Journal of Colloid and Interface Science 338 (2009) 491–499

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Journal of Colloid and Interface Science

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Preparation of silane-coated TiO2 nanoparticles in supercritical CO2

Carlos A. García-González *, Julio Fraile, Ana López-Periago, Concepción Domingo *
Instituto de Ciencia de Materiales de Barcelona, ICMAB-CSIC, Campus de la UAB s/n, E-08193 Bellaterra, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Nanometric inorganic pigments are widely used as fillers for hybrid composite materials. However, these
Received 31 March 2009 nanometric powders are hydrophilic in nature and their surface must be functionalized before use. In
Accepted 16 June 2009 this work, titanium dioxide (TiO2) nanoparticles were coated using silane coupling agents with alkyl
Available online 21 June 2009
functionality. A supercritical carbon dioxide (scCO2) method was used for surface silanization. Five
alkylalkoxysilanes with different alkyl chain length and structure were studied: methyltrimethoxy,
Keywords: isobutyltriethoxy, octyltriethoxy, octyldimethylmethoxy and octadecyltrimethoxysilane. The microstruc-
Silane
ture and thermal stability of deposited monolayers were characterized using thermogravimetric analysis,
Nanoparticles
Supercritical carbon dioxide
ATR–IR spectroscopy, transmission electron microscopy, wettability characterization and low-tempera-
Wettability ture N2 adsorption/desorption analysis. The use of scCO2 as a solvent provided an effective approach to
Self-assembled functionalize individual inorganic nanoparticles due to the enhanced diffusivity of the solution molecules
Monolayer in the aggregates interparticle voids. The trifunctional silanes employed here yielded surfaces with better
thermal stabilities and greater hydrophobicities than the used monofunctional silane.
Ó 2009 Elsevier Inc. All rights reserved.

1. Introduction the molecules [5–8]. Nanoparticles coating with organosilanes

Inorganic particles act as fillers for soft materials, and are essen-
tial components of many industrial composite products: the fillers
market value in Europe in 2007 was about 2.3 billion Euros [1]. Fill-
ers are basically divided into inactive and functional pigments.
Inactive fillers are mainly used to reduce final material cost, while
functional fillers modify some properties of the end product, such
us density, shrinkage, expansion coefficient, conductivity, perme-
ability and mechanical or thermal behavior. It is known that con-
siderable improvements in the properties of soft materials can be
attained by adding nanofillers to make composites. However, the
dispersion of the inorganic nanopowder into the soft organic or
polymeric phase is technically challenging, due to the different
polarity of the constituents and the high surface area of the nano-
metric phase. In this aspect, hydrophobic modification of the
nanoparticulate material has been envisaged as a solution to in-
crease the poor interfacial adhesion between inorganic and organic
phases. Titanium dioxide (TiO2) nanometric powder was chosen in
this work as the pigment to be coated. Modified TiO2 is widely em-
ployed in the engineering of photocatalysts and dye-sensitized so-
lar cells, as well as a filler in the paper, plastic, cosmetic and
biomaterials industries [2–4]. Among the large variety of mole-
cules used for the preparation of hydrophobic surfaces, organo-
functional silanes are widely used due to the dual character of
* Corresponding authors. Fax: +34 93 5805729.
E-mail addresses: cgarcia@icmab.es (C.A. García-González), conchi@icmab.es (C.
Domingo).
can be performed either by in situ deposition during synthesis
(e.g., dispersion and microemulsion processes) or by post-synthe-
sis grafting (e.g., Langmuir–Blodgett and vapor or liquid self-
assembly methods) [8–16]. Post-silanization in solution is the
most common approach, since it is not restricted to the use of vol-
atile silanes. However, nanoparticle aggregation is a drawback of-
ten accompanying the reaction in liquid media or the drying step
[17–24]. In the search for a more efficient coating process, the
use of supercritical carbon dioxide (scCO2) as a solvent has been
envisaged as an alternative silanization method [18,21,25–30].
scCO2 is a commonly used supercritical fluid with moderate critical
pressure and temperature (Pc = 7.4 MPa, Tc = 304.2 K, respectively),
being at the same time an excellent solvent for most alkoxysilanes
[31]. Moreover, scCO2 properties of gas-like diffusivity and viscos-
ity and zero surface tension facilitate the complete wetting of
the internal surface of the mesoporous aggregates formed by
nanoparticles.
In this work, a scCO2 method was used for coating the surface of
TiO2 nanoparticles by silanization. The supercritical process was
studied for several alkylalkoxysilane molecules having different
lengths and configurations of the alkyl chains: methyltrimethoxy-
silane (C1), isobutyltriethoxysilane (C4), octyltriethoxysilane (C8),
octyldimethylmethoxysilane ðC8 C21 Þ and octadecyltrimethoxysi-
lane (C18). Structure and properties of resulting monolayers were
investigated using thermal analysis, ATR–IR spectroscopy, trans-
mission electron microscopy, wettability studies and textural char-
acterization performed by low-temperature N2 adsorption. Firstly,
the extension of the advantages encountered on the use of scCO2

