You are on page 1of 9

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 (surface of the particles, aqueous phase, micelles, monomer
synthesis and stabilization of polymer latexes. Anionic droplets) by a dynamic equilibrium. This behavior de-
surfactants provide electrostatic stability as described by termines phenomena such as the overall stability of the
the DLVO theory.1,2 The efficiency of such surfactants is latex, the nucleation of new particles, and limited ag-
highly dependent on many parameters such as ionic gregation. Therefore, it is very important to study and
strength and pH. This dependency can be a major quantify the interaction between the surfactant molecules
drawback in terms of the stability of the latex. Nonionic and the polymer particles. Adsorption isotherms of a
or polymeric surfactants provide steric stabilization. The surfactant on a latex particle surface are usually deter-
repulsion between particles is provided by the thermo- mined by following the change of the aqueous bulk
dynamically favored steric repulsion of the adsorbed surfactant concentration with increasing amounts of
materials.3,4 It is therefore practical to use mixtures of emulsifier in the system. Various techniques have been
anionic and nonionic surfactants in emulsion polymeri- used to determine adsorption isotherms of surfactants on
zation to combine different stabilization mechanisms. Most polymer particles.5,6
industrial emulsion polymerization processes use mixtures Although the adsorption of various nonionic surfactants
of anionic and nonionic emulsifiers. A common process on latex particles has been widely studied,7-12 only a small
can be described as follows: the reaction is started with amount of work has been published on the competitive
the anionic surfactant, and the nonionic is added at a adsorption of mixtures of anionic and nonionic surfactants
higher conversion or as a poststabilizer. In emulsion on latex particles. Kronberg and his team13,14 applied a
polymerization, the interaction between the surfactants (5) Maron, S. H.; Elder, M. E.; Moore, C. J. Colloid Sci. 1954, 9, 104.
and the polymer particles is fundamental in the control (6) Ahmed, S. M.; El-Aasser, M. S.; Pauli, G. H.; Poehlein, G. W.;
of the process and the final properties of the latex. The Vanderhoff, J. W. J. Colloid Interface Sci. 1980, 73, 388.
(7) Kronberg, B.; Kall, L.; Stenius, P. J. Dispersion Sci. Technol.

1981, 2, 215.
Lehigh University. (8) Kronberg, B.; Stenius, P. J. Colloid Interface Sci. 1984, 102, 410.
‡Max Planck Institute for Colloid and Interface Science. (9) Zhao, J.; Brown, W. J. Phys. Chem. 1996, 100, 3775.
* To whom correspondence should be addressed. (10) Zhao, J.; Brown, W. J. Phys. Chem. 1996, 100, 5908.
(1) Derjaguin, B. V.; Landau, L. Acta Physicochim. USSR 1941, 14, (11) Haggerty, J. F.; Roberts, J. E. J. Appl. Polym. Sci. 1995, 58, 271.
633. (12) Colombié, D.; Landfester, K.; Sudol, E. D.; El-Aasser, M. S. J.
(2) Verwey, E. J. W.; Overbeek, J. G. In Theory of Stabilization of Colloid Interface Sci. 1998, 202, 554.
Lyophobic Colloids; Elsevier: Amsterdam, 1948. (13) Hulden, M.; Kronberg, B. J. Coat. Technol. 1994, 66, 67.
(3) Ottewill, R. H. J. Colloid Interface Sci. 1977, 58, 357. (14) Kronberg, B.; Linstrom, M.; Stenius, P. In Phenomena in Mixed
(4) Napper, D. H. In Polymeric Stablilization of Colloidal Dispersions; Surfactant Systems; Scamehorn, J. H., Ed.; ACS Symposium Series
Academic Press: New York, 1983. 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 Colombié et al.

thermodynamic model to the adsorption of such a mixture Aldrich) were used as received. Diimidium bromide (Aldrich),
by extending an existing model for mixed micelles. The sodium chloride (Aldrich), and the citrate buffer solution (Aldrich)
surface composition was governed in a manner similar to were used as received.
the composition of the mixed micelles. The model was Synthesis and Characterization of the PEO Grafted
correlated with experimental values obtained by solvent Polystyrene Latex. The seeded emulsion polymerization was
carried out as follows. The seed latex (100 g of uncleaned latex,
depletion. It showed both theoretically and experimentally
20% solids) was filtered to remove any large aggregates and
that when a small amount of Triton X-100 was added to poured into a glass bottle. The surfactant (0.07 g of sodium lauryl
a surface precovered with SLS, the nonionic surfactant sulfate) and buffer (0.05 g of sodium bicarbonate) were added,
adsorbed readily and displaced the anionic surfactant. and the mixture was stirred at 300 rpm for 2 h using a magnetic
Thus, there was a strong preferential adsorption in favor bar. The monomers (0.80 g of styrene and 1.60 g of PEGMA)
of the nonionic surfactant. The results of Kronberg et al. were then added to swell the latex particles with overnight mixing.
were corroborated by Bolze et al.15 using small-angle X-ray The initiator (0.22 g of potassium persulfate) was then added,
scattering (SAXS) as a technique to probe the adsorption and the bottle was capped and placed in a bottle polymerizer at
of mixtures of SLS and Triton X-405 on the surface of 60 °C for 24 h.
polystyrene latex particles. The latex particles were The resulting latex was cleaned for 3 weeks by serum
covered with SLS and increasing amounts of Triton X-405 replacement to remove the surfactant and impurities in the latex.
