A New Method and Apparatus for Measuring Foam Stability

GARY NISHIOKA 1
NASA, George C. Marshall Space Flight Center, Huntsville, Alabama 35812

AND

SYDNEY ROSS
Chemistry Department, Rensselaer Polytechnic Institute, Troy, New York 12181
Received March 5, 1980; accepted September 24, 1980

The decay of foam with time, whether caused solely by gas diffusion through foam lamellae
without rupture, or by a combination of that effect and occasional concomitant rupture, is given,
most fundamentally, by the rate of decrease of the total area of extended liquid surface. This property
can be measured directly, by photographing sections of the foam at measured intervals of time,
but the technique and subsequent reduction of the observations to numerical values require so
much effort that the direct method is seldom used. The equation of state of foam (Ross, S.,
Ind. Eng. Chem. 61, (10), 48 (1969)), however, relates the total area of liquid surface within a foam
to the pressure of its contained gas, and so makes it possible to quantify foam decay in fundamental
terms, by determining the rate of the build-up of gas pressure at constant volume and temperature
in the head space above the foam. An apparatus is described that uses this principle. Pressure
differences of the order of a few torricelli are measured by means of a differential pressure trans-
ducer, connected to a strip-chart recorder. The total area of extended liquid surface determined
with this apparatus is in excellent agreement with results obtained simultaneously by direct photog-
raphy of the foam during its decay, thus confirming the validity of the Ross derivation. The
method of differential pressures was also used to confirm the effect, already well known, that
the stability of foam made from an aqueous solution of sodium lauryl sulfate is enhanced by the
presence of small amounts of lauryl alcohol in the solution.

INTRODUCTION ods of measurement (5). However, none of

The requirements to stabilize or, alterna-
tively, to destroy foam are problems that
occur in a number of industrial processes,
such as pulp and paper manufacture, froth
flotation, distillation towers, coating proc-
esses, fire fighting, and food processing.
Many different methods exist for the meas-
urement of foam stability, such as the Ross-
Miles method (1), Bikerman method (2), op-
tical transmission methods (3), photographic
techniques (4), and various qualitative meth-
I U.S.R.A. Visiting Scientist (1978-1979). Present
address: Technical Center, Owens-Coming Fiberglas
Corporation, P.O. Box 415, Granville, Ohio 43023.
these methods is simultaneously versatile,
easily reproducible, experimentally conveni-
ent, and fundamental. We describe in this
paper a method and an instrument that satisfy
the above desiderata.
The method is based on the equation of
state for foam, as derived by Ross (6). A
foam is considered to consist of cells,
whether spherical or polyhedral in shape,
each containing gas at an excess pressure
corresponding to the radius of curvature of
its equivalent sphere (see Ref. (6) for the
concept of the equivalent sphere). The total
area of the foam is related to pressure,
volume, temperature, and quantity of gas by

0021-9797/81/050001-07502.00/0
Copyright © 1981 by Academic Press, Inc.
lournal of Colloid and Interface Science, Vol. 81, No. 1, May 1981 All rights of reproduction in any form reserved.
 2 NISHIOKA AND ROSS

