J Sol-Gel Sci Technol (2010) 56:310–319
DOI 10.1007/s10971-010-2307-5
ORIGINAL PAPER
Polydimethylsiloxane/silica/titania composites prepared
by solvent-free sol–gel technique
Mihaela Alexandru • Maria Cazacu • Alexandra Nistor
Valentina E. Musteata • Iuliana Stoica •
Cristian Grigoras • Bogdan C. Simionescu
Received: 7 May 2010 / Accepted: 10 August 2010 / Published online: 21 August 2010
 Springer Science+Business Media, LLC 2010
Abstract Composites based on polydimethylsiloxane
incorporating silica and titania were prepared by mixing
polydimethylsiloxane with proper oxides precursors, tet-
raethyl-orthosilicate and tetrabutyl-orthotitanate. In the
presence of environmental humidity and in acid catalysis,
hydrolysis/condensation processes take place with forma-
tion of oxides and concomitantly polymer crosslinking.
Partial replacement of SiO2 in a polydimethylsiloxane/
silica composite with titania (both generated in situ by
sol–gel process) affects surface hydrophilicity (evaluated
by dynamic contact angle), water vapor sorption ability
(determined by dynamic vapor sorption) and thermal sta-
bility. The dielectric properties are also controlled by
composition.
Keywords Composites  Sol–gel technique 
Polysiloxanes  Titania  Silica
1 Introduction
The obtaining of composite materials by sol–gel technique
has been widely investigated [1–5]. As compared to other
techniques, the sol–gel approach has several advantages:
low costs, low temperature of heat treatment, unique ability
to achieve molecular level uniformity in the synthesis of
M. Alexandru (&)  M. Cazacu  A. Nistor 
V. E. Musteata  I. Stoica  C. Grigoras  B. C. Simionescu
‘‘Petru Poni’’ Institute of Macromolecular Chemistry, Aleea Gr.
Ghica Voda 41 A, Iasi 700487, Romania
e-mail: amihaela@icmpp.ro
B. C. Simionescu
Department of Natural and Synthetic Polymers, ‘‘Gh. Asachi’’
Technical University of Iasi, Iasi 700050, Romania
123
•
organic–inorganic composites, and strong adhesion of the
coating to the substrate [6, 7].
Polydimethylsiloxane/SiO2 composites prepared by the
reaction of polydimethylsiloxane (PDMS) and tetraethyl-
orthosilicate (TEOS) have also been extensively studied
[8–16]. These materials can be considered as ‘‘ceramic
rubbers’’ depending on the TEOS/PDMS molar ratio.
When PDMS concentration is increased, the final material
presents rubber-like properties. For high TEOS concen-
trations, hard composites are obtained. The rubbery prop-
erties are dependent on various reaction parameters, such
as temperature, acid concentration, reaction time, etc.
The incorporation of different inorganic components,
instead of or aside from TEOS, into the hybrid structure is
usually carried out in order to improve the mechanical,
thermal, and optical properties or to obtain new properties
derived from the hybrid nature of the material [17–22].
Due to their interesting properties such as elasticity,
insulating ability and easy processing, silicones are used in
microelectromechanical systems (MEMS) where they play
a structural role as protective layers, encapsulating ele-
ments, valves and diaphragms. However, by using active
fillers, the dielectric properties of silicones can be modified
[23, 24]. Titania has a high dielectric constant (e * 89)
being of real interest for this purpose. In addition, it is an
important inorganic functional material, with good physical
properties, which make it suitable for thin film applica-
tions. Films containing TiO2 have been often used in
microelectronic devices, e.g. in capacitors, or as a dielectric
gate in metal-dielectric-semiconductor devices. Titania
occupies also an important place as a photocatalyst, due to
its high photocatalytic activity, excellent functionality,
high chemical and thermal stability and non-toxicity [25].
The preparation of PDMS/SiO2/TiO2 composites by
the sol–gel method has already been reported in literature
J Sol-Gel Sci Technol (2010) 56:310–319
[19, 26, 27] and phase-separated materials in which SiO2
and TiO2 particles are dispersed in the silicone matrix were
generally obtained [28, 29]. As an alternative to literature
approaches, the present paper deals with the obtaining of
PDMS/SiO2/TiO2 composites in the absence of solvents.
Solvent-free systems present environmental advantages
and, on the other hand, this method diminishes the problem
created by the solvent removal at the end of the reaction,
which determines porosity in the material. In addition, this
would be a preferred alternative when a high molecular
