D

J. Chem. Chem. Eng. 7 (2013) 120-131

DAVID

PUBLISHING

Study and Characterization of Organically Modified

Silica-Zirconia Anti-Graffiti Coatings Obtained by
Sol-Gel
M. Rosario Elvira, M. Alejandra Mazo*, Aitana Tamayo, Fausto Rubio, Juan Rubio and Jos Luis Oteo
Ceramic and Glass Institute, CSIC, Madrid 28049, Spain
Received: November 28, 2012 / Accepted: December 21, 2012 / Published: February 25, 2013.
Abstract: In this work, it is presented the synthesis and characterization of transparent and colorless organic-inorganic hybrid
anti-graffiti protective materials obtained by sol-gel method. This type of materials is based on MTES (methyltriethoxysilane), TPOZ
(tetrapropoxide of zirconium) and PDMS (polydimethylsiloxane). The synthesis has been carried out at 25, 35 and 45 C in order to
evaluate the role of temperature in the structure, microstructure and anti-graffiti behavior as well. The incorporation of zirconium
within the organic modified silica network, of sols after being gelled and dried, is evident by a shoulder which increased with
temperature situated at 950 cm-1 (Si-O-Zr bonds), and it is homogenously dispersed inside the matrix avoiding the formation of large
ZrO2 precipitates. As the temperature increases, the hydrolysis and condensation reactions occur in more extension and thus, the
obtained sols are more cross-linked and present more Si-O-Zr linkages. The promising anti-graffiti behavior of the protective hybrids
was qualitatively determined being the spot removal higher than 90%.
Key words: Sol-gel, organic-inorganic hybrid, anti-graffiti coatings, hydrophobic materials.

1. Introduction
Anti-Graffiti materials have attracted much attention
during the last decades because graffiti paintings are
present in the routine life, especially in big cities.
Graffiti can affect to all class of surfaces materials and
in the majority of the cases, the cleaning is very
expensive and quite often, the penetration into the
pores contained in the substrate material induces an
irreparable effect onto the painted surface. The first
attempts to remove the graffiti, basically included the
removal of the painting by employing pressurized
water and brush, but these methods are not so effective
and require a large amount of water and labor, with the
risk of damaging the painted surface during the
cleaning process. Based on these facts, it came out the
*

Corresponding author: M. Alejandra Mazo, Ph.D., research

fields: materials science (organic-inorganic hybrids, silicon
oxycarbide
glasses,
composites,
etc.).
E-mail:
sandra@icv.csic.es.

necessity of developing new products that could be

used as permanent protective coatings easily applied
over the surfaces sensitive of being damaged. The most
recent efforts consist on the application of a product
which makes the surface highly hydrophobic
independently on its nature and protects it against water,
minimizes the adhesion of the graffiti paint and
facilitates the removing process with water, soft
detergents [1] or hand cleaning by employing a cloth.
Organic-inorganic hybrids based on methyl-derived
silanes present highly hydrophobic properties and high
specific surface energy avoiding the adherence of the
graffiti paint [2, 3]. The combination of these
properties gives as a result a new family of materials
susceptible of being used for anti-graffiti purposes
making the subsequent removal lighter [2]. Other
family of anti-graffiti coatings developed in the last
few years also include the use of polysiloxane modified
polyurethanes

whose

weathering

resistance

is

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

121

of being used for this purpose containing a mixture of

energy and the chemical composition of surface

coating [15]. Anti-graffiti protective coatings reduce
the surface energy of the substrates which hinders the
interaction with the graffiti paint and makes the
removal easier [14].
With all these considerations, the aim of this work is
to develop an anti-graffiti protective organic-inorganic
hybrid coating by employing silicon and zirconium
derivates MTES, TPOZ and PDMS and the study of the
influence of synthesis conditions on the structure,
microstructure and the final anti-graffiti behavior.

