RICHARD C. CHANG, HERBERT M. SCHOEN, and C. S. GROVE, JR.

Syracuse University, Syracuse, N. Y.

Bubble Size and Bubble Size Determination

Quick Freezing of Foam

b Stabilizes fresh foam as it i s generated

1 Holds bubble size and bubble size distribution
unchanged
h Provides data on relation between dispersity and other
physical properties

A L T H O U G H a large amount of work
has been done on foams in general, in-
vestigations of dispersity of foams and
the relationships between dispersity of
foam and other physical properties are
rather scarce.
Distribution of bubble sizes in a very
stable froth was studied by Sibree (4,
who used a photomicrographic tech-
nique. Clark and Blackman (7), using
a similar technique to study foams,
found that the larger bubbles grow and
the smaller bubbles shrink as a function
of time.
During their study of foam structure
Clark and Blackman ( 2 ) observed a rela-
meters of the gas-liquid interface in 1 ml.
of foam.
However, when Clark and Blackmans
light transmission method is applied to a
foam system, which changes during
standing, errors may be introduced be-
cause time is required to take the photo-
micrographs and the light transmission
readings.
Stenuf (6,7) modified Clark and Black-
mans technique and studied foam dis-
p.-I
persity under flow conditions. He com-
pared the light transmission to the ex-
pansion ratio and to actual photomicro-
graphs of the flowing foam.
Another method of obviating the insta-
bility of foam, used by Sovitskaya ( 5 ) ,
was the quick-freezing technique with
liquid oxygen. Photomicrographs were
taken after the foam was frozen, and the
bubble sizes were determined from them.
She found that freezing and thawing
did not affect the dispersity and that the
frequency distribution of the bubbles
was nearly the same in the surface layer
as in any other section of the foam mass.

71
tionship between foam dispersity and the 0.4w.
Experimental Apparatus and
opacity of the dispersed system, caused
by the scattering of incident light by
multiple reflections and refractions.
Later they found that the loss of light on
transmission through a layer of foam can
be expressed as a function of the degree
of dispersion of the air. They made
photomicrographs of foam at various
degrees of dispersion under static con-
A-

BM5bF&rpR
ditions at atmospheric pressure and then
calibrated light transmission data with
these photomicrographs as standards.
They claimed that this method can be
used to measure specific surface of
foam. Specific surface was defined as
the total surface area in square centi-
B-
7 r5ci.W.
Techniques
Freezing Apparatus. Because foams
are usually unstable, bubble sizes and
bubble size distribution change on
standing. I n order to study these prop-
erties, fresh foam was stabilized by quick
freezing as it was generated. The rate
of freezing is important, because bubble
size and bubble size distribution may
change while the foam is being frozen.
Several freezing chamber designs were
/.oCM tested, the final design, shown in Figure
Figure 1.
I
/-
Freezing apparatus
1, being a modification of Sovitskayas
apparatus. The freezing chamber, A , is
a 1.9 X 1.0 X 0.4 cm. brass sheet. B is a

