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Wettability of silica nanoparticle–surfactant nanocomposite interfacial layers
Armando Maestro,†*a Eduardo Guzm
an,ab Eva Santini,b Francesca Ravera,b Libero Liggieri,b
a
on G. Rubio*a
Francisco Ortega and Ram

Received 25th July 2011, Accepted 11th October 2011
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E

DOI: 10.1039/c1sm06421e

The hydrophobicity of a particle surface can be tuned by the addition of surfactants that change the
surface free energy for their attachment to a liquid interface. In this work, we report an experimental
study where the wettability properties of silica nanoparticles are modified by the adsorption of
alkyltrimethylammonium surfactants (CnTAB, n ¼ 12, 16) on the surface of the particles. We have
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pointed out that the wettability of the complexes is controlled by an intricate balance of electrostatic
and hydrophobic interactions between the particle surface and the surfactant. These interactions play
an important role in the structure of the surfactant–particle nanocomposite interfacial layer.

1. Introduction wettability of the particles, thus making q an essential parameter

for the determination of the strength of the attachment to fluid
The hydrophilic–lipophilic balance of colloidal nanoparticles interfaces of micro- or nanoparticles. Indeed, if the interfacial
plays a key role in their affinity for fluid interfaces because it energy exceeds the thermal energy, it is possible to consider that
changes the adsorption ability of the nanoparticles to fluid particles irreversibly adsorb at the interface, e.g., at q ¼ 90 ,
interfaces.1 An effective way to tune this balance is the addition DEp z gR2 [ kT.12 This situation is schematically shown in
of surface active modifiers (e.g. long-chain surfactants2 or even Fig. 1a where completely hydrophilic (q ¼ 0 ) or hydrophobic
short-chain alcohols3) to the particle dispersions. Adsorption at particles (q ¼ 180 ) are immersed in the respective bulk phase,
fluid interfaces of binary systems formed by colloidal nano- water or air/oil. Only if the particles are partly hydrophilic/
particles and surfactants is currently a subject of increasing hydrophobic (0 < q < 180 ), they may attach irreversibly to
interest, mainly due to their use in the formation and stabiliza-
tion of foams and emulsions.1,4–11 Although the properties of
these systems and the mechanisms through which they stabilize
the interfaces are not yet completely understood, it has been
suggested that the efficiency of particles in the stabilization
process is related to their ability to irreversibly accumulate at the
fluid interface. The particle attachment energy4 usually takes
values of the order of several kT. In fact, the free energy, DEp,
associated with the transfer of one spherical particle of radius R
from the bulk phase to a planar fluid–fluid interface can be
expressed in terms of the three-phase contact angle, q, of the
particles with the interface as well as the interfacial tension g and
the particle radius R:4

DEp ¼ pR2g(1  cos q)2 (1)

where the sign in (1  cos q)2 corresponds to particles whose

centers are below () or above (+) the interface. Eqn (1) points
out a strong dependence of the interfacial energy DEp on the
a
Departamento de Qu
ımica F
ısica I, Universidad Complutense de Madrid,
Ciudad Universitaria s/n, 28040 Madrid, Spain. E-mail: armando.
maestro@u-psud.fr; rgrubio@quim.ucm.es
b
Istituto per L’Energetica e le Interfasi, CNR-IENI, Via de Marini 6,
16149 Genoa, Italy
† Present address: Laboratoire de Physique des Solides, B^atiment 510,
Universit
e Paris-Sud XI, 91405-Orsay, France.
Fig. 1 (a) Position of a particle in an arbitrary fluid–fluid interface
depending on the free energy of their attachment DEp accounted by the
phase contact angle q. From left to right correspond to the increase in the
hydrophobicity of the particle; i.e., from q ¼ 0 a totally hydrophilic
particle to q ¼ 180 a totally hydrophobic one. (b) Change of the
hydrophobicity of an arbitrary colloidal particle negatively charged due
to the interactions with cationic surfactants. At high enough surfactant
concentration, hydrophobic interactions lead to the adsorption of addi-
tional surfactant molecules, rendering the nanoparticles again
hydrophilic.