0021-9797/$ - see front matter Ó 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2009.06.035
492 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499
for the silanization of flat or porous silica surfaces [25,27,32,33] to
nanoparticulate materials was examined, since less research has
been performed on the processing of this kind of materials
[18,21,26,28,30]. Then, the characteristics of the obtained mono-
layers were compared with those described by other authors using
chloro or hydridesilanes and vapor or liquid post-deposition meth-
ods [8,12,13,34,35].
2. Experimental section
2.1. Materials
TiO2 nanometric particles (20 nm in diameter) were supplied
by Degussa (TiO2 P25). Degussa silanized TiO2 T805, which corre-
sponded to TiO2 P25 treated on the surface with octyltrimethoxysi-
lane (C8), was studied for comparison (sample labeled TiC8-com).
CO2 (Carburos Metálicos SA) was used as a solvent. The chemical
structure of the used organosilanes is shown in Table 1 together
with selected physicochemical characteristics.
2.2. Equipment and procedure
Supercritical silanization of nanometric TiO2 powder was per-
formed using the experimental setup depicted in Fig. 1a. A 100 mL
high-pressure autoclave (TharDesign, Re1) running in the batch
mode was used for silane deposition. The reactor was charged with
0.7 g of TiO2 powder, previously enclosed in a cylindrical cartridge
made of 0.45 lm pore filter paper, which was suspended on the
upper part of the autoclave. Liquid silane (1 mL) was added at the
bottom of the reactor. CO2 was liquefied through a cooling unit
(EX1) and compressed by a syringe pump (TharDesign SP240, P1)
used to settle the chosen value of pressure (P). The vessel was heated
at the chosen temperature (T) using resistances. The system was stir-
red at 300 rpm during the complete running time (t). At the end of
each experiment, the system was depressurized by means of valve
V3 at a CO2 flow rate of 1.2 g min1 and let cool to room tempera-
ture. Recovered samples were labeled as as-prepared.
The supercritical cleaning of the samples was carried out in a
stainless steel apparatus (Fig. 1b). Cylinders of the as-prepared
samples were introduced into 10-mL tubular reactors (Re1 and
Table 1
Used organosilanes and their physicochemical characteristics.
Organosilane Chemical formula
Methyltrimethoxy CH3Si(OCH3)3
Isobutyltriethoxy (CH3)2CHCH2Si(OCH2CH3)3
Octyltriethoxy CH3(CH2)7Si(OCH2CH3)3
Octyldimethylmethoxy CH3(CH2)7Si(CH3)2(OCH3)
Octadecyltrimethoxy CH3(CH2)17Si(OCH3)3
a
At 0.1 MPa.
b
Calculated value using Advanced Chemistry Development (ACD/Labs) Software v9.04, presented in SciFinder database.
Re2), which were placed into a circulating air-oven. Liquefied
CO2 (EX1) was compressed to the operating pressure by means
of a membrane pump (P1, Lewa EK-M-210). The system pressure
was controlled with a back pressure regulator (V8, Tescom 26-
1761). The possible excess of deposited organosilane was elimi-
nated by passing a continuous flow of scCO2 (3–5 g min1) at
22.5 MPa and 318 K during 30 min. Samples resulting after the
cleaning stage were labeled as washed (w) samples.
2.3. Characterization
The quantification of the amount of deposited silane and the
study of the thermal stability of obtained coatings were performed
using thermogravimetric analysis (TG, Perkin Elmer 7). To confirm
the presence of the coupling agent in the treated samples, ATR–IR
spectra were recorded using a Perkin Elmer Spectrum One spec-
trometer equipped with a Universal ATR sampling accessory. Spec-
tra were collected with 2 cm1 spectral resolution in the 4000–
1000 cm1 range using four scans. A goniometer PG-2 (PocketGon-
iometer Inc.) equipped with a built-in camera was used to measure
the static contact angle of a deionized water droplet (1 lL) applied
on the surface of a disk of compacted powder. Compacted disks
(12.7 mm in diameter) were prepared in a manual hydraulic press
(model 15.011, Perkin Elmer Co., USA) at a force of 100 kN for a
pressing time of 60 s. Electronic micrographs of the samples were
recorded using a transmission electron microscope (TEM, JEOL
JEM-1210). The nanoparticles were first dispersed in acetonitrile,
an aprotic chromatographic solvent with intermediate polarity
(dielectric constant = 37). Textural characteristics of raw and silan-
ized samples were studied by low-temperature N2 adsorption–
desorption analysis (ASAP 2000 Micromeritics). Prior to measure-
ments, samples were dried under reduced pressure (<1 mPa) at
393 K for 18 h. Specific surface area (as) was determined by the
BET method. Mean pore diameter (dp) was estimated using the
BJH method.
3. Results and discussion
The general formula of organoalkoxysilanes is RnSi(OR0 )4n
[5,6,36], where the organic functional group R is expected to inter-
Abbr. Mw (gmol1) Boiling pointa (K) Supplier
C1 136.22 375 Aldrich
C4 220.39 462 Fluka
C8 276.49 538 Fluka
C8 C21 202.41 495 ABCR
C18 374.68 567 ± 8b Fluka
 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499 493

a PI TI PI
PIC
001 101 201 101
M

V1 P1 V2 Re1 V3
EX1 LG TIC
M 101 201

T1

b
TI PI PIC
101 02 201

TI TI FI
102 103 101
PI
V8
01
Re1 Re2
PI EX2 R3 PI
101 R1
02
S PSV
V5 V6 V7 001

V1 V2 P1
EX1
V3 V4

TIC
R4 201

T1 OVEN

Fig. 1. Process flow diagrams of the high pressure equipment: (a) batch supercritical silanization reactor (Re1) with sapphire windows, where cooled (EX1) CO2 is compressed
by a syringe pump and V1–V3 are valves used to regulate the flow of CO2 and (b) 10-mL tubular reactors (Re1 and Re2) for excess silane removal with a continuous scCO2 flow
compressed by a membrane pump (P1) and heated in a air-oven.

act with organic phases. The surface silanization reaction is de-
scribed to start with the hydrolysis of the alkoxy OR0 groups of
the silane molecule to form silanols (RnSi(OH)4n), which can then
interact with the OH groups on the surface of the inorganic parti-
cles (titanols) by hydrogen bonding (Ti–OH. . .HO–Si) or with other
silane molecules (Si–OH. . .HO–Si) [11,34,35]. Then, dehydration of
the formed hydrogen bonds produced siloxane linkages between
silane and the surface (Ti–O–Si), and self-assembled monolayers
by condensation of neighboring silane molecules (Si–O–Si). In this
work, the properties of surfaces prepared by the reaction of mono
(RR002 SiðOR0 Þ with R = C8 and R00 = C1) and trialkoxysilanes (RSi(OR0 )3
with R = C1, C4, C8 and C18) with TiO2 in a scCO2 medium were eval-
uated as a function of the chemical formula and physicochemical
characteristics of the different silanes used (Table 1). For trialkoxy-
silanes, where three silanol groups could be formed after hydroly-
sis (RSi(OH)3), interaction with the surface together with
horizontal self-assembly forming a siloxane network, and vertical
polycondensation were all possible processes [35]. On the other
hand, for the monoalkoxysilane with a single hydrolyzable group
in the molecule (RR002 SiðOHÞ), grafting was only possible by covalent
attachment to the surface [34].
Octyltriethoxysilane (C8) was considered as the silane with
intermediate characteristics to evaluate the results obtained for si-
lanes with a shorter (C1 and C4) or a longer (C18) alkyl chain. More-

Table 2
Supercritical silanization operating conditions and some obtained results: TG estimated amount of deposited silane (ds) in the intervals 325–525 K (1), 525–650 K (2) and
650–850 K (3), surface area (as) and mean pore diameter (dp).

