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Nanoscale structure of surfactant-induced nanoparticle monolayers at the
oil–water interface†
Davide C. E. Calzolari,‡a Diego Pontoni,*a Moshe Deutsch,b Harald Reichertac and Jean Daillantd
Published on 20 September 2012. Downloaded by Open University on 18/06/2013 04:09:37.

Received 30th June 2012, Accepted 20th August 2012

DOI: 10.1039/c2sm26520f

Water-dispersed silica nanoparticles (NPs) do not adsorb to the interface between immiscible bulks of
water and hexane. Adding, however, a surfactant (cetyltrimethylammonium bromide, CTAB) to water
induces the formation of a NP monolayer (ML) at this model liquid–liquid interface. We determined
the ML’s structure in situ at deeply buried planar water–hexane interfaces with sub-nanometer
resolution by high energy X-ray reflectivity. Detailed modeling of the data yields the NPs’ interfacial
concentration and water immersion depth, allowing calculation of the NP average contact angle Q. At a
CTAB concentration fc ¼ 0.75 mM, comparable to the critical micelle concentration, a dilute NP
monolayer is found with Q  128 . At lower surfactant concentration (fc ¼ 0.05 mM) we find a dense
ML of close-packed NPs with an unexpectedly high Q  146 . The structure and adsorption scenarios
of the NPs at the interface are discussed, highlighting the relevance of the present method for
quantitative studies of a broad range of systems and applications.

1 Introduction neglected in the standard DE calculation.14 The latter yields

(24  10)kT and (5  2)kT for the high and low fc systems,
Self-assembly of nano-particles (NPs) at liquid–liquid interfaces respectively, thus highlighting the need for more advanced
is of fundamental scientific interest1–3 and has a great techno- interfacial binding theories, particularly in the case of dense MLs
logical impact.4,5 It is, therefore, intensely studied both theoret- of interacting nano-sized particles.
ically6–10 and experimentally.11–13 Accurate measurements of the
NP’s contact angle Q (Fig. 1(a)) and binding energy DE14 are very
challenging, particularly for NPs residing at deeply buried
interfaces between immiscible liquids. We report Q measure-
ments and classical DE calculations for silica NPs adsorbed at a
flat interface between hexane and aqueous solutions of cetyl-
trimethylammonium bromide (CTAB) surfactant. The interfa-
cial structure is determined with Angstr€
om resolution by
high-energy X-ray reflectivity (XRR) for two CTAB concentra-
tions, fc, well below and near the critical micelle concentration,
fcmc. At a low fc (0.05 mM) we find a dense ML of close-packed
NPs with Q ¼ (146  4) , while a higher fc (0.75 mM) yields a
less dense ML with lower Q ¼ (128  6) . The NP close-packing
scenario suggests a solid-like character for the low-fc ML, which
is likely stabilized by strong inter-NP interactions that are

a
European Synchrotron Radiation Facility, 6 rue Jules Horowitz, BP220,
38043 Grenoble, France. E-mail: pontoni@esrf.fr
b
Physics Department and Institute of Nanotechnology and Advanced
Materials, Bar-Ilan University, IL-52900 Ramat Gan, Israel Fig. 1 System description and X-ray scattering geometry. (a) Schematic
c
Max-Planck-Institut f€
ur Metallforschung, Heisenbergstr. 3, D-70569 representation of two silica nanoparticles at the buried water–hexane
Stuttgart, Germany
d
interface. The particle’s contact angle Q is obtained from modeling of the
CEA, IRAMIS, LIONS, bat. 125 CEA Saclay, F-91191 Gif-sur-Yvette
X-ray reflectivity data. The other parameters are described in the text. (b)
Cedex, France
† Electronic supplementary information (ESI) available. See DOI: Schematic cross-section of the sample environment (not to scale).
10.1039/c2sm26520f The concentric 2 mm thick glass beakers (dashed black) are centered by a
‡ Present address: Physics Department, Fribourg University, Ch. du 2 mm thick Teflon ring (dashed white). The inner diameter of the external
Musee 3, CH-1700 Fribourg, Switzerland. beaker is 58 mm.

