j. Soc.Cosmet. Chem.

,39, 201-209 (May/June 1988)

Microemulsions: commentary their preparation A on

HENRI L. ROSANO, JOHN L. CAVALLO,

DAVID L. CHANG, andJAMES H. WHITTAM, Department of Chemistry, City University New York,New York,NY 10031 of (H. L. R. ), ClairolResearch Stamford, (D. L. C. ), andShaklee Labs, CT U.S., Inc. SanFrancisco, 94111 (J.H.W.), General CA Foods USA, Tarrytown, 10625 (J.L.C.). NY
Received February 1987. 24,
Synopsis

A detaileddescription the concept microemulsions, they can be formed,factors on of how which affect stability,and recentapplications the focus this commentary. simplemethodfor determining are of A the amountof primary surfactant a given microemulsion shown,as well as data which emphasize for is the importance the orderof mixing based thermodynamic of on calculations six differentmicroemulsion for systems. We conclude that the formationreactions thesemicroemulsions of studies entropy-driven are reactions thus quite differentfrom the formationof coarse and emulsions their thermodynamic in properties.

INTRODUCTION

Emulsions play a key role in many of the cosmetics usetoday. Through the years we much has beenwritten on the formationand stabilityof theseoil-dispersed-in-water (o/w) or water-dispersed-in-oil (w/o) systems. Nevertheless, the cosmeticformulator still seeks understand create mostfavorable to and the cosmetically eloquent and functional products possible. Aesthetically appealing products can be formulatedas transparento/w or w/o dispersions calledmicroemulsions. possible The application these for systems rangefrom products with an extended shelflife to deliverysystems active for ingredients.

The pioneering work on microemulsions startedin 1943 (1). It wasonly in 1959 that Schulman coworkers coined word microemulsion thesecleartransparent and (2) the for dispersions. Thesesystems offer a great deal of uniqueness, only because their not of novel transparency, but also because the small dispersed of phase,usually having a

droplet diameter between 50-400fk.Today are there numerous theories thenature on

of their formationand stability, yet the practicalaspects their preparation still of are vague.Nevertheless, can be seen somerecent as by patents (TableI), specific applicationsfor microemulsions beingrecognized. are This reviewwill elucidate practical one
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approach the scientistor cosmeticchemistto consider for when formulating these

unique transparentsystems.

The generalingredients requiredto make suchtransparent dispersions consist an oil of phase,an aqueous phase,a primarysurfactant (whichwill determine whetherthe emulsion is of the o/w or w/o type), and a secondsurfactant,known as a cosurfactant. Typically the cosurfactant a mediumchainlength (C5 - Co) alcohol.The primary is surfactant mainly absorbed the oil/waterinterface determines initial curvais at and the ture of the dispersed phase.The cosurfactant alsointeractsat the interfaceto form a mixedduplexfilm. The cosurfactant appears actin a dynamicstate.Initially it causes to a transitorylowering of the interfacialtensionnecessary during the formationof the dispersion.Secondly,as the cosurfactant distribution reaches equilibrium, it further distributes the interface become at to part of the interfacial film (oil/aqueous/surfactant molecules) with the primary surfactant. this point, the systemcan be a thermodyAt namicallystableswollenmixed micelie(o/w) or inverse mixed micelie(w/o) system.

SPECIFIC

COMBINATIONS

FORM

MICROEMULSIONS

What will becomeclear to the formulator is that unlike coarse emulsions, the formulaTable I

Microemulsion Technologies Documented RecentPatents in

Patent (Date)
1.

Tertiary oil recovery US 4587879 (860701), US 4556495 (851203). Diesel fuel composition, lubricant, antifreeze solution US 4599088 (860708), US 4605422 (860812), 4610222 (860909)
Pharmaceutical

2.

3.

JP 61044809 (860304)
4. Ink

US 4409039 (831011)

5.

Liquid detergent,household products JP 60106898 (850612), GB 2144763 (850313)

Reaction medium

6.

US 4611055 (860909), US 4521580 (850313)

7.

