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Abstract
The effect of oils, hardness, and calcium soap on foam stability of aqueous solutions of commercial surfactants was investigated. For
conditions where negligible calcium soap was formed, stability of foams made with 0.1 wt% solutions of a seven-EO alcohol ethoxylate
containing dispersed drops of n-hexadecane, triolein, or mixtures of these oils with small amounts of oleic acid could be understood in terms
of entry, spreading, and bridging coefficients, i.e., ESB analysis. However, foams made from solutions containing 0.01 wt% of three-EO
alcohol ethoxysulfate sodium salt and the same dispersed oils were frequently more stable than expected based on ESB analysis, reflecting
that repulsion due to overlap of electrical double layers in the asymmetric oilwaterair film made oil entry into the airwater interface more
difficult than the theory predicts. When calcium soap was formed in situ by the reaction of fatty acids in the oil with calcium, solid soap
particles were observed at the surfaces of the oil drops. The combination of oil and calcium soap produced a synergistic effect facilitating
the well-known bridging instability of foam films or Plateau borders and producing a substantial defoaming effect. A possible mechanism of
instability involving increases in disjoining pressure at locations where small soap particles approach the airwater interface is discussed. For
both surfactants with the trioleinoleic acid mixtures, calculated entry and bridging coefficients for conditions when calcium soap formed
were positive shortly after foam generation but negative at equilibrium. These results are consistent with the experimental observation that
most defoaming action occurred shortly after foam generation rather than at later times.
2003 Elsevier Inc. All rights reserved.
Keywords: Foam stability; Defoam; Antifoam; Soap; Thin film; Pseudoemulsion film
1. Introduction
The stability of foams made with aqueous surfactant solutions is important in a variety of applications. Sometimes
a strong and stable foam is desired, e.g., during hand dishwashing or personal cleaning with shampoos, where most
individuals perceive that foam is desirable. Sometimes foam
must be minimized to avoid technological problems, as
in paper making, painting, and cleaning applications using
energy-efficient horizontal-axis washing machines.
Oil drops and solid particles dispersed in a foaming liquid
can affect foam stability. Existing knowledge of how they
do so either alone or in combination has been reviewed by
Garrett [1], Aveyard et al. [2], Schramm [3], and Exerowa
and Kruglyakov [4], among others. Subsequent to these reviews, a series of papers providing additional insight on how
* Corresponding author.
(1)
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H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
(2)
(3)
Even when S 0, so that the oil drop forms a lens at the air
water surface instead of spreading, the foam will become
unstable once the drop has entered its other surface so that
it spans the film, provided that B > 0 [1,11]. Denkov [6]
developed a modified bridging criterion, removing certain
assumptions in Garretts original analysis, and showed that
sometimes an oil lens spanning a foam film can stretch extensively before ultimately rupturing.
Wasan et al. [12] found that foam stability, in the presence of emulsified oil drops, is controlled by the stability of
the film formed between the airwater interface and an approaching oil drop. They named this the pseudoemulsion
film. These asymmetric films might be stabilized by various thin-film forces [1317] which suppress drop entry and
impede the antifoam action of oil. Furthermore, if the pseudoemulsion film is stable, the introduction of oil into the
foaming solution might lead to a foam-boosting effect [18].
The correspondence between the classical entry coefficient E and drop entry is not exact because E does not
take into account the properties of the pseudoemulsion film,
e.g., the geometry of the system or the influence of thin-film
forces. To quantify the entry barrier for oil drops, Bergeron
et al. [15] suggested the so-called generalized entry coefficient, Eg , accounting for disjoining pressure effects:
AS
(hE )
Eg =
h dAS .
(4)
AS (h) is the disjoining pressure and hE is the equilibrium thickness of the asymmetric film at a certain capillary pressure. The evaluation of Eg requires knowledge of
the disjoining pressure isotherm for the asymmetric (pseudoemulsion) film, AS (h). A negative Eg defines the system
as nonentering and a positive one defines it as entering. Both
electrostatic and steric repulsion reduce the value of Eg and
can cause it to be negative even though E is positive.