both oxides [7, 8]. In this sense, organic-inorganic

2. Experiments

increased by adding silica nanoparticles [4]. The

development of fluorinated polyurethane dispersions
as

anti-graffiti

materials

provides

even

super-hydrophobic surfaces but their main drawback is

that these solutions possess as non-environmentally
friendly compounds because of the presence of fluorine
in their compositions [5, 6]. The enhanced chemical
and

mechanical

properties

of

the

ZrO2-SiO2

combinations compared with silica or zirconia leaded

to the appearance of different compounds susceptible

hybrids with excellent homogeneity, mechanical

integrity and transparency have been synthetized by

2.1 Reagents

employing

The sol-gel procedure was used to obtain

MTES/TPOZ/PDMS
organic-inorganic
hybrid
coatings. The reagents used in the synthesis are methyl
triethoxysilane (MTES, 98% purity, ABCR GmbH &
Co.), zirconium (IV) propoxide solution (TPOZ, 70%
wt. in n-propanol, Sigma Aldrich Co.), and hydroxyl
terminated polydimethylsiloxane (PDMS, 4%-6% OH
content, ABCR GmbH & Co.). The solvent used was
n-propanol (n-PrOH, Sigma Aldrich Co.).

PDMS

(polydimethylsiloxane),

as

precursor of organically modified silica, and zirconium

TPOZ solutions [9, 10]. The combination of both
solutions into a single material and the addition of
MTES, produced a sol-gel organic-inorganic hybrid
highly transparent and colorless coating [11]. When
they are applied over a dense material (granite and
marble) the color of the substrate remains unchanged
and also presents good anti-graffiti properties which
also remains unaltered against weathering conditions
(rain and UV radiation) and made them suitable as a
protective coating for building facades. When the
material presents some amount of porosity (i.e.,
sandstone) the coating penetrates inside the pores
inducing significant changes in the material color while
the anti-graffiti effect is reduced.
Several authors studied the effectiveness of
MTES/PDMS/TPOZ
organic-inorganic
hybrid
anti-graffiti protective coatings by measuring the
degree of penetration in the materials, durability
against pollution and the determination of the surface
dispersive energy after being deposited over different
building materials (cement paste, lime mortar,
limestone, granite and brick) [12-14]. Numerous
factors are decisive in order to explain the anti-graffiti
behavior of protective coatings some of them are: the
wettability, the morphology, the roughness, the surface

2.2 Synthesis
The synthesis was carried out by a method
previously described by Oteo, Rubio and Rubio [16].
This
procedure
yields
a
homogeneous
organic-inorganic network from an organic modified
silicate (MTES), an organic derived siloxane polymer
(PDMS) and a zirconium second inorganic network
formed by employing a zirconium tetrapropoxide as
precursor (TPOZ).
The weight ratio employed of MTES/PDMS/TPOZ
is 50/40/10 and the molar ratio of MTES/n-PrOH is 1/5.
First, MTES, PDMS and the half volume of n-PrOH
are mixed during approximately 10 min to ensure the
homogeneous mixing of the precursors. Separately, the
other half of n-PrOH and the TPOZ are also mixed.
Then, the mixtures were added into a flask under reflux,
magnetic stirring and thermo-stated, varying with a

122

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

temperature controller in order to study the influence of

this parameter in the organic-inorganic hybrid from 25
to 45 C. According with preceding studies, the
reaction time was set to 22 h [11]. After that,
transparent and homogeneous sols are obtained and
when ambient temperature is reached they can be
transferred into hermetically sealed containers. Sols
can be maintained in these air and humidity-free
containers until use, avoiding further hydrolysis,
gelling and solvent evaporation processes during
several months.
Hybrids synthetized at different temperatures (25, 35
and 45 C, named as R25, R35 and R45, respectively)
were poured within a PS (polystyrene) petri dish and let
for 5 days until gelling, and then they were dried at 50
C for another 6 days. After that, one part was reduced
to powder and used for the full characterization of the
material and other part was used to test the anti-graffiti
behavior.
The anti-graffiti behavior is analyzed by using spray
painting and a permanent marker. The spray (PINTY
PLUS Basic NOVASOL SPRAY S.A.) application
was carried out at a distance of 10 cm distance from the
gel surface placed perpendicularly to the sprayed
substance. It was used a circular template to produce
sprayed spots as similar as possible for comparison of
the effectiveness of the cleaning. After the paint is
dried, the sprayed spots were tried to be clean with a
cotton tissue. The second experiment for testing the
anti-graffiti properties was performed with a
permanent marker Edding 3000 by writing down a
line over the organic-inorganic coating surface. Once
the ink was dried, the marker spot was tried to be clean
with a cotton tissue. In both experiments, a blank
surface (the original Petri Dish) with no treatment
applied was used to compare the results obtained.
2.3 Material Characterization
Organic-inorganic samples were analyzed by means
of infrared spectroscopy. Sol samples after 22 h of
sol-gel reaction were studied by infrared spectroscopy

