J. Soc. CosmeticChemists, 19, 683-697 (Sept.

16, 1968)

Effect of Initial Surfactant Locations

on the Viscosityof Emulsions

TONG JOE LIN, Ph.D.*

PresentedDecember6, 1967, New York City

Synopsis--Viscosities of emulsions immediately following homogenization were studied as a

function of HLB and the initial surfactant locations. Keeping the total surfactant concen-
tration constant, the ratios of the initial concentration of the hydrophilic surfactant to that
of the lipophilic surfactant in each phase were varied. The experimental results indicate
that the initial locations of the surfactants not only affect the initial viscosity of the emulsions
but also the emulsion stability, particle size distribution, and emulsion type as well.

INTRODUCTION

There are literally unlimited ways by which a given emulsioncan

be prepared (1, 2). Unquestionably,the method of preparationhas a
great influence on the physical properties of the finished emulsion.
Stanko et al. (3) conducteda seriesof expehmentswith a mineral oil
emulsionstabilized with nonionicsurfactants. They discoveredthat the
method of addition, the rate of addition, and the temperature of each
phaseat the time of emulsificationall had someeffectson the droplet size
distribution, viscosity, and the emulsionstability.
Using a two-level fractional factohal design,Bensonet al. (4) con-
ducted an extensiveinvestigationof six preparative variablesincluding:
order of addition, emulsifier location, emulsifier concentration, propor-
tion of water, emulsification temperature, and type of agitation. Four
oils were used and thirteen different surfactants were employed in their
investigation. They discoveredthat the chemical and physical nature

* Max Factor & Co., 1655 N. McCadden Place, Hollywood, Calif. 90028.
68.3
684 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

of the emulsifiersand oils had most significant effect on the stability of

the emulsions,and lessthan half of the systemsstudied showedstatisti-
cally significantdependenceon the preparative variables.
Most of the emulsionsin cosmeticpreparationsare stabilizedwith a
mixture of hydrophilic and lipophilic surfactants. These surfactants
may be incorporatedinto the emulsionin many different ways. Becher
(1) describesfour different ways of preparingan emulsiondependingon
the methodsof incorporatingemulsifyingagents:
1. Agent-in-water method. The emulsifying agent is dissolvedin
the water.
2. Agent-in-oil method. The emulsifyingagent is dissolvedin the
oil phase. The mixture is then addedto the water or water is addedto
the mixture.
3. Nascentsoap(in situ) method. The fatty acidis predissolved in
the oil and the alkaline part in the water so that the soapis sponta-
neouslyformed during emulsification.
4. Alternate addition method. The water and oil are added alter-
nately, in small portions,to the emulsifyingagent.
Since most emulsifyingagents have some solubility in both oil and
water, if a mixture of a hydrophilic and a lipophilic surfactant is dis-
solvedin the oil phaseprior to emulsification,a great part of the hydro-
philic surfactant and a small part of the lipophilic surfactant will un-
doubtedly migrate to the aqueousphase after emulsificationuntil an
equilibriumis established. A similar situationwill occurwhen the sur-
factant mixture is dissolvedor dispersedin the water prior to emulsifica-
hon.
It can be reasonedthat if the rate of surfactant migration from one
phaseto anotheris finite, the initial locationof the surfactantmay have
significanteffect on the physicalpropertiesof the freshly prepared emul-
sion. Since many surfactantshave marked effectson the viscosity of
the phasein which they are dissolvedor dispersed,the initial surfactant
location can, therefore, influencethe viscosity of a fresh emulsionbefore
it reachesequilibrium.
Undoubtedly, the rate of surfactant migration in an emulsifiedsys-
tem would be a complexfunction of the viscositiesof both phases,sur-
factant concentration,surfactant solubility, surfactant diffusivity, inter-
facial area, the property of the interfacial film, etc. It is expected
that the migration rate of a surfactant from the internal phase to ex-
ternal phasewould be relatively low if the viscosityof the internal phase
were sufficientlyhigh or if the resistanceof the interfacial film to mass
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 685

transfer were high. Conceivably,slowsurfactant migration may be one

of the reasons why some emulsions exhibit time-dependency of the
rheologicalproperties.
In this work, systemsinitially containingvarying proportionsof sur-
factants in each phase were emulsifiedunder carefully controlled condi-
tions and the viscositiesof the freshly formed emulsionswere determined
immediately after homogenization. In addition to the viscosity, effects
of the initial surfactant location on the particle sizedistribution, emulsion
type, and emulsionstability were alsoinvestigated. The main purpose
of this work was not to examine the causesof time-dependency, but
rather, an attempt was made to explore the ways by which initial sur-
factant locations affected the properties of the freshly prepared emul-
sions.

