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 polymericsurfactants.

The main breakdownprocesses
in emulsionsarebrieflydescribed.
A sectionis devotedto
the structureof polymericsurfactantsand their conformationat the interface.
Particularattention3
is given
to two polymericsurfactants
that 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 50C. The reasonfor this high
stabilityis describedin termsof the multipoint anchoringof the polymericsurfactant(by severalalkyl
groups),the stronghydrationof the inulin (polyfructose)
chains,andthe high concentration
of 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 50C.
The last two sectionsare concerned
with 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.
Syneresis
of the eulsions
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 50C.

INTRODUCTION

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

water-in-oil(W/O) emulsions.
Thesesystems
areonlykineticallystablesincethe energy
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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 nonspontaneous
(energyis requiredto form the emulsion),and the systemis thermodynamicallyunstable.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 surfactantbecomessolublein the oil phase,and hencea W/O emulsionis produced.

In orderto overcomethe above-mentioned

breakdownprocesses,
a numberof stabilization 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,coalescence,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
AT

OF POLYMERIC

SURFACTANTS

AND

THEIR

CONFORMATION

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 preferentialattachment 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

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

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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-blockcopolymers
havebeensynthesized:
diblocksof polystyrene
block-polyvinylalcohol;triblocksof poly(methylmethacrylate)-block
polyethyleneoxide-poly(methyl
methacrylate);
diblocksof polystyrene-polyethylene
oxide;andtriblocks
of polyethyleneoxide-polystyrene-polyethylene
oxide.
An alternative(andperhapsmoreefficient)polymericsurfactantis the amphipathicgraft
copolymerconsistingof a polymericbackboneB (polystyrene
or polymethylmethacrylate) 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
consisting 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(hydroponicallymodified 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

OH

(GFn)
Figure 2. Structureof hydrophobically
midfield inulin (HMI).

interface.

EMULSION

STABILIZATION

157

They will also adsorbon the oil dropletswith the alkyl groups strongly attached
(multipoint anchoring),leavingthe polyfructosechainsdangling in solutionand probablyforminglargeloops.As we will seelater, thesegraft copolymers
canproducehighly
stableemulsions,in particularat high electrolyteconcentrations.
An exampleof commerciallyavailableHMI 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
conformation
of the polymermoleculeat the interface.Thesemoleculesadoptvarious
conformations,
dependingon their structure.A schematicrepresentation
of the confor-

PH

i,

PE
Figure 3. Schematicrepresentation
of the structureof PHS-PEO-PHSblockcopolymer.

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Figure 4. Conformation
of hydrophobically
modifiedinulin (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 polymerconfigurations
that for full characterizationof the process
of adsorption,it is necessary
to know the followingparameters,

namely,
theamount
ofpolymer
adsorbed
perunitareaofthesurface,
17(molem 2ormg
m--2),thefraction
ofsegments
in close
contact
withthesurftce,
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

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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
layerthickness,8) approach
a distanceof separation,
h, wherebytheselayersbeginto overlap,i.e.,
whenh < 28, repulsion
occurs
asa 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,
p6,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.

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

volumeof the solvent,andNv 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-Hugginsinteraction 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 increases
very rapidlywith decreasing
h, when the latter is lower than

28. This explainswhy the hydrophobically

modifiedinulin (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(hydroxystearicacid) (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 represented
by a simplerod with oneattachmentpoint to the surface.When the two
surfaces
are separated
at infinite distance,eachchainwill havea numberof configurations,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

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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....

increases
veryrapidlywith a decrease
in h assoonash becomes
smallerthan28 (andX
< 0.5). Gd alsoincreases
veryrapidlywith a decrease
in h on furtheroverlap.Combinationof 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 adsorbed
layerthickness.
With an increase
of 8, Ginin decreases,
and at sufficientlyhigh valuesof 8 (of the orderof 5-10 nm), it reaches
smallvalues
(fractionof kT units). This showsthat with stericallystabilizeddispersions,
thereis only
weak attractionat relativelylong distancesof separation,which in most casesis overcomeby 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

G
h

Figure 8. Schematicrepresentation
of the variationof G.... Gd, G^, and G. with h.

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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 concentratedemulsions.A value of of the orderof 5-10 nm is usuallysufficient.

O/W

EMULSION

INULIN

(HMI)

STABILIZATION

BASED POLYMERIC

USING

HYDROPHOBICALLY

MODIFIED

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
consisted
of 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 highspeedstirrer,anUltra-Turrax(CAT X620). The emulsionqualitywasassessed
by optical
microscopy.
Samplesof the emulsionswerestoredat roomtemperatureandat 50C,and
the droplet size was qualitativelyassessed
by taking optical micrographsat various
intervals

of time.

Figure 9 showstypical micrographs

of diluted 50/50 IsoparM/water emulsionscontaining2 (w/v)% INUTEC surfactant
that werestoredforperiodsof 1.5 and 14 weeks
at 50C.As canbe seen,thereis no apparentincreasein dropletsizeduring this storage
time, and this wastakenasan indexof stability againstcoalescence.
Similar resultswere

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

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163

alsoobtainedfor ennuisions
storedat roomtemperature.No oil separation
wasdetected
after this period at RT and 50C.
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 50C. Thesesamplesdid not showany apparentoil separationeven
after storagefor 10 monthsat 50C. Basedon theseresults,it was shownthat for 50/50
(v/v) O/W emulsions,an emulsifierconcentrationin the region of 0.5 (w/v)% is sufficient 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 50Cfor 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
considers
the 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 temperaturesthan thoseexperiencedon storage(usuallythe X parameteris lessthan 1/2
below80C).With inulin, it doesnot showany dehydrationup to 100C.