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interfaces. The behavior of partly hydrophobic particles irre-
versibly adsorbed at the interface differs from that of surfactant
molecules that adsorb and desorb in a relatively short
timescale.1,13
The addition of surfactants to a particle dispersion modifies
the wettability of the particles due to the adsorption of surfactant
molecules onto the particles’ surface, and hence, their attachment
to a fluid interface might be controlled as schematically shown in
Fig. 1b,1,5 i.e., nanoparticle–surfactant complexes attached to
fluid interfaces adopt different structures according to the
different interactions among them.14 These interactions depend
on the size, shape and chemical nature of the particles, as well as
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E
on the nature and composition of the surfactant molecules.1,15
The partitioning of particle–surfactant composites between
aqueous bulk and fluid interfaces has been extensively investi-
gated from the thermodynamic point of view,16,17 and it has been
found that, according to the energetic picture sketched above, it
strongly depends on the wetting properties of the particles.1,18 It
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is noteworthy that the nanoparticle-laden interfacial layer should
be viewed as a multiphase region with three interfaces: one of
them between two fluid interfaces, i.e., air/oil–water, and when
the particles are partially wetted, two solid–fluid interfaces.19,20
The interaction between ionic surfactants and charged nano-
particles may add significant complexity to the structure and
dynamics of the laden interfaces (for instance, an equilibrium
between the particle–surfactant composite and free surfactant
might exist at the interface), and in particular to the mechanical
properties of the interface.16 It should be noted that the interfa-
cial macroscopic mechanical properties, to be precise the dila-
tional and shear surface complex viscoelastic moduli, may be
strongly modified by the attachment of particles onto the inter-
face14,21,22 and therefore they are controlled by the wettability
properties of the particles.2 Many studies of fluid interfaces
stabilized by nanoparticles have appeared in the last decade
focusing on the rheological characterization,23 and on the
possible correlation between rheological properties and the
mechanism of stabilization of emulsions and foams.1,7,9
However, little is known about the mechanism of formation and
the structure of the particle layer attached to fluid interfaces.
Studies in this direction may shed light on the interfacial
behaviour of these systems.
The aim of this work is to study the equilibrium properties,
basically surface tension and wettability of fluid interfaces
stabilized by silica nanoparticle–surfactant composites. We have
mainly focused our attention on the role of the surfactant
adsorption on the particles, and its effect on the wettability of the
particles. We have studied two systems formed by hydrophilic
silica nanoparticles and two cationic surfactants, alkyl-
trimethylammonium bromide, CnTAB, with CTAB for n ¼ 16
and DTAB for n ¼ 12 using drop profile analysis tensiometry and
Scheme 1 General chemical structure of alkyltrimethylammonium
bromide: CTAB (n ¼ 15) and DTAB (n ¼ 11).
838 | Soft Matter, 2012, 8, 837–843
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ellipsometry (Scheme 1). The analysis of the ellipsometric data
has allowed evaluation of not only the thickness of the interfacial
layers, but also the wetting contact angle q of the nanoparticles
attached to the fluid interface. These results confirm the change
in hydrophobicity of the nanoparticles due to the interaction of
their surfaces with the surfactants.
2. Materials and methods
2.1. Chemicals
We used a commercial colloidal silica dispersion Levasil 200/30
kindly supplied by H. C. Stark-Bayern (Germany). Levasil is an
aqueous colloidal dispersion at 30.38 wt% of spherical silica
nanoparticles, free from stabilizing additives and then more
suitable as a model dispersion. In fact, the dispersion has a pH of
9.2 due to negatively charged nanoparticles. These are charac-
terized by a specific BET area of 200 m2 g1.
Two different cationic surfactants, hexadecyl-
trimethylammonium bromide, CTAB (Mw ¼ 346.46 g mol1),
and dodecyltrimethylammonium bromide, DTAB (Mw ¼ 308.35
g mol1), purchased from Sigma-Aldrich, with a purity of $99%,
were used without further purification. The double distilled and
deionized water used in this work was produced by a Milli-Q RG
system from Millipore, having a resistivity higher than 18 MU cm
and a surface tension, stable over hours, of g ¼ 72.5 mN m1 at
20  C. As usual for studies involving ionic surfactants, salt was
added to the surfactant solutions to promote their adsorption.
Hence, for all the experiments, the surfactant solutions always
include 1 mM of NaCl. NaCl was purchased from Sigma-
Aldrich, it was roasted at 600  C for 24 h before use in order to
eliminate any organic impurity. The purity grade of the salt
aqueous solution was checked by measuring the surface tension g
over a long time. A stable value of g ¼ 72.5  0.2 mN m1 was
found at 20  C.
Furthermore, to avoid any particle aggregation during the
dispersion preparation, the original Levasil dispersion was
diluted to 1 wt% by adding drop-by-drop the surfactant solution
while continuously stirring, following the procedure reported by
Ravera et al.19
2.2. Methods
Dynamic light scattering (DLS) experiments were performed to
characterize the size and polydispersity of the nanoparticles in
water using an ALV (CGS-8) apparatus, working in pseudo-
cross-correlation mode with an argon ion laser (l ¼ 514.5 nm).
From the DLS results, it was possible to calculate the hydrody-
namic radius Rh, by means of the Stokes–Einstein relation, Rh ¼
kT/6phD ¼ 15  2 nm (h is the viscosity of the solvent, and D the
diffusion coefficient of the nanoparticles).24 We have measured
the z-potential (Zeta Nanosizer, Malvern Instruments, UK) of
the colloidal silica dispersions obtaining z ¼ 42  1 mV, which
confirms that the particles are negatively charged.
