I. Soc.Costttel.Chem.

,22, 323-337 (May 27, 1971)

Mechanisms and Control of Gas

Bubble Formation in Cosmetics

TONG JOE LIN, Ph.D.*

PresentedSeptember20-2_5,1970, Sixth IFSCC Congress,

Barcelona,Spain

Synopsis--Thepresetace of GAS BUBBLES iu cosmeticand pharmaceuticalpreparationsis

generallyundesirablenot only from the appearancevicwpoint, but alsofrom physical,chem-
ical, and biologicalstability considerations.The air bubblesin a product can affect emul-
sion stability, promote oxidation, and, in someinstances,encouragemicrobial growth. EX-
TERNAId ENTRAINMENT of gasbubblescan result from mixing, pumping, pouring, jet-
ting operation,or addition of powderedmaterials. INTERNAL GENERATION of gasbub-
blesmay be due to chemicalreactionsor physicalchanges. Each MECHANISM of bubble
formation is analyzcdand somepossiblcsolutionsare suggested.

INTRODUCTION

Control of dissolvedand undissolvedgasesin a product is a diffi-

cult but extremelyimportant problem in cosmeticand other industries.
Some cosmetic preparations, such as shampoosand aerosol shaving
creams,are designedto producemany gasbubblesor foam during their
usage. In somefood preparationsthe presenceof air bubblesis quite
essential. However, in most cosmeticand pharmaceuticalpreparations,
the presenceof air or other undissolvedgasesas bubbles is generally
undesirable[or severalreasons. The presenceof air bubblesin cosmetic
emulsionsnot only makesthe texture appearcoarse,but it can alsoaffect
the emulsionstability by adsorbingthe emulsifiermoleculesat the air-
liquid inter[aces(1). The trapped air bubblesin an emulsifiedcream
* Shen Hsiang Tang Chetnical Works, 19 Fn Shin Road, Section4, Taichung, Taiwan.
323
324 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

or fluid make-upcan sometimesencouragemicrobial growth or undesir-

able oxidation. The pinholesin a lipstick or make-upstick can create
poor appearanceand weaken the stick. Excessiveincorporationof air
in clear gel-typeproductscan be unsightlyor createan under-fill ap-
pearanceupon standingon the shelf.
Air bubblesin cosmetics are usually introducedduring the manu-
facturing processes.If the viscosityof the product is low, the incor-
porated air can escapeinto the atmospherein a short time and the
productwill becomebubble-free. If, on the other hand,the productis
very viscous,the rate of escapemay be very low. From the theological
viewpoint, if the product has an appreciableyield value, the entrained
bubblesmay not escapeat all and the productcan remain aeratedduring
the entire shelf life. Control of gas bubblesis thus particularly im-
portant in plastic or thixotropic products. However, since there are
many waysby which gasbubblescan be incorporatedduring numerous
manufacturingsteps,control of gasbubblesin finishedproductsis not
alwayseasy.
The purpose of this paper is to examine in detail the common
sourcesand mechanisms of bubble incorporationinto cosmeticprepara-
tionsduring variousmanufacturingprocesses, and to suggestpreventive
methods.

DISCUSSION

External Entrainment

The mechanisms of bubble formation often encountered in cosmetic

preparationsmay be divided into two main categories: bubble incor-
poration due to the entrainment of the external gasand bnbble forma.-
tion due to the internal generationof gases. There are many variations
but four important operationswhich are frequently the sourcesof ex-
ternal entrainment of air will be discussed.

Mixing Operations
Broadlyspeaking,mixing coversagitation, blending, homogenizing,
and milling; it is probablythe mostcommonsourceof air incorporation
into productssuchasfacialcreams,hand lotions,and liquid make-ups.
Propelleror turbine mixersare widelyusedto process flowableliquids
or emulsions. Dependingon the mixer speed,impeller size,and loca-
tion, a vortex suchasthe one illustrated in Fig. 1 can form. If the vortex
 GAS BUBBLE FORMATION 325

