Journal of Colloid and Interface Science 279 (2004) 539–547

www.elsevier.com/locate/jcis

Defoaming effect of calcium soap

Hui Zhang a , Clarence A. Miller a,∗ , Peter R. Garrett b , Kirk H. Raney c
a Department of Chemical Engineering, Rice University, Houston, TX 77251-1892, USA
b Department of Chemical Engineering, UMIST, PO Box 88, Manchester, M60 1QD, UK
c Shell Chemical L.P., P.O. Box 1380, Houston, TX 77251-1380, USA

Received 27 January 2004; accepted 30 June 2004

Available online 28 July 2004

Abstract
The effect of calcium oleate on foam stability was studied for aqueous solutions of two commonly used surfactants (anionic and nonionic)
under alkaline conditions in the absence of oil. For the anionic surfactant, defoaming by calcium oleate appears to involve two mechanisms.
One is that oleate and calcium ions are presumably incorporated into the surfactant monolayers with a resulting decrease in the maximum
of the disjoining pressure curve and therefore produces less stable thin films. The other is bridging of the films by calcium oleate particles.
The latter mechanism was especially important in freshly made solutions where precipitation in the aqueous phase was still occurring when
the foam was generated. Foams generated after aging (hours) when precipitation was nearly complete were more stable even though solution
turbidities were greater. Foams of the nonionic surfactant were less stable than those of the anionic surfactant but were also destabilized
by sufficient amounts of calcium oleate and exhibited a similar aging effect. A simplified model was developed for estimating the sodium
oleate concentration at which precipitation commences in solutions of the anionic surfactant containing dissolved calcium. It includes en-
hancement of calcium content in the electrical double layers of the surfactant micelles. Predictions of the model were in agreement with
experiment.
 2004 Elsevier Inc. All rights reserved.

Keywords: Foam; Thin film; Sodium soap; Calcium soap; Defoaming; Aging effect

1. Introduction of foam films or Plateau borders and producing a substantial

antifoam effect. However, the defoaming effect of calcium
Foam stability in the presence of soluble/insoluble soaps and magnesium in the absence of oils is not yet well under-
is of practical importance in applications such as laun- stood. Peper [2] proposed that rapid defoaming of detergent
dry, personal and home cleaning, the potential use of foam solutions by soap or fatty acid occurs when conditions are fa-
for mobility control in alkaline/surfactant processes for im- vorable for the formation of a solid monolayer by the action
proved oil recovery, etc. In hard water the precipitation of of calcium ion. He advanced the hypothesis that the surfaces
calcium and magnesium soaps of long chain fatty acids may of the foam bubbles are heterogeneous and consist of a con-
occur and destabilize the foam. Soap is sometimes added to tinuous film of adsorbed detergent in which there are islands
laundry products for defoaming action and can also form in of solid calcium soap film. He suggested that these islands
situ during the detergency process due to the presence of make the film unstable because of their inflexible, brittle na-
ture. In this paper we describe a systematic study of oil-free
fatty acids in sebum-like soils. We have shown in a previous
solutions containing calcium soap, which was formed by
study [1] that the combination of oil and calcium soap pro-
adding sodium oleate to surfactant solutions with dissolved
duces a synergistic effect facilitating the bridging instability
calcium chloride and pH adjusted to 9 by sodium hydroxide.
Alkalinity was applied to limit the hydrolysis of oleate to
* Corresponding author. Fax: +1-713-348-5478. oleic acid, which would otherwise be significant due to easy
E-mail address: [email protected] (C.A. Miller). incorporation of oleic acid into micelles. Measurements of
0021-9797/$ – see front matter  2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.06.103
540 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547

