Progress in Organic Coatings 77 (2014) 880891

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Polymerization of hybrid organicinorganic materials from several

silicon compounds followed by TGA/DTA, FTIR and NMR techniques
M. Criado , I. Sobrados, J. Sanz
Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Ins de la Cruz 3, Cantoblanco, 28049 Madrid, Spain

a r t i c l e

i n f o

Article history:
Received 20 February 2013
Received in revised form 17 January 2014
Accepted 20 January 2014
Available online 12 February 2014
Keywords:
Organicinorganic hybrids
Polymerization
Dimensionality
Solgel synthesis
NMR

a b s t r a c t
Hybrid organicinorganic lms have been prepared by hydrolysis and condensation of several silicon compounds: 3-methacryloxypropyltrimethoxysilane (MPTS) or methyltriethoxysilane (MTES) and
tetraethyl orthosilicate (TEOS) or tetramethyl orthosilicate (TMOS) precursors using four [TEOS] or
[TMOS]/[MPTS] or [MTES] molar ratios: 0, 0.5, 1 and 2.
The progress on the organic and inorganic polymerizations was followed employing thermogravimetric
analysis (TGA), differential thermal analysis (DTA), Fourier transform infrared spectroscopy (FTIR), 13 C
and 29 Si nuclear magnetic resonance (NMR). These techniques have provided information about the
hybrid network formation inside lms. The formation of the hybrids prepared from [TEOS]/[MPTS] and
[TMOS]/[MPTS] mixtures was accomplished through the reaction of Si OR groups, via condensation of
silanols (inorganic condensation), and opening of the C C double bond in MPTS (organic polymerization).
The formation of the hybrids prepared from [TEOS]/[MTES] and [TMOS]/[MTES] mixtures was mainly
accomplished through the reaction of Si OR groups.
The increment of TEOS or TMOS in MPTS mixtures favored the inorganic (Q3 and Q4 units) condensation.
Total degrees of condensation for hybrids synthetized with [TEOS] or [TMOS]/[MTES] were higher than
those obtained with [TEOS] or [TMOS]/[MPTS], so MTES favored the formation of hybrids with branched
organic structures.
2014 Elsevier B.V. All rights reserved.

1. Introduction
The study of hybrid organicinorganic Si polymers is a very
active eld of the solgel process [1]. The importance of these
compounds derives from the possibility of obtaining novel materials in optics, electronics, mechanics and electrochemistry elds
[2]. One of the most diffused commercial application is their use
as coating lms [36]. These hybrid lms combine properties of
organic polymers and ceramics materials [7]. The inorganic components improve durability, scratch resistance, and adhesion to the
metal substrates, while the organic components increase exibility,
density, and functional compatibility with organic polymer paint
systems [8].
The solgel process is mainly based on hydrolysis and condensation reactions of metal alkoxides (M(OR)n ). During the
hydrolysis (rst stage), the replacement of alkoxide groups ( OR)
by hydroxyl groups ( OH) occurs during interaction of alkoxide

Corresponding author. Tel.: +34 91 334 9000; fax: +34 91 372 0623.
E-mail addresses: mcriado@icmm.csic.es, mcriado@cenim.csic.es (M. Criado).
0300-9440/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2014.01.019

molecules with water. The second stage consists on the condensation of two OH groups or of a OH with a OR group, which
produces M O M bonds [9]. The resulting oxide materials vary
from nanoparticulate sols to continuous polymer gels depending on
the rate of reactions and drying and processing steps. The hybrid
organicinorganic solgel materials can be constituted by stable
organic and inorganic groups linked by stable chemical bonds or by
organic components embedded into an inorganic material, or vice
versa [9].
Following the classication of Sanchez et al. [1], hybrids of class
II are those exhibiting covalent bonding between organic and inorganic components. The organic groups can be directly connected
to the inorganic network and their role can behave as network
modiers. A peculiar group of class II hybrids is characterized by
the presence of polymerizable vinyl, acrylate, or epoxy groups.
They can be partially or completely polymerized directly in the sol
depending on synthesis conditions and photo or thermal curing
[10].
The polymerization of organic and inorganic precursors may
be carried out sequentially or simultaneously [11,12]. When the
organic polymerization is performed rst, linear polymers or
copolymers are formed, which are functionalized with inorganic

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

polymer precursors, present either in the polymer backbone or

at chain ends [13,14]. When the inorganic polymerization is rst
started in the sol stage, the coating is formed and both organic and
inorganic polymerizations are produced in the coated material. In
general, it is difcult to achieve high conversion degrees in both
organic and inorganic networks.
The nal physicochemical properties of the hybrid organic
inorganic materials depend on the extent of the hydrolysis
condensation reactions, the branching degree of the polymers and
the gel homogeneity [15].
The aim of this study was to investigate the local structure of
hybrid polysiloxane materials prepared from polymerization of Si
compounds containing different alkoxide groups. This will permit
the future design of new metal coatings that enhance stability of
reinforced concrete structures (RCS) against corrosion caused by
chloride ions or carbon dioxide.