The equilibrium surface tension of the surfactant and the
nanocomposite interfacial layers has been measured using a drop
profile analysis tensiometer model PAT1 (Sinterface, Germany),
this instrument allows the measurement of the surface tension
with a resolution of 0.1 mN m1. For our measurements,
a pendant drop of the aqueous dispersion is formed at the tip of
This journal is ª The Royal Society of Chemistry 2012

a Teflon capillary tube. Thus, the aging of the interface can be
accurately characterized by measuring the dynamic interfacial
tension of a drop, keeping the interfacial area constant. The
thickness of the interface has been evaluated using an imaging
ellipsometer (EP3-Nanofilm, Germany) at a single wavelength of
532 nm to obtain information about the organization of the
mixed nanocomposite system in the interfacial region. The
aqueous dispersions were placed in a quartz dish (diameter ¼ 10
cm, depth ¼ 5 cm) and the laser beam was directed at the surface
in the middle of the cell where the meniscus effect is negligible.
The dependence on the incidence angle of the ellipsometric angles
was measured and averaged using a 4-zone nulling scheme.25 The
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E
analysis of the ellipsometric angles, D and J, was done assuming
that the interfacial layer can be described as a bilayer following
the model recently reported in the literature.26,27 This method
allows one to evaluate not only the thickness of the interface, but
also the wetting contact angle of the nanoparticles attached
to the fluid interface. The accuracy of D and J was better
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than 0.1 and 0.05 degrees, respectively. Brewster angle
microscopy (BAM) was also performed in the same instrument
(Brewster angle of the water–air interface ¼ 53.1 ). All the
experiments carried out in this work were conducted at room
temperature, 20  1  C.
3. Results and discussion
3.1 Surface tension of silica nanocomposite layers
Pure hydrophilic silica nanoparticles do not show any appre-
ciable adsorption onto the air/water interface at any particle
concentration, as demonstrated by the surface tension
measurements of dispersions previously reported in the litera-
ture.19 In contrast, CnTAB cationic surfactants are highly surface
active.28 Fig. 2 shows the equilibrium surface tension g of both
CTAB and DTAB as a function of their bulk concentration C.
The surface tension dependence on the concentration for the
pure surfactant layers may be explained using the Frumkin
equation of state,19,29 in accordance with previous results repor-
ted for similar systems.30 From the curves shown in Fig. 2,
the cmc of both surfactants is estimated to be 9.2  104 M and
Fig. 2 Equilibrium interfacial tension as a function of the surfactant
concentration; symbols as follows: CTAB (-), SiO2–CTAB (B), DTAB
(,) and SiO2–DTAB (C). Solid lines represent the Frumkin equation of
state for the pure surfactant as it is defined in ref. 19 with 1/GN ¼ 0.439
nm2 per molecule, a ¼ 0.66 mM and h/RT ¼ 1.85 for CTAB and 1/GN ¼
0.468 nm2 per molecule, a ¼ 8.35 mM and h/RT ¼ 1.40 for DTAB. The
inset shows the comparative data g  C for the SiO2–CnTAB complex;
symbols as in the main figure.
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1.3  102 M for CTAB and DTAB, respectively. These values
obtained for the cmc are in good agreement with those previously
reported by other authors.30
To evaluate the effect of surfactant on the transfer of silica
nanoparticles (1 wt% concentration) into the liquid–air interface,
we have measured the surface tension of the dispersion–air
interface for different initial concentrations of the surfactants
added to the particle suspension below the cmc of the pure
surfactants (results shown in Fig. 2). It must be remarked that
data for SiO2–CTAB complexes have been previously reported
by Liggieri et al.,23 and part of them have been included here for
the sake of comparison between different systems.
In the 105 to 103 M surface concentration range, the surface
tension of both complexes SiO2–CnTAB is relatively close to the
surface tension of the bare air/water interface; furthermore,
within this dilute range, the particles surface modified by both
surfactants present comparable values of g (see the inset of
Fig. 2). The similar tendency of g vs. the surfactant concentration
in this regime can be explained taking into account the following
factors: (i) the transfer of the tuned nanoparticles from the bulk
to the fluid interface is basically due to the electrostatic interac-
tion of their negatively charged surface with cationic CnTAB
surfactants; and (ii) the surface coverage of these surfactant-
decorated nanoparticles attached to the air/water interface is—at
least in this range—very small, as it was previously demonstrated
by Liggieri et al.23 Besides, the physically adsorbed CnTAB
cations can associate at the interface through hydrocarbon
chain–chain interactions, thus resulting in the formation of
surface aggregates commonly called hemi-micelles. The inset of
Fig. 2 shows that apparently the length of the alkyl chain in the
surfactant does not play a significant role in the surface tension
of the particle–surfactant suspensions. Also, from the results
shown in Fig. 2, we point out that contrary to the systems formed
by polyelectrolyte and surfactant of opposite charges,31 there is
no synergic effect between particles and surfactants in lowering
the surface tension.