The serum was clear during the whole course of the cleaning
were added. Most of the Triton adsorbed and replaced the process, suggesting the absence of any secondary nucleation
SLS on the surface. When the particles were saturated during the synthesis. This was confirmed by transmission electron
with Triton X-405 and increasing amounts of SLS were microscopy (Phillips 400 transmission electron microscope). A
added, the SLS also was able to remove some of the Triton sample of the resulting latex was dried in an oven at 70 °C for
X-405 from the surface. 24 h. The sample was redissolved in deuterated chloroform for
1H NMR analysis (details given in the following section).
The objective of the current study is to obtain a better
qualitative and quantitative understanding of the mixed Resonances for the protons of the polystyrene backbone chain
adsorption of SLS and Triton X-405 on polystyrene (-CH(Ph)-CH2-) were visible between 1.2 and 2.2 ppm.
particles, as a prelude to conducting emulsion polymer- Aromatic protons resonances were observed between 6.5 and 7.5
ppm. The solvent peak (chloroform) was located at 7.2 ppm. A
izations with this pair of stabilizers. First, the adsorption peak at 3.6 ppm representing the resonance of ethylene oxide
isotherms of SLS and Triton X-405 used as sole emulsifiers protons (-O-CH2-CH2-) was noted. These data confirmed that
are determined. Then various techniques are used to the grafting of some PEGMA onto the PS particles was successful
determine the competitive adsorption of a 1/1 molar during this reaction. From the NMR spectrum, it was possible
mixture of SLS and Triton X-405. The adsorption of Triton to evaluate the fraction of grafted PEGMA by integration of the
X-405 on PS particles precoated with SLS is next reported. phenyl protons and the ethylene oxide protons. From the ratio
Similarly, the adsorption of SLS on PS particles precoated of the areas of these peaks, the fraction of grafted PEGMA was
with Triton X-405 is performed. As a comparison, the estimated to be 45% of the initial amount (i.e., 1.74 × 10-4 mol).
adsorption isotherm of SLS on PS particles on which PEO This amount corresponds to a density of 8.5 × 1016 molecules of
PEGMA per m2 of particle surface.
segments are grafted is determined. All the adsorption
Determination of the Adsorption Isotherms. Filtration.
results are correlated with the competitive desorption of
This technique is based on the extraction a small volume of the
the two emulsifiers (using “serum replacement”). The aqueous phase from a latex for surfactant analysis. To reduce
surface packing is estimated in all experiments. the perturbations created by the extraction of the samples
containing varying amounts of surfactant, the following procedure
Experimental Section was applied. The desired amount of surfactant was added to
Materials. The anionic surfactant used in this study was approximately 25 g of cleaned monodisperse polystyrene latex
Ultrapure Bioregeant sodium lauryl sulfate (99+% pure, J.T. diluted to 1.9% solids. The sample was allowed to equilibrate by
Baker, Inc.). The cmc of this surfactant in water at 25 °C was stirring for 24 h before the extraction was performed. A 50 cm3
experimentally determined to be 6.0 mM. No further purification serum replacement cell (Advantec MFS) with a polycarbonate
was performed. The nonionic surfactant is a 70% aqueous solution membrane (pore size 100 nm, Osmotics) was rinsed thoroughly
of Triton X-405 (octylphenoxy poly(ethylene oxide) with an with DI water and allowed to dry for 24 h. The latex sample was
average number of ethylene oxide (EO) units of 40, Aldrich). The poured in the cell, and approximately 3 cm3 of the aqueous phase
nonionic surfactant is polydisperse, the number of EO units was extracted and analyzed.