in the transmission mode from 4,000-600 cm-1 by a

FT-IR (fourier transform infrared) spectrometer. The
measurements were carried out by adding one drop of
the sol between two KRS-5 windows, which are
transparent to the infrared radiation. Powdered samples
were analyzed by ATR (attenuated total reflection)
mode in the spectral range 4,000-600 cm-1 using the
MIRacleTM attenuated total reflectance device. In
both cases, it were used a perkin elmer spectrometer
model Spectrum BX. Eight scans were used to obtain
each spectrum and the background was subtracted from
all spectra. The resolution was 4 cm-1 in the spectral
range.
Also, ATR was made in the Far-IR spectral range
(600-200 cm-1) with a Thermo Scientific Nicolet
6700 FT-IR spectrometer. The spectrometer was
equipped with the Thermo Scientific ETC EverGlo*
ceramic IR source and Far-IR optics (solid substrate
beamsplitter and polyethylene DTGS detector). 512
scans were collected at 4 cm-1 resolution. Powdered
samples were also analyzed by raman spectroscopy;
the spectra were carried out in a spectrometer of
renishaw model In via with an excitation wavelength of
514 nm corresponding to Ar+ laser. 29Si MAS NMR
spectra of organic-inorganic hybrids were collected
with an AV-400-WB Bruker Corp, NMR spectrometer
(79.49 MHz). The spinning rate for samples was 10
KHz, the spectra were recorded using a pulse /6 (2 s)
at 50 kHz and delaying time of 60 s. The observed
silicon units were designed according to the usual
notation employed in silicon chemistry: Q [SiO4], T
[SiCO3], D [SiC2O2], M [SiC3O] and X [SiC4]. The
number added to the unit symbol as a subscript
indicates the number of oxo bridges bonds to the
corresponding Si site.
TG (thermogravimetric) studies and DTA
(differential thermal analysis) experiments were
carried out in a TA Instruments SDT Q600 with
simultaneous TGA/DTA analysis. The analysis
conditions were heating rate of 5 C/min under flowing
air (100 mL/min).

123

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

The total carbon and hydrogen contents were

performed by using elemental analyzers, LECO model
CS-200 and RC-412, respectively. Silicon and
zirconium content was determined by X-ray
fluorescence, Philips model Magix. Oxygen content
was determined by difference.
The microstructure of the protective films was
observed by field emission scanning electron
microscopy (FE-SEM, Hitachi 4700) working at 20 kV.
In selected areas, mapping experiments were also
performed for silicon and zirconium elements.

3. Results and Discussion

29

3.1 IR, Raman and Si-MAS NMR

Fig. 1 shows the FT-IR spectra of the sols obtained at
different synthesis temperature in the spectral range
1,350-600 cm-1. As reported by Rubio et al. [17], the
band appearing at 1,153 cm-1 and corresponding to the
propoxy groups of TPOZ is the most suitable in order
to follow the hydrolysis of this compound. In the
spectra, it is clearly observed that as the temperature
increases the intensity of the referred band drastically
decreases from R25 to R45, as consequence of the
major extension of the hydrolysis reactions. The
decrease of the intensity of this band occurs together
with the increase of the bands related to n-PrOH
because of the formation of new molecules of alcohol.
Moreover, the bands centered at 1,170 and 960 cm-1
(Si-O-C asymmetric and symmetric stretch, respectively)

Fig. 1 FT-IR spectra of the sols obtained at different

synthesis temperature after 22 h.