Figure 1. Aeration from vortex formation

isdeepenoughto touchthe impeller,the surroundingair maybe sucked

in to form bubbles.
Exceptwhen it is desiredto deliberatelyaerate the fluid or to draw
the floatingmaterial from the fluid surface(e.g.,to wet the dry pigments
placedon the fluid surface),the formation of vortex is generallyunde-
sirableasit will reducethe mixing efficiency.A reductionin the mixer
rpm may eliminate the vortex but it will alsoreducethe intensityof
mixingandshearforcerequiredto obtaina fine emulsion. In a jacketed
kettle, it may also reduce the rate of heat transferand result in poor
coolingor heating of the batch.
One way to suppress the vortex and, at the sametime, increasethe
mixing efficiencyis to usebaffles(2). In a cylindricaltank, for example,
four vertical baffles,eachone-tenthtank diameter in width, placedequally
around the tank will serve such a purpose. The bafflesreduce the
tangentialvelocitycomponentbut increasethe radial and vertical flow.
The effectis that the fluid doesnot merely rotate around the tank axis
326 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Figure 2. Elimination of vortex by using spatula

but is mixed uniformly. The photographin Fig. 2 was taken at the

samemixer rpm as Fig. 1 but a spatulawasplacedon one sideof the
beaker to serve as a baffle. The absenceof vortex and bubbles clearly
indicates the effect of the baffle.

Another effectiveway to suppress a vortex when usinga propeller

mixer is to tilt the mixer and placeit off-center. This will createa dif-
ferencein the velocitywith which the fluid impingeson the tank wall
and a vortex formationis thuspreventedwithout usingbaffles.
Somehigh-speed mixersare providedwith built-in bafflesto mini-
mize the chance of surface turbulence and aeration. However, it is gen-
erallybetterto placethe headoœa high-speed mixer asnear the bottom
oœthe process kettle aspossibleto avoidair entrapment.
In the cosmeticindustry,an anchor-typemixer is often usedto pro-
cesshigh-consistency creams. Although such a mixer is normally op-
eratedat a relativelylow rpm, air entrapmentis still possibleif the mixer
tipsare not completelycoveredby the product. As illustratedin Fig. 3,
 GAS BUBBLE FORMATION 327

MIXER
TIP
• CAVITY

Figure 3. Cavity formation in anchor-typemixer

if a high-consistencycream is made in sucha kettle, the uncoveredmixer

tips can create cavitiesbehind them as they rotate in the cream. As
thesetrailing cavitiesare filled, air is often trapped and dispersedinto
the product. For a similar reason,a planetary-typemixer can often in-
corporatea considerableamount of air into a viscousproduct during its
operation.
The aboveproblemin an anchor-typemixer can be solvedsimplyby
increasingthe batch size or shortening the mixer tips so that they are
completelycoveredby the product. But in other cases,it may be
necessary to redesignthe mixer so that suchcavitiesare not createddur-
ing the mixer operation.
Paddlemixersare alsowidely usedin the cosmeticindustry to process
creamsand pastes. In using thesemixers, the fluid level should be suf-
ficiently high to cover the paddle completelyso as to avoid excessive
surfaceturbulence. A processing kettle equipped with a paddle mixer
fitted with scraperblades plus a built-in high-speedhomogenizeris
quite ideal in processing cosmeticemulsionsand suspensions.If neces-
sary,sucha kettle can be designedto operateunder vacuum for a com-
pletelyair-freeoperation.*
In some instances,bubble entrainment in a mixing processcan be
minimizedby revisingthe manufacturingprocedure. For example,the
emulsifiersused in making a cream can often encouragebubble forma-
tion during the emulsification. Since cosmeticemulsionsare usually
made at a high temperatureat which the viscosityof the emulsion is
usuallylow, mostof the entrainedbubblescan escapeduring the initial
stageof emulsification. To obtain a goodemulsion,mixers or homoge-

* Eppenbach
Agi-Mixers
madebvGiffo}'-Wood
Co.ofNew
York,
N.Y.,
have
these
features.
328 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

nizersshould be turned on at high speedsduring this stage. After the

coolingwater is turned on, the temperature of the batch will drop and
the viscosityas well as the yield value of the emulsion will increase
greatly. Since any entrappedair will have difficulty in escapingafter
this period, further mixing shouldbe done with extreme care to avoid
permanent aeration. If possible,the thickenersused to increasethe
viscosityof the emulsion should not be added at the beginning but
should be added after emulsification to allow the entrained air bubbles
to escape(3).