ranging from 20 to 60. The nonionic emulsifier was dried at 70 Desorption by Serum Replacement. In some cases, the tech-
°C for 24 h prior to use. The cmc of this dried surfactant in water nique developed by Ahmed et al.6 was used. The experimental
at 25 °C was experimentally determined to be 0.8 mM. The procedure is as follows. In experiment DC-SR1, SLS (0.23 g) was
monodisperse polystyrene (PS) latex used (LS-1039E, The Dow added to a 100 g sample of cleaned monodisperse polystyrene
Chemical Co.) has a number-average diameter of 92 nm latex diluted to 1.9% solids. In experiment DC-SR2, SLS and
(determined by electron microscopy16). In one experiment, this Triton X-405 were added to the latex in combination (0.38 and
monodisperse polystyrene latex was modified by grafting PEO 0.55 g, respectively). The samples were stirred for 24 h prior to
segments on the surface via a seeded copolymerization. For this the experiment. A 400 cm3 serum replacement cell (Advantec
synthesis, styrene monomer (Aldrich) was washed with a 10 wt MFS) with a polycarbonate membrane (pore size 100 nm,
% NaOH solution to remove the inhibitor and distilled no more Osmotics) was rinsed thoroughly with DI water and allowed to
than 2 weeks before the polymerization was run. The comonomer, dry for 24 h. The latex was then charged into the serum replace-
poly(ethylene glycol) methyl ether methacrylate (PEGMA, 50% ment cell. DI water was passed through the cell, and the surfact-
solution in water, Mn ) 2080 g/mol Aldrich), was used as received. ant content in the exit stream was monitored over approximately
Prior to use, the latexes (5.7% solids) used in these adsorption 8 h. The amounts of water extracted from the cell were carefully
studies were cleaned for 3 weeks by serum replacement to remove weighed to perform an accurate mass balance on the system.
any surfactant and electrolyte remaining from their preparation. Surfactant Concentrations. The SLS concentration in the
The surface charge density of this cleaned latex was 2.5 µC/cm2. aqueous phase samples was monitored by two techniques. The
The conductivity of the effluent was monitored to determine the conductivity of the aqueous solutions was determined at 25 °C
extent of cleaning. The water used was deionized (DI). D2O using a YSI model 32 conductance meter, and the SLS concen-
(Cambridge Chemical Laboratories) and chloroform (99%+, tration was determined via a calibration curve. However, the
conductivity of mixed surfactant solutions can be affected by the
(15) Bolze, J.; Horner, K. D.; Ballauf, M. Colloid Polym. Sci. 1996, presence of micelles, which cannot be readily calibrated. As a
274, 1099. consequence, colorimetry was also used to determine the SLS
(16) Miller, C. M. Ph.D. Dissertation, Lehigh University, 1995. concentration.
SLS and Triton X-405 on Polystyrene Latex Langmuir, Vol. 16, No. 21, 2000 7907

The colorimetry technique used here, first reported by Orthgieb polymer particles,19 one of which is the Langmuir ap-
and Dobias,17 allows one to measure the concentration of sulfate proach, which has been used successfully in many cases.
or sulfonate groups and was successfully applied by Urquiola et This approach is based on the following assumptions. The
al.18 to monitor the concentration of the reactive surfactant, surface of the particles is energetically uniform. No
sodium dodecyl allyl sulfosuccinate, in an emulsion polymeri-
zation. A 200 mL solution of diimidium bromide dye was prepared
interaction exists between the adsorbed molecules. All
as follows: 0.1 g of diimidium bromide and 5.0 g of sodium chloride mechanisms for adsorption are identical. The adsorption
were mixed in 100 mL of citrate buffer solution (pH ) 4) and is up to (and including) a complete monolayer on the
diluted to 200 mL with DI water. Surfactant solution samples surface. Although all of these assumptions are not typically
were diluted 10, 15, or 40 times so that their concentration ranged met by surfactant adsorption, the Langmuir model has
from 2 × 10-5 to 3 × 10-4 M. A 2.0 g sample of dye solution was nonetheless been accepted to provide an adequate de-
added to 2.0 g of the diluted surfactant solution. The sample was scription of the process. In the Langmuir adsorption model,
shaken vigorously for 2 min to allow the formation of the dye- eqs 1 and 2 can be derived:
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 asc
Γ) (1)
of the tube, purple color) was separated from the aqueous phase. 1 + bc
The optical absorbance of the chloroform phase at a wavelength
of 525 nm was measured against a reference solution of pure
where Γ is the moles of solute adsorbed per unit surface
chloroform using a Spectronics Genesys 2 UV/vis spectrometer.
The Triton X-405 aqueous concentration was monitored by
area, c is the aqueous surfactant concentration, and as
measuring the absorbance of the phenyl ring (π f π* transitions) and b are Langmuir constants. b is the ratio of the rate
in the UV range at 223 and 274 nm using the UV/vis spectrometer. constant for adsorption over the rate constant for de-
NMR Technique. This technique was described in detail in a sorption. as is the area occupied by one molecule of
previous article.12 Due to a large water signal in the proton NMR surfactant at saturation for a monolayer of emulsifier on
spectrum of the latex itself, the polystyrene latex had to be the surface of the polymer particles. Equation 1 can be
prepared carefully by replacing the water with D2O. An 8.73 g transformed into eq 2, the linear Langmuir form, to allow
amount of cleaned monodisperse latex (5.74% solids) was placed the experimental determination of as and b.