EXPERIMENTAL

Since the viscosity of an emulsionis strongly dependent on the pre-

parative variables, effortswere madeto controlall variablesto insurethe
reproducibility of the experiments.
In most instances,coarseemulsionswere preparedin a 2-1.rectangular
clear plastic vesselshown in Fig. 1. The mixing equipment used was
Model ELB ExperimentalAgitator Kit* designedfor bench-scale experi-
mental purposes. The kit consistsof 3 hp motor, variable speed drive,
and varioustypes of calibratedimpellers. The impellerchosenfor most
of the experimentswas a 2-in. flat 6-blade turbine. The locationof
the impeller was 3 in. from the bottom of the vesseland, unlessstated
otherwise,the mixer speedwas set at 400 rpm. In more viscoussystems
two 2-in. impellersset apart by 3 in. were used. The mixing time
used was mostly 3 minutes but in someviscoussystemsa longer mixing
time was used.
To keep the emulsionreasonablystable, the coarseemulsionprepared
in the vesselwas immediately passedthrough an ultrasonichomogenizer
once. The homogenizerused was a laboratory size Minisonic IV Ultra-
sonicEmulsifiert which operateson the mechanicalcavitation principle.
The valve setting used was such that the rate of dischargeof water at
24C was 1960 cc/min.
Prior to emulsification,emulsifierswere dissolvedor dispersedin each
phasewith a laboratory propellermixer at 600 rpm. Theseliquids were

* Manufactured by Chetnineer Inc., Dayton, Ohio.

p Manufactured by Sonic Engineering Corporation, Norwalk, Conn.
686 JOURNAL OF THE SOCIETY OF COSMETIC CItEMISTS

then placedin a constanttemperaturebath until the temperaturereached

24 = 0.1 C. The water phasewasfirst placedin the emulsificationves-
seland the oil phasewasthen slowlyplacedon the top of it. This opera-
tion was done very carefully to avoid emulsificationprior to turning on
the mixer.
All viscositymeasurementswere donewith BrookfieldSynchrolectric
ViscometerModel LVT,* and particle sizedistributionswere determined
from the enlargedphotographstaken througha microscope.
Emulsionstability wasjudgedby placingthe emulsionin a graduated
cylinder and determiningthe degreeof separationwith time.
The oil usedfor the experimentsis a light mineral oilt and deionized
water was usedfor the water phase. Surfactantsusedinclude: Tween
80, Arlacel 80,t,AmercholL-101,and Solulan98. These
surfactants are commercial grades and they were used without further
purification. The followingHLB valuessuggestedby the manufacturers
were usedfor computingthe HLB of the surfactant mixtures:
Tween 80 15
Ariaeel 80 4.3
Amerchol L-101 8
Solulan 98 13

RESULTS AND DISCUSSION

Effect on Emulsion Viscosity

The effect of initial locationsof the hydrophilic surfactant on the im-
mediate viscosities of emulsions stabilized with Tween 80-Ariaeel 80 is
shownin Fig. 2. The total surfactantconcentrationwaskept at 5% by
weight in all casesbut the HLB valuesfor each systemvaried from 6 to
14. The amount of the hydrophilic surfactant (Tween 80) originally
present in the aqeuousphase was varied from 0 to 100% of the total
amount employed. All the lipophilic surfactant (Arlacel 80) was placed
in the oil phaseprior to emulsificationin this seriesof experiments. The
emulsionscontained30% mineral oil and the coarseemulsionpreparedin
the emulsificationvesselwas passedthrough the homogenizeronce.