A drastic increase in the contribution of the surface modified
particles attached to the air/water interface to the surface tension
is observed for DTAB concentrations above 103 M, providing
values of g which coincide with those of pure DTAB solutions as
can be seen in Fig. 2. This finding indicates that a significant
fraction of modified particles attach to the interface beyond this
critical concentration. It should be noted that increasing the
surfactant concentration above 103 M—for a fixed particle
content—leads to a further adsorption of the DTA+ cations on
the surface of silica particles, thus promoting their adsorption
onto the interface, and also the hydrophobic chain interaction
between the adjacent surfactant molecules, thus decreasing the
equilibrium surface tension.23
To sum up, these results point out that not only the electro-
static interaction between the nanoparticles and CnTAB surfac-
tants, but also the chain–chain hydrophobic interaction between
the adjacent surfactant molecules plays an important role in the
adsorption of the complexes at the interface. The above consid-
erations are supported by the depletion of the surfactant solution
due to surfactant adsorption onto the nanoparticle surface.
Previous results obtained by Ravera et al.,19 based on ultracen-
trifugation of the dispersions, indicated that for SiO2 concen-
tration larger than 0.4 wt%, within the concentration range of
Soft Matter, 2012, 8, 837–843 | 839

CTAB below cmc, the surfactant is almost completely removed
from the bulk aqueous phase, as demonstrated by the fact that
the values of g obtained for the supernatants, after ultracentri-
fugation, are similar to the value of the pure water in all the range
of surfactant concentrations analyzed. Hence, for the composi-
tions studied in this work one can consider that there are only
residual amounts of free surfactant available in the bulk, and the
decrease in interfacial tension can be mostly attributed to the
attachment of the CnTAB–nanoparticle complexes to the air–
water interface.23
3.2. Brewster angle microscopy (BAM)
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E
Fig. 3 shows the Brewster angle images obtained for several
interfacial layers of nanoparticle–CTAB. For all the experiments
performed, also with DTAB, we have observed the formation of
a homogeneous compact layer that rules out the existence of
aggregation of the complexes as isolated islands of radius larger
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than 0.5 mm on the interface. The homogeneous character of the
interfacial layer allows the ellipsometric data to be analyzed and
the thickness of the latter to be obtained as well as the contact
angle of the particle–surfactant composites.
3.3. Ellipsometry: interface thickness and nanoparticle contact
angle
Ellipsometric measurements have been performed for obtaining
the layer thickness h,31–33 and the three-phase contact angle q of
the nanocomposite SiO2–CnTAB at the air–water interface as
a function of the surfactant concentration C.26,27,34
The model used to analyze the ellipsometric data26,32 considers
that the air/liquid interface is formed by two layers: air/silica and
silica/water layers, and takes into account the finite contact angle
q of the silica nanoparticles at the air–water interface, as sche-
matically shown in Fig. 4. The model assumes that the upper
layer (Layer 1) is formed by a mixture of adsorbed nanoparticle–
surfactant composites and air, while the lower layer (Layer 2) is
formed by a mixture of the silica–surfactant composites and
water. It is also taken into account that both layers behave as
distinct homogeneous reflectance ones, and therefore any influ-
ence of particle light scattering is ignored. This model has been
previously found to be valid for nanoparticle layers attached to
the air/water interface.35 In Fig. 4, hSi–air and nSi–air are the
thickness and the complex refractive index of the upper silica–air
layer, and hSi–H2O and nSi–H2O are the thickness and the complex
refractive index of the lower silica–water layer. Fig. 4 allows the
relation between the particle contact angle q and the upper layer
thickness (hSi–air) to be found by means of the following
equation:27
Fig. 3 Brewster angle microscopy images for interfacial nanocomposite layers of silica nanoparticles and different CTAB concentrations.
840 | Soft Matter, 2012, 8, 837–843
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Fig. 4 Scheme of the two-layer ellipsometric model used to analyze the
nanocomposite interfacial system formed by silica and CTAB. The silica
spheres of radius r and refractive index nSi are attached to the air–water
interface; note that surfactant molecules are adsorbed onto the particle
surface. h is the vertical distance between the centre of the sphere and the
air–water interface. hSi–air and hSi–H2O represent the thickness of the two
layers, respectively; i.e., the part of the nanocomposite in air and water,
respectively. q is the contact angle of the particle at the air–water interface
measured in water.