Another measure of asymmetric film stability has been
discussed, namely, the critical capillary pressure leading to
rupture of the asymmetric film [15,19]. As shown by Aronson et al. [20], the measured value of the foam collapse
pressure (which acts as to suck liquid from the foam) was
close to the rupture pressure of a single foam film, as determined by the porous plate method [21]. However, sometimes disturbance caused by rupture of a few foam films or
Plateau borders can initiate rupture of others [22]. Recently,
H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
2. Materials
As foaming agents, the commercial anionic surfactant
Neodol 25-3S (denoted as N25-3S later on) and nonionic
surfactant Neodol N25-7 (denoted as N25-7 later on) were
used. The former is an alkyl ethoxy sulfate sodium salt with
a predominantly linear C12 C15 hydrocarbon chain and an
average of three ethylene oxide (EO) groups. It is of typical
use in hand dishwashing and shampoo products. The latter
is a linear alcohol ethoxylate also with a C12 C15 hydrocarbon chain but with an average of seven EO groups. It
is representative of nonionic surfactants which are used in
combination with anionic surfactants in household laundry
products. These two surfactants were both supplied by Shell
Chemical L.P. (Houston, TX).
As antifoaming agents, liquid oils including triolein (with
a purity of 99%, from Fluka Chemie), n-hexadecane (with
a purity of 99%, from the Humphrey Chemical Company),
and their mixtures with oleic acid (with a purity of 95%,
from Fisher Scientific Company) were studied as models of
nonpolar lubricating oils, vegetable oils, and nonpolar/polar
sebum soil, respectively. In subsequent sections, the mixture of hexadecane and oleic acid at a weight ratio of 9
to 1 is denoted as C16/HOl, and the mixture of triolein and
oleic acid at a weight ratio of 9 to 1 is denoted as TO/HOl.
Sodium oleate with a purity 99% was purchased from
Fluka Chemie. Hardness and alkalinity were provided by
calcium chloride (from Alfa Products, reagent grade) and
sodium hydroxide (from Fisher Scientific, assay of NaOH
98.5%), respectively.
3. Methods
3.1. Foam stability tests
A foam test apparatus (see Fig. 1) obtained from SEN,
Inc. was used for the foaming studies. Foam is formed in a
clear Plexiglass cylinder by entrainment of air in a surfactant
solution that is pumped through a recycle loop. The point
where the recycle pipe joins the foam cylinder is about 2 cm
635
below the 0-cm mark of the cylinder. The experimental procedure consists of filling the apparatus by pouring approximately 440 ml of solution from above the cylinder (with the
faucet closed) to the 0-cm mark. The pump is turned on for
5 min without the air valve open to provide uniform mixing of the solution. Air is then allowed into the recycle line
and foam is generated. The elapsed time in seconds when the
20-cm mark is reached by the foam is recorded and used to
calculate an average foam formation rate. The pump is then
shut off, and foam decay in the graduated cylinder is monitored. To study the effect of oil, liquid oils were added to the
aqueous solution in increments. After each oil addition, the
solution was circulated for 5 min prior to the foam formation
step to provide uniform emulsification and solubilization of
the oil phase. All initial tests were performed at room temperature using deionized water. However, the temperature of
the surfactant solution did increase slightly during each test
due to warming by the pump. In general, the surfactant solution temperature was controlled in the range of 25 to 28 C
during a single test.
3.2. Interfacial tension measurement
A University of Texas Model 300 Spinning Drop Tensiometer equipped with video camera (JEM6222, Javelin)
and video micrometer (VIA-100, Boecheler) was utilized for
measuring interfacial tensions.
3.3. Video-microscopy contact experiments
Samples of the surfactant solutions to be studied were
introduced into rectangular optical glass cells (50 4
0.4 mm, Vitrodynamics, Inc.) by capillary suction. Individual oil drops about 150 m in diameter were injected into
the cells through micropipettes [26]. The dynamic behavior
upon oil/water contact was observed and recorded using a
video-microscopy system (Nikon Metallurgical Microscope,
Javelin JE7362 Video Camera), which is also equipped with
a JV6000 video micrometer to measure drop diameter.
3.4. Optical observation of horizontal foam film
Millimeter-sized foam films were observed in reflected
monochromatic light with wavelength 546 nm using the
method of Scheludko and Exerowa [27,28]. The film is
formed from a biconcave drop placed in a capillary (i.d.
3 mm, height 1.2 mm) by sucking out liquid from a side
orifice. The film is illuminated and observed in a direction
perpendicular to its surfaces with the videomicroscopy system described in the preceding section.
In order to study the effect of oils on the stability of foam
films, a suitable amount of oil was added to the surfactant
solution. Before being loaded into the capillary cell, the solution was shaken intensively by hand in a test tube to achieve
mixing and emulsification.
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H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
Fig. 3. Effect of pure oils on the stability of foams with 0.01 wt% N25-3S.
