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Multiple-phase oil-in-water emulsion

Article  in  Journal of the Society of Cosmetic Chemists · January 1990

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j. Soc.Cosmet.
Chem.,41, 1-22 (January/February
1990)

Multiple-phase
oil-in-wateremulsions

GILLIAN M. ECCLESTON,Department ofPharmacy,

University
of
Strathclyde,
Glasgow
GI IXW, Scotland,
U.K.

Received
November
8, 1989. Presented
at theAnnualMeeting
of the
Society
ofCosmetic
Chemists,
New York,December1989.

Synopsis
Cosmeticoil-in-water emulsionssuchas lotionsand creamsare complexmultiple-phasesystems.In their
preparation,combinations of fatty amphiphiles(glycerylmonoestersor fatty alcohols)
andionicor nonionic
surfactantsarewidely used.The mixedemulsifiercombinations interactin the aqueous continuousphases
to form lameliaror crystallinestructures.Theseboth stabiliseand sometimescontrolthe consistencies of
emulsions betweenwide limits. Thereis, however,confusion asto the typeof lameliarphasethat formsin a
specificemulsion.The majorityof the literaturefailsto distinguishbetweenthe lamellarliquid crystalline
stateandthe equallyimportantlamellargel state.Althoughliquid crystallinephasesform in manyemul-
sionsat the high temperaturesof manufacture,theseoftenconvertto gel phaseswhen the emulsioncoolsso
that the propertiesof this phasedominatethe emulsion.
In thisarticlethe structures
andswellingpropertiesof the differentlameliarphasesthat occurin emulsions
arediscussed, aswell asthe formationof othercrystallinephases.Attentionis givento the conditionsover
which eachtype of phaseformsand, in particular, the relevanceof the gel-liquid crystallinetransition
temperatureto emulsions.It will be shownhow the behaviourof manycomplexemulsions during manu-
facture,storage,and usecanbe relatedto the componentphases.

INTRODUCTION

Most of the literaturepublishedaboutemulsionsis basedon attemptsto applyclassical

theoriesof colloidstabilityto well characterised
"model"systems.Theseare invariably
dilute, monodispersed, two-phase oil-and-wateremulsionsstabilisedby a singlesurfac-
tant emulsifier. The surfactant forms a monomolecular film at the oil-water interface
whereit introducesadditionalrepulsive(e.g., electrostatic,
steric,or hydrational)forces
that providean energybarrierto dropletcoalescence.
Cosmeticand pharmaceuticalemulsionssuch as lotions and creamsare rarely such
simple two-phasepreparations.They are more likely to be complexpolydispersed
systemscontainingseveralsurfactantand amphiphilicemulsifiersand to be composed
of additionalphasesto oil-and-water.The additionalphasesgenerallyform in aqueous
systemswhen the emulsifier,in excessof that requiredto form a monomolecular film,
interactswith continuous-phase water. Thus investigationinto the phasebehaviourof
emulsifiersand their mixturesin water providesvaluableinformationaboutthe micro-
structuresof emulsionspreparedwith them.
2 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Thereis nowsubstantial
evidencethat theformationof specific
lamellarphases
that are
capableof incorporating
largequantitiesof wateris an essential
requirementfor the
stabilityof manycommercialemulsions.Suchphases canalsoimparttherequiredrheo-
logicalproperties(for example,rangingfrom mobilelotionsto thick semisolidcreams)
to someproducts(1-3). However,thereis muchconfusion asto the typeof lameliar
phasethat forms in a specificemulsion.Most of the literature concentrates on the
formationof liquid crystalline
phases
and fails to identifythe equallyimportantgel
phases,eventhougheachphaseimpartstotally differentpropertiesto emulsionscon-
taining them. It is not alwaysappreciated that the lameliarliquid crystallinestateis
rarelydominantin cosmeticemulsions containinglong-chainalcohols,acids,or mon-
oglycerides as co-emulsifiers.
The commercialliteraturecontainsmany articlesthat
incorrectlydiscussthe presenceof bilayerliquid crystalline
phases in emulsions that are
actuallycomposed mainlyof gel phases.
In this paper,the microstructures andproperties of multiple-phase oil-in-wateremul-
sionsof cosmeticuse(in particulardermatological) will be described.Particularatten-
tion will be givento the variouslameliarliquid crystallineandgel phases aswell asto
other crystallinephasesthat occurin suchemulsions.It will be shownhow the behav-
iour of manyreal emulsions duringmanufacture, storage,anduse(i.e., afterapplica-
tion to the skin)canbe relatedto their component
phases.