* Manufactured by Brookfield Engineering Lab., Stoughton, Mass.

t Carnation P-I oil, Witco Chemical Co., SonnebornDivision, New York, N. .
$ Tween 80 (polyoxyethylenesorbitan monooleate)and Arlacel 80 (sorbitan monooleate),
Atlas Chemical Industries, Wihnington, Del.
Amerchol L-101 (multisterol) and Solulan 98 (ethoxylated lanolin), American Cholesterol
Products, Edison, N. J.
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 687

I THERMOMETER TWEEN
80-ARLACEL
80
(5%TOTAL)

LEVEL
-
RBINE o o

IMPELLER
I I I I
0 20 40 60 80 moo
% TWEEN 80 IN AQUEOUS PHASE

5" Figure 2. Effect of initial hydrophilic sur-

factant location on the immediate viscosity
Figure 1. Emulsification vessel of emulsions

The emulsionsobtained showedpseudoplasticbehavior. Sincethe

main interest was to determine the relative effects of the initial surfactant
locationson emulsionviscosity, Brookfield viscometerreadingson 100
scaleswere usedrather than the absoluteviscosityunits. The viscom-
eter readingswereobtainedwith the No. 1 spindleat 30 rpm.
As indicated in Fig. 2, for the emulsionshaving relatively low HLB
values,the immediateviscosityfollowinghomogenization increaseswith
the amount of Tween 80 initially present in the aqueousphase.As the
HLB value increasesbeyond 8, this effect appearsto becomesmallerand
finally at HLB 14, the initial location of Tween 80 has no appreciable
effecton the immediateviscosityof the emulsion.
In Fig. 3, the systemsstudied were identical to the correspondingsys-
temsgivenin Fig. 2. However, insteadof varying Tween 80, the ratio of
the lipophilic surfactant, Arlacel 80, in the oil phase and the aqueous
phase was varied. All the hydrophilic surfactant was placed in the
aqueousphase before emulsification. The data show that the effect of
varying Arlacel 80 in the oil phasewas not as pronouncedas the effectof
varying Tween 80 in the aqueousphase. And again, virtually no effect
wasobservedin the highHLB systems.
As pointed out by a number of authors ($-7), emulsionviscosityis a
very complexfunction of the viscosity of the external phase, volume
fraction of the dispersedphase,viscosityof the internal phase,particle
size distribution, nature of the interfacial film, emulsifier concentration,
the extent of flocculation,etc. If the rate of surfactantmigration is rela-
688 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

w/o
,/
o/w

TWEEN 80 - ARLACEL 80
( % TOTAL)
30 % OIL

HLB 12 -

LB 14.
( 5% TOTAL)
TWEEN 80- ARLACEL80
HLB 6
0 I I I I I
0 20 40 60 80 I00 7'0% OIL

% ARLACEL 80 IN OIL PHASE

o 2o ,,o ;,o eo ,oo

% TWEEN 80 IN AQUEOUS PHASE

Figure 3. Effect of initial lipophilic sur- Figure 4. Effect of initial hydrophilic

factant locationon the immediateviscosity surfactant location on viscosity and type of
of emulsions emulsions

tively slow,conceivably,
the locationof initial surfactantin the aqueous
phasecan affect many of the abovementionedfactors. In this work, no
attempt was made to isolateeachfactor and determinethe mannerby
which the emulsionviscosityis influenced. However, as it will be
shownlater,the initial surfactantlocationcanhavea significant
effecton
the particlesizedistributionof the emulsionformedand, consequently,
on the emulsionviscosity.

Effect on the Type of Emulsion

In the systemswhere the HLB of the surfactants and the volume of
the internalphaseare suchthat it canformeitheran O/W or W/O type
emulsion,the initial surfactantlocationappearsto play an important
role in determiningthe type of the emulsion. In the systemsinvesti-
gated,placingof the entiresurfactants in the oil phaseappearedto pro-
moteformationof a W/O emulsion or a multipleemulsion. Ontheother
hand,placingof the surfactantsin theirrespective phases(i.e.,thehydro-
philic surfactantin water and lipophilicsurfactantin oil) seemedto en-
courageformulation of an O/W emulsion.
For example,in a 70% mineraloil systemstabilizedwith Tween 80-
Arlacel80 combinationat HLB 0, the viscosityincreasedsharplywhen
the initial concentration
of Tween80 in the aqueous
phasewasincreased
from0 to 10% (Fig. 4). Conductivitymeasurements indicatedthat the
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 689

