. Peristerpoulou,P. P. Christov,K. Booten,B. Levecke,A. Vandamme,
N. Pittevils, and Th.F. Tadros,BiomacromolecMe•,
2, 1256 (2001).
(4) E. L. Hirst, D. I. McGilvary,and E.G. Percival,J.Chem.Soc.,1297 (1950).
(5) M. Suzuki,in Sdence andTechnology
ofFructans,
M. Suzukiand N.J. Chatterton,Eds.(CRC Press,Boca
Raton, Fl., 1993) p. 21.
(6) Th.F. Tadros, C. Dederen, and M. C. Taelman, Cosmet.Toilerr., 112, 75 (1997).
(7) Th.F. Tadros,in Polymer Colloids,
R. Buscall,T. Comer,andStagemanAppliedSciences, Eds.(London,
Elsevier, 1985), p. 105.
(8) D. H. Napper, Polymeric Stabilizationof Dispersion•
(AcademicPress,London, 1983).
(9) P.J. Flory, Principlesof Polymer Chemistry (CornellUniversityPress,New York, 1953).
(10) Th.F. Tadros,A. Vandamme,K. Booten,B. Levecke,andC. V. Stevens,Colloids Surf, 250, 133 (2004).
(1 1) J. Esquena, F. J. Dominguez,C. Solans,B. Levecke,K. Booten,andTh.F. Tadros,Langmuir,19, 10469
(2003).
(12) P. Walstra,in Emyclopediaof Emulsion
Technology,
P. Becher,Ed. (MarcelDekker, New York, 1985),
Vol. 4, p. 1.
(13) Th.F. Tadros,in Emulsiom•AF•mdamen•a/and Practical Approach,J. Sjoblom,Ed. (NATO ASI Series,
Vol. 363, 1992), p. 173.
(14) I. M. KriegerandM. Dougherty,Trans.Soc.Rheol.,3, 137 (1959); I. M. Krieger,Adv. ColloidInterface
Sci., 3, 111 (1972).
(15) Th.F. Tadros,Adv. ColloidInterface
Sci., 108-109, 227 (2004).
(16) K. Shinodaand H.J. Saito,ColloidInterface
Sci,,30, 258 (1969).