Drug deliverysystem

Jp 61044809 (860304)
8. Fiber finishes soil and water repelling for US 4566981 (860128)
Herbicide, pesticide JP 60231604 (851118)

9.

10. Personal products care

US 4460570 (840717)

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203

tion of a stablemicroemulsion more specific is and thus greatly limited in variety. Coarse emulsions be stabilized a wide varietyof surfactants, can by application highof energyapparatus (turbinemixers,sonicators, etc.), and excipientingredients alter to viscosity and separation (gums, gelling agents).In general,stablemicroemulsions are veryspecific the ratioof surfactant/cosurfactant to disperse in used phase in a continA uousphase Six systems described Table II. An example this specificity the B. are in of is emulsion system consisting 2 X 10-3 molestearic of acid, 2 ml oil, and 16 ml 0.375 N KOH (System5, Table II). The authors reportedthat out of fifty-two alcohols, (3) only five weresuitablecosurfactants capable producing of transparent systems. o/w More recently, Rosano coworkers havemadea systematic and (4) studyon the formation of microemulsions prepared with alkyl sodiumsulfate (with the alkyl chaincontaining 12 to 16 carbon atoms)as the surfactant, and alkanes (octane throughhexadecane) as the oil, an aqueous solutionof alkyldimethylamine oxide(dodecyl throughhexadecyl) as the cosurfactant, and aqueous 5% NaC1, pH 12 brine solutionas the continuous phase.Table III summarizes systems the studied. It is readily seenthat out of the forty-fivecombinations, only fifteen resultedin the formationof transparent microemulsions, demonstrating highly specific the natureof the process.

THE

METHOD

A recognized and classical approach microemulsion to formulationis to utilize phase diagrams. Friberget al. havebeengreat supporters this technique of and haveelucidatedthe methodology numerous in papers (5-8). A majordrawback this approach to is the time it takesto develop phase the diagram,especially when one hasa variety of surfactants cosurfactants oils at his disposal useand evaluation. and and for Recently, automated systems havebeencommercialized offsetthe laborious to titrationsto determine the variousphases.The chief drawbackat the presenttime is the cost of such instrumentation, as well as accuracy.An alternative simpler approachis discussed
below.

Rosano suggested way to determinethe minimum amountof primary surfactant (9) a needed a particularsystem.In this theoretical for calculation,the minimum amountof primary surfactant requiredfor the microemulsion calculatedby determining the is
Table II

MicroemulsionSystems Continuous phase Dispersed phase

Systems 1

Surfactant

Cosurfactant

X ml water

2 ml n-octane

2 3

X ml water X ml water

0.5 ml C9Phenol-1.5-EO Csphenol-9-EO + 0.5 ml C9phenol-4-EO 2 ml n-decane 0.5 ml C9Phenol1.5-EO C9Phenol10-EO + 0.5 ml C9phenol-4-EO 2 ml n-hexadecane 0.5 ml C9Phenol-1.5-EO C9Phenol-9-EO

4 5
6

X ml toluene X ml 0.375 N KOH

+ 0.5 ml C9Phenol-4-EO 2 ml water 1.98 X 10-3M SDS 1-pentanol 2.3 ml n-hexadecane2.3 X 10-3M stearic acid 1-pentanol
1 gm SDS DDAO

x ml 5% NaC1 saline 1 ml n-decane

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Table III

Microemulsion Formation From a GivenOil/Aqueous System

Cosurfactant(ADAO)

Na cetyl sulfate(surfactant) Paraffin phase oil

C8
NC

LDAO C16 C14

C12

C 10
NC

C 12
NC

C 14
NC

C 16
NC

5.5 (90%)* 3.0 (88%)

NC NC

NC NC

NC NC

NC NC

Cosurfactant(ADAO)

Na myristyl sulfate(surfactant) Paraffinoil phase

C8 ClO C12

LDAO

C14
NC

C16
NC
NC NC

C16 C14
C12

NC

NC

NC

6.6 (100%) 3.6 (96%)

6.9 (95%) 5.4 (97%)

7.8 (92%)
NC

7.3 (96%)
NC

Cosurfactant(ADAO)

Na lauryl sulfate (surfactant) Paraffin phase oil

C8 C 10 C 12
NC

LDAO

C 14
NC

C 16
NC NC NC

C16 C14 C12

9.0 (100%) 3.3 (90%)* 1.8 (99%)

NC 2.1 (98%)
3.3 (100%)

3.O (9O%)
NC

4.O (88%)
NC

Primarysurfactants: Sodiumalkyl sulfates. Cosurfactants: Alkyl dimethylamine oxide(ADAO). Oil phase: Co, C2, C4, C6 n-paraffins. C8,

Temperature: 30C.
*Viscousgel.