STRUCTURE OF LAMELLAR LIQUID CRYSTALLINE AND GEL PHASES

Lamellarphasesin which surfactantmoleculesare arrangedin bilayersseparatedby

layersof waterareformedin waterby a rangeof surface-active materialsunderspecific
conditions.The hydrocarbon chainsof the bilayerscan exist in a numberof physical
states(4,5), the mostrelevantto emulsionsbeing the so-calledordered,or gel, and
disordered,or liquid crystalline,states(Figure 1). In the gel state the hydrocarbon
chainsare packedin a hexagonal subcellwith rotationalmotionaboutthe long axes,
whereasin the liquid crystallinestatethey are disordered and liquid-like. The order-
disordertransition,Tc, is essentially
the meltingof the hydrocarbonchainswithoutany
lossof long-rangestackedbilayerstructure.The transitionoccursat a characteristic
temperature,influencedprimarily by the characteristics of the hydrophobicportion of
the surfactant.Transitiontemperaturesincreasewith increasingacyl chainlength and
decreasewhen unsaturatedor branchedchainsare present.
Suchbilayerstatesare of interestin severalscientificareas,and consequently a con-
fusing number of different nomenclatures are used to describethem. The lameliar
liquid crystallinephasesthat occurabovethe phasetransitiontemperaturehavebeen
calledneat, G, or L= phase.Bilayergel phasesthat occurbelowthe transitiontempera-
turearealsoreferred
toasc•-crystalline
gelorL• phase
(4),andthetransition
tempera-
ture asthe chainmelting temperature,CMT, or the penetrationtemperature,Tpen (1).
The designationL, i.e., lameliar,with the subscriptc•- for the disordered
liquid crys-
tallinephaseand the subscript[3- for the morerigid gel phase,is not entirelysatisfac-
tory. Confusioncanarisebecause identicalGreeklettersc•- and [3-areusedto describe
crystallinepolymorphsof someamphiphilicemulsifiers,includingthe fatty alcohols.In
this paperthe orderedand disordered stateswill be described
simplyasgel and liquid
crystallinephases.Severalother typesof gel phasehavebeenreportedin the general
 OIL-IN-WATER EMULSIONS 3

//

Below Above --
WAT E R T½ • Tc WATER

GEL LIQUID CRYSTAL

Figure l. The order-disorder
transition,To and the lameliargel and liquid crystallinephasesthat form
spontaneously
whena naturalsurfactant(polarlipid) is dispersed
in water.

literature
aboutsurfactants
(forexample,
thetiltedL•' gelphases
or inderdigited
monolayer
phases
(4-6)), but thesehavenot beenreportedin emulsions.
Both the gel and liquid crystallinestatesformedby bi-alkyllipids(Figure1) arewell
known to biologicalscientists,as they representthe fundamentalstructureof most
animal cell membranesand are alsoan importantstructuralelementin the barrier
functionof the stratumcorneum(7). Many polar lipids suchasthe lecithinsare natural
surfactantswith a hydrophobic portioncomposed of two hydrocarbon chainsof different
lengthsanddegrees of unsaturation.
In cellmembranes thesearefinelybalanced to give
the requiredlevelsof order and disorder,and the transitiontemperatureis closeto
physiological temperature.Smallchanges of temperature,pressure,or otherbiological
stimuli canlocallyfluidiseor crystallise
the membraneto makeit moreor lessperme-
able. In the skin the long hydrocarbon chainsand high transitiontemperatures of the
stratumcorneumlipids imply that the normalorganisation of this barrieris the gel
state.

There is lessinformationabout thesestatesin the emulsionliterature, althoughboth

naturaland syntheticemulsifiersoftenform liquid crystallineand gel phasesin water
4 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

over the rangeof temperatures relevantto the manufactureand storageof emulsions.

The rest of this paperwill describethe importanceof thesephasesin emulsiontech-
nology.

EMULSIFIERS USED IN MULTIPHASE EMULSIONS

Most commercial emulsions contain mixtures of emulsifiers formed from combinations

of fatty amphiphilesandsurfactants.Mixturesof sparinglysolublelong-chainalcohols
or glycerylesters,suchasglycerylstearate
(G.M.S.) with moresolubleionicor nonionic
surfactants,are well known in cosmeticscience.The emulsifiercomponents
are either
addedseparately
duringthemanufacture of theemulsion bydispersing thesurfactant in
waterandthe amphiphilein the oil with the aid of gentleheat,or, alternatively,they
areaddedcombinedasa previouslyblendedemulsifyingwax. A selection of commonly
usedsurfactants,
amphiphiles, andemulsifyingwaxesis includedin TableI.
The surfactants,which aloneare capableof stabilisingsimpleoil-in-wateremulsions,
aregenerallyreferredto asthe primaryemulsifier,andthe fatty amphiphiles,whichare
too lipophilicto promoteoil-in-wateremulsions,as the secondary, auxiliary,or co-
emulsifier.It will be shownthat this terminologyis misleading,for the fatty amphi-
phile is usuallythe dominantor primaryemulsifierin suchmixtures.

INTERACTION OF EMULSIFIERS IN WATER

EMULSIFIER COMPONENTS

Surfactants.
Polarlipidssuchasthe soybean lecithinsaresometimes
usedin preference
to syntheticsurfactants
in dermatological
emulsions, astheyareconsidered
lessharmful
to the skin. Lecithinsfrom this sourceare usuallycomposedof homologueadmixtures
of unsaturatedC•6-C18 acidsand may havegel-liquid crystallinetransitiontempera-
turesas low as -22 ø (8). This meansthat althoughtheoreticallythey canform gel
phases,liquid crystalsarepresentin mostof the aqueous solutions
studied.