mass polydimethylsiloxane is used as polymer matrix,
taking into account that this is insoluble in solvents com-
monly used in sol–gel technique. A series of composites
based on PDMS filled with in situ generated SiO2 and TiO2
was prepared. The influence of TiO2 content on the
dielectric properties was investigated. Other properties of
interest in dielectric applications, namely surface (dynamic
contact angle, dynamic vapor sorption) and thermal prop-
erties were also studied.
2 Experimental
2.1 Materials
Polydimethylsiloxane-a,x-diol (Mv ¼ 48; 000) was pre-
pared according to a previously described procedure [8, 30].
Tetraethyl-orthosilicate (TEOS), purchased from Fluka
(purity [ 98%, b.p. = 163–167 C, d20 4 = 0.933) was used
as received. Tetrabutyl-orthotitanate (TBT) (d = 0.966
g/cm3, b.p. = 310–314 C, m.p. = -55 C, d20 4 = 1.486).
Dibuthyltin dilaurate (DBTDL, d20 4 = 1.055) was received
from Merck-Schuchardt, and was used as received.
2.2 Equipments
Fourier transform infrared (FTIR) spectra were obtained on
a Bruker Vertex 70 FTIR analyzer. The analyses were
performed in transmission mode, in the 400–4,100 cm-1
range, at room temperature with 2 cm-1 resolution and
accumulation of 32 scans. The ground samples were
incorporated in dry KBr and processed as pellets.
Water vapors sorption capacity of the film samples was
measured by using the fully automated gravimetric ana-
lyzer IGAsorp supplied by Hiden Analytical, Warrington
(UK). An ultrasensitive microbalance measures the weight
change as the humidity is modified in the sample chamber
at a constant regulated temperature. The measurement
system is controlled by a user-friendly software package.
Dynamic contact angles (DCA) and contact angle hys-
teresis were measured on films by using a KSV Sigma 700
tensiometer system—a modular high-performance, com-
puter controlled surface tension/contact angle meter. The
311
measurement parameters were: advancing–receding speed,
5 mm/min; start depth, 0 mm; immersion depth, 8 mm;
number of cycles, 3; the average values were taken into
consideration.
Thermogravimetric measurements (TGA) were per-
formed in the 0–750 C temperature range at a heating rate
of 10 C/min in air using a Q-1500D System.
Glass transition and melting processes of PDMS based
composites were followed using a Pyris Diamond DSC
(Perkin Elmer USA) instrument. The samples were cooled
from room temperature to -150 C, held at this tempera-
ture 2 min, and then heated up to 50 C at a heating rate of
20 C/min. Helium gas was purged through the cells at
20 ml/min to assure an inert atmosphere and good thermal
conductivity. Before measurements, the DSC instrument
was calibrated for temperature and energy scale using n-
hexane and pure water as recommended standards for LN2
range of DSC analysis. The glass transition temperature
was calculated as a midpoint of the heat capacity of the
sample.
Novoncontrol setup (Broadband dielectric spectrometer
Concept 40, Germany), integrating an ALPHA frequency
response analyzer and a Quatro temperature control sys-
tem, was used to investigate the dielectric properties of the
polymer composites over a broad frequencies window,
100–106 Hz, in the -140 7 30 C temperature range. The
bias voltage applied across the sample was 1.0 V. Samples
having uniform thickness in the 0.2–0.9 mm range were
placed between gold plated round electrodes, the upper
electrode having a 20 mm diameter.
The AFM measurements were made on a Scanning
Probe Microscope Solver Pro-M platform (NT-MDT,
Russia), in air, in semi-contact mode, using a rectangular
NSG10/Au cantilever with a nominal elasticity constant
KN = 11.5 N m-1 and a 10 nm radius of curvature of the
tip. A 257.8 kHz oscillation frequency was used. The scan
area was 20 lm 9 20 lm, 256 9 256 scan point size
images being thus obtained. The AFM image processing
and the calculation of the surface texture parameters were
realized by the Nova Software (NT-MDT, Russia).
2.3 Composites preparation
The synthesis of a polydimethylsiloxane/silica/titania com-
posite was carried out as follows. 1.000 g (0.020 mmol) of
PDMS with Mv ¼ 48; 000 was introduced in a Teflon dish
and mixed with 0.500 g (2.400 mmol) TEOS and 0.038 g
(0.111 mmol) TBT. After about 10 min of stirring, 0.003 g
(0.005 mmol) of DBTDL was added and the stirring was
continued for another 10 min. The mixture was poured on a
Teflon foil and vacuumed for 10 min to eliminate the
incorporated air. This sample was labeled as T5. The other
123
312 J Sol-Gel Sci Technol (2010) 56:310–319

