Journal of Colloid and Interface Science 216, 242–249 (1999)

Article ID jcis.1999.6318, available online at http://www.idealibrary.com on

Adsorption of a Cationic Surfactant on Na–Montmorillonite: Inspection

of Adsorption Layer by X-Ray and Fluorescence Spectroscopies
Abdesselam Tahani,† ,1 Mohamed Karroua,† Henri Van Damme,* Pierre Levitz,* and Faı̂za Bergaya*
*Centre de Recherche sur la Matière Divisée, CNRS et Université d’Orléans, 45071 Orléans cedex 02, France; and †Laboratoire de Cinétique et Catalyse,
Université Mohamed 1 er, Faculté des Sciences, BP 524 60.000 Oujda, Morocco

Received October 28, 1998; accepted May 19, 1999

stage of the adsorption process, the cations exchange with

The adsorption of the cationic surfactant BDDAC on a hydro-
philic smectite (montmorillonite) surface has been investigated,
especially in the range of low coverage ratios where surfactant ions
are adsorbed through cation-exchange with the counterions of the
clay. The surfactant coions (Cl 2) were found to be adsorbed
simultaneously with the cationic part after a complete alkyl am-
monium ion-exchange of montmorillonite (CEC). We observe that
organoclay particles remain flocculated in aqueous medium in
almost all the range of adsorption isotherms up to 1.38 CEC and
afterward redisperse incompletely. The intercalation of surfactant
in the interlamellar space was followed by X-ray measurements.
Fluorescence spectroscopy was used to obtain information about
the adsorption layer at the interface. A calculation from geomet-
rical considerations and from adsorption isotherms shows that
below 1.38 CEC, there is a flat double layer in the interlamellar
space and after this amount of adsorbed surfactant, an interstrati-
fied clay-surfactant mixed system is formed. © 1999 Academic Press
Key Words: adsorption; montmorillonite; cationic surfactant;
coions; fluorescence; X-ray.
INTRODUCTION
The adsorption of cationic surfactants on clay at the solid–
liquid interface is of great technological interest and funda-
mental importance and has been investigated by several exper-
imental techniques (1, 2). The adsorption of surfactants from
water on mineral substrates is governed mainly by electrostatic
and hydrophobic interactions (1) which include both the inter-
action between the surfactant and the surface and the mutual
interaction between surfactant molecules (the main factors
involved are (i) electrostatic interactions between the surfactant
head group and the surface, (ii) the interaction between the
tails, and (iii) the electrostatic repulsion between the head
groups). Usually a “two-step” adsorption isotherm of cationic
surfactants was found for silica (3, 4) and for several clays such
as kaolin (5), mica (6, 7), and smectite (8 –11) surfaces. At low
surface coverage, surfactant cations adsorb physically as indi-
vidual ions on the negatively charged surface sites. In this first
1
To whom correspondence should be addressed. E-mail: tahani@
sciences.univ-oujda.ac.ma.
protons or other counterions present at the solid–water inter-
face. This exchange depends on the properties of the solid–
water interface and the type of surfactant (12). Once the
surface charge has been compensated, the “electrostatic” driv-
ing force for surfactant adsorption is annihilated and the ad-
sorption will only increase if the low affinity of the hydropho-
bic part of the surfactant for water can promote self-association
and consequently, adsorption. From this review, it appears that
the adsorption of cationic surfactants onto nonswelling silicates
is well rationalized and can be satisfactorily described by
theoretical models (1, 15).
The adsorption of alkyl ammonium on swelling clay exhibits
different structures depending on the density of the negative
layer charges, the geometry of the surface, and the degree of
exchange (13). They can be arranged in monolayers and bilay-
ers or in pseudotrimolecular arrangements as well as paraffin-
type arrangements (13). Recent studies of adsorption of cat-
ionic surfactants on montmorillonite have shown that the
hexadecyltrimethyl ammonium chloride (HDTMAC) is ran-
domly arranged on the surfaces for highly dispersed clays (9),
and hexadecyl pyridinium chloride (HDPC) was organized into
monolayers slightly tilted from the normal plane to the basal
surface with an alternate orientation of the cationic polar head
group (8). Thus, adsorption on swelling clays is very compli-
cated, and rationalized results are obtained only on nonswell-
ing silicates such as mica covered with cethyl trimethyl am-
monium chloride (CTAB) (7). This study was performed by
the measure of interface separations between two mica sur-
faces. It has been demonstrated that a step-wise from mono-
layer to complete bilayer on each mica surface was obtained in
the vicinity of the critical micelle concentration (cmc) of
CTAB at 10 23 mol.l 21 and giving rise to thickness separation
from 1.8 nm for a monolayer to 3.35 nm for a bilayer. De-
pending on the structure of the adsorption layer, surfactant-
coated clay particles aggregate or disperse (11). At equilibrium
concentration of the surfactant equivalent to the cationic ex-
change capacity (CEC) of the clay, a monolayer of surfactant
is formed, with the alkyl chain of the surfactant pointing
toward the solution; the particles then become hydrophobic and