[18] that correspond to the ethoxy groups of MTES

permit the evaluation of the degree of hydrolysis and
condensation of MTES molecules. As observed in the
analysis of the TPOZ bands, MTES bands, especially
the one located at 1,170 cm-1 are getting smaller and
almost disappear as the synthesis temperature increases,
but the bands of pure EtOH increases in intensity from
R25 to R45 (seen 1,230 cm-1 band in Fig. 1).
The

overlapping

of

multiple

vibrations

is

represented as a broad band in the 940-980 cm-1

spectral range which difficult the evaluation of the
contribution of each one to the total intensity of the
band. These vibrations correspond to the stretching
mode of Si-OH groups (~ 950 cm-1), the ethoxy groups
of MTES molecule (~ 960 cm-1), the n-PrOH molecule
(~ 969 cm-1) and Si-O-Zr new linkages (~ 980 cm-1)
[19]. A careful analysis of the spectra indicates that the
950 cm-1 (Si-OH) and 960 cm-1 (Si-OCH2CH3) bands
decrease with temperature but the 969 cm-1 band
(n-PrOH) becomes stronger. These facts imply a major
extension of the hydrolysis and condensation reactions
of MTES and TPOZ molecules, as commented before.
On the other hand, the band centered around 980-920
cm-1 exhibits a shift to lower wavenumbers with the
synthesis temperature. The shift is attributed to the
formation of new linkages Si-O-Zr, as occurs in the
case of PDMS/Metal alcoxide hybrids in which is
reported that the Si-O-M band shifts to 910-930 cm-1
because of the presence of the mixed bonds [19].
IR-ATR spectra of the hybrid materials obtained
after gelling and drying are presented in Fig. 2a and 2b
for MIR and FIR spectral range, respectively. The
bands related to the methyl groups of the precursors
MTES and PDMS appear all over the spectra whose
main characteristics are the absorption bands centered
at 2,966, 2,908 cm-1 attributed to the asymmetric and
symmetric C-H stretching vibrations. The symmetric
bending mode of CH3 groups appears as a very intense
band placed at 1,260 cm-1 which it is related to
D (SiMe2) and T (SiMe) units present in PDMS and

124

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

Fig. 2 ATR spectra of the hybrids obtained at different

temperatures heat-treated at 50 C for 6 days: (a) MIR and (b)
FIR.

MTES precursors, respectively [20]. The band placed

at 857 cm-1 is related to symmetric rocking of CH3,
whereas band centered at 700 cm-1 is associated to the
symmetric stretching of Si-C bonds. The asymmetric
stretching of Si-C bonds appears as a very broad band
centered at wave numbers below 800 cm-1. In the case
of PDMS polymers, the position of this band is related
to linear (800 cm-1) or cyclic (810 cm-1) polymer chains
conformation [21]. The shift of the band to a lower
wave numbers suggests that the polymer chains of the
organic-inorganic hybrid could adopt a linear
conformation. This band is slightly overlapped with the
symmetric stretching of Si-O-Si bonds at 756 cm-1.
Other bands related to Si-O bonds coming from
MTES and PDMS are located approximately at 1,080
and 1,010 cm-1 and are assigned to asymmetric
stretching of Si-O bonds in the LO (longitudinal) and
TO (transversal) active modes, respectively [22]. In the
far IR range, the band placed at 370 cm-1 and
corresponding to bending mode of O-Si-O bonds is
shifted with respect of the same vibration in pure silica
gels [23]. This downshift is reported in modified silica
network with polymers or other type of oxides (i.e.,
metallic oxides or ZrO2, TiO2, Al2O3, etc.) because of
the continuous interruption of the tridimensional
Si-O-Si network with Si-CH3 or Metal-O linkages [3, 9,
24]. The shift of the TO mode of the Si-O asymmetric
stretching to lower wave number (approximately from
1,100 to 1,040 cm-1) has been also reported in
Zr-modified silica because of the formation of Si-O-Zr