the rate of collapse of a foam column were supplemented by 3.2. Optical observation of horizontal foam film
microscopic observations of individual foam films and by
measurement of turbidity and surface tensions. Millimeter sized foam films were observed in reflected
monochromatic light with wavelength of 546 nm by using
the method of Sheludko and Exerowa [3,4]. The film was
2. Materials formed from a biconcave drop placed in a capillary (i.d.
3 mm, height 1.2 mm) by sucking out liquid from a side
Two commercial surfactants supplied by Shell Chemical orifice. The film was illuminated and observed in a direction
L.P. (Houston, TX) were used as foaming agents. One is an perpendicular to its surfaces with a videomicroscopy system.
anionic surfactant, an alkyl ethoxy sulfate sodium salt with a
straight C12 –C15 hydrocarbon chain and an average of three 3.3. Surface tension measurement
ethylene oxide (EO) groups, denoted as N25-3S later on. It is
typical of surfactants used in hand dishwashing and shampoo A University of Texas Model 300 spinning drop ten-
products. The other is a nonionic surfactant, a linear alcohol siometer was utilized to measure surface tensions. Measure-
ethoxylate also with a C12 –C15 hydrocarbon chain but with ments were made by introducing a small air bubble to the
an average of seven EO groups, denoted as N25-7 later on. sample tube which was filled with surfactant solution. Data
It is representative of nonionic surfactants which are used in were collected after running the sample for at least 20 min.
combination with anionic surfactants in household laundry
products. 3.4. Turbidity measurement
Sodium oleate with a purity
99% was purchased
from Fluka Chemie. Calcium chloride (from Alfa Products,
Turbidity was measured by a Brinkmann PC 800 col-
reagent grade) was dissolved in deionized water to prepare
orimeter. The original measured datum was the percentage
hard water. The concentration of hardness was calculated
of transparency, T%, of the solution. Turbidity was then cal-
as CaCO3 in accordance with the usual convention, i.e., the
culated from 100 T%. The colorimeter was calibrated be-
concentration that would exist if the same amount of cal-
fore each measurement with deionized water which gives
cium had been added as CaCO3 . Alkalinity was provided
100 − T%.
by sodium hydroxide purchased from Fisher Scientific with
assay of NaOH
98.5%. Water used for experiments was
distilled and deionized. 3.5. Ultrafiltration and titration
Mixtures of triolein (with a purity of 99%, from Fluka
Chemie) or n-hexadecane (with a purity of 99%, from the Ultrafiltration (UF) was used to separate free electrolyte
Humphrey Chemical Company) with a small amount of oleic solution from surfactant micelles. Hutchinson [5] showed
acid (with a purity of 95%, from Fisher Scientific Company) that this could be achieved at sufficiently high rates of fil-
were sometimes used as defoaming agents in experiments tration through UF membrane. UF membranes used in this
conducted for comparison with the oil-free systems. The study were Amicon YM3 with 3000 nominal molecular
mixture of hexadecane and oleic acid at weight ratio of 9 weight limit (NMWL) from Millipore Corp. The material
to 1 is denoted as C16/HOl, and the mixture of triolein and was regenerated cellulose. Surfactant and electrolyte solu-
oleic acid at weight ratio of 9 to 1 is denoted as TO/HOl. tions were charged to a stirred filtration cell of 50 to 55 mL
capacity and forced through UF membrane with 330 kPa
[48 psi] nitrogen pressure. Filtration rates were 0.48 to
0.53 g/min. During each filtration, successive samples of
3. Methods
filtrate were collected and analyzed for surfactant and cal-
cium.
3.1. Foam stability tests Concentration of anionic surfactant and calcium ion were
analyzed by potentiometric titration. The apparatus was
Foam stability was determined by measuring the rate of an automatic titrator, Metrohm Titrino Model 716, pur-
collapse of a vertical foam column formed by mixing air chased from Brinkman Instruments. For analysis of anionic
with a surfactant solution at the base of the column [1]. The surfactant, the titrant solution is 0.004 M benzothonium
procedure consisted of filling the apparatus with approxi- chloride (Hyamine 1622), reagent, ordered from Gallord–
mately 440 ml of solution to the 0-cm mark of the gradu- Schlesinger, Inc. The indicator is a combination anionic sur-
ated cylinder. Foam was generated while the solution was factant specific electrode purchased from Phoenix Electrode
pumped through a recycle loop and air was allowed into the Co., Cat. No. SUR1502R. For analysis of calcium ion, the
recycle line. The pump was shut off when the foam reached titrant is reagent EDTA, a product of Fisher Chemicals. The
the 20-cm mark, and foam decay was recorded as a function indicator is a calcium ion-specific electrode purchased from
of time. Phoenix Electrode Co., Cat. No. CAL1502R.
 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547 541

