1668 Langmuir 1993,9, 1668-1677

Mechanisms of Aqueous Foam Stability in the Presence of

Emulsified Non-Aqueous-Phase Liquids: Structure and
Stability of the Pseudoemulsion Film
Lloyd Lobo+and Darsh T . Wasan’
Department of Chemical Engineering, Illinois Institute of Technology, Chicago, Illinois 60616
Received January 20,1993

The influence of the emulsified oil drops on the stability of an aqueous foaming system is investigated
at the thin film level. In the first part of the paper we evaluate the theories that use the classical entering
and spreading coefficients to predict the effect of oil drops on foam stability. A differential interference
microscope was used to observe the configuration of oil drops at the air-water surface, which ia likened
to the air-water surface of foam lamellae. The microscopic observations show that the entering and
spreading coefficients cannot consistently predict the configuration of the oil at the air-water surface and,
consequently, cannot predict the effect of oil on foam stability. The reason for this inconsistency is that
the classical theories do not account for the role of the pseudoemulsion f i ,which is formed between an
air-water surface and the surface of an oil drop which is approaching it. It is the Stability of this film that
determines the configuration of the oil drop, as it was earlier suggested by Wasan and Nikolov (refs 10
and 11). In the second part of the paper, we use reflected light interference microscopy to observe the
drainage and stability of the pseudoemulsion film. We observed, for the first time, that the f i thins
in discrete steps, which is indicative of the presence of an ordered micellar structure within the film, and
this structure was found to enhance the film stability. The f i excess energy, which is determined from
the f i contact angles, is used to quantitatively characterize €he stability of the f i . The contact angles
of the curved, asymmetric pseudoemulsion f i were measured by wing interference microscopy in
conjunction with the Laplace equations for the film meniscuses. The f i excess energy calculations show
that the equilibriumfilm thickness increaseswith increasing micellar concentrationaswell as with decreasing
oil drop size or film area. The effect of these two parametera on the f i stability is explained due to the
formation of the ordered micellar structure (i.e.,micellar layering) within the pseudoemuleion film.

Introduction foam stability. We had also shown2 that the effect of

Oil dispersed in a foaming system is encountered in
several applications; foam mobility control processes in
enhanced oil recovery @OR) applications, food foams,
and antifoamers are a few examples. It has been found
that, in some cases, the oil acts as a foam stabilizer (food
foams),l whereas, in other cases, it acts as a foam
destabilizer (antifoamers). When studying the &.ability
of three-phase foams (aqueous foams containing oil), it is
important to identify the system variables that could play
a role in the foamstability. In many practical applications
it is fairly common to employ surfactants at several times
their critical micelle concentration (cmc), and in these
circumstancesthe oil can exist in two forms: (i) solubilized
within the micelles and (ii)as macroemulsions or oil drops.
In these micellar systems the amount of solubilized oil is
generally small (about 0.2-0.5 w t 5% 1, and is usually very
minor compared to the amount of macroemulsions.
However, it is important to realize that the two oil
confiiation types (solubilizedlemulsified)can have very
different effects on the foam stability.
In an earlier paper,2 we have discussed the effect of
solubilized oil on foam stability. It was found that the
presence of solubilized oil inhibited the formation of an
ordered micellar structure within the foam films which,
according to Nikolov et al.,3 enhances the foam film
stability. Thus, solubilized oil is always detrimental to
* To whom correspondence should be addreseed.
t Presently with Photographic Research Labe, Eaetman Kodak
Co., Rochester, NY 14660.
(1) German,J.B.InFoodEmuLsionsandFoams: TheoryandPractice;
Wan, P. J., Ed.; AIChE Symposium Series 277; American Institute of
Chemical Engineers: New York, 1990; p 62.
(2) Lobo,L.A.;Nikolov,A.D.;Wasan,D. T.J. DispersionSci.Technol.
1989, 10, 143.
(3) Nikolov, A. D.; Wasan, D. T. J. Colloid Interface Sci. 1989,133,
1.
macroemulsions on foam stability should be considered
independently of the effect of solubilized oil.
In this study, we investigated the interactions of the oil
drops with the foaming system, in order to elucidate the
mechanism of aqueous foam stability in the presence of
oil drops. The results of our findings are also compared
with someof the prevalentclassicaltheorieson this subject.
When the oil is dispersed into the foaming system, the
drops are initially present in the foam lamellae as well as
within the Plateau borders of the foam films. The most
widely accepted mechanism for foam stability in the
presence of oil is that the oil drops, dispersed within the
foam films, spread on the air-water surfaces of the foam
films and, due to a variety of reasons (discussed below),
enhance the film rupture and decrease the foam stability.
The interactions of the oil drops with the foam film are
characterized by the degree of oil spreading and the final
configuration of the oil drop at the air-water surface.
Robinson and Woods,4 as well as ROSS,~ have defied two
coefficients-an entering coefficient, E, and a spreading
coefficient, S-that can be used to predict the oil drop
configuration at the air-water surfaces and to quantify
the degree of spreading. These are given by
where u is the interfacial tension and the subscripts 0, w,
and a refer to oil, water, and air, respectively.
The entering coefficient, E, represents the decrease in
the free energy that occurs when an oil drop, which is
within a solution (see Figure la), ‘enters” or forms a lens
at the airwater surface as shown in Figure lb. The
spreading coefficient, S, represents, quantitatively, the
(4) Robinson,J. V.;Woods, W. W. J. SOC.Chem. Znd. 1948,67,361.
(6)Ross, S. J. Phys. Colloid Chem. 1950, 54, 429.

0743-7463/93/2409-1668$04.00/00 1993 American Chemical Society

Mechanism of Aqueous Foam Stability
a air
water @-oil
b
C drop from an air-water surface.
oil film
/ +
Figum 1. Configuratioasof the drops aspredicted by the classical
theory: (a)oil drop within the solution,(b) oil lens,and (c) spread
oil at the surface.
Figure 2. Mechanism of foam rupture in the presence of oil.
driving force for the oil to spread on the surface and is also
derived from the decreasein the free energy resulting from
the oil spreading at the surface.