Table 1 The recipes used to prepare PDMS/SiO2/TiO2 composites Si–OH PDMS end groups, a crosslinking of PDMS occu-
Sample Inorganic Organic Catalyst
red. Obviously, TEOS and TBT also act as crosslinking
agents (Scheme 1).
TEOS TBT PDMS DBTDL The method used for the samples preparation in this study
(wt. %) (wt. %) (wt. %) (wt. %)
is based on the same principle as the room temperature
T0 35 0 65 0.165 vulcanization of the silicone rubber (RTV), in which the
T5 32.5 2.5 65 0.196 crosslinking of the polydimethylsiloxane-a,x-diol occurs by
T7.5 31 4 65 0.245 polycondensation reactions in the presence of environmental
T10 30 5 65 0.222 humidity, and needs a few days for curing. Water must dif-
T15 28 7 65 0.132 fuse deep into the film, while low molecular condensation
T20 26 9 65 0.166 compounds (i.e. alcohol) migrate outwards [31]. Therefore,
Tm 63 5 32 0.174 the films were kept in the laboratory environment for about
2 months before investigations, when the weighting dem-
onstrated the mass stabilization. In our case there was a
composites were obtained following the procedure described relative humidity of 40–60% in the laboratory. The obtained
above but using amounts of reactants according to Table 1. white opaque films (of about 0.2–0.9 mm thickness) were
easily peeled off from the substrate.
The inorganic part of these composites is considered to
3 Result and discussions be the sum of SiO2 and TiO2, while the organic one is
represented by PDMS. The SiO2/TiO2 ratio was varied, but
A polydimethylsiloxane-a,x-diol was used as matrix for their cumulated amounts remained constant. While silica is
preparing composite materials with SiO2 and TiO2 by introduced as a reinforcing material, the expected effect of
adapting a solvent-free sol–gel procedure. We chose this titania is to modify PDMS dielectric properties [32].
way because as is known, PDMSs of high molecular mass
(e.g., 48,000) have a low solubility in solvents that are 3.1 Fourier transform infrared spectroscopy
common for sol–gel technique, such as alcohols, ketones
and dimethylsulfoxide. Instead, they are soluble in non- Figure 1 shows the FT-IR spectra of PDMS based com-
polar solvents like hydrocarbons and their halogenated posites obtained by using different TEOS/TBT mass ratios
derivatives, many of them being toxic. in the spectral range between 4,100 and 400 cm-1. The
For this purpose, oxide precursors (TEOS and TBT) and composites show absorption bands around 2,900 and
a condensation catalyst (DBTDL) were added in pre- 2,964 cm-1, assigned to stretching vibrations of C–H in
established amounts to the polymer. After energic stirring methyl groups. The absorption band around 1,262 cm-1 is
and gas removing, the mixtures were processed as films. the main characteristic band of methyl groups bonded to
The hydrolysis of the corresponding precursors took place silicon and assigned to the symmetric deformation of C–H.
under the influence of the atmospheric humidity followed The absorption bands around 1,020–1,097 cm-1 are
by catalytic condensation with the formation of silicon and assigned to Si–O–Si stretching vibrations in siloxane
titanium oxides networks [26]. In addition, as a result of network [33, 34]. The broad peaks of OH bond are
the reactions of the alkoxydes and their hydrolysates with observed at 3,000–3,500 cm-1 for all samples [29]. TBT