Table 1 Table 3
Turbidity measurements with 0.01 wt% N25-3S, 300 ppm (0.03%) Ca, pH 9 Turbidity measurements with 0.1 wt% N25-7, 300 ppm (0.03%) Ca, pH 9
Transmittance, T% Transmittance, T%
0.0001% NaOl 0.0004% NaOl 0.001% NaOl NaOl 0.001% 0.002% 0.003% 0.004% 0.005% 0.01%
Fresh 99.9 98.8 96.3 Fresh 99.9 99.6 99.4 91.4 88.7 69.5
4h 99.9 97.7 92.6 4h 99.9 99.7 2 h 95.0 83.0 7 h 59.3 34.6
23 h 99.8 96.8 89.6 23 h 99.9 99.3 25 h 92.2 77.3
29 h 99.9 96.6 89.6 29 h 99.9 99.5 34 h 93.1 79.7

Table 2
Turbidity measurements with 0.05 wt% N25-3S, 300 ppm (0.03%) Ca, pH 9
Transmittance, T%
0.0005% NaOl 0.001% NaOl
Fresh 99.8 97.9
2h 99.9 96.5
25 h 99.7 95.8
50 h 99.6 96.1

4. Results and discussion Fig. 1. Foam stability with 0.01% N25-3S at different concentrations of
sodium oleate.

4.1. Turbidity centration. Again aging effects over periods of hours were
observed.
As indicated previously, the main objective of this study
was to determine the effect of calcium soaps on foam sta- 4.2. Foam stability
bility. For this purpose it is important to know whether solid
soap is present. Most calcium soaps have low solubility in Foam stability was tested by the method described in Sec-
water, e.g., the solubility product of calcium oleate is ten to tion 3.1. Reproducibility was confirmed by running each
the power of −15.4 at 295 K and zero ionic strength [6]. So system twice or more.
when sodium oleate (NaOl) is added to an alkaline aqueous
phase containing hardness, turbidity of the solution is ex- 4.2.1. Experiments with freshly mixed solutions
pected to increase. Accordingly, a series of turbidity studies A series of fresh solutions containing 0.01 wt% N25-3S
was carried out by measuring the transmittance as a function and different amounts of sodium oleate and hardness were
of the concentration of NaOl and aging time. Samples were tested at pH 9 for foam stability. Fig. 1 illustrates the results
blanketed by nitrogen during aging. at 300 ppm hardness. At the lowest studied concentration of
Transmittances of solutions containing N25-3S at two NaOl, 0.0001 wt%, foam stability was not influenced by the
concentrations, 0.01 wt% (cmc) and 0.05 wt%, are given in addition of NaOl. Nor was turbidity, according to Table 1,
Tables 1 and 2, respectively. Water hardness was 300 ppm. which indicates that calcium oleate particles were absent. As
Regarding the stoichiometry of calcium oleate, CaOl2 , cal- the concentration of sodium oleate increased, foam stabil-
cium is in excess for all compositions of NaOl studied. Here, ity decreased. The lower the concentration of sodium oleate,
fresh solution means that the measurements were conducted the longer the delay before the initiation of foam decay, and
within 30 min after the samples were prepared. the larger the final stable foam height. Substantial decrease
Clearly, turbidity increased with aging time over periods in foam stability was found for NaOl concentration up to
of hours except for the first solutions of Tables 1 and 2. 0.005% with little additional effect beyond that point. So-
This increase shows that solid calcium oleate particles are lutions containing 0.0004 and 0.0008 wt% sodium oleate
growing. Turbidity increased as the concentration of NaOl were visually transparent, although transmittance was less
increased, indicating more precipitate formed in the solution. than 100% as shown in Table 1. With 0.001% NaOl, the so-
As concentration of N25-3S increased, turbidity decreased, lution was bluish. When the concentration of sodium oleate
indicating fewer particles were formed because more oleate increased to 0.005% and 0.01%, solutions were quite turbid.
and calcium were incorporated in micelles. Foam stability was tested for a hardness range of 20–
For solutions of the nonionic surfactant N25-7 at 0.1 wt%, 300 ppm, the range of interest for laundry, dishwashing, and
transmittances were measured at 300 ppm hardness and dif- other cleaning applications. Trends similar to those of Fig. 1
ferent concentrations of sodium oleate, as shown in Table 3. were observed for other calcium concentrations, as shown in
The solutions are clear up to 0.002% NaOl. Beyond that Table 4, which gives foam heights after 20 min when foam
point, transmittance decreased rapidly with increasing con- stability curves reached equilibrium heights. Since calcium
542 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547

