Thermal Properties of PMMA/TiO2 Nanocomposites
Prepared by In-Situ Bulk Polymerization
E. Džunuzović,1 M. Marinović-Cincović,2 J. Vuković,3 K. Jeremić,1 J.M. Nedeljković2
1
Department of Physical Chemistry and Electrochemistry, Faculty of Technology and Metallurgy,
University of Belgrade, Karnegijeva 4, 11120 Belgrade, Serbia
2
Vinča Institute of Nuclear Sciences, 11001 Belgrade, Serbia
3
Institute for Chemistry, University of Osnabrück, Barbarastrabe 7, 49069 Osnabrück, Germany
The surface of anatase TiO2 nanoparticles, obtained by
the controlled hydrolysis of titanium tetrachloride, was
modified by 6-palmitate ascorbic acid. The surface
modified TiO2 nanoparticles were dispersed in methyl
methacrylate and mixed with a appropriate amount of
poly(methyl methacrylate) to obtain a syrup. The nano-
composite sheets were made by bulk polymerization of
the syrup in a glass sandwich cell using 2,20 -azobisiso-
butyronitrile as initiator. The molar masses and molar
mass distributions of synthesized poly(methyl methacry-
late) samples were determined by gel permeation chro-
matography. The content of unreacted double bonds in
synthesized samples was determined by 1H NMR spec-
troscopy. The influence of TiO2 nanoparticles on the
thermal stability of the poly(methyl methacrylate) matrix
was investigated using thermogravimetric analysis and
differential scanning calorimetry. The synthesized sam-
ples of poly(methyl methacrylate) have different molar
mass and polydispersity depending on the content of
the surface modified TiO2 nanoparticles. The values of
glass transition temperature of so prepared nanocom-
posite samples were lower than for pure poly(methyl
methacrylate), while the glass transition temperature of
samples preheated in inert atmosphere was very similar
to the glass transition temperature of pure poly(methyl
methacrylate). The thermal stability of nanocomposite
samples in nitrogen and air was different from thermal
stability of pure poly(methyl methacrylate). POLYM. COM-
POS., 30:737–742, 2009. ª 2008 Society of Plastics Engineers
INTRODUCTION
In recent years the design and synthesis of polymer/
metal oxides nanocomposites has been the subject of
many studies in polymer and material sciences [1, 2]. Tita-
Correspondence to: Katarina Jeremic; e-mail: kjeremic@tmf.bg.ac.yu
Contract grant sponsor: Ministry of Science, Republic of Serbia; contract
grant numbers: 142066, 142023.
DOI 10.1002/pc.20606
Published online in Wiley InterScience (www.interscience.wiley.com).
C 2008 Society of Plastics Engineers
V enabled phase transfer of the particles from water into
POLYMER COMPOSITES—-2009
nium dioxide (TiO2) is one of the most investigated metal
oxides since it is inexpensive and nontoxic material, which
has high refractive index and possesses the ability to
absorb ultraviolet light. Incorporation of TiO2 in polymer
matrix can provide significant improvement in the wea-
therability and durability of polymer products. Thermal
and flammability properties of poly(methyl methacrylate)
(PMMA) matrix were also improved by incorporation of
TiO2, alone or in combination with organoclays [3, 4].
Polymer nanocomposites are two-phase systems and the
main problem is how to supress agglomeration of inor-
ganic particles in polymer matrix. One of the approaches
is surface modification of inorganic particles [1, 5, 6].
Different coupling agents have been used to modify the
surface of TiO2 and improve the interfacial interactions
necessary for successful incorporation of these hydrophilic
nanoparticles in hydrophobic polymer matrices [7]. Caris
et al. used conventional emulsion polymerization to encap-
sulate TiO2 in PMMA [8, 9]. Sidorenko et al. investigated
the radical polymerization of styrene and methyl metha-
crylate (MMA) initiated from the surface of TiO2 particles
by adsorbed hydroperoxide macroinitiators [10]. Erdem
et al. encapsulated TiO2 nanoparticles by miniemulsion
polymerization of styrene, polybutene-succinimide pen-
tamine being used as the stabilizer at the oil/water inter-
face [11–13]. Rong et al. [14] used TiO2 nanoparticles
modified by 3-(trimethoxysilyl)propylmethacrylate (MPS)
to copolymerize styrene with the methacrylate group of
MPS by free radical polymerization. A similar approach
was used by Yang and Dan [15] who graft polymerized
MMA from the surface of modified TiO2 particles.
