Journal of Colloid and Interface Science 215, 270 279 (1999)

Article ID jcis.1999.6233, available online at http://www.idealibrary.com on

Role of Silicone Surfactant in Flexible Polyurethane Foam

X. D. Zhang,* C. W. Macosko,* ,1 H. T. Davis,* A. D. Nikolov, and D. T. Wasan
*Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave. SE, Minneapolis, Minnesota 55455;
and Department of Chemical Engineering, Illinois Institute of Technology, Chicago, Illinois 60616
Received August 11, 1998; accepted March 26, 1999

bubble network and cell window stabilization, (3) polymer

stiffening and cell opening, and (4) final curing (2, 3).
Silicone surfactants, which consists of a polydimethylsiloxane (PDMS) backbone and polyethylene oxide-co-propylene
oxide (PEO-PPO) random copolymer grafts, are used as surfactants in flexible polyurethane foaming systems. It was
shown that these surfactants do not alter the reaction kinetics in
the flexible polyurethane foaming process (4). In the absence
of these surfactants, a foaming system will experience catastrophic coalescence and eventually cause foam collapse.
These surfactants are efficiently adsorbed at the airpolyol
interface and thus may have a significant effect on both the
bubble generation and the cell window stabilization steps in the
polyurethane foaming process. The silicone surfactant structure is shown to have a great impact on the foam cell size and
air permeability of the final foam product which is directly
related to the open cell window percentage of a foam (4). Many
physical properties of flexible polyurethane foam are highly
affected by its porosity and cell size (5). However, porosity as
well as foam cell size are not perfectly regulated in industry
because the effect of the surfactant is not well understood.
Traditionally, it is believed that the silicone surfactant can
lower surface tension, emulsify incompatible formulation ingredients, promote generation of bubbles during mixing, and
stabilize cell windows (3). Among these functions, cell window stabilization is the most important. During foaming, the
bubbles initially introduced by mechanical mixing will grow.
As the volume fraction of the gas bubbles exceeds 74%, the
spherical bubbles will distort into multisided polyhedrals and
cell windows with Gibbs Plateau Borders are formed. Due to
capillary pressure, pressure inside the plateau borders is lower
than that in the cell windows. This pressure difference will
cause liquid in the cell window to drain into the struts. Without
adding silicone surfactant, this drainage rate will be very fast
so that film rupture and bubble coalescence occur rapidly. It is
shown in this work that due to the surface tension gradient
generated by the silicone surfactant the cell window drainage
rate is slower. Different surfactant structures will have different effects on cell window drainage, resulting in a distribution
of different cell window thicknesses at the time of cell opening
(4). Thus the porosity or the air permeability of the solid

Grafted copolymers which consist of a polydimethylsiloxane

backbone and polyethylene oxide-co-propylene oxide pendant
groups are used as surfactants to stabilize the foam cells in the
flexible polyurethane foaming process. The mechanical properties
of the cured polyurethane foam such as air permeability and foam
cell size are affected significantly by the structure of the silicone
surfactant used in the formulation. It is shown that silicone surfactant has an important impact on both the bubble generation
and the cell window stabilization stage. A series of silicone surfactants with different structures was tested. Surfactants with higher
silicone content will provide lower surface tension and thus help
increase the number of air bubbles introduced during mixing.
These air bubbles serve as the starting point for foam cell growth.
As a result, the cured polyurethane foam made with higher silicone content surfactant has a smaller bubble size. It is also shown
that silicone surfactant can reduce the cell window drainage rate
due to the surface tension gradient along the cell window. The
Gibbs film elasticity, the dynamic film elasticity, and the film
drainage rate were measured for the first time versus surfactant
composition. Surfactants with longer siloxane backbones are
shown to give higher film elasticity. Using the vertical film drainage and foam column tests, it is shown that surfactants with higher
film elasticity will yield slower drainage rate and better foam cell
stability. 1999 Academic Press
Key Words: polyurethane foam; silicone surfactant; film tension;
film elasticity; nucleation; foam stability; film drainage.