Table I
Selection
of CommonlyUsedAmphiphiles,Surfactants,
andEmulsifyingWaxes

Amphiphiles Surfactants

Cetearylalcohol Triethanolamine
stearate
Cetylalcohol Sodiumlaurylsulphate
Stearylalcohol Cetrimoniumbromide
Glycerolstearate Ceteth20
Stearic acid Lecithin
Cholesterol PEG-20 stearate

EmulsifyingWaxes Components

Emulsifyingwax U.S.N.F. Cetearylalcohol,polysorbate

Cationicemulsifyingwax B.P.C. Cetearylalcohol,cetrimoniumbromide
Glycerylstearate,S.E. Glycerylstearate,soap
Cetomacrogol emulsifyingwax B.P.C. Cetearylalcohol,ceteth20
 OIL-IN-WATER EMULSIONS 5

In contrast,syntheticsurfactantemulsifiersdo not form bilayergel phases,although

liquid crystallinephasesare common.The chemicalstructuresof syntheticsurfactants
in generalare much simplerthan thoseof the naturallipids, as mosthaveonly one
hydrocarbon
chain,containing
12-18 carbonatoms.In water,asthe surfactant
con-
centrationis increased,
a varietyof structures,includingthe bilayerneat phase,can
form(Figure2a). In the neatphase,the hydrocarbon chains arein thedisorderedor
liquidcrystalline
state,similarto thatdescribedabove forlipidsabove thephasetransi-
tion temperature.The thickness of the waterlayersis limitedbecause excesswater
inducesa phasetransitionto a miceliarsolution.
Oncooling theneatphase to belowthe
transitiontemperature,
the surfactant
crystallises
out (Figure2a).
Fattyamphiphiles.
Fattyamphiphilessuchaslong-chain alcohols,acids,andmonoglyc-
eridesandpuresaturated synthesised
lecithins
aretoolipophilicto formbilayerphases
in water, althoughthey do exhibitmarkedcrystallinepolymorphism. For example,
purelong-chain alcohols
showat leatthreesolidmodifications.Thehigh-temperature
o•-formseparatesfirst from the melt and is stableovera narrowtemperaturerange.In
this form the'hexagonallypackedhydrocarbon chainsare fully extendedin the trans-
conformation
andthereisrotational
motionaboutthelongaxisof themolecule
(cf.L•
phasedescribed above).At lowertemperatures the [3 and 'y forms,wherethe hydro-
carbonchainsare non-rotating([3-form)or tilted ('y-form),canco-exist,althoughthe
[3-formis usuallyin excess.The o•-[3(or 'y-) transitiontemperatureis loweredin the
homologueadmixturessuchascetearylalcoholand in the presence of water, wherethe
crystals
oftenshowlimited swelling(9-11). Thesehydratedcrystals(Figure2b) arenot
usually referredto as gel phase, for their swelling is limited by the considerable
strengthof the van der Waals attractiveforcesbetweenthe lipid layersthat balance
osmoticrepulsions. They aresometimes called"coagel"phase whendispersed asmicro-
crystalsin water.

MIXTURES OF SURFACTANTS AND AMPHIPHILES

It is emphasised
abovethat gel phases do not form wheneithersurfactants or fatty
amphiphilesaloneare dispersedin water. However,undercertainconditions(for ex-
ample,in thepresence
of charged groups),thelimitedswellingof thefattyamphiphiles
describedabovecan be increasedmarkedlyto give gel phases.When heatedto above
the hydrocarbonchainmelting temperature,the gel phasetransforms to swollenla-
meliar liquid crystallinephase(Figure2c).
The chargemayarisefrom ionisablepolargroupsin the amphiphileitself.This is the
casewith neutralised
monoglyceride emulsifiers,
whereneutralisation of freefatty acids
normallypresentin the crudesourcematerialintroduces smallquantitiesof ionicsur-
factant(12-14). Alternatively,the chargecanarisefrom the additionof an ionicsur-
factant,as in somefatty alcoholemulsifyingwaxesand the glycerylmonoesterself-
emulsifyingwaxes.Gel phasesalsoform with fatty alcoholsin the presence of small
quantitiesof nonionicsurfactant.
Both the gel and liquid crystallinephasesformedfrom thesemixturescan swell to
incorporate
significantquantitiesof waterin the interlamellar
space.This distinguishes
themfromthe "neat"liquid crystalline phases describedabove,whereexcess waterwill
inducea phasetransition.The swellingthat occurs
in thepresence
of charged
groupsis
electrostaticand in somesystemsis so extensiveat high water concentrations
that it is
 6 JOURNAL OF THE SOCIETY OF COSMETICCHEMISTS

(a) (b) (c)

Water

liquid crystal molten state

swollen liquid crystal

Above Tc

i Above
Tc
TcBelow Tc
I,c Below Tc
'IT•
bøve
Tc
Below Tc

Water

Soap crystal hydrated crystal swollen gel phase

Figure2. Summary
of theaqueous
phases
thatformbelowandabove
thehydrocarbon
chain-melting
temperature
formixedemulsifiers
andtheircomponents.
(a)hydrophilic
surfactant:
soapcrystals
below
and
liquidcrystals
abovethetransition
temperature.
(b)fattyamphiphile:
hydrated
crystals
belowandthemelt
abovethe transition
temperature.
(c) fattyamphiphilecombined
with smallquantities
of surfactant:
swollen
gelphasesbelowandswollen
liquidcrystalline
phases
above
thetransition
temperature.