o/w
--W/O [ O/W = w/o ;=

( 5 % TOTAL)
TWEEN
80- ARLACEL
80 / SOLULAN 98 - AMERCHOL L-IOI

HLB
I0 / ( 5% TOTAL)
HLB I0 60% OIL

70/001L
--

./ 20 40 60
% TWEEN 80 IN AQUEOUS PHASE
80 00

0 20 40 60 BO I00
% SOLULAN 98 IN AQUEOUS PHASE

Figure 5. Effect of initial hydrophilic sur- Figure 6. Effect of initial hydrophilie sur-
factant location on viscosity and type of factant location on viscosity and type of
emulsions emulsions

sharpincreasein the emulsionviscositywas due to phaseinversionfrom

W/O type to O/W type.
Figure 5 showsthe viscositychangefor a similar systemat HLB 10.
In this system, the inversion took place when the amount of Tween 80
initially in the aqueousphasecorresponded to approximately70% of the
total Tween 80 used. Figure 6 showsa similar curve for a Solulan98-
Amerchol L-101 system. In these three systemsthe viscosity readings
were taken with the No. 3 spindleat 30 rpm.
It has been known that the type of surfactantsas well as their con-
centration have marked effect on the type of emulsionformed (8, 9).
The presentwork indicatesthat not only the surfactanttype and concen-
tration are important, but the initial distribution of the hydrophilic sur-
factant prior to emulsificationcan also have a significanteffect on the
type of the emulsionformed.
Davies reasonedthat the type of emulsion formed as the result of
shakingofamixtureof oil andwaterwith an emulsifying
agentis deter-
minedby the relative coalescence
rates (10). He suggested
that:
Rate 2
O/Wemulsion
preferentially
stableif Rate>>1
and,
Rate 2
W/O emulsionpreferentiallystableif --- << 1
Rate 1
090 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

where:

Rate 1 = coalescencerate of an O/W emulsion

Rate 2 = coalescencerate of a W/O emulsion
From thermodynamicconsiderations,Davies further suggestedthat
the ratio of coalescence rates could be related to the HLB value of the
surfaetantand alsoto thepartitioncoefficient
of the surfaetantby the fol-
lowing equation:

CiRate
C2 2
1- (c,,'
Rate \/ '7 (1)
where:

C = collision factor for Rate 1

C2 = collision factor for Rate 2
c = surfactant concentration in water
Co = surfactant concentration in oil
0 = fraction of interface covered

This equationqualitatively agreeswith Bancroft'srule that the phase

in which the emulsifying agent is more soluble will be the continuous
phase (11).
If Coand c can be considered as the initial surfactant concentrations
in eachphase,it can be shownthat the aboveequationalso qualitatively
explainsthe resultsof the presentwork. For example,the data presented
in Fig. 5 indicatethat whenthe c is small(or Cois large) the systemwill
form a W/O emulsion. Examination of the above equation would also
indicatethat reductionof c,,,/Co
ratio wouldfavor a W/O emulsion.
In some systems studied which had relatively low HLB values,
multiple emulsionswereobservedunder the microscope. An exampleof
sucha systemat HLB 6 is shownin Fig. 7. A conductivity measure-
ment indicated that the continuous phase of this emulsion was water.
As can be seen from the photograph, most of the oil droplets contain
somevery smallwater particlesand the resultis a (W/O)/W type emul-
sion.
Interestingly, the initial surfactant locationswere also found to in-
fluencethe formation of such an emulsion. The emulsionshownin Fig.
7 was preparedby initially placing all the surfactantsin the oil phase.
Figure8 showsa microphotographof an identicalsystemstabilizedwith
Tween 80-Arlacel 80 at HLB 6. The only differencebetween this emul-
sionand the previousone is the fact that all the surfactants in this sys-
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 691

Figure 7. Microphotograph
ofa 30%mineraloilsystem
stabilized
with5% Tween80-Arlacel
80 at HLB 6. All surfactants initially in the oil phase

ternweredispersed in the aqueousphasepriorto emulsification.