( )% transmittance (clarity)of system 520 nm. at

NC = non-clear system.

surface or, morereadily,the mono-molecular area interfacial film areanecessary form to between dispersed the phase and the continuous phase.

If a given volume (ml)ofa phase dispersed spherical V is into dropletsradius(), of r

the total volumeof the dispersed phase be expressed can as
V = a(4/3)'rrr 3 (1)

wherea is the total numberof droplets formedby the dispersed phase. The total surface areaA of the droplets is
A = a4'rrr 2
A = cn

(2)
(3)

wherec andn are the areaper surfactant molecule the number surfactant and of molecules,respectively. CombiningEqs. 1, 2 and 3 and solvingfor n, we find
n = (3V)/cr (4)

The value of c can be obtainedfrom the surface tensionvs. log concentration plot of the surfactantsolution or from monolayermeasurements. microemulsions, For the

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upperlimit of r is 40 'nm (1/4 the wavelength visible of light), whilethe lowerlimit is

set by the surfactant chainlength. This simplecalculation provides minimum amountof surfactant the necessary cover to the interface.It doesnot take into account amountof surfactant the that is dispersed in both the aqueous oil phases otheraggregates and and that may form in solution.
continuous

Using the estimated amounts surfactants, coarse of a emulsionof dispersed phasein - ' formed by simple mixing o,-,,,rnonr since viscosity level. are

alwayslow.

To determine a transparent if dispersion possible, cosurfactant gradually is a is addedto the coarse emulsion. general, In mostcosurfactants liquidsandcanbe easilytitrated are into the emulsion while gentlemixing is applied the system If does not turn clearafter adding the cosurfactant an amountequivalent that of the primary surfactant, in to the system be considered can unacceptable. formulator The then hasan optionto alter the components the system. general,the cosurfactant usuallythe nonspecific of In is component,and soit is first altered.For example,if octanol the cosurfactant was used,one would consider selecting alcoholwith a differenthydrocarbon an chain length suchas decanol hexanol.New solutions the basecoarse or of emulsion prepared are and titrated
with the alcohol of choice.

Cosurfactants shouldbe chosen suchthat they do not prefer either the continuousor dispersed phase.The propercosurfactant be onethat will migrateto the oil-water will
interface and form a mixed surfactant/cosurfactant film.

The next optionavailable the cosurfactant if selection failsis to consider newprimary a surfactant. Recalculation the amountof surfactant madeand repeattitrationswith of is
the cosurfactant are conducted.

If the microemulsion does form by variationof the cosurfactant primary surfacnot and tant, the dispersed phaseshouldbe altered, in a logicalmanner.For example,if the dispersed phase an alkane,eitherincrease decrease chainlengthof the alkane is or the depending the requirements the formulation. on of An example this routineis shown Table III. While at first appearing of in complicated, this progression be conducted can rapidly by redetermining variety of cosurfactant/ a surfactant and dispersed-phase options

ORDER

OF MIXING

The question the orderor methodof preparation microemulsions long been on of has debated.One school thoughtis that these of systems thermodynamically are stableand thus the orderof mixing is inconsequential productstability. Anotherapproach to (10) is to consider these transparent dispersions true emulsions, thusthe stabilityis a as and functionof preparation. will attempt to shedsome We furtherlight on this question by
the following experiments.