INTRODUCTION

The addition polymerization reaction of diisocyanates with

alcohols was discovered by Bayer and co-workers in 1937 (1).
The discovery provided the fundamental chemistry for the
polyurethane industry. Of all the polyurethane products, flexible polyurethane foam has the largest production and is most
widely used. During flexible polyurethane foam formation,
water reacts with the isocyanate group and produces carbon
dioxide gas. The carbon dioxide gas will provide volume for
bubble expansion and occupy over 95% of the final volume of
the product. Figure 1 shows the four stages of the foaming
process: (1) bubble generation and growth, (2) packing of the
1

To whom correspondence should be addressed.

0021-9797/99 $30.00
Copyright 1999 by Academic Press
All rights of reproduction in any form reserved.

270

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SILICONE SURFACTANT IN FLEXIBLE POLYURETHANE FOAM

FIG. 2. The structure of a typical silicone surfactant used in polyurethane

foam systems.

MATERIALS

FIG. 1. Macroscopic view of different stages during foaming. The four

regions of the process are: (1) Bubble generation and growth, (2) packed
bubble network (foam expansion), (3) urea microphase separation (polymer
stiffening) and cell opening, and (4) final curing. [Adapted from Ref. (2)]

polyurethane foam is significantly affected by the structure of

the silicone surfactant used in the formulation.
Surface elasticity is known to be caused by a surface
tension gradient along the cell window upon expansion and
will retard the cell window drainage rate. This effect is
called the GibbsMarangoni effect and was reviewed by
Scriven and Sternling (6). Owen and co-workers studied the
dynamic surface tension of a series of surfactant solutions
and stressed the importance of surface elasticity (7). Similar
work was performed by Zhang and co-workers (8). In this
work, the drop volume method has been used to evaluate the
effect of surfactant composition on dynamic surface tension
in the process of bubble growing. However, surfactant behavior in thin films may be significantly different from the
behavior of a single interface (9). No film elasticity or film
drainage measurements on model polyurethane foam systems have been reported in the literature.
In this work, a series of silicone surfactants was used by
varying surfactant structure, namely, silicone backbone length
and polyether percentage. Different foam cell sizes and final
foam porosity have been observed for foams made with these
surfactants. A surfactant solution in polyether polyol is used as
a model nonreactive system to evaluate surfactant performance. The effects of surfactant structure on surface tension,
surface elasticity, and vertical film drainage rate were measured to characterize the surfactant properties. Effects of surfactant chemical structure on final polyurethane foam properties were discussed as well.

All surfactants used in this study were synthesized by the

OSi Group of Witco Corporation. Structures of the surfactants are shown in Fig. 2 and Table 1. Typical nomenclature
of silicone surfactant is MDxD9yM, where M is trimethylsiloxane ((CH 3 ) 3 SiO) or ((CH 3 ) 3 Si), D is dimethylsiloxane
((CH 3 ) 2 SiO), D9 is methylsiloxane with polyoxyalkylene
substitute (CH 3 RSiO) where R is composed of polyethylene
oxide and polypropylene oxide, and x and y are the number
of units of D and D9, respectively. Siloxane backbone
length ( x 1 y 1 2) and silicone/polyether ratio ((M Wsurfactant 2
y*M W(polyether branch))/y*M W(polyether branch)) are the two variables that
are studied in this work. The solvent used in this work is
Voranol 3137 supplied by Dow Chemical. Voranol 3137 is a
polyether consisting of 87% ethylene oxide and 13% propylene
oxide with a molecular weight of 3100.
EXPERIMENTAL

Effect of Surfactant on Bubble Formation

Polyurethane foam formulation and preparation. Foam
formulation used in this work is listed in Table 2. Procedures