0021-9797/99 $30.00 242

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All rights of reproduction in any form reserved.
 CATIONIC SURFACTANT ADSORPTION ON Na–MONTMORILLONITE
the long-range hydrophobic forces between the alkyl chains on
the surface are one of the factors which play a role in the
aggregation of the particles. Upon subsequent adsorption of the
surfactant at the interface, at high equilibrium concentration
but still below the cmc, the adsorption layer generally develops
into clusters like bilayers (11, 12) with the ionic head groups
toward the solution. Because of the long range electrostatic
forces, clay particles such as laponite redisperse partially (12).
With montmorillonite at higher adsorption amounts of cationic
surfactants, progressive redispersion is obtained depending on
the adsorption rate of the surfactant (9, 14). The flocculation
process of clay particles therefore mainly depends on the
structure of the adsorbed layer of the surfactant and the charge
of the interface. As a consequence, the adsorption onto swell-
ing clays such as montmorillonite or hectorite is complicated
by the evolution of the aggregation state of the clay platelets
upon the adsorption of cationic surfactants. Smectite clay has a
tendency to form particles with aggregation of elementary
sheets. The size of the particles is dependent on the solid
concentration and the ionic strength (25, 24). The interparticle
interactions can also be modified by the nature of the interlayer
cation and the adsorbed species (8, 26). The main objective of
the present work was the study of the mechanism of cationic
surfactant adsorption from water on the montmorillonite sur-
face, as seen by the fluorescence of pyrene and X-ray spec-
troscopy. Cation exchange effects upon adsorption were taken
into account.
MATERIALS AND METHODS
Na-montmorillonite was used, namely Wyoming (SPV); it
was purified and sodium exchanged before use. The unit cell
formula was [(Si 7.89 Al 0.11) IV(Al 3.11Fe 310.38 Mg 210.49) VI O 20
1 1
(OH) 4 (Na 0.59 K 0.03 21
Ca 0.02] and the CEC measured was 93
meq/100 g of ignited material. The charge density of the clay
was 0.65.
The benzyldimethyldodecyl ammonium chloride (BDDAC)
surfactant (from Merck) was used as received; HPLC analysis
showed that the alkyl chain was mainly C 12. The pyrene from
EGA Chemie was used as received (purity .99%).
Montmorillonite suspensions at 20 g.l 21 (2% w/w) were
prepared by dispersing 5 g of dehydrated montmorillonite (the
clay was dried overnight at 110°C) in 250 ml of bidistilled
water. The suspension was then stirred for about 48 h in order
to swell the montmorillonite. This former solid/liquid ratio for
the dispersion of montmorillonite was chosen in order to avoid
sedimentation in longtime range.
Adsorption Isotherm
The adsorption isotherms were determined using the residue
method: 5 ml of the homogeneous colloidal clay suspension
(20 g.l 21) were placed in a glass flask and 20 ml of calibrated
solution of surfactant added. The flask was covered with a
243
polyvinyl chloride film and the cap put on. The mixture was
gently stirred for 24 h to be at equilibrium. For the determi-
nation of the adsorption isotherm, the samples were centri-
fuged in tightly stoppered teflon containers for 30 min at
16,000 rpm to separate the clay particles. The clear supernatant
was drawn with a syringe and the concentration of surfactant
determined spectroscopically (Beckman UV-ACTA MIV) in
the interval 250 –300 nm at l max 5 262 nm. Adsorption exper-
iments in the presence of pyrene 10 26 mol.l 21 were conducted
with the same procedure. However, 0.5 ml of a 10 24 mol.l 21
solution of the pyrene in methanol were first placed in a flask
and the methanol evaporated. The pyrene was then solubilized
in 50 ml of calibrated solution of surfactant. The montmoril-
lonite suspensions are obtained as described above. Fluores-
cence behavior of both clay particles and supernatant were
studied after centrifugation, and the surfactant concentration in
the supernatant was determined as described above.
The sedimented clay particles put into a 2-mm thick quartz
window, and fluorescence was observed under excitation at
45°. The excitation beam passed through an interference filter
(336 nm) to eliminate background. The spectrofluorometer
used was a Perkin-Elmer LS-5, the bandwidth of excitation
was 2.5 nm, and the recording speed 30 nm.mn 21. Fluores-
cence analysis of the supernatant, after adsorption equilibrium
was reached, indicated no fluorescence characteristic of pyrene
emission, showing that at the concentration of pyrene used, the
fluorescence probe was entirely located on the clay surface.
Some of the adsorption amounts were expressed in function
of the CEC as X CEC, where X was the rate between the
surfactant adsorption amount and the CEC of the clay (1
CEC 5 9.3 3 10 24 mol.g 21).
Cl 2 Determination
The concentration of Cl 2 in the supernatant was determined
potentiometrically with an Ag/AgCl electrode, after adding
known amounts of AgNO 3 solutions with known concentra-
tion.
Turbidimetric Measurements
Suspensions of organoclay montmorillonite or Na-montmo-
rillonite were gently shaken after the equilibrium time. Then,
the particles were allowed to settle quiescently by sedimenta-
tion and sedimentation flocculation. After 2 h, an aliquot of the
slurry was carefully withdrawn and its turbidity at 375 nm
measured in a quartz cell of 10 mm with spectrophotometer
Acta M IV.
X-Ray Measurements
For air-dried samples, the suspensions were placed on glass
plates and allowed to dry under atmospheric conditions. Al-
though, for wet samples, the initial suspensions were centri-
fuged and residue was set under paste form on deeper sample
support and immediately passed to X-ray measurements. The
244 TAHANI ET AL.

