Colloids and Surfaces A: Physicochem. Eng.

Aspects 384 (2011) 318–322

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Preparation and characterization of surface modified silica nanoparticles with

organo-silane compounds
Chang Hun Lee, Sun Hee Park, Wonkeun Chung, Joong Yeon Kim, Sung Hyun Kim ∗
Department of Chemical and Biological Engineering, Korea University, Anam-dong, Seongbuk-Gu, Seoul 136-701, Republic of Korea

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

Article history: In this study, surface functionalized silica nanoparticles were prepared through a continuous two-step
Received 30 January 2011 sol–gel process. After the TEOS-derived silica particles were synthesized, silane compounds were added
Received in revised form 1 April 2011 during the second sol–gel process without any filtration or purification processes. The introductions of the
Accepted 8 April 2011
organic chains to their surfaces were measured using 13 C solid-state NMR. The effects of the hydrophilicity
Available online 15 April 2011
of the organo-chains on the silica particles were evaluated and analyzed by water contact angle and water
wettability tests. The differences of surface charge in the dispersion state were analyzed by measuring
Keywords:
the zeta-potential and the variations in the charge were measured as a function of pH.
Silica nanoparticles
Surface functionalized silica particles © 2011 Elsevier B.V. All rights reserved.
Organo-silane compounds

1. Introduction ticles were characterized by FT-IR. Hah et al. [21] studied

Nanoparticle-based technologies have been investigated and
applied in many fields, such as colloidal materials [1–3], nanocom-
posites [4–6], and supporting material of catalysis [7,8], drugs
[9,10], and biomaterials [11,12]. The surface properties of the
nanoparticles have been shown to be critical factors in determining
the performance and characteristics of the nanoparticles. For exam-
ple, the surface properties of the particles, such as surface charge
[13], steric interaction [14], and Hamaker constant [15], determine
the dispersion properties according to DLVO theory [16] in colloidal
system. In pharmacology and biotechnology, the surface interac-
tion, which determines the degree of adhesivity between target
materials and nanoparticles is an important factor [17,18].
Surface modified silica nanoparticles hold promise for use in a
wide range of different applications. In previous research, inorganic
silica particles have been functionalized with silane compounds
containing organic chains. Jesionowski and Krysztafkiewicz [19]
prepared hydrophobic/hydrophilic silica particles from sodium
metasilicate derived silica particles in an acidic solution using
silane coupling agents. The surface characterizations of the mod-
ified silica particles were assessed by the heat of immersion
in benzene. Lee and Jo [20] synthesized a hybrid thin film
using methyltriethoxysilane (MTES)-functionalized silica parti-
cles. The functionalized silica particles were prepared through
the Stöber method using MTES and a colloidal silica water
suspension as starting materials and the surface of the par-
modified the surface of phenyltrimethoxysilane (PTMS) silica
particles with tetraethyl orthosilicate (TEOS), methyltrimethoxysi-
lane (MTMS), and vinyltrimethoxysilane (VTMS). They synthesized
TEOS-modified PTMS particles in an ethanolic solution under a
basic condition and MTMS- and VTMS-modified silica particles in
aqueous solution under an acid condition. The modified PTMS par-
ticles were characterized by 29 Si and 13 C MAS NMR.
In these previous studies, the surface modified silica particles
were prepared by discontinuous processes or the effect of these
surface modifications on the hydrophilic/hydrophobic properties
of the particles were evaluated indirectly. Thus in this study surface
functionalized silica particles were prepared through a continuous
two-step process based on the Stöber method without filtration and
washing steps. The introductions of organic chains from silane com-
pounds to the surface of the silica particles were confirmed by 13 C
MAS NMR. The surface properties of the particles were evaluated
based on hydrophilicity/hydrophobicity and surface charges. The
surface hydrophilic/hydrophobic properties were evaluated based
on the water contact angle (WCA) and the amount of water vapor
that absorbed to the surface of the modified particles. Finally, the
surface charge of the particles was evaluated by measuring the
zeta-potential of the silica/water suspensions.
2. Experimental
2.1. Materials

Tetraethyl orthosilicate, 98% (TEOS); methyltriethoxy silane,

∗ Corresponding author. Tel.: +82 02 3290 3297; fax: +82 02 926 6102. 99% (MTES); vinyltrimethoxy silane, 98% (VTMS); 3-amino(propyl)
E-mail addresses: kimsh@korea.ac.kr, bonecar@korea.ac.kr (S.H. Kim). trimethoxy silane, 97% (3-APTMS); 3-mercapto(propyl)-