It is
clearlyseenthat, although therearesomemultipleemulsion dropletsin
thephotograph,mostoftheoildroplets donotcontainanother phase.
If the formationof a multipleemulsioncanbe regardedas the ten-
dencyofthesystem
to formaninverted
emulsion
(W/O), theequation
of
Daviescanbe againusedto explainthe observed
difference.
Effecton DropletSizeDistribution
Dropletsizedistributionsof thefreshlyprepared emulsions werede-
terminedfrom enlargedmicrophotographs. Due to the limitedresolu-
tionof theopticalmicroscopeused,it wasnot possibleto obtainaccurate
measurements of emulsions
containingmany submicronrangedroplets.
692 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Figure8. Microphotographof a 30% mineraloil systemstabilizedwith 5% Tween 80-Arlacel

80 at HLB 6. All surfactants initially in the aqueous phase

For this reason,measurementswere limited to the systemshomogenized

at a relatively low homogenizingpressurecorrespondingto 786 cc/min
throughput of water at 24 C.
Between 500 to 2000 droplets were measuredfor each system and the
result was expressedin terms of mean volume diameter, din,defined by
the following equation:

dm= Zn
(2)
wheren is the number of dropletsand d is the droplet diameter.
The resultsfor the systemscontaining30% mineraloil stabilizedwith
Tween 80-Arlacel 80 mixture at HLB 10 are given in Table I.
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 098

Table I

Effect of Initial Surfactant Locations on Mean Droplet Diameter

(Tween 80-Arlacel 80 at HLB 10, All Arlacel 80 Dissolved in the Oil Phase
Prior to Emulsification)

Combined Surfactant Tween 80 Initially in the

Concentration in the System Aqueous Phase Mean Volume Diameter,
(% by weight) (% of total) d (cm)

1 100 2.8 X 10 -3
1 40 2.8 X 10-3
1 0 4.8 X 10 -3
8 100 2.8 X 10 -3
3 20 2.5 X 10 -3
3 0 3.2 X 10-3

Although the amount of data presentedhere doesnot allow generali-

zation, for the systemsinvestigated, however, there is a tendency to
producea coarseremulsionaslesshydrophilic surfactantis presentin the
aqueousphaseprior to emulsification.
A possibleexplanationfor the observeddifferencein the droplet size
distributionmay be given from the surfactantmigration viewpoint. In
order that the freshly formed droplets remain stable, the surfactant
moleculesmust be adsorbed at the oil-water interface. From the dy-
namic surfacetensionmeasurementsmade by a number of authors using
the oscillatingjet method, it is evident that a finite time is required for
the systemcontainingsurfactantsto reachits surfaceequilibrium(12-
14). Conceivably,the presenceof a surfactantin the oil phaseor aque-
ous phaseprior to emulsificationcan affect the accessibilityof the sur-
factant at the interface and hencethe droplet sizedistribution.

Effect of Emulsion Stability

The effect of the initial surfactant location on emulsionstability was
studiedboth by a shakingmethod as well as by using the emulsification
vessd describedin Fig. 1.
In the shakingexperiment,the oil phaseand the aqueousphasecon-
taining various amount of surfactants were shaken together in an en-
closedjar using a mechanicalshaker for a predeterminedlength of time.
The emulsionthusformedwasthen pouredinto a graduatedcylinderand
the amount of separationwas observedas a function of time. However,
in many systems,shakingproduceda considerableamount of foam which
made it difficult to interpret the data obtained. For example,in a series
of experimentsusingTween 80 and Arlacd 80, the emulsionpreparedby
694 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