This study represents continuation of our efforts to de-
velop methods for preparation of PMMA/TiO2 nanocom-
posites. In our previous study [16] the surface of the TiO2
nanoparticles with average diameter of 4.5 nm was modi-
fied with 6-palmitate ascorbic acid (6-PAA), which
toluene. The modified TiO2 nanoparticles dissolved in
toluene were encapsulated in PMMA by in situ radical
polymerization of MMA initiated by 2,20 -azobisisobut-
yronitrile (AIBN). In this case, instead of polymerizing
MMA in solution with dispersed nanoparticles, PMMA/
TiO2 nanocomposite was prepared by bulk polymerization
of MMA in the so-called glass sandwich cell at elevated
temperature, using AIBN as initiator. The influence of the
TiO2 nanoparticles on the molar mass, molar mass distri-
bution, glass transition temperature (Tg), as well as on the
thermal stability of PMMA matrix in nitrogen or air was
investigated using gel permeation chromatography (GPC),
1
H NMR spectroscopy, differential scanning calorimetry
(DSC) and thermogravimetric analysis (TGA).
EXPERIMENTAL
Materials
Titanium tetrachloride, methyl methacrylate, methanol
and toluene were obtained from Merck. AIBN was
obtained from Fluka, and 6-palmitate ascorbic acid from
Aldrich. Commercially available PMMA Diakon CMG
314V (Mw ¼ 90,000; Mw/Mn ¼ 2.195) was purchased from
Lucite International. All chemicals except MMA were
used as received without further purification. MMA was
purified in the standard manner. Inhibitor was removed by
washing the monomer with aqueous NaOH and then with
distilled water. The monomer was dried with calcium
chloride and then vacuum distilled.
Preparation of PMMA/TiO2 Nanocomposites
Colloid consisting of anatase TiO2 particles with aver-
age diameter of 4.5 nm was prepared by the controlled
hydrolysis of titanium tetrachloride as described else-
where [17]. After synthesis, the colloid concentration was
determined from the concentration of the peroxide com-
plex obtained after dissolving the colloid in concentrated
HClO4 [18].
Surface modification of colloidal TiO2 nanoparticles
was performed by the procedure described previously
[16, 19]. Briefly, 20 ml of 0.15 M aqueous TiO2 colloid
solution was mixed with 6-PAA (0.2486 g) dissolved in
mixture of methanol (4 ml) and toluene (10 ml). After
shaking, a dark-red toluene phase containing the surface
modified TiO2 particles (TiO2/6-PAA) separated from the
aqueous phase. The obtained red toluene solution was
poured into a large excess of methanol to remove free 6-
PAA molecules. The surface modified TiO2 particles were
separated by centrifugation and redispersed in MMA. The
residual methanol was removed by purging the solution
with argon.
To prepare samples of PMMA/TiO2 nanocomposite
sheets, 1.5 g of PMMA (Diakon CMG 314V) was added
to 7.5 g of MMA which contained appropriate amount of
738 POLYMER COMPOSITES—-2009
TiO2/6-PAA particles. After that, the dispersion was
stirred at room temperature over night. The dispersion
was heated up to 508C and 13.5 mg of the initiator
(AIBN) disolved in 0.8 g of MMA was introduced. The
obtained dispersion was stirred at 508C for 20 min and
then poured into the glass sandwich cell with 1-mm Tef-
lon spacer and polymerized at 608C for 4 h and subse-
quently at 1208C for 1 h. The polymerization of MMA
without the presence of TiO2 nanoparticles was performed
under the same experimental conditions.
Characterization
The molar masses and molar mass distribution of syn-
thesized PMMA samples were determined using Spectra-
Physics chromatograph equipped with differential refrac-
tive index detector and a set of two gel columns (MZGPC
columns) with porosities of 1,000 Å. Tetrahydrofuran was
used as the mobile phase (1.0 ml/min). Narrow molar mass
polystyrene standards (Polymer Standards Service) were
used for the calibration. The molar mass characteristics of
examined samples were calculated using the Chrom Gate
3.1.4. software (Knauer). For GPC measurements, PMMA
was extracted from PMMA/TiO2 nanocomposite with ace-
tone. Subsequently, PMMA was obtained from the acetone
solution by acetone evaporation.