n f R T = PeVf + 2o'A/3, [1] The area of liquid surface in f o a m is

where nf = n u m b e r of moles of gas con- A ( t ) = Ao + A A , [7]
tained in the foam, P~ = pressure external
w h e r e A ( t ) = area at time t andA0 = initial
to the foam, Vf = volume of gas in the foam,
area of the foam. When the f o a m com-
o- = surface tension and A = area of liquid
pletely collapses,
surface in the foam. Consider a closed sys-
tem at constant volume containing a foam. 3VAP~
The total amount of gas in the s y s t e m is A(~) = 0 = A0
2or ' [8]
ne + F/f, where n~ = moles of gas external
to the foam, or and therefore
3VzXP~
P~Ve (P~Vf + 2o-A/3) A 0 - [9]
n~ + nf - + , [2] 2~r
RT RT and
where Ve = volume external to the foam. A ( t ) = (3V/2o')(AP= - A P ( t ) ) . [10]
L e t the f o a m d e c a y at constant t e m p e r a t u r e , Interfacial area of a f o a m can be meas-
then: ured, therefore, simply by monitoring the
P'~V[ (P'~V~ + 2~rA'/3) change in pressure external to a f o a m in a
t t _
n~ + nf + [3] container of constant volume and tempera-
RT RT
ture, if the total volume of the system and
where the primes indicate later values after the surface tension of the foamed liquid are
decay. Since known. The value Ap~ can be obtained by
! letting the f o a m d e c a y for a sufficiently long
ne + nf = n e + h i , time or by injecting a small quantity of anti-
(P~Vf + 2o-A/3) foam through a septum in the container.
-PeVe
- +
RT RT Hitherto, the only use made of Eq. [10]
to measure foam stability was by Kruglyakov
P'~V; (PeVr + 2o-A/3) and T a u b e (7). We suspect the method went
- + , [4]
RT RT unnoticed because they used a w a t e r ma-
n o m e t e r to measure the small but rapidly
or, after some rearrangement: changing pressure differences, which is a
3VAP + 2o-AA = 0, [5] tedious and inexact method at best. Also,
because of their method of f o a m generation,
whereV= Vt-Ve= V ~ + V r = V ' + V~; problems in reproducibility m a y have oc-
APe=P~-P~; and AA = A ' - A ; Vt curred. U s e of a pressure transducer and a
= total volume of the vessel; V~ = volume different method of f o a m generation gets
of solution in the vessel. around both disadvantages.
Equation [5] is the theoretical basis of our
device; it relates pressure changes external PROCEDURE
to a f o a m to changes in its internal area.
It is analogous to the constant-pressure re- The f o a m m e t e r is depicted in Fig. 1. T w o
lation derived for bubbles by Tait and gen- j a c k e t e d glass vessels of a p p r o x i m a t e l y l-
eralized by Ross for foams with polyhedral liter capacity are connected to two ends of a
or spherical cells, indifferently: differential pressure transducer (Dynisco
Model PT14-03). The pressure transducer
3PAV + 2o-AA = 0. [6]
requires dc at 6 V; its dc millivolt output
Values of absolute area of f o a m can be ob- is c o n n e c t e d directly to a strip-chart re-
tained in the following manner. corder. Differential pressures of the order
J o u r n a l o f C o l l o i d a n d I n t e r f a c e S c i e n c e , Vol. 81, N o . 1, M a y 1981
 FOAM STABILITY MEASUREMENT 3

i DIFFERENTIAL STRIP
PRESSURE CHART
TRANSDUCER RECORDER
SEPTUM
~

TO THERMOSTAT
" I
;OERMOSTAT

JACKETED ~'N JACKETED

REFERENCE T GLASSFRIT SAMPLE
BOTTLE 80TTLE
FROM
THERMOSTAT
FI6. 1. A schematic of the apparatus used. The jacketed sample vessel is graduated for rough
estimates of foam volume.