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The NPs are rendered surface-active by adsorbing surfactant
molecules on their surface, thus transforming them from
hydrophilic to partially hydrophobic. This partial wettability
modification drives the NPs to the oil–water interface, forming
and stabilizing oil-in-water (o/w) or water-in-oil (w/o) emul-
sions, depending on the degree of particle hydrophobicity.
Extensive studies15–18 of these systems uncovered numerous
fascinating effects including the spectacular microemulsion
double phase inversion.19,20 We study a typical water-dispersed
silica NPs–CTAB–hexane model system to allow a direct
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ID02 beamline of the ESRF25 using 12.4 keV X-rays and an
image-intensified CCD detector.26 CTAB–NP adsorption was
pre-characterized (Fig. 2(c) and (d)) by interfacial tension
measurements using a Wilhelmy-type tensiometer with a
roughened glass plate that ensured complete wetting. The XRR
measurements (Fig. 3 and 4) were performed using a High
Energy Micro-Diffractometer27,28 at the ID15A beamline of the
ESRF using a 69.8 keV X-ray beam delivering 5  1011
photons per second in a focal spot of 5  20 mm2 (V  H). The
sample environment consisted of two concentric cylindrical

comparison with rheology and optical microscopy measure- PYREX beakers separated by a thin Teflon ring (Fig. 1(b)).
ments of the same system,21,22 which suggested that surfactant– The inner beaker (5 cm diameter) was over-filled with the water
NP reorganization occurs at the interface before equilibrium is
reached. Computer simulations23 support these conclusions,
indicating post-adsorption surfactant detachment from the
NPs, causing their expulsion from the interface. Experimental
corroboration of these novel insights requires direct determi-
nation of the layer’s nano-scale structure, and, in particular, the
NPs’ immersion depth, hav (Fig. 1(a)), Q and DE. For non-
interacting particles of known size, DE is obtainable from the
macroscopic interface tension, gow,24 and yields hav and Q. The
resultant hav values were verified by direct optical microscopy24
for micro-particles, which is not possible for nano-particles.
Conversely, our method determines directly hav and Q for NPs
by X-ray reflectivity, without requiring binding energy
measurements or assuming the absence of lateral interactions
between the interfacially absorbed NPs.

2 Materials and method

We used charge stabilized water dispersions of bare silica NPs
(concentration  15 wt%) having a nominal specific area of
500 m2 g1 (Bindzil 15/500 from Akzo-Nobel). Both hexane
and CTAB (Sigma-Aldrich) had a purity $99%. CTAB was
used as received while hexane was further purified by double
filtering through alumina powder. High purity ($99.999%)
NaCl (Sigma-Aldrich) was roasted at about 600  C for several
hours before adding it to the water phase at 1 mM concen-
tration in order to promote CTAB adsorption onto the silica
particles.21 The solutions were prepared using ultrapure
deionized water (resistivity 18.2 MU cm1) produced by an
ELGA purification system. Particle sizing (Fig. 2(a)) was per-
formed by small-angle X-ray scattering (SAXS) at the
Fig. 3 Conventional box-model fitting. X-ray reflectivity from the
interface of hexane with a water solution of 1 wt% silica NPs, but no
surfactant (,,  104), only CTAB molecules at 0.05 mM concentration
(O,  102), and both 1 wt% NPs and 0.05 mM CTAB (B). The curves
have been vertically shifted from each other for clarity. The nanoparticle
monolayer formation at the interface requires the presence of both the
surfactant and nanoparticles. The continuous lines are box-model
reflectivity fits corresponding to the electron density profiles presented in
the inset (a). The orange lines indicate the box-model density profile with
(thick line) and without (thin line) interfacial roughness. Dashed red lines
indicate the best fit of the physical model discussed in Fig. 4. The circle
representing the particles in the inset is drawn to scale based on the
average particle size determined by SAXS (5.34 nm).