TABLE 1
Experimental Silicone Surfactants
Surfactant
structure

Silicone/polyether
ratio

Siloxane
backbone length

MD x D9y M a
MD x D9y M
MD x D9y M
MD x D9y M
MD x D9y M
MD x D 0y M b

119
85
51
54
57
51

21
15
9
6
3
9

0.324
0.326
0.331
0.501
1.013
0.124

142
102
62
62
62
62

a
Branched copolymer of polydimethylsiloxane and polyether where M 5
[(CH 3 ) 3 SiO] or [(CH 3) 3Si], D 5 (CH 3 ) 2 Si-O, D9 5 (CH 3 ) RSi-O, R 5 60%
propylene oxide and 40% ethylene oxide polyether, 1500 mW, acetoxy capped.
b
D0 5 (CH 3 ) R9Si-O, R9 5 60% propylene oxide and 40% ethylene oxide
polyether, 4000 Mw, acetoxy capped.

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ZHANG ET AL.

TABLE 2
Polyurethane Foam Formulation
Chemicals

Parts (pphp a)

Voranol TM 3137 b
Water
Dabco TM 33LV c
Dabco TM T-9 d
Silicone surfactant e
Voranate TM T-80 f index

100
4.0
0.30
0.20
1.0
110

Parts per hundred parts polyol Voranol TM 3137 (by weight).

A 1000 equivalent weight triol containing 13% ethylene oxide, 87%
propylene oxide and all secondary hydroxyl groups (Dow Chemical).
c
33% triethylenediamine in dipropylene glycol (Air Products and Chemicals).
d
Stabilized stannous octoate (Air Products and Chemicals).
e
Polysiloxanepolyoxyalkylene block copolymer (Witco Corp.).
f
An 80:20 mixture of 2,4-, and 2,6-toluene diisocyanate (Dow Chemical).
b

to make polyurethane foam are provided in our previous paper

(4). The polyurethane foams were allowed to cure at room
temperature for at least 48 h before foam specimens were cut
out from the foam bun for further testing.
Surface tension measurements. Surface tension measurements were made by the Wilhelmy method using digital tensiometer K10ST. Surfactant solutions in polyether polyol
Voranol 3137 were measured. Prior to each run the surface
tension of pure water was measured. Samples were prepared at
least 48 h before the measurements.
Bubble formation tests. In the polyurethane foam system,
air bubbles are introduced in the mixing step using a high speed
mixer. These air bubbles will serve as starting points for the
foam growth. This is the bubble dispersion stage. No more new
bubbles form during the bubble expansion (10). The energy
required for formation and growing of a bubble is related to the
surface tension of the surfactant solution. Silicone surfactant
can reduce surface tension and thus reduce the energy needed
to form a bubble. As a result, the number of bubbles introduced
into the system as well as the final foam cell size will be
determined by the surface tension lowering ability of the added
surfactant.
Since the actual polyurethane foam system is reactive and it
is hard to perform initial bubble count, model systems of 1
wt% surfactant solutions in polyol Voranol 3137 were used for
the bubble generation test. This surfactant solution was agitated using a high speed mixer. A small sample of the agitated
mixture was transferred onto a glass slide with a defined gap of
0.3 mm between the cover glass and the glass slide. Optical
microscope images were then obtained and analyzed to give
the number of bubbles per unit volume of solution. A sample
image is shown in Fig. 3.
Scanning electron microscopy. Scanning electron microscopy was used to take images of cured solid polyurethane

FIG. 3. Images of air bubbles in 1 wt% MD 51 D 09 M solution in Voranol

3137 after high speed mixing.

foams. The size of the foam cell can be evaluated from these
images. All images were taken at an accelerating voltage of 15
kV. All samples were coated with 5 nm of Au/Pt. A sample
image is shown in Fig. 4.
Effect of Surfactant on Foam Stabilization
Air flow. Air permeability of the cured polyurethane foams
was measured according to American Society for Testing and

FIG. 4. A typical cured polyurethane foam image by scanning electron

microscopy.