(5 % TOTAL}
40- TWEEN 80-ARLACEL 80

-
HLB
I0
/

20-
co

0 20 40 60 80 I00
% TWEEN 80 IN AQUEOUS PHASE

Figure 9. Effect of initial hydrophilic sur-

factant location on emulsion stability

predissolving all Tween 80 in the aqueousphasewas lessstablethan an

equivalent emulsionpreparedby initially placing Tween 80 in the oil
phase. However, the former emulsionproduceda considerablygreater
amount of foam than the latter emulsionduring the shaking.
The presenceof foam during and after emulsification could have
affectedthe emulsionsin many ways: (a) Foam coulddamp the shaking
action to reducethe intensity of mixing operation, (b) adsorptionof the
surfactants at the liquid-air interface could deplete the surfactants
neededat the oil-water interfaceto stabilizethe emulsion,(c) retainingof
the liquid in the foam laminascouldaffect true readingof the degreeof
separation. For this reason,shakingexperimentswere abandonedand a
limited study was made using the turbine mixer in the emulsification
vessel.
The emulsionsprepared in the emulsificationvesselwere virtually
free of air bubblesand the data were fairly consistent. The example
shownin Fig. 9 representsa seriesof emulsionsstabilizedwith Tween 80
and Arlacel 80 at the requiredHLB value of the mineral oil. The emul-
sionstability was determinedby measuringthe per cent of the volume
of water separatedin a graduatedcylinder.
In this system,placing of the surfactantsin their respectivephases
produceda lessstable emulsionthan the one prepared by placing all
surfactantsin the oil phase. However,this observationdid not apply to
others as an exactly oppositeeffect was noted in many other systems.
Sinceemulsionstability is an extremelycomplexfunctionof droplet
size distribution,rheologicalpropertiesof eachphase,surfactanttype,
concentration,etc., the limited experimental data obtained here do not
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 69.5

permit generalization. However, it is evident that the initial surfactant

distribution can have a significanteffect on the stability of somesystems.
Davies discoveredthat HLB values of many surfactants could be cal-
culated from the empirically determinedstructural group numbers (10,
15). He further suggestedthe followingrelationshipbetweenthe coales-
cence rates and HLB number:

In(CRate
')=2.20(HLB-7)
Rate (3)
Combiningequations1 and 3, an equation relating the HLB number
to the partition coefficientof the surfactant can be obtained:

(HLB-7)
=0.36
In(c) (4)
If therateosurfactant
migration
isrelatively
slow,andif equation
4
is applicable, the surfactant mixture in an emulsified system can have
different HLB valuesdependingon the distribution of the constituent in
the oil and water phases. Assuming that an emulsion having a maxi4
mum stability is obtained when the HLB value of the surfactant system
equals that of the oil phase,it is clear that the initial surfactant location
may be a significantfactor affecting the emulsionstability.
The HLB systemdevelopedby Griffin has been a very useful tool for
emulsionchemistsin spite of its limitations (16-18). The presentwork
suggeststhat for the systemswhere the rate of surfactant migration is
slow, it may be necessaryto take this factor into account when determin-
ing the HLB value by an empirical method. For example, a common
practice of preparing an emulsionis to mix all emulsifiersinto the oil
phase before emulsification (19). Conceivably, for a certain system,
determinationof the required HLB value of the oil by suchmethod may
give a different value from that obtained by mixing all emulsifiersinto
the aqueousphaseprior to emulsification.
CONCLUSIONS

Experimental studies using various nonionic surfactants indicated

that the initial surfactant location could have significant effect on the
physical properties of the emulsion produced. The emulsion viscosity
immediately after homogenizationwas affectedby the initial surfactant
locationalthoughthe effectappearedto diminishwith the increaseof the
HLB number of the systemsstudied. Placing of the surfactantsin the
oil phaseappearedto encouragethe formation of a W/O emulsionor a
multiple emulsion. The experimental results were consistentwith the
090 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

theory advancedby Davies (10). The emulsiondroplet sizedistribution

was also influenced by the initial surfactant location. Placing of the
hydrophilic surfactant in the aqueousphasefavored formation of emul-
sionshaving smaller droplets than the emulsionsformed by placing all
surfactantsin the oil phase. The effect of initial surfactant locationson
emulsionstability was alsosignificant.
Due to the complexity of the nature of emulsions,it is difficult to
generalizethe results beyond the scopeof the experiments. It is prob-
able, however, the initial surfactant location plays an important role in
determining the characteristicsof many practical emulsions. Particu-
larly, if the systems are such that the rate of surfactant migration is
slow, the initial surfactant location may be an important consideration
from the manufacturing viewpoint. The optimum initial surfactant
location for a given system would be dependent on the end results de-
sired.
For example,if the final emulsionshouldbe a W/O emulsionbut the
phasevolume is such that an Of W emulsioncan be formed, it would
probably be best to place all the surfactants in the oil phase to avoid
phaseinversion. On the other hand, if it is desiredto producean O/W
emulsion having finest droplet size, it may be better to place all the
surfactantsin the aqueousphase. If the surfactant migration from one
phaseto another can produceviscositychangeand if sucha changeis un-
desirablefrom the product viewpoint, it may be best to distribute the
surfactantsaccordingto their solubility in eachphaseprior to emulsifica-
tion.