Table 4
Foam height (cm) after 20 min
NaOl (wt%) Hardness
20 ppm 50 ppm 100 ppm 300 ppm
0.0004 8.0 7.7 7.4 7.9
0.001 6.2 6.1 6.1 6.0

Fig. 3. Foam stability with N25-7 at different concentrations of sodium

oleate.

tration of Ca(OH)+ also decreases. This may be why foam

stability returns to that for solutions formed at neutral pH.
For studies with nonionic surfactant N25-7, surfactant
concentration was kept at 0.1 wt%. Foam stability of pH 9
Fig. 2. Effect of pH on foam stability with solution containing 0.01%
N25-3S and 300 ppm hardness. solution containing 300 ppm hardness and different amounts
of sodium oleate was tested. The results are shown in Fig. 3.
No significant decrease in foam stability was seen up to
is in excess, foam stability is relatively insensitive to hard-
0.002 wt% NaOl. Indeed, foam stability seemed to increase
ness.
slightly, probably owing to the surface charge introduced
Without any sodium oleate, it was observed that alkaline
by adsorbed oleate ions. At this concentration the solution
pH influences the stability of foam of 0.01% N25-3S con-
has virtually 100% transmittance (per Table 3). Decrease
taining hardness (CaCl2 ). As shown in Fig. 2, foam is less
in foam stability was noticeable with 0.003% NaOl, which
stable at pH 9 than at neutral pH for a freshly mixed solu-
made the solution a little bit bluish. At higher concentrations
tion. The difference in stability occurs after 10 min when
of sodium oleate, which made the solutions turbid, foam sta-
the dry foam consists of very thin film lamellae. It is found
bility was further decreased. Substantial decrease in foam
that pH of the initially alkaline solution decreased as the so-
stability was found up to 0.005% NaOl with little additional
lution aged. When the solution was tested again after about
effect for further increases.
43 h, pH was around 7.5 and foam stability was similar to
that of the freshly mixed solution at neutral pH. On the con-
trary, pH did not change in the absence of N25-3S, implying 4.2.2. Experiments with aged solutions—aging effect in
that some component in this commercial surfactant seems to foam stability
slowly consume the hydroxide ions. We saw previously that turbidity changed with time for
Behavior similar to that of Fig. 2 was observed at other solutions containing calcium soap particles. Now, we look
hardness levels besides 300 ppm, e.g., 50 ppm. A possi- at how aging affects foam stability. When the solutions were
ble explanation is suggested by the work of Rutland and mixed, foam stability was not tested until after overnight or
Pugh [7]. They made measurements with surface forces ap- longer. During the aging process, the solutions were blan-
paratus of forces between negatively charged mica plates keted with nitrogen. Results are compared with those of the
separated by alkaline aqueous solutions. When the only preceding section for fresh solutions.
counterion in solution was Na+ , there was a strong short- With concentration of the anionic surfactant N25-3S be-
range repulsion, i.e., hydration force. But when calcium was ing fixed at 0.01 wt% and hardness at 300 ppm, foam sta-
present at pH 9, they reported that substantial Ca(OH)+ was bility was tested at several concentrations of sodium oleate.
specifically adsorbed at the negatively charged surfaces and Fig. 4 shows the results at 0.0004% and 0.01% NaOl. Fig. 5
hydration forces were minimal. This is because the water shows the results at 0.001% NaOl. Compared with the fresh
of hydration of Ca(OH)+ was less strongly bound than that solutions, foam stability increased after aging. The change
of Na+ and Ca2+ . The relevance of our case to their study is was significant with 0.0004% and 0.01% NaOl, while even
(1) the two surfaces of our foam films are negatively charged larger at the intermediate concentration of 0.001% NaOl.
due to presence of anionic surfactants; (2) Na+ , Ca2+ and The solution with 0.0004% NaOl looked transparent even
Ca(OH)+ are the only cations present; (3) a strong short- after aging (refer to Table 1). The solution with 0.01% NaOl
range repulsion helps stabilize thin film; (4) instability of was quite turbid from the beginning, obviously with substan-
foam at alkaline pH occurs only when foam lamellae become tial amount of insoluble soap particles. The solution with
very thin. Thus, the decrease of foam stability as pH changes 0.001% NaOl looked bluish, indicating the existence of solid
from 7 to 9 may be related to Rutland and Pugh’s finding. As particles, but they must have been small. The pH of these so-
the solution ages, pH decreases with the result that concen- lutions decreased from 9 to about 7.5 after aging.
 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547 543

Fig. 4. Foam stability of fresh and aged solutions of N25-3S containing

0.0004% and 0.01% NaOl.