SILICONE SURFACTANT IN FLEXIBLE POLYURETHANE FOAM

273

(2) Bubbles were expanded at four different rates ranging

from 0.02 to 0.16 mm 2/s. Dynamic film tension was recorded.
Film elasticity can be calculated. An expansion rate of 0.08
mm 2/s was used to obtain dynamic film elasticity for different
surfactant solutions. The bubble expansion rates are of the
same magnitude as those in the actual polyurethane foam
process.
(3) Gibbs elasticity was obtained by sudden expansion of
the initially formed bubble to a different area expansion ratio
( A/A 0 ). Immediately after expansion, film tension was recorded. Gibbs elasticity was calculated using film tension
FIG. 5. Schematics of the film elasticity measurement.

Materials (ASTM) standard D 3574. Foam specimens of 5 3

5 3 2.5 cm in size were cut out from the top part of the foam
buns in the buckets. The 5 3 5 cm surface was always
horizontal, i.e., perpendicular to the blowing direction. Air
flow rate was measured by a rotameter with a pressure drop of
1.27 cm H 2O across the specimen thickness (2.5 cm). It was
shown that the air flow of a foam increases linearly as the open
cell window percentage increases (4). Thus the open cell
window percentage of a foam can be estimated from its air
permeability.
Film elasticity. Details of this instrument are described
elsewhere (9). A diagram is shown in Fig. 5. A glass capillary
provides good wettability, and a surfactant solution in Voranol
3137 can form a stable bubble on the tip of the glass capillary.
For film tension and dynamic film elasticity measurements,
initial bubble radius was set to 0.39 mm which is slightly above
hemisphere. The capillary used has a diameter of 0.6 mm. The
pressure inside the bubble can be measured by a highly sensitive pressure transducer. The bubble diameter can be obtained
by direct imaging with an optical microscope. Film tension and
surface tension can be obtained from the YoungLaplace equation. At equilibrium, the film tension is twice the surface
tension.
f < 2g 5

pR
,
2

[1]

where R is the film radius, p is the measured capillary pressure,

g is the surface tension of the film, and f is the film tension
(dyne/cm). The bubble can be expanded using a syringe pump
with a constant rate while the pressure inside the bubble is
recorded versus time.
Silicone surfactants with different structures were tested. All
the tests were performed with 0.2 wt% surfactant solution in
Voranol 3137. The following tests were performed.
(1) Equilibrium film tensions for different surfactant solutions were obtained and compared with results from the Wilhelmy plate method.

FIG. 6. A typical vertical film drainage curve obtained by light interference microscopy.

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ZHANG ET AL.

FIG. 7. Schematics of the foam column test.

values obtained with four different area expansion ratios as

well as the initial tension without expansion.
Vertical film drainage tests. There are many vertical films
in the foam system. One way to evaluate is the vertical film
drainage method. A 1 wt% surfactant solution was placed in a
vial with a Teflon frame of size 1 3 2 cm. A film was formed
in the Teflon frame by pulling the frame out of the solution.
White light was reflected off the film with a 45 angle and a
color video camera was used to capture the interference patterns. The film thickness at 1 cm from the top of the frame was
obtained from the interference pattern (11). The film thickness
change against time can be recorded for solutions made with
different surfactants. The film thinning rate against film thickness can be evaluated by taking the slope of the curve. A
sample result is shown in Fig. 6.
Foam column test. A static foam column test was performed in a glass column with a 2.5 cm I.D. glass frit (maximum pore size 10 15 mm) to evaluate foam stability (Fig. 7).
Forty milliliters of a 1 wt% surfactant solution were placed in
the column. Compressed air was then injected at rate of
22.525 ml/min until the foam height reached 14 cm, at which
time inlet air was stopped. As the foam collapsed, foam height
was recorded until it reached 7 cm. The time to reach 7 cm is
T 1/ 2 , the half time of the foam. A typical foam column result is
shown in Fig. 8.
Light interferometry. Cell window thickness was measured using light interferometry. Interference patterns from
white light were used to determine the thickness of a cell
window and the thin-point thickness of each window. Similar
results were obtained using the differential interference technique (12). The average values of thin-point thicknesses were
obtained for both the high air flow formulation and the low air
flow formulation.

