Langmuir 2000, 16, 7905-7913 7905

Competitive Adsorption of the Anionic Surfactant SLS and

the Nonionic Surfactant Triton X-405 on Polystyrene Latex
Particles
Damien Colombié,† Katharina Landfester,‡ E. David Sudol,† and
Mohamed S. El-Aasser*,†
Emulsion Polymers Institute and Department of Chemical Engineering, Lehigh University,
Iacocca Hall, 111 Research Drive, Bethlehem, Pennsylvania 18015, and Max Planck Institute
for Colloid and Interface Science, Am Muehlenberg, 14424 Golm, Germany

Received December 3, 1999. In Final Form: July 13, 2000

The competitive adsorption of an anionic surfactant (SLS) and a nonionic surfactant (Triton X-405) on
monodisperse polystyrene particles (92 nm) was studied and quantified using a variety of experimental
techniques (filtration, desorption via serum replacement, 1H NMR spectroscopy). All experiments were
performed at 25 °C using a cleaned polystyrene latex (2% solids). In the competitive adsorption of a 1/1
molar ratio of SLS to Triton X-405 on the polystyrene particles, Triton X-405 adsorbed preferentially at
total surfactant concentrations in the aqueous phase below 2.5 × 10-3 M, due to its low free energy of
adsorption. At higher surfactant concentrations, the particle surface became saturated with Triton X-405,
and cooperative interaction between the two surfactants took place. An excess amount of the two surfactants
was noted on the surface. Triton X-405 was observed to adsorb on polystyrene particles precovered with
SLS. Approximately 20% of the SLS was removed from the surface below 7.0 × 10-4 M Triton X-405
aqueous concentration. However, cooperative adsorption occurred at higher concentrations, and a large
excess of the two surfactants was noted on the surface at saturation. SLS was also shown to adsorb on
polystyrene particles precovered with Triton X-405. The adsorption was small at SLS aqueous concentrations
below 2.5 × 10-3 M. At higher concentrations, more of the SLS was adsorbed, and an excess surfactant
content was present at the surface. No significant effect on the adsorption of Triton X-405 was noted for
increasing SLS concentrations in the system. Competitive desorption experiments were performed with
the two surfactants using serum replacement. SLS was found to desorb more readily than Triton X-405.
The particle surface composition was richer in Triton X-405 as the total surfactant concentration in the
system decreased.

Introduction surfactant molecules distribute between various locations

Various types of surfactants have been used in the
synthesis and stabilization of polymer latexes. Anionic
surfactants provide electrostatic stability as described by
the DLVO theory.1,2 The efficiency of such surfactants is
highly dependent on many parameters such as ionic
strength and pH. This dependency can be a major
drawback in terms of the stability of the latex. Nonionic
or polymeric surfactants provide steric stabilization. The
repulsion between particles is provided by the thermo-
dynamically favored steric repulsion of the adsorbed
materials.3,4 It is therefore practical to use mixtures of
anionic and nonionic surfactants in emulsion polymeri-
zation to combine different stabilization mechanisms. Most
industrial emulsion polymerization processes use mixtures
of anionic and nonionic emulsifiers. A common process
can be described as follows: the reaction is started with
the anionic surfactant, and the nonionic is added at a
higher conversion or as a poststabilizer. In emulsion
polymerization, the interaction between the surfactants
and the polymer particles is fundamental in the control
of the process and the final properties of the latex. The
†
Lehigh University.
‡Max Planck Institute for Colloid and Interface Science.
* To whom correspondence should be addressed.
(1) Derjaguin, B. V.; Landau, L. Acta Physicochim. USSR 1941, 14,
633.
(2) Verwey, E. J. W.; Overbeek, J. G. In Theory of Stabilization of
Lyophobic Colloids; Elsevier: Amsterdam, 1948.
(3) Ottewill, R. H. J. Colloid Interface Sci. 1977, 58, 357.
(4) Napper, D. H. In Polymeric Stablilization of Colloidal Dispersions;
Academic Press: New York, 1983.
(surface of the particles, aqueous phase, micelles, monomer
droplets) by a dynamic equilibrium. This behavior de-
termines phenomena such as the overall stability of the
latex, the nucleation of new particles, and limited ag-
gregation. Therefore, it is very important to study and
quantify the interaction between the surfactant molecules
and the polymer particles. Adsorption isotherms of a
surfactant on a latex particle surface are usually deter-
mined by following the change of the aqueous bulk
surfactant concentration with increasing amounts of
emulsifier in the system. Various techniques have been
used to determine adsorption isotherms of surfactants on
polymer particles.5,6
Although the adsorption of various nonionic surfactants
on latex particles has been widely studied,7-12 only a small
amount of work has been published on the competitive
adsorption of mixtures of anionic and nonionic surfactants
on latex particles. Kronberg and his team13,14 applied a
(5) Maron, S. H.; Elder, M. E.; Moore, C. J. Colloid Sci. 1954, 9, 104.
(6) Ahmed, S. M.; El-Aasser, M. S.; Pauli, G. H.; Poehlein, G. W.;
Vanderhoff, J. W. J. Colloid Interface Sci. 1980, 73, 388.
(7) Kronberg, B.; Kall, L.; Stenius, P. J. Dispersion Sci. Technol.
1981, 2, 215.
(8) Kronberg, B.; Stenius, P. J. Colloid Interface Sci. 1984, 102, 410.
(9) Zhao, J.; Brown, W. J. Phys. Chem. 1996, 100, 3775.
(10) Zhao, J.; Brown, W. J. Phys. Chem. 1996, 100, 5908.
(11) Haggerty, J. F.; Roberts, J. E. J. Appl. Polym. Sci. 1995, 58, 271.
(12) Colombié, D.; Landfester, K.; Sudol, E. D.; El-Aasser, M. S. J.
Colloid Interface Sci. 1998, 202, 554.
(13) Hulden, M.; Kronberg, B. J. Coat. Technol. 1994, 66, 67.
(14) Kronberg, B.; Linstrom, M.; Stenius, P. In Phenomena in Mixed
Surfactant Systems; Scamehorn, J. H., Ed.; ACS Symposium Series
311; American Chemical Society: Washington, DC, 1986.