Scheme 1 Proposed OC2H5 CH3 CH3 CH3 OC4H9

networking within composites
C2H5 O Si OC2H5 + HO Si O Si O Si OH + C4H9 O Ti OC4H9
n
OC2H5 CH3 CH3 CH3 OC4H9

room
DBTDL
temp.

Si O Si Si O Si
O O CH3 CH3 CH3 O O O

Si O Si O Si O Si O Si O Si O Si O Ti O Ti
n
O CH3 CH3 CH3 O O O

Si Si O Si O Si

123
J Sol-Gel Sci Technol (2010) 56:310–319
Fig. 1 IR spectra of the PDMS/SiO2/TiO2 composites
self-condensation reaction gives Ti–O–Ti bonds, while its
copolymerization with TEOS or PDMS gives Ti–O–Si
bonds [27]. Some reports suggest that the Ti–O–Si bonds
formed as a result of the reactions between TBT, TEOS and
PDMS are unstable, disappearing during the aging process
[35]. However, a certain amount of Ti–O–Si bonds can be
found in the final material. To verify the formation of the
Si–O–Ti bond, not visible in our spectra due to the higher
content in PDMS as compared with the inorganic part, a
model sample was prepared based on an inversed mass ratio
between the organic and inorganic components (sample Tm,
Table 1). One can observe, in the FTIR spectrum of the Tm
sample, a shoulder in the 910–960 cm-1 region, shoulder to
be assigned to the Si–O–Ti bond [36]. Due to the fact that in
this region Si–OH bond could be also present [37], the
sample was calcinated at 900 C (Tm-c), the band centered
around 951 cm-1 and corresponding to Si–O–Ti vibration
thus becoming well defined. According to literature [38],
the intermolecular interaction between titania and silica
in composites with predominant SiO2 content occurs by
replacement of silicon atoms in the SiO-4 4 tetrahedra with
titanium atoms, while maintaining the tetrahedral coordi-
nation of titanium with respect to oxygen. The reverse
313
substitution in the titanium dioxide-enriched composite is
difficult, probably due to the limited coordination ability
[38]. A strong band is developed at 478 cm-1 assigned to
both Si–O–Si and Ti–O–Ti overlaped bonds [39].
3.2 Vapor sorption capacity
Water vapors uptaking capacity for the samples at 25 C in
the 0–90% relative humidity range (RH) was investigated
by using the IGAsorp equipment. The vapors pressure was
increased in 10% humidity steps, every having a pre-
established equilibrium time between 30 and 40 min
(minimum time and time out, respectively). At each step,
the weight gained was measured by electromagnetic com-
pensation between tare and sample when equilibrium was
reached. An anti-condensation system was available for
vapor pressure very close to saturation. The cycle was
ended by decreasing the vapor pressure in steps to obtain
also the desorption isotherms. The drying of the samples
before sorption measurements was carried out at 25 C in
flowing nitrogen (250 ml/min) until the weight of the
sample was in equilibrium at RH \ 1%. The sorption/
desorption isotherms registered in these conditions are
presented in Fig. 2.
The partial replacement of SiO2 in a PDMS-silica
composite with TiO2 (both generated in situ by the sol–gel
process) yielded an increase of water vapor sorption
capacity from 0.4 (T0) up to 1.0–1.1 (T5–T20). According
to IUPAC classification, the sorption–desorption curves
can be associated to type III curves. These types of iso-
therms describe sorption on hydrophobic/low hydrophilic
material with weak sorbent–water interactions [40]. GAB
and BET kinetic models applied to the obtained data gave
the values presented in Table 2.
Fig. 2 Rapid water vapors sorption isotherms for composites
123
314 J Sol-Gel Sci Technol (2010) 56:310–319

Table 2 Maximum water

Sample The average Weight BET analysis (5–35%) GAB analysis (5–80%)
vapors sorption values for the
pore size (nm) (% d.b.)
composites Area Monolayer Area Monolayer
(m2/g) (g/g) (m2/g) (g/g)

T0 1.37 0.4552 6.622 0.001886 – –

T5 1.27 1.0891 17.107 0.004873 20.866 0.005943
T7.5 1.39 1.0947 15.773 0.004492 18.806 0.005356
T10 1.59 1.0282 12.996 0.003702 15.207 0.004331
T15 1.25 1.0414 16.675 0.004749 20.703 0.005897
T20 1.44 1.1290 15.679 0.004466 18.422 0.005247

As one can see, the surface area values increase with
TiO2 content although the average pore size remains
almost constant (1.2–1.6 nm). The incompatibility between
the oxide and the polymer, leading to the increasing pore
number, can explain this behavior [41].
3.3 Dynamic contact angle
Film surface wettability was analyzed by measuring the
dynamic contact angle on composites films by using the
tensiometric method (Wilhelmy plate technique). Water
was used as measurement liquid. The DCA runs were
performed on rectangular films. The obtained contact angle
values are given in Table 3.
The water contact angle depends on the polarity of the
surface, i.e. by increasing the polarity, the hydrophilicity
increases. This happened by incorporating TiO2 in the
studied composites. The presence of Ti–O–Ti bonds con-
tributes to the hydrophilicity. A decrease of advancing
contact angles was observed with increasing titania content
in the samples. The differences between the maximum
advancing and minimum receding contact angle values,
known as contact angle hysteresis—a measure of surface
heterogeneity and roughness [42]—were calculated. The
decreasing hysteresis value is determined by the surface
smoothing caused by the increase of TiO2 content in the
sample.
3.4 Thermogravimetric measurements
Results of thermogravimetric analysis of the prepared
composites in the 0–750 C temperature range in air are
shown in Fig. 3.
Two weight loss stages are observed, below 350 C and
between 350 and 550 C, the latter one being a significant
weight loss stage. The weight loss below 350 C is
attributed to the evaporation of free water, the volatiliza-
tion and the thermal decomposition of the remnant organic
solvents. Between 350 and 550 C, the weight losses could
be probably ascribed to the further combustion of organic
moieties [43, 44].
The samples containing TiO2 yield a larger amount of
residue during the thermo-oxidative decomposition than
sample T0 that contains only SiO2. It was previously
shown [31, 45, 46] that traces of organometallic catalyst
favors depolymerisation with formation of volatile com-
pounds and lowers the residue amount. According to the