of a few torricelli are typically attained. A
differential method for measuring pressure
has the advantage over absolute methods
in that casual pressure changes, due to tem-
perature fluctuations, can be made to cancel.
To do so most effectively, a reference bottle
of nearly identical internal volume is made
part of the system. Both vessels are kept
at constant temperature by means of cir-
culating fluid, which in the present experi-
ments was held at 25.00 _+ 0.02°C. Higher
or lower temperatures could be maintained
by the same device.
Foam is generated with a coarse glass frit
fitted into the bottom of the sample vessel.
The sample vessel has a narrow internal di-
ameter near the bottom (not shown in Fig. 1)
so that 500 ml of foam can be created from
100 ml of liquid while keeping the frit always
immersed in liquid. This prevents air from
being blown through the foam as it is being
created.
The procedure for the measurement of
foam stability is as follows. One hundred
milliliters of the liquid is poured into the
sample chamber. To reach temperature
equilibration and to provide time for residual
bubbles to disappear, the sample liquid is
allowed to remain undisturbed in the cham-
ber for several hours. Air displaced by 500
ml of water is then passed through the flit
and creates the foam. This method of foam
generation gives reproducible data; attempts
to generate foam with compressed gas from
a cylinder are not as satisfactory. Immedi-
ately after the foam is created the septum
is attached, all valves are closed to seal the
systems, and the two chambers are sepa-
rated. The differential pressure between
them increases as the static foam decays.
After a sufficient time 10/xl of an antifoam
is injected in order to obtain Ap~.
The total volume of the sample chamber
was measured by applying the ideal gas law
to changes of pressure of helium on expan-
sion out of a gas burette into the sample
chamber. The surface tension of the solution
was measured at 25.00 _+ 0.02°C using a
Wilhelmy plate attached to an electrobal-
ance, with a precision of 20.1%.
RESULTS AND CONCLUSIONS
As an indication of reproducibility, suc-
cessive measurements of foam decay are
shown in Fig. 2. Two representative curves
for foams from an aqueous solution con-
taining 0.52 wt% sodium lauryl sulfate (un-
Journal o f Colloid and Interface Science, Vol. 81, No. 1, May 1981
4 NISHIOKA AND ROSS

10.0 8.0

9.0 Z,0

8.0 '~ 6.0

I
,- 7.O
t
5.0 0T-
x ~
------ SLS

'~ 5.O :3.O ~

i1

o: °.or 1:,.o :,,"

'~ 3.0 ~" ~, 1.0 ~
U

2.0 0.0

1.0

0 10 20 30 40 50 60 70 80 90

TIME -- MINUTES

FIG. 2. Two measurements of the stability of foam made from aqueous 0.52 wt% sodium lauryl
sulfate solution (dashed curves). Two other curves, not shown, virtually overlap the curves shown.
Also shown (solid curves) are three measurements of the decay of foam made from aqueous 0.40 wt%
CTAB solution.

purified) are shown. The agreement of four
successive runs is excellent; for clarity only
two are shown.
Reproducibility of foam d e c a y curves for
an aqueous solution containing 0.40 wt% hex-
adecyltrimethylammonium bromide (CTAB)
is not as good, as is also shown in Fig. 2.
C T A B is a cationic surface-active solute that
creates a nonwetting condition on the glass
walls of the sample vessel, which in turn af-
fects the structure of the f o a m during its
formation and decay. This circumstance is
probably the cause of poorer reproducibility.
The d e c a y with time of a f o a m made from
an aqueous solution of sodium lauryl sulfate
was recorded on movie film while simultane-
ously m e a s u r e m e n t s were made of the in-
crease in pressure in the sample chamber.
The calculation of the area of liquid surface
in a f o a m by observing the cross section
against a glass wall has been shown to be
feasible (8). The area of the f o a m lamellae
was estimated at selected frames of the
movie in the following manner. At early
stages in the d e c a y f o a m cells are essentially
all spheres; the distribution of radii was
measured and the mean of the reciprocals
of the radii calculated. This quantity, meas-
ured in a cross section, has been shown (8)
to equal the reciprocal of the mean radius
in a foam, i.e.,
1 1
- , [11]
rs