FIG. 8.

A typical static foam stability curve obtained by foam column test.

step. Thus, surface tensions of the surfactant with different

compositions were measured. These results are shown in Figs.
9 and 10. As the polyether percentage of the surfactant increases or the silicone content decreases, the surface tension
increases significantly. As the silicone/polyether ratio of the
surfactant increases, the surfactant becomes more surface active and provides a lower surface tension. On the other hand, if
the silicone/polyether ratio is kept constant, the surface tension
of the surfactant solution does not seem to be affected by the
size of the surfactant or the silicone backbone length of the
surfactant.
A surfactant solution in Voranol 3137 was used as a model
system for the dispersion test. The result is plotted in Fig. 11.
It can be seen that as the surface tension decreases, more air

RESULTS AND DISCUSSION

It is known that silicone surfactant can reduce the surface

tension of the foaming system (3). This reduction of surface
tension may have a significant impact on the bubble dispersion

FIG. 9. Effect of silicone/polyether ratio of the silicone surfactants on

surface tension of 1 wt% surfactant solution in Voranol 3137. Silicone backbone length is kept constant at 62 (SiO) units.

SILICONE SURFACTANT IN FLEXIBLE POLYURETHANE FOAM

FIG. 10. Effect of silicone backbone length of the surfactants on surface

tension of 1 wt% surfactant solution in Voranol 3137. Silicone/polyether ratio
is kept between 0.32 0.33.

bubbles per unit volume of solution were generated in the

system. The energy required to generate the bubble surface
with radius r is 4 p r 2 g , where g is the surface tension of the
solution. Surfactants with higher silicone/polyether ratios will
give a lower surface tension value and thus reduce bubble
generation energy. As a result, a higher bubble count was
obtained after mixing for systems with a high silicone/polyether ratio surfactant. On the other hand, if the silicone/polyether ratio is kept constant, surfactants with different silicone
backbone lengths give similar surface tension values (24.4
24.6 dyne/cm). Therefore, it is not surprising to see little or no
effect of the surfactant backbone length on the model system
nucleation tests. The cell size for the cured solid polyurethane

FIG. 11. Effect of surface tension of 1 wt% surfactant solution on number

of air bubbles entrained after high speed mixing.

275

FIG. 12. Effect of surface tension of 1 wt% surfactant solution on cured

solid polyurethane foam cell size.

foams made with different surfactants is shown in Fig. 12.

Surfactant performance in actual polyurethane foam confirms
the effect of silicone surfactant composition (silicone/polyether
ratio) on bubble dispersion observed in the model system. That
is, for a surfactant with a lower polyether percentage, more
bubbles can be introduced into the system and the resulting
polyurethane foam will have a finer cell size. Surfactants with
different backbone lengths do not affect the bubble count after
mixing, nor do they affect the final cell size of the solid
polyurethane foam. These results suggest that to get smaller
size cells, surfactants with high silicone content should be
used. However, the surfactant with a very high silicone/polyether ratio yields collapsed foams. This leads to the issue of the
effect of the surfactant composition on the foam porosity.
Another effect of the surfactant is on the rate of cell
window drainage. Polyurethane foam develops from a liquid
foam to a solid foam in a short period of time. It is very
important for the surfactant to stabilize the cell window
before the solidification of the foaming material. This is
accomplished by establishing a surface tension gradient
along the foam lamella and reducing the rate of thinning of
the cell window. A schematic diagram is shown in Fig. 13.
Due to the capillary suction in the plateau border, the liquid
inside the lamella will drain into the plateau border. Without
addition of the surfactant, the gasliquid interface cannot
support any stress and this interface will have a slip boundary condition. The thin liquid film will rapidly thin and
result in cell window rupture and foam collapse. When a
silicone surfactant is added, a surface tension gradient will
develop along the gasliquid interface and this interface can
have a finite surface stress. As the bubble size increases, the
cell window is formed and expanding. During the cell
window expansion, a surface tension gradient is generated
on the gasliquid interface. The surface tension gradient

276

ZHANG ET AL.