Fig. 2 System pre-characterization by complementary techniques. (a) Particle size characterization by small-angle X-ray scattering. (b and c)
Time dependence of the water–hexane interface tension at low (0.05 mM) and high (0.5 mM) CTAB concentrations in the absence (b) and presence (c) of
1 wt% silica nanoparticles.

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Fig. 4 Physical model fitting. Measured reflectivity curves R (symbols) normalized by the theoretical Fresnel reflectivity Rf. Continuous lines indicate
physical model fits for the 1 wt% NP system with 0.05 mM CTAB (B) and 0.75 mM CTAB (O). The dashed lines are model calculations in which only
the particle average immersion hav (Fig. 1(a)) is varied by 0.2 nm. The best-fit density profiles are plotted in the inset (a), where the circles representing
the particles are drawn to scale and positioned at the fitted hav values of 0.45 nm (B, red profile) and 1.04 nm (O, green profile). For the high density
monolayer (B), the XRR can be fitted only by close packed NPs, with a lateral separation (Fig. 1(a)) s ¼ 0.2  0.3 nm, as depicted in the inset (b). For
the low density monolayer (O), the XRR can be fitted either by a uniform interface covered by well-separated NPs (s ¼ 1.9 nm, inset (c)) or close packed
NPs covering only 60% of the interface (s ¼ 0 nm, inset (d)).

phase such that its surface was 1 mm above the beaker edge.
The upper edge of the beaker was precisely cut and mechan-
ically roughened in order to favor a stable pinning of the water
triple-phase line thus avoiding water overflowing into the
external beaker. Hexane was gently poured into the external
beaker until it completely covered the water surface thus
forming a buried water–oil interface. All parts in contact with
the liquid phases were cleaned by immersing in Piranha solu-
tion followed by extensive rinsing in ultrapure water. XRR
profiles were measured repeatedly at various lateral sample
positions between 1 and 12 hours after the formation of the
interface to ensure that the final stable state was being
probed and to exclude any irradiation-induced structural
modifications.
3 Results and discussion
3.1 Interface tension and SAXS measurements
Before discussing the XRR results, two issues must be
addressed. First, the attainment of structural equilibrium was
ensured by monitoring the time evolution of gow, as shown in
Fig. 2(b). At fc ¼ 0.05 mM, well below fcmc ¼ 0.92 mM of the
NaCl-free solution,29 gow x 28 mN m1, significantly below the
pure water–hexane gow ¼ 50.8 mN m1.30 A 10-fold higher fc ¼
0.5 mM ( fcmc reduces gow to (5 mN m1. For both fc a
stable gow is reached minutes after interface formation, con-
firming a fast CTAB adsorption and thermodynamic equilib-
rium attainment. Adding fnp ¼ 1 wt% of NPs constrains gow at
30–35 mN m1 at both fc (Fig. 2(c)), suggesting no increase in
the interfacial CTAB with increasing bulk fc, but rather an
increased CTAB adsorption onto the water-suspended NPs’
surfaces. Furthermore, the NPs cause gow to decrease slowly
over 1 to 2 hours. Rheological studies22 suggest that during
this period CTAB-coated NPs slowly adsorb to the interface
where the NPs and CTAB molecules rearrange until a ther-
modynamically stable structure is reached. Our XRR
measurements address this structure, several hours after inter-
face formation.
The second issue is the determination of the NPs size distri-
bution, needed to model the measured XRR, as discussed below.
This distribution was measured by bulk small-angle X-ray scat-
tering (SAXS), as shown in Fig. 2(a). Here q ¼ (4p/l)sin(qs/2),
l ¼ 0.1 nm, and qs are the wavevector transfer, X-ray wavelength,
and scattering angle, respectively.
The maximum at qm x 0.38 nm1, due to the system’s struc-
ture factor S(q), indicates an average inter-NP distance of 2p/qm
x 16.5 nm. The local minimum at qp x 0.15 A
1, due to the
particle’s form factor P(q), yields an approximate average
particle radius of rav x 4.5/qp x 3 nm. A 100-fold dilution (black
diamonds, Fig. 2(a)) eliminates the peak, which further confirms
that the original stock solution contains mostly individual, un-
aggregated NPs. A fit (line) to a Schultz distribution P(q) model31
yields an average NP radius rs ¼ 2.7 nm and a distribution width
ss ¼ 0.9 nm.
3.2 XRR measurements
We now return to our main results, the XRR measurements,
shown in Fig. 3(b) (symbols), where R(qz), qz ¼ (4p/l)sin(a), a,
and l ¼ 0.0178 nm are the reflected fraction of the incident
X-ray beam’s intensity, the interface-normal wavevector trans-
fer, the X-ray’s incidence angle (Fig. 1(b)) and wavelength,
respectively. In the absence of either CTAB or NPs (lower
curves), R is monotonic, implying an interfacial electron density
profile (r) varying monotonically between r of water and
hexane. The top curve, however, exhibits a pronounced dip, the