hetero-linkages being the shift directly related to the

ZrO2 content [25-27].
The broad shoulder centered at ~ 950 cm-1 can
include both Si-OH groups (Si-OH stretching mode)
and to Si-O-Zr bonds. The absence of the OH vibration
bands at around 3,500 cm-1, suggests that the shoulder
could indicate the presence of Si-O-Zr linkages [28].
The broadness of the shoulder is attributed to the
presence of Si-O-M bonds with Si coming either form
MTES or PDMS, in which the band shifts to 910-930
cm-1 [10]. It is observed that as the synthesis
temperature increases, the 950 cm-1 shoulder is getting
bigger and well resolved which implies a higher
Si-O-Zr concentration.
The bands placed at 650 cm-1 (Zr-OX, X = H,
CH2CH2CH3) and 500-460 cm-1 (Zr-O-Zr bonds)
appearing in pure zirconia based gels [7, 9, 29] are
practically imperceptible in the FT-ATR spectra. This
fact implies that TPOZ is almost completely
hydrolyzed and zirconium oxo networks are mixed
with PDMS and MTES building a mixed organic
modified silica-zirconium oxide network and ZrO2 is
not segregated. The steric hindrance of PDMS and the
copolymerization through end chain silanol groups
with metal alkoxide prevents the growth of ZrO2
particles during the hydrolysis and condensation
reactions [10]. ZrO2 small clusters are mixed
homogeneously with PDMS and MTES molecules and
the zirconium oxo networks (Zr-O-Zr stretching
vibrations) only appears as a very small band located
approximately at 500 cm-1.
Fig. 3 contains the Raman spectra of the
organic-inorganic hybrid materials. Similarly to the
infrared analysis, the bands related to the organic
groups in either the PDMS or MTES molecules
contained in the hybrid material, are the most
characteristic bands in the spectra. These bands are
assigned to the asymmetric and symmetric CH
stretching vibrations (2,968 and 2,908 cm-1) and
asymmetric and symmetric bending mode to CH3
groups of both D and T groups (1,416 and 1,261 cm-1,

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

Fig. 3 Raman spectra of organic-inorganic hybrids obtained

at different synthesis temperatures heat-treated at 50 C for 6
days.

respectively). Another bands related to organic methyl

groups are placed at 860, 707 and 683 cm-1 which are
related to symmetric rocking of CH3 groups,
symmetric stretching of Si-C bonds and symmetric
rocking of Si-CH3 bonds [30]. Asymmetric LO and
TO stretching modes of the Si-O bonds (1,200 to
1,000 cm-1) yield a low intensity Raman band while
its symmetric modes are very intense (790 and 760
cm-1, respectively). The asymmetric stretching mode
of four members rings of the modified silica network
the siloxane units in the middle of PDMS chains
appears as an intense band at 490 cm-1 [28]. Galleener
et al. [31] in their studies with quartz associated the
formation of these four member rings with the
presence of defects in the crystalline network. In the
organic-inorganic hybrid materials described in the
present work, the presence of PDMS molecules and
ZrO4-x could also be the responsible of the formation
of these four member rings [32, 33].
Finally, in the case of R45, a small band placed at ~
900 cm-1 is noticeable. This band could be assigned to
Si-O-Zr linkages as well as it was observed in ATR
spectrum and agreed with the supposition that as the
temperature increases the amount on Si-O-Zr linkages
are higher.

125

Fig. 4 29Si MAS NMR spectra of the organic-inorganic

hybrids synthetized at different temperatures heat-treated at
50 C for 6 days.
29

Si MAS RMN spectra of organic-inorganic hybrids

are presented in Fig. 4. In the spectra, there are clearly

distinguishable two types of signals related to the
different structures of PDMS and MTES, D (SiC2O2)
and T (SiCO 3 ) units, respectively, which permit
authors to elucidate the silicon backbone of the
organic-inorganic hybrid material. Short PDMS chains
(n 5), which presents peaks placed below -22 ppm,
and long PDMS chains (n >> 10) are distinguishable in
terms of the chemical shift because the peak is
presented at higher chemical shift when the polymeric
chain increases [34]. In all the cases, a peak at
approximately 22.5 ppm (Table 1) corresponding to D2
units of lineal PDMS chains [23] indicates that the
organic-inorganic hybrids are formed mainly by long
lineal PDMS chains. Several authors [28, 35] reported
in the 29Si MAS NMR cross polarization experiments
(29Si-CP MAS NMR) of PDMS/Metal oxides hybrids a
broadness of this signal at chemical shifts higher than
-22 ppm with respect to

29

Si-MASNMR spectrum

without cross polarization and associated the intensity

of the peak to less mobile units, like for example cross
linking points with metal oxides or the end of the