Fig. 7. Foam stability of fresh and aged solutions of N25-7 containing NaOl.

4.3. Horizontal foam film

In order to obtain a better understanding of the defoam-

ing mechanism of calcium soap and of the intriguing aging
effect on foam stability, we studied individual foam films
with diameters between 0.6 and 1 mm in Sheludko cell.
A film produced from the pH 9 solution containing 0.01 wt%
N25-3S and 300 ppm hardness but no NaOl was taken as a
Fig. 5. Foam stability of fresh and aged solutions of N25-3S containing reference. It went through the thinning process illustrated
0.001% NaOl. in Fig. 8. Asymmetric drainage of the dimple took place
within 1–2 s after the film was formed (Fig. 8a). Channels
disappeared and a white planar film formed at around 1 min
(Fig. 8b). After further continuous drainage, a uniform sta-
ble black film formed at around 3 min (Fig. 8c).
Film thinning behavior was not influenced by addition of
NaOl at concentrations lower than 0.001 wt%. Ten films pro-
duced from a freshly mixed pH 9 solution containing 0.01%
N25-3S, 300 ppm hardness, and 0.001% NaOl were studied.
Eight of them behaved similarly to the film with no NaOl
Fig. 6. Comparison of foam stability between fresh and aged solutions of additive. Two of them showed a different thinning pattern.
N23-3S in the presence of oil. After the initial asymmetric dimple drainage (within 2 s),
a new dimple-like pattern formed, as shown in Fig. 9. A par-
As a comparison, solutions containing both oils and cal- ticle was observed in the middle of the newly formed dimple.
cium soap were also tested after aging. The systems studied Film drainage was somewhat slowed down due to the dim-
were pH 9 solutions of 0.01 wt% N25-3S plus 300 ppm hard- ple. No white planar film was observed. A uniform black
ness and 0.01 wt% oil mixtures containing n-hexadecane or film finally formed after approximately 3 min.
triolein with 10 wt% oleic acid, C16/HOl or TO/HOl. As At a higher concentration of sodium oleate, 0.005%, rapid
demonstrated in our previous work [1], calcium soaps form initial asymmetric dimple drainage was again observed.
in situ at the oil–water interface in these systems. Fig. 6 However, at around 1 min the white film was not uniform
shows that foams were still quite unstable after aging in the (Fig. 10a); at around 3 min, the black film was not uniform
presence of these oils. either (Fig. 10b).
Results with N25-7 are given in Fig. 7. Foam stability of At an even higher concentration of sodium oleate, 0.01%,
fresh and aged solutions were compared at two concentra- we saw stable films and less stable films with similar fre-
tions of NaOl, 0.005 and 0.01 wt%. Clearly, stability of the quency. After the initial quick asymmetric dimple drainage,
foams increased after the solutions aged. In contrast to the a new dimple formed, and it was still there after 1 min. Some
system of anionic surfactant N25-3S, alkalinity of these so- films broke after several minutes. Some films were still sta-
lutions did not change as the solutions aged. ble after 8 min with effect of particles visible, as seen in
When an oil mixture was present, that is for pH 9 solu- Fig. 11. Many particles were seen in these films.
tions containing 0.05 wt% C16/HOl and 300 ppm hardness, When the solutions containing the above three concentra-
foam was even less stable than without oil, as indicated by tions of NaOl were tested again after aging 40 h, the phe-
the curve marked by ‘+’ for a fresh solution, and the an- nomena described above were not observed. The thinning
tifoam effect actually increased with aging, as indicated by process was the same as for solutions without any oleate
the curve marked by dots in Fig. 7. (Fig. 8). Although the presence of solid soap particles in
544 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547

(a)
(a)

(b)
(b)
Fig. 10. Foam film with pH 9 solution containing 0.01% N25-3S, 300 ppm
hardness, and 0.005% NaOl. (a) Nonuniform white film formed at around
59 s; (b) nonuniform black film formed at around 3 min.