VOL. 48, NO. 11 NOVEMBER 1956 2035

 of the chamber to prevent evaporation
and condensation of moisture during the
freezing process. The freezing chamber
is constructed with only two sides, in-
stead of four, to allow any excess foam to
flow out when the chamber is covered.
The time required for complete freezing
is 15 to 30 seconds (average of 16 ob-
servations).
Photomicrographic Apparatus and
Techniques. The photomicrographs
were taken with a photomicrographic
camera at magnifications of 20 and 40
diameters. Foam in the freezing cham-
ber was placed directly under the camera,
as shown in Figure 2, and a picture was
taken within a few seconds to represent
the unfrozen foam. Another picture of
the same foam was taken about 1 minute
later, when complete freezing was as-
sured. The bubble sizes were computed
from the negatives with the aid of a com-
parator. Averages were calculated for
a number of plates before and after
Figure 2. Photomicrographic camera freezing. Statistical analysis was applied
and freezing apparatus to evaluate the difference between aver-
ages of the tw-o groups.
To photograph the bubble distribution
solid brass bar, attached to the bottom of within the foam mass, the frozen foam
A , which serves as the cooling conductor. was sliced with a razor blade at several
The freezing apparatus is precooled by different depths.
dipping the brass bar in liquid oxygen; Expansion Ratio and Foam Dis-
then the freshly generated foam is de- persity. A Blackmer sliding vane pump
livered into the freezing chamber. A was employed in studying the relation-
small glass plate is quickly placed on top ship between expansion ratio and foam
I I
/ pressure gages were used to measure the
1 anolamine, morpho-
PZD
PE*d?///vg.
PUMP
4 PUMP
8 sulfate
Figure 3. Flowsheet of Blackmer vane pump foam-generating system
2036 INDUSTRIAL AND ENGINEERING CHEMISTRY
dispersity. A flowsheet showing this
method used for generating foam of
variable expansion ratio is presented in
Figure 3. Foam liquid (6y0 Mearl-
foam), preheated to a desired tempera-
ture, was pumped from the solution
tank by pump A at a constant rate of
11.4 gallons per minute, as measured by
a rotameter. iVhen the foam liquid was
delivered into a tee, air was also sucked
into the tube by the adjustable speed of
the Blackmer sliding vane pump, B, and
thus foam was generated. ,4s the speed
of pump B was varied, the amount of
feed air differed accordingly. Thus,
foams of different expansion ratios were
obtained. The foam was then passed
through a column packed with Berl
saddles to a height of 40 inches. The
packed column served as a homogenizer.
Foam samples obtained were frozen
immediately, and a photomicrograph of
each sample was taken.
This study was also carried out using a
centrifugal pump instead of the Blackmer
sliding vane pump, to generate the foam.
A flowsheet of this generating equip-
ment is shown in Figure 4.
Foam liquid was pumped from the
solution tank by means of the two cen-
trifugal pumps. The flow rate of the solu-
tion was measured by means of a rotam-
eter. The liquid feed rate was controlled
by means of the valve located between
the pump and rotameter. The foam
solution and air were mixed in a tee and
the foam formed was passed through one
of the two packed columns. Both
columns were constructed of l1/z-inch
standard iron pipe packed with Berl
saddles. One column was 9 inches high
(homogenizer I), the other 36 inches high
(homogenizer 11). The foam generated
was delivered to a reservoir tank. Two
pressure drop across the column, AP =
PI - Pz,in Figures 3 and 4.
Foam formed during each test was
photomicrographed and the developed
plates \vere enlarged twice on paper
prints. Bubble sizes and bubble size
distribution \vere evaluated from these
positive prints.
Foam Agents Used
Ultravon '\I' Heptadecyl benzini-
midazol compound
(Ciba Co.)
Saponin AK 500 Plant glucosides (A. K.
Peters Go.)
Unox Phf-1000 Mixture of sodium hep-
tadecyl sulfate. butyl
Carbitol, monoeth-
line, and sodium ni-
trate (Union Car-
bide and Carbon)
Sodium lauryl
Mearlfoam
(Raymond Labs.)
Protein hydrolyzate
(Mearl Corp.)
 AQUEOUS FOAMS

Figure 5. Outer surface of drained

foam of 3% sodium laurylsulfate( X 4 0 )

Figure 6. Cut surface of foam of

&PA.
Figure 5 (X40)
Figure 4. Flowhseet of centrifugal pump foam-generating system

Results and Discussion rather than bv any real difference is

Effect of Freezing on Bubble Size
and Bubble Size Distribution. Table
I lists the bubble size groups of five
samples of foam generated with 0.5%
Ultravon W, before and after freezing.
When the plates taken before freez-
ing were compared with those taken after
freezing, three out of five gave identical
values for the average bubble sizes. The
other two samples showed slight varia-
tions in bubble size during freezing, but
the differences were too small to be
statistically significant. The t value (3)
of the difference between the two groups
was calculated to be 0.064, indicating
that the probability of producing such a
difference in these samples by chance
roughly about 94 oui of 100.
Results obtained with Ultravon W a t
other concentrations, and with 4%
Mearlfoam, are summarized in Table
11. One pair showed identical average
bubble size, while the other three pairs
varied slightly. Again, the differences
were not statistically significant.
Figure 7. Second cut surface of foam
Bubble Size Distribution in Outer
Surface and in Foam Mass. In this
of Figure 5 (X40)
series, after a photomicrograph of the
outer surface of each sample was taken,
two inner surfaces were obtained by
cutting with a razor blade. Bubble sizes
and bubble size distribution were meas-
ured on these pictures (Table 111).
Photomicrographs of outer and inner