describedas"infinite."Gelphases
thatformin thepresence of nonionic
surfactants
are
a resultof hydrationmechanisms.
Thesignificanceof lamellar
phaseswelling
to emul-
sionstabilitywill bediscussed
in moredetailwith specific
examplesbelow.
 OIL-IN-WATER EMULSIONS 7

EMULSIONS STABILISED BY LIQUID CRYSTALLINE PHASES

Liquidcrystals
formin the continuous
phases
of emulsions
containing
single-surfactant
emulsifiersand variousnonionicsurfactantmixtures.They alsoform in emulsionspre-
paredwith commercial lecithins,andwith mixturescomposed of surfactants
combined
with medium-chain(lessthan C•2) alcoholswherethe liquid crystalline-geltransition
temperatures
are below the storageand testingtemperatures of the emulsions.Such
medium-chainalcoholsare not usedas bodyingagentsbecause of their low transition
temperatures.

The reasons for the increasedemulsionstability in the presence of liquid crystalline

phases arenot fully understood.
Fribergandhisschool(15-16) relatethisphenomenon
to the equilibrium conditionsin ternary phasediagrams.They showedthat stable
emulsions are producedin the regionsof the phasediagramwherethe oil, water, and
lameliarliquid crystal(Lb) phaseare in equilibrium.They suggestthat multilayersof
liquid crystalsform aroundthe oil droplets(Figure 3) that protectthe dispersephase
from coalescence by two major mechanisms: first, the reductionof the van der Waals
forcesof attractionbetweenoil dropletsto a verylow value,andsecond,the retardation
of the film-thinningprocess duringcoalescence due to the increased "viscosity"of the
liquid crystallinephase.
Rydhagand co-workers(17-18) demonstrated that emulsionstability is further en-
hancedwhenthe liquid crystallinemultilayersareextensively swollenwith water. With
phospholipid emulsifiers,the swellingis controlledby the numberof dissociated ionic
groupsandcanbe enhanced furtherby the additionof ionicsurfactant.Batchvariations
in the amountsof negativelychargedlipidscontainedin commercial lecithinscanlead
to differingemulsifyingpowersbecause of the variationsin swellingpropertiesof the
resultantliquid crystallinemultilayers.
Liquid crystallinephasesalsoform in emulsionscontaininglong-chainfatty alcohols
during the high temperaturesof manufacture.Theseare of a transientnature,for they
convertto gel phasesas the emulsionscool, andwill be discussed
in the next section.

EMULSIONS STABILISED BY GEL PHASES

The gel-liquid crystallinetransitiontemperaturesof manyamphiphile/surfactantcom-

binationsare aboveambient, so that liquid crystallinephasesoccuronly during the
high temperatures of preparation.On cooling,gel phasesform, which are responsible
for the structureand stabilitiesof many "bodied"oil-in-wateremulsions.

THE GEL NETWORK THEORY OF EMULSION STABILITY

The gel networktheoryof emulsionstability givesa coherentexplanationfor the

mannerin whichfatty amphiphilesandsurfactants combinedasmixedemulsifiersnot
only stabilisemultiphaseoil-in-waterlotionsand creamsbut alsocontroltheir consis-
tencies.Although most of the early work was performedusing long-chain(i.e.,
C16-C18)fatty alcohols,the theoryis general,and the samebroadprinciplesapply
whicheveramphiphileor surfactant(ionicor nonionic)is used.The theoryrelatesthe
stabilitiesand physicochemicalpropertiesof multiphaseoil-in-wateremulsions to the
presence or absenceof viscoelastic
gel networksin theircontinuous
phases.
The network
8 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Figure3. Schematic
diagram
of anemulsion
dropletstabilised
bymultilayers
of lamellarliquidcrystals.

phases
formwhenthefattyamphiphile
andsurfactant,
in excess
of thatrequiredto form
a mixed monomolecular
film at the oil-water interface,interactwith water. Thus the
properties
andphasebehaviour of mixedemulsifiers
andtheircomponent surfactantsin
water both aboveand belowTo as well as the corresponding emulsions,are often
investigatedin parallel.Equilibratedemulsifier/water
ternarysystemscontaining con-
centrations
of mixedemulsifiersimilarto thoseusedto stabilise
emulsionshaveproved
usefulasstructural"models"forthecontinuous phasesof theemulsions
(TableII). Data
usedto develop
thegelnetworktheory,includingevaluation
of theviscoelastic
proper-
ties of ternarysystemsand emulsions,are summarised
in reviews(1,2).