The 1H NMR spectra of synthesized samples were
recorded in deuterated chloroform using Bruker DRX 500
NMR spectrometer. Tetramethylsilane was used as internal
standard.
The thermal stability of PMMA and PMMA/TiO2
nanocomposites was investigated by nonisothermal TGA
using Perkin Elmer TGS-2 instrument. The measurements
were conducted in dynamic nitrogen and air atmosphere
(flow rate was 25 cm3/min) at heating rate of 108C/min.
DSC was performed at heating rate of 208C/ min in
nitrogen atmosphere using Perkin Elmer DSC-2 instrument.
RESULTS AND DISCUSSION
The detailed characterization of surface modified TiO2
particles with 6-PAA including surface structure, optical
properties and nature of charge transfer complex between
TiO2 and 6-PAA has been described elsewhere [19], and
discussion of that subject will be avoided further in the
text.
The PMMA and three samples of PMMA/TiO2 nano-
composites with different content of inorganic phase were
prepared by bulk polymerization of MMA under the same
experimental conditions (Table 1). Small amount of Dia-
kon CMG 314V was added to dispersion to prevent
autoacceleration of polymerization reaction, shrinking of
polymeric material during the polymerization and to
reduce the polymerization time [20]. At the same time,
addition of PMMA increased viscosity of dispersion
reducing a possibility of particle aggregation and phase
separation.
DOI 10.1002/pc
TABLE 1. Properties of the prepared PMMA and PMMA/TiO2 6.03 and 5.49 ppm) and the protons of the methyl groups
samples. bound to oxygen from ester groups (at 3.35–3.75 ppm). It
Content Mn
1025, Tg,
was found that the content of unreacted double bonds was
of TiO2, (wt%) (g/mol) PDI (8C) over three times larger for pure PMMA than for nano-
composite samples.
PMMA 0 2.93 4.97 111 The thermooxidative stability of synthesized samples
PMMA/TiO2 (1) 0.2 2.92 4.68 105 was also studied and the TG and DTG curves for the pure
PMMA/TiO2 (2) 0.4 2.52 5.47 99
PMMA/TiO2 (3) 0.8 1.96 5.86 86
PMMA and PMMA/TiO2 (3) samples, obtained in air, are
presented in Fig. 2. The mechanism of thermooxidative
degradation of PMMA is more complex than mechanism
The values of molar mass and molar mass distribution, of degradation in nitrogen. The oxygen suppresses degra-
presented as polydispersity index (PDI), of synthesized dation of free radically polymerized PMMA caused by
PMMA samples were determined by GPC (Table 1). The the presence of the weak linkages in the PMMA chains at
obtained values of molar mass and PDI for pure PMMA the low temperature but it enhances PMMA degradation
were as expected for high-conversion vinyl polymers [21] at higher temperatures [26, 31]. DTG curve of pure
where the termination reactions during the polymerization PMMA shows two overlapped peaks (about 300 and
occur only by disproportionation and combination. The 3408C). The thermooxidative stability of the PMMA
molar masses of PMMA extracted from nanocomposite matrix is much more influenced by the TiO2/6-PAA nano-
sheets were lower than molar mass of pure PMMA and particles than its inherent thermal stability. Incorporation
decreased with the increasing content of TiO2. Also, the of the TiO2/6-PAA nanoparticles shift decomposition to
increase of the content of inorganic phase led to increase higher temperature and leads to decrease of the first DTG
of polydispersity of PMMA samples. The obtained results peak, so the DTG curve of the PMMA/TiO2 (3) sample
indicate that termination reactions during polymerization shows only one peak at 3728C. The explanation of the
were influenced by the presence of nanoparticles. It has observed behavior probably lies in inhibiting effects of
been shown that ascorbic acid and its derivatives could the TiO2/6-PAA particles on some degradation stages of
act as radical scavengers [22–24], which consequently the thermooxidative degradation of PMMA. Namely,
leads to the decrease of molar mass of PMMA and TiO2 is most widely used material in sensors for oxygen
increase of PDI with the increasing content of the TiO2/ detection. The reaction between the oxygen and TiO2
6-PAA nanoparticles in the reaction mixture.