Table 1. Effect of Freezing

[Material. 0.5% Ultravon W concentration (by weight)] . Figure 8. Outer surface of freshly
Grouped Bubble S i z e , Microns prepared foam of 0.3% Saponin
26- 76- 125- 176- 225- 275- 516- 576- Av. Diarn , AK500 ( X 4 0 )
26 76 125 176 126 276 516 576 426 LNa P
N o . of Bubbles
Beforeb 210 85 25 12 14 13 12 11 2 274 92.5
After 100 85 25 12 14 13 12 11 2 274 92.5
Before 148 34 16 20 21 17 14 3 ,. 273 87
After 139
Before 232
31 21 25 20 18 13 2 .. 269 88
32 23 25 26 20 4 5 1 368 73.5
After 232 32 23 25 26 20 4 5 1 368 73.5
Before 67 99 14 6 15 19 16 7 1 244 102.5
After 67 99 14 6 15 19 16 7 1 244 102.5
Before 84 31 4 9 17 16 15 2 3 181 107.5
After 67 40 2 7 16 23 6 3 1 165 104.0
a Total number of bubbles.
Before and after freezing. Figure 9. Cut surface of foam of
Figure 8 (X40)

VOL. 48, NO. 11 NOVEMBER 1956 2037

 Table II. Effect of Freezing on Difference Surfactants
Grouped Bubble S i z e , Microns
Av. t
Material 25-76 76-1?25 126-176 175-2$26 226-275 276-526 325-376 376-426 425-475 ZN D i a m . , p Value
iVo. of Bubbles -
Beforea 0 . 1 % Ultravon W 49 34 37 19 20 16 6 5 3 189 161.0 0.2
After 0.1% Ultravon W 44 39 33 21 21 16 7 2 2 185 159.0 0.2
Before 4% Mearlfoam 54 49 47 24 9 .. .. .. .. 183 119.0 1.04
After
Before
4% Mearlfoam
1% Ultravon W
78
11
91
6
62
5
32
5
5
3
..2 ..
2
..
2
. e

4
268
40
112.0
189.0
1.04
0.07
After 1% Ultravon W 10 10 4 6 6 3 3 4 a 47 1187.0 0.07
a Before and after freezing.

Table 111. Bubble Size Distribution o f Outer Surface and of Inner Surface after Cut
Grouped Bubble S i z e , Microns Av.
Surface 25-50 60-100 100-160 160-200 200-260 250-300 300-350 560--400 400-450 460-500 BN Diam., p

No. of Bubble8
3% Sodium Lauryl Sulfate
Outer .. 2 2 7 6 9 6 6 3 44 284
Inner .. ..1 1
.. 5
1
6
2
8
6
2
2
2 3 29 283.8
3 1 19 309.8
..
I .

Outer 2 5 3 2 5 5 5
Inner ..
..
..
1
4
2
2
4
3
5
4
5
5
5
5
4
3
1
3
37
29
31
295.8
300.2
286
Outer
Inner
12
..
17
7
8
11
12
7
6
2
1
1
.
.. ..
e . ..
..
56
28
115
106.4
0.37, Saponin AI( 500
Outer .. 18 39 18 9 1 1 .. .. 86 140.8
Inner
Outer
1
4
26
26
45
34
50
27
6
5
* *
1
..
..
.... *.
.. .. .... 129
96
139.2
127.2
.. ..
m .