Fig. 4. Effect of pure oils on the stability of foams with 0.1 wt% N25-7.
dry applications. Oils were added in increments up to an oilto-surfactant ratio of about one. Foam heights after 20 min
are compared in Fig. 4. In the absence of oil, foam height
after 20 min was about 15 cm. Triolein again showed no defoaming effect while hexadecane exhibited a much greater
effect, than it did with the anionic surfactant.
4.1.2. Individual foam films
The experiments with small horizontal foam films in the
Sheludko cell with solutions containing 0.01 wt% N25-3S
and 0.02 wt% oily additives (hexadecane or triolein) showed
that the addition of the studied oils did not significantly
change the film-thinning rate, while the movement of oil
drops was clearly detectable under microscopy. When the
oily additive was hexadecane, most of the dozens of studied
foam films were stable. Oil drops were either trapped at the
periphery of the film without breaking the film or swept out
of the film into the meniscus as the film thinned. Occasionally, oil bridge configurations formed and led to film rupture.
When the oily additive was triolein, the oil drops were always swept out of the film and did not affect film lifetime at
all.
Foam films made from solutions of 0.1 wt% N25-7 were
also studied. The addition of 0.1 wt% oils did not change
the slow drainage process of this surfactant solution. With
hexadecane as oily additive, most of the film samples broke
before or around 2 min instead of lasting more than 6 min as
in the oil-free system. With triolein as oily additive, however,
film lifetime was not affected.
H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
637
Table 1
Equilibrium entry, spreading, bridging coefficients and foam stability for solutions of 0.01 wt% N25-3S and 0.1 wt% N25-7 with pure oily soils
Solution
0.01 wt% N25-3S
Oil
AW
OW
AO
H 0 (cm)
H 20 (cm)
No oil
Hexadecane
Triolein
33.1
33.0
9.7
9.5
26.3
31.9
16.5
10.6
2.9
8.4
498
162
20
20
20
18.1
16.6
17.9
No oil
Hexadecane
Triolein
29.7
29.5
1.7
8.4
26.3
31.9
5.1
6
1.7
10.8
193
77
20
20
20
14.9
7.3
14.8
Note. H 0 is initial foam height; H 20 is foam height after 20 min. The units of interfacial tensions are mN/m. For systems containing N25-3S, oil/surfactant = 1;
for systems containing N25-7, oil/surfactant = 0.5. The AW tensions are measured after equilibration with corresponding amounts of dispersed oil.
Fig. 5. Effect of oil mixtures on stability of foams with 0.01 wt% N25-3S
solution.
Fig. 6. Effect of oil mixtures on stability of foams with 0.1 wt% N25-7
solution.
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H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
(a)
(a)
(b)
(b)
(c)
Fig. 8. Video-microscopy contact experiments: a drop of C16/HOl contacted the pH 9 solution containing 0.01 wt% N25-3S and 300 ppm hardness. (a) Initial state; (b) about 5 min later; (c) a spinning drop.
tact. As time went on, the interface became more rigid and
was no longer smooth (Fig. 8b). In order to check the rigidity of the interface, we rotated an oil drop at a certain speed
in a spinning drop tensiometer and then suddenly reduced
the speed. The interface crumpled (Fig. 8c) as the area decreased, indicating the rigidity of the interface. We conclude
that calcium oleate, which has very low solubility in water, with a solubility product in the range of 1015 [29],
was formed at the oilwater interface due to the reaction between oleic acid and divalent calcium ions. Figure 9 shows
a TO/HOl drop in the same solution as in Fig. 8. Obviously,
a new phase formed at the interface after several minutes
(Fig. 9a). Again, the spinning drop (Fig. 9b) showed that the
new phase was solid.
Similar phenomena were observed with the nonionic surfactant, i.e., insoluble calcium soap formed at the oilwater
interfaces when oil mixtures contacted an alkaline solution
of 0.1 wt% N25-7 containing calcium.
It is worth noting that these dynamic phenomena involving calcium soap formation did not occur in neutral solutions
within the time scale we studied, which was about half an
hour. This implies that alkaline pH is crucial to the speed
and extent of oleic acid ionization.
4.2.3. Horizontal foam films
Effect of formation of calcium soap at the oilwater interface on the stability of foam films was checked by a Sheludko cell. We studied tens of foam films produced from a
H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
(a)
(b)
Fig. 10. Foam films produced with pH 9 solution of 0.01 wt% N25-3S containing 0.02 wt% C16/HOl and 300 ppm hardness. (a) Particle with irregular
shape pierced the periphery of the film and broke it. (b) Film broke because
of oil bridging.
639
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H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
(a)
(b)
(c)
(d)
Fig. 11. Pseudoemulsion films. (a) Asymmetric drainage of dimple. (b) Stable film between oil phase (C16/HOl) and aqueous phase (0.01 wt% N25-3S).