126

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

Table 1 Data extracted from deconvolution of 29Si MAS

NMR spectra of the organic-inorganic hybrids synthesized at
different temperatures (25, 35 and 45 C).
T (ppm/%)
R25
R35
R45

-67.7
30
-66.7
24
-67.7
22

-66.1
12
-66.1
11
-66.2
12

-22.4
52
-22.5
57
-22.4
57

D (ppm/%)
-19.9
6
-19.9
8
-19.9
9

PDMS chains. The sharpness of the mentioned peak

indicates the high mobility of PDMS chains and
explains the high flexibility of hybrids made them
suitable for being obtained as crack free coatings [35].
Besides the main D2 peak, centered at -19.9 ppm
appears a small peak which could be associated to
cyclic oligomers entrapped into hybrid network. The
intensity of this band rises from 6%, 8% and 9% as the
temperature increases from 25, 35 to 45 C,
respectively (Table 1).The T3 peak corresponding to T3
units derived from the MTES molecule is quite broad
but it is possible to differentiate between two peaks
close to -66.1 and to -67.7 ppm, assigned to Si-O bonds
with different chemical environment. These two peaks
are tentatively assigned to Si-O-Zr and Si-O-Si
linkages, respectively (Table 1).

3.2 Thermal and Chemical Analysis

With the aim of distinguishing the changes induced
into the hybrid network because of the synthesis at
different temperatures, thermogravimetric and
differential thermal analysis have been carried out. In
Fig. 5 (a, b) it is represented the TG/DTG (derivate of
thermogravimetric analysis) and DTA experiments of
the organic-inorganic hybrid synthetized at the three
analyzed temperatures. According with the
thermogramme, thermal degradation occurs mainly in
four steps showing a total weight loss of 31%, 32% and
27% for samples obtained at 25, 35 and 45 C. Beyond
600 C the thermal degradation is almost complete in
all the materials and no significant changes were
observed. According to DTA curves, all the
phenomena occurring during the four decomposition
stages are exothermic. Table 2 collects the
temperatures and weight loss associated with the
referred temperature corresponding to the main peaks
in the DTA curve.
In the first step, from room temperature to ~ 430 C,
it is produced the evaporation of the entrapped solvent
within the coating and a further cross-linking processes
between remainder SiOR groups (R = H, CH2CH3)

Fig. 5 (a) TG/DTG and (b) DTA curves of the hybrids obtained at 25, 35 and 45 C.
Table 2 Main thermal data obtained by TG/DTG and DTA curves: temperature ranges, DTG peaks, weight losses (total weight
loss (WLt) and related to each stage (WLs) measured in the organic-inorganic hybrid synthetized at 25, 35 and 45 C.

R25
R35
R45

First
stage
(C)
r.t-435
r.t-417
r.t-416

First
peak
(C)
359
373
371

WLt
(WLs1)
(%)
12 (12)
13 (13)
13 (13)

Second
stage
(C)
435-462
417-441
416-439

Second
peak
(C)
450
423
429

WLt
(WLs2)
(%)
15 (3)
15 (2)
15 (2)

Third
stage
(C)
462-500
441-481
439-478

Third
peak
(C)
485
459
464

WLt
(WLs3)
(%)
23 (8)
20 (5)
18 (3)

Fourth
stage
(C)
500-551
481-559
478-557

Fourth
peak
(C)
516
510
507

WLt
(WLs4)
(%)
30 (7)
28 (8)
26 (8)