10.1021/la9915825 CCC: $19.00 © 2000 American Chemical Society

Published on Web 09/19/2000
7906 Langmuir, Vol. 16, No. 21, 2000
thermodynamic model to the adsorption of such a mixture
by extending an existing model for mixed micelles. The
surface composition was governed in a manner similar to
the composition of the mixed micelles. The model was
correlated with experimental values obtained by solvent
depletion. It showed both theoretically and experimentally
that when a small amount of Triton X-100 was added to
a surface precovered with SLS, the nonionic surfactant
adsorbed readily and displaced the anionic surfactant.
Thus, there was a strong preferential adsorption in favor
of the nonionic surfactant. The results of Kronberg et al.
were corroborated by Bolze et al.15 using small-angle X-ray
scattering (SAXS) as a technique to probe the adsorption
of mixtures of SLS and Triton X-405 on the surface of
polystyrene latex particles. The latex particles were
covered with SLS and increasing amounts of Triton X-405
were added. Most of the Triton adsorbed and replaced the
SLS on the surface. When the particles were saturated
with Triton X-405 and increasing amounts of SLS were
added, the SLS also was able to remove some of the Triton
X-405 from the surface.
The objective of the current study is to obtain a better
qualitative and quantitative understanding of the mixed
adsorption of SLS and Triton X-405 on polystyrene
particles, as a prelude to conducting emulsion polymer-
izations with this pair of stabilizers. First, the adsorption
isotherms of SLS and Triton X-405 used as sole emulsifiers
are determined. Then various techniques are used to
determine the competitive adsorption of a 1/1 molar
mixture of SLS and Triton X-405. The adsorption of Triton
X-405 on PS particles precoated with SLS is next reported.
Similarly, the adsorption of SLS on PS particles precoated
with Triton X-405 is performed. As a comparison, the
adsorption isotherm of SLS on PS particles on which PEO
segments are grafted is determined. All the adsorption
results are correlated with the competitive desorption of
the two emulsifiers (using “serum replacement”). The
surface packing is estimated in all experiments.
Experimental Section
Materials. The anionic surfactant used in this study was
Ultrapure Bioregeant sodium lauryl sulfate (99+% pure, J.T.
Baker, Inc.). The cmc of this surfactant in water at 25 °C was
experimentally determined to be 6.0 mM. No further purification
was performed. The nonionic surfactant is a 70% aqueous solution
of Triton X-405 (octylphenoxy poly(ethylene oxide) with an
average number of ethylene oxide (EO) units of 40, Aldrich). The
nonionic surfactant is polydisperse, the number of EO units
ranging from 20 to 60. The nonionic emulsifier was dried at 70
°C for 24 h prior to use. The cmc of this dried surfactant in water
at 25 °C was experimentally determined to be 0.8 mM. The
monodisperse polystyrene (PS) latex used (LS-1039E, The Dow
Chemical Co.) has a number-average diameter of 92 nm
(determined by electron microscopy16). In one experiment, this
monodisperse polystyrene latex was modified by grafting PEO
segments on the surface via a seeded copolymerization. For this
synthesis, styrene monomer (Aldrich) was washed with a 10 wt
% NaOH solution to remove the inhibitor and distilled no more
than 2 weeks before the polymerization was run. The comonomer,
poly(ethylene glycol) methyl ether methacrylate (PEGMA, 50%
solution in water, Mn ) 2080 g/mol Aldrich), was used as received.
Prior to use, the latexes (5.7% solids) used in these adsorption
studies were cleaned for 3 weeks by serum replacement to remove
any surfactant and electrolyte remaining from their preparation.
The surface charge density of this cleaned latex was 2.5 µC/cm2.
The conductivity of the effluent was monitored to determine the
extent of cleaning. The water used was deionized (DI). D2O
(Cambridge Chemical Laboratories) and chloroform (99%+,
(15) Bolze, J.; Horner, K. D.; Ballauf, M. Colloid Polym. Sci. 1996,
274, 1099.
(16) Miller, C. M. Ph.D. Dissertation, Lehigh University, 1995.
Colombié et al.
Aldrich) were used as received. Diimidium bromide (Aldrich),
sodium chloride (Aldrich), and the citrate buffer solution (Aldrich)
were used as received.
Synthesis and Characterization of the PEO Grafted
Polystyrene Latex. The seeded emulsion polymerization was
carried out as follows. The seed latex (100 g of uncleaned latex,
20% solids) was filtered to remove any large aggregates and
poured into a glass bottle. The surfactant (0.07 g of sodium lauryl
sulfate) and buffer (0.05 g of sodium bicarbonate) were added,
and the mixture was stirred at 300 rpm for 2 h using a magnetic
bar. The monomers (0.80 g of styrene and 1.60 g of PEGMA)
were then added to swell the latex particles with overnight mixing.
The initiator (0.22 g of potassium persulfate) was then added,
and the bottle was capped and placed in a bottle polymerizer at
60 °C for 24 h.
The resulting latex was cleaned for 3 weeks by serum
replacement to remove the surfactant and impurities in the latex.
The serum was clear during the whole course of the cleaning
process, suggesting the absence of any secondary nucleation
during the synthesis. This was confirmed by transmission electron
microscopy (Phillips 400 transmission electron microscope). A
sample of the resulting latex was dried in an oven at 70 °C for
24 h. The sample was redissolved in deuterated chloroform for
1H NMR analysis (details given in the following section).
Resonances for the protons of the polystyrene backbone chain
(-CH(Ph)-CH2-) were visible between 1.2 and 2.2 ppm.
Aromatic protons resonances were observed between 6.5 and 7.5
ppm. The solvent peak (chloroform) was located at 7.2 ppm. A
peak at 3.6 ppm representing the resonance of ethylene oxide
protons (-O-CH2-CH2-) was noted. These data confirmed that
the grafting of some PEGMA onto the PS particles was successful
during this reaction. From the NMR spectrum, it was possible
to evaluate the fraction of grafted PEGMA by integration of the
phenyl protons and the ethylene oxide protons. From the ratio
of the areas of these peaks, the fraction of grafted PEGMA was
estimated to be 45% of the initial amount (i.e., 1.74 × 10-4 mol).
This amount corresponds to a density of 8.5 × 1016 molecules of
PEGMA per m2 of particle surface.
Determination of the Adsorption Isotherms. Filtration.