Sample Silane P (MPa) T (K) t (min) Washing ds 1 (%wt) ds 2 (%wt) ds 3 (%wt) as (m2g1) dp (nm)
TiO2 – – – – – – – – 54 11
TiC1-1 C1 10.0 348 50 No 0.0 0.3 0.5
TiC1-2 C1 22.5 318 15 No 0.3 0.7 0.3
TiC1-2w C1 22.5 318 15 Yes 0.2 0.4 0.5
TiC4-1 C4 10.0 348 50 No 3.7 2.2 0.9
TiC4-2 C4 22.5 318 15 No 9.6 1.8 0.9
TiC4-2w C4 22.5 318 15 Yes 0.2 0.9 1.0 48 18
TiC8-com C8 – – – – 0.0 1.6 1.8 48 11
TiC8-1 C8 10.0 348 50 No 5.4 1.5 1.8 55 13
TiC8-1w C8 10.0 348 50 Yes 0.0 1.6 1.8 52 18
TiC8-2 C8 22.5 318 15 No 4.8 1.7 1.9 57 11
TiC8-2w C8 22.5 318 15 Yes 0.0 1.8 1.8 53 17
TiC8 C21 -2 C8 C21 22.5 318 50 No 1.3 1.1 1.2
TiC8 C21 -2w C8 C21 22.5 318 50 Yes 0.2 1.2 1.2
TiC18-1 C18 10.0 348 50 No 0.3 0.2 0.7
TiC18-2 C18 22.5 318 15 No 0.6 4.3 4.4 48 14
TiC18-2w C18 22.5 318 15 Yes 0.1 4.7 2.4 50 16
494 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499
over, two different molecules with a C8 chain were used, an octyl
group (C8) in a triethoxysilane and an octyldimethyl group (C8 C21 )
in a monomethoxysilane. The characteristics of TiO2 powders mod-
ified with silanes capable to form a self-assembled monolayer (C1–
C18) and a covalently attached monolayer (C8 C21 ) [12] were thus
compared. Employed experimental conditions are shown in Table
2, together with obtained results.
3.1. Silanization strategy
Silanization conditions were first optimized for the C8 molecule
using two different experimental strategies. The first strategy con-
sisted in choosing a set of silanization conditions corresponding to
high temperature and low pressure (strategy 1: 348 K and 10 MPa),
in which the amount of added silane was in excess with respect to
the concentration of saturation in scCO2. The excess of silane was
visually observed through the sapphire windows of the reactor,
in the form of liquid droplets. In the second approach, the silaniza-
tion was carried out at low temperature and high pressure (strat-
egy 2: 318 K and 22.5 MPa), conditions at which the added silane
fully solubilized in scCO2 and no liquid phase was visually ob-
served during the complete run. In the first strategy, the silane con-
tent in the scCO2 medium remained constant at the concentration
of saturation during the complete run. For the second strategy, the
silane concentration in the scCO2 phase decreased as the silaniza-
tion reaction progressed. However, the used silanes had different
solubilities in scCO2 due to their different molecular weight and
structure [31,37,38]. As a consequence, the strategy of partial sol-
ubilization by using the operating conditions optimized for the
C8 chain (strategy 1) led to fully solubilization of the short silane
molecules (C1 and C4) and negligible solubilization of the octadec-
ylsilane (C18). Nevertheless, in order to facilitate data comparison,
the two set of described operating conditions were used to study
the behavior of the five tested silanes.
3.2. Thermal studies
Thermal behavior of silane treated samples was studied by ther-
mogravimetric analysis. Thermal analysis indicated that a mass
loss of 0.6 wt% occurred for raw TiO2 in the temperature range
325–600 K. The presence of water adsorbed on the TiO2 surface
a 2
25
TiC8 -2w
% weight loss [a.u.]
20
15
TiC8 -1w
10
TiC8 -1
5 d[TiC8 -com]
TiC8 -com
0 0
325 425
Fig. 2. Thermogravimetric curves and derivative profiles obtained for TiO2 samples silanized with: (a) C8 and (b) C1, C4 and C18 silanes. Measurements were carried out under
Ar atmosphere from room temperature to 850 K with a heating rate of 5 K min1.
was necessary to initiate the silanization reaction [5,6,36]. The
most evident features of the recorded TG thermographs of the
as-prepared C8 trialkoxysilane samples were three characteristic
regions of weight loss in the temperature ranges 325–425, 525–
650 and 650–850 K (Fig. 2a) [30]. The amount of silane deposited
on the TiO2 powder for the different performed experiments was
estimated from the recorded weight decay curves in the mentioned
temperature ranges (Table 2). Deposition of raw silane on the sur-
face of the as-prepared samples TiC8-1 and TiC8-2 was evidenced
by a first decay at relatively low temperature (325–425 K). Evapo-
ration of the non-hydrolyzed silane occurred at temperatures low-
er than the silane boiling point (Table 1), as expected for a non-
interacting deposited layer. A further treatment of these samples
with a continuous flow of scCO2 at 22.5 MPa and 318 K during 30
min led to the elimination of those unbounded molecules (samples
TiC8-1w and TiC8-2w). Next, the observed weight loss in the range
525–650 K, occurring for both as-prepared and washed samples,
was assigned to the desorption of hydrolyzed silane chains inter-
acting by hydrogen bonding with the OHs on the TiO2 surface. In
addition, within this temperature region some of the weight loss
was attributed to the elimination of water coming from the con-
densation of silanol groups interacting either with OHs on the sur-
face or laterally with other silanols [8,12,35,39]. Moreover, some
desorption of residual TiO2 physisorbed water could also take
place, although most of the adsorbed water was expected to be
consumed during the silanization reaction [40]. Finally, the weight
loss observed in the highest temperature region (650–850 K) was