Table 3 The main parameters of the water contact angle

measurements
Sample %TiO2 H2O
A R H

T0 0 109.89 77.82 32.07

T5 5 97.13 74.63 22.5
T7.5 7.5 83.74 75.06 8.68
T10 10 94.42 81.6 12.82
T15 15 84.46 73.70 10.76
T20 20 76.39 77.32 –
Fig. 3 The TGA curves of PDMS/SiO2/TiO2 composites

123
J Sol-Gel Sci Technol (2010) 56:310–319 315

here reported data, in the presence of TiO2 this process is Table 4 The main parameters of the DSC curves registered for the
hindered. composites
Sample Tg (C) DCp J/g(C) Tm (C) DHm (J/g)
3.5 Differential scanning calorimetry
T0 -118.93 0.09 -44.60 24.425
PDMS is well known as a polymer having very low glass T5 -123.27 0.229 -40.61 19.145
transition and melting temperatures down to 0 C. Glass T7.5 -123.52 0.073 -41.89 18.38
transition processes in PDMS/SiO2/TiO2 systems resulted T10 -123.32 0.269 -41.23 19.713
from DSC scans are shown in Fig. 4a for all samples, T15 -123.36 0.089 -40.84 17.634
including the T0 sample. It is noticeable that the T0 sample T20 -123.66 0.059 -40.58 17.65
has a higher glass transition temperature (-118 C) as
compared to the composites with TiO2 (T5….T20)
(Table 4) which show glass transition processes around amorphous phase of the material is affected by both the
-123 C for all compositions (with small, insignificant chemical linking of SiO2 and by the addition of TiO2 (no
differences up to 1 C). It is reasonable to consider that, by matter the amounts added).
filling with SiO2 and crosslinking of PDMS, a reduction of The melting endotherms of PDMS/SiO2/TiO2 compos-
chain mobility occurs, which leads to the increase of Tg. ites are shown in Fig. 4b. Sample T0 clearly shows a
The incorporation of TiO2 in the PDMS/SiO2 system in melting process around -45 C. This sharp endothermic
various fractions generally has a contrary effect; the peak suggests that the PDMS/SiO2 system has a crystalline
increasing of the free volume and the increased chain morphology consisting of well-defined crystallites that
mobility allows a lower glass transition temperature. The need a high thermal energy to melt (24.42 J/g). All com-
posites containing TiO2 present lower-energy melting en-
dotherms with enthalpy values decreasing from T5 to T20,
as shown in Table 4. The shape of melting endotherms for
samples which contain TiO2 shows a duality of their
crystalline morphology, which comes from the develop-
ment of two major types of crystallites. The first one is
formed by the PDMS/SiO2 composite and melts at -47 C,
while the second type is developed by the PDMS/SiO2/
TiO2 composite and has a melting interval around -43 C.
This duality of morphology is not very clearly separated
because the two types of crystallites have almost the same
thermodynamic stability, and, in addition, at least one
polymer chain that forms a crystallite type may pass
through the other crystallite type. According to Fig. 4b, for
higher contents of TiO2 (higher than 15%) in the PDMS/
SiO2 system the dual morphology becomes well defined.
The morphology developed only by PDMS/SiO2 fraction
seems to be preserved.

3.6 Dielectric measurements

Measurements of the complex dielectric permittivity

Fig. 4 Glass transition (a) and melting endotherms (b) in PDMS/
SiO2/TiO2 composites
e* = e0 - ie00 (where e’ is the storage component and e00 is
the loss component) were carried out at seven fixed fre-
quencies, by sweeping the temperature from -140 C up to
30 C with 5 C/min heating rate. The real and imaginary
parts of complex dielectric permittivity have a direct
physical interpretation. e0 is related to the reversible energy
stored in the material by polarization, whereas e00 is pro-
portional to the energy which is dissipated per cycle,
divided into relaxation and conductivity contribution
(energy required to align dipoles and move ions).