Ross5 has proposed a mechanism, based on the oil
spreading phenomenon, by which the oil drops rupture
the foam films. The schematicof this mechanism is shown
in Figure 2 and is summarized as follows: The oil drop
initially within the film (Figure 2a) will enter one of the
film surfaces if E > 0 (Figure 2b). Due to foam film
thinning, the second film surface comes into contact with
the oil drop and the oil enters this surface and bridges the
film (Figure 2c). Robinson and Woods4have suggested
that the formation of the oil bridge is sufficient to rupture
the foam film (Figure 2d). Ross,however, postulates that,
in order for the rupture to occur, the oil bridge must also
spread as a duplex film on either side of the original film,
thereby driving out the original aqueous film liquid and
leaving a thin oil film which is not stable and easily
ruptured. According to this theory, the antifoaming
efficiency of the oil drops increases with the value of the
spreadingcoefficient. Other mechanismsproposed on this
subject are basically variations of the spreading theory.
The spreading theory has been experimentally tested
and many different investigators have found exceptions
to the rule. Ross,himself, has found no direct relationship
between the degree of antifoaming by the oil and the
magnitude of the spreading coefficient, although he does
find a 1:l relation between the sign of the spreading
coefficient and the effect of the oil on the foam stability
(positive values of S result in decreased foam stability).
Langmuir, Vol. 9, No. 7, 1993 1669
elr
pseudoemulsion film
I?X
Figure 3. Thin film of the continuous phase separatingan oil
Ross and Mcbain6found systems which were good anti-
foamersbut had negativespreadingcoefficients. Robineon
and Woods+ in comparing different spreading oils, found
that there is no correlation between the spreading coef-
ficient and the degree of foam inhibition. Tsuge et al.7
have found systems in which the oil spreads but does not
inhibit foaming. Kuhlman8suggested that the definition
of the spreading coefficient should be modified by taking
into account the geometry of the oil drops and the foam
bubbles, but he still does not obtain a correlation between
the spreading coefficient and foam stability. Garrettg
suggests that the dynamic values of the interfacial and
surface tensions should be used when determining the
entering and spreadingcoefficients,but it is not clear what
rates of surface/interfacial expansion should be used.
Thus, the classical spreading theory is not consistent
with many experimental findings. The main flaw in this
approach is that it does not take into account the presence
of a film (see Figure 3) that is formed between the oil drop
and the air-water surface. Wasan et al.'OJ1 were the first
to point out that this film, which they called the "pseu-
doemulsion film", can exhibit, in the presence of Surface-
active substances, a stability similar to that of foam and
emulsionf h . Unless this pseudoemulsion film ruptures,
the oil drop cannot enter the &water surface, irrespective
of the value of the entering coefficient. An analogy of the
classical theories, regarding the concept of entering and
spreading coefficients,can be drawn to both the foam and
emulsion systems. In these systems, the interfacial and
surface tensions are usually positive, implying that the
systems should coalesce in order to decrease their free
energy. However,the stability of these systemsis derived
from the stability of the films of the continuous phase
that prevent the disperse phase from coalescing. In order
for the disperse phase to coalesce, an energy barrier,
associated with the drainage and rupture of these films,
has to be overcome.
The importance of the pseudoemulsion film was f i t
identified by Wasan and co-workerslOJ1in studies with
enhanced oil recovery type foams,where they showed that
the foam stability in the presence of emulsified oil is
(6) Ross, S.; McBain, J. W. Ind. Eng. Chem. 1944, 36,670.
(7) Teuge,H.; Uehida,J.; Hibino, S. J. Colloid InterfaceSei. 1984,100,
176.
(8) Kuhlman, M. I. Paper presented at the SPE/DOE Enhanced Oil
Recovery Symposium, Tulsa, OK,1988; SPE/DOE No. 17356.
(9) Garrett, P. R.; Moore, P. R.; Ward, D. Foam and Dynamic Surface
Properties of Micellar Anionic Surfactant. Paper presented a t the 8th
Symposium on Surfactanta in Solution, Gainesville, FL, June 1990.
(10)Wasan, D. T.; Nikolov, A. D.; Huang, D. D.; Edwards, D. A. In
Surfactant Eased Mobility Control; Smith, D. H., American Chemical
Society: Washington, DC, 1988; p 136.
(ll)Nikolov,AD.;Wasan,D.T.;Huang,D.W.;Edwards,D.A.Paper
presentedatthe 61st Annual Technical Conferenceof SPE, New Orleane,
1986; SPE No. 15443.
1670 Langmuir, Vol. 9, No. 7, 1993
controlled by the stability of the pseudoemulsion film.
Later, Manlowe and Radke12also showed that the pseu-
doemulsion film stability controls the stability of single
foam lamellae within porous media. The latter have
suggested that the stability of the pseudoemulsion film is
kinetic in nature. However, in many system and especially
at high surfadant concentrations, the pseudoemulsionfilm
can reach a thermodynamically metastable state. In
studies with foam films, Nikolov e t ale3have shown that,
at high micellar concentrations, the formation of an ordered
structure within the f ilm increased its stability due to the
structural contributionsto the micellar interactions. This
structure was also found to stop the thinning process of
the film.
In the present study, we discuss the validity of the
classical theories by qualitatively studying the pseu-
doemulsion film stability of different systems. Further,
for one of the systems, we have investigated the role of
micellar structuring on the stabilityof the pseudoemulaion
films by (i) studying the film drainage characteristics and
(ii) measuring the thermodynamic properties of the films,
such as the contact angles and the excess film energies.
Experimental Section
Materialand Solutions. Two surfactantswere used in these
studies-anionic and nonionic. The nonionic surfactant is an
ethoxylated alcohol supplied by Shell Development Co. with a
product name of C1215 AE30.'The surfactant molecule has a
12-15 carbon atom chain with an average of 30 ethoxy group per
surfactant molecule. The average molecular weight of the
monomer is 1530,and the micellar aggregationnumber obtained
from light scatteringmeasurementsis 46. The concentration of
the surfactant used in these studies was 4 wt % which was 1300
times the critical micelle concentration. The anionic surfactant
was d u m dodecyl benzenesulfonate with a commercial name
of Siponate DS10-which was supplied by Rhone Poulenc Inc.
The concentrationused was 4 wt % ,which is severalt i " higher
than the critical micelle concentration (cmc = 0.042%).
n-Octane, n-decane, n-dodecane, hexadecane, and benzene
were used as the oils. They were obtained from Fisher and were
reagent grade. The surfactant solutions were equilibrated with
the oils for 10-14 days to allow for complete solubilization,and
the surfactant solutions were then separated from the oils by
wing a separatoryfunnel. All the experimentswere made using
the respective, equilibrated solutions.