The thermal stability of the synthesized samples was
examined by non-isothermal thermogravimetry. The TG
and derivative thermogravimetric (DTG) curves obtained
for the pure PMMA and PMMA/TiO2 (3) samples in
nitrogen atmosphere are shown in Fig. 1. It is well known
that PMMA thermally decomposes by depolymerization
and that the thermal stability of free radically polymerized
PMMA is significantly affected by the presence of unsatu-
rated end groups and head-to-head bonds obtained by dis-
proportionation and combination termination reactions,
respectively [25–30]. The DTG curve of pure PMMA
(Fig. 1B) has a peak at 3678C, which corresponds to de-
polymerization initiated by random main chain scission
and a peak at 2938C which corresponds to depolymeriza-
tion initiated by unsaturated vinylidene chain-end. The
DTG curves of nanocomposites contain only one peak at
3748C originating from the depolymerization initiated by
random main chain scission. These results show that
amount of PMMA chains with double bond at the end,
generated by disproportionation termination reactions, are
larger in the pure PMMA than in the PMMA in nanocom-
posite samples indicating that the TiO2/6-PAA nanopar-
ticles react as radical scavengers during the polymeriza-
tion reducing the number of unsaturated vinylidene chain-
ends. The content of unreacted double bonds in prepared
samples was calculated using 1H NMR spectroscopy
(spectra not shown) by comparing the signal intensities of FIG. 1. TG (A) and DTG (B) curves of pure PMMA and PMMA/TiO2
the methylene protons from double bonds (the peaks at (3) nanocomposite obtained under nitrogen atmosphere.

DOI 10.1002/pc POLYMER COMPOSITES—-2009 739

 FIG. 3. DSC curves of the pure PMMA and PMMA/TiO2 nanocompo-
sites.

increasing content of inorganic phase. This result for the

samples prepared in bulk is different compared to our
published results [16] when the PMMA/TiO2 nanocompo-
site was prepared by solution polymerization of MMA in
FIG. 2. TG (A) and DTG (B) curves of the pure PMMA and PMMA/ toluene in the presence of TiO2/6-PAA nanoparticles. In
TiO2 (3) nanocomposite obtained in air. that case the obtained Tg values were almost independent
on the content of inorganic phase. In the case of bulk po-
lymerization, the obtained TGA and DSC results clearly
may occur either on the TiO2 surface, when the exchange
of free electrons from the TiO2 with the adsorbed gas
takes place, or in the bulk material, when the exchange of
oxygen ions from the gas with the oxygen vacancies in
the TiO2 takes place. The surface reaction usually takes
place at lower temperatures (300–5008C) while the bulk
reaction takes place at higher temperatures (700–9008C).
Anatase crystalline phase has more free electrons than ru-
tile and oxygen detection can be associated with surface
reactions. According to this, it could be assumed that
oxygen which diffused into the nanocomposite material
was adsorbed on the surface of titanium dioxide and its
amount in the PMMA matrix was lower than in the pure
PMMA leading to the slower thermooxidative degradation
of the PMMA matrix [32, 33].
It can be noticed from the TG curves in Figs. 1 and 2,
that the nanocomposite samples start losing mass at lower
temperature (at about 1508C) than the pure PMMA sample.
The onset of mass loss of nanocomposite samples is
approximately at the same temperature in nitrogen and in
air indicating that this mass loss is atmosphere independ-
ent. Also, the onset of mass loss in nanocomposite samples
decreased with the increasing content of inorganic phase.
The glass transition behavior of the synthesized
PMMA/TiO2 samples was investigated by DSC. The ob-
tained DSC thermograms are shown in Fig. 3. The values
of glass transition temperature were taken as the midpoint
of the glass transition event. The obtained results are FIG. 4. TG (A) and DTG (B) curves of the preheated pure PMMA and
collected in Table 1. The Tg values decreased with the PMMA/TiO2 (3) sample obtained under nitrogen atmosphere.