(c) Unstable film between oil phase (C16/HOl) and aqueous phase (0.01 wt% N25-3S + 300 ppm hardness, pH 9). Interference fringes are the last stages of
the dimple draining asymmetrically. Bright dots evidence the presence of solid particles in the film. (d) Oil lens formed after the oil drop entered the airwater
surface.
H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
(a)
(b)
(c)
(d)
641
Fig. 13. Pseudoemulsion film formed by TO/HOl in pH 9 solution containing. 0.1 wt% N25-7 and 300 ppm hardness. (a) A dimple. (b) The dimple approached
one side of the film and water entered from the other side of the film. (c, d) Water gradually spread over the entire film.
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H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
Table 2
Equilibrium entry, spreading, bridging coefficients and foam stability for solutions of 0.01 wt% N25-3S and 0.1 wt% N25-7 with oil mixtures
Oil
CaCl2 (ppm)
pH
AW
OW
OA
H 0 (cm)
H 10 (cm)
H 20 (cm)
C16/HOl
TO/HOl
300
300
9
9
30.1
29.2
0.1
0.8
26.5
31.4
3.7
1.4
3.5
3
204
133
20
20
4.0
7.5
2.1
7.4
0.1wt% N25-7
C16/HOl
TO/HOl
300
300
9
9
29.0
29.3
0.1
1.6
26.5
31.4
2.6
0.5
2.4
3.7
139
125
20
20
5.1
7.2
3.0
6.9
Solution
Note. Same as for Table 1 except that H 10 is foam height after 10 min.
Table 3
Dynamic and equilibrium entry, spreading, and bridging coefficients
Solution
Oil
CaCl2
pH
(ppm)
0.01 wt% N25-3S
TO/HOl
E = AW + OW AO
S = AW OW AO
B = AW 2 + OW 2 AO 2
300
Equilibrium
Defoaming effect
Expected
Observed
1.4
3.0
125
None
Large
Time (min)
AW
1
4
8
33.8
31.5
29.7
2.8
0.5
0.9
1.3
1.0
2.5
131
18
103
Fig. 14. Synergistic effect on foam stability between oil drops and soap
particles.
H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
643
(a)
(b)
Fig. 15. Foam of solution containing oil (system III). For explanation, see
text.
(c)
Fig. 16. Schematic presentation of a drop (or particle) in foam film.
(a) A drop with smooth surface. (b) A drop with rough surface. (c) The
disjoining pressure isotherm.
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H. Zhang et al. / Journal of Colloid and Interface Science 263 (2003) 633644
(5)
5. Summary
For foams made with 0.1 wt% of the nonionic surfactant
N25-7, measurement of the various tensions showed that the
conventional ESB approach correctly predicted the defoaming characteristics of these oils for the nonionic surfactant.
For foams made with 0.01 wt% of the anionic surfactant
N25-3S, ESB analysis yielded positive values of E and B for
both n-hexadecane and triolein. However, neither oil caused
substantial reductions in foam stability. This discrepancy reflects the stability of the oilwaterair asymmetric film due
to the electrical contribution to disjoining pressure in the
pseudoemulsion film of surfactant solution. This contribution caused entry to the airwater surface to be more difficult
than predicted by the usual equation for E (Eq. (1)).
When drops of triolein/oleic acid (TO/HOl) or n-hexadecane/oleic acid (C16/HOl) mixtures were dispersed in solutions of the same surfactants containing small amounts
of calcium ions under mildly alkaline conditions (pH 9),
a large defoaming effect was observed. Results from several types of experiments indicate that solid calcium oleate
particles form and collect at the drop surfaces. A mechanism
has been proposed in which these small particles facilitate
drop entry to the airwater surface, enabling the well-known
bridging instability of foam films or Plateau borders to occur. With this mechanism, electrical disjoining pressure in
the oilwaterair pseudoemulsion film can no longer prevent
foam instability. For C16/HOl drops, calculated spreading
and bridging coefficients for both surfactants are consistent
with the observed defoaming effect. Results with TO/HOl,
however, are consistent with entry/bridging coefficients only
taking account of the decrease in AW and OW with time,
so that E > 0 initially but later decreases to values near zero
or slightly negative. Experiments demonstrated that most of
Acknowledgments
This project was supported by the National Science Foundation. The authors are grateful to Dr. N. Denkov and
K. Marinova for their valuable advice on pseudoemulsion
film study and to G. Shpakoff for helping with foam testing
experiments.
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