attributed to the cleavage of C–C and/or Si–C bonds in highly con-
densed siloxanes and chemisorbed silane [12,41,42].
For the octyltriethoxysilane C8, despite of the two different used
silanization strategies (1 and 2), the silane content in the scCO2
medium did not significantly affect either the amount of silane
deposited on the TiO2 surface (Table 2) or the thermal stability of
the obtained coating (Fig. 2a). In both cases, the second decay
had the maximum slope at temperatures around 600 K, and the
third at about 750 K (curves d[TiC8-1w] and d[TiC8-2w]). More-
over, similar values of both, the amount of deposited silane and
decomposition temperature, were found for the commercial sam-
ple (curves TiC8-com and d[TiC8-com]), and the C8 supercritically
coated and washed TiO2 powders. On the other hand, the octyldim-
ethylmethoxysilane C8 C21 formed a less dense (Table 2) and less
12
d[TiC8 C1 -2 ] b
TiC1 -2w
2 TiC4 -2w
TiC8 C1 -2 10
% weight loss [a.u.]
d[TiC8 -2w ]
8
TiC8 -2 d[TiC18 -2w ]
6
d[TiC8 -1w ] TiC18 -2w
4
2 TiC18 -2
525 625 725 825 325 425 525 625 725 825
T [K] T [K]
 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499
thermally stable silane coating (curves TiC8 C21 -2 and d[TiC8 C21 -2])
than C8. For sample TiC8 C21 -2, the maxima weight decay slopes
vs. temperature for the second and third stages were estimated
at 530 and 670 K, respectively. The reason of the different behavior
of both C8 silane molecules was related to the fact that octyltrieth-
oxysilane had three hydrolyzable groups, while octyldimethyl-
methoxysilane had only one. For the monoalkoxysilane, after
interaction of its single silanol group with the TiO2 surface, the ab-
sence of the extra hydrolyzable groups prevented the cross-linking
with vicinal silane molecules on the surface. The lateral condensa-
tion occurring for the octyltrialkoxysilane enhanced the thermal
stability of the coating.
Due to the low molecular weight of methyltrimethoxysilane C1
in comparison with the other silane molecules used in this work
(Table 1), the measured weight loss in the TG analysis was very
low (curve TiC1-2w in Fig. 2b) and the sensibility of the used ther-
mal apparatus was not enough to determine precisely neither the
silane content in the samples nor the temperature of thermal
desorption and decomposition. For the isobutyltriethoxysilane C4,
a similar silane content was calculated for samples obtained using
either strategy 1 or 2 (Table 2). Finally, for octadecyltrimethoxysi-
lane C18, the solvation power of scCO2 under the first set of operat-
ing conditions (strategy 1) was not enough to solubilize an
appreciable amount of silane because of its high molecular weight
(Table 1). Therefore, TiO2 particles were not significantly silanized
under this set of operating conditions (Table 2). In contrast, the sil-
anization process was effective by using the second set of scCO2
conditions (strategy 2). The thermal stability of the obtained C18
coating (curve d[TiC18-2w] in Fig. 2b) was similar to that obtained
for the C8 compound. However, both as-prepared and washed sam-
ples using strategy 2 (TiC18-2 and TiC18-2w, respectively) pre-
sented only the two high temperature decays of weight loss
(Fig. 2b). It should be taken into account that octadecyltrimethoxy-
silane was solid under ambient conditions (melting point of 290 K).
Therefore, non-hydrolyzed C18 silane molecules deposited on the
as-prepared TiC18-2 sample were not easily evaporated and could
have undergone intermolecular condensation forming polyhedral
oligomers during the heating of the sample in the TG analysis
[43,44]. These condensed structures were degraded by further
heating, being this the reason why the as-prepared sample had a
higher total mass loss than the washed material in the temperature
range 650–850 K.
3.3. ATR–IR spectroscopic analysis
ATR–IR spectroscopy was used to chemically characterize the
silane layer deposited on the TiO2 surface. Fig. 3 shows the ATR–
IR spectra of raw TiO2, the commercial silanized material, and
the C1, C4, C8, C8 C21 and C18 silanized and washed samples prepared
using strategy 2. The as-prepared materials and the samples ob-
tained applying strategy 1 had similar spectra to that shown in
Fig. 3. Characteristic bands corresponding to the organic part of
the different used silane molecules were those appearing at around
2955 and 2870 cm1 (CH3 antisymmetric and symmetric stretch-
ing, respectively), 2918 and 2851 cm1 (CH2 antisymmetric and
symmetric stretching, respectively) and 1467 cm1 (CH2 symmet-
ric bending) [12,40,45,46]. The pattern of alkyl groups in the silane
monolayer was assessed by means of the position of the CH2
stretching bands [12], which has a value of 2924 cm1 for disor-
dered structures like liquid alkane and is shifted to a lower wave-
number (2915–2918 cm1) in crystalline alkanes [47]. Hence,
according to the literature CH2 stretching frequencies obtained
for supercritically silanized samples corresponded to well-ordered
structures.
Recorded spectra showed that the intensity of bands due to CH2
diminished, as the number of CH2 groups in the alkyl chain of the
495
TiO 2
TiC 1-2w
TiC 4-2w
2
TiC 8C1 -2w
TiC 8-com
TiC 8-2w
TiC 18-2w
3500 3000 2500 2000 1500 1000
-1
Wavenumber [cm ]