FIG. 13. Schematics of cell window drainage and surface tension gradient formation.

will establish a surface stress and will reduce the drainage

flow rate of the thinning film. This surface tension gradient
is characterized by film elasticity. The effect of surface
elasticity on thin liquid film drainage rate was investigated
by Malhotra and Wasan (13) using numerical simulation. A
significant effect of the surface elasticity on film drainage
rate was observed. Larger surface elasticity will cause
slower film drainage rate. Measuring the film tension of the
surfactant solution versus time at different expansion rates
can provide information on the film elasticity and the surface tension gradient.
The film rheometer is used to measure the film tension and
film elasticity of different surfactants. First, the static surface
tensions of various surfactant solutions were measured and
compared with values obtained by the Wilhelmy plate method.
Good agreement was observed. The surface tension values
obtained by the two methods are typically within 1%.
Gibbs elasticity was obtained by recording the surface tension after the sudden expansion of a bubble. When the bubble
is expanded suddenly, the surface concentration of the surfactant will decrease due to the increase in the surface area of the
bubble. Since the expansion is a sudden event, surfactant
diffusion is ignored. By expanding the bubble at a very rapid

rate, different surface tensions right after expansion will be

obtained. The Gibbs elasticity is defined as

Ef 5

df
,
d ln~ A/A 0 !

[2]

where A and A 0 are the expanded and the initial film areas,
respectively, and f is the film tension. A typical result is shown
in Fig. 14. As we can see, good reproducibility is obtained. The
Gibbs elasticities for different surfactant solutions are listed in
Table 3. The Gibbs elasticity of the silicone surfactant solution
does not seem to be affected by the composition of the surfactants.
In a polyurethane foam system, bubbles grow at a finite rate
of about 0.02 mm 3/s rather than sudden expansion. Assuming
the average bubble diameter to be 1 mm, the area expansion
rate will be 0.12 mm 2/s. The finite expansion rate allows some
surfactant diffusion and adsorption to reduce surface tension as
the bubble expands. As a result, the dynamic film elasticity
obtained under the finite expansion rate is always lower than
the Gibbs elasticity which is obtained by sudden expansion.
Figure 15 shows that as the expansion rate increases, the

SILICONE SURFACTANT IN FLEXIBLE POLYURETHANE FOAM

277

FIG. 14. Reproducibility of Gibbs elasticity measurements of 0.2 wt%

MD 51 D99 M solution in Voranol 3137.

dynamic film elasticity will increase because of the decreased

time for surfactant diffusion and adsorption.
From above, it is shown that the film rheometer can give
accurate, reproducible results. Next, the dynamic film elasticities of different surfactants were evaluated with an expansion
rate of 0.084 mm 2/s, which is close to the actual polyurethane
foam system. The higher the dynamic film elasticity, the higher
the surface tension gradient that can be obtained in the expanding cell window.
As shown in Figs. 16 and 17, as the silicone backbone length
of the surfactant increases, the surface elasticity increases
linearly versus the backbone length of the surfactant. As a
result, a higher film elasticity and lower cell window drainage
rate can be expected for foams made with these larger silicone
surfactants. This will lead to a smaller open cell window
percentage in the cured polyurethane foam. On the other hand
(Fig. 17), when the silicone/polyether ratio is varied, a less
clear trend is observed. The surfactant with very low film
elasticity results in a collapsed foam due to its low drainage
retarding ability. The surfactant with elasticity higher than 4.6
dyne/cm will result in a stable foam. When the silicone/polyether ratio of the surfactant is too low (0.124), the film elasticity test cannot be performed since the bubble on the tip of the
capillary is highly unstable. Due to the low stability of the
lamella, one can expect such a surfactant to result in an