MICROSTRUCTURE OF THE GEL NETWORK PHASE

Thefinestructure of theternaryviscoelastic
continuousphaseis complex.
Recenthigh-
andlow-angle x-raydiffraction
studies
(sometimes usinga powerfulsynchrotron
radia-
tion source),togetherwith light andelectronmicroscopy,haveconfirmedunequivo-
 OIL-IN-WATER EMULSIONS 9

Table II
Composition
of Emulsions
andCorresponding
TernarySystems

Emulsion Ternarysystem

Liquidparaffin 100 -- g
Water 300 300 g
Fatty amphiphile
(cetearyl
alcohol) Varied7-57 Varied7-57 g
Surfactant
(ionicor nonionic) Varied0.8-6.4 Varied0.8-6.4 g

cablythat complexcrystallinegel phasesarea major componentof emulsionsstabilised

by combinationsof fatty alcoholsandionicor nonionicsurfactants
(19-21).
Figure4 showsa schematic diagramof a typicalo/w emulsionstabilisedin thismanner.
At leastfour phasescanbe identified:
1. Dispersedoil phase
2. Crystallinegel phasecomposedof bilayersof surfactant
andamphiphileseparated
by
"thick" layersof water
3. Crystallinehydratesof amphiphile
4. Pockets of bulk "free water"

The oil dropletsaresurrounded by multilayersof gel phasethat becomemorerandomly

orientedasthey progress furtherinto the continuousphase.The gel phasecanexistin
equilibriumwith crystallineregionsand pocketsof bulk water. The oil dropletsare

Surface of
Oil Droplet
Interlamellar
Water

GEL PHASE

Figure 4. Schematic diagramof a typicalmultiple-phase

oil-in-watercreamto illustratethe composition
of the viscoelastic
continuous
phase(redrawnfrom ref. 19).
10 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

essentiallyimmobilisedin the structuredcontinuousphase,and both flocculationand

coalescence on storageare inhibited. Theseemulsionsare more stablethan thosecon-
taining liquid crystalsdescribedabovebecauseof the large amountsof incorporated
waterand the substantialmechanical strengthof the crystallinechains.It is interesting
to note that in thesemultiple-phaseemulsionsthe forcesof repulsion(electrostatic or
hydrational)betweenthe bilayers,ratherthan similarforceson the surfaceof the oil
droplets,areresponsible for preventingthe closeapproach of droplets.
Thesecrystallineand swollengel phasescan be identifiedmicroscopically. In model
mixed emulsifier/water
ternarysystems,crystallinemasses of alcoholappearto form a
focusfor variousbilayer structures(vesicles)of heterogeneouscomposition,size and
complexity.In emulsions, thegelphasebilayersarefocused asa rigid matrixaroundoil
droplets(Figure 5).
More detailedanalysisof the viscoelastic
phaseshasbeenobtainedfrom x-ray investi-
gationsof both emulsionsand emulsifier/watersystemsusinga synchrotronradiation
source(20). The progressive
swellingproperties
in water(0-94%) of a series
of emulsi-
fying waxescomposed of cetearylalcoholcombinedwith either ionic (cetrimonium
bromide)or nonionic(ceteth20) surfactants
are shownin Figures6 and 7a. They dem-
onstratethat differentswellingmechanisms are involvedin gel phaseformationwith
eachtype of surfactant.
Cetrimide emulsifyingwax exhibits the phenomenalswelling observedwith some
charged
lipids(14);thelameliar
spacing
thatincorporoates
theinterlamellar
waterin-
creases
from75• at 28%watertoapproximately500Aat 93%water(model contin-
uousphase).
Thehydrocarbon
bilayer
distance
(-50•) does
notchange markedly
asthe
watercontentincreases(Figure6). In contrast,thereis comparatively
limited incorpo-
rationof water betweenthe bilayersof the alcoholin the presence
of nonionicsurfac-
tant.Thewaterthicknesses
ofgelphase
varyfromapproximately75• at 10%w/w
waterto approximately
! 10• for84%water(Figure
7). Bothtypesofsystemshow
phaseseparationat high water concentrations.
The x-ray data confirmedthat swollengel phaseof similar bilayerthicknesses
was
presentin significantamountsin emulsionscontainingthesemixtures.The infinite
swellingwith ionic surfactantsis essentiallyelectrostaticin nature. Chargedgroupsat
the surfaceof the bilayerssignificantlyincreasethe forcesof repulsionbetweenthe
bilayers.In the presenceof nonionicsurfactant,the swellingis dueto hydrationof the
polyoxyethylene chainsof the interpositioned surfactantthat are orientatedand ex-
tendedinto the interlamellarwater layer(Figure 7b). Stabilisationof the nonionicgel
phaseis essentiallyby stericrepulsions
(22).