Fig. 3. ATR–IR spectra in the range 1000–3750 cm1 of bare TiO2, commercial (TiC8-
com) and silanized (strategy 2) samples after washing.
used modifier decreased (C1: 0, C4: 1, C8 and C8 C21 : 7 and C18: 17).
The contribution of the length of the alkyl group to the intensity of
the CH2 bands measured with respect to the CH3 bands was quan-
tified for C8 and C18 silanes. Bands selected for analysis were the
CH2 peak at 2916 cm1 and the CH3 peak at 2955 cm1. The
estimated intensity ratios of these bands were in good agreement
with the CH2:CH3 molar ratio in the molecular formula of the C8
and C18 silane molecules, i.e., 7:1 for C8 (samples TiC8-2w and
TiC8-com in Fig. 3) and 17:1 for C18 (sample TiC18-2w in Fig. 3).
Similar intensity ratios of CH2:CH3 bands were found for samples
coated with either C8 or C8 C21 , since there was no contribution of
the CH3 group linked to the silicon atom in the C8 C21 silane to the
intensity of the CH3 band in the alkyl chain. Stretching bands from
CH3 at 2916 and 2850 cm1 and CH2 at 2955 and 2870 cm1 were
not observed for samples coated with the C1 silane. In this case, the
presence of the silane on the TiO2 surface was confirmed by the
appearance of the CH3 stretching symmetric band from Si–CH3 at
1275 cm1 [48].
The broad bands at 1106 and 1035 cm1, visible for TiO2 coated
with C1, C4, C8 and C18, were originated by Si–O stretching vibra-
tions [49], and indicated Si–O–Si cross-linking (Fig. 3). This band
was not found in the spectrum of sample TiC8 C21 -2w, since Si–O–
Si cross-linking was not possible for this monoalkoxysilane. The
band at 1620 cm1, assigned to the flexural vibration of the H–
O–H bond of the adsorbed water on the surface of TiO2 [50], dimin-
ished in intensity after TiO2 silanization (Fig. 3), indicating surface
hydrophobization.
3.4. Wettability study
The most widely test used to describe the wettability of solids is
the contact angle measurement [51]. Advancing and receding con-
tact angle hysteresis is reported as the most important parameter
for quantitatively characterizing hydrophobicity [52,53]. Neverthe-
496 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499
less, for powders the measurement of contact angles is compara-
tively more complex than for smooth flat surfaces [51,54]. For par-
ticulate material, contact angles are commonly measured on a
compressed disk of particles [55,56], which was the used method
in this work. Problems associated with measurement of contact an-
gles on surfaces of compressed disks basically stem from the fact
that the probe liquid can penetrate the compacted powder [54].
Hence, in the present study, the initial contact angle value was
measured immediately after the drop made contact with the disk
surface and was released from the needle. Accurate and repetitive
measurements of advancing and receding contact angles could not
be performed in the silanized samples. Moreover, overestimated
hysteresis between advancing and receding contact angles are gen-
erally obtained on compacted disks, due to the intrinsic surface
roughness of compacted particles [51]. Hence, the static contact
angles measured in this work provided only qualitative informa-
tion related to the surface properties of the powder, and were used
for comparative (bare vs. silanized nanoparticles) rather than abso-
lute purposes [53,54]. Using water as the probe fluid, the disk con-
stituted by untreated TiO2 nanoparticles exhibited a contact angle
of 27°, standard value observed for water deposited on hydro-
philic surfaces where the droplet spread out wetting the solid sur-
face. On the contrary, for disks formed by compacting silanized
TiO2 nanoparticles with isobutyl (sample TiC4-2w), octyl (sample
TiC8-2w) or octadecyltrialkoxysilane (sample TiC18-2w), the water
contact angle had a value of 115–120°, regardless of the alkyl
chain length [35]. For samples prepared using methyltrimethoxysi-
lane (sample TiC1-2w), the measured contact angle had a value of
90°. The higher values of the measured contact angles with re-
spect to bare TiO2 indicated a pronounced hydrophobic character
of the surface after silanization [57]. Coating with octylmonoalkox-
ysilane (sample TiC8 C21 -2w) led to a material with a relatively low
contact angle (50°). The reason of this low contact angle in com-
parison to the value measured for C8 (120°) was related to the ab-
sence of lateral silane polymerization on the coating formed by
C8 C21 silane [35].
It should be taken into account that, for the analyzed com-
pacted disks, the changes in contact angle may reflect variability
in the compaction process and surface energies [51,54]. Whilst
Fig. 4. Photographs of bare TiO2 and TiC8-2w dispersions (0.5 wt%) in (a) water, (b) hexane, and (c) 50:50 v/v water/hexane mixture; and dispersions in avocado oil of (d) TiO2,
(e) TiC1-2w, (f) TiC4-2w, (g) TiC8-2w, (h) TiC18-2w, and (i) TiC8 C21 -2w nanoparticles. Powders were dispersed in the liquids by shaking vigorously to completely wet the solids
and then by sonication for 5 min. The photographs were taken after allowing them to stand for 24 h. The appearance of the samples did not change significantly after 2 weeks
of standing.
initial contact angles measured using the static drop method
may be a valid qualitative measurement, it could not reflect