Pumping
Considerable air can be entrained sometimes when a cosmetic
preparationis pumped from one kettle to another. A commonsource
of aerationin this type of operationis a leakagein somesectionof the
line. This can be due to a faulty gasket,a poor connection,or pinholes
in the line. The entire line shouldbe inspectedfor the sourceof leak-
age. Sinceair incorporationis most likely to take placein the suction
sideof the pump, it is generallyadvisableto connectthe pump asclosely
to the originating tank as possibleto reduce the number of connections
in the suction side and thus reduce the chance of air entrainment.

Jettingand Pouring Operations

The jetting operationdiscussed here is a dischargingof a fluid
througha nozzle,tube, or hose,into atmosphereor throughatmosphere
into anotherfluid. In thissensepouringmay be considered asa special
kind of jetting. Theseoperationsare very commonin cosmeticprocess-
ing as in the filling of a hand lotion or liquid shampoointo bottles,
transferringof a batchof creamfrom a kettle to a storagetank through
a rubber hose,or pouringof a drum of liquid into a batchin a process
tank as illustrated in Fig. 4. These jetting or pouring operationscan
often be the source of the troublesome air bubble entrainment.
In somecasesthe solution may be fairly simple. For example, the
problemof air entrainmentin transferringinto a storagetank (Fig. 4, B)
canbe correctedby pumpingthe material through the inlet locatednear
the tank bottom. A more careful pouring or use of a deflectiveplate to
force the fluid to fall along the kettle wall can also minimize the prob-
lem of pouring in Fig. 4, C. However, sometimesthe problemis much
more complexand requiresthoroughanalysisbeforean intelligent solu-
tion can be prescribed.
 GAS BUBBLE FORMATION 329

(A)

(c)

(B)

Figure 4. Air entrainmentby jetting and pouring

To explain the basicmechanismof air entrainment by jets, Fig. 5

illustrates the dischargeof a fluid through a small nozzle into a ves-
sel containing the samefluid. The jet in (A) is perfectly smoothand
there is no air in the receivingfluid. The jet in (B) is dischargedat a
much higher rate and the jet surfaceis irregular and the surroundingair
is trapped by the jet surfaceand carried into the bulk. The jet in (A)
is evidentlyin a laminar flow and (B) is in a turbulent flow.

DV•
Re - •

(A) (B)
LAMINAR TURBULENT

Figure 5. Laminar and turbulent jets

330 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

In fluid mechanics, transition from a laminar flow to turbulent flow

is related to a dimensionless
parameter,Reynoldsnumber defined as
follows:

where
Re = Reynolds number
D = diameter of the jet
V = linear velocity of lhe jet
0 = density of the fluid
/• = viscosityof the fluid
When the nozzleis perfectlysmoothand sufficientlylong the transi-
tion from a laminarflow to turbulentflownormallyoccursat a Reynolds
numberabove1000. However,if the nozzleis not smooth,straight,or
too short,the jet may be in a turbulent flow at a lower Reynoldsnum-
ber. The turbulentjetscanoftenbe the causeof bubbleproblemsin
cosmeticprocessing.
For example, if a hot lipstick is toouredfrom a kettle into a mold
througha valvewith a shortexit pipe, the productmay becomeaerated.
This is because,in flowingthroughthe valve and elbow, the velocity
distribution in the pipe becomesirregular causinguneven streamsur-
face which traps the sun-oundingair as the liquid plungesinto the
mold. By lengtheningthe exit with a smoothpipe, it is possibleto
smooththejet streamandreducethe chanceof air entrapmentby turbu-
lence. The length o[ the tube required to smooththe flow of a jet is
dependenton the jet velocityas well as the physicalpropertiesof the
fluid. Generally, the lower the viscosity,the longer the pipe length
should be to achieve a smooth laminar flow.