2hSiair
cos q ¼ 1  (2)
d
where d ¼ hSi–air + hSi–H2O, and therefore, it has been found that
hSi–air governs the wettability of the silica nanocomposite at the
air–water interface. To get reliable values of the two-layer
thickness, as well as the phase contact angle, the ideal response is
modelled by means of the effective medium approximation
(EMA).36 Here, the real refractive indices of air (na ¼ 1.0) and
water (nw ¼ 1.337) are known,37 while the refractive index of the
silica nanoparticles was considered to be nSi ¼ 1.46.27 This
allowed the effective real refractive index of each two-mixed layer
(nSi–air and nSi–H2O) to be calculated assuming that the extinction
coefficient of each pure substance is zero. For moderate surface
concentrations, silica nanoparticles are considered to form
a hexagonal close-packed layer23,38 at the interface characterized
by the following parameters: R is the silica sphere radius
(¼ 15  2 nm), h accounts for the distance from the centre of the
particle to the air–water interface (we adopted the convention
h > 0 for q # 90 and h < 0 for q > 90 ), and f is the surface
coverage of particles in the interfacial layer (¼ total particle
cross-sectional area/total area).26 Therefore, Layer 1 is charac-
terized by a thickness r  h and the second one by a thickness
r + h. The EMA approximation36 considers that the nano-
composite system is a dispersed spherical component (B)
completely surrounded by a host component (A). Here, the
dielectric constant 31 of a heterogeneous layer can be obtained by
the relation:
3B ð1 þ 2 fB Þ  3A ð2 fB  2Þ
31 ¼ 3A ; (3)
3A ð2 þ 2 fB Þ  3B ð1 þ fB Þ
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where fA and fB are the volume fractions (fA + fB ¼ 1). Eqn (3) is
then applied to each of the two layers previously described. The
silica nanoparticle–surfactant mixture is component B in all the
cases. Further details about the application of the EMA for
obtaining the thickness and the three-phase contact angle, q, of
nanoparticle interfacial layers may be found in the
literature.26,27,34
Fig. 5 shows the ellipsometric thickness for Layers 1 (hSi–air)
and 2 (hSi–H2O) as a function of the surfactant concentration.
Similar qualitative trends have been found for the two different
surfactants studied (CTAB and DTAB). For both systems, hSi–air
increases as the surfactant concentration increases up to
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E
a maximum value at 104 M. Above 104 M, the thickness of
Layer 1 decreases as the surface concentration increases,
approaching the cmc of both surfactants. hSi–H2O has the opposite
behaviour (see Fig. 5b). It is noteworthy that the average values
of the total ellipsometric thickness obtained for the different
compositions evaluated—roughly close to the nanoparticle
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size—are comparable. This fact means that the ellipsometric
measurements do not allow obtaining further details on the
disposition of the surfactant molecules interacting with the SiO2
nanoparticles at the interfacial layers. Therefore, the only
information that can be discussed with confidence is the relative
thickness of the interfacial layer mainly constituted by the
surface-modified particles, which allows one to relate the varia-
tion of the ellipsometric thickness with the wettability of the
tuned nanoparticles studied.
As expected the surfactant concentration plays a key role in
the wettability of the particle-network at the air–water interface
due to the balance between electrostatic and hydrophobic
interactions.39 Furthermore, the wettability of the complexes as
shown in Fig. 6 agrees with previous studies on the dispersion–
flocculation–redispersion sequence of SiO2 colloids by the addi-
tion of cationic surfactants,40,41 and can be described in terms of
the reverse orientation model of the surfactant molecules
proposed by Somasundaran and Fuerstenau.42 The addition of
a low concentration of CnTAB to the dispersion of silica nano-
particles leads to an increase in the hydrophobicity of the
complexes as a result of the favourable electrostatic interaction
between the nanoparticles and the surfactant molecules which
Fig. 5 Ellipsometric thicknesses obtained by means of the two-layer
model, for the silica–surfactant nanocomposite at the air–water interface
as a function of the surfactant concentration; symbols as follows: CTAB
(,) and DTAB (B). (a) represents the thickness of the silica–air
layer (hSi–air) while (b) represents the thickness of the silica–water layer
(hSi–H2O).
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Fig. 6 (a) Contact angle, obtained from the analysis of the ellipsometric
results by means of the two-layer model proposed, for the silica–surfac-
tant nanocomposite at the air–water interface as a function of the
surfactant concentration; symbols as follows: CTAB (,) and DTAB
(B). (b) Attachment energies of the nanoparticle–surfactant complexes
at the air–water interface. (c) Dependence of the z-potential on the CTAB
concentration for composite CTAB–SiO2 obtained by Wang et al.39
favours their adsorption as individual ions onto the surface of the
nanoparticles.39 Further increases of the surfactant concentra-
tion lead to the increase of the hydrophobic interactions between
the hydrocarbon tails of surfactant molecules attached to the
particle surface. This interaction could change the structure of
the adsorbed surfactant layer onto the silica nanoparticles,
inducing the formation of a more hydrophilic interfacial layer.