This technique is based on the extraction a small volume of the
aqueous phase from a latex for surfactant analysis. To reduce
the perturbations created by the extraction of the samples
containing varying amounts of surfactant, the following procedure
was applied. The desired amount of surfactant was added to
approximately 25 g of cleaned monodisperse polystyrene latex
diluted to 1.9% solids. The sample was allowed to equilibrate by
stirring for 24 h before the extraction was performed. A 50 cm3
serum replacement cell (Advantec MFS) with a polycarbonate
membrane (pore size 100 nm, Osmotics) was rinsed thoroughly
with DI water and allowed to dry for 24 h. The latex sample was
poured in the cell, and approximately 3 cm3 of the aqueous phase
was extracted and analyzed.
Desorption by Serum Replacement. In some cases, the tech-
nique developed by Ahmed et al.6 was used. The experimental
procedure is as follows. In experiment DC-SR1, SLS (0.23 g) was
added to a 100 g sample of cleaned monodisperse polystyrene
latex diluted to 1.9% solids. In experiment DC-SR2, SLS and
Triton X-405 were added to the latex in combination (0.38 and
0.55 g, respectively). The samples were stirred for 24 h prior to
the experiment. A 400 cm3 serum replacement cell (Advantec
MFS) with a polycarbonate membrane (pore size 100 nm,
Osmotics) was rinsed thoroughly with DI water and allowed to
dry for 24 h. The latex was then charged into the serum replace-
ment cell. DI water was passed through the cell, and the surfact-
ant content in the exit stream was monitored over approximately
8 h. The amounts of water extracted from the cell were carefully
weighed to perform an accurate mass balance on the system.
Surfactant Concentrations. The SLS concentration in the
aqueous phase samples was monitored by two techniques. The
conductivity of the aqueous solutions was determined at 25 °C
using a YSI model 32 conductance meter, and the SLS concen-
tration was determined via a calibration curve. However, the
conductivity of mixed surfactant solutions can be affected by the
presence of micelles, which cannot be readily calibrated. As a
consequence, colorimetry was also used to determine the SLS
concentration.
SLS and Triton X-405 on Polystyrene Latex
The colorimetry technique used here, first reported by Orthgieb
and Dobias,17 allows one to measure the concentration of sulfate
or sulfonate groups and was successfully applied by Urquiola et
al.18 to monitor the concentration of the reactive surfactant,
sodium dodecyl allyl sulfosuccinate, in an emulsion polymeri-
zation. A 200 mL solution of diimidium bromide dye was prepared
as follows: 0.1 g of diimidium bromide and 5.0 g of sodium chloride
were mixed in 100 mL of citrate buffer solution (pH ) 4) and
diluted to 200 mL with DI water. Surfactant solution samples
were diluted 10, 15, or 40 times so that their concentration ranged
from 2 × 10-5 to 3 × 10-4 M. A 2.0 g sample of dye solution was
added to 2.0 g of the diluted surfactant solution. The sample was
shaken vigorously for 2 min to allow the formation of the dye-
SLS complex. A 3.0 g sample of chloroform was added. The
mixture was stirred for 3 min to allow the extraction of the dye-
SLS complex into the oil phase. The chloroform phase (bottom
of the tube, purple color) was separated from the aqueous phase.
The optical absorbance of the chloroform phase at a wavelength
of 525 nm was measured against a reference solution of pure
chloroform using a Spectronics Genesys 2 UV/vis spectrometer.
The Triton X-405 aqueous concentration was monitored by
measuring the absorbance of the phenyl ring (π f π* transitions)
in the UV range at 223 and 274 nm using the UV/vis spectrometer.
NMR Technique. This technique was described in detail in a
previous article.12 Due to a large water signal in the proton NMR
spectrum of the latex itself, the polystyrene latex had to be
prepared carefully by replacing the water with D2O. An 8.73 g
amount of cleaned monodisperse latex (5.74% solids) was placed
in a serum replacement cell with 16.32 g of D2O. Three successive
additions of 35 g of D2O were performed, and 35 g of the serum
was recovered after each addition so that most of the water was
replaced by D2O (>99%). At the end of the procedure, 24.42 g of
polystyrene latex (1.9% solids) in deuterated water was recovered.
This procedure was repeated four times so that approximately
100 g of latex was available for sample preparation. Three stock
solutions of Triton X-405 in D2O (9.70 × 10-2, 9.22 × 10-3, and
1.06 × 10-3 M) and two stock solutions of SLS in D2O (9.35 ×
10-3 and 9.90 × 10-2 M) were subsequently prepared. The
different samples were prepared from these solutions to adjust
the initial surfactant concentrations. All samples had an ap-
proximate volume of 1 cm3. The evaluation is based on the ratios
of the peaks to each other. As a consequence, the precise volume
was not important.
All NMR spectra were obtained using a Bruker 500 MHz
spectrometer. The pulse length was 3.0 µs. To minimize the water
proton contribution in the spectra, they were presaturated with
the frequency of the water peak. To obtain a good signal-to-noise
ratio in the spectra, 200-1500 scans were accumulated. The
repetition delay was chosen to be 6 s to ensure full relaxation of
all protons. Tetramethylsilane (TMS) was used as an external
standard.
Results and Discussion
Adsorption Behavior of Each Individual Surfact-
ant. Adsorption of SLS on PS Particles. The adsorption
isotherm of SLS on polystyrene particles was determined
using the serum replacement technique (experiment DC-
SR1). The objective of this determination was to charac-
terize the adsorption of SLS by itself for comparison to its
adsorption in the presence of Triton X-405. The adsorption
isotherm at 25 °C is shown in the Supporting Information
(Figure a), where the number of molecules of SLS adsorbed
(for a particle surface of 1 m2) is plotted as a function of
the aqueous concentration of the surfactant. The adsorp-
tion behavior is as expected; at low SLS concentrations
most of the SLS is adsorbed with the proportion (SLS
adsorbed/SLS aqueous phase) decreasing as the surface
approaches saturation.
Several models have been used to describe qualitatively
and quantitatively the adsorption of surfactants on
(17) Orthgieb, E.; Dobias, B. Poster presented at the 7th Symposium
on Surfactants in Solution, Ottawa, 1988.
(18) Urquiola, M. B. Ph.D. Dissertation, Lehigh University, 1994.
Langmuir, Vol. 16, No. 21, 2000 7907
polymer particles,19 one of which is the Langmuir ap-
proach, which has been used successfully in many cases.