A similartroublesomebubble entrainmentproblemcan occurin the

filling of cosmeticpreparationsusing a straight circular nozzle. The
modernfilling machinesgenerallyoperateat a very high speedand the
dischargedfluid can easilybe in turbulentflow dependingon the nozzle
designand fluid properties. Often the lengtheningof the filling nozzle
alonewill not solvethe problemcompletely.
Reductionin the filling rate is a possiblesolntion but it will affect
the production rate. One possibleway to minimize the turbulent en-
trainmentis to usea fillingnozzlewith a largerdimneter. For example,
1)ydoublingthe jet diameter,D, while keepingthe volnmetricflow rate
 GAS BUBBLE FORMATION 331

constant, the linear flow rate, V, will be reduced to one-fourth. There-

fore, the Reynoldsnumber for the larger jet will be only one-halfof the
smaller jet and this might bring the jet to the laminar flow region to
avoid turbulent bubble entrainment.
The abovecalculationassumes no changein the fluid viscosityas the
jet nozzleis enlarged. This will be true only with a Newtonian fluid,
the viscosityof which is independent of the rate of shear. Many cos-
metic preparationsare non-Newtonian and particularly emulsion prod-
ucts are generally pseudoplasticor thixotropic, i.e., shear-thinning.
Shear-thinningmeansthat the viscositydecreases with increasingrate of
shear. Becauseof the high linear velocity, the shear stresson the fluid
while it flows through the nozzle is much greater in the smaller nozzle
than in the larger nozzle. Therefore, if the fluid is shear-thinning,
the viscosityof the fluid in the smaller jet may be much smaller than
the viscosityof the same fluid flowing through a larger nozzle. Nat-
ura]ly, this will make the Reynoldsnumber even greater in the smaller
jet and increase the chance of aeration when the filling material is
thixotropic. For thesereasons,filling nozzleswith very small discharg-
ing holes should be avoided. In addition to the bubble problem, dis-
charging of a thixotropic emulsion through very small openings can
sometimescausea permanentviscositybreakdown.
At times, the turbulent bubble entrainment problem can be solved
by varying the filling temperature. Many cosmeticcreamsare filled at
an elevated temperature for practical or aestheticreasons. Since the
viscosityof an emulsion is usually low at a high temperature, reduction
of filling temperaturemay increasethe fluid viscosityand hence reduce
the Reynoldsnumber at which the productis filled.
The mechanismof bubble formation by jet discussed aboveinvolves
turbulent entrainment. However, depending on the physical proper-
ties of the fluid, the dischargingrate, and the geometry of the nozzle,
air can be entrainedevenwhen the jet is perfectlysmoothand in laminar
flow (4). The author investigatedthe bubble entrainment by such
laminar jets usinghigh-speedphotographyand, as illustrated in Fig. 6,
this is due to the formation of a very thin film of gaswhich breaksaway
to form air bubblesin the product. Figure 7 is a photographtaken by
the author showingformation and breakup of such a cylindrical air
film.

This typeof bubble entrainmentby a laminar jet is quite common

in the filling of viscouscosmeticpreparations. The author has ob-
332 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

o o- •
__
-

Figure 6. Laminar bubblc cntrainment

Figure 7. Gas film formation

 GAS BUBBLE FORMATION 333

servedthis type of entrainmentfrom a perfectlysmooth,viscousjet at a

Reynoldsnumber as low as 10. Furthermore,a studyon suchlaminar
jets indicatedthat bubble entrainmentcould occuronly when the linear
velocity of the jet exceededa critical value termed "minimum entrain-
ment velocity." By keepingthe jet velocity below this value, laminar
jet entrainment by the film breakup mechanismcan be eliminated.
The minimum entrainmentvelocityis a [unction of the jet diameteras
well as the physicalpropertiesof the jetting fluid. For Newtonian jets
having a uniform velocityprofile, the following correlationwas found
by the author (5):
We = 10 Re ø'74

or

L • J

where
We = Weber number
Re = Reynolds number
D = jet diameterat the point wherejet meetsthe receivingfluid
Ve = minimmn entrainment velocity
p = density of the liquid
3' = surfacetensionof the liquid
• = viscosityof the liquid
By solvingthe equation for minimum entrainment velocity, the fol-
lowing equationis obtained:
•yo.794
6.22
•)0.206
•00.206
•0.587