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

rendering new Si-O-Si linkages. Both the temperature

range and the total WLs1 (weight loss observed in this
first step) are quite similar for all the synthesis
temperature analyzed with a weight loss of about 13%.
The broadness of the peak found in the DTA curve is
attributed to the simultaneous reactions that take place
in this temperature range.
The second step that is shown as a small peak in the
DTA curve, is attributed to the removal of volatile
cyclic oligomers (essentially three and four member
rings D3c and D4c, respectively) derived from PDMS. In
this second stage, the relative weight loss with respect
to the remainder after the first decomposition (WLs2)
decreases with synthesis temperature, from 3% (R25)
to 2% (R45) (Table 2), and suggest a more cross-linked
structure because of a larger extent of the hydrolysis
and condensation reactions during sol-gel process
when the synthesis temperature increases.
The main weigh losses in the thermogramme
correspond to the third and fourth stages, and are
associated with the depolymerization and oxidation of
the PDMS. As shown in Table 2, the contribution to the
total weight loss of each decomposition step is deeply
influenced by the synthesis temperature being the
WLs3 of about 8% in the R25 sample and around 3% in
R45, whereas the WLs4 remains practically invariable.
These observations are in accordance with Camino et al.
[36], that reported that the Si-O/Si-O and Si-O/Si-C
exchange reactions in PDMS materials produce the
elimination of polymer chains through the formation of
volatile cyclic oligomers (mainly D3c and D4c) together
with the oxidation of the methyl groups bonded to the
silica network. At the same time, the temperature also
promotes the cross-linking of the structure and
enhances its thermal stability, which is translated in a

delay in the oxidative thermal degradation of the

organic part still present into the thermally degraded
hybrid network. The thermal oxidative degradation
takes place in a temperature range that increases with
the synthesis temperature increases which denote a
more cross-linked structure [37]. The lower WLs3 in
the hybrid obtained at 45 C compared with the one
synthesized at 25 C is explained in terms of the higher
condensation degree of the structure in the former one.
Table 3 shows the results obtained from the chemical
analysis of the obtained organic-inorganic hybrids. It is
found that the empirical formula of the synthesized
products is slightly dependent on the synthesis
temperature. The ratio C/H equal to 3 in all the cases
indicates that the hydrolysis is almost complete and
comparing with the theoretical formula, it is observed
that O/Si molar ratio slightly decrease with the
synthesis temperature. This result suggests the
presence of non-condensated Si-OH moieties,
especially in the material synthesized at the lowest
temperature.
3.3 SEM
Fig. 6 presents the microstructural and
compositional SEM analysis performed in R25 and
R45 samples. The images of the surface (left images)
show almost fully dense hybrid materials. This fact is
very important because the presence of pores may
reduce the effectiveness of the anti-graffiti protective
coating. These images display nodes and groove marks
associated to the shrinkage experimented during
gelling and subsequent drying which are more evident
in the material synthetized at 25 C than the one
obtained at 45 C. This surface morphology is
directly related with the roughness of gel, so the mayor

Table 3 Analytical results, theoretical and experimental formula of the organic-inorganic hybrid materials.
Sample
Theoretical
R25
R35
R45

Si (%)
36.04
33.70
33.65
33.35

O (%)
27.63
29.68
28.05
28.52

C (%)
25.50
25.60
27.25
26.88

127

Zr (%)
4.46
4.63
4.24
4.58

H (%)
6.37
6.39
6.81
6.67

Empirical formula
SiO1.25C1.65H4.95Zr0.04
SiO1.54C1.77H .31Zr0.04
SiO1.46C1.89H5.67Zr0.04
SiO1.50C1.88H5.60Zr0.04

128

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

roughness in R25 may reduce its durability. During sol

to gel transformation and also in drying stage, the
condensation reactions produce a shrinkage which
produces the above mentioned nodes and grooves, in
the case of R25 more unreacted groups are susceptible
to react and as a result the total amount of shrinkage is
greater. This assumption agrees perfectly with above
mentioned results found in TG/DTG analysis, chemical
analysis and FT-IR spectra.
SEM-mapping of silicon and zirconium was
performed and the images are also displayed in Fig. 6
(center and right images, respectively). Mapping shows
that silicon and zirconium are well and uniformly
dispersed within the coating. As expected, the silicon
amount is higher than zirconium according to the
chemical composition (Table 3), but in any case large
aggregates of zirconium are observed.

also evaluated according to different CN (classification

numbers) [38, 39], which varied from CN 0 (total
removal) to CN 5 (no cleaning effect). The
classification number displayed for all the protective
coatings are assigned to CN 1.5 which means that the
spot persists as a single laminar residue of color.
An analogous experiment was carried out by
employing a permanent marker, as shown in Fig. 8. The