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
1 1
was recovered after each addition so that most of the water was ) as + (2)
replaced by D2O (>99%). At the end of the procedure, 24.42 g of Na bc
polystyrene latex (1.9% solids) in deuterated water was recovered.
This procedure was repeated four times so that approximately
where Na is the number of molecules of SLS adsorbed per
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 unit area when the aqueous concentration of the surfactant
1.06 × 10-3 M) and two stock solutions of SLS in D2O (9.35 × is c. The standard molar free energy for adsorption (∆Gads,
10-3 and 9.90 × 10-2 M) were subsequently prepared. The J/mol) can be calculated from eq 3.
different samples were prepared from these solutions to adjust
the initial surfactant concentrations. All samples had an ap- ∆Gads ) -RT ln(bω) (3)
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. where T is the absolute temperature (K) and ω is the
All NMR spectra were obtained using a Bruker 500 MHz number of water molecules per dm3 of water (55.6 mol/
spectrometer. The pulse length was 3.0 µs. To minimize the water dm3). From the Langmuir adsorption isotherm, the surface
proton contribution in the spectra, they were presaturated with area per molecule of SLS is 44 Å2, the adsorption constant
the frequency of the water peak. To obtain a good signal-to-noise is 550 dm3/mol, and the Gibbs adsorption free energy is
ratio in the spectra, 200-1500 scans were accumulated. The -25.6 kJ/mol. The surface area per molecule found here
repetition delay was chosen to be 6 s to ensure full relaxation of is the same as that reported by Ahmed20 for the same
all protons. Tetramethylsilane (TMS) was used as an external
standard.
system (44 Å2). A similar molar energy for adsorption of
SLS on PBMA particles has been reported by Kronberg
Results and Discussion et al.14 (-23.7 kJ/mol).
Adsorption Isotherm of Triton X-405 on PS Particles
Adsorption Behavior of Each Individual Surfact- via Proton NMR. In a recent study,12 the adsorption
ant. Adsorption of SLS on PS Particles. The adsorption isotherm of Triton X-405 molecules on polystyrene par-
isotherm of SLS on polystyrene particles was determined ticles was determined using 1H NMR spectroscopy (Figure
using the serum replacement technique (experiment DC- b in the Supporting Information). The corresponding
SR1). The objective of this determination was to charac- Langmuir parameters can be calculated from the data up
terize the adsorption of SLS by itself for comparison to its to and including the plateau region. Above this concen-
adsorption in the presence of Triton X-405. The adsorption tration, the Langmuir approximation is no longer valid
isotherm at 25 °C is shown in the Supporting Information due to the greater than monolayer coverage of the particles.
(Figure a), where the number of molecules of SLS adsorbed From the adsorption isotherm, the surface area per
(for a particle surface of 1 m2) is plotted as a function of molecule of Triton X-405, the adsorption constant, and
the aqueous concentration of the surfactant. The adsorp- the Gibbs free energy for adsorption can be determined.
tion behavior is as expected; at low SLS concentrations The estimated surface area per molecule (172 Å2) is similar
most of the SLS is adsorbed with the proportion (SLS to that found by Kronberg et al.7 for a similar poly(ethylene
adsorbed/SLS aqueous phase) decreasing as the surface oxide) type surfactant (200 Å2 for an emulsifier having an
approaches saturation. average chain length of 50 EO units). The molar energy
Several models have been used to describe qualitatively for adsorption (-36.2 kJ/mol) is similar to that of PEO on
and quantitatively the adsorption of surfactants on PBMA particles as reported by Kronberg et al.14 (-34.1

(17) Orthgieb, E.; Dobias, B. Poster presented at the 7th Symposium (19) Adamson, W. A. Physical Chemistry of Surfaces; 5th ed.; Wiley:
on Surfactants in Solution, Ottawa, 1988. New York, 1990.
(18) Urquiola, M. B. Ph.D. Dissertation, Lehigh University, 1994. (20) Ahmed, S. M. Ph.D. Dissertation, Lehigh University, 1979.