0927-7757/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2011.04.010
 C.H. Lee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 318–322 319

Fig. 2. The SEM image of TEOS-derived silica particles (seed particles).

trimethoxy silane 95% (3-MPTMS); and ammonium hydroxide

(NH4 OH content 28–30%) were purchased from Sigma–Aldrich
Korea and used without any further purifications. Ethanol
(J.T. Baker) and DI water (18.2 ) were used throughout the
experiments.
Fig. 1. The two step sol–gel process used to prepare surface functionalized silica
particles.
2.2. Synthesis of functionalized silica nanoparticles

The surface modified silica nanoparticles were prepared by a

continuous two-step process and each process was based on the

Fig. 3. The SEM images of silica particles functionalized with (a) MTES, (b) VTMS, (c) 3-APTMS and (d) 3-MPTMS.
320 C.H. Lee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 318–322
13
Fig. 4. C CP MAS NMR spectra of silica functionalized with (a) MTES, (b) VTMS, (c) 3-APTMS, and (d) 3-MPTMS.
Stöber method. A diagram of the whole procedure is shown in Fig. 1.
The first step was the hydrolysis and condensation process of TEOS
in ethanol, DI water, and ammonium hydroxide solution. The sec-
ond step involved the surface modification of the silica particles. In
this process, silane compounds were hydrolyzed and reacted with
the silanol groups of the TEOS-derived silica particles. All these
reactions were performed at 40 ◦ C. After the reactions, the silica
powders were filtrated and dried at 105 ◦ C for 1 h.
2.3. Characterizations
The size and morphology of silica particles were observed by
field emission scanning electron microscope (FE-SEM) (S-4700,
Hitach) and 13 C solid-state NMR spectra were obtained using
200 MHz solid-state NMR spectrometer (Unity Inova 200, Varian)
at Korea Basic Science Institute (KBSI). The water contact angles
(WCA) of the silica samples were measured using a contact angle
analyzer (Phoenix 300, SEO). The samples were prepared by grind-
ing the silica powders using a mortar and pressing them. The
surface wettability of the silica particles was determined by mea-
suring the amount water adsorbed on the silica surface. Adsorption
of water vapor on to the silica surface was performed using a
humidifier and chamber. Before the experiment, the silica was dried
in a vacuum oven at 100 ◦ C for 2 h. At 70 ◦ C, air and vapor was flown
into the chamber for 12 h. The wettability values were determined
by the weight difference of the silica particles per weight of the par-
ticles. The pH of the silica suspensions was adjusted by the addition
of hydrochloric acid or sodium hydroxide to the predetermined val-
ues. The zeta-potential of each suspension sample was measured
using an electrophoretic light scattering spectrometer (ELS-8000,
Otsuka).
3. Results and discussion
3.1. Size and morphology of silica particles
The SEM images of TEOS-derived silica particles (seed particles)
and surface modified particles are in Figs. 2 and 3. The seed parti-
cles in Fig. 2 had the size of about 100–150 nm and the spherical
shape. The size of modified silica particles was also in the range
of 100–150 nm and the morphology of the modified particles was
spherical shape (Fig. 3). These showed that the agglomerates did not
be formed during the first sol–gel reaction and the surface modified
silica particles of similar size and spherical shape could be prepared
from the continuous sol–gel process.
3.2. Characterization of modified silica particles
13 C MAS NMR spectra verified that the carbon-based organic
groups were introduced onto the functionalized silica powder
(Fig. 4). Fig. 4(a) shows the spectrum of the organic-silica pow-
der derived from MTES. The peak at ı = −3.588 ppm was assigned
to the methyl carbon bond with silicon atom [22,23]. The spectrum
of the vinyl-functionalized silica particles is shown in Fig. 4(b). The
two peaks at ı = 131.373 and 136.681 ppm corresponded to car-
bon atoms labeled 1 and 4, respectively [23,24]. Three peaks were
observed in the spectrum of the APTMS silica powder at chem-
ical shifts ı = 9.565, 23.381, and 43.232 ppm. These peaks were
 C.H. Lee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 318–322 321

Fig. 5. The water contact angle (WCA) results for the surface of silica particles modified by (a) MTES (left = 142.31, right = 143.65, avg = 142.98), (b) VTMS ((left = 147.65,
right = 140.00, avg = 143.82), (c) APTMS (absorbed), and (d) MPTMS (absorbed).