(c)

Fig. 8. Thinning process of a film produced from solution containing 0.01%

N25-3S and 300 ppm hardness. (a) Asymmetric drainage of the dimple
within 1–2 s after the film was formed; (b) white planar film formed at
around 48 s; (c) a uniform stable black film formed at around 3 min. Fig. 11. Foam film with pH 9 solution containing 0.01% N25-3S, 300 ppm
hardness, and 0.01% NaOl.

4.4. Mechanism of defoaming by calcium soap

For foams made from alkaline solutions containing

0.01% N25-3S and 300 ppm Ca2+ , foam stability decreased,
according to the results presented above, whenever enough
NaOl was added to decrease light transmittance through
the solution, i.e., whenever some calcium oleate particles
formed. In contrast, at the lowest NaOl content investigated,
0.0001%, both transmittance and foam stability were the
same as in the absence of NaOl.
Visual observations in this system revealed that at low
Fig. 9. Foam film with pH 9 solution containing 0.01% N25-3S, 300 ppm concentrations of NaOl (0.0004–0.0008%) where turbidity
hardness, and 0.001% NaOl. was low and relatively few soap particles were formed, the
foams had quite uniform bubble size and decayed from
the solution was obvious, particles were all expelled during the top of the foam column. Moreover, the height of the
drainage and unable to stay in the film. residual relatively stable foam decreased as NaOl concen-
 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547 545

be less easily swept from the film during drainage, thereby

providing more time for them to enter the opposite surface
and bridge the film. Whether or not such nucleation occurs,
the higher supersaturation of oleate in the fresh solutions
should facilitate particle entry. For instance, entry might be
favored by a lower surface charge of the surfactant mono-
layers (see above). For the fresh solutions bridging clearly
occurs more rapidly at higher NaOl concentrations, where
Fig. 12. Foam stability of 0.01% NaOl at pH 9, 0.01% N25-3S, and their the greater turbidity suggests that there are enough large par-
mixture. ticles to destabilize the films even during foam generation.
It is noteworthy that the capillary pressures reached in the
tration increased (Fig. 1). At high concentrations of NaOl— foam column (some 1000 Pa in a column 10 cm high) are
at least 0.005%—where solutions were much more turbid considerably higher than those in our Sheludko cell (40 Pa).
indicating that many solid particles formed, some coales- This difference is one possible reason that films in the She-
cence of air bubbles was observed during foam generation, ludko cell with NaOl concentrations up to 0.005% were sta-
and film breakage was observed throughout the foam during ble, whereas the corresponding foams were not. Moreover,
drainage. Monin et al. found that foam films in bulk foams break at
It is suggested that two mechanisms contribute to the de- lower capillary pressure than do isolated films due to the
crease in foam stability produced by added NaOl. One is very different perturbations in the two situations [10]. Higher
incorporation of oleate and calcium ions into the surfactant capillary pressures also favor particle entry into the film sur-
monolayers with a resulting decrease in foam film stabil- faces. Thus, even though we did not observe particle entry
ity. Even in the absence of calcium, NaOl foams are less for the aged solutions in the Sheludko cell, we cannot ex-
stable than those of N25-3S (Fig. 12). In the present experi- clude the possibility of entry for the same solutions in the
ments the oleate which adsorbs with N25-3S likely promotes foam column. What we can conclude, as indicated above, is
additional calcium adsorption with a resulting decrease in that entry is facilitated in the fresh solutions.
surface charge. Whatever the precise monolayer composi- For solutions containing the nonionic surfactant N25-7
tion this mechanism is supported by the observation that for no significant adverse effect on foam stability was seen ex-
the aged solutions where the Sheludko cell results indicate cept at concentrations of NaOl of at least 0.003% (Fig. 3).
that few particles enter the film surfaces, foam stability is Indeed, at lower concentrations of NaOl the turbidity results
less than in solutions containing N25-3S alone. Also pro- indicate that no calcium soap particles formed. Moreover,
viding support is that the nearly constant heights of foams adsorption of oleate ions provided a surface charge, which
for the fresh solutions after 20–30 min, when most particles actually increased foam stability slightly. Particle bridging is
have left the films, are only slightly less than the correspond- also an important defoaming mechanism, as indicated by ob-
ing heights for the aged solutions (Figs. 4 and 5). The small servations of coalescence during foam generation for fresh
difference is due to the higher supersaturation of oleate in solutions with NaOl concentrations of at least 0.004%. The
the fresh solutions, as also indicated by their slightly higher increase in foam stability after aging is similar to that for
surface tensions (Table 5). the anionic surfactant and presumably occurs for the same
The second mechanism is bridging by calcium oleate par- reason.
ticles. That hydrophobic particles can destabilize foam films When oils were present, foam stability did not increase
is well known [8]. The Sheludko cell results show that many after aging. As discussed previously [1], the defoaming
more particles are present in the film surfaces in the fresh mechanism when both oil and insoluble soap are present
than in the aged solutions. This behavior suggests that parti- is a synergistic effect. The small soap particles formed at
cle bridging is likely responsible for much of the defoaming the surfaces of the much larger oil drops help destabilize
action observed at short times for fresh solutions. Perhaps the pseudoemulsion films between the drops and the film
some particles actually nucleate in the film surfaces when surfaces, thereby facilitating entry of the drops into the sur-
foam is generated during the early stages of precipitation, faces. Then bridging by the drops destabilizes the films. This
as suggested by Raghavachari et al. [9]. If so, they would mechanism is not expected to change after aging.