the true wettability when the compound is to be used in a
free-flowing powdered form [55]. Hence, we further estimated
the changes in powder wettability by using a second method
consisting in partitioning the solids between both air/liquid (dis-
persibility) [23,58] and oil/aqueous phases [51,59,60]. Firstly, the
wettability of TiO2 and TiC8-2w samples towards their dispersion
in polar (water with a dielectric constant of 80) and apolar (hex-
ane with a dielectric constant of 2) liquids was observed (Fig. 4a
and b). Bare TiO2 was easily dispersed in water as observed in
Fig. 4a. Conversely, aggregates of TiO2 nanoparticles were formed
in hexane, which were deposited at the bottom of the glass bot-
tle (Fig. 4b). On the other hand, the C8 coated nanoparticles pro-
duced a transparent suspension when being dispersed in a
completely apolar solvent such as hexane (Fig. 4b), and they
were not dispersible at all in water (in Fig. 4a particles are lo-
cated at the interface air/liquid). In a second trial, TiO2 and
TiC8-2w nanoparticles were introduced in a mixture of hexane
and water (Fig. 4c) [61]. Particles in the immiscible liquids were
redistributed to the phase with the most favorable particle-liquid
interaction: bare TiO2 partitioned into the hydrophilic water
phase, while TiC8-2w migrated into the hydrophobic hexane
phase. Finally particles coated by different silanes were dis-
persed in avocado oil, a hydrophobic component often used in
cosmetic formulations (Fig 4d–i). Stable dispersions were ob-
tained for particles coated with C1 (Fig. 4e), C4 (Fig. 4f), C8
(Fig. 4g) and C18 (Fig. 4h) silanes. On the other hand, TiO2
(Fig. 4d) and TiC8 C21 -2w (Fig. 4i) nanoparticles aggregated and
deposited at the bottom of the bottle.
From the results obtained, we can establish that the nanoparti-
cles were hydrophobized during the self-assembly supercritical
procedure carried out with C1–C18 silanes, and the formation of
strong aggregates was inhibited since the nanoparticles were eas-
ily dispersed in hydrophobic liquids. No evidences of influence of
the length of the alkyl chain in the silane molecule on wettability
were observed using either the contact angle or the partition test.
Hydrophobization using covalent attachment of a monoalkoxysi-
lane was less effective than using trialkoxysilanes.
 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499
Fig. 5. TEM images of: (a) bare TiO2, (b) TiC1-2w, (c) TiC4-2w, (d) TiC8-2w, (e) TiC8-com, (f) TiC8 C21 -2w, (g) TiC18-2w, and (h and i) sample TiC18-2w where the C18 layer was
made evident with a staining agent (white coating observed surrounding the particles).
3.5. Morphological and textural characterization
Electronic micrographs of bare TiO2 (Fig. 5a) and silane coated
materials (Fig. 5b–g) showed that these nanometric powders
formed aggregates with a mesoporous structure, confirmed by
the H2 hysteresis loop [62] observed for the N2 adsorption–
desorption isotherms. It was expected that the deposition of si-
lane molecules on the particles surface implied a decrease in
mean pore diameter and surface area, attributed to both enlarged
particle diameter after coating and potential pore blocking of the
mesoporous aggregates. However, the deposition of the different
alkoxysilane molecules on TiO2 particles did not diminished the
values of the textural properties with respect to the raw material
(Table 2). On one side, the increase in particle diameter occurring
after silane deposition could be noticed by TEM characterization
employing a negative stain for coated nanoparticles. The used
negative staining solution was an electron opaque heavy metal
salt (uranyl acetate), deposited around the electron transparent
silane layer. On the TEM images, the staining of the sample
caused the silane layer to appear pale against the dark back-
ground and TiO2 matrix. Following this procedure, only the thick-
497
ness of the C18 alkyl chain (2 nm) was enough to be clearly
visible in the TEM micrographs (Fig. 5h and i). On the other hand,
after supercritical silanization, the size of the aggregates dimin-
ished considerably (Fig. 5b–f), particularly for systems treated
with trialkoxysilanes with a C4 (Fig. 5c), C8 (Fig. 5d and e) and
C18 (Fig. 5g) chains, with respect to those formed by bare TiO2
(Fig. 5a). After coating, the nanoparticles still coalesced together,
but had a more airy arrangement. Hence, the decrease in nano-
particles aggregation resulted in an increase in surface area for
N2 adsorption. TEM images of the TiO2 nanoparticles treated with
C8 C21 silane showed large aggregates (Fig. 5f). Nanoparticles
whose surface groups have been partially derivatized by hydro-
phobic groups often have insufficient dispersion capacity and
aggregate spontaneously in liquid media.
Morphological and textural results showed that using the
supercritical coating method, the organosilanes were not preferen-
tially deposited on the exterior of the aggregates as often occurs
using conventional liquids as solvents for surface modification
[17–24]. The low viscosity and the absence of surface tension in
scCO2 solutions allowed the wetting and silane deposition on the
internal surface of the TiO2 aggregates.
498 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499