123
316 J Sol-Gel Sci Technol (2010) 56:310–319

For the T5 sample the data are represented as the real the sample during the heating scan. The idea of crystalli-
part of complex dielectric permittivity (e0 ) and the imagi- zation is supported by e0 behavior, which displayed a
nary part or dielectric loss (e00 ) as a function of temperature decrease at the same temperature; at this temperature the
and frequency in Fig. 5a and 5b, respectively. mobility of the dipoles is reduced due to the immobiliza-
The temperature dependence of dielectric parameters, e0 tion and/or constraint of some fractions of the responding
and e00 , exhibits three regions which are associated to the dipoles by increasing bulk crystallinity.
mobility of the polymer chains. Initially, e0 presents an At temperatures higher than -40 C, an increase in the
increasing step and e00 a peak which corresponds to the permittivity of composites by increasing temperature is
segmental a relaxation associated with the glass transition observed, especially at lower frequencies, due to the
of amorphous PDMS. The shifting of these peaks to higher
temperatures by increasing frequency is a characteristic of
the dielectric relaxation. Due to the frequency of the
dielectric measurement, the loss peak appears at a tem-
perature significantly higher (-100 C) than the calori-
metric Tg (-123 C). A a relaxation peak follows, this one
being partly superposed by a smaller peak at higher tem-
peratures. The last one could result from crystallization of

Fig. 6 Dielectric permittivity, dielectric loss versus temperature at

1 kHz

Fig. 5 Dielectric permittivity e0 (a) and dielectric loss e00 (b) as a

function of temperature and frequency for T5 sample Fig. 7 Dielectric permittivity versus TiO2 percent at 25 C

123
J Sol-Gel Sci Technol (2010) 56:310–319 317

Fig. 8 AFM images of the composites

interfacial polarization at electrode/sample or amorphous/ From dielectric measurements, it appears that e00
crystalline interface. This process appears at lower fre- increases with temperature, especially at low frequencies,
quencies, when the mobile charges have enough time to this behavior being attributed to the increased conductivity;
migrate between boundaries. the mobility of the charge carriers increase by increasing

123
318 J Sol-Gel Sci Technol (2010) 56:310–319

Table 5 Surface particles characteristics and roughness parameters of T0–T10 films, corresponding to the 2D AFM images
Sample AFM scanned Particle characteristics Surface roughness parameters
area (lm2)
Number of particles Average particle Average roughness, Root mean square
measured length (nm) Saa (nm) roughness, Sbq (nm)

T0 20 9 20 10 812 13.56 23.37

T5 20 9 20 10 1169 10.13 13.15
T 7.5 20 9 20 10 922 4.10 5.48
T 10 20 9 20 10 1427 6.03 10.40
a
The average roughness parameter, Sa, is the most used surface roughness parameter. It is the arithmetic mean or average of the absolute
distances of the surface points from the mean plane. The digital equation that represents this algorithm is displayed below, where M is the number
of columns in the surface and N is the number of rows in the surface:
1
P
N P M  
Sa ¼ MN jzj xi ; yj ð1Þ
j1 i1
b
The root mean square (RMS) roughness parameter, Sq, is the root mean square of the surface departures from the mean plane within the
sampling area:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1
PN P M  
Sq ¼ MN z2 xi ; yj ð2Þ
j1 i1