Table 5
Surface tension (mN/m) of solutions containing soap and hardness
0.01 wt% N25-3S, 300 ppm hardness, pH 9 plus
0.0% NaOl 0.001% NaOl 0.005% NaOl 0.05% NaOl
Freshly mixed solution 27.5 27.8 28.8 30.1
Aged 40 h 27.5 27.6 27.9
Aged 140 h 27.4 27.7 27.5
546 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547

4.5. Precipitation of calcium oleate in micellar solutions 0
COl − = Ksp/C 0 2+ . With cmc of NaOl at pH 9 (COl cmc
)
Ca
of N25-3S as 0.052 mM [12], the composition of oleate in the mixed
micelle is calculated by x = COl 0 /C cmc . The concentration
− Ol
In micellar solutions, precipitation of calcium soap is a of N25-3S in micelles is the difference between total sur-
more complex process than that in the absence of micelles. factant concentration, CST , and monomer concentration, CS0 .
Since some calcium and oleate are incorporated in the mi- The latter is based on measured surfactant concentration in
celles, concentrations of molecularly dissolved calcium and the filtrate at the same total calcium concentration. These
oleate are less than the total amounts added. This effect micelles are expected to contain oleate in the amount of
m = x(C T − C 0 ). Therefore, the total oleate added at the
COl
should be taken into account in the analysis to determine − S S
the conditions for precipitation. In this section, a simplified precipitation boundary is COl m + C0 .
− Ol−
approach is applied to model such behavior. The objective is The precipitation boundary calculated this way was com-
to estimate the precipitation boundary of calcium oleate, i.e., pared with that found experimentally, which is the boundary
the amount of sodium oleate which must be added to a solu- between the isotropic region (100% transmittance) and the
tion with given concentrations of N25-3S and CaCl2 before region with turbidity (with transmittance less than 99.8%).
calcium oleate starts to precipitate. Results for surfactant concentrations between 0.01 and
Our interest here lies in systems where the molar concen- 0.05 wt% are given in Fig. 13. The calculated and experi-
tration of oleate is much less than that of N25-3S and cal- mental boundaries match well in spite of the limitations of
cium. Owing to the low solubility product of calcium oleate, our simplified model. As Fig. 13 shows, the effect of the
the monomer concentration of oleate ion will be very low micelles must certainly be included. Fig. 13 is based on ex-
for significant amounts of calcium in bulk solution. There- periments and calculations summarized in Table 6. It is clear
fore, there should be very little oleate in the micelles, and from the fifth column in Table 6 that the percentage of oleate
their behavior should be similar to N25-3S micelles. So we in mixed micelles was as low as 1%. This justifies our as-
assume that binding of calcium with micelles in the presence sumption that there was very little oleate in the micelles, and
of a small amount sodium oleate and alkalinity can be esti- that binding of calcium should be similar to that of N25-
mated by the same model as for a solution without sodium 3S micelles. In fact, experimental values of calcium binding
oleate. Hirasaki and Lawson [11] have studied the associa- were compared for solutions containing 0.05% N25-3S and
tion of calcium with micelles of N25-3S and justified their
electrostatic model, which does not consider the fine points
of ion binding interaction, by data obtained with an ultrafil-
tration (UF) membrane. We performed UF when NaOl was
also present, determined the concentration of free calcium
ions, C 0 2+ , in the filtrate, and used this value to approxi-
Ca
mate free calcium concentration in the micellar solution. If
the measured concentration of free calcium ions is not avail-
able, it can be estimated from the model of Hirasaki and
Lawson [11].
Anionic surfactants have been found to mix ideally in
micelles. Accordingly, we assume here ideal mixing of N25-
3S and oleate, even though the former is ethoxylated. Thus,
with a solubility product Ksp of calcium oleate of 10−15 [6], Fig. 13. Precipitation boundary of calcium oleate in micellar solution of
the monomer concentration of oleate, COl 0 , is calculated by N25-3S.
−