Concretely, it is assumed that the hydrophobic interaction
between the tails of the adsorbed surfactant molecules can lead to
the rearrangement of the surfactant molecules on the nano-
particle–water interface. This situation leads to the formation of
adsorbed complexes in which a second layer of surfactant is
adsorbed, even though in the initial bulk species, these bilayers or
hemimicelles were not presented onto nanoparticle surfaces. This
fact renders the complexes more hydrophilic thus decreasing the
contact angle of the nanoparticles attached to the interface. A
similar effect of the alkyltrimethylammonium based surfactant
on the wettability of alumina nanoparticles was reported by Fan
et al.43 It should be noted that, in accordance with Liggieri
et al.,23 the values of G/Gsaturation are in the order of 102 for all
surfactant concentrations. Thus, to explain the formation of
hemimicelles and bilayers of surfactant onto the nanoparticles,44
one can consider that surfactant-modified nanoparticles act as
carriers of cationic surfactants to the interface, and once there,
the surfactants can be rearranged into the interfacial layer
formed by the tuned nanoparticles. Indeed, once at the interface,
the surfactants adsorbed at the particle surface should be fav-
oured to migrate to the particle surface exposed to air. In fact, the
surfactant molecules do not expose their hydrophobic chains to
the water phase. The particle surface in contact with water is
therefore depleted and could adsorb new surfactant molecules (to
maintain the adsorption equilibrium at the water–silica surface)
through the interaction with particles (decorated with surfactant
molecules) arriving from the aqueous bulk. These ‘‘carrier
particles’’ are mostly rejected in the bulk since they become less
hydrophobic. Such process has the net effect of enriching the
surfactant adsorbed on the particles at the liquid interface. The
presence of this process is supported by the dilational rheological
Soft Matter, 2012, 8, 837–843 | 841

response of this type of systems.23 However, complementary
experiments are necessary to get further insight into this naive
model. In addition to the ‘‘carrier particles’’ mechanism, one also
has to consider the exchange of residual amounts of free
surfactant molecules from the bulk to the interface.
A similar trend was observed for the contact angle q-depen-
dence on CnTAB concentration, as shown in Fig. 6a. The
nanoparticles become more hydrophobic as the surface concen-
tration increases until 104 M. Then, they become more hydro-
philic as the concentration approaches its cmc. Additionally, the
attachment energies DEp of the nanoparticles at the interface—
calculated by eqn (1) and plotted in Fig. 6b—allowed us not only
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E
to confirm that the nanoparticles are attached irreversibly to the
interface, but also that DEp depends on the hydrophobicity of the
composite particles. Furthermore, the changes in the wettability
of the nanoparticles are consistent with the z-potential results of
Wang et al. for the composite particles reproduced in Fig. 6c40 It
is observed that the increase in the surfactant concentration leads
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to an increase of the z-potential until the isoelectric point at
which the composite particles become more hydrophobic due to
the neutralization of the nanoparticle surface charge by the
surfactant charges (charge inversion).11 Further addition of
surfactants leads to the charge inversion45 of the composite
particles in agreement with a new decrease in the hydro-
phobization degree due to the potential formation of a second
layer of surfactant molecules stabilized via chain–chain interac-
tions. Note that the isoelectric point for silica nanoparticles–
CnTAB surfactant composites reported by Wang et al.39 is found
at surfactant concentrations in the 104 to 2  104 M range, in
agreement with the maximum degree of hydrophobization found
for our composite particles. This is in agreement with that
proposed by Binks et al.11 Similar correlations between z-
potential, wettability and orientation of the surfactant molecules
at the solid surface were found by Fuerstenau and Jia for the
effect of alkypiridinium chlorides in the interfacial behaviour of
quartz.46 Nevertheless, in order to confirm the above picture the
use of grazing-angle scattering techniques is necessary.
To sum up, the exchange of surfactant molecules between the
composite particles in the bulk and the interfacial layer must be
considered as an important factor to tune the hydrophilic/
hydrophobic balance of the adsorbed layer. In other words, the
mechanism based on the nanoparticles acting as carriers for the
surfactant ions from the bulk to the interface can be realistic, and
it should be taken into consideration for the redistribution of these
ions within the composite interfacial layer. Thus, this mechanism
could explain the changes in the hydrophobicity of the interfacial
complexes. However, the z-potential values obtained by Wang
et al.39 prove that the surfactant aggregates similar to bilayers are
likely to form at the silica surface already in the bulk resulting in an
inversion from hydrophobic to hydrophilic, which may occur also
in the bulk. The formation of bilayers of CTAB around nano-
particles has been previously reported by Mandal et al.47 for the
stabilization of gold nanoparticles.