Interfacialand SurfaceTension. A Krw tensiometerwas
used to measure the interfacial and surface tensions with a
platinum Wilhelmy plate. These measurementa were used to
calculate the entering and spreading coefficients. A spinning
drop tensiometer was used to measure the interfacial tension
when the vlaues were below 3 dynlcm.
PseudoemulsionFilm Observations. We used an Aus Jena
Epival Interphako microscope in order to determine the con-
figuration of the oil at the h a t e r surface. This microscope
is capable of viewing objects in transmitted light as well as in
reflected light. The microscope is also equipped with a Max
Bender interferometer, which splits the original beam of the
image into two beams of different optical paths which, when
recombined,give a shearing-typedifferentialinterferencepattem;
this can be used to measure the curvature of s u r f a ~ e s . ~The
~J~
glass cell used for these studies is shown,schematically,in Figure
4. It consists of two concentricglass cylinders fused at one end
to an optical glass plate. The surfactant solution is placed in the
inner cylinder, and clean water (3-mm depth) is placed in the
outer cylinder. A small oil drop (0.3-O.Ekmmdiameter)is i n j d ,
with a 0.25-pL Hamilton syringe, below the &water surface of
the surfactant solution in the inner glass cylinder. By viewing
the drop in both transmitted and in reflected light, as well as by
(12) Manlowe, D. J.; Radke, C. J. SPE Reeervoir Eng. 1990, 5, 496.
(13) Beyer, H. Jenaer Rundsch. 1971,16,82.
(14)Nikolov, A. D.; Dimitrov, A. 5.; Kralcheveky, P. A. Opt. Acta
1986, 33.
Lobo and Wasan
plastic shield
I air
oil droD
glass cuvette \ \
surfactant solution water
Figure 4. Schematic of the glass cell used for the microscopic
studies.
b
P
Figure 6. Possible confiiations of the oil depending on the
pseudoemulsion film stability: (a) stable pseudoemulsion film
and (b) unstable pseudoemulsion film.
using the differential interference (DI) technique, it is possible
to determine the confiiation of the oil drop at the air-water
surface. The surfactant solutionwas protected from the outside
environment by a plastic shield which fitted on the objective.
The shield ale0 provided a saturated vapor environment around
the &water surface of the surfactant solution.
The two possible configurations of the oil drop are shown in
Figure 5. In confiiation a, the pseudoemulsion f ilm is stable,
andintransmittadlight( l i g h t s o ~ b e l o w t h e d r o p ) , i t i s ~ b l e
to o b e e ~ ethe circumference of the drop whereas, in reflected
light, only the circumference of the film is visible. The radius
of the film (rc)is considerablysmaller thanthe radius of the drop
(R)is this configuration. Confiiation b is an oil lens which ia
formed after the oil drop has entered the akvater surface. In
this confiiguration, both refleded and transmitted light mi-
croscopies revealed the circumference of the lens. Another way
to differentiate between the two confiiations ia by observing
the differentialinterferencepa" of the drop in reflected light.
The photomicrograph of the differentialinterferencepattern of
the pseudoemulsion film, for the 4 wt 9% C1215 AEso-octane
system, is shown in Figure 6. It is similar to the differential
interference pattem, obse~edby Nikolov et aL:6 of a foam f h
formed by a floating air bubble. Mingins and NikoloP have
studied oil lenses using the DI technique, and the differential
pattem they obtained is quite different from that shown in Figure
6. From the differential interference pattern it is poeeible to
conclude that the confiiation of the drop is similar to the one
seen in Figure 5a.
From Figure 6 it is also seen that the thin pseudoemulsion
film appears bright, as opposed to the thin foam and emulsion
f i i , which are black. The reason for this difference can be
explained by the electromagnetic wave theory of light. Light
rays which are incident on the fiilm reflect from the two surfacea
of the film, and these reflected light rays interfere optically. When
light rays of wavelength A are incident on a thin (zerothickneee)
foam or emulsion film, they encounter, alternately, an optically
dense and opticallyrare medium (the order depends on the type
of emulsion). As a result, the two reflected rays from each of the
(16) Nilrolov, A. D.;Kralcheveky,I. B.;Ivanov,I. B. J. ColloidZnterface
Sci. 1986,112, 122.
(16) Mingins, J.; Nikolov, A. D. Ann. Unio. Sofia (Fac. Chim.) (in
Bulgarian) 1981, 76, 3.
Mechanisms of Aqueous Foam Stability
Figure 6. Photomicrograph of the differential interference
pattern of the pseudoemulsion film (4w t % C1215 AE30 and
octane).
filmsurfacesdiffer by a path length of X/2. This is the condition
for the destructive interference of light, which is why the thin
foam and emulsion filmsappear black in reflected light. On the
other hand, light rays incident from the air side of a pseu-
doemulsion film encounter an optically denser medium at both
the film surfaces (air to water and water to oil). Thus, both the
reflected rays are shiftedby A/2, and the path differencebetween
the two reflected rays is A. This is the conditionfor constructive
interference, which is why the pseudoemulsion film appears
bright.
In order to study the effect of drop size on the film stability,
a new drop was created each time and the size of the oil drop was
controlled by the syringe. Once the pseudoemulsion film was
formed and stopped thinning, the system was allowed to stand,
undisturbed,for 15min, to allowfor saturationof the environment
above the air-water surface and also for complete surfactant
adsorption. After this, the microscope stage is gently tapped, so
that the oil drop detaches and submerges below the surface. In
this way, a new film is formed when the drop rises again, and
usingthe reflectedlight mode, it is possible to observethe drainage
characteristics of the film. The new film is left undisturbed for
30 min to allow the film to reach equilibrium, after which
photomicrographsof the oil drop are taken in transmitted light,
in reflected light, and with the use of the interferometer. These
photographs are used to measure the common and differential
interferencepatterns as well as the drop diameter. The common
interference pattern is formed by the interference of the light
raysrefleded from the wedge which is bound by the filmmeniscus
and bubble surfacenear the three-phasecontactline. The pattern
appears as concentriccircles which are similar to Newton rings.
The distances between the interference patterns are measured,
from the photomicrographs, by using an x-y translator (least
count of 1pm) which is mounted on a goniometric microscope.