3.6. Grafting density of 3 molecules per nm2 for mesoporous aggregates of nano-
particles, suggested the formation of closely packed silane
Measurements of specific surface area of raw TiO2 and weight surfaces.
loss data from the TG assays of C4, diverse C8 and C18 coated From the three tested C8 compounds (Fig. 6b), prepared TiC8-2w
TiO2 samples (Table 2) were used to further estimate the con- and commercial TiC8-com led to very similar surface densities of
centration per nm2 of silane molecules on the surface of treated silane molecules on the TiO2 surface. Conversely, the silane graft-
particles. Firstly, it was taken into account that the weight loss ing density diminished significantly when the monoalkoxy C8 C21
data depicted in Table 2 were dependent on the molecular was used (surface density of 1.5 molecules per nm2). This mono-
weight of the different used silanes. Consequently, for the series alkoxy could not form closely packed structures because of the two
C4, C8 and C18 the weight loss increased as the chain length and methyl groups. Hence, covalently attached monolayers were differ-
the molecular weight of the used silanes augmented. In order to ent in structure than those prepared by self-assembly [12,63],
suppress the effect of the chain length in the weight loss, depos- since molecules were attached to the substrate by covalent bond,
ited silane measured data (ds ½gðsilaneÞ g1
ðTiO2Þ ) were divided by the and the distance between molecules was significantly longer than
respective molecular weight of each used silane molecule. in self-assembled monolayers.
Washed samples, in which the amount of raw silane deposited
on the surface was regarded as insignificant, were used for cal- 4. Conclusions
1
culation. Molecular weight calculations ðM0w ½gðsilaneÞ mol Þ were
performed independently for the trapped silanols (molecular Closely packed self-assembled monolayers were successfully
weight calculated as CxSi(OH)3) eliminated in the temperature prepared by reacting different chain length (from C1 to C18) alkyl-
interval 525–650 K and for the siloxanes (molecular weight cal- trialkoxysilanes with TiO2 nanoparticles in a scCO2 medium. The
culated as Cx) eliminated at temperatures higher than 650 K. process led to the formation of a densely packed alkylsiloxane net-
Next, the obtained molar density was expressed as the number work (3 molecules per nm2 calculated by TG analysis). In con-
of silane molecules per gram of TiO2. Finally, data were trans- trast, covalently attached monolayers prepared from
formed to number of silane molecules per nm2 by dividing by trialkylmonoalkoxysilane had a grafting density of only 1.5 mol-
the specific surface area measured for raw TiO2 (as(TiO2) ecules per nm2. Obtained surface densities were comparable to
[nm2 g1]). Grafting density was calculated using the formula that obtained using chloro or hydridesilanes and traditional liquid
post-deposition methods. However, since the powder was coated
ds  6  1023 in a dry medium, the aggregation problems commonly observed
¼ Grafting density ½molecules nm2 
M 0w  asðTiO2Þ during the redispersal of coated nanoparticles prepared in liquid
media were not found. After supercritical silanization of the nano-
After performing this conversion for the second and third TG powder, the mesoporous character of the aggregates was main-
decays, it became apparent that the amount of adsorbed silanol tained as confirmed by N2 adsorption–desorption analysis and
molecules increased with the molecular weight of the used tri- TEM characterization. Coated nanoparticles were easily dispersible
alkoxysilane from C4 to C18, while the amount of sorbed silox- in several types of hydrophobic organic solvents, including oil
ane decreased (Fig. 6a), i.e., the longer the alkyl chain in the (avocado) compounds used in cosmetic applications. TiO2 nanopar-
silane molecule, the lower the ratio of siloxane to silanol. On ticles are widely used as a white filler and UV-filter in cosmetic
the other hand, the grafting density on the TiO2 surface was products. The results of this work established the value of prepared
similar for the C4, C8 and C18 analyzed molecules, corresponding materials and the used methods to significantly improve both the
to a value of 3 molecules per nm2. Using 20 Å2 as an estimate understanding of surface modification of nanoparticles with alk-
of the cross-sectional area of the alkyl chains [9,10,35], a theo- oxysilanes and the methods for the preparation of hybrid compos-
retical limit of 5 molecules per nm2 has been estimated as the ites. In addition, surface modified nanoparticles are important for a
maximum surface density for a close-packed silane monolayer fundamental understanding of properties and performance of
deposited on a flat surface [12,57,63]. For porous systems, the model colloids and colloidal dispersions. Improved surface hydro-
surface concentration of alkyl residues reached as high as 2.6– phobicity control is needed if more versatile and effective applica-
2.8 molecules per nm2 [34]. Hence, a value of grafting densities tions of nanoparticles are expected to be developed.