This approach is based on the following assumptions. The
surface of the particles is energetically uniform. No
interaction exists between the adsorbed molecules. All
mechanisms for adsorption are identical. The adsorption
is up to (and including) a complete monolayer on the
surface. Although all of these assumptions are not typically
met by surfactant adsorption, the Langmuir model has
nonetheless been accepted to provide an adequate de-
scription of the process. In the Langmuir adsorption model,
eqs 1 and 2 can be derived:
asc
Γ) (1)
1 + bc
where Γ is the moles of solute adsorbed per unit surface
area, c is the aqueous surfactant concentration, and as
and b are Langmuir constants. b is the ratio of the rate
constant for adsorption over the rate constant for de-
sorption. as is the area occupied by one molecule of
surfactant at saturation for a monolayer of emulsifier on
the surface of the polymer particles. Equation 1 can be
transformed into eq 2, the linear Langmuir form, to allow
the experimental determination of as and b.
1 1
) as + (2)
Na bc
where Na is the number of molecules of SLS adsorbed per
unit area when the aqueous concentration of the surfactant
is c. The standard molar free energy for adsorption (∆Gads,
J/mol) can be calculated from eq 3.
∆Gads ) -RT ln(bω) (3)
where T is the absolute temperature (K) and ω is the
number of water molecules per dm3 of water (55.6 mol/
dm3). From the Langmuir adsorption isotherm, the surface
area per molecule of SLS is 44 Å2, the adsorption constant
is 550 dm3/mol, and the Gibbs adsorption free energy is
-25.6 kJ/mol. The surface area per molecule found here
is the same as that reported by Ahmed20 for the same
system (44 Å2). A similar molar energy for adsorption of
SLS on PBMA particles has been reported by Kronberg
et al.14 (-23.7 kJ/mol).
Adsorption Isotherm of Triton X-405 on PS Particles
via Proton NMR. In a recent study,12 the adsorption
isotherm of Triton X-405 molecules on polystyrene par-
ticles was determined using 1H NMR spectroscopy (Figure
b in the Supporting Information). The corresponding
Langmuir parameters can be calculated from the data up
to and including the plateau region. Above this concen-
tration, the Langmuir approximation is no longer valid
due to the greater than monolayer coverage of the particles.
From the adsorption isotherm, the surface area per
molecule of Triton X-405, the adsorption constant, and
the Gibbs free energy for adsorption can be determined.
The estimated surface area per molecule (172 Å2) is similar
to that found by Kronberg et al.7 for a similar poly(ethylene
oxide) type surfactant (200 Å2 for an emulsifier having an
average chain length of 50 EO units). The molar energy
for adsorption (-36.2 kJ/mol) is similar to that of PEO on
PBMA particles as reported by Kronberg et al.14 (-34.1
(19) Adamson, W. A. Physical Chemistry of Surfaces; 5th ed.; Wiley:
New York, 1990.
(20) Ahmed, S. M. Ph.D. Dissertation, Lehigh University, 1979.
7908 Langmuir, Vol. 16, No. 21, 2000
Figure 1. Adsorption isotherm of SLS and Triton X-405 on
polystyrene particles (1 m2 surface area) at 25 °C from a 1/1
molar SLS/Triton X-405 mixture obtained via filtration/
conductivity/colorimetry (SLS) and proton NMR (Triton X-405).
kJ/mol). This energy is very low compared to the free
energy of adsorption for SLS (-25.6 kJ/mol).
Competitive Adsorption of SLS and Triton X-405
on PS Particles. As shown in the previous section, SLS
and Triton X-405 have very different adsorption behaviors
on the PS particles, when used alone. Triton X-405 has
a significantly lower free energy for adsorption than SLS.
This energy as well as the possible interaction between
the two types of surfactants will be determining param-
eters in the competitive adsorption of the two emulsifiers.
Even though the NMR technique was very powerful in
the determination of the adsorption behavior of nonionic
surfactants, it was not possible to use it for the deter-
mination of the SLS adsorption behavior. The SLS
molecules adsorbed on the surface are not mobile enough
to be detected within the 5 MHz window of the proton
NMR spectrum. At high SLS concentrations, a signal for
the aqueous SLS protons was detected, but the correlation
to the actual concentration was not successful. As a
consequence, a variety of techniques are used in combina-
tion for the determination of the competitive adsorption
of SLS and Triton X-405 (filtration/colorimetry and
filtration/conductivity for SLS; proton NMR and filtration/
UV spectroscopy for Triton X-405). To simplify the
experimental determination of the adsorption isotherms,
all experiments were performed at 25 °C using a mono-
disperse polystyrene latex (1.9% solids, 92 nm). All
adsorption results are reported for a sample of latex having
1 m2 of surface available for adsorption.
Adsorption of a 1/1 Molar Ratio of SLS and Triton X-405.
Figure 1 depicts the adsorption isotherms of SLS and
Triton X-405 on polystyrene particles at 25 °C from 1/1
molar SLS/Triton X-405 solutions. The first three data
points for SLS were determined by colorimetric titration
only since the conductivity technique was not sensitive
enough to detect the aqueous SLS at extremely low
concentrations. However, both techniques are consistent
for the determination of the adsorption of SLS at the higher
concentrations. At very low surfactant concentrations, both
surfactants adsorb strongly on the surface of the poly-
styrene particles. The slope of the number of adsorbed
surfactant molecules as a function of total aqueous
surfactant concentration is high. However, this slope
decreases significantly above 3 × 10-4 M total aqueous
surfactant concentration, indicating less adsorption of both
surfactants with further increases in their concentrations.
Up to 2 × 10-3 M total aqueous surfactant concentration,
Triton X-405 adsorbs preferentially on the surface of the
polystyrene particles as more Triton X-405 molecules
occupy the surface of the particles than SLS molecules.
Between 2 × 10-3 and 3 × 10-3 M total aqueous surfactant
Colombié et al.
Figure 2. (a) Molar ratio of SLS to Triton X-405 in the overall
system (solid line), in the aqueous phase, and on the polystyrene
particle surface and (b) percentage of adsorbed SLS and Triton
X-405 as a function of the total surfactant concentration in the
aqueous phase.
concentration, the adsorption of the two surfactants
becomes more competitive. Eventually there is more SLS
on the surface than Triton X-405.