FIG. 15. Effect of bubble expansion rate on dynamic film elasticity of 0.2
wt% MD 51 D99 M solution in Voranol 3137.

unstable polyurethane foam. In experimental studies, polyurethane foams made with this surfactant experience foam collapse.
As discussed above, a film with higher elasticity will have a
higher surface tension gradient along the film to retard drainage. As a result of the slower drainage rate of the foam cells,
thicker film will be formed. The higher the film elasticity, the
thicker the average cell window and the lower percentage of
rupture cell windows there will be. To verify this, the remaining cell window thickness in the cured solid foam is measured

TABLE 3
Gibbs Elasticity for 0.2 wt% Surfactant
Solution in Voranol 3137

Gibbs elasticity
(dyne/cm)

MD 119 D921 M

MD 85 D915 M

MD 51 D99 M

MD 54 D96 M

22.6

23.1

23.1

26.0

FIG. 16. Effect of silicone backbone length of silicone surfactant on

dynamic film elasticity of 0.2 wt% surfactant solution in Voranol 3137 as well
as air permeability of the cured solid polyurethane foam. Silicone/polyether
ratio is kept between 0.32 0.33.

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ZHANG ET AL.

FIG. 19. A window thickness distribution for foams made with two
different surfactants. The less open foam is made with surfactant MD 85 D915 M
while the more open foam is made with surfactant MD 51 D99 M.

FIG. 17. Effect of silicone/polyether ratio of silicone surfactant on surface

tension of 0.2 wt% surfactant solution in Voranol 3137 as well as air permeability of the cured solid polyurethane foam. Silicone backbone length is kept
constant at 62 (SiO) units.

for foams made with different surfactants and different film

elasticities. Surfactants with different backbone lengths
(MD 85 D915 M and MD 51 D99 M) are used since they result in
foams with the same cell size. Figure 18 shows a differential
interference pattern of a cell window; the thickness profile
shows a dimple formation, which is a strong indication of the
existence of a surface tension gradient. The thin part of the
window was measured. Fifty windows were tested for foams
made with these two surfactants. Figure 19 shows the thin-

point window thickness distribution of the remaining cell windows. MD 85 D915 M has a higher film elasticity value (7.1 dyne/
cm) than that of MD 51 D99 M (5.2 dyne/cm). A different
distribution is observed as well: foam with a higher elasticity
has higher film density toward the thicker films while foam
with a low elasticity has higher film density toward the thinner
films.
The short time foam stability for different surfactant solutions can be evaluated by obtaining the actual thinning rate of
thin liquid lamella as well as the foam column test. Since there
are many vertical lamella in a foam, where gravity plays an
important role, a vertical film drainage test is performed. A
typical graph is shown in Fig. 6. The film thinning rate against
film thickness is plotted as well. The driving force for vertical
film thinning is the hydrodynamic pressure and the capillary
pressure in the film. As the film thickness decreases, the
drainage rate decreases significantly.
The results of the vertical film drainage test for different

FIG. 18. A cell window thickness profile determined by differential light interference microscopy.

SILICONE SURFACTANT IN FLEXIBLE POLYURETHANE FOAM

FIG. 20. Effect of silicone backbone length of the surfactants on vertical

film drainage rate as well as static foam stability of 1 wt% surfactant solution
in Voranol 3137. Silicone/polyether ratio is kept between 0.32 0.33.