FIG. 1. Representation of the I III/I I vibronic bands ratio of the pyrene FIG. 2. Adsorption isotherm of BDDA 1 and simultaneous adsorption of
fluorescence against the concentration of the surfactant. its Cl 2 coion onto montmorillonite clay (Wyoming).

apparatus was a Siemens D-500 X-ray diffractometer using that the surface of montmorillonite is 770 m 2.g 21 and is totally
CuK a radiation (l ' 1.54 Å). accessible (17), the calculated apparent packing area by each
molecule is 159 Å 2. Above this domain of highly energetic
RESULTS adsorption and below the cmc, the increase in adsorption with
increasing equilibrium surfactant concentration is less pro-
Determination of BDDAC cmc’s nounced. At the cmc (4 3 10 23 mol.l 21) a plateau appears
without reaching the CEC (1.7 CEC) twice. In this case, the
Steady-state experiments with the pyrene probe are used to
apparent packing area covered by each molecule is 79.9 Å 2.
gain information on the microenvironment where the probe is
The plateau corresponds to the formation of micelles in solu-
solubilized. The I III/I I ratio of the intensity bands of the pyrene
tion. The molecular equilibrium between the solid surface and
fluorescence spectrum is known to be sensitive to the polarity
the aqueous solution is only dependent on the monomeric
of the environment in which the pyrene molecules reside (16):
chemical potential. After the cmc, this chemical potential is
a value close to or below 0.6 characterizes a highly polar
constant. The free surfactant concentrations are not strictly the
environment and a value much above 0.6 a weakly polar
equilibrium concentrations, because the surfactant molecules
environment.
are in monomer and micelle forms that do not adsorb on the
Figure 1 shows the evolution of the I III/I I ratio for an aqueous
surface. The adsorption mechanism is conducted by the sur-
solution of BDDAC with pyrene (6 3 10 26 mol.l 21) as a
factant molecules in the monomeric form.
function of the surfactant concentration. For concentrations
Turbidimetric measurements are shown in Fig. 3. The clay
between 10 23 mol.l 21 and 4 3 10 23 mol.l 21 this ratio changes
from the value of 0.6 (corresponding to the pyrene in the
presence of surfactant monomers in aqueous media) to 0.78
(corresponding to the pyrene in BDDAC micelles). In deion-
ized water, following the published procedure (16), this evo-
lution allows the determination of the cmc of the surfactant
BDDAC which is 4 3 10 23 mol.l 21.