In Figure 2a, the SLS to Triton X-405 molar ratio in the
aqueous phase and on the particle surface is plotted as a
function of the total aqueous surfactant concentration.
The same trend described above is observed: at low
concentrations, the aqueous phase is richer in SLS. As
reported in a previous section and in the literature,8
nonionic surfactants such as Triton X-405 have been shown
to have a strong affinity for the surface of the particles
(∆Gads ) -36 kJ/mol). This has been attributed to an
exclusion of the surfactant from the water phase (to
prevent hydrophobe-water interactions). Lateral interac-
tions on the particle surface also play an important role
in decreasing the total free energy in the system. With
increasing concentration, the ratio of the two surfactants
in the aqueous phase becomes close to the total ratio of
the two surfactants in the system. At intermediate
concentrations, the particle surface may be saturated with
the nonionic surfactant. Some of the Triton X-405 remains
in the water phase and associates with SLS as described
in the literature.21 Finally, the presence of mixed micelles
affects the partitioning of both surfactants, and more of
the Triton X-405 will be present in the aqueous phase.
The cmc of a 1/1 molar solution of SLS and Triton X-405
was measured to be 1.3 × 10-3 mol/dm3 total surfactant
concentration at 25 °C (determined by surface tension
measurements). Of course, this was measured in the
absence of particles and may not be the same ratio as
when micelles appear in the presence of the particles.
Figure 2b depicts the partition of both SLS and Triton
X-405 between the particle surface and the aqueous phase
as a function of the total aqueous surfactant concentration.
(21) Cabane, B. J. Phys. Chem. 1977, 81, 1639.
SLS and Triton X-405 on Polystyrene Latex
Table 1. Comparison between the Theoretical and Experimental Polystyrene Particle Surface Coverage (for a Particle
Surface of 1 m2) at Saturation in the Competitive Adsorption Experiments
1/1 molar SLS/Triton
X-405 adsorption on
experiment bare PS particles
nSLS sat theoretical (molecules) 5.2 × 1017
nSLS sat experimental (molecules) 1.0 × 1018
excess SLS (%) 192
nTriton X-405 sat theoretical 4.5 × 1017
(molecules)
nTriton X-405 sat experimental 8.8 × 1017
(molecules)
excess Triton X-405 (%) 194
SLS/Triton X-405 molar ratio at 1.1
saturation
At low surfactant concentrations, the proportion of Triton
X-405 adsorbed is almost constant (around 88%, over a
narrow range however), whereas a smaller and increasing
proportion of SLS is adsorbed (from 60 to 70%). As the
concentration of the surfactants increases, a smaller
proportion of both surfactants is adsorbed as might be
expected as the surfaces become more crowded. Above 1.5
× 10-3 M, however, the proportion of SLS adsorbed
increases again, this being attributed to a cooperative
adsorption of the two surfactants. Eventually, above 3.0
× 10-3 M, the proportion of both adsorbed surfactants
decreases as the surface becomes fully saturated.
To determine the surface packing at saturation, the
following approach was used. The theoretical number of
molecules of the two surfactants packed on the polystyrene
particles (having 1 m2 of available surface area) is
calculated, knowing the experimental molar ratio of the
two surfactants. This calculation is based on the monolayer
unit surface coverage for each surfactant (determined in
the previous section). No interaction between the two
surfactants is taken into account in the calculation. The
number obtained for each surfactant is subsequently
compared with the actual number determined experi-
mentally in the adsorption isotherm (in which SLS/Triton
X-405 interactions may occur). The excess surfactant on
the surface of the particles is then calculated.
For a particle surface of 1 m2, the theoretical number
of molecules of the two surfactants (nSLS th and nTriton X-405 th,
respectively) at saturation in a monolayer without in-
teraction should be described by
nSLS thas0 SLS + nTriton X-405 thas0 Triton X-405 ) 1 (4)
where as0 SLS is the surface area occupied by one molecule
of SLS on polystyrene particles in the absence of Triton
X-405 and as0 Triton X-405 is the surface area occupied by
one molecule of Triton X-405 on polystyrene particles in
the absence of SLS. At saturation, the molar ratio of the
two surfactants (r) can be determined experimentally. By
assuming the theoretical ratio would be equal to the
experimental ratio at saturation:
nSLS th
r)
nTriton X-405 th
Equations 4 and 5 can be solved, and the result is given
in the following equations:
r was to adsorb on the latex particles with a 44 Å2 surface
nSLS th )
ras0 SLS + as0 Triton X-405
1
nTriton X-405 th )
ras0 SLS + as0 Triton X-405
Langmuir, Vol. 16, No. 21, 2000 7909
Triton X-405 SLS adsorption on SLS/Triton X-405
adsorption on SLS Triton X-405 competitive desorption
covered PS particles covered PS particles from PS particles
7.2 × 1017 1.5 × 1018 8.0 × 1017
1.6 × 1018 2.3 × 1018 1.5 × 1018
222 159 187
4.0 × 1017 2.1 × 1017 3.8 × 1017
9.8 × 1017 3.3 × 1017 7.1 × 1017
244 155 187
1.6 7.0 2.1
The excess surfactant (e) on the particle surface is defined
as
nsurf exp
e) × 100 (8)
nsurf th
The theoretical and experimental values for the number
of molecules of both emulsifiers on the surface of the
polystyrene particles (for 1 m2 of surface) are given in
Table 1. The results indicate a large excess of both of the
surfactants on the particles at saturation when they ad-
sorb simultaneously (>190%). Several possible explana-
tions can be proposed for this cooperative adsorption.
When more Triton X-405 is available in the aqueous
phase, the association with SLS21 may lead to a greater
adsorption of the hydrophobic complex. Just as in the
formation of mixed micelles, the exclusion of the SLS/
Triton X-405 complex from the aqueous phase is ener-
getically favored. Furthermore, some interactions on the
particle surface can decrease the free energy for adsorp-
tion. The electrostatic repulsion between the sulfate end
groups of the SLS molecules could be shielded by the
presence of the nonionic surfactant, allowing a closer
packing on the surface. The Triton X-405 may also
reorganize its structure by being in a more extended
conformation. In this case, the loss of entropy due to the
extended conformation of the polymeric chain can be
balanced by energetically favored side chain interactions
(limiting water-hydrophobe interactions). Eventually, it
is possible that SLS adsorbs in the hairy layer created
by the nonionic surfactant in the vicinity of the particle.