7908 Langmuir, Vol. 16, No. 21, 2000 Colombié et al.

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 Figure 2. (a) Molar ratio of SLS to Triton X-405 in the overall
the determination of the adsorption behavior of nonionic system (solid line), in the aqueous phase, and on the polystyrene
surfactants, it was not possible to use it for the deter- particle surface and (b) percentage of adsorbed SLS and Triton
X-405 as a function of the total surfactant concentration in the
mination of the SLS adsorption behavior. The SLS aqueous phase.
molecules adsorbed on the surface are not mobile enough
to be detected within the 5 MHz window of the proton concentration, the adsorption of the two surfactants
NMR spectrum. At high SLS concentrations, a signal for becomes more competitive. Eventually there is more SLS
the aqueous SLS protons was detected, but the correlation on the surface than Triton X-405.
to the actual concentration was not successful. As a In Figure 2a, the SLS to Triton X-405 molar ratio in the
consequence, a variety of techniques are used in combina- aqueous phase and on the particle surface is plotted as a
tion for the determination of the competitive adsorption function of the total aqueous surfactant concentration.
of SLS and Triton X-405 (filtration/colorimetry and The same trend described above is observed: at low
filtration/conductivity for SLS; proton NMR and filtration/ concentrations, the aqueous phase is richer in SLS. As
UV spectroscopy for Triton X-405). To simplify the reported in a previous section and in the literature,8
experimental determination of the adsorption isotherms, nonionic surfactants such as Triton X-405 have been shown
all experiments were performed at 25 °C using a mono- to have a strong affinity for the surface of the particles
disperse polystyrene latex (1.9% solids, 92 nm). All (∆Gads ) -36 kJ/mol). This has been attributed to an
adsorption results are reported for a sample of latex having exclusion of the surfactant from the water phase (to
1 m2 of surface available for adsorption. prevent hydrophobe-water interactions). Lateral interac-
Adsorption of a 1/1 Molar Ratio of SLS and Triton X-405. tions on the particle surface also play an important role
Figure 1 depicts the adsorption isotherms of SLS and in decreasing the total free energy in the system. With
Triton X-405 on polystyrene particles at 25 °C from 1/1 increasing concentration, the ratio of the two surfactants
molar SLS/Triton X-405 solutions. The first three data in the aqueous phase becomes close to the total ratio of
points for SLS were determined by colorimetric titration the two surfactants in the system. At intermediate
only since the conductivity technique was not sensitive concentrations, the particle surface may be saturated with
enough to detect the aqueous SLS at extremely low the nonionic surfactant. Some of the Triton X-405 remains
concentrations. However, both techniques are consistent in the water phase and associates with SLS as described
for the determination of the adsorption of SLS at the higher in the literature.21 Finally, the presence of mixed micelles
concentrations. At very low surfactant concentrations, both affects the partitioning of both surfactants, and more of
surfactants adsorb strongly on the surface of the poly- the Triton X-405 will be present in the aqueous phase.
styrene particles. The slope of the number of adsorbed The cmc of a 1/1 molar solution of SLS and Triton X-405
surfactant molecules as a function of total aqueous was measured to be 1.3 × 10-3 mol/dm3 total surfactant
surfactant concentration is high. However, this slope concentration at 25 °C (determined by surface tension
decreases significantly above 3 × 10-4 M total aqueous measurements). Of course, this was measured in the
surfactant concentration, indicating less adsorption of both absence of particles and may not be the same ratio as
surfactants with further increases in their concentrations. when micelles appear in the presence of the particles.
Up to 2 × 10-3 M total aqueous surfactant concentration, Figure 2b depicts the partition of both SLS and Triton
Triton X-405 adsorbs preferentially on the surface of the X-405 between the particle surface and the aqueous phase
polystyrene particles as more Triton X-405 molecules as a function of the total aqueous surfactant concentration.
occupy the surface of the particles than SLS molecules.
Between 2 × 10-3 and 3 × 10-3 M total aqueous surfactant (21) Cabane, B. J. Phys. Chem. 1977, 81, 1639.
SLS and Triton X-405 on Polystyrene Latex Langmuir, Vol. 16, No. 21, 2000 7909

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 Triton X-405 SLS adsorption on SLS/Triton X-405
X-405 adsorption on adsorption on SLS Triton X-405 competitive desorption
experiment bare PS particles covered PS particles covered PS particles from PS particles
nSLS sat theoretical (molecules) 5.2 × 1017 7.2 × 1017 1.5 × 1018 8.0 × 1017
nSLS sat experimental (molecules) 1.0 × 1018 1.6 × 1018 2.3 × 1018 1.5 × 1018
excess SLS (%) 192 222 159 187
nTriton X-405 sat theoretical 4.5 × 1017 4.0 × 1017 2.1 × 1017 3.8 × 1017
(molecules)
nTriton X-405 sat experimental 8.8 × 1017 9.8 × 1017 3.3 × 1017 7.1 × 1017
(molecules)
excess Triton X-405 (%) 194 244 155 187
SLS/Triton X-405 molar ratio at 1.1 1.6 7.0 2.1
saturation

At low surfactant concentrations, the proportion of Triton The excess surfactant (e) on the particle surface is defined
X-405 adsorbed is almost constant (around 88%, over a as
narrow range however), whereas a smaller and increasing
proportion of SLS is adsorbed (from 60 to 70%). As the nsurf exp
concentration of the surfactants increases, a smaller e) × 100 (8)
nsurf th
proportion of both surfactants is adsorbed as might be
expected as the surfaces become more crowded. Above 1.5 The theoretical and experimental values for the number
× 10-3 M, however, the proportion of SLS adsorbed of molecules of both emulsifiers on the surface of the
increases again, this being attributed to a cooperative polystyrene particles (for 1 m2 of surface) are given in
adsorption of the two surfactants. Eventually, above 3.0 Table 1. The results indicate a large excess of both of the
× 10-3 M, the proportion of both adsorbed surfactants surfactants on the particles at saturation when they ad-
decreases as the surface becomes fully saturated. sorb simultaneously (>190%). Several possible explana-
To determine the surface packing at saturation, the tions can be proposed for this cooperative adsorption.