Adsorption Isotherm
Figure 2 shows the adsorption isotherm of BDDAC on SPV
Na-montmorillonite and the simultaneous Cl 2 adsorption. The
BDDAC adsorption isotherm exhibits features usually encoun-
tered for cationic surfactants on clay minerals (8, 9). It shows
a domain of highly energetic adsorption at low surfactant
concentration, existing up to a coverage of adsorbed 8 3 10 24
mole BDDA 1 per gram of clay. This value is slightly lower
than the CEC of the clays (9.3 3 10 24 mol g 21). If we assume FIG. 3. Turbidimetric measurements against surfactant adsorption rate.
 CATIONIC SURFACTANT ADSORPTION ON Na–MONTMORILLONITE 245

cations (Fig. 4). The adsorption saturation of Cl 2 ions reaches

a plateau when the cmc of the surfactant is reached in a similar
way to surfactant adsorption (Fig. 2). This result can be inter-
preted by a two-stage adsorption mechanism: (i) surfactant
cation-exchange adsorption at the beginning of the isotherm,
and (ii) surfactant cation-coion (Cl 2) simultaneous adsorption
after the CEC of the clay is reached.

Analysis of Adsorption Layer by Fluorescence and X-Ray

Spectroscopies
Pyrene fluorescence. The spectroscopic properties of
pyrene were examined as a function of the concentration of the
surfactant to get direct information on the structure of the
adsorbed layer on the clay surface. The adsorption isotherm of
the surfactant is not modified by the presence of pyrene. The
FIG. 4. Relationship between Cl 2 and surfactant ions adsorbed on mont-
monomeric fluorescence spectrum of pyrene located on an
morillonite. organoclay surface for surfactant loading of 0.4 CEC shown in
Fig. 5 exhibits a different relative intensity of I III as compared
to that of pyrene in a monomeric surfactant aqueous solution.
montmorillonite in the absence of BDDAC forms a stable
In Fig. 6, the representation of the I III/I I ratio of pyrene in the
dispersion, and the optical density is high. In the highly ener-
adsorbed layer shows that it is in a polar environment. When
getic domain of the adsorption isotherm, the organo-montmo-
the surfactant molecules are adsorbed on the surface, the ratio
rillonite particles still disperse in the solution up to 0.2 CEC,
I III/I I grows progressively, and a constant value of this ratio is
the aggregates formed are dense, and the optical density is
increased. Close to this value, the flocs formed flot more and
more at the air–water interface by settling for a few hours.
When surfactant concentration increases up to approximately
0.86 CEC (8 3 10 24 mol.g 21), corresponding to the one mono-
layer formation on clay particles, the flocs sedimented in the
flask and the bulk solution is clear leading to a sharp decrease
in the optical density. After 1.6 CEC, we obtain a turbid
solution and sedimented flocs, corresponding to incomplete
redispersion. For HDTMA–montmorillonite systems, a pro-
gressive redispersion was obtained just after the CEC of the
clay (9). Thus, the possibility of deflocculation of clay particles
can be connected to the nature of the surfactant and the
structure of the adsorbed layer. The morphological structure
and the nature of the clay can also influence the aggregation of
the organo-clay particles (11, 9).
In the first step of the isotherm with the sharp increase and
up to the CEC, adsorption occurs by ion exchange between the
surfactant cations and sodium exchangeable cations as shown
previously by other authors (3, 9, 27). Concentration chloride
determination (Fig. 4) in the supernatant shows that approxi-
mately all the chloride ions remain in the solution up to the
CEC and do not adsorb on the surface along with the cationic
surfactant monolayer, as recently found by other authors (8). In
this domain, the Cl 2 ions are repelled from negatively charged
particles and are located in the bulk solution.
Cl 2 adsorption starts slightly after the CEC is reached, as
shown in Fig. 4 at a corresponding concentration of 9.34 3
10 24 mol.g 21 of adsorbed surfactant on clay. Thus Cl 2 adsorp- FIG. 5. Pyrene monomeric fluorescence spectra for (1) surfactant solution
tion starts after the total neutralization of the surface charge, at 10 23 mol.l 21 and (2) clay–surfactant complex at 0.38 CEC of adsorbed
then increases linearly with the adsorption of the surfactant BDDA 1.
246 TAHANI ET AL.