ACKNOWLEDGMENT

The author gratefully acknowledgesthe assistanceof John C.

Lambrechts in collecting the experimental data and the assistanceof
William E. Gardner of Sloan Research Industries in preparing micro-
photographs.

(ReceivedDecember8, 1967)

REFERENCES

(1) Beeher, P., Emulsions: Theory and Practice, 2nd ed., Reinhold Publishing Corp., New
York, 1965, pp. 267-325.
(2) Sumner, C. G., Clayton's Theory of Emulsion and Their Technical Treatment, 5th ed.,
Chemical Publishing Co., New York, 1954, pp. 480-528.
(3) Stanko, G. L., Fiedler, W. C., and Sperandio, G. J., The effect of physical factors on the
formation of cosmeticemulsions,J. Soc. CosmeticChemists,5, 29-50 (1954).
 EFFECT OF SURFACTANT LOCATION ON EMULSIONS 697

(4) Benson, F. R., Griffin, W. C., and Truax, H. M., Statistical approach to common
variables in emulsion preparation, Ibid., 13, 437-48 (1962).
(5) Osipow, L. E., Sinface Chemistry, Theory and Industrial Applications, Reinhold Pub-
lishing Corp., New York, 1962, pp. 305-9.
(6) Sherman, P., The Influence of Emulsifier Concentrationon the RheologicalPropertiesof
Emulsions, in Sherman, P., Rheologyof Emulsions, The MacMillan Co., New York,
1963, pp. 73-90.
(7) Becher, P., Emulsions: Theory and Practice, 2nd ed., Reinhold Publishing Corp., New
York, 1965, pp. 59-85.
(8) Sherman, P., Factors influencing emulsion viscosity and stability, Research(London), 8,
396-401 (1955).
(9) Becher, P., The effect of the nature of the emulsifying agent on emulsion inversion, _f.
Soc. CosmeticChemists,9, 141-8 (1958).
(10) Davies, J. T., and Rideal, E. K., Interfacia! Phenomena,Academic Press, New York,
1963, pp. 366-83.
(11) Bancroft, W. D., The theory of emulsification, J. Phys. Chem., 17, 501-19 (1913).
(12) Addison, C. C., The measurement of surface and interfacial tension at fresh surface by
the vibrating jet method, Phil. Mag., 36, 73-100 (1945).
(13) Rideal, E. K., and Southerland, K. L., The variation of the surface tension of solution
with time, Trans. Faraday Sot., 48, 1109-23 (1952).
(14) Schwartz, A.M., and Perry, J. W., Surface Active Agents: Their Chemistryand Tech-
nology,Vol. 1, Interscience, New York, 1943, pp. 286-8.
(15) Davies, J. T., A quantitative kinetic theory of emulsion type, I. Physical chemistry of
the emulsifying agent. Proc. Intern. Congr. Surface Activity, 2nd, London, 1957, 1,
426-38.
(16) Griffin, W. C., Classification of surface-active agents by "HLB," _f. Soc. Cosmetic
Chemists,1, 311-26 (1949).
(17) Griffin, W. C., Calculation of HLB values of nonionic surfactants, Ibid., 5, 249-56
(1954).
(18) Griffin, W. C., Ranauto, H. J., and Adams, A.D., Further studies on emulsion systems,
Am. Perfumer Cosetics, 81, 31-42, (Sept., 1966).
(19) Guide to the Useof Atlas Surfactantsand Sorbito!in Cosmeticand Pharmaceutica!Products,
Atlas Chemical Industries, Wilmington, Del., 1965, p. 40.