From this equation, it can be seen that a fluid with low surface
tension and high viscositywill have a low minimum entrainment velo-
city and will be likely to trap air by this mechanism. A solution to
this problem is then to use a nozzleand filling rate such that the linear
jet velocityis alwaysbelow the minimum entrainment velocity.
In someinstances,a reduction of jet velocity may not be possibleor
desirableand it may be necessaryto solve the problem by redesigning
the filling nozzle. Ideally, the filling nozzle should be submergedinto
the receiving fluid at all times to avoid air entrainment; however, this is
not always possiblein modern filling machines. Some filling nozzles
334 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

are designedso that the jets do not hit the receivingfluid vertically,
but rather they are to flow alongthe wall of the bottle being filled (Fig.
8). Among thoseillustrated,(B) and (C) are usually the better types
from the aeration viewpoint. The type (D) with multiple pinhole
orifices can sometimes introduce more air than a vertical nozzle because
of the high jetting velocity.

(A) (B)

(C) (D}

Figure 8. Various typesof filling nozzles

(A) Vertical nozzle (B) J-shapednozzle
(C) Double-orificenozzle (D) Pinhole nozzle

Incorporationof PowderedMaterial
In cosmeticprocessing,as in the preparation of a liquid eyeliner or
fiuid make-up,it is often necessary to add powderedmaterialssuch as
pigments or zinc stearate into a liquid. During such addition, the
powderscan carry into the liquid bulk an appreciableamount of air
which may remain in the product.
This is a very commonproblem but not alwayseasyto solve. Often
a slow and uniform addition or a sprinkling of the powders rather
dumpingthem into the batchwill easethe problem. If the batchunder-
goesviscositychangesduring the manufacturingprocess,the powdered
material should be added when the batch is at its lowestviscosity(e.g.,
while the batchis hot) sothat any entrainedair bubblescan be freed.
 GAS BUBBLE FORMATION 335

If a very large quantity of powderedmaterial must be incorporated

in a batchand if the resultingmixture hasa very high consistency, the
useof a vacuummixing kettle may be necessary.For example, a tooth-
pasteis most commonlymade in a vacuum mixing kettle or it must be
passedthrough vacuum deaerating equipment afterwards to remove
the entrappedair bubbles. A moltenlipstickbulk is sometimes processed
in an evacuatedkettle to free entrappedair bubbles. The useof sucha
vacuumkettle for a lipstickwould be unnecessary if the formula can be
revisedto lower the yield value of the bulk at its molten state. In some
applications,the presenceof air is undesirableonly becauseit contains
oxygen. In suchinstances,nitrogen or other inert gasescan be used to
purge the air from the enclosedsystem.
One possibleway of mixing a batch of a fluid without air entrainment
is to recirculatethe fluid with a pump. An in-line mixer or homogenizer
canbe addedin the line to achieveeffectivemixing or dispersing.To be
effective, however, care must be taken to make sure that the circulation
is not localized. Sucha systemis quite ideal for many applicationsbut
the consistency
of the batchcannotbe too high.

Internal Generation of Bubbles

All of the mechanisms discussed so far involve entrainment of the
externalair, i.e., the air which wasnot originallypresentin the liquid
bulk. However,in addition to thesemechanisms, it is also possibleto
form bubblesthroughinternal generationof gases.
Chemical Reaction

As in a fermentationprocess,many gasescan be generatedthrough

chemicalreactions. If a viscousproduct undergoesa chemical reaction
during the manufacturingoperationor shelflife resultingin a liberation
of a gas,the productcan obviouslycontaingasbubbles. Although there
are many chemicalreactionswhich can lead to the liberation of gases,
mostcosmeticingredientsare relatively inert and this type of generation
is relatively uncommon.