Validity of the Classical Theories
The microscopic technique was used to determine the
oil drop configuration for the systems listed above. The
predictions of the classical theories can be obtained by
measuring the interfacial and surface tensions of the
equilibrated solutions and oils and then calculating the
entering and spreading coefficients. In this way, it is
possible to check the validity of the classical theories.
Table I shows the measured values of the interfacial
and surface tensions as well as the calculated values of the
entering and spreading coefficients. It is seen that, for all
but one of the system (NaDBS + benzene), the entering
and spreading coefficients are positive. According to the
Langmuir, Vol. 9, No. 7, 1993 1671
Table I. Entering and Spreading Coefficients
NaDBS-hexedecane 31.1 26.6 0.09 4.6 4.4
NaDBS-decane 28.2 23.2 0.06 5.1 6.0
NaDBS-dodecane 28.2 25.4 0.09 2.9 2.7
NaDBS-benzene 27.3 28.2 0.02 -0.88 -0.92
C1215AESO-octane 43.5 21.3 10.2 32.4 12.0
C1215 AE30-dodecane 43.5 25.4 9.4 27.5 8.7
classical theories, the oil drop in these systems should
have entered and spread at the air-water surface. Using
the microscopic technique described above, it was found
that the pseudoemulsion films in all these systems were
stable, even after they stopped draining, which prevented
the oil drops from entering the air-water surface. The
configuration of the oil drops in these cases is shown in
Figures 3 and 5a.
Thus, the classical theories do not predict the behavior
of the oil drop at the air-water surface. The reason for
this, as mentioned earlier, is that the decrease in the
surface energies can be used only as a necessary but not
as a sufficient condition to predict the behavior of the oil
drop at the air-water surface. It is clearly evident that
an additionalfactor, i.e., the pseudoemulsionf i i stability,
should be taken into account. The stability of the
pseudoemulsion film can be kinetic or thermodynamic in
nature. The kinetic stability of a film is governed by the
film drainage characteristics, and this aspect of stability
has been analyzed by Manlowe and Radke.12 They used
the Reynolds equation, which is valid for rigid or immobile
film surfaces, to describe the film drainage rates. They
also accounted for the disjoining pressure II,by using the
DLVO model, which is valid for ionic surfactants. In the
systems investigated in our present study, the pseu-
doemulsion films stopped draining and remained in a
stable configuration for over 1h. This implies that the
stability is thermodynamic in nature. In the subsequent
section, the thermodynamic properties of the stable film
are calculated, with the objective of characterizing the
film stability.
Thermodynamic Stability of the Pseudoemulsion
Film
Among the systems listed in Table I, the one with the
highest spreading coefficientwas the C1215AESO-octane
system. According to the classical theories, the foams of
this system should be destabilized by the oil, by the highest
degree. This was also one of the systems common to those
studied in our previous p a p e r ~ , ~where
J ~ we found that
the effect of oil drops is to stabilize the foams-a result
contradictory to the predictions of the classical theories.
For this reason, this system was selected by us for the
studies on the thermodynamic stability of the pseu-
doemulsion film. Two concentrations of the surfactant
were used for this part of the study-4 and 1wt % Figure .
7 shows the configuration of the oil drop at the air-water
surface with the respective geometrical parameters that
are used in the analysis below.
At equilibrium,the excess pressure in the film,Pf, equals
the disjoining pressure, n,
The above equation is an approximate one. In the case
of symmetric systems (when the two tensions are equal),
(17) Koczo, K.;Lobo, L. A.; Wasan, D.T.J. Colloid Interfuce Sci.
1992,150,492.
1672 Langmuir, Vol. 9,No. 7, 1993
Figure 7. Geometrical parameters of the oil drop at the ai^
water surface.
,e, air
water
-=---------
--- -.,ah
Figure 8. Definition of the contact angles for an asymmetric
fii.
the disjoiningpressure of a curved film is half the capillary
pressure (equal to 2ulR). For plane parallel films, the
excess film pressure, Pf,equals the capillary pressure.
The disjoining pressure arises due to the interactions
between the film surfaces, and the stable film represents
an energy barrier for the oil drop to enter the air-water
surface. The total energy barrier of the film, from its
formation to its rupture at the critical thickness h,,, is
given by
AE = Jmh-n
dh (3)
This represents the total work done in order for the film
to drain from its formation to its rupture. The necessary
condition for the oil drop to form a lens is for the oil drop
to overcome the energy barrier given in eq 3. When the
pseudoemulsion film stops thinning and reaches an
equilibrium state at a thickness h, larger than the critical
thickness h,,, the part of the energy barrier, bE, that is
overcomeis given by the negative of the specificinteraction
energy of the film, -W,
-W = Jmhhn dh (4)
The specific interaction energy of the film is equivalent
to the energy of the film in exces~of the energy of the two
free film surfaceswhich are not interactingwith each other.
Henceforth, we shall refer to this energy as the film excess
energy. Thus, the film excess energy, of a film having a
thickness h, is, in a thermodynamic sense, a measure of
the stability of the pseudoemulsion film.
In order to determine the film excess energy, it is
necessaryto measure the contact angles of the film. Figure
8 shows a plane parallel pseudoemulsion film with the
contact angles a1and (r2. It is important to point out that
the plane parallel configuration of the pseudoemulsion
film is not realistic because these types of films are usually
curved (see Figure 7). However, Figure 8 is introduced to
illustrate the definitions of the contact angle and the
differentiating features of the pseudoemuleion film. The
angle a1 is made by the oil-water meniscus of the film,
Lobo and Wasan
and cy2 is the angle made by the h a t e r m e n k of the
film. At equilibrium, the film tension is given by (ya/w+
yo/w),where Y ~ and ~ are the tensions of each of the
/ yOlw
film surfaces given by
--
= uo/w cos "1; Yalw q w cos a2
Yo/w (6)
The film excess energy, -W, is given by
-W = -Y ~ /+
~ (ua/w
) - r,/d = uo/w(l- cos q)+
-
ua/w(l cos cy2) (6)
The main oddity of the pseudoemulsion film is that it
is an asymmetrical type of film; Le., it has two different
phaeee on either side of the film, unlike foam or emulsion
films. Consequently,the contact anglesof the asymmetric
films, cy1 and a2, are not equal. On the other hand, foam
or emulsionfilms, which are symmetrical,have equal angles
which simplifies the measurement technique. For sym-
metrical films,the film excess energy is given by
- w =2@(1-c08((rh/2))
where u is the surface tension for both the meniscuses of
the symmetricalfilm. The above equation holds true for
(7)
a curved film only if the effect of the line tension is
neglected. In this treatment we assume the effect of the
line tension to be negligible, which is reasonable, since the
size of the drops is larger than 100 pm and the film radii
are of the order of 30pm. Thus, the value of the totalfilm
contact angle, (rh (see Figure 81, is sufficient to determine
the film excess energy, of symmetric films. The angle a h
is easily determined (and fairly accurately) using purely
optical techniques such as those of Princen and Frankells
and Schel~dko.'~
In the case of asymmetric films, the independent
determination of angles cy1 and cy2 cunnot be made from
purely optical measurements. Additional information of
the exact shapes of the two meniscuses around the three-
phase contact line is needed. A technique which we had
developedm earlier, for foam films, is ideally suited for
asymmetricfilms. In this technique,the Laplace equations
for the drop/bubble surface and the meniscus are inte-
grated to obtain the shapes of the two surfaces. The
Laplace equations are used in conjunction with the
information obtained from the common interference
fringes (Newton rings) that are observed in the three-
phase contact region, to obtain the exact profiles of the
drop surfaceand the meniscus and, subsequently,the three
phase contact angles, 4, and $, (shown in Figure 7).