As a final remark concerning the nature of the surfactants, the
ellipsometric measurements have shown that differences on the
hydrocarbonated chain length of the surfactants – basically, due
to the large chain length that exhibits CTAB in relation to DTAB
– does not result in a stronger effect on the wettability properties
of the complexes. Although, as expected, the values of q for the
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DTAB complexes are always higher than for CTAB ones, the
slightly lower values of q for CTAB complexes may be due to
a higher hydrophobic interaction between surfactant tails and
the steric hindrance in the particle–surfactant composites.
4. Conclusions
We have carried out an experimental study of the structural
conformation of the interfacial nanocomposite system consti-
tuted by silica nanoparticles interacting with cationic surfactants
such as CnTAB, with CTAB for n ¼ 16 and DTAB for n ¼ 12. It
is well known that the addition of surfactants modified the
intrinsic hydrophilic–lipophilic balance of the particles and then
their affinity for the fluid interfacial environment. We thus
pointed out the arrangement, and the reorganization of the
nanoparticles decorated with surfactants at the air–water inter-
face by ellipsometry. We have interpreted the ellipsometric
results in terms of a two-layer model in order to get further
insight into the plausible structure adopted by the mixed layers at
the air–water interface that it is controlled for the balance
between electrostatic and hydrophobic interactions. This model
allows us to know the particle’s hydrophobicity and determine
the grade of affinity for the fluid interfacial environment that
shows a strong dependence on the surfactant concentration.
To summarize, it must be considered that the results presented
here point out the important role of the composition of the
dispersion in the attachment of the nanoparticles to the interface.
However, the meaning of the wettability properties of the inter-
facial complexes must be considered as effective parameters.
Since the theory defines it under simple conditions that should
probably be reconsidered for a more rigorous analysis of these
complex nanocomposite systems. However, the significance of
this work is related to the interesting information obtained from
the evaluation of the energy of transference of the particles to the
interface.
Acknowledgements
This work was supported in part by MICINN under grant
FIS2009-14008-C02-01, by the European Space Agency under
grant MAP AO-00-052 (FASES) and PASTA, by EU under
MULTIFLOW excellence network of the 7th FP, and fostered by
the networking activities within the ESF COST-Actions D43
‘‘Surface Chemistry for Nanotechnology’’ and P21 ‘‘Physics of
Droplets’’. A.M. and E.G. were supported by a FPU fellowship
from MICINN. The authors are grateful to the UIRC of the CAI
of Spectroscopy of Complutense University for the use of its
ellipsometer.
References
1 Colloidal Particles at Liquid Interfaces, ed. B. P. Binks and T. S.
Horozov, Cambridge University Press, Cambridge, UK, 2006.
2 E. Santini, J. Kr€agel, F. Ravera, L. Liggieri and R. Miller, Colloids
Surf., A, 2011, 382, 186–191.
3 A. Maestro, L. J. Bonales, H. Ritacco, R. G. Rubio and F. Ortega,
Phys. Chem. Chem. Phys., 2010, 12, 14115–14120.
4 B. P. Binks, Curr. Opin. Colloid Interface Sci., 2002, 7, 21–41.
5 R. Miller, V. B. Fainerman, V. I. Kovalchuk, D. O. Grigoriev,
M. E. Leser and M. Michel, Adv. Colloid Interface Sci., 2006, 128–
130, 17–26.
This journal is ª The Royal Society of Chemistry 2012

6 R. Aveyard, B. P. Binks and J. H. Clint, Adv. Colloid Interface Sci.,
2003, 100–102, 503–546.
7 A. Stocco, E. Rio, B. P. Binks and D. Langevin, Soft Matter, 2011, 7,
1260–1267.
8 A. Stocco, J. Crassous, A. Salonen, A. Saint-Jalmes and D. Langevin,
Phys. Chem. Chem. Phys., 2011, 13, 3064–3072.
9 E. Santini, F. Ravera, M. Ferrari, M. Alf^e, A. Ciajolo and L. Liggieri,
Colloids Surf., A, 2010, 365, 189–198.
10 S. Limage, J. Kr€ agel, M. Schmitt, C. Dominici, R. Miller and
M. Antoni, Langmuir, 2010, 26, 16754–16761.
11 B. P. Binks, M. Kirkland and J. A. Rodrigues, Soft Matter, 2008, 4,
2373–2382.
12 P. Pieranski, Phys. Rev. Lett., 1980, 45, 569–572.
13 S. Levine, B. D. Bowen and S. J. Partridge, Colloids Surf., 1989, 38, 325.
14 D. Y. Zang, E. Rio, D. Langevin, B. Wei and B. P. Binks, Eur. Phys.
J. E, 2010, 31, 125–134.
Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1SM06421E
15 D. Frydel, S. Dietrich and M. Oettel, Phys. Rev. Lett., 2007, 99,
118302.