Its adsorption may be favored by side-chain interac-
tions.
Adsorption of Triton X-405 on PS Particles Pre-
covered with SLS. In most industrial emulsion polym-
erization processes, the surfactants are added at various
process times in the reaction. Very often, the latex is
synthesized using an anionic surfactant. At the end of the
reaction, a nonionic surfactant can then be added to
enhance stability of the system. As a consequence, it can
be helpful to know what is the adsorption behavior of a
nonionic surfactant on latex particles already stabilized
with an adsorbed anionic surfactant. In this experiment,
(5) 0.3269 g of SLS was first added to 249.52 g of the cleaned
monodisperse polystyrene latex (2% solids, 92 nm). The
SLS was allowed to adsorb for 24 h to ensure equilibrium.
The amount of SLS added to the system is that required
to cover 100% of the surface of the particles if all the SLS
(6) area per molecule. The Triton X-405 was then added to
the latex. The mixture was stirred for 24 h before any
measurement was performed. Under these conditions,
(7) equilibrium was assumed to be established between all
the components of the system.
7910 Langmuir, Vol. 16, No. 21, 2000 Colombié et al.

Figure 3. Number of molecules of SLS and Triton X-405 on

1 m2 of polystyrene particles (precovered with an amount of
SLS sufficient to theoretically cover 100% of the surface) at 25
°C for increasing Triton X-405 concentrations obtained via
filtration/colorimetry (SLS) and proton NMR (Triton X-405).

The adsorption isotherm (25 °C) of Triton X-405 on the

polystyrene particles precovered with SLS is depicted in
Figure 3. At low concentrations, Triton X-405 adsorbs
readily on the surface of the particles, despite the presence
of SLS at the surface. As a consequence, some of the SLS
initially present on the surface is displaced by the Triton
X-405 (between 0 and 8 × 10-4 M aqueous Triton X-405)
as seen in Figure 3. This displacement reaches a minimum
at 2.5 × 10-4 M aqueous Triton X-405. After this point, Figure 4. (a) Molar ratio of SLS to Triton X-405 in the whole
the SLS begins to readsorb, reaching (and exceeding) its system (total), in the aqueous phase, and on the polystyrene
original level of adsorption at about 8 × 10-4 M aqueous particles (precovered with SLS) at 25 °C and (b) percentage of
Triton X-405. As reported in the previous section, some SLS and Triton X-405 adsorbed for increasing Triton X-405
cooperative adsorption probably occurs as SLS and Triton concentrations obtained via filtration/colorimetry (SLS) and
proton NMR (Triton X-405).
X-405 increasingly associate in the aqueous phase and on
the particle surface. The adsorption of Triton X-405 has
been reported to be extremely strong, and the removal of
SLS from the surface has already been observed by Bolze
et al.15 using SAXS (small-angle X-ray scattering).
In Figure 4a, the molar ratios of SLS to Triton X-405
in the whole system, on the surface of the particles, and
in the aqueous phase are plotted as a function of the
aqueous phase concentration of Triton X-405. At low
nonionic surfactant concentrations (below 8.0 × 10-4 M
aqueous Triton X-405), the molar ratio of SLS to Triton
X-405 in the aqueous phase is significantly higher than
the ratio of the two surfactants in the entire system. Figure
4b describes the partition of both SLS and Triton X-405
between the particle surface and the aqueous phase as a
function of the Triton X-405 aqueous surfactant concen- Figure 5. Number of molecules of SLS and Triton X-405 on
tration. The desorption and readsorption of SLS at low 1 m2 of polystyrene particles (precovered with an amount of
Triton X-405 concentrations is also reflected in this curve; Triton X-405 sufficient to cover 100% of the surface) at 25 °C
for increasing SLS concentrations obtained via filtration/
the proportion of adsorbed SLS decreases (from 62% to colorimetry (SLS) and proton NMR (Triton X-405).
53%) and then increases (from 53% to 70%) with increasing
concentration of Triton X-405. This indicates that more 0.4832 g of Triton X-405 was added to 250.02 g of a cleaned
SLS is finally adsorbed on the particles in the presence monodisperse polystyrene latex (2% solids, 92 nm). This
of the nonionic surfactant than in its absence. amount of Triton X-405 added to the system was enough
Equations 4-7 were also applied to this adsorption data, to cover 100% of the surface of the particles if all the Triton
and the results are given in Table 1. Once again, a strong X-405 was to adsorb on the latex particles with a 170 Å2
excess of both surfactants (more than 200%) is noted. The area per molecule. The Triton X-405 was allowed to adsorb
molar ratios of SLS to Triton X-405 at different locations for 24 h. The SLS was then added to the latex. The mixture
(aqueous phase, particle surface, whole system) are very was stirred for another 24 h before any measurement was
close at the high Triton X-405 concentration. The total performed. As in the previous section, a dynamic equi-
ratio of the two emulsifiers is close to 1.9, as well as the librium is assumed to be established between all the
ratio on the surface (with a slight predominance of SLS components of the system.
over Triton X-405) and in the aqueous phase. The adsorption isotherm (25 °C) of SLS on the poly-
Adsorption of SLS on PS Particles Precovered styrene particles precovered with Triton X-405 is given in
with Triton X-405. The experiment described in the above Figure 5. No Triton X-405 was removed from the surface
section can be reversed by fully covering the polystyrene of the polystyrene particles when SLS was added to the
particles with Triton X-405. The adsorption isotherm of system even though SLS is shown to adsorb. The results
SLS is determined subsequently. In this experiment, given by NMR and UV spectroscopy are consistent, even
SLS and Triton X-405 on Polystyrene Latex
Figure 6. (a) Molar ratio of SLS to Triton X-405 in the whole
system (total), in the aqueous phase, and on the polystyrene
particles (precovered with Triton X-405) and (b) percentage of
SLS and Triton X-405 adsorbed at 25 °C for increasing SLS
concentrations obtained via filtration/colorimetry (SLS) and
filtration/UV spectroscopy (Triton X-405).
though some systematic discrepancy is noted between the
two techniques. These results confirm that the Triton
X-405 is bound tightly to the polymer surface, once it has
been adsorbed. The addition of another adsorbing species
does not seem to affect its affinity for the surface. This
should be important with respect to the resulting latex
properties particularly in terms of stability, especially
when the latex is formulated with a lot of additives.