following approach was used. The theoretical number of When more Triton X-405 is available in the aqueous
molecules of the two surfactants packed on the polystyrene phase, the association with SLS21 may lead to a greater
particles (having 1 m2 of available surface area) is adsorption of the hydrophobic complex. Just as in the
calculated, knowing the experimental molar ratio of the formation of mixed micelles, the exclusion of the SLS/
two surfactants. This calculation is based on the monolayer Triton X-405 complex from the aqueous phase is ener-
unit surface coverage for each surfactant (determined in getically favored. Furthermore, some interactions on the
the previous section). No interaction between the two particle surface can decrease the free energy for adsorp-
surfactants is taken into account in the calculation. The tion. The electrostatic repulsion between the sulfate end
number obtained for each surfactant is subsequently groups of the SLS molecules could be shielded by the
compared with the actual number determined experi- presence of the nonionic surfactant, allowing a closer
mentally in the adsorption isotherm (in which SLS/Triton packing on the surface. The Triton X-405 may also
X-405 interactions may occur). The excess surfactant on reorganize its structure by being in a more extended
the surface of the particles is then calculated. conformation. In this case, the loss of entropy due to the
For a particle surface of 1 m2, the theoretical number extended conformation of the polymeric chain can be
of molecules of the two surfactants (nSLS th and nTriton X-405 th, balanced by energetically favored side chain interactions
respectively) at saturation in a monolayer without in- (limiting water-hydrophobe interactions). Eventually, it
teraction should be described by is possible that SLS adsorbs in the hairy layer created
by the nonionic surfactant in the vicinity of the particle.
nSLS thas0 SLS + nTriton X-405 thas0 Triton X-405 ) 1 (4) Its adsorption may be favored by side-chain interac-
tions.
where as0 SLS is the surface area occupied by one molecule Adsorption of Triton X-405 on PS Particles Pre-
of SLS on polystyrene particles in the absence of Triton covered with SLS. In most industrial emulsion polym-
X-405 and as0 Triton X-405 is the surface area occupied by erization processes, the surfactants are added at various
one molecule of Triton X-405 on polystyrene particles in process times in the reaction. Very often, the latex is
the absence of SLS. At saturation, the molar ratio of the synthesized using an anionic surfactant. At the end of the
two surfactants (r) can be determined experimentally. By reaction, a nonionic surfactant can then be added to
assuming the theoretical ratio would be equal to the enhance stability of the system. As a consequence, it can
experimental ratio at saturation: be helpful to know what is the adsorption behavior of a
nonionic surfactant on latex particles already stabilized
nSLS th with an adsorbed anionic surfactant. In this experiment,
r) (5) 0.3269 g of SLS was first added to 249.52 g of the cleaned
nTriton X-405 th
monodisperse polystyrene latex (2% solids, 92 nm). The
Equations 4 and 5 can be solved, and the result is given SLS was allowed to adsorb for 24 h to ensure equilibrium.
in the following equations: The amount of SLS added to the system is that required
to cover 100% of the surface of the particles if all the SLS
r was to adsorb on the latex particles with a 44 Å2 surface
nSLS th ) (6) area per molecule. The Triton X-405 was then added to
ras0 SLS + as0 Triton X-405
the latex. The mixture was stirred for 24 h before any
measurement was performed. Under these conditions,
1
nTriton X-405 th ) (7) equilibrium was assumed to be established between all
ras0 SLS + as0 Triton X-405 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 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
Figure 6. (a) Molar ratio of SLS to Triton X-405 in the whole comparative experiment was performed by determining
system (total), in the aqueous phase, and on the polystyrene the adsorption isotherm of SLS on a PS latex with
particles (precovered with Triton X-405) and (b) percentage of chemically bound PEO segments (Figure 7). The chemical
SLS and Triton X-405 adsorbed at 25 °C for increasing SLS nature of the grafted PEO segments is close to the Triton
concentrations obtained via filtration/colorimetry (SLS) and X-405 based on the average number of ethylene oxide units
filtration/UV spectroscopy (Triton X-405). (45 for the PEGMA, as opposed to 40 for the Triton X-405).