2. Experimental
The reagents used in this work 3-methacryloxypropyl(CH2 = C(CH3 )COO(CH2 )3 Si(OCH3 )3 ,
trimethoxysilane
MPTS,
methyltriethoxysilane
((CH3 )Si(OCH2 CH3 )3 ,
SigmaAldrich),
MTES, SigmaAldrich), tetraethyl orthosilicate (Si(OCH2 CH3 )4 ,
TEOS, SigmaAldrich), tetramethyl orthosilicate (Si(OCH3 )4 , TMOS,
SigmaAldrich) and benzoyl peroxide (BPO, VWR International
Eurolab) were laboratory grade.
Solgel coatings were prepared from condensation and polymerization of TEOS and MPTS, TEOS and MTES, TMOS and MPTS
or TMOS and MTES. Solgel reactions were achieved by mixing
5 g of MPTS or MTES with the TEOS or TMOS amounts required
to obtain the four molar ratios: 0, 0.5, 1 and 2. Afterwards, HNO3 acidied water (pH = 1 and [H2 O]/[Si] = 3.5) was added. All reagents
were stirred (700 rpm) for 1 h at 60 C, using ethanol as solvent
([ethanol]/[H2 O] = 1). At the same time, the thermal initiator of
polymerization (BPO) was added to the mixtures ([BPO]/[MPTS] or
[MTES] = 0.01).
The lms were prepared by drying sols in a Petri dish at 65 C
for 24 h. After curing at 160 C for 3 h, lms were detached from the
dish and analyzed by TGA/DTA, FTIR and MAS-NMR techniques.
The TGA/DTA curves of hybrid lms were recorded using a SDT
Q600 TA Instruments, with nitrogen as purge gas at a ow rate of
100 ml min1 . Samples were heated from 25 to 600 C at a rate of
10 C min1 .
FTIR spectra (4000250 cm1 ) were recorded in two spectrophotometers: a Nicolet 20 SXC for liquid samples (pure reagents)
and a Bruker IFS 66V/S was used for solid samples (synthetized
lms). In both apparatus the spectral resolution was 2 cm1 . The
KBr pellet method was used to prepare solid samples.
Solid-state 29 Si MAS and 13 C CPMAS-NMR spectra were
recorded using a Bruker Avance-400 pulse spectrometer. Spectra
were recorded after irradiation of samples with a /2 (5-s) pulse.
The resonance frequencies used were 79.5 and 100.63 MHz (9.4 T
magnetic eld). In order to avoid saturation effects, the recycle
delay time used was 10 s. The spinning rate used in MAS-NMR
experiments was 10 kHz. A contact time of 2 ms and a recycle delay of 5 s were used in 13 C CPMAS-NMR experiments. All
measurements were taken at room temperature with TMS (tetramethylsilane) as external standard. The error in chemical shift values
was estimated to be lower than 0.5 ppm. NMR spectra deconvolutions were performed by using the DMFIT software [16]. Chemical
shift (position of the line), intensity (integrated area), width (width
at half height) and line shape (Lorentzian or Gaussian) of components were deduced.