FORMATION OF THE GEL NETWORK PHASE

Emulsionsare manufacturedby mixing the moltencomponents

and then coolingto the
storagetemperature. At thehightemperatures of manufacture,
theemulsion formedby
homogenisation is stabilisedby an adsorbedmonomolecularfilm at the oil droplet/
waterinterface.During the coolingprocess,
fattyamphiphilebecomesprogressivelyless
solublein the oil and diffusesfrom this phaseinto the aqueousmiceliarenvironmentto
formeitherspherical
mixedmiceliesor lameliarliquidcrystalsthatwill furtherstabilise
theemulsion.A smallportionof theoil is alsosolubilised.
Whenthetemperature falls
belowthe transitiontemperature,which is between40ø and 50øCfor mostfatty
 OIL-IN-WATER EMULSIONS 11

Figure 5. Photomicrographs of (a) a cetearylalcohol/cetrimoniumbromide/waterternarysystem(93%

water) and (b) a diluted semisolidliquid paraffin-in-wateremulsionstabilisedby cetearylalcoholand
cetrimonium bromide.
12 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

6OO

30O

0 I I I I I
20 40 60 80 100
OloWater
(w/w)
Figure6. Lowanglex-raydiffraction
(synchrorron
radiation
source)
of theswellingof an ioniccetearyl
alcohol/cetrimonium
bromideemulsifyingwax in water (20).

alcohol/surfactantsystems,the liquid crystalsconvertto the gel phaseand any

unreactedalcoholprecipitatesto give the complexviscoelasticgel networks.If the gel
phaseis thermodynamically stable,then furtherinteractionbetweenunreactedcrystal-
line alcoholand surfactantsolutionmay occuron storage,with the formationof addi-
tional gel phase.

SETTING TEMPERATURE

The transitiontemperatureis sometimesreferredto as the "settingtemperature,"as

many commercialemulsions,especiallythose containing ionic emulsifying waxes,
changefrom milky fluidsto thick semisolids
at this temperatureduring the manufac-
turing process.

INFLUENCE OF PROCESSING VARIABLES, STORAGE, AND USE

Differences
in manufacturing
techniques
suchasthe rateof the heatingor coolingcycle
and the extent and orderof mixing cancausevariationsin the consistencies and rheol-
ogy of the final product,ascanbatchvariationsof eitheremulsifiercomponent.Many
of thesephenomena canbe directlyrelatedto the formationand microstructuresof the
phasesdescribedabove.Of particularrelevanceto the propertiesof real emulsionsare
the mechanisms of formationand the stability of the gel phase,the thicknessof the
 OIL-IN-WATER EMULSIONS 13

200

160

z
120

40

I i i I

20 40 60 8O 100
• WATER (W/W)
Figure7a. Lowanglex-raydiffraction
(synchrotron
radiation
source)
oftheswelling
ofa nonionic
cetearyl
alcohol/ceteth20 emulsifyingwax in water (20).

•i(-7' "-Z-Z-7'-Z-Z-Z-Z-Z%Z-Z-Z-'
....-Z-Z-Z-'

50A Interlamellar distance

BilayerL
I I
120-170 A

Figure7b. Schematic
diagram
ofthegelphase
formed
fromcetearyl
alcohol
andnonionic
polyoxyethylene
surfactant(ceteth 20).
14 JOURNALOF THE SOCIETYOF COSMETIC
CHEMISTS

interlamellarwaterlayers,and the relativeamountsof the crystalline,gel, and water

phases.

CONSISTENCY CHANGES ON STORAGE

Emulsionspreparedwith fatty alcoholsand ionic surfactantsreachtheir final consis-

tencieswithin hoursof manufacture.
This is because
interaction
to formbothliquid
crystals
abovethe transition
temperature
andgel phasebelowthe transition
tempera-
ture is rapid. Phaseequilibriumis reachedsoonafter preparationso that there are
relativelyminormicrostructuralchanges on extendedstorage.In contrast,systems
pre-
paredwith fattyalcohols
andnonionic surfactants
oftengelup considerably onextended
storage(Figure8a), andthis may resultin a cosmetically
unacceptableproduct.
Structural
build-upoccursin nonionicemulsions
because
significant
amounts of gel
phaseformbelowthetransitiontemperature
onstorage
aftermanufacture
(23). A very
complexphasesituationis envisaged
during the preparationof suchemulsionsbecause
hydrationof the polyoxyethylene (POE)chainsis limitedat high temperaturebut in-
creasesprogressivelyas the emulsioncools.Abovethe transitiontemperature,large
masses of moltensurfactant and alcoholarepresentin additionto liquid crystals.In
these,thehydrocarbon chainsof thesurfactant
aredispersedamongthoseof thealcohol,
and clustersof POE groupsarepresentboth at the surfaces
andwithin the masses.
As
systems cool,the POEgroupsbecome moresolubleand,if hydrationforcesarestrong
enough,lamellarliquid crystalsseparate. When the transitiontemperatureis reached,
the liquid crystalstransformto gel phaseandthe unreacted emulsifierprecipitatesas
crystallinemasses.The partially interactedmassesof alcoholand surfactantare often
visiblemicroscopically in freshlypreparedformulations (Figure8b). On storage,
aqueous surfactant
continuesto penetratethe crystalline
mases,whichdisappear asad-
ditionalgel phaseforms.As this involves the incorporation
of significant
quantitiesof
water,therearemarkedconsistency increases.The structure
buildsup relativelyslowly
because thecrystalline
natureof thehydrocarbon chainslimitsboththerateofpenetra-
tion by waterandthe subsequent rearrangement intoswollenbilayers.