740 POLYMER COMPOSITES—-2009 DOI 10.1002/pc


FIG. 5. DSC curves of the preheated pure PMMA and PMMA/TiO2
(3) nanocomposite.
indicated the existence of low molar mass components in
the PMMA/TiO2 samples, which were generated during
the polymerization due to the presence of the TiO2/
6-PAA nanoparticles acting as radical scavengers. The
low molar mass components behave as typical plasticizers
leading to decrease of Tg. Their presence can also explain
the increase of PDI in nanocomposite samples with the
increasing amount of TiO2/6-PAA nanoparticles.
To prove this assumption, the PMMA and PMMA/
TiO2(3) samples were heated to 2578C with heating rate
of 108/min and cooled down to room temperature with
cooling rate of 208/min. This procedure does not influence
the PMMA degradation since it is known that isothermal
heating of the PMMA in nitrogen atmosphere in the tem-
perature range from 200 to 3258C does not significantly
decrease PMMA molar mass [29]. The mass loss of ther-
maly treated PMMA and PMMA/TiO2 (3) was 1.5 and
9.0% of their initial mass, respectively. The TG and DTG
curves of preheated samples, obtained in nitrogen atmos-
phere, are presented in Fig. 4. It can be noticed that the
DTG curves of the preheated samples contain only one
peak at 3788C which corresponds to depolymerization ini-
tiated by random main chain scission. Also, the onset of
mass loss of the preheated PMMA/TiO2 (3) sample is
shifted to higher temperature. The DTG curve of the pre-
heated PMMA sample does not show detectable mass loss
caused by depolymerization initiated by unsaturated vinyl-
idene chain ends probably because some of them reacted
during the heating and their total amount decreased in
examined sample.
Figure 5 shows the DSC curves of the pure PMMA
and PMMA/TiO2 (3) samples preheated in the same man-
ner as for the TG measurements. The Tg of these samples
are 118 and 1148C, respectively. It is clear that the TiO2/
6-PAA nanoparticles in the investigated concentartion
range do not significantly influence Tg of PMMA matrix
when the low molar mass components were removed by
DOI 10.1002/pc
preheating. The Tg values of preheated samples are in
agreement with the Tg values obtained in our previous
work [16], where the low molar mass components were
removed from nanocomposite samples by precipitation.
The mass loss of 9.0% during the heating, the shift of the
onset of mass loss to the higher temperature after heating
and the increase of Tg for 288C after heating undoubtedly
confirm assumption that original nanocomposite samples
contained some amount of volatile low molar mass com-
ponents which can be removed by preheating.
CONCLUSIONS
The PMMA/TiO2 nanocomposite sheets with different
content of inorganic phase were prepared by bulk radical
polymerization of the MMA syrup in glass sandwich cell,
using AIBN as initiator. The syrup was obtained by mixing
appropriate amount of the PMMA and MMA in which the
surface modified TiO2 nanoparticles were previously dis-
persed. The molar mass and molar mass distribution of the
pure PMMA and PMMA extracted from the nanocomposite
sheets were determined by GPC. The molar mass decreased
while polymer dispersity index increased with increasing
content of inorganic phase in nanocomposite because the
surface modified TiO2 particles reacted as radical scav-
engers during the polymerization. The pure PMMA ther-
mally decomposed mainly by depolymerization initiated by
random chain scission. Depolymerization of small amount
of the pure PMMA in nitrogen was initiated by unsaturated
vinylidene chain-ends. Thermal decomposition of nano-
composite samples occurred only by depolymerization initi-
ated by random chain scission because the TiO2/6-PAA
nanoparticles reacted as radical scavenger during the poly-
merization, reducing the number of unsaturated vinylidene
chain-ends of PMMA in nanocomposite samples. The shift
of DTG peak temperature of nanocomposite samples and its
dependence on the content of the TiO2 nanoparticles were
larger for the degradation in air than in nitrogen atmos-
phere, probably because the TiO2/6-PAA particles inhibited
some degradation stages of the thermooxidative degrada-
tion of PMMA. The differences between the TG curves of
the PMMA and PMMA/TiO2 nanocomposites in nitrogen
atmosphere or in air were due to the presence of low molar
mass components in the nanocomposites. The nanocompo-
site samples have lower Tg than the pure PMMA. Tg
decreases with the increasing content of inorganic phase.
This is also consequence of the presence of low molar mass
components which act as plasticizer. The removal of these
components by preheating led to significant Tg increase.
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