However, it may be a problem when the latex must be
coagulated by chemical means or when the surfactant
must be removed for other studies. The adsorption of the
SLS is not very strong as shown in Figure 5. The SLS
continues to adsorb on the particles up to the highest
concentration used here ([SLS]aq ) 5 × 10-3 M). This is
evidence for cooperative adsorption. As expected, the
aqueous phase also becomes richer in SLS molecules.
In Figure 6a, the molar ratios of SLS to Triton X-405
in the whole system, on the surface of the particles, and
in the aqueous phase are plotted as a function of the
aqueous phase concentration of Triton X-405. Since the
amount of Triton X-405 on the surface is not varying, the
main factor determining the SLS to Triton X-405 ratio in
the aqueous phase and on the particle surface is the
adsorption behavior of the SLS. Figure 6b describes the
partitioning of both SLS and Triton X-405 between the
particle surface and the aqueous phase as a function of
the SLS aqueous surfactant concentration. No variation
in the Triton X-405 partitioning is observed over the range
of concentrations studied. The SLS partitioning also
reflects the cooperative adsorption that takes place in the
system.
Once again, eqs 4-7 were applied to these data, and
the results are given in Table 1. As before, a strong excess
of adsorbed surfactants is noted when mixtures of surf-
actant are used. The surface packing is greatly increased
Langmuir, Vol. 16, No. 21, 2000 7911
Figure 7. Number of molecules of SLS on 1 m2 of polystyrene
particles (precovered with Triton X-405 or functionalized with
PEO segments) at 25 °C for increasing SLS concentrations
obtained via filtration/colorimetry.
when both surfactants are used in combination. The
proposed mechanism for this cooperative adsorption is
similar to the one described in the previous sections.
Adsorption of SLS on a PS Latex with Grafted
PEO Segments. The previous section showed that SLS
adsorbed on a PS latex precoated with Triton X-405. The
nonionic surfactant was physically bound to the surface
during this experiment as no desorption of Triton X-405
was noted over the range of concentrations studied. A
comparative experiment was performed by determining
the adsorption isotherm of SLS on a PS latex with
chemically bound PEO segments (Figure 7). The chemical
nature of the grafted PEO segments is close to the Triton
X-405 based on the average number of ethylene oxide units
(45 for the PEGMA, as opposed to 40 for the Triton X-405).
However, the end group is a methyl group, as opposed to
the hydroxyl at the end of the chain in Triton X-405. For
a sample having 1 m2 of particle surface area, there are
8.5 × 1016 molecules of grafted PEO segments. This is
lower than the density of Triton X-405 precoating the latex
particles in the previous section (4.4 × 1017 molecules).
As noted in Figure 7, SLS adsorbed on the surface of
the polystyrene particles, regardless of whether the PEO
segments were physically or chemically bound. When the
nonionic emulsifier was used, the adsorption of the SLS
was lower than in the case of the latex functionalized
with PEO segments, where a somewhat stronger initial
adsorption was noted. However, this difference may reside
in the number of PEO chains at the surface of the particles
(lower density). The initial adsorption on the bare surface
is higher for similar reasons. At higher concentrations,
the adsorption on the bare surface approaches saturation.
When chemically or physically bound PEO are used, an
increased adsorption of the SLS is noted. These results
suggest that the adsorption of the SLS may not occur
directly at the surface of the particles in the presence of
PEO segments. Instead, SLS/PEO complexes21 may form
at the interface and a multilayer adsorption phenomenon
is likely to occur.
Competitive Desorption. An increased understanding
of the adsorption behavior of surfactants can be obtained
by desorbing them from the surface of the latex particles
(92 nm, 1.9% solids). In experiment DC-SR2, the initial
total concentrations were 13 and 3 mM for SLS and Triton
X-405, respectively. To perform the competitive desorption
experiment, two separate methods of monitoring the
surfactant concentration must be used: conductivity for
SLS and UV spectroscopy for Triton X-405. The concen-
tration profile in the exit stream from the serum replace-
ment cell for experiment DC-SR2 is plotted in Figure c of
the Supporting Information as a function of the number
7912 Langmuir, Vol. 16, No. 21, 2000
Figure 8. Adsorption isotherms of SLS and Triton X-405 on
PS particles obtained by the desorption technique at 25 °C.
Figure 9. Ratio of SLS to Triton X-405 in the overall system
(total), in the aqueous phase, and on the particle surface as a
function of the total surfactant concentration in the aqueous
phase obtained by desorption at 25 °C.
of residence volumes (q/v, where q is the volume of serum
recovered and v is the volume of the aqueous phase
contained in the cell). The desorption rates are different
for the two surfactants. SLS has a high rate of desorption
compared to Triton X-405. As a consequence, the ratios
and amounts of the two surfactants will vary simulta-
neously. Even though, it is not possible to control this
variation, the partition of the two surfactants can still be
determined by mass balance for the different ratios and
amounts sampled during the experiment.
The number of molecules of both surfactants adsorbed
on the surface of the polystyrene particles at 25 °C as a
function of the total aqueous surfactant concentration is
given in Figure 8. The data obtained from the desorption
experiment are very similar to the data obtained through
the adsorption studies. At low surfactant concentrations,
there is a preferential adsorption of Triton X-405 on the
surface. Little desorption of the nonionic surfactant is
observed during the experiment. Above 5 × 10-3 M, SLS
is in the majority on the surface of the particles. This
preferential adsorption can be characterized by comparing
the molar ratio of the two surfactants at the particle surface
and in the water phase to the total ratio of the two
surfactants in the system, since there is a continuous
variation of the total composition. These ratios are plotted
in Figure 9. The initial total molar ratio of SLS to Triton
X-405 (before desorption) is 4.5. The total molar ratio of
SLS to Triton X-405 decreases with decreasing surfactant
concentration (from 4.0 to 1.3), since the anionic surfactant
desorbs more readily (as mentioned above). As a conse-
quence, the aqueous phase is rich in SLS (SLS/Triton X-405
molar ratio ranging from 8 to 12) as compared to the whole
system. The strong preferential adsorption of the nonionic
surfactant is shown by the low SLS to Triton X-405 ratio
at the surface as compared to the total ratio in the system
Colombié et al.
(ranging from 2.1 to 0.2). In terms of the surface composi-
tion, the trend observed in this desorption experiment is
very similar to that observed in the adsorption experi-
ments.