Journal of Colloid and Interface Science, Vol. 81, No. 1, May 1981
 FOAM STABILITYMEASUREMENT
where rs = radius in a cross section and ?
= mean radius in a foam. Equation [11] is
valid only if values of the radii of bubbles are
randomly distributed throughout the foam.
Assuming the foam to consist of close-
packed spheres of radius ?, the volume of
foam and the total number, n, of spheres
were determined; the total area of liquid sur-
face was calculated as
A = 4nTr~2. [12]
It should be noted here that in a foam
consisting of spheres surrounded by liquid
the interface associated with a sphere is
given by Eq. [12]. For a single bubble, con-
sisting of a double interface, the area is
doubled. Similarly, the trAA coefficient is
doubled going from the R os s - T ai t law for
foams (Eq. [1]) to the original law derived
for single bubbles (6). Therefore, Eq. [12]
is correct for calculating total area.
At intermediate stages in decay the area
could not be accurately determined from the
photographs for two reasons. First, the vol-
ume of the foam could not be easily esti-
mated due to uneven breakage. Second, the
foam appeared to be a mixture of spheres
and polyhedra so analysis for a determina-
tion of area could not be accomplished.
At late stages in the decay the cells were
all polyhedra. The total interfacial area is
given by
A = Vft = V Ldx [13]
where A = area of liquid interface per cubic
centimeter, V = volume of the foam, L
= total length of gas-liquid interface against
the glass per square centimeter (twice the
length of liquid lamellae), and x = depth of
the foam normal to the glass. Assuming L
is constant in the x direction,
/ rl
ft = L I dx. [14]
J0
By Eq. [14] A is numerically equal to L and
the total interfacial area can then be approxi-
mated as the product V L .
The photographic estimates of total inter-
facial areas are compared in Fig. 3 with the
areas obtained by application of Eq. [10]
to the pressure data as a function of time.
Agreement is excellent, though the assump-
tions underlying the photographic estimates
led us to expect much poorer agreement than
these results demonstrate.
The stabilizing effect of lauryl alcohol on
sodium lauryl sulfate foams is well known
(9) and is also shown in Fig. 3. The sodium
lauryl sulfate was obtained commercially and
was recrystallized 3 times from water, 10
times from absolute ethanol, and extracted
with anhydrous ether for 48 hr. The surface
tension-concentration curve was in excel-
lent agreement with previous studies (10).
The lauryl alcohol was fractionally distilled
once under vacuum. Enough lauryl alcohol
was added to the sodium lauryl sulfate solu-
tion so that films would become slow drain-
ing at 25°C (11); this effect enhanced foam
stability, which the foam decay curves in
Fig. 3 clearly reflect.
A point that should be considered is the
effect of adsorption in the foam and its ef-
fect on surface tension. If enough surface
is created in a foam and the solution is
dilute enough, then adsorption of surface-
active solute at the surface would essentially
denude the lamellar liquid of solute and
change its surface tension. As shown below,
this was not the case even for our dilute
sodium lauryl sulfate solutions.
The Gibbs excess, F(G), for aqueous
sodium lauryl sulfate solutions is 3 x 10-1°
mole/cm 2. The total initial area is 5 x 104
cm 2. Therefore, the total amount adsorbed
initially is 1.5 x 10-5 mole or about 5 mg.
This represents a few percent of the total
solute available. The corresponding change
in surface tension would then be small.
It would be interesting to study a foam
in which decay would cause a large decrease
in lamellar surface tension. However, in
most foaming systems, which usually consist
of concentrated surfactant solutions, virtu-
Journal of Colloid and Interface Science, Vol. 81, No. 1, M a y 1981
6 NISHIOKA AND ROSS

2
\ _._ o.2 GM. s,s,,oo M,. SO,OT,O,,
/ L\ ---- 0., GM. S S,100 M,. SO,°T,ON
i ~ ® PHOTOGRAPHICESTIMATES

".,..
0 I i i a i I i,
0 20 40 60 80 100 120 140

TIME -- MINUTES

FIG. 3. Comparison of the change with time of surface area of foam from aqueous solution of
0.10 wt% sodium lauryl sulfate ( T = 25.00°C) determined by the method of differential pressures ( - - - )
and by direct measurement from photographs (@). Also shown is the stability of foam made from an
aqueous solution of purified sodium lauryl sulfate solution ( - - - ) compared with that from the same
solution to which lauryl alcohol has been added (- ).