temperature. These effects on e0 and e00 values are more
pronounced in the composite samples containing TiO2.
No significant variation of the a relaxation temperature
with composition is observed, this demonstrating that the
glass transition of polymer matrix is not considerably
influenced by the introduction of TiO2, as also emphasized
by DSC (Fig. 6).
As shown by the vapor sorption study, the samples with
higher TiO2 content have an increased hydrophilicity,
suggesting that it’s possible for those samples to have a
higher content of absorbed atmospheric water. It is known
that the dielectric constant of a material increases by
uptaking water [47] because the concentration of mobile
dipoles becomes higher, leading to the increase of the
permittivity [48, 49]. Therefore, the increase of the
dielectric constant by rising the TiO2 content could have
two causes: the polarity of TiO2 (e = 89) and the polarity
of water (e = 78.5 at 25 C) [50]. Taking into account that
the amount of absorbed water is smaller (*1.1%) than the
TiO2 content (5–20%), it is presumed that the increase in
dielectric constant is mainly due to the titania amount.
However, the increase in dielectric loss at positive tem-
peratures for the samples containing TiO2 could be due to
the absorbed water molecules.
On the other hand, the slight increasing of the dielectric
constant values of the samples with TiO2 against those
without (Fig. 7) implies that the TiO2 particles are uni-
formly dispersed in the PDMS matrix. Otherwise, the
porosities associated with the agglomerated TiO2 particles
would significantly degrade the dielectric constant.
3.7 Atomic force microscopy
Figure 8 shows AFM images of the T0–T10 composites.
The films have relatively high surface roughness (the root
mean square roughness is about 10 nm). Table 5 presents
the surface particles characteristics and roughness param-
eters of T0–T10 films, with 20 9 20 lm2 scanned areas,
corresponding to the 2D AFM images.
Although the T0 particles are smaller (the average of 10
measurements is 812 nm), roughness parameters have
higher values (Sa is 13.56 nm and Sq is 23.37 nm), and the
particles tend to agglomerate. In the case of T10 sample,
the particles have a larger average diameter, about
1427 nm, but are not crowded, thus determining a lower
film roughness (Sa is 6.03 nm and Sq is 10.40 nm). The
introduction of TiO2 in PDMS/SiO2 composites leads to an
increase of particle size, but one can not differentiate
between TiO2 and SiO2 particles.
4 Conclusions
A series of PDMS/SiO2/TiO2 composites have been pre-
pared by solvent-free sol–gel technique. The amounts of
TiO2 were quite small and didn’t induce spectacular
effects, but higher amounts of TiO2 yield low quality films
and structuration processes. The partial replacement
of SiO2 in a PDMS-silica composite with TiO2 (both
generated in situ by the sol–gel process) increases the