Meaeumment of the Contact Angles. Figure 9 shows
a detailed section of the three-phase contact region of the
drop. In this case, the contact angles are defined for a
film having a finite thickness, unlike the treatment in ref
20 where the angles are determined for films of zero
thickness. The three main angles are qC,4, and 6. The
angles a1 and a2 are related to the former angles by
a1 = dc-6 a2 =w, (8)
Determination of the Angles & and rLC. The angles
$c and 4, are determined from the common interference
pattern (Newton rings) using the procedure described in
ref 20 with slight modifications. Figure 9 shows the
definitions of the angles at the three-phase contact region
of a film with a finite thickness, h. The technique in ref
20 extrapolates the film meniscuses till they meet (point
(18)Princen, H.M.;Frankel, S . J. Colloid Interface Sci. 1971,36,386.
(19) Scheludko, A. Adu. Colloid Interjace Sci. 1967, I, 391.
(20) Lobo, L. A.;Nikolov, A. D.; Dimitrov, A. S.; Kralcheveky, P.A.;
Wasan, D.T.Langmuir 1990,6,996.
Mechanisms of Aqueous Foam Stability
... * .
water
I =. . .. .water
Figure 9. Three-phase contact region of the pseudoemulsion
film.
A), and the contact angles &' and #: are defined for a film
of zero thickness (point A). The film excess energy can
be obtained from either of the two sets of contact angles
bY
where 11 is the disjoining pressure and h is the film
thickness. Again, the above equations are valid only if
the effect of the line tension is neglected. [It is important
to mention that the extrapolation procedure may not
always result in the intersection of the two meniscuses,
and this would occur if W became positive. In that case,
the contact angles cannot be defined. In our systems,
however, the extrapolation procedure resulted in the
intersectionof the two meniscuses.] In Figure 9, the actual
boundary of the thick film is at point B, and the
measurement technique in ref 20 extrapolates the drop
surface and the meniscus by integrating the Laplace
equations up to A (zero thickness). The Laplace equation
for the drop surface is given by21
where R and 2 are dimensionless variables of X and 2 (2
= X/Rb;2 = Z/Rb)and O d is the angle made by the tangent
to the drop surface and the horizontal (measured counter
clockwise from the horizontal), fld = (Apd)gRb2/ud,where
h p d is the differencein the density between the oil and the
aqueous phase, Ud is the interfacial tension between the
drop phase (=uoIw)and the aqueous phase, and Rb is the
radius of curvature of the bottom of the drop. The value
of Rb can be calculated from the equatorial radius of the
drop, R, using the equation derived by Kralchevsky et
aL2' R is directly measured using transmitted light
microscopy.
The Laplace equation for the meniscus is given by
dsino,
-=-- -sin"
d2 R fflm
(21) Hartland,5.;Hartley, R. Axisymmetric Fluid-Liquid Interfaces;
Elsevier Science Publishing Co.: New York, 1976.
Langmuir, Vol. 9, No. 7,1993 1673
d2
-=-tanom
d.2 (11)
om is the angle made by the normal to the meniscus and
the vertical. The other variables remain the same as before
except that they relate to the properties of the air-water
phases rather than the oil-water phases.
At point A the contact angles 42 and $2 are determined
using the followingtwo equations: The first equation was
derived by Kralchevsky et al.22where they obtained an
asymptotic solution for the Laplace equation for the
meniscus (eq 11).
where ye = 1.781 072 418 is Euler's number, h, is defined
in Figure 7, and r: is the radius of the film after it is
extrapolated to zero thickness. The above equation is a
truncated form of their asymptoticsolution,and from their
error analysis it is seen that it is sufficientlyaccurate for
determiningthe contact angles. The second equation was
originally proposed by P r i n ~ e nand ~ ~modified by Kral-
chevsky et aL2* This equation is obtained from the
condition of the constancy of pressure at all pointa of the
horizontal planes situated in the bulk aqueous and air
phases. The hol'izontal planes selected are the one just
abovethe film (situated in the bulk air phase) and the one
just below the apex of the drop (situated in the bulk
aqueousphase). The pressure drop acrossthese two planes
along the axis of the bubble ( x = 0) is given by
pailis the density of the oil phase and Rf is the radius of
curvature of the film. The definitions for the notations
in the above equation are shown in Figure 7,and the prime
refers to the film of zero thickness.
The pressure drop acrossthe sametwo horizontal planes,
taken at r = OD, is given by
hp, -(zc - h,)p,gg - (h, + Rf - (R: - re1211/2 )p,& (14)
By equating the two pressure drops, a modified version of
Princen's equation is obtained for asymmetric f h
sin $: = [g( 3 + (z, - h,)Ap,g +
Rb
where Ape/, is the density difference between the oil and
air phases.
The values of &', &',h,, and zc can be determined from
the integration of the Laplaceequations and by successive
approximations between eqs 12 and 15,using exactly the
same calculation procedure described in ref 20 (the only
difference is that eq 10 in ref 20 should be substituted by
eq 15derived above). The value of Rt, in eq 15,is obtained
from the differential interference pattem, as discwed
later in this paper.
(2!2) Kralchevsky,P.A.;Ivanov,I. B.;Nikolov,A. I>. J. Colloidlnterface
Sci. 1986, 112, 108.