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clear signature of an interfacial layer. The dip’s position, qz z
1.9 nm1, yields a thickness of d ¼ (2p/qz) x 3.5 nm, showing
the layer to be a monolayer as sketched in Fig. 3(a). Thus,
Fig. 3 demonstrates that an interfacial monolayer forms only
when both CTAB and the NPs are present. Moreover, Fig. 4
demonstrates that the monolayer’s structure varies with fc. The
lower-qz, and slightly shallower, dip at high fc in Fig. 4 implies
a thicker monolayer of a lower average r. However, deriving
quantitative conclusions from the XRR curves requires a
physically motivated model for r. This we discuss next.
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The two monotonic Rs in Fig. 3 are well fitted (solid lines) by
an error-function model r (eqn (2) below) increasing mono-
tonically from rhe ¼ 228 e nm3 of hexane to rw ¼ 334 e nm3
of water over a width si, due to the interfacial roughness
caused by thermally excited capillary waves (CWs).32 The fit
yields si ¼ 0.43 nm for NP-only (,) and si ¼ 0.54 nm for
CTAB-only (O) not too far from sCW x 0.35 nm calculated32
for a typical g ¼ 32 mN m1 and an instrumental resolution
dqz ¼ 0.15 nm 1. Small remaining fit discrepancies (Fig. 3)
may arise from interface adsorption of surfactants (CTAB-
only),33 or marginal interfacial NP layering (NP-only). Both
effects can also induce a small increase of the interface
roughness as indeed found experimentally.
Modeling the top R in Fig. 3 is more complicated. A simple
box model, approximating the interfacial layer by a uniform
high-density slab, yields a good fit (orange line), showing the
layer to be single-NP thick and to consist of densely packed
NPs, mostly immersed in hexane, thus confirming the NPs’
hydrophobicity when CTAB is present in the solution.
However, this averaged density-level model provides no infor-
mation on the NPs’ packing within the monolayer. In addition,
this box model allows only a generic assessment of the hydro-
phobic versus hydrophilic character of the particles based on the
degree of asymmetry of the interfacial r(z) peak and on a
qualitative evaluation of its position with respect to the low
density oil phase and higher density water phase.
3.3 Physical model for XRR
A more physically motivated model is needed to extract quan-
titative conclusions from the measured data. Such a model
should contain, in addition to the conventional error function
describing the liquid–liquid interface (eqn (2)), a term
describing the exact electron density profile of solid spherical
particles bound to the interface. Instead of the generic box
thicknesses and roughnesses, the parameters of a physical
model should be directly related to physical properties of the
system, such as the particles’ average radius and polydispersity,
and the average vertical separation between the particles’
centers and the position of the liquid–liquid interface. An
implementation of such a model, including also the NPs’ in-
plane packing details and Gaussian (G) size and water immer-
sion distributions, is given by:
ðð
   
rðzÞ ¼ ri ðrhe ; rw ; si ; zÞ þ r0 s; rp ; z  r0 ðs; ri ðzÞ; zÞ
Gðrav ; sr ; rÞGðhav ; sh ; hÞdrdh: (1)
ri describes the si-wide pure water–hexane interface:
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rhe  rw z
ri ðzÞ ¼ ri ðrhe ; rw ; si ; zÞ ¼ 1 þ erf pffiffiffi : (2)
2 2si
r0 describes the NPs’ contribution to the interfacial electron
density:
 