PhysicalChange
In the absenceof a chemical reaction, gas bubbles can sometimes
form asa result of a physicalchange. For example, if the changein en-
vironment is suchas to producea decreasein the solubility of the dis-
solvedair in a product, the excessair can be liberated as air bubbles.
336 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Sucha solubility decreasecan occur not only as a result of temperature

increaseor pressuredecrease,but can also occur in the mixing ot5two
or more liquids. If the mixing resultsin a decreaseof the solubility ot5
the dissolvedgas, a liberation of the gas will take place until a new
equilibrium is established.
Accordingto the experimentsconductedby the author, this mech-
anism is believed to be responsiblefor air bubble formation in the
preparationof hydroalcoholicCarbopol©* gels (6). Mixing of ethanol
and water, both saturated with air, will result in a decrease of the air
solubility and liberation of air bubbles. The liberated air can escape
from an ethanol-water solution readily. However, if an alcohol dis-
persionof a Carbopol resin is neutralized with an aqueoussolution of
triethanolamine, the liberated free air bubbles may be trapped in the
newly formed gel becauseof the high viscosityand yield value of the
Carbopol gel. Thus, no matter how much care is taken to avoid ex-
ternally entrainedair, it is still possibleto form air bubb!esby this mech-
anism.

To obtain a bubble-freegel, one candisperseCarbopolin a preblend

of alcohol and water and neutralize the dispersiononly after all the
excess bubblesare freed. SinceunneutralizedCarbopoldispersions have
very low viscosities,
air liberated before neutralizationcan readi!y escape
from the system. To hasten the bubble liberating process,the un-
neutralized dispersionshould be agitated with a mixer. A more rapid
way to remove the excessbubbles is to passthe unneutra!ized dispersion
through an ultrasonicmachine. By a cavitationprocess,the excessair
can be removed quickly and the gel obtained by neutralizing such a
dispersioncan be completelybubble-free,providedthat no external air
is entrained during the neutralization process.
Finally, another possiblemechanismof bubble formation as a result
of a physicalchangeis due to a densitychange. As somemelted waxes
are solidified,a densityincreasemay occurand resultin a productshrink-
age. Sometimes,the wax mixture may harden before the full shrinkage
takesplaceand result in a gradualformation of bubbles. An example
would be the solidificationof paraffin-basedhair pomades. In some
formulations,the full shrinkagemay take severaldaysresulting in the
pulling awayof the productfrom the sidesof the jar or formation of
many bubbles. Sometimesa gradualcoolingrather than a rapid cooling

* Carboxy vinyl resins,B. F. GoodrichChemical Co., Cleveland,Ohio.

 GAS BUBBLE FORMATION 337

will minimize the problem but frequently a reformulation will be re-

quired to solvethe proble•n completely.
CONCLUSIONS

Control of gasbubblesin cosmeticpreparationsis a difficult but ex-

tremelyimportant problemin making stableand aestheticallypleasing
products. Although there is deaerationequipment* designedto remove
gasbubblesfrom the products,it is generallybest to prevent the gas
from gettinginto the productsin the firstplace. As hasbeenshown,once
the mechanisms and sourcesof bubble formationare correctlyidentified,
it is generally possibleto prescribesolutionswhich will prevent or
minimize the problem.
(ReceivedOctober 21, 1970)
REFERENCES

(l) Martin, A. N., and Banker, G. S., Rheology, in Bean, H. S., Beckett, A. H., and Carless,
j.E., A•'dvanc•s
in Pharmd•euticM
Sciences,
Vol. 1, AcademicPrfiss,New York, 1964,p. 58.
(2) SterbJcek,Z., and Tausk, P., Mixing in the Chemical Industry, PergamonPress,Oxford,
1965,pp. 278-82.
(3) Lin, T. J., RheologyFundamentalsand Applications in CosmeticIndustry, in deNavarre,
M. G., Chemistryand Manufacture of Cosmetics,Vol. 1, Van Nostrand, Princeton, N.J.,
1962, pp. 332-6.
(4) Lin, T. J., and Donnelly, It. G., Gas bubble entrainment by plunging laminar liquid
jets, AIChE ]., 12, 563-71 (1966).
(5) Lin, T. J., Ph.D. dissertation,Wayne State University, Detroit (1963); Univ. Microfilms,
N. 64-9539, Ann Arbor, Mich.
(6) Lin, T. J., Bubble formation in hydroalcoholicgels, ]. Soc. Cosmet. Chem., 20, 795-805
(1969).

• Examples, Versatot© from Cornell Machine Co., Springfield, N.J., or Sontrifuge© from
Teknika Inc., Dayton, Ohio.