a 3.5 b 3.5
Surface density [molecules nm-2]

Surface density [molecules nm-2]

3.0 3.0

2.5 2.5

2.0 2.0

1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0
C4-2w C8-2w C18-2w C8-2w C8-com C8C12-2w
2
Fig. 6. Silane density, expressed as silane molecules per nm , on the surface of TiO2 for: (a) C4, C8, and C18 treated materials and (b) different C8 prepared samples. ()
physisorbed silanols, (h) chemisorbed siloxanes, () ratio chemisorbed: physisorbed silane, and (N) total (physisorbed plus chemisorbed) deposited silane.
 C.A. García-González et al. / Journal of Colloid and Interface Science 338 (2009) 491–499 499

Acknowledgments [25] C. Cao, A.Y. Fadeev, T.J. McCarthy, Langmuir 17 (2001) 757.
[26] C.K. Luscombe, H.-W. Li, W.T.S. Huck, A.B. Holmes, Langmuir 19 (2003) 5273.
[27] B. McCool, C.P. Tripp, J. Phys. Chem. B 109 (2005) 8914.
The financial support of EU Project SurfaceT NMP2-CT-2005- [28] W. Gu, C.P. Tripp, Langmuir 22 (2006) 5748.
013524, and the Spanish Projects MAT-2007-63355-E and [29] C.A. García-González, N. El Grouh, A. Hidalgo, J. Fraile, A.M. López-Periago, C.
Andrade, C. Domingo, J. Supercrit. Fluids 43 (2008) 500.
CTQ2008-05370/PPQ are greatly acknowledged. Financial support
[30] C.A. García-González, J.M. Andanson, S.G. Kazarian, C. Domingo, J. Saurina,
from Carburos Metálicos-Air Products Group, under the Project Anal. Chim. Acta 635 (2009) 227.
CEN-2008-1027, a CENIT Project belonging to the Program Ingenio [31] Y. Sun, Supercritical Fluid Technology in Materials Science and Engineering,
Marcel Dekker, New York, 2002.
2010, from the Spanish Government (CDTI), is also acknowledged.
[32] Y. Shin, T.S. Zemanian, G.E. Fryxell, L.-Q. Wang, J. Liu, Microporous Mesoporous
C.A. García-González and A. López-Periago give acknowledgment Mater. 37 (2000) 49.
to CSIC for its funding support through I3P program. [33] X. Jia, T.J. McCarthy, Langmuir 18 (2002) 683.
[34] A.Y. Fadeev, T.J. McCarthy, Langmuir 15 (1999) 3759.
[35] A.Y. Fadeev, T.J. McCarthy, Langmuir 16 (2000) 7268.
References [36] J.B. Brzoska, I.B. Azouz, F. Rondelez, Langmuir 10 (1994) 4367.
[37] Z.-R. Yu, B. Singh, S.H. Rizvi, J.A. Zollweg, J. Supercrit. Fluids 7 (1994) 51.
[1] R.N. Rothon, Fillers and their surface modifiers for polymer applications, [38] T. Furuya, A.S. Teja, J. Supercrit. Fluids 29 (2004) 231.
Plastics Informations Direct, 2007. [39] S. Marcinko, R. Helmy, A.Y. Fadeev, Langmuir 19 (2003) 2752.
[2] N.J. Lowe, N.A. Shaath, M.A. Pathak, Sunscreens: Development, Evaluation, and [40] C.P. Jaroniec, R.K. Gilpin, M. Jaroniec, J. Phys. Chem. B 101 (1997) 6861.
Regulatory Aspects, second ed., Marcel Dekker, New York, 1997. [41] G.J. Kluth, M.M. Sung, R. Maboudian, Langmuir 13 (1997) 3775.
[3] R.D. McConnell, Renew. Sust. Energ. Rev. 6 (2002) 271. [42] J. McElwee, R. Helmy, A.Y. Fadeev, J. Colloid Interface Sci. 285 (2005) 551.
[4] J.-M. Herrmann, Top. Catal. 34 (2005) 49. [43] C. Ramírez, M. Rico, J.M.L. Vilariño, L. Barral, M. Ladra, B. Montero, J. Therm.
[5] E.P. Plueddemann, Silane Coupling Agents, second ed., Plenum Press, New Anal. Calorim. 80 (2005) 153.
York, 1991. [44] G. Kickelbick, Hybrid Materials: Synthesis, Characterization, and Applications,
[6] P. Somasundaran, A. Hubbard, Encyclopedia Surface Colloid Science, second Wiley-VCH, Weinheim, 2007.
ed., Taylor & Francis, London, 2006. [45] A.N. Parikh, D.L. Allara, I.B. Azouz, F. Rondelez, J. Phys. Chem. 98 (1994) 7577.
[7] S.A. Kulkarni, S.B. Ogale, K.P. Vijayamohanan, J. Colloid Interface Sci. 318 (2008) [46] Y.S. Li, P.B. Wright, R. Puritt, T. Tran, Part A: Spectrochim. Acta 60 (2004) 2759.
372. [47] D.W. Britt, V. Hlady, Langmuir 15 (1999) 1770.
[8] I. Anac, T.J. McCarthy, J. Colloid Interface Sci. 331 (2009) 138. [48] S.D. Bhagat, A.V. Rao, Appl. Surf. Sci. 252 (2006) 4289.
[9] S.R. Wasserman, G.M. Whitesides, I.M. Tidswell, B.M. Ocko, P.S. Pershan, J.D. [49] K.V.P.M. Shafi, A. Ulman, X. Yan, N.L. Yang, M. Himmelhaus, M. Grunze,
Axe, J. Am. Chem. Soc. 111 (1989) 5852. Langmuir 17 (2001) 1726.
[10] C.R. Kessel, S. Granick, Langmuir 7 (1991) 532. [50] Z. Shaofeng, M. Yuedong, O. Qiongrong, S. Xingsheng, Plasma Sci. Technol. 8
[11] A.Y. Fadeev, T.J. McCarthy, J. Am. Chem. Soc. 121 (1999) 12184. (2006) 321.
[12] A.Y. Fadeev, R. Helmy, S. Marcinko, Langmuir 18 (2002) 7521. [51] T. Dang-Vu, R. Jha, S.-Y. Wu, D.D. Tannant, J. Masliyah, Z. Xu, Colloids Surf. A
[13] R. Helmy, R.W. Wenslow, A.Y. Fadeev, J. Am. Chem. Soc. 126 (2004) 7595. 337 (2009) 80.
[14] M. Wang, K.M. Liechti, Q. Wang, J.M. White, Langmuir 21 (2005) 1848. [52] D. Öner, T.J. McCarthy, Langmuir 16 (2000) 7777.
[15] K. Paso, R.M.L. Helberg, S. Raaen, J. Sjöblom, J. Colloid Interface Sci. 325 (2008) [53] L. Gao, T.J. McCarthy, Langmuir 24 (17) (2008) 9183.
228. [54] G. Buckton, P. Darcy, D. McCarthy, Colloids Surf. A 95 (1995) 27.
[16] K. Wen, R. Maoz, H. Cohen, J. Sagiv, A. Gibaud, A. Desert, B.M. Ocko, ACS Nano 2 [55] G. Buckton, J.M. Newton, Powder Technol. 46 (1986) 201.
(2008) 579. [56] J. Bachmann, R. Horton, R.R. van der Ploeg, S. Wochem, Soil Sci. Soc. Am. J. 64
[17] T. Jesionowski, Pigm. Resin Technol. 30 (2001) 287. (2000) 564.
[18] E. Loste, J. Fraile, M.A. Fanovich, G.F. Woerlee, C. Domingo, Adv. Mater. 16 [57] A. Ulman, Chem. Rev. 96 (1996) 1533.
(2004) 739. [58] M. Iijima, M. Kobayakawa, H. Kamiya, J. Colloid Interface Sci. 1 (2009) 61.
[19] Y.S. Chung, S.A. Song, S.B. Park, Colloids Surf. A 236 (2004) 73. [59] S. Levine, B.D. Bowen, S.J. Partridge, Colloids Surf. 38 (1989) 325.
[20] J.J. Bruce, T. Sen, Langmuir 21 (2005) 7029. [60] M.A. Hoeben, R.G.J.M. van der Lans, L.A.M. van der Wielen, Am. Inst. Chem. Eng.
[21] C. Domingo, E. Loste, J. Fraile, J. Supercrit. Fluids 37 (2006) 72. 50 (2004) 1156.
[22] E. Ukaji, T. Furusawa, M. Sato, N. Suzuki, Appl. Surf. Sci. 254 (2007) 563. [61] Y. Qi, M. Chen, S. Liang, J. Zhao, W. Yang, Colloids Surf. A 302 (2007) 383.
[23] K. Luo, S. Zhou, L. Wu, G. Gu, Langmuir 24 (2008) 11497. [62] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierott, J. Rouquerol, T.
[24] M. Sabzi, S.M. Mirabedini, J. Zohuriaan-Mehr, M. Atai, Prog. Org. Coat. (2009) Siemieniewska, Pure Appl. Chem. 57 (1985) 603.
222. [63] R. Helmy, A.Y. Fadeev, Langmuir 18 (2002) 8924.