(23) Princen, H.M.J. Colloid Interface Sci. 1968, 18, 178.
(24) Kralcheveky,P.A.:Nikolov.A.D.:Ivanov,I.B.J. ColloidInterfoce
Sci. 1986, 112, 132.
1674 Langmuir, Vol. 9,No. 7, 1993
a b
Figure 10. Thinning pseudoemulsion f i i (a) thick film with dimple, (b) film undergoing stratification, two thickness transitions,
and (c) enhanced image of a film undergoing stratification. The film has three discrete thicknesses resulting from the first two
transitions.
The radius of curvature of the film, r:, at zero thickness
cannot be directly measured from the photomicrographs,
when the film has a finite thickness. Thus, the measure-
ment procedure in ref 20 uses the radii of the Newton
rings in order to obtain r,'. The Newton rings are formed
due to optical interference of the reflected light rays in
the region immediately adjacent to the perimeter of the
film. By using the equations that satisfy the conditions
of optical interference,we obtained information about the
variation in the distances between the drop surface and
the top meniscus, in this region. The value of r,' is used
as a variable, in an iteration procedure which minimizes
the square of errors between the distances (between the
film menisci) obtained by the integration procedure and
the distances obtained from the common interference
pattern. For our experimentalmeasurements we used the
maxima and minima in the optical interference pattern,
such that we could determine the radii of seven Newton
rings, which were subsequently used in the minimization
procedure. The experimentalvalue of the vertical distance,
de, between the film meniscuses, at the point of constructive
or destructive interference (ie., along the circumference
of the bright or dark Newton rings), is given by de = kX/
4N,where k = 0, 1,2,3, ...,k increases away from the film
perimeter with k = even numbers representing the
constructive and k = odd numbers representing the
destructive interference patterns. The details of this
procedure are also given in ref 20.
In order to determine the film excess energy, -W, we
need to determine the values of the contact angles, 4, and
$, for the film of finite thickness, i.e., at point B. The
radius of contact of the film, r,, at point B, can be measured
from the photomicrographs with a fair degree of accuracy
(=tl pm). In order to compute the angles at point B, the
meniscus and the drop surfaces are extended from point
A (whose location is determined from the minimization
procedure) to point B, by integratingthe respective Laplace
equations of the two surfaces. The anglesO d and O m (from
eqs 10and 11)of the surfacesat point B are used to obtain
$c and 4 c (4, = - Wd; $c Om)*
Determination of 8. The angle 8 -is obtained by
measuringthe curvatureof the f i i R f ,from the differential
interference pattern, seen in Figure 6. By measuring the
distances between the parallel stripes in Figure 6, Rf is
determined using the following equation, proposed by
Nikolov et al.:15
where lk = kX/4, k is the order of interference of the streak
(k = 1,2,3, ...,k increases away from the central streak),
Lobo and Wasan
film edge
\
I
1st thickness transition
X is the wavelength of incident light, d is the shearing
distance of the image which depends on the settings on
the microscope, and x k is the distance of the kth streak
from the central streak (position of zero order of inter-
ference). Further details of this measurement technique
are given in ref 15. The value of Rf, obtained using the
above equation, can be used in eq 15. The angle 8 is
calculated by
sin 8 = rJRf
Once the vlaues of $, $, and 8 are determined, the angles
a1 and cy2 are obtained from eq 8, and subsequently, the
film excess energy, -W, is determined using eq 6.
Results
Film Drainage Observations. The drainage char-
acteristics of the pseudoemulsion film were observed, in
reflected light, by submerging the oil drop and allowing
it to rise as described in the Experimental Section. The
drainage characteristics for the solution of the higher
surfactant concentration (4 wt %) are as follows: As the
rising oil drop reached the surface, a thick, nonuniform
film (with a dimple) was initially formed as seen in Figure
loa. The film drained, continuouslyand rapidly, to form
a parallel film without the dimple. After the film passed
the last minimum in the intensity of reflected light (which
correspondsto film thickness h = X / 4 N = 104nm; N is the
refractiveindex of the solution),the film stopped thinning
momentarily. After this, a spot of brighter intensity
appeared at one edge of the film. The spot represented
a portion of the film having a smaller thickness than the
rest of the film. The distinct borders of the spot indicated
that there is a sharp thickness transition within the film.
The spot expanded, indicating that the film changed its
thickness by a discrete jump. Three such thickness
transitionswere observed (eachtime to a lower thickness),
after which the film stopped thinning, and the final
thickness of the bright film was approximated to about 20
nm. The thickness transitions are shown in Figure lob,
where the upper right side of the film is in the state before
transitions begin (approximately 8&100 nm). As one
traverses from the right to the left of the film, the film
thickness decreases sharply in three stages, and the
brightest portion of the film representsthe thinnest section
of the film. The photograph shows only the first two
transitions; the third could not be captured photograph-
ically. Figure 1Oc shows a section of a film which is
undergoing stratification. The image is enhanced with an
image analyzer, to sharpen the contrast between the
transitions. Again, these are the first two transitions. For
the solution containing 1wt % surfactant, only one such
Mechanism of Aqueous Foam Stability
...........
............
......... V'
0.0.
ordered structure
mice"eS
............
............
........... ~~ ~
Figure 11. Schematic of the model for stepwise f i b thinning
due to the formation of colloid crystal structure.
1.00
-4 wt% C1215 AE30
ww. 1 wt% C1215 AE30
0.00
100 200 300 400
Drop Radiur (microns)
Figure 12. Variation of a1 with drop size.
transition was observed, with the final thickness being
approximately the same as that of the film formed from
the 4 w t 9% solution.
The stepwise film thinning, observed here, is similar to
the stratification phenomenon studied by Nikolov et al.
(formicellar system^).^ Accordingto the model of Nikolov
et al.,%the three step transitions that we observed suggest
that an ordered structure of micelles, which initially
contains three layers of micelles, is formed within the film.
The stepwise thinning was due to the layer-by-layer
expulsion of the micelles from the film. Figure 11
schematicallyshows a section of a film which thins in such
a stepwise manner. Nikolov et al.= also observed three
thickness transitions, for thinning foam films stabilized
by the same surfactant, used in this study,at approximately
the same concentration (4 w t % ). They found that, upon
decreasing the micellar concentration, the colloid crystal-
like structure was less developed and the total number of
thicknesstransitions decreased. The fiidings of this study
are consistent with their observations.