The surface coverages were calculated as before, and
the results are given in Table 1. Once again, a strong
excess of adsorption (around 185%) is noted when mixtures
of surfactant are used. The results are consistent with the
data obtained from the adsorption isotherms.
Conclusions
In this work, the competitive adsorption of mixtures of
SLS and Triton X-405 on PS particles was studied at 25
°C. First, the individual adsorption behaviors of SLS and
Triton X-405 were determined. The adsorption isotherm
of SLS was determined using the desorption technique.
The adsorption data were fitted to the Langmuir equation.
The area occupied by one molecule of SLS on the PS
particles was determined to be 44 Å2, and the Gibbs free
energy for adsorption was -26 kJ/mol. The adsorption
isotherm of Triton X-405 was monitored by a quantitative
nondisruptive technique based on proton NMR. At low
surfactant concentrations, the adsorption data were fitted
to the Langmuir equation. The area occupied by one
molecule of Triton X-405 on the PS particle surface was
172 Å2, and the Gibbs free energy for adsorption was -36
kJ/mol, showing a lower adsorption energy than SLS.
Deviations from the Langmuir model were observed at
higher concentrations. This was possibly due to incipient
phase separation between the surfactant molecules in the
aqueous phase (containing micelles) and those at the
surface of the particles. Other possible reasons are the
adsorption of a second layer or an effect of the polydis-
persity of the nonionic surfactant.
In the adsorption from 1/1 molar ratio solutions of SLS
and Triton X-405, the following features were noted. At
low surfactant content, there was a strong adsorption of
Triton X-405 and SLS, the nonionic surfactant being
preferentially adsorbed at the surface of the particles. At
higher concentrations, the surface composition approached
the initial 1/1 molar ratio. A strong excess of adsorbed
surfactant was noted when both surfactants were used
together. When Triton X-405 was adsorbed on PS particles
precovered with SLS, the anionic emulsifier was removed
from the surface at low Triton X-405 contents, due to its
higher energy of adsorption. With further increases in
the Triton X-405 concentration, the anionic surfactant
readsorbed, and a large excess of both adsorbed surfactants
was noted at the surface. When SLS was adsorbed on
particles precovered with Triton X-405, the amount of
adsorbed anionic emulsifier was small at first. It increased
with increasing SLS concentration as the surface packing
increased and cooperative adsorption took place. The
Triton X-405 was not directly affected by the adsorption
of SLS. Similarly, SLS was shown to adsorb on a PS latex
surface containing grafted PEO segments. In the com-
petitive desorption of SLS and Triton X-405, the same
trends were noted. At high emulsifier contents, there was
a cooperative adsorption of the two surfactants. The
anionic surfactant desorbed at a higher rate than the
nonionic surfactant and the surface of the particles was
richer in Triton X-405 at low emulsifier concentrations.
From these experiments, a qualitative mechanism for
the competitive adsorption of SLS and Triton X-405 on
PS particles is proposed as illustrated schematically in
Figure 10. At low surfactant concentrations, both SLS
and Triton X-405 exist as individual molecules, and the
surface of the particles is largely free of surfactants. As
SLS and Triton X-405 on Polystyrene Latex
Figure 10. Schematic of the proposed mechanisms of com-
petitive adsorption of SLS and Triton X-405 on PS particles.
a consequence, the surfactant with the lowest energy for
adsorption (i.e., Triton X-405) adsorbs strongly and
preferentially. There is little Triton X-405 remaining in
the aqueous phase, in which SLS is predominant. As the
surfactant concentration increases, the surface becomes
saturated with Triton X-405. More of the Triton X-405 is
available in the aqueous phase, and it can associate with
SLS to form hydrophobic complexes as described in the
literature.21 In the absence of latex particles, the favored
configuration for these complexes would be to form
aggregates of mixed composition in order to lower the free
energy of the system. The formation of mixed micelles
has been shown to be a nonideal process, which occurs at
emulsifier concentrations lower than what would be
expected considering the cmc of each individual surfact-
ant.22 In the present study, an additional effect should be
added. The surface of the particles is a favorable location
for the surfactant complexes in terms of decreasing free
(22) Rubingh, D. N. In Solution Chemistry of Surfactants; Mittal, K.,
Ed.; Plenum Press: New York, 1979.
Langmuir, Vol. 16, No. 21, 2000 7913
energy. As the surface is already crowded with Triton
X-405, a reorganization must occur to allow the cooperative
adsorption to take place. The packing of the surfactant
molecules can be increased according to the following
mechanisms. The charge on the anionic surfactant may
be shielded by the presence of the nonionic surfactant.
The limiting factor in terms of packing of an anionic
surfactant on a polymer particle is the electrostatic
repulsion between the charged end groups of two adjacent
molecules. In the presence of a nonionic surfactant, this
repulsion effect may decrease, allowing for better packing.
Another possible explanation is a reorganization of the
nonionic surfactant chains. At low concentrations, nonionic
surfactants have been shown to adsorb in a relatively flat
conformation on the surface of polystyrene. At higher
concentrations, a more extended conformation has been
observed.6 This occurrence is not favored in terms of
entropy. However, it allows better hydration of the poly-
(ethylene oxide) segments and side chain interactions.
Eventually, the adsorption of the two surfactants may
lead to a complex multilayer structure. The SLS may
adsorb in the adsorbed Triton X-405 layer, either by
interacting directly with the hydrophobe of the nonionic
emulsifier or by lateral side chain interactions.
In terms of stability during the course of an emulsion
polymerization, the combination of the two surfactants
may lead to either enhanced or decreased stability. The
combination may be powerful if the anionic surfactant
content at the particle surface is initially high and the
nonionic surfactant is added during or after the polym-
erization. However, the addition of a little nonionic
surfactant on particles covered with a little anionic
surfactant may be detrimental, since the Triton X-405
was shown to remove some of the SLS at low surfactant
contents.
Acknowledgment. Financial support from Elf Aqui-
taine and Elf Atochem and the research assistance of
undergraduate students Keisha Antoine and Vincent
Colombié are greatly appreciated.
Supporting Information Available: Adsorption iso-
therms of SLS on PS particles and profile of aqueous concentra-
tions of SLS and Triton X-405. This material is available free of
charge via the Internet at http://pubs.acs.org.
LA9915825