attributed to different carbon environments in the organo-chain

denoted as 3, 2, and 1 and indicated incorporation of amine func-
tional groups [25]. Two peaks at 12.555 and 28.480 ppm were
observed in the spectrum of the silica particle functionalized
MPTMS (Fig. 4(d)). The first peak at 12.555 ppm was assigned to
the methylene carbon atom labeled 1, and the other peak corre-
sponded to the methylene carbon atoms at the 3- and 2-positions
of the mercaptopropyl bonded silicon[26]. Only peaks for the alkyl
groups (R–) were observed and, not for the residual methoxy and
ethoxy in Fig. 4. Because the R groups were nonhydrolyzable and
the alkoxy groups were hydrolyzed, only the R groups remained on
the surface of the organo-silica powders after the sol–gel reactions.

3.3. Measurement of surface hydrophilicity

The water contact angle results clearly demonstrate that organic Fig. 6. The wettability (the weight of adsorbed water/the weight of silica) of surface
chains affect on the surface properties of the silica particles (Fig. 5). functionalized silica particles.

The contact angles of MTES- and VTMS-silica particles were 142.98

and 143.82, respectively. These are relatively high contact angle
values, which indicate that the surfaces of the modified silicas
derived from MTES and VTMS were hydrophobic. For the APTMS-
and MPTMS-silica particles, water drops were absorbed and a trace
of the absorbed water was left on the surface of the samples. These
results demonstrate that the surface of two different functionalized
particles were hydrophilic.
The wettability of the silica surface is shown in Fig. 6. The
wettability value of MTES-(M-silica) and VTMS-(V-silica) func-
tionalized silica particles was 0.013 g (H2 O)/g (silica) and 0.043 g
(H2 O)/g (silica), respectively. The values for the APTMS-(A-silica)
and MPTMS-(S-silica) functionalized silica particles were 0.20 and
0.19, respectively. In an ambient air atmosphere, molecular water is
absorbed on the surface and surface organic materials can change
the wettability [27]. For M-silica and V-silica samples, the intro-
duction of each hydrophobic carbon-based chain lead to a decrease
in the portion of silanol (–OH) groups on the silica surface and
this lowered the hydrophilicity and wettability of the surface. In
the case of surface modified silica samples by APTMS and MPTMS,
although hydrophobic propyl chains were introduced on the sur-
face, the hydrophilic property was maintained due to the presence
of the amine and mercapto groups at the end of the chains.
3.4. Analysis of dispersion property
The zeta-potential of the APTMS and MPTMS silica particles
were determined to measure the surface charge and assess the
effect of pH on the surface charge. As shown in Fig. 7, the zeta-
potential of the A-silica suspension was positive and that of the
S-silica suspension was negative. In addition, the potential of the
A-silica particles increased as the pH was decreased. Inversely, the
potential of the M-silica particles increased as pH was increased.
The TEOS derived silica nanoparticles (T-silica) have silanol groups
on their surface which contains a hydrogen atom, which can disso-
322 C.H. Lee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 318–322
Fig. 7. -potentials of TEOS (䊉), APTMS (), MPTMS () silica suspensions at differ-
ent pH values.
ciate, and produces a negative charge. Thus, in a lower pH solvent,
more hydrogen ions were dissociated, which produced a negative
zeta-potential (Fig. 7). Like TEOS silica, the mercapto groups of the
M-silica particles contain a hydrogen atom that can dissociate from
the surface of the silica producing a negative zeta-potential. On the
other hand, the surface of A-silica can associate with a hydrogen
ion, thus the dependency of its surface charge differed from that of
the M-silica particles (Fig. 7).
4. Conclusion
Surface functionalized silica particles were prepared through
a continuous two-step sol–gel process with different silane
compounds. During the fabrication process, all of the alkoxy
groups of the silane modifying agents were hydrolyzed and non-
hydrolzable organo-chains were introduced on the surface of
TEOS-derived silica nanoparticles. The surface of the silica par-
ticles functionalized with methyl and vinyl groups had a high
contact angles and low wettability. In contrast, APMTS and
MPTMS functionalized silica particles were hydrophilic due to
the presence of the amine and mercapto groups, respectively.
In addition, the amine groups induced a positive charge on the
APTMS silica due to the dissociation of hydrogen, and this pos-
itive charge continued to increase as the pH was decreased.
For MPTMS-derived silica particles, the surface was negatively
charged which become more negatively charged as the pH was
increased.
Acknowledgement
This work was partially supported by the National Research
Foundation (NRF) grant (No. 20100027568).
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