Measurement of Film Properties. After it stopped
thinning, the thermodynamic properties of the pseu-
doemulsion film were measured, and for each concentra-
tion, three different drop sizes were studied. The contact
angles a1 and a2 were determined using the calculation
procedure described above. The variation of a1 and a2,
with the drop size, is shown in Figures 12 and 13,
respectively. It is seen that both a1 and a2 increase with
an increase in the film or drop size (the film radius, rc, is
(26) Nikolov, A. D.; Kralcheveky, P. A.; Ivanov, I. B.; Wasan,D. T. J.
Colloid Interface Sei. 1989,133,13.
(26) Nikolov, A. D.;Wpan, D. T.;Kralchevsky, P. A.; Ivanov, I. B. In
Ordering and Organization in Ionic Solutiona, Proceedinp of Yamada
Conferenca XIX, he, N., Sogami, I., Eds.; World Scientific Publishing
Co.: Singapore, 1988; p 302.
Langmuir, Vol. 9, No. 7, l S 3 1676
1.00 1
-4
YI
wbs C1215 AE30
1 wbs C1215 AE30
4 0.50
7
,0.00 (100 200 300
Drop Radiue (microne)
400
Figure 13. Variation of CYZ with drop size.
related to the drop size, R,as rc2 = (2/3)R44&[(~m +
Ud)/UmUd]). It is also seen that, at the same film size, the
contact angle increases with the decreese in the micellar
concentration. The contact angle increases when it gets
thinner, due to the larger interaction between the film
surfaces. The results in Figures 12 and 13 indicate that
the films are thinner when the micellar concentration ie
lower, or when the drop size is larger.
Effect of Micellar Concentration. Nikolov et d.*3
found that with the increasein micellar concentration the
ordering started at an earlier stage of the film thinning
process. They also found that, when the initial number
of layers is large, the films could stop t b h g while there
are still some layers within the film. The reaaon for this
can be explained by their model;% the micellar ordering
offera an additional componentof the disjoining preamre,
which they termed the structural component, Thus, as
the number of Iayers increases,thisstructural component
also increases, and at some point, the disjoining pressure
counterbalances the excesa film pressure at even lnrger
film thicknesses. Their results can qualitatively explain
thefindingsof thisstudy, which showsthat the equilibrium
films are thicker at higher micellar concentrations.
Effect of Film Size. Kralchevsky et al." p r o w a
mechanism for the formation and expansion of the spota,
which represents the transitions, from one thickness to
the next. The colloid crystal structure is postulated to
have a number of defeds or vacancies in it, and the
concentration (number per unit volume) of vacanciee
increases with the decrease in the micellar concentration.
Since the structure is formed in the liquid fikn, theae
vacancies are in a dynamicconditiondue to the movement
of the micelles within the structure, and consequently,
the vacanciesare said to 'diffuse" (itis actuallythemicelles
that diffuse). According to their model, a spot is formed,
in the f b , by the diffusing vacancies condensing (or
meeting) at one point. They showed that, in order for thia
spot to expand and the thickness transition to occur,the
total number of vacancies should be greater thana critical
value. At a given micellar concentration,the total number
of vacancies is proportional to the size of the film, and
thus, if the thickness transition is to occur, the size of the
film should be greater than a critical value. If the film
size is below this value, the thickness transition will not
occur and the film will remain in equilibrium a t ita thicker
state. Nikolov et al.= showed, experimentally,that, at a
constant micellar concentration in the bulk, as the size of
the film was decreased it stopped t h h i n g at a higher
(27) Krqlchevaky, P. A.; Nikolov, A. D.; Wasan,D. T.; Ivauov, I. B.
Langmir lWH), 6,1180.
(28) Nikolov,A. D.;Wasan,D. T. Surface ForceBalancefor F h with
Fluid Interfacee. Paper presented at the Artnd Meeting of AI-,
Chicago, 1m.
1676 Langmuir, Vol. 9, Nu. 7, 1993
0'015
1 -4
n+n 1 wt%
WM C1215 AE30
C1215 AE30
1 not only the intensive propedies of the system (temper-
-
s
-0.010
. (film area). This fact differentiates these f i (films
F
7 0.005
. 0
0 surfactant concentrations below the cmc. In the latter
1 continuous, is only a function of the intensive properties
0.000
100.0 200.0 300.0 400.0
Radiue of drop (microne)
Figure 14. Variation of the excess film energy with drop size.
equilibrium thickness with an increasing number of
micellar layers remaining inside the stable film. The
results of Figures 12and 13showthat, at the same micellar
concentrations, the smaller sized films have a smaller
contact angle, implying thicker films, which is also
consistent with their findings.
Film Excess Energy. The contact angles obtained
were used to calculate the film excess energy according to
eq 6, which is plotted in Figure 14. This f i e shows,
qualitatively, the same trend as the contact angle mea-
surements. The small value of the film excess energy,
which implies a thicker film,decreaseswith the increasing
micellar concentrationas well as with decreasingfilm area.
NikoIov et al.25 have made theoretical estimates of the
film excess energy, for anionic surfactant system, when
there are different numbers of layers in the film. They
found that every stage of the film (i.e., film with three
layers, two layers, etc.) represents a metastable state and
a thickness transition occurswhen the system moves from
one metastable state to the next. They calculatedan excess
energy associated with each of these metastable states
taking into account the film surface interactions as well
as the structural component of the disjoining pressure
that arises due the ordered micellar structure. Thus, when
the thicknessof the film pasees through severaltransitions,
the total excess energy is given by the sum of the excess
energy for each of those metastable states. If the film
stops thinning before all the micellar layers are expelled,
some of the metastable states will be missing and the total
excess energy of the film will be less than that if the film
had thinned completely. Thus,it is seen that when the
area of the film is decreased, the f i i excess energy is
lower, and this indicates that the smaller films have not
thinned completely because some part of the micellar
structure still remains in the stable films. A similar
argument can be drawn for the effect of micellar concen-
tration, although the total number of layers in the initial
structure may be smaller.
In the case when we have micellar structuring, the film
excess energy is given by
S,:"n,,
where is the disjoining pressure due to surface
interactions (steric forces in the case of nonionic surfac-
tants), avw is due to the van der Waals forces, and u, and
u,,-1 are the structural components of the disjoining
pressure where the subscripts refer to the number of
micellar layers present in the f i between transitions in
thickness, which are given by the limits of the respective
Lobo and Wasan
integrals. AB mentioned above, the transition from one
thickness to the next is dependent on the film area.