r0 ðzÞ ¼ r0 s; rp ; z
2prp  
¼ pffiffiffi  z2 þ 2hðh þ rÞz  hðh þ 2rÞ (3)
2
3ð2r þ sÞ
for h # z # h + 2r, and r0(z) ¼ 0 otherwise. Eqn (3) is the density
profile of a monolayer of hexagonally ordered spheres of radius
r, immersion depth h (h > 0 denotes water immersion), lateral
separation s (Fig. 1(a)), and electron density rp, fixed at 630 e
nm3, as calculated from the pNP’s
 density, (2.1  0.1)
ffiffiffiffiffiffi mass  g
cm3.34 Gðxav ; sx ; xÞ ¼ ð1=sx 2pÞexp  ðx  xav Þ2 =2sx 2 are
the normalized Gaussian distributions of r and h, with averages
rav and hav and widths sr and sh. G(hav,sh;h) describes the NP’s
vertical disorder mostly due to CWs, but also to thermal fluc-
tuations in the NP’s immersion depth around the instantaneous
interface position. The subtracted term in eqn (1) accounts for
the liquid displaced by the NPs. The r(z) model above was fitted
to the Fresnel-normalized reflectivity profile R/Rf (Fig. 4) using
Parratt’s recursive algorithm,35 keeping rw, rhe and rp fixed, and
varying the roughness and particle size parameters only within
narrow ranges straddling the values derived from the SAXS and
XRR control measurements discussed above. Since the NPs’
vertical disorder is correlated with, and dominated by, the CWs’
si, we limited si < sh < 2si. It is important to note that only hav
and s were completely free fit parameters, with hav controlling the
position and s the height of r(z)’s interfacial peak (Fig. 4(a)).
Thus the number of completely free parameters in our physical
model is not larger than that of a simple box model. Limiting or
fixing the other parameters of our model by independent
measurements or theoretical calculations is essential for avoiding
inter-parameter correlations in the fit, which may lead to
unphysical parameter values. The fits based on eqn (1) yield the
solid lines in Fig. 4, the corresponding r(z) profiles in Fig. 4(a),
and the parameter values in Table 1.
Table 1 Physical model parameters for fits reported in Fig. 4 and dis-
cussed in the text. fc indicates the surfactant concentration, with an
uncertainty of 0.02 mM. rav (Fig. 1(a)) and sr are the average NP radius
and standard deviation of the Gaussian radius distribution, respectively.
hav (Fig. 1(a)) and sh are the average immersion of the NPs in the water
subphase and the corresponding Gaussian standard deviation, respec-
tively. si is the CW-induced roughness of the hexane–water interface. The
error bar associated with the NP and interface-normal structural
parameters is (0.1 nm. s is the lateral separation between the surfaces
of neighboring silica NPs (Fig. 1(a)), with an associated uncertainty of
(0.3 nm. Q is the NP’s contact angle (Fig. 1(a)) calculated using the
fitted values for rav and hav. DE is the NP’s binding energy calculated
using the fitted hav and the measured interface tension gow  28 mN m1.
Only the two parameters in bold were left completely free for fitting the
XRR profiles. The remaining parameters were fixed (rav and sr) or
strongly constrained (si and sh) by complementary measurements and
theoretical calculations
fc/mM rav/nm sr/nm si/nm sh/nm hav/nm s/nm Q/ DE/kT
0.05 2.67 0.44 0.60 0.60 0.45 0.2 146  4 5  2
0.75 2.67 0.44 0.58 0.59 1.04 1.9 128  6 24  10
Soft Matter, 2012, 8, 11478–11483 | 11481