Table 6
Calculation of precipitation boundary at 300 ppm hardness (CaCl2 )
Conc. of Conc. of Conc. of Conc. of mol% of Conc. of Total oleate Calculated Experiment
N25-3S N25-3S free Ca2+ mono. Ol− Ol− in Ol− in micelle Cm − + C0 boundary boundary
Ol Ol−
(wt%) CST C 0 2+ a C 0 − × 104 micelles C m − × 104 (mM × 104 ) (wt% × 105 ) (wt% ×105 )
Ca Ol Ol
0.0 0.0 3.00 5.77 0.0 0.0 5.77 1.76 –
0.01 0.22 2.87 5.90 1.13 7.9 13.8 4.22 9
0.02 0.44 2.79 5.99 1.15 33.4 39.4 12.0 15
0.03 0.66 2.73 6.05 1.16 59.4 65.4 19.9 22
0.04 0.88 2.59 6.21 1.19 87.2 93.4 28.5 30
0.05 1.10 2.47 6.36 1.22 128.5 134.9 41.1 42
Note. Unit of concentration is mM if not otherwise specified; conc. of mono. is monomeric concentration.
a Obtained by direct measurement of filtrate composition; C 0 (cmc of N25-3S at 300 ppm hardness) used is 0.15 mM based on the measured surfactant
S
concentration in the filtrate.
 H. Zhang et al. / Journal of Colloid and Interface Science 279 (2004) 539–547 547

300 ppm hardness with and without 0.0003% NaOl. No dif- foam stability after aging is similar to that for the anionic
ference was found. surfactant and presumably occurs for the same reason.
Although precipitation boundaries for hardness less than A simplified model for estimating the precipitation bound-
300 ppm were not actually determined experimentally, theo- ary including the enhancement of calcium content in the
retical calculation shows that the assumptions made for this electrical double layers of anionic surfactant (N25-3S) mi-
model are reasonable for calcium concentrations as low as celles yielded results in agreement with experiment. This
50 ppm for N25-3S concentrations up to 0.05 wt%. Thus, for model assumes that mixing of N25-3S and oleate in the mi-
other situations such as low concentration of NaOl at hard- celle is ideal; that micelles with a small amount of sodium
ness less than 300 ppm, a frequently occurring situation in oleate behave similarly to N25-3S micelles; and that calcium
laundry applications, this model can be used to predict the binding with micelle can be described by an electrostatic
amount of N25-3S needed to prevent calcium oleate from approach. It is demonstrated that predictions of this model
precipitating. Also, this same method could be used to esti- gave reasonable agreement with the measured precipitation
mate the precipitation boundary (or at least turbidity bound- boundary.
ary) for other anionic surfactants.

Acknowledgment
5. Summary
The authors acknowledge the National Science Founda-
Calcium soap, without dispersed oil, can decrease foam tion for supporting this work under grant CTS-9911954.
stability for both anionic (N25-3S) and nonionic (N25-7)
surfactants. For the anionic surfactant, defoaming by cal-
cium oleate appears to involve two mechanisms. One is in- References
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