kinds of sample preparations: air-dried surfactant complexes

FIG. 6. Representation of I III/I I ratio of the pyrene at the interface of the
montmorillonite against equilibrium concentration of the surfactant.
and the wet paste clays. For the first ones at 0.2 CEC we have
a peak corresponding to d 001 of 15 Å, and after this surfactant
coverage at 1.7 CEC value, we have two peaks corresponding
to interlamellar distances of both 18 and 34 Å (Fig. 7A). The
relative intensity of the peak at 18 Å decreases and that of the
peak at 34 Å increases when the surfactant coverage increases.
This can be explained by the delamination of sheets with the
interlamellar distance of 18 Å upon adsorption of surfactant
molecules in excess of 1.38 CEC.
However, wet paste clays in an uncontrolled hydrated state
exhibit only one peak for different surfactant loadings as
shown in Fig. 7B for an adsorption surfactant of 0.2 and 1.7
CEC (d 001 5 18 Å). The second peak is not observed for wet
paste or suspension, because the spacing (d . 40 Å) is too
large to be recorded by the diffractometer or the silicate layers
are arranged very irregularly with respect to one another, but

obtained after the equilibrium surfactant concentration of

2.9 3 10 23 mol.l 21. The change of ratio from 0.35 to about 0.5
suggests that pyrene solubilization sites are more apolar than in
the initial state. This suggests that the local concentration of the
surfactant increases and that solubilization of pyrene occurs
preferentially in this relative hydrophobic site. The increase of
the I III/I I ratio of pyrene in the adsorbed phase of the surfactant
starts at a concentration of adsorbed surfactant above the CEC
value. In a study of the adsorption of tetra-n-butylammonium
on hectorite (19), it was suggested that the butyl groups ex-
pelled the surface water molecules, thus exposing the pyrene
molecules directly to the clay interlayer surfaces. In our case
we can suppose that when the concentration of adsorbed sur-
factant molecules is lower than that corresponding to a com-
plete exchange with the sodium cations of montmorillonite, the
hydrophobic pyrene molecules are adsorbed by the siloxane
groups of the clay (18) and are influenced by the polarized
effect of the hydrated sodium exchangeable cations leading to
a polar environment (I III/I I 5 0.35). When the surface is cov-
ered by the surfactant molecules beyond the CEC, the I III/I I
ratio of the emission spectrum of the pyrene increases, but the
maximum value of this ratio is lower than that in the spectrum
corresponding to the pyrene in a micellar core (Fig. 1), sug-
gesting that no complete hydrophobic environment is formed.
Thus, there is no formation of a cluster instead of a hemi-
micelle on the montmorillonite surface at high coverage.
X-ray diffraction. Usual X-ray measurements showed that
at saturation of interlamellar space by the alkyl chain of or-
ganic compounds and especially alkyl ammonium ions, the
basal space d 001 measured for the moist and dried organoclay
suspensions does not undergo variation between the two kind
of samples. Thus the initial feature of alkyl chains into the
interlamellar space of swelled clay in aqueous solution does
not exhibit a great change. FIG. 7. Selected X-ray diffraction patterns of BDDA 1 Na–Wy for dried
In Figures 7A and 7B we report the X-ray spectra for two suspensions (A) and for wet paste clays (B).
 CATIONIC SURFACTANT ADSORPTION ON Na–MONTMORILLONITE
FIG. 8. Representation of the basal spacing of montmorillonite Na–Wy
against adsorption of surfactant ions for wet pastes and dried samples.
for dried clays the dominant spacing of 34 Å corresponds to the
re-organization of the clay particles.
Figure 8 represents the evolution of d 001 for different sur-
factant loadings on the clay surface for the two kinds of
preparations. For air-dried samples, the basal spacing increases
up to 18 Å and remains constant below 0.8 CEC of adsorbed
surfactants, which indicates that the cation exchange in the