Before discussing the parameter values reported in Table 1, it
is important to note that the two experimental profiles presented
in Fig. 4 appear to be markedly different already upon simple
visual inspection: surfactant addition causes an overall decrease
of the measured R/Rf profile, while the local dip at qz z 1.9 nm1
shifts to lower qz and becomes shallower. The observed changes
of measured reflectivity are connected to variations in the NP
ML’s surface-normal electron density profile r(z). Several
attempts to fit both curves in Fig. 4 by changing only the liquid–
liquid roughness (si) and the vertical NP disorder parameter (sh)
were unsuccessful. Conversely, similar si and sh values but
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different water immersion hav and in-plane NP spacing s values
(Table 1) yield good fits to both experimental datasets (Fig. 4).
The existence of multiple r(z) profiles agreeing well with a single
reflectivity curve cannot be excluded a priori. A systematic search
for alternative solutions was performed using model-indepen-
dent stochastic approaches in which the only input parameters
are the materials’ bulk electron densities and the expected
thickness of the interfacial layer. As shown in the ESI, Fig. 5,†
such stochastic searches converge to solutions that are in rather
good agreement with the physical model results.
The parameter values summarized in Table 1 lead to the
following conclusions: at low-fc the NPs are mostly immersed in
hexane, hav ( 0.5 nm, and basically in lateral contact with each
other, s  0.2  0.3 nm (Fig. 4(b)). At high-fc, the particles are
less oil-immersed (hav T 1 nm) thus suggesting lower NP
hydrophobicity. The NP monolayer density is lower, as
demonstrated by a lower r(z) peak (Fig. 4(a), green line) and a
larger s  1.9 nm (Fig. 4(c)). However, since XRR is sensitive
only to the average density, not to the actual in-plane NP order,
an identical fit is obtained assuming a 60% interface coverage by
close packed (s ¼ 0 nm) NPs, and a 40% coverage by CTAB
molecules (Fig. 4(d)). Grazing-incidence small angle X-ray
scattering (GISAXS), which could, in principle, resolve the in-
plane NP packing,36 was found to be unfeasible since the stronger
background scattering from the bulk liquid masked the weaker
scattering from the monolayer. By contrast, the fit’s high sensi-
tivity to the surface-normal order is demonstrated by the model-
calculated R/Rf (Fig. 4, dashed lines) obtained when hav is
changed by 0.2 nm from the best fit values, keeping all other
parameters unchanged. The pronounced deviations demonstrate
that hav is determinable to better than 0.2 nm (see also the ESI,
Fig. 1 and 2†).
3.4 Discussion
A well-defined hav value allows determining accurately two
physically important NP properties: the contact angle and the
binding energy. The former, given by Q ¼ arccos(1 + hav/rav),
yields Ql ¼ 146.1 and Qh ¼ 127.6 for low and high fc. Simula-
tions, using eqn (1), provide estimates for the systematic errors
arising from neglecting immersion depth variations due to NP size
polydispersity, non-CW induced disorder in the NPs vertical
positions, and the CTAB contribution to the monolayer’s r.
The resulting maximum error bars yield QL ¼ 146  4 and QH ¼
128  6 . Clearly, even with these relatively large error estimates Q
remains significantly different for the two fc values. Using the
classical formula for non-interacting particles DE ¼ pgowhav2,14,16
with an average gow ¼ 28  4 mN m1 for the varying, yet close,
11482 | Soft Matter, 2012, 8, 11478–11483
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interfacial tensions of both high- and low-fc cases (Fig. 2(c)),
yields, respectively, DEh ¼ 23.6 kT and DEl ¼ 4.5 kT. Error
estimations focusing in particular on the role of interfacial
CTAB molecules (ESI, Fig. 3 and 4, and Table 1†) yield the cor-
responding maximum error estimates DEH ¼ 24  10 kT and
DEL ¼ 5  2 kT.
The classical DE calculations would suggest that at low fc,
DE is only slightly above kT and the NPs’ binding is very weak,
while at high fc the binding is five-fold stronger. The low DE
obtained at low fc, however, contrasts starkly with the highly
stable, close-packed (s z 0 nm) XRR-determined monolayer
structure. The two quantities used to calculate DE are accu-
rately determined by either direct measurements (gow, Fig. 2) or
detailed XRR modeling (hav), which we believe to be physically
robust and comprehensive. We must conclude, therefore, that
the classical formula itself14,16 is inaccurate,37 particularly at low
fc. This is not too surprising, since that formula assumes non-
interacting particles, while the observed close packing implies
strongly interacting NPs, possibly leading to irreversible
aggregation into a solid-like interfacial NP monolayer, as
found by light microscopy22 for the same system studied here. A
solid-like character would make single-particle detachment
impossible, thus stabilizing the monolayer even at the high
measured Q  146 .
The s z 0 spacing also implies a non-simple NP self-assembly
process for the monolayer at low-fc. In the bulk, there is no
reason to assume non-uniform CTAB adsorption on the NP’s
surface. However, s z 0 implies no CTAB intrusion between the
NPs. Thus, the CTAB coating of the monolayer’s NPs must be at
least anisotropic, if not completely absent, indicating that a
surfactant/NP structural rearrangement indeed occurs during
interfacial NP adsorption, as suggested by computer simulation23
and surface tension and rheology measurements.21 The rear-
rangement is possible because CTAB is only electrostatically
physisorbed, not chemically bound, to the NP surface. Aniso-
tropic CTAB coverage imparts anisotropic hydrophobicity,
which may drive the NPs’ interfacial self-assembly. The drive is
evidently strong enough to overcome, at the surface, the inter-
particle repulsion provided, in the bulk, by the colloidal charge
stabilization mechanism.
For low fc the bulk NPs are known22 to become hydrophobic,
albeit insufficiently so to aggregate. Thus, the bulk NPs’ surface
activity is maximal. At high fc, the NPs can undergo partial
flocculation in the bulk, yielding a lower interfacial activity. This
may explain the monolayer’s lower r at high fc. An alternative
explanation may be found by invoking the formation, at high fc,
of a more compact and dense CTAB shell covering the surface of
the water-dispersed NPs. Such a dense surfactant shell would
prevent the NPs from coming into close contact once they reach
the interface.
XRR cannot discriminate between a phase-separated NP–
surfactant film (Fig. 4(d)) and a uniformly expanded NP layer
(Fig. 4(c)). However, the local structure of aggregated NP
patches (Fig. 4(d)) at high fc and of a uniform close-packed
monolayer at low fc are identical, and thus expected to yield the
same Q  146 , in spite of the different average monolayer
densities. Finding a smaller contact angle (128 ) at higher fc
supports, therefore, a uniformly expanded NP layer (Fig. 4(c))
over a phase-separated layer (Fig. 4(d)).
This journal is ª The Royal Society of Chemistry 2012