3.4 Anti-graffiti Behavior

The anti-graffiti behavior was tested by using
different types of ink, a spray painting and a permanent
marker as shown in Figs. 7 and 8, respectively.
Fig. 7 shows the results obtained when a spray is
applied over the protective gel synthetized at different
temperatures. A substrate without any coating is used
as blank surface (PS Petri dish). As it can be seen,
except in the case of the blank substrate, the behavior
of the protective gel after being sprayed and cleaned is
almost similar independently of the synthesis
temperature. As a qualitative approximation of the total
amount of ink-spot removal, it is estimated that in all
the cases the elimination is higher than 90%. However,
in the case of blank substrate, the ink-spot cannot be
removed. Due to the hydrophobic nature of the
protective gel, after the application of the spray the ink
is not well adhered over the protective coating and this
fact allows the easy removal of the majority of the spot
produced by the spray. However the removal is not
totally complete and an exterior circular halo of ink is
still present after the cleaning procedure regardless of
the synthesis temperature. The cleaning efficiency was

Fig. 6 SEM characterization of organic-inorganic hybrids.

Left images correspond with surface of coatings synthetized
at 25 C (a) and 45 C (b), center and right images are
associated to SEM-mapping analysis of silicon and zirconium,
respectively.

Fig. 7 Anti-graffiti behavior against spray painting of the

hybrids obtained at different temperatures (45, 35 and 25 C).

Fig. 8 Anti-graffiti behavior against permanent marker of

the hybrids obtained at different temperatures (45, 35 and
25 C).

Study and Characterization of Organically Modified Silica-Zirconia

Anti-Graffiti Coatings Obtained by Sol-Gel

ink spot is easily and totally removed (100%) in all the

cases except in the blank substrate. The cleaning
efficiency employing the classification numbers [38,
39] is CN 0 assigned to a total removal of the paint.
The anti-graffiti behavior could be related both to the
gel hydrophobic character due to the hydrophobic
nature of the material attributed to the presence of
organic groups (methyl groups) and to the densification
as well to the homogeneous and non-porous surface
reached after drying. Therefore, these gels may act like
a protective barriers and do not permit the spot
penetration inside the coating and allow the easy
removal of the paint.

4. Conclusions
A catalyst free sol-gel procedure is used to
synthetize an organic-inorganic hybrid solution mainly
formed by organic modified silica and zirconium,
which can be used as anti-graffiti protective gel. As the
synthesis temperature is increased from 25 to 45 C, the
hydrolysis and copolymerization reactions occur in a
larger extent and as a result, the resulting sol is more
cross-linked and the presence of Si-O-Zr new linkages
is more obvious. During sol to gel transformation and
drying step the protective materials formed present in
all the cases Si-O-Zr new linkages detected by a broad
shoulder centered at ~ 950 cm-1 in IR-ATR
spectroscopy. A shift in both Si-O stretching and
bending bands is also observed and is due to
incorporation of both polymer and zirconium within
the silica network. Based on the structural analysis
performed, the organic-inorganic hybrid material is
formed by long lineal chains of PDMS polymer
condensed with both TPOZ and MTES derived
molecules, additional D4 cyclic oligomers are
entrapped inside this structure with increasing amounts
with the synthesis temperature.
The organic-inorganic gel surface also displays a
nonporous and homogeneous final appearance.
SEM-mapping analysis shows zirconium is
homogeneously
dispersed
within
the

129

organically-modified silica matrix, and large zirconia

precipitates are not detected. However as the
temperature increases, when sol to gel transformation
is produced, the final protective material synthetized at
45 C undergoes lower shrinkage which minimizes the
apparition of voids and grooves and as a result the
surface is smoother which imply more durability. The
anti-graffiti response of the protective coating is very
promising for spray and marker paint, and the spot
removal determined qualitatively is > 90 and of 100%,
respectively.
Moreover, these products can be used as protective
coatings of a great variety of materials, like for
example glass, metals, alloys, stones (marble, granite,
sandstone), concrete, etc.. Other experiments are now
under consideration in order to test other properties
useful for different kind of applications, i.e., color,
gloss, water absorption, durability, etc..

Acknowledgments
The authors thank the Spanish Ministry of Economy
and Competitiveness for the financial support of the
project Sntesis de nanopartculas multifuncionales de
oxicarburo de silicio para aplicaciones biomdicas,
reference number MAT2009-14450.

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