interlamellar space is complete. Consequently, further surfac-
tant adsorption up to the CEC occurs on the external surface of
clay particles.
At 1.38 CEC of adsorbed surfactants, a second an interla-
mellar distance of 34 Å appears and remains constant for high
loadings. This corresponds to the rearrangement of the alkyl
chains of some clay particles leading to the low redispersion
observed. From the wet paste X-ray data, the surfactant ad-
sorption is accompanied by the removal of the water molecules
up to 0.8 CEC of the adsorbed surfactant. Close to and below
1.38 CEC, the molecular surfactant adsorption is accompanied
by the penetration of the water molecules in some of the
interlamellar spaces.
DISCUSSION
Adsorption Isotherm
The adsorption isotherm of the BDDAC surfactant is char-
acterized by a first region with high adsorption resulting from
cationic exchange with exchangeable sodium cations of the
clay (27). In this region and below the CEC, when the surfac-
tant molecules are adsorbed with pyrene, the I III/I I ratio of the
fluorescence bands is small and equal to 0.35, indicating that
the pyrene is located in a polar environment. This can be
interpreted by the direct contact of pyrene with the oxygen
247
atoms of the clay surface close to the hydrated exchangeable
sodium cations (18). In this domain, there are no Cl 2 ions
located at the adsorption interface; they are located in the bulk
solution (20). After the CEC, the amount of surfactant mole-
cules adsorbed increases slightly and corresponds to the hy-
drophobic adsorption by the alkyl chains (9). In this domain
some association of surfactant molecules is also proved by the
fluorescence measurements. After a complete exchange of so-
dium cations by the BDDA 1 cation, the I III/I I ratio of emission
bands of pyrene increases which suggests that it is located in a
relatively more apolar environment.
The presence of sodium cations released and the chloride
ions which are not adsorbed up to the CEC in the medium gives
a small change in ionic strength. This favors the adsorption on
the clay surface of further surfactant molecules added. A
constant value of the I III/I I ratio of pyrene emission bands
appears at a concentration of 2.9 3 10 23 mol.l 21 (Fig. 6)
corresponding to a surfactant adsorption of 1.3 3 10 23 mol.g 21
(1.38 CEC). This plateau corresponds to the formation of a
relative hydrophobic domain on the clay or to the restructuring
of the adsorption layer.
The organization of adsorbed cationic surfactants is depen-
dent on their location either in the interlamellar space or on the
external surface. We can assume that the pyrene located in the
interlamellar space is influenced by the polarized effect of the
hydrated sodium exchangeable cations or by the surfactant
polar head group for different loadings of BDDAC and is not
removed from direct contact to the surface. On the external
surface, the environment of pyrene molecules changes for
BDDAC loadings beyond the CEC of the clay. After this stage,
the I III/I I ratio measured ('0.5) at high loadings (1.7 CEC) is
the polarity result of the pyrene distributed in the internal and
the external surfaces. In the interlamellar space, the polarity of
the pyrene would be equal to the value measured below the
CEC (I III/I I 5 0.35). However, in the external surfaces, this
value changes with the adsorption level of surfactant mole-
cules, and at high loadings it would be greater than the value
actually measured (for example, I III/I I 5 0.7 for hydrophobic
domains on kaolin surfaces (21)). When the exchange of so-
dium cations by BDDA 1 cations is complete, Cl 2 ions are
adsorbed and the slope of chloride adsorption versus surfactant
adsorption is close to unity (Fig. 4) indicating simultaneous
adsorption of the two ionic parts. Cl 2 ions are also probably
localized at the interface of the hydrophobic domains of
BDDA 1 on the external surfaces as was suggested by other
authors (8).