16 V. N. Paunov, B. P. Binks and N. P. Ashby, Langmuir, 2002, 18,
6946–6955.
17 V. B. Fainerman, V. I. Kovalchuk, E. H. Lucassen-Reynders,
D. O. Grigoriev, J. K. Ferri, M. E. Leser, M. Michel, R. Miller and
H. M€ ohwald, Langmuir, 2006, 22, 1701–1705.
Downloaded by Stanford University on 16 March 2013
18 R. Aveyard, B. P. Binks, P. D. I. Fletcher and C. E. Rutherford,
Colloids Surf., A, 1994, 83, 89–98.
19 F. Ravera, E. Santini, G. Loglio, M. Ferrari and L. Liggieri, J. Phys.
Chem. B, 2006, 110, 19543–19551.
20 F. Ravera, M. Ferrari, L. Liggieri, G. Loglio, E. Santini and
A. Zanobini, Colloids Surf., A, 2008, 323, 99–108.
21 J. Lucassen, Colloids Surf., 1992, 65, 131–137.
22 L. J. Bonales, H. Ritacco, J. E. F. Rubio, R. G. Rubio, F. Monroy
and F. Ortega, Open Phys. Chem. J., 2007, 1, 25–32.
23 L. Liggieri, E. Santini, E. Guzm
an, A. Maestro and F. Ravera, Soft
Matter, 2011, 7, 7699–7709.
24 B. Berne and R. Pecora, Dynamic Light Scattering, John Wiley, New
York, 1975.
25 R. M. A. Azzam and N. M. Bashara, Ellipsometry and Polarized
Light, Elsevier, North-Holland, 1987.
This journal is ª The Royal Society of Chemistry 2012
View Article Online
26 D. Y. Zang, A. Stocco, D. Langevin, B. B. Wei and B. P. Binks, Phys.
Chem. Chem. Phys., 2009, 11, 9522–9529.
27 N. T. Hunter and J. G. Jameson, Langmuir, 2009, 25, 3440–3449.
28 M. J. Rosen, Surfactant and Interfacial Phenomena, Wiley-
Interscience, New Jersey, USA, 2004.
29 A. Prosser and E. Franses, Colloids Surf., A, 2001, 178, 1–40.
30 K. Szymzyk and B. Janezuk, Langmuir, 2010, 26, 2491–2496.
31 M. G. Mu~ noz, F. Monroy, F. Ortega, R. G. Rubio and D. Langevin,
Langmuir, 2000, 16, 1083–1093.
32 E. Guzm
an, H. Ritacco, F. Ortega, T. Svitova, C. J. Radke and
R. G. Rubio, J. Phys. Chem. B, 2009, 113, 7128–7137.
33 A. Maestro, E. Guzm
an, R. Chuli
a, F. Ortega, R. G. Rubio and
R. Miller, Phys. Chem. Chem. Phys., 2011, 13, 9534–9539.
34 N. T. Hunter, J. G. Jameson and E. Wanless, Aust. J. Chem., 2007, 60,
651–655.
35 N. Nagy, A. Deak, Z. Horvolgyi, M. Fried, A. Agod and I. Barsony,
Langmuir, 2006, 22, 8416–8423.
36 D. E. Aspnes, Thin Solid Films, 1982, 89, 249–262.
37 D. R. Lide, CRC Handbook of Chemistry and Physics, CRC Press,
Boca Raton, Florida, USA, 2004.
38 L. J. Bonales, J. E. F. Rubio, H. Ritacco, C. Vega, R. G. Rubio and
F. Ortega, Langmuir, 2011, 27, 3391–3400.
39 W. Wang, B. Gu, L. Liang and W. A. Hamilton, J. Phys. Chem. B,
2004, 108, 17477–17483.
40 K. Esumi, J. Colloid Interface Sci., 2001, 241, 1–17.
41 B. Kitiyanan, J. H. O’Haver, J. H. Harwell and S. Osuwan, Langmuir,
1996, 12, 2162–2168.
42 P. Somasundaran and D. W. Fuerstenau, J. Phys. Chem., 1966, 70,
90.
43 A. Fan, P. Somasundaran and N. J. Turro, Langmuir, 1997, 13, 506–
510.
44 P. Kekicheff, H. K. Christenson and B. W. Ninham, Colloids Surf.,
1989, 40, 31–41.
45 E. Guzm
an, H. Ritacco, J. E. F. Rubio, R. G. Rubio and F. Ortega,
Soft Matter, 2009, 5, 2130–2142.
46 D. W. Fuerstenau and R. Jia, Colloids Surf., A, 2004, 250, 223–231.
47 S. Mandal, S. K. Arumugam, S. D. Adyanthaya, R. Pasricha and
M. Sastry, J. Mater. Chem., 2004, 14, 43–47.
Soft Matter, 2012, 8, 837–843 | 843