Vapor pressure experiments wereundertaken o/w microemulsions gain someinfor to sight into the mechanism particleinteractionin thesesystems of (11). The microemulsionswere preparedwith 20 ml 5% NaC1, pH 11.2 (NaOH) solution, I gm sodium

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tetradecyl sulfate (STS), varying amounts octane, titrated clarity of and to withdodecyldimethylamine (DDAO,30%active). oxide Using Clausius-Clapeyron the equation
ln(p/po) -(AHvR)(1/T - 1/To) = (7)

where and arethevapor p Po pressureT and Hv theheat vaporization, R at To, of and thegas constant, vapor the pressure heats vaporizationbedetermined. and of can Figure

VOL. OCTAN[ ml

Figure Vapor 1. pressure for microemulsions5%NaCI 12)/sodium diagramthe system: (pH hexadecyl
sulfate/n-octane/dodecyldimethylamine 15-40C. oxide between Plotted a function amount n-ocas of of
tane.

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207

1 depicts vaporpressure a functionof n-octane the as volumeat various temperatures. The presence an oil significantly of reduces vaporpressure the solution,similarto the of regularcolloidalsolutions high-molecular-weight or polymersolutions, wherebythe vaporpressure the system lessthan that of the continuous of is phase. Also revealed in the plots is the existence two microemulsion of regions distinguished the sharp by transition.In the low-pressure regionand hencelower oil content, the microemulsion particles isolated are non-interacting droplets encapsulated a surfactant andare by film dispersed uniformly in the continuous medium. At high oil contenr, the rise in the vapor pressure a reflection thedynamic is of equilibrium between particle merging and reforming. Using the data in Figure 1, it is possible estimate thermodynamic to the properties of this systemwith increasing adsorption cosurfactant. a given microemulsion of For system a particular at temperature, minimum amountof cosurfactant the requiredto form the microemulsion varies with the amountof continuous phase the system in while the quantities surfactant dispersed of and phase being held constant. are Plotting the amountof cosurfactant the volumeof continuous vs. phase reveals linearrelationship a (4,9,12,13). The mole fraction of the cosurfactant the interface,x, and in the at aqueous phase, b, canbe determined x from the intercept and the slope,respectively.
From the equation

AG -

-RT In Xi/Xb

(5)

the change free energywhich corresponds the adsorption cosurfactant the in to of at oil-waterinterface the presence surfactant in of film duringmicroemulsification be can calculated. the the same If procedure repeated various is at temperatures the change and in free energyis plotted vs. temperature, entropychange the accompanying cosurfactant adsorption be calculated can via

-- AS = (/AG//T)p
TableII liststhe six systems investigated TableIV summarizes calculated and the free

energy, enthalpy, entropy and values each thesystems. values AG areall for of The of
negative,signifyingthat microemulsification a spontaneous is process. However, the driving forces small;therefore, are other factors must be considered explainthe to formationof microemulsions satisfactorily. Also consider systems and 3: the differ1 encein their AG values resulted froma difference carbon in chainlengthof the oilsand AG changes a value - 275J/molperCH2 unit. It is interesting notethat in with of to the case w/o microemulsions, AG changes of the with a valueof + 230 J/mol per CH 2
unit (13).

Basedon thesecalculations experiments, formationof this set of microemuland the

sions an entropy-driven is process (4,12). The largeincrease interfacial and the in area formation a flexiblesurfactant/cosurfactant film whichproduces transitory of mixed a low interfacial tensionbetweenoil and water oppose entropyof the system.In the microemulsification freeenergy the decrease caused the entropyof dispersion by outweighs increase interfacial energy the in free from dispersion. the systems For studied, theentropy values all positive are with oneexception. Ruckenstein showed the (14) that adsorption surfactant the surface a dropisanother of at of factorwhichfavors dispersion; an increase interfacial in areais accompanied a decrease freeenergy an adsorbed by in of

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

surfactant molecule compared that of a molecularly to dispersed statein the bulk phase. More recently,Rosano (12) hasshownthat the adsorption cosurfactant of molecules at the dropsurface alsoreduces system the freeenergy.Miller and Neogi (15) developed a thermodynamic modelfor dilute microemulsion systems whichincludes combined the effects surfactant of film bendingand dispersion. The duplexfilm modelwas usedfor the interface.Their model yieldsinterestingpredictions microemulsion of behaviors, but some the parameters of used characterize to bending effects not readilyrelatedto are knownproperties the surfactant of (16).
Thus the freeenergyassociated formationof microemulsions negative,but quite with is
Table IV