279

varied, due to the effects of surface tension and lamella elasticity, a strong impact of surfactant composition on foam
quality was observed. The surfactant siloxane backbone to
polyether ratio affects both the foam cell size and foam cell
lamella opening. Silicone surfactants with higher silicone content provide lower surface tension and this leads to a decrease
in bubble size and an increase in bubble generation rate.
However, due to low lamella elasticity these foams are unstable and contained cells with open lamella. The silicone surfactants with a longer backbone improve the cell lamella elasticity, but because of higher surface tension these foams have
cells with larger lamellae and as a consequence of larger
lamella size, these foams are unstable and contained open
lamellae. Due to the moderated balance of surface tension and
lamella elasticity, surfactants with siloxane backbone to polyether ratio from 0.32 to 0.5 have a good performance on
polyurethane foam quality.
ACKNOWLEDGMENTS

surfactant solutions are shown in Fig. 20. All drainage rates

were taken when the film thickness was 0.5 mm. A similar
trend is observed for film drainage rate at different film thickness. The higher the backbone length of the surfactant, the
slower the drainage rate. In vertical films, the drainage flow
towards the plateau borders will create a stretching motion
along the surface. A surface tension gradient along the film will
be created to counteract the stretching drainage flow. The
higher the surface tension gradient a surfactant can establish,
the slower the cell window drainage will be. It was shown that
with the silicone/polyether ratio constant, the surfactant with a
longer silicone backbone can provide a higher surface tension
gradient, and a slower cell window drainage rate will be
obtained. The lifetime of the foams in a static foam column
increase as the backbone length of the surfactant increases. It is
found that the surfactant composition is extremely important to
polyurethane foam quality. There is an optimal point of silicone/polyether ratio for the best polyurethane foam quality
(Fig. 17).
SUMMARY

The effects of silicone surfactant composition (siloxane

backbone to polyether ratio) on the polyurethane foam quality
such as foam cell size and cell lamellae opening (stability)
were studied. When the siloxane backbone/polyether ratio was

The surfactants used in this study are synthesized by Witco Corp., Osi
Specialities Group. Support for this research was provided by the Center of
Interfacial Engineering, a NSF engineering research center at the University of
Minnesota. Part of the bubble formation and foam column tests were performed by Ms. Lise Bertsch.

REFERENCES
1. Bayer, O., Mod. Plast. 24, 149 (1947).
2. Artavia, L. D., and Macosko, C. W., in Low Density Cellular Plastics
(N. C. Hilyard and A. Cunningham, Eds.), Chap. 2. Chapman & Hall,
London, 1994.
3. Herrington, R., and Hock, K., Flexible Polyurethane Foams. Dow
Chemical Co., Midland, MI, 1991.
4. Yasunaga, K., Neff, R. A., Zhang, X. D., and Macosko, C. W., J. Cell.
Plast. 32, 427 (1996).
5. Jones, R. E., and Fesman, G., J. Cell. Plast. 1(1), 200 (1965).
6. Scriven, L. E., and Sternling, C. V., Nature 187, 186 (1960).
7. Owen, M. J., Kendrick, T. C., Kingston, B. M., and Lloyd, N. C., J.
Colloid Interface Sci. 24, 141 (1967).
8. Zhang, X. D., Macosko, C. W., and Davis, H. T., in Polymeric Foams
(K. C. Khemani, Ed.), Chap. 9, ACS Symposium Series 669. American
Chemical Society, Washington, D.C., 1997.
9. Kim, Y. H., Koczo, K., and Wasan, D. T., J. Colloid Interface Sci. 187, 29
(1997).
10. Kanner, B., and Decker, T. G., J. Cell. Plast. 5(1), 48 (1969).
11. Mysels, K. J., Shinoda, K., and Frankel, S. P., Soap Films-Studies on
Their Thinning and a Bibliography. Pergamon Press, New York, 1959.
12. Nikolov, A. D., and Wasan, D. T., J. Colloid Interface Sci. 113, 1 (1989).
13. Malhotra, A. K., and Wasan, D. T., Chem. Eng. Commun. 55, 95 (1987).