Geometrical Considerations
For high loadings (1.7 CEC) the X-ray data show an almost
similar distance with a 00l value about 18 Å for dried samples
and wet paste of clay–surfactant complexes and a second
distance at 34 Å for the latest ones. The orientation and the
packing density of the surfactant molecules between the layers
248 TAHANI ET AL.
TABLE 1
Structure of the Adsorption Layer for Various Surfactant
Adsorption Rates on Montmorillonite
BDDA 1 orientation
BDDA 1
relative to clay BDDA 1
adsorption d 001 (Å) d 001 2 9.5 basal surface intercalation
,0.8 CEC 14.6–18 5.1–8.5 random monolayer
0.8–1.38 CEC 18 8.5 flat bilayer
1.38–1.7 CEC 18 8.5 flat bilayer
33 23.5 perpendicular alternate
bilayer
can be derived from X-ray data combined with quantitative
adsorption measurements. The basal spacing of organic com-
plexes of montmorillonite can be measured from Van Der
Waals dimensions of organic molecules in function of their
orientation between the layers.
The geometrical volume estimated for BDDA 1 is approxi-
mately 520 Å 3. The apparent packing area of the BDDA 1, as
calculated from the plateau region of the adsorption isotherm,
is about 79.9 Å 2, not so far from the cross-section value (70.5
Å 2) found by Trompette et al. using surface tension measure-
ments for a compact surfactant monolayer at the air–water
interface (3). Assuming this value (79.9 Å 2) we obtain a
thickness molecule of 6.4 Å, which is smaller than the inter-
layer distance obtained by X-ray measurements (8.5 Å). The
BDDA 1 ions in the interlamellar space therefore form an
alternate monolayer of surfactant molecules in a “head-to-tail”
arrangement with a tilted position of 18° from the basal space
(22). In this assumption the evolution of the accessible surface
with the surfactant adsorption is not taken into account as
shown by the apparition of the interlamellar distance of 34 Å.
Elsewhere, if we consider as a first approximation the Van Der
Waals thickness of the methyl or methylene group of 4 Å, the
resulting flat laying surfactant cation BDDA 1 is close to 136.6
Å 2 and is approximately equal to the inverse of charge density
(surface are per charge; 137 Å 2). Possible configurations
adopted by the adsorption layer of the cationic surfactant using
Lagaly’s model (13) are given in Table 1.
Generally, up to surfactant coverage of 1.38 CEC, interla-
mellar spaces are relatively weak (18 Å) and dense and a
compact bilayer is formed parallel to the basal space of mont-
morillonite particles, and this explains that the mixed system
flocculates.
For higher surfactant coverage beyond 1.38 CEC, two charac-
teristic distances appears close to 18 and 34 Å. At 34 Å, the
adsorption layer is formed by surfactant molecules perpendicular
to the basal surface and forms an interdigitated bilayer. This
rearrangement of the adsorption layer coexists with the dense
packed bilayer molecules in the interlamellar space. At these
higher surfactant concentrations, we can assume that additional
molecules in excess adsorb and form a partially hydrophilic bi-
layer in the internal space. Elsewhere, water molecules can pen-
etrate to internal surfaces and contribute to a partial delamination
or the redispersion observed. At this stage, interstratified struc-
tures of clay–surfactant complexes are formed.
As the initial clay montmorillonite suspensions at 2% w/w
are totally delaminated in aqueous solution (24, 25), the ad-
sorption of the surfactant on the clay surface in the aqueous
suspension promotes the formation of the so-called interlamel-
lar space and thus the aggregation and flocculation depending
on the surfactant adsorption layer. The external surface, cor-
responding to both the basal external faces and edges of the
tactoids and also internal basal faces, can be estimated using
the projected surface area of the adsorbed surfactant molecules.
From Cl 2 coion adsorption (Fig. 2), and assuming that it
adsorbs with the corresponding surfactant cations on the ex-