Thermodynamic Properties O/W Microemulsions Table II of in

AG AH AS

System
1
2

(kJ/mole)
-17.4 -18.1 -19.6 -6.4 -14.8 - 13.9

(kJ/mole)
-6.8 -6.0 -25.0 18.7 8.7 11.3

(kJ/K mole)
3.5 X X -1.8 X 8.2 X 7.8 X 8.3 X
4.0

3 4 5 6

10 -2 10 -2 10 -2 10 -2 10 -2 10 -2

small.Therefore, orderof mixingplaysan importantrolein accelerating formathe the

tion of thesesystems.

SUMMARY

Microemulsions uniquelystablesystems the cosmetic are for formulator consider. to They, in general, moredifficultto formulate are compared regular to emulsions to due the specificity formulation of and, in manycases, orderof mixing. An approach the is summarized help develop to such systems an orderly in andrapidtime period.

REFERENCES

(1) T. P. Hoar andJ. H. Schulman, Transparent water-in-oil dispersions: oleopathic The hydromicelle,
Nature, 152, 102 (1943).

(2) J. H. Schulman, Stoeckenius, L. M. Prince,Mechanism formation structure miW. and of and of croemulsionselectron by microscopy,Phys. J. Chem., 1677(1959). 63,
(3) H. L. Rosano, Lan, A. Weiss, W. E. F. Gerbacia,andJ. H. Whittam, Transparent T. dispersions:

An investigation some thevariables of of affecting their formation, Colloid J. Interface 72, 233 Sci.,
(1979).

(4) H. L. Rosano, L. Cavallo, G. B. Lyons, J. and Microemulsion (Marcel Systems Dekker,New York,
1987), p. 259.

(5) S. Friberg, Microemulsions theirpotentials, and Chem. Technology, 6, 124-127 (1976). (6) R. ZanaandJ. Lans,Dynamics microemulsion, Microemulsions.' andDynamics of in Structure (CRC,
BocaRaton, FL, 1987), pp. 153-172.

(7) A. Belloca D. Roux, Phase and diagram criticalbehavior a quanternary and of microemulsion system, Microemulsions: Structure Dynamics and (CRC, BocaRaton, FL, 1987), pp. 33-77. (8) S. FribergandP. Bothorel, Microemulsions.' andDynamics, in Structure (CRC, Boca Raton,FL, 1987),
p. 219.

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209

(9) H. L. Rosano, Microemulsions, J Colloid Interface 44, 242 (1973), andMethodfor Preparing Sci.,
Microemulsions U.S. Patent 4, 146, 499 March 27, 1979.

(10) W. Gerbacia H. L. Rosano, and Microemulsions: Formation stabilization, Colloid and J. Interface Sci.,
44, 242 (1973).

(11) J. L. Cavallo, and H. L. Rosano, Vaporpressure measurements an o/w microemulsion of system, J. Phys.Chem.,90, 6817 (1986). (12) H. L. Rosano, G. B. Lyons, and Freeenergy, enthalpy entropy and changes duringthe formation a of n-hexadecane/potassium stearate/water/1-pentanol microemulsion system, Phys.Chem.,89, 363 J.
(1985).

(13) K. S. Birdi, Microemulsions: Effectof alkyl chainlengthof alcohol and alkane,Colloid Polymer Sci.,
260, 628 (1982).

(14) E. Ruckenstein, The originof thermodynamic stabilityof microemulsions, Chemo Phys. Lett., 57, 517
(1978)

(15) C. A. Miller and P. Neogi, Thermodynamics microemulsions: of Combined effects dispersion of entropy dropsand bendingenergy surfactant of of films, Aiche, 26, 212 (1980). J., (16) S. Mukherjee, A. Miller, andT. Fort, Theoryof dropsizeand phase C. continuity microemulof sions, Colloid J. lnterfaceSci., 223 (1983). 91,