Inner 4 16 30 29 9 *. e . 88 138.8

surfaces of two samples are presented in
Figures 5 to 9 as examples. These
samples were statistically analyzed for
significance. The t values obtained in-
dicated that the deviations of average
bubble size were not significant.
Relationship between Expansion Ra-
tio and Foam Dispersity. The relation-
ship between the expansion ratio and
bubble size distribution, as studied with
the Blackmer sliding vane pump using
670 Mearlfoam, is presented in Table
IV. Results obtained with the centrifu-
gal pump, using 670 Unox PM-1000
and Mearlfoam solutions a t several con-
centrations, are summarized in Tables V
and VI, respectively.
In Table IV, the average bubble sizes
obtained with 6% Mearlfoam were
found to be inversely proportional to the
expansion ratios. This fact is in agree-
ment with Stenufs (7) investigation
made using the light transmission
method. The change of average bubble
size was less noticeable when the expan-
sion ratio increased from 9.7 to 11.0 as
compared to the increase from 7.6 to
9.7. This seems to indicate that there is a
maximum limit in the ability of a given
foam system to reduce bubble sizes.
Photomicrographs of the resulting
foam produced by the three different
expansion ratios are presented in Figures
10 to 12.
Using the centrifugal pump, B, Figure
4, the 670 Unox PM-1000 solutions
showed results similar to the 670 Mearl-
foam solution (using the Blackmer sliding
vane pump) when the pressure range
was held between 10 and 20 pounds per
square inch gage. Within this pressure
range the foam was produced in a steady
stream, but slug flow was observed
when the pressure was increased to 29
pounds per square inch gage.
When the 4.5 and 3y0Unox PM--1000
solutions were studied, slug flow was ob-
tained only within the pressure range of
11 to 21 pounds per square inch gage.
With this slug-flow type of foam, the re-
lationship between expansion ratio and
foam dispersity, as $hewn in Table V,
was very different from that obtained
with steady flow. Contrary to the re-
sults obtained with 670 Unox PiM-1000
solution, a high inlet air pressure re-
sulted in a low expansion ratio, which
gave smaller average bubble sizes with
Unox PM-1000 at lower concentrations.
This apparent anomaly can be explained
as follows: When the foam is generated
in a steady flow condition, most of the
air forced into the pump is trapped by
the foam solution. When a foam solu-
tion of lower concentration is used, the

Figure 10. Foam made with 6% Figure 11. Foam made with 6% Figure 12. Foam made with 6%
Mearlfoam solution ( X 2 0 ) Mearlfoam solution ( X 2 0 ) Mearlfoam solution (X20)
Expansion ratio 7.6 Expansion ratio 9.7 Expansion ratio 1 1 .O