However, the end group is a methyl group, as opposed to
though some systematic discrepancy is noted between the the hydroxyl at the end of the chain in Triton X-405. For
two techniques. These results confirm that the Triton a sample having 1 m2 of particle surface area, there are
X-405 is bound tightly to the polymer surface, once it has 8.5 × 1016 molecules of grafted PEO segments. This is
been adsorbed. The addition of another adsorbing species lower than the density of Triton X-405 precoating the latex
does not seem to affect its affinity for the surface. This particles in the previous section (4.4 × 1017 molecules).
should be important with respect to the resulting latex As noted in Figure 7, SLS adsorbed on the surface of
properties particularly in terms of stability, especially the polystyrene particles, regardless of whether the PEO
when the latex is formulated with a lot of additives. segments were physically or chemically bound. When the
However, it may be a problem when the latex must be nonionic emulsifier was used, the adsorption of the SLS
coagulated by chemical means or when the surfactant was lower than in the case of the latex functionalized
must be removed for other studies. The adsorption of the with PEO segments, where a somewhat stronger initial
SLS is not very strong as shown in Figure 5. The SLS adsorption was noted. However, this difference may reside
continues to adsorb on the particles up to the highest in the number of PEO chains at the surface of the particles
concentration used here ([SLS]aq ) 5 × 10-3 M). This is (lower density). The initial adsorption on the bare surface
evidence for cooperative adsorption. As expected, the is higher for similar reasons. At higher concentrations,
aqueous phase also becomes richer in SLS molecules. the adsorption on the bare surface approaches saturation.
In Figure 6a, the molar ratios of SLS to Triton X-405 When chemically or physically bound PEO are used, an
in the whole system, on the surface of the particles, and increased adsorption of the SLS is noted. These results
in the aqueous phase are plotted as a function of the suggest that the adsorption of the SLS may not occur
aqueous phase concentration of Triton X-405. Since the directly at the surface of the particles in the presence of
amount of Triton X-405 on the surface is not varying, the PEO segments. Instead, SLS/PEO complexes21 may form
main factor determining the SLS to Triton X-405 ratio in at the interface and a multilayer adsorption phenomenon
the aqueous phase and on the particle surface is the is likely to occur.
adsorption behavior of the SLS. Figure 6b describes the Competitive Desorption. An increased understanding
partitioning of both SLS and Triton X-405 between the of the adsorption behavior of surfactants can be obtained
particle surface and the aqueous phase as a function of by desorbing them from the surface of the latex particles
the SLS aqueous surfactant concentration. No variation (92 nm, 1.9% solids). In experiment DC-SR2, the initial
in the Triton X-405 partitioning is observed over the range total concentrations were 13 and 3 mM for SLS and Triton
of concentrations studied. The SLS partitioning also X-405, respectively. To perform the competitive desorption
reflects the cooperative adsorption that takes place in the experiment, two separate methods of monitoring the
system. surfactant concentration must be used: conductivity for
Once again, eqs 4-7 were applied to these data, and SLS and UV spectroscopy for Triton X-405. The concen-
the results are given in Table 1. As before, a strong excess tration profile in the exit stream from the serum replace-
of adsorbed surfactants is noted when mixtures of surf- ment cell for experiment DC-SR2 is plotted in Figure c of
actant are used. The surface packing is greatly increased the Supporting Information as a function of the number
7912 Langmuir, Vol. 16, No. 21, 2000 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
Figure 8. Adsorption isotherms of SLS and Triton X-405 on °C. First, the individual adsorption behaviors of SLS and
PS particles obtained by the desorption technique at 25 °C. 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
Figure 9. Ratio of SLS to Triton X-405 in the overall system phase separation between the surfactant molecules in the
(total), in the aqueous phase, and on the particle surface as a aqueous phase (containing micelles) and those at the
function of the total surfactant concentration in the aqueous surface of the particles. Other possible reasons are the
phase obtained by desorption at 25 °C. adsorption of a second layer or an effect of the polydis-
of residence volumes (q/v, where q is the volume of serum persity of the nonionic surfactant.