PROCESSING VARIABLES

It is well knownthat processingvariables

affectthe structureandproperties
of emul-
sions.However,theseeffectsarenot dramaticwith fatty alcoholscombinedwith ionic
surfactants. Differences
in consistencies
of oil-in-watercreams prepared
with cetearyl
alcohol and an ionic surfactant(cetrimonium bromide) were shown to be due to varia-
tionsin sizeof the crystalline
hydratesratherthanto variationsin the gel phasestruc-
ture (24).
In contrast,preparationtechniques,in particularcoolingratesand mixing procedures,
havea markedeffecton initial andfinal consistencies
of emulsions
preparedwith fatty
alcoholsand nonionicsurfactants. For example,"shock"coolingand limited mixing
produces initially verymobilesystems, whereas slowcoolingwith adequate mixing
produces semisolidemulsions (25). Thesevariationsin rheological
propertiesare also
relatedto the mechanisms by which nonionicgel phasesform. Little gel phaseis
presentinitially in the systemafter shockcooling.Mixing time, when the emulsifiers
are in the molten state, influencesthe distribution of surfactant within the molten
masses
andbilayersandthe relativelamellarorderwithin the system.
 OIL-IN-WATER EMULSIONS 15

Initial l'5hr 8hr

1671

-1 24hr

•/•"• 32•80
I I

1640 328O

Shear Stress (dynecm-2)

Figure8. Emulsion
prepared
withcetearyl
alcohol
andceteth
20:(a)flowcurves
fortheemulsions
agedfor
thestatedtimes;(b) photomicrograph
of thefreshlyprepared
emulsion.
16 JOURNAL OF THE SOCIETYOF COSMETICCHEMISTS

The situationis morecomplexwhenfatty acidsare usedasthe amphiphile.Gel phases

formedwith stearicacid are metastableand convertto coagelphases(microcrystals and
water) when mixed at high shearrates.Thus a semisolidproductresultsif mixing is
discontinuedat the transition(i.e., setting)temperatureandthe emulsionis allowedto
cool undisturbed. A more mobile emulsion is formed if it is mixed below the transition
temperature,asconsiderable
mobilecoagelphasedevelops.

BATCH VARIATIONS OF EMULSIFIERS

Batch variationsin the emulsifiercomponentsas well as in the mixed emulsifiercom-

positioncaninfluencethe microstructureand propertiesof emulsions.
Fattyalcohols.Homologuecomposition of fatty alcoholsmarkedlyinfluences the quality
and propertiesof lotionsand creamspreparedwith them and may be the causeof
unexpected instabilitiesin established
formulations(26-28). For example,emulsions
preparedwith purealcoholsandionicsurfactants, althoughsemisolidinitially andof a
relatively high consistency,break down on storageto form mobile liquids. These
changesoccurbecause the gel phaseformedby pure amphiphilesafterthe heatingand
coolingcycleof manufacture is metastableat low temperatures. On storagethe interla-
mellar watergraduallyreducesto morestable[3- and %forms,accompanied by poly-
morphicphasetransitions,possiblyfrom the u-crystallineconfiguration.As the net-
worksentrappingthe oil dropletsdisintegrate,emulsions thin, andthe lamellarstruc-
turesvisiblemicroscopically in emulsionsdisappearand are replacedby crystals(cf.
Figures9b and 5b). Concurrently,in DSC a low-temperature endothermrepresenting
networkcrystallization developsand increases in intensity(Figure9).
Thesedifferences betweenthe abilitiesof pure and mixed homologueamphiphilesto
form stablegel phaseshavecausedmuch confusionin the past. In earlywork the gel
networkphasewascalled"frozenliquid crystalline"phasebecause it wasthoughtto be
a metastablestate that formedon coolinglamellar liquid crystallinephasesto below
their chain-melting temperatures.More recentinformation indicatedthat this termi-
nologywasmisleading,as it is now knownthat metastablegel phasesform only with
pure homologueamphiphiles.With mixed homologues suchas cetearylalcohol,ther-
modynamically stablegel phases canform spontaneously at low temperaturewithouta
prior heatingandcoolingcycle.In fact, emulsionscanbe preparedat roomtemperature
using solid micronisedcetearylalcohol,althoughthe extensivemixing requiredand
the resultantaerationof the productdo not makethis a commercially viablemethodof
preparation.(2).
Surfactants.
The homologue composition of the ionicsurfactantdoesnot markedlyinflu-
enceconsistency, probablybecause it is presentin smallamountsand its functionis
essentially
to providechargedgroups.With nonionicsurfactants, batchvariationsin
the lengthsof the POE chainscaninfluenceconsistency. If longerPOE chainsareused,
more water is trappedinterlamellarly,and henceconsistencies are higher (23).
Ratioofsurfactanttofattyalcohol.
Traditionally,commercial emulsifying
waxesandthose
of the variouspharmacopoeas containa largeexcessof alcohol.Forexample,the official
waxesof the BritishPharmacopoea contain! part by weightof surfactant
to 9 (ionic)or
4 (nonionic)partsof cetearylalcohol,representingapproximate molarratiosof 1:9 and
1:20, respectively.Althoughtheseratiosarenot critical,forgelphasecanformwith as
 OIL-IN-WATER EMULSIONS 17