ally no change in surface tension would
result with a 10,000-fold increase in area.
The present method of measuring foam
decay can readily be adapted to different
conditions. The jacketed vessels need not
be transparent and can be made out of any
material suited to the conditions of meas-
urement. Extreme pressures and tempera-
tures, or corrosive liquids, pose no special
difficulties. With the advent of sturdy dif-
ferential pressure transducers these condi-
tions can be handled. An improvement in
accuracy would be obtained by using capaci-
tance manometer devices, available com-
mercially under the trade n a m e " Baratrons."
These devices are more sensitive and re-
sponsive and, in their recent development,
Journal of Colloid and Interface Science, Vol. 81, No. 1, May 1981
are inert to most vapors. Foam decay can
also be measured at constant pressure, in-
stead of at constant volume. A slug of liquid
in a capillary replaces the pressure trans-
ducer: its position as a function of time gives
the volume change vs time. Analysis then
depends on Eq. [61 rather than Eq. [5].
The curves shown in Figs. 2 and 3 repre-
sent the decline of liquid interface in the
foam, which is both a more fundamental
and a more sensitive index of foam decay
than either the rate of liquid draining out of
the foam or the rate of final escape of gas
from the foam, which have previously been
suggested for that purpose (8). As a unit of
foam stability, therefore, we propose L, the
average lifetime of unit area of liquid surface

in the foam, which can be evaluated, by
means of the expression
Ls - 1
Ao i0 Adt
by integrating curves of surface area (cm 2)
versus time (minutes).
Equation [15] shows that absolute values
of the liquid surface in the foam cancel out
in the determination of Ls; therefore, meth-
ods that yield only relative values of A can
equally well be used to determine Ls. One
such is the optical transmission method. The
relative intensity of the light transmitted
through a foam increases directly as the de-
cline of the area of liquid surface in the path
of the light beam; therefore,
Ls - - - 1 l~ (I~
I~ I0 0
whereI0 = initial intensity of the transmitted
light (t = 0) andI~ = final intensity (t = ~).
The shape of the curves of A vs t in the
present work closely resembles that of (I~
- I) vs t obtained by light transmission (3).
More detailed comparisons of results ob-
tained by the two techniques are reserved
for presentation elsewhere.
As well as providing a more fundamental
way for characterizing and measuring foam
stability the present technique is suited for
an experimental confirmation of computed
models of the kinetics of foam decay, which
have recently been developed by Lemlich
(12) and Ranadive and Lemlich (13) based on
the change of the initial distribution of bub-
ble sizes as the contained gas diffuses from
Journal o f Colloid and Interface Science, Vol. 81, No. I, May 1981
FOAM STABILITY MEASUREMENT 7
smaller (higher pressure) bubbles to larger
(lower pressure) bubbles. Observations of
slow-draining foams can be matched against
, [15] the computed change of total surface area
with time, to evaluate the original distribu-
tion of bubble sizes and the diffusion con-
stant of the gas through the liquid lamellae
of the foam.
ACKNOWLEDGMENTS
The authors are grateful for the work of Ms. C.
Woodcock, Mr. G. Crochiere, and Mr. K. Hrebenar
at Rensselaer Polytechnic Institute, and Ms. B.
Facemire at NASA for their assistance in the con-
struction and modifications of this device.
REFERENCES
1. "1975 Annual Book of ASTM Standards," Dl173-
53, Part 30, p. 180.
- I)dt, [16] 2. Bikerman, J. J., Trans. Faraday Soc. 34, 634
(1938).
3. Ross, S., and Cutillas, M. J., J. Phys. Chem. 59,
863 (1955).
4. Savitskaya, E. M., Kolloidn. Zh. 13, 309 (1951).
5. Bikerman, J. J., "Foams." Springer-Verlag, New
York, 1973.
6. Ross, S., Ind. Eng. Chem. 61, (10), 48 (1969).
7. Kruglyakov, P. M., and Taube, P. R., J. Appl.
Chem. USSR 38, 2211 (1965).
8. de Vries, A. J., "Adsorptive Bubble Separation
Techniques" (R. Lemlich, Ed.), pp. 7-31.
Academic Press, New York, 1972.
9. Shah, D. O., Djabbarah, N. F., and Wasan, D. T.,
Colloid Polym. Sci. 256, 1002 (1978).
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11. Epstein, M. B., Wilson, A., Jakob, C. W., and
Ross, J., J. Phys. Chem. 58, 860 (1954).
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(1978).
13. Ranadive, A. Y., and Lemlich, R.,J. Colloidlnter-
face Sci. 70, 392 (1979).