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
electrolyteconcentrations
whencomparedto PEO chains,andthis is probablythe reason
for the higherstabilityobtainedwhenusingthe hydrophobically
modifiedinulin asan
emulsion

stabilizer.

To confirmthe above-mentioned
effects,we havecarriedout cloudpoint measurements
for PEO with 4000 molecularweightin the presence
of 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.

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PEG 4000 - Cloud point (C)

PEG 4000 - Cloud Point (C)

120

0 M NaCI

-*-

2M NaCI

3M NaCI

4M NaCI

4.5M NaCI

5M NaCI

6M NaCl

IO0

OOM
MgSO

[]
0.5M MgSO4
-- 1M MgSO4
:)1( 2M MgSO4
2O
0

% PEG 4000

% PEG 4000

Figure 10. Cloudpointsof PEO 4000 at variousNaC1(A) andMgSO4 (B) concentrations

asa functionof
PEO concentrations.
Cloud points of 100C 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 100C 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 (C)

120

"

0 M NaCI

100

[]

1M NaCI

8O

.".

2M NaCI

''

4M NaCI

6M NaCI

4o
2O
0
0

% PEG 20000

Figure 11. Cloudpointsof PEO 20000 at variousNaC1concentrations

asa functionof PEO concentration.

EMULSION

STABILIZATION

INUTECN 25 - Cloud points (C)

INUTECN 25 - Cloud points (C)

-,_

_-,

165

MNaCI

IM
NaCl
--- 2MNaCI
3M
NaCI

---)K--4MNaCl
5M NaCI
6M

1M MgS04

1.5M MgS04

2M MgS04

NaC
0

% INUTEC125

OM MgS04

% INUTEC125

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,thecloudpointisabout60C,
andif thepolymerconcentration
will reach,for example,20%, the cloudpoint couldbe
lower than 50C. Thus, for emulsion stabilizersbasedon PEO, stability cannot be

maintained
at 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 about100Cupto4 tooldin- NaC1,andhence
onewould
expectstableemulsionsat temperaturesexceeding50C up to this electrolyteconcentration. With MgSO4 stability can be maintainedat high temperaturesup to 1 tool

dm-3. Thus,thesecloud-point
measurements
giveconclusive
evidence
of the unique
behaviorof polymericsurfactants
basedon inulin. The polyfructosechain remainshydrated 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

50Cformorethanoneyear.Emulsions
prepared
in thepresence
of 1 tooldm-3 NaC1
and MgSO4 were alsostableup to 50C 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 according
to equation2); and (iv) enhanced
steric
stabilization
assuggested
by 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 molecules
will 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 dilatational
elasticity,thusreducingthe
process
of 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 50C for severalmonths,

and there was no evidenceof flocculationand/or coalescence,

as assessed
by using
rheologicalmeasurements
for concentrated
W/O emulsions.This stability is expected
sincethe anchorchain(PEO) is solublein water and insolublein oil, thus ensuringlack
of displacement
of the polymermolecules.
The PHS chainsremainedstronglysolvated
by the oil moleculesboth at room temperatureand at 50C, and this ensuredeffective
steric stabilization.

CONTROL

OF CREAMING

OR SEDIMENTATION

OF EMULSIONS

Creamingor sedimentationcan be controlledby addition of "thickeners"in the continuousphase.Most of thesethickenersare high-molecular-weight

polymerssuchas
hydroxyethylcellulose(or its hydrophobically
modifiedversion,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 discussed
before(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 "structured" 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 oscillatory 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 conditions,e.g., an increasein temperaturewith emulsionsstabilizedby ethoxylatedsurfacrants.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 increasing 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
surfactants
suchashydrophobically
modifiedinulin (HMI). This polymericsurfactantis
not oil-solubleat any temperature,and henceby increasing
the 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
modified 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, Polymeric

Surfactants,
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, Principles
of Polymer
Chemistry
(CornellUniversityPress,New York, 1953).
(10) Th.F. Tadros,A. Vandamme,K. Booten,B. Levecke,andC. V. Stevens,Colloids
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(1 1) J. Esquena,
F. J. Dominguez,C. Solans,B. Levecke,K. Booten,andTh.F. Tadros,Langmuir,19, 10469
(2003).

(12) P. Walstra,in Emyclopedia

of Emulsion
Technology,
P. Becher,Ed. (MarcelDekker, New York, 1985),
Vol. 4, p. 1.
(13) Th.F. Tadros,in EmulsiomAFmdamena/and
Practical
Approach,
J. Sjoblom,Ed. (NATO ASI Series,
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(14) I. M. KriegerandM. Dougherty,Trans.Soc.Rheol.,3, 137 (1959); I. M. Krieger,Adv. ColloidInterface
Sci., 3, 111 (1972).
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(16) K. Shinodaand H.J. Saito,ColloidInterface

Sci,,30, 258 (1969).