Cetyl Alcohol Emulsion

I mv/cm
I day

Exo

7 days

Endo -- 10 days

I ,,I, I 1
20 4'0 60 80 100
øC

Figure9. Emulsion
preparedwith cetrimonium bromide
andpurecetylalcohol:(a)differential
scanning
calorimetry
asemulsion
ages;(b) emulsionaftersixmonthsagingshowingplatycrystals.
18 JOURNAL OF THE SOCIETY OF COSMETICCHEMISTS

1:10

1:20

Exo

1:30

1:60

1:120
__

,,,

Endo

I I I
t 50 6•0 70
TEMPERATURE (øC)
Figure10. Differential
scanning
calorimetry
scans
of agedternary
ceteth20/cetearyl
alcohol/water
systems.
Thenumbers
arethemolarratios
ofsurfactant
toalcohol
(29).

little as 1 mole% surfactant,

theredoesappearto be a definiterangeof surfactant
concentrationsoverwhichtheternaryviscoelastic gelnetworkphases
form.Within the
range,the relativeproportions
of the gel, crystalline,
andbulkwaterphases
changeas
surfactant concentration alters.
 OIL-IN-WATER EMULSIONS 19

The effect of surfactantconcentrationin a ceteth 20/cetearylalcohol/waterternary

systemwas investigatedrecently(29). At surfactantconcentrations greater than t0
mole % (l:t0), there is little crystallinephaseand the systemis translucent.As the
surfactantconcentration reduces,the crystallinephasesbecomemoreprominentandthe
gel phasesreduces,until at a molar ratio of 1:120 little gel phaseis present. The
changesin the relative proportionsof the phaseswere followedby DSC where the
low-temperaturecrystallineendothermdevelopsand the high-temperaturegel en-
dothermdiminishesas surfactantconcentrationincreases (Figure t0). With high sur-
factantconcentrations (greaterthan approximately30 mole %), the gel networkscon-
vert to an isotropicphaseand systems aremobile.

4'0-

3.0

>

.> 2.0

1'0

' 2'5 3'5 I •'5 •5 6'0 '

Temperature (øC)
Figure 11. Variationof apparent
relativeviscosity
with temperature
for a cetearylalcohol/cetrimonium
bromide emulsi•ingwaxin 94% wateranda liquidparaffin-in-wateremulsion prepared with thesame
wax (1).
20 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

I: I i i i I
•o ao •o 70 90 s(iA)
Time {min)
Figure 12. Correlationbetween(a) the weight of waterevaporatedfrom a ternarycetearylalcohol/cetri-
moniumbromide/water systemand(b) thechanges in thelowanglex-raydiffractionpatternof thissystem
duringevaporation.Eachframerepresents a two-minutecollectionperiod(31).

ACCELERATED STABILITY

A commonmethodof assessing the physicalstabilityof emulsionsis to subjectthem to

adversestorageconditions,includingextremevariationsin temperature(30). Attempts
are then madeto correlatestability at an elevatedtemperaturewith that at roomtem-
peratureover a much longer time scale.Such data can, however,be misleadingin
emulsionsstabilisedby gel phasesif the testingtemperatureis abovethe phasetransi-
tion temperature(unless,of course,suchtemperaturesare relevantto normalstorage
anduse).Figure11 showsthe effecton rheological properties
of heatinganionicternary
systemand emulsionto abovethe transitiontemperature.Consistency increaseswith
increasein temperatureup to the transitiontemperature,possiblybecause of increased
incorporationof waterbetweenthe bilayers,andthen rapidlydecreases aboveT c asthe
systems becomemobile. The informationgainedat temperatures abovethe transition
temperatureis thus of limited usefulness in the evaluationof instabilitiesthat might
occuron extendedstorageat lowertemperatures.

MICROSTRUCTURAL CHANGES DURING USE

Sofar the bulk microstructural propertiesof complexmultiphaseemulsionshavebeen

considered. However,when an aqueous emulsionsuchasa "bodied"lotionor creamis
appliedto the skinasa thin film, its composition will changeasa resultof theshearing
forcesof application,the penetrationof skinsecretions into, or the evaporation
of water
and volatile solventsout of the film. In recentwork, the microstructuralchangesthat
occurwhen thin layersof o/w emulsionsand their corresponding ternarysystems
evaporatewere followedby simultaneous evaporationand x-ray diffractionmeasure-
ments(Figure 12). The evaporation process
proceeded in threedistinctstages:an initial
rapid stagewhereapproximately 25% of the bulk waterwaslost and therewaslittle
changein interlamellardistance;a secondstagewherea further 15% of the water was
releasedandthe first orderdiffractionpatternsmovedto shorterinterlamellardistances,
implying somelossof interlamellarwater; and the final very slow stagewhereonly
interlamellarwater is lost and diffractionpeaksmoveto shorterdistances.Evaporation
 OIL-IN-WATER EMULSIONS 21

undercontrolledconditionswasnot completeafter 90 minutes, and the microstructural

changes
werekineticallydriven.

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(2) G. M. Eccleston,The microstructure of semisolidcreams,PharmacyInternational,
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22 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

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