123
J Sol-Gel Sci Technol (2010) 56:310–319
hydrophilicity, porosity, and thermal stability of the com-
posites. While the Tg value is only slightly influenced by
TiO2 addition, the crystallization and melting temperatures
values change as compared to those of the blank sample.
Both e0 and e00 values increase throughout the studied range
of temperatures and frequencies following the addition of
TiO2. The temperature dependence of both curves show
inflections at Tg, Tm, and Tc values close to those detected
by DSC. The possibility to control the dielectric parameters
recommends these materials as elastic dielectric—active
elements for nano-actuation devices.
Acknowledgments This research was financially supported by
European Regional Development Fund, Sectoral Operational Pro-
gramme ‘‘Increase of Economic Competitiveness’’, Priority Axis 2
(SOP IEC-A2-O2.1.2-2009-2, ID 570, COD SMIS-CSNR: 12473,
Contract 129/2010-POLISILMET).
References
1. Schmidt H (1994) J Sol-Gel Sci Technol 1:217–231
2. Lev O, Wu Z, Bharathi S, Glezer V, Modestov A, Gun J, Rabi-
novich L, Sampath S (1997) Chem Mater 9:2354–2375
3. Sanchez C, Julián B, Belleville P, Popall M (2005) J Mater Chem
15:3559–3592
4. Shindou T, Katayama S, Yamada N, Kamiya K (2003) J Sol-Gel
Sci Technol 27:15–21
5. Hüsing N, Bauer J, Kalss G, Garnweitner G, Kickelbick G (2003)
J Sol-Gel Sci Technol 26:73–76
6. Fabes BD, Uhlmann DR (1990) J Am Ceram Soc 73:978–988
7. Simionescu B, Aflori M, Olaru M (2009) Constr Build Mater
23:3426–3430
8. Alexandru M, Cristea M, Cazacu M, Ioanid A, Simionescu BC
(2009) Polym Compos 30:751–759
9. Hu Y, Chung YJ, Mackenzie JD (1993) J Mater Sci 28:6549–
6554
10. Sun CC, Mark JE (1989) Polymer 30:104–106
11. Mark JE, Pan SJ (1982) Macromol Rapid Commun 3:681–685
12. Rajan GS, Sur GS, Mark JE, Schaefer DW, Beaucage G (2003)
J Polym Sci Polym Phys 41:1897–1901
13. Mark JE, Jiang C-Y, Tang M-Y (1984) Macromolecules
17:2613–2616
14. Ning Y-P, Tang M-Y, Jiang C-Y, Mark JE, Roth WC (1984)
J Appl Polym Sci 29:3209–3212
15. Tang M-Y, Mark JE (1984) Macromolecules 17:2616–2619
16. Ning Y-P, Mark JE (1985) J Appl Polym Sci 30:3519–3522
17. Yamada N, Yoshinaga I, Katayama S (2000) J Sol-Gel Sci
Technol 17:123–130
18. Rojas-Cervantes ML, López-Peinado AJ, Martı́n-Aranda RM,
Gómez-Serrano V (2003) Carbon 41:79–86
19. Pẽna-Alonso R, Téllez L, Rubio J, Rubio F (2006) J Sol-Gel Sci
Technol 38:133–145
319
20. Enescu D, Hamciuc V, Timpu D, Harabagiu V, Simionescu BC
(2008) J Optoelectron Adv M 10:1473–1477
21. Epure V, Hamciuc V, Pricop L, Pinteala M, Airinei A, Harabagiu
V, Simionescu BC, Enescu D, Perichaud A (2007) High Perform
Polym 19:270–282
22. Racles C, Cazacu M, Ioanid A, Vlad A (2008) Macromol Rapid
Commun 29:1527–1531
23. Cazacu M, Ignat M, Vlad A, Alexandru M, Racles C, Zarnescu G
(2009) Polym Int 58:745–751
24. Cazacu M, Ignat M, Vlad A, Alexandru M, Zarnescu G (2010)
Optoelectron Adv Mater Rapid Commun 4:349–351
25. Raileanu M, Crisan M, Dragan N, Crisan D, Galtayries A, Bra-
ileanu A, Ianculescu A, Teodorescu VS, Nitoi I, Anastasescu M
(2009) J Sol-Gel Sci Technol 51:315–329
26. Rubio F, Rubio J, Oteo JL (2000) J Sol-Gel Sci Technol
8:105–113
27. Téllez L, Rubio J, Rubio F, Morales E, Oteo JL (2003) J Mater
Sci 38:1773–1780
28. Lantelme B, Dumon M, Mai C, Pascault JP (1996) J Non-Cryst
Solids 194:63–71
29. Lee B-S, Kang D-J, Kim S-G (2003) J Mater Sci 38:3545–3552
30. Cazacu M, Marcu M (1995) Macromol Rep A 32:1019–1029
31. Alexandru M, Cazacu M, Vlad S, Iacomi F (2009) High Perform
Polym 21:379–392
32. Dire S, Babonneau F, Sanchez C, Livage J (1992) J Mater Chem
2:239–244
33. Pirson A, Mohsine A, Marchot P, Michaux B, Van Cantfortc O,
Pirard JP (1995) J Sol-Gel Sci Technol 4:179–185
34. Brusatin G, Guglielmi M, Innocenzi P, Martucci A, Battaglin G
(1997) J Non-Cryst Solids 220:202–209
35. Babonneau F (1994) Polyhedron 13:1123–1130
36. Gu H, Bao DH, Wang SM, Gao DF, Kuang AX, Li XJ (1996)
Thin Solid Films 283:81–83
37. Noggin M (1985) J Non-Cryst Solids 69:415–423
38. Murashkevich AN, Lavitskaya AS, Barannikova TI, Zharskii IM
(2008) J Appl Spectro 75:730–734
39. Kochkar H, Figueras F (1997) J Catal 171:420–430
40. Ng E-P, Mintova S (2008) Microporous Mesoporous Mater
114:1–26
41. Yang Y, Zhang H, Wang P, Zheng Q, Li J (2007) J Memb Sci
288:231–238
42. Yeh K-Y, Chen L-J, Chang J-Y (2008) Langmuir 24:245–251
43. Que W, Zhou Y, Lam YL, Chan YC, Kam CH (2001) J Sol-Gel
Sci Technol 20:187–195
44. Wang B-L, Hu L-L (2005) Mater Chem Phys 89:417–422
45. Cazacu M, Vlad A, Alexandru M, Budrugeac P, Racles C, Iacomi
F (2010) Polym Bull 64:421–434
46. Chiang C-L, Ma C-CM (2004) Polym Degrad Stab 83:207–214
47. Fraga AN, Frullloni E, de la Osa O, Kenny JM, Va0 zquez A
(2006) Polym Testing 25:181–187
48. Li Y, Cordovez M, Karbhari VM (2003) Compos Part B
34:383–390
49. Pethrick RA, Hayward D (2002) Prog Polym Sci 27:1983–2017
50. Weast RC (ed) (1985) CRC handbook of chemistry and physics.
CRC, Boca Raton
123