2038 INDUSTRIAL AND ENGINEERING CHEMISTRY

 AQUEOUS FOAMS
~~~ ~~~

Table VI. Average Bubble Size, Expansion Ratio, and Pressure Drop
Material. Mearlfoam
Packing column height. 9 inches
Packing column diameter. Il/pinch std. pipe
Packing material. Berl saddle
Solution rate. 1.5 gallons per minute
6% Concn. 4.6% Concn. 3% Concn. 1.5% Concn.
Photo No. 187.00 192.00 193.00 194.00 195.00 197.00 202.00 198.00 199.00 204.00 205.00 207.00
Expansion ratio 14.2 35.5 10.35 15.00 21.7 32.00 11.75 23.2 42.0 12.0 17.0 32.0
Av. diameter, fi 167.00 88.00 231.00 215.00 196.00 56.8 275.00 105.00 90.4 280.00 154.5 90.6
Inlet air pressure, P 10.00 28.00 11.00 15.00 21.00 37.00 12.00 12.00 37.00 12.00 16.00 28.00
Pressure drop ( A P ) , lb./
sq. inch 2.00 12.00 4.00 4.00 6.00 21.00 4.00 7.00 11.00 4.00 5.00 9.00
Temp., O C. 28.00 30.00 28.00 28.00 28.5 28.5 28.00 27.6 28.00 29.5 30.00 30.00

solution can no longer trap all of the air;
hence slug flow is obtained. The higher
the inlet air pressure, the more the air
escapes trapping by the foam solution,
resulting in a lower expansion ratio. O n
the other hand, a reduction of bubble
sizes is caused by the mixing action of
the air in the packed column. The
higher the air pressure, the greater the
mixing action; therefore, in spite of the
low expansion ratio, a smaller average
bubble size is produced.
A steady-flow foam was again ob-
tained with 3% Unox PM-1000 solution
when the height of the homogenizing
column was increased from 9 to 38
inches. This , was attributed to the
greater resistance offered by the longer
packing column, which made steady
flow possible. Under this condition the
results were similar to those obtained
with 6% Mearlfoam solutions and Unox
P-1 000 solutions at higher concentra-
tions. These foams were produced a t
expansions of 7.33, 12.7, and 18.8; here
again smaller average bubble sizes were
produced a t the higher expansion ratios.
Results of the tests with 1.5, 3.0, 4.5,
and 6.0% Mearlfoam, using the centrif-
ugal pump, showed a relationship be-
tween expansion ratio and foam dis-
persity similar to those obtained using
the Blackmer sliding vane pump. The
air pressure range used was between 1 0
and 37 pounds per square inch gage.
A steady flow was produced in all cases;
hence the results agree with those ob-
tained with the 60/, Unox PM-1000
solutions.
A decrease in average bubble size was,
in all cases, accompanied by an increase
in the pressure drop across the homogen-
izing column, whether the foam was in
steady or slug flow. Presumably the
smaller bubble sizes caused an increase
in the apparent foam viscosity and hence
an increase in the pressure drop. These
results were in agreement with the find-
ings of Stenuf (6).
It is apparent from the above three
series of tests that the bubble sizes and
bubble size distribution were affected
not only by the expansion ratio, nature
of foaming agent, and concentration, but
also by the type of generating system, in-
let air pressure, and height and/or na-
ture of the packed column.
Conclusions
The quick-freezing of foam does not
significantly change the structure of the
foam with respect to bubble sizes and
bubble size distribution.
Bubble sizes and bubble size distribu-
tion of the outer surface of a foam mass
and those within the foam mass are
almost the same. The occasional small
differences are not statistically significant.
Expansion ratio, bubble sizes, and
bubble size distribution are related.
However, the type of generating system,
nature of the foaming agent, concentra-
tion of the solution, inlet air pressure, and
height and/or nature of the refining
section are also important in determining
the foam dispersity.
The pressure drop across the homogen-
izer (packed column) is directly affected
by the bubble sizes and bubble size dis-
tribution of the foam.

Acknowledgment

Table IV. Relationship between Expansion Ratio and Bubble Size The authors wish to thank the Engi-
neer Research and Development Labora-
(Material. 6% Mearlfoam. Liquid rate, 11.4 gallons per minute) tories of the United States Army, the
Figure Grouped Bubble Size, Microns Av. Naval Research Laboratories, and the
No. APO ab 85-75 76-125 126-176 176-236 225-275 Diam., I.( Office of Naval Research, under whose
10 11.9 7.6 46 23 22 18 12 120 sponsorship this research was carried
11 15.5 9.7 108 82 49 10 5 95.5 out.
12 18.0 11.0 136 70 72 15 e . 94
a Pressure drop, across homogenizer lb./sq. inch. literature Cited
Expansion ratio.
(1) Clark, N. O., Blackman, M., Trans.
Faraday SOC.44, 1 (1948).
Table V. Average Bubble Size, Expansion Ratio, and Pressure Drop ( 2 ) Ibid., p. 7.
( 3 ) Davies, 0. L., Statistical Methods in
(Material. Unox PM - 1000) Research and Production, p. 58,
Homogenizer I Homogenizer 11 Imperial Chemical Industries, Lon-
6% Concn. 4.6% Concn. 8% Concn. 3% Concn.
don, 1947.
(4) Sibree, J. V., Trans. Faraday SOC.
30,325
Photo No. 215.0 217.0 224a 223 22ga 227 233.0 234.0 235.0 (1 934).
01 8.38 9.45 9.67 10.45 9.0 15.8 7.33 12.7 18.8 ( 5 ) Sovitskaya, E. M., Kolloid. Zhur. 13,
D av., p 47.6 31.85 46.9 67.3 34.0 61.4 66.3 52.9 47.1 309 (1951).
PI, lb./sq. inch
gage 10.0 20.0 21.0 15.0 21.0 11.0 11.0 16.0 22.0
.,
( 6 ) Stenuf, T. J.. unmblshed M.Ch.E.
thesis, Syracuse Qniversity, 1951.
AP = Pi - Pa 3.5 8.0 9.0 6.0 9.0 4.0 6.0 9.0 12.0 ( 7 ) Stenuf, T. J., unpublished Ph.D. thesis,
Temp., O C. 26.0 26.0 26.0 26.0 24.8 24.0 26.0 26.4 26.0 Syracuse University, 1953.
Slugging flow. RE~EIVED
for review November 25, 1955
ACCEPTEDJuly 3, 1956

VOL. 48, NO. 11 NOVEMBER 1956 2039