4 Conclusions
In conclusion, combining conventional gow measurements with
cutting-edge synchrotron techniques we have determined with
high precision the interface-normal nano-scale structure of
CTAB/nano-silica monolayers formed at buried water–hexane
interfaces. The NP–water contact angle was observed to vary
with fc within the high hydrophobicity range (Q T 130 ).
Classical calculations14,16 yield weak NP adsorption, DE ¼
5–25 kT. The contrast between the low DE values and the
observed high stability of the NP monolayers demonstrates the
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inaccuracy of the binding energy calculations, in particular at
low fc. The microscopic structural scenarios revealed by our
measurements are supported by computer simulations23 and
macroscopic measurements.21,22 The present method, which
allows studying quantitatively a broad spectrum of interfacial
NP binding phenomena, should prove useful for basic sciences
and applications alike. We hope that this study will motivate also
theoretical and simulation work leading to a deeper under-
standing of the energetics, formation, and hydrophobicity-
related properties of these technologically important nano-scale
multi-component interfaces.
Acknowledgements
We thank Theyencheri Narayanan (ESRF) for access to the
ID02 beamline and for helpful suggestions concerning SAXS
data modeling, Ran Teller (Bar-Ilan) for assistance with interface
tension measurements, Peter Greenwood and Bo Larsson (Akzo
Nobel) for providing colloids and detailed sample information,
Ben Ocko, Dominique Langevin and Luc Belloni for helpful
discussion, and the ESRF for support and provision of beam-
time. Support to M.D. by the US-Israel Binational Science
Foundation, Jerusalem, is gratefully acknowledged.
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