recovered and v is the volume of the aqueous phase In the adsorption from 1/1 molar ratio solutions of SLS
contained in the cell). The desorption rates are different and Triton X-405, the following features were noted. At
for the two surfactants. SLS has a high rate of desorption low surfactant content, there was a strong adsorption of
compared to Triton X-405. As a consequence, the ratios Triton X-405 and SLS, the nonionic surfactant being
and amounts of the two surfactants will vary simulta- preferentially adsorbed at the surface of the particles. At
neously. Even though, it is not possible to control this higher concentrations, the surface composition approached
variation, the partition of the two surfactants can still be the initial 1/1 molar ratio. A strong excess of adsorbed
determined by mass balance for the different ratios and surfactant was noted when both surfactants were used
amounts sampled during the experiment. together. When Triton X-405 was adsorbed on PS particles
The number of molecules of both surfactants adsorbed precovered with SLS, the anionic emulsifier was removed
on the surface of the polystyrene particles at 25 °C as a from the surface at low Triton X-405 contents, due to its
function of the total aqueous surfactant concentration is higher energy of adsorption. With further increases in
given in Figure 8. The data obtained from the desorption the Triton X-405 concentration, the anionic surfactant
experiment are very similar to the data obtained through readsorbed, and a large excess of both adsorbed surfactants
the adsorption studies. At low surfactant concentrations, was noted at the surface. When SLS was adsorbed on
there is a preferential adsorption of Triton X-405 on the particles precovered with Triton X-405, the amount of
surface. Little desorption of the nonionic surfactant is adsorbed anionic emulsifier was small at first. It increased
observed during the experiment. Above 5 × 10-3 M, SLS with increasing SLS concentration as the surface packing
is in the majority on the surface of the particles. This increased and cooperative adsorption took place. The
preferential adsorption can be characterized by comparing Triton X-405 was not directly affected by the adsorption
the molar ratio of the two surfactants at the particle surface of SLS. Similarly, SLS was shown to adsorb on a PS latex
and in the water phase to the total ratio of the two surface containing grafted PEO segments. In the com-
surfactants in the system, since there is a continuous petitive desorption of SLS and Triton X-405, the same
variation of the total composition. These ratios are plotted trends were noted. At high emulsifier contents, there was
in Figure 9. The initial total molar ratio of SLS to Triton a cooperative adsorption of the two surfactants. The
X-405 (before desorption) is 4.5. The total molar ratio of anionic surfactant desorbed at a higher rate than the
SLS to Triton X-405 decreases with decreasing surfactant nonionic surfactant and the surface of the particles was
concentration (from 4.0 to 1.3), since the anionic surfactant richer in Triton X-405 at low emulsifier concentrations.
desorbs more readily (as mentioned above). As a conse- From these experiments, a qualitative mechanism for
quence, the aqueous phase is rich in SLS (SLS/Triton X-405 the competitive adsorption of SLS and Triton X-405 on
molar ratio ranging from 8 to 12) as compared to the whole PS particles is proposed as illustrated schematically in
system. The strong preferential adsorption of the nonionic Figure 10. At low surfactant concentrations, both SLS
surfactant is shown by the low SLS to Triton X-405 ratio and Triton X-405 exist as individual molecules, and the
at the surface as compared to the total ratio in the system surface of the particles is largely free of surfactants. As
SLS and Triton X-405 on Polystyrene Latex 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
Figure 10. Schematic of the proposed mechanisms of com- interacting directly with the hydrophobe of the nonionic
petitive adsorption of SLS and Triton X-405 on PS particles. emulsifier or by lateral side chain interactions.
In terms of stability during the course of an emulsion
a consequence, the surfactant with the lowest energy for polymerization, the combination of the two surfactants
adsorption (i.e., Triton X-405) adsorbs strongly and may lead to either enhanced or decreased stability. The
preferentially. There is little Triton X-405 remaining in combination may be powerful if the anionic surfactant
the aqueous phase, in which SLS is predominant. As the content at the particle surface is initially high and the
surfactant concentration increases, the surface becomes nonionic surfactant is added during or after the polym-
saturated with Triton X-405. More of the Triton X-405 is erization. However, the addition of a little nonionic
available in the aqueous phase, and it can associate with surfactant on particles covered with a little anionic
SLS to form hydrophobic complexes as described in the surfactant may be detrimental, since the Triton X-405
literature.21 In the absence of latex particles, the favored was shown to remove some of the SLS at low surfactant
configuration for these complexes would be to form contents.
aggregates of mixed composition in order to lower the free
energy of the system. The formation of mixed micelles Acknowledgment. Financial support from Elf Aqui-
has been shown to be a nonideal process, which occurs at taine and Elf Atochem and the research assistance of
emulsifier concentrations lower than what would be undergraduate students Keisha Antoine and Vincent
expected considering the cmc of each individual surfact- Colombié are greatly appreciated.
ant.22 In the present study, an additional effect should be Supporting Information Available: Adsorption iso-
added. The surface of the particles is a favorable location therms of SLS on PS particles and profile of aqueous concentra-
for the surfactant complexes in terms of decreasing free tions of SLS and Triton X-405. This material is available free of
charge via the Internet at http://pubs.acs.org.
(22) Rubingh, D. N. In Solution Chemistry of Surfactants; Mittal, K.,
Ed.; Plenum Press: New York, 1979. LA9915825