Consequently, the film excess energy w(h)is a function of
ature and concentration) but also an extensive property
stabilized by a micellar structure) from the films at
case, the disjoining pressure isotherm is continuous with
film thickness, as in the case predicted by the DLVO
theory, and the film excess energy w(h), which is also
of the system. Thus, for our system, due to the fact that
we have stratification, each point in Figure 14 is unique
to a film of a given area and represents the energetics of
the finalstate of the film. The points in Figure 14are not
connected because we have not determined, in a continuous
manner, how the film excess energy changes with a change
in film area. For this reason also, we cannot use eq 18 to
determine the structural components of the disjoining
pressure, from the data in Figure 14.
Table I1 shows the various measured and calculated
properties of the pseudoemulsion film for the two con-
centrations tested. It is important to point out that when
the f i area decreaseswith decreasingdrop size,the excess
film pressure,Pf,increases simultaneowly. The increasing
excessfilm pressure and the decreasing film area have two
opposing effecta on the film drainage. The excess film
pressure, Pf(given by eq 21, is the difference between the
pressures in the film and the meniscus and represents the
driving force for film drainage. At high excess film
pressures, the driving force for film drainage is higher,29
which tends to drive the film to a lower equilibrium
thickness. However, at the same time, as the film area
decreases, the total number of vacancies in the colloid
cryetal structure reduces-according to the model of
Kralchevsky et aL2' Consequently, the expansion of the
spotsin the film (or the transition to a lower film thickness)
takes a longer time to occur. Additionally, as discueeed
earlier, the thickness transition may not even occur below
a critical film area, which will result in a higher value of
the structural component of the disjoiningpressure. Thus,
when the drop size (and the film size)is reduced, the effect
of the increasing excess film pressure is to drive the film
to a lower thickness,while the effect of an ordered micellar
structure is to stop the films from thinning. The resulta
in Table 11 show that the excess energy of the films is
smaller for the smaller drops-indicating thicker
films-which implies that the stabilizing effect of the
micellar structuring overwhelms the effect of the excess
film pressure.
Summary
It isshown that the classical understanding, whichuses
the spreadingand enteringcoefficientswithoutaccounting
for the presence of the pseudoemulsion f i , does not
represent the complete physical picture of the behavior
of oil drops in a foaming system. AB a result, it may not
accurately predict the effect of oil on foam stability. Our
dh + ... (18) previous studies2J7with the same surfactant-oil system
(C1215 A E 3 h t a n e ) show that t h d oil drops do not
destabilize the foam even though the entering and
spreading coefficients are positive. In fact simple bottle
tests showed that, upon the introduction of oil drops (17
vol %) to the system, the foam stability increased from
2.5 to over 10 h. The mechanism of foam stabilization by
(29) Ivauov, I. B. Pure Appl. Chem. 1980,62, 1241.
Mechanism of Aqueous Foam Stability Langmuir, Vol. 9, No. 7,1993 1677
Table 11. Propertier of the Pneudoemulrion Film for the C1216 AE3Octane Syrtem
surfactant
concn (wt %) R (10' cm) r, (10' cm) film area (10' cm) II = Pf(dyn/cm2) ai (deg) a2 (deg) -w X 102 (erg/cm2)
1.0 368.2 72.25 1.64 448.7 2.38 0.45 1.01
277.6 42.87 0.58 596.3 2.13 0.46 0.84
241.7 32.40 0.33 W.6 1.68 0.37 0.53
4.0 267.0 69.7 1.52 469.8 1.85 0.34 0.6
275.6 40.32 0.51 699.6 1.45 0.3 0.39
156.4 14.23 0.064 1056 1.37 0.31 0.36

the oil drops, in this system, is discussed in ref 17. Thus,
for this particular system,the classicaltheories incorrectly
predict the effect of oil on foam stability. While the surface
energies are a useful measure of the tendency of the oil to
destabilizea foam, they cannot, as seen fromthe qualitative
observations of the pseudoemulsion f i i s , be used for
absolute predictions because they fail to predict the
configuration of the oil drop at the air-water surface. The
reason for this, as mentioned earlier, is that while the
entering and spreading coefficients are necessary condi-
tions, they are not sufficient to predict the entering and
spreadingof oil drops at the +water surfaces. In addition
to the surfaceenergies, thestability of the pseudoemulsion
film should also be considered since it is the main factor
that determines if the oil drop can or cannot enter the
ail-water surface.
The f i i drainage studies with the C1215 AE30-0ctane
system revealed, for the first time, the presence of an
ordered structure of micelles in the pseudoemulsion film.
The concentrations used in these studies were 300-1300
times greater than the critical micelle concentration. As
a result the f i exhibited three layers of micelles at the
higher concentration (4 wt %) and one layer at the lower
concentration (1 wt %).
When the pseudoemulsion films reach an equilibrium
film thickness, they are said to be stable, and a relative
measure of their stability is the value of the film excess
energy. When the excess energy is small, the films are
relatively thick and more stable, and when the excess
energy is large, the films are relatively less stable. The
f i i excess energy can be determined from the contact
angle measurements. Due to the asymmetric nature of
the pseudoemulsion film, the contact angle cannot be
determined from pure optical measurements and, in
addition to these, the exact shape of the f i meniscuses
should be known. We have adopted the measurement
technique describedin ref 20 to study the pseudoemulsion
film properties. Thistechnique usesthe informationfrom
common interferometry (Newton ring@ and differential
interferometry in conjunction with the Laplace equation
for the film meniscuges,in order to obtain the exact shape
of the meniscuses and the contact angles. The values of
the contact angle and the excess f i i energy were used to
evaluatethe role of the micellar structuring in the stability
of the pseudoemulsion film. We found that, due to the
stabilization by micellar layering, the film stability was
promoted by a higher micellar concentration. It was also
found that smaller drops had a film with a lower excess
energy and were, therefore, more stable. Thie result is
consistent with the findingsof Nikolovet ale3Thus,when
micelhr stabilization is operative, the relative stability
of the pseudoemulsion film is higher for the small drop
sizes.
Acknowledgment. This study was funded in part by
grantsfrom Kraft GeneralFoods, Inc., the National Science
Foundation, and the Department of Energy. The authors
gratefully acknowledge the assistance provided by Dr. A.
D. Nikolov.