ternal surface (8), at high loadings the surfactant adsorption on
the external surface is close to 5.1 3 10 24 mol.g 21. Considering
the adsorption by the lateral interaction with preadsorbed sur-
factants, the mean molecular area is about 68 Å 2 (23). The total
surface area being 770 m 2.g 21, the external surface represents
208.8 m 2.g 21 and the interlamellar surface of 561.2 m 2.g 21 is
covered. Thus, the montmorillonite clay particles are com-
posed of 3.7 elementary layers of sheets on average.
Elsewhere, as the maximal interlayer distance deduced from
X-ray measurements below the CEC of the clay is 8.5 Å, the
number of BDDA 1 cations that would be filled in the interla-
mellar volume is close to 7.55 3 10 24 mol per gram of
montmorillonite. This result agrees with that obtained by as-
suming a double layer of flat-lying BDDA 1. The calculated
amount is close to the saturation point value 0.81 CEC, from
which there is no change in X-ray interlamellar distance (Fig.
8). It should be noted that the CEC of smectite represents the
number of exchangeable cations that is found inside the inter-
lamellar space and also that on the external surface of the clay
particles. After a complete exchange of the exchangeable cat-
ions in the interlayer, there is no further adsorption in the
interlamellar space upon further addition of the surfactant
below the CEC of montmorillonite. If we consider the CEC
value of 9.3 3 10 24 mol.g 21, and the fact that the full adsorp-
tion by a cationic exchange in the interlamellar space corre-
sponds to 7.55 3 10 24 mol.g 21 adsorbed with flat laying
bilayer, we can deduce the number of the adsorbed molecules
on the external surface that corresponds to 1.8 3 10 24 mol.g 21.
The corresponding calculated external and internal surfaces
are, respectively, 148 m 2.g 21 and 622 m 2.g 21, giving 5.2 ele-
mentary layers of sheets on average. These results are summa-
rized in Table 2; we note that the aggregation of the clay
montmorillonite particles changes with the adsorption of the
cationic surfactant.
Thus, cationic surfactant adsorption depends on the evolu-
tion of the aggregation state of clay particles during the ad-
sorption process (26). In spite of the double layer formation on
external surfaces, the system is mainly flocculated with the
progressive and incomplete redispersion at higher surfactant
 CATIONIC SURFACTANT ADSORPTION ON Na–MONTMORILLONITE
TABLE 2
Calculation of the Different Surface Areas for Two Surfactant
Adsorption Rates
Adsorption rate St S int S ext Mean number of the layers
0.8 CEC 770 148 620 5.2
1.7 CEC 770 208 562 3.3
adsorption. The flocs are due to some of the persistent alkyl
chain links between clay particles.
CONCLUSION
In this study, we have shown the correlation between the
adsorption isotherm of the surfactant (BDDA 1 ) and its
coion (Cl 2 ) and the exchange capacity of the clay. This last
value can be estimated by (i) fluorescence of pyrene coad-
sorbed with a surfactant and by (ii) the coion adsorption for
which the adsorption occurs after the complete exchange of
Na 1 cations by cationic surfactant. Below 0.8 CEC of ad-
sorbed surfactant on the montmorillonite, the surfactant
cations adsorb with a random configuration and coexist with
some water molecules in the interlamellar space. Adsorbed
BDDA 1 cations form bilayers with the surfactant cations
being flat and parallel to the clay layers between 0.8 and
1.38 CEC of adsorbed surfactant. After this last value, the
adsorption of excess surfactant cations gives an alternate
bilayer perpendicular to the basal space coexisting with the
compact flat bilayer, giving an interstratified surfactant–
clay system. At this stage, we assist in the penetration of
some water molecules leading to an incomplete dispersion.
From an adsorption isotherm and X-ray data, the internal
and external surfaces of the clay were estimated as well and
the average number of sheets by the clay particles deduced.
249
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