881

3. Results and discussion

3.1. TGA/DTA analysis of the lms
In order to understand the thermal behavior of the hybrid
organicinorganic materials, thermogravimetric (TGA) and differential thermal analysis (DTA) were carried out.
The TGA curves of Fig. 1a indicate the existence of three different weight losses. The rst loss, visible in the temperature range
25125 C (was comprised between 1.3 and 1.9%), was associated with evaporation of solvent, specically ethanol and/or water
[17]. The sample mass remained essentially invariable until 300 C.
Above this temperature, a second degradation was detected with
weight losses of 40.5, 31.5, 27.7 and 20.0% for R0, R0.5, R1 and R2
ratios, respectively. This second step can be attributed to random
scissions within the polymer chains [6,18]. The last loss took place
from 470 C to 600 C, displaying 16.8, 14.7, 13.8 and 12.0% weight
losses for R0, R0.5, R1 and R2 ratios, respectively. This loss was
attributed to the dehydration of silanol groups present in the SiO2
network [18].
The DTA curves of Fig. 1b show three minima at about 4763 C,
386402 C and 479550 C, attributed to three detected stages.
The three weight losses presented an endothermic character.
Finally, two other minima were observed in R0, R1 samples at about
340350 C, that were ascribed to scissions of chains produced at
the terminal vinylidene groups [6,18].
The TGA curves of Fig. 1c show a small weight loss (0.134.46%)
below 160 C, assigned to the evaporation of residual small
molecules, such as water, alcohol, and ethanol [17]. The amount of
water and ethanol lost in this series of hybrids is higher than that
added in the synthesis hybrids formed from TEOS and MPTS. In the
temperature range 160440 C (minimum peak around 340 C in
absence of TEOS and around 240 C in presence of TEOS), a new
degradation was observed, see Fig. 1c. This could be assigned to
volatile compounds produced in condensation of Si OH and Si OR
groups [19]. The weight loss was between 3.2 and 5.1%. The last loss
should result from the oxidation and degradation of methyl groups
of MTES, that probably cause the formation of Si C Si bonds at
536 C [20,21]. The associated weight loss was between 2.6 and
5.6%.
DTA curves of Fig. 1d shows three minima between 3862 C
(rst stage), 229339 C (second stage) and 527548 C (third
stage). The three peaks display an endothermic character. As the
[TEOS]/[MTES] ratios and temperatures increases, suggesting a
higher thermal stability of formed hybrids.
Thermograms of the hybrid polysiloxanes synthetized from
TMOS and MPTS (see Fig. 2a) are very similar to those obtained
for hybrid polysiloxanes prepared by mixing TEOS and MPTS (see
Fig. 1a). In these thermograms, three degradation stages were
detected; the rst visible below 110 C, due to the evaporation of
ethanol and water [17], with weight losses between 1.3 and 1.5%.
The second stage, produced between 110 C and 470 C, attributed
to scission within the polymer chains [6,18], with weight losses of
40.5, 31.5, 26.4 and 19.5% for R0, R0.5, R1 and R2. Finally, the third
stage produced between 470 and 600 C, ascribed to the dehydration of silanol groups present in SiO2 networks [18], with weight
losses between 13.1 and 16.8%. The DTA curves of this family of
hybrids (see Fig. 2b) are also similar to those obtained for the hybrid
polysiloxanes synthetized from TEOS and MPTS (see Fig. 1b), which
presented three minima at 4750 C, 390402 C and 479527 C
for three weight losses. Finally it should be highlighted the presence of an additional endothermic peak between 197 and 209 C
for R1 and R2 ratios, associated to the scissions of head-to-head
linkages in the polymethylmethacrylate homopolymer [18].
The temperatures corresponding to each degradation stage
were similar for the hybrid polysiloxanes synthetized from TEOS

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M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

100

(a)

Temperature Difference ( C)

80

Weight loss (%)

1,5

60

R0
R0.5
R1
R2

40

1,0

(b)

R0
R0.5
R1
R2

0,5

0,0

-0,5

-1,0

-1,5

20
0

100

200

300

400

500

100

600

200

400

500

600

Temperature ( C)

100

1,2

(c)

Temperature Difference/ C

0,8

Weight loss (%)

300
0

Temperature ( C)

90

80

R0
R0.5
R1
R2

0,4

(d)

R0
R0.5
R1
R2

0,0
-0,4
-0,8
-1,2
-1,6

70
0

100

200

300

400

500

600

Temperature ( C)

100

200

300

400

500

600

Temperature ( C)

Fig. 1. TGA and DTA curves of the hybrid polysiloxanes synthetized with [TEOS]/[MPTS] (a and b) and with [TEOS]/[MTES] (c and d) in molar ratios of: 0 (R0), 0.5 (R0.5), 1
(R1) and 2 (R2).

and MPTS and TMOS and MPTS. However, it must be remarked

that, the organic polymerization through C C bond was favored in
[TEOS]/[MPTS] system (minimum at 340350 C in the DTA curves,
Fig. 1b), while the organic polymerization took place through the
SiOR groups ( CH2 Si(OR)3 ) in [TMOS]/[MPTS] system (peak at
197209 C in the DTA curves, Fig. 2b).
The TGA curves of the hybrids synthetized from TMOS and
MTES (see Fig. 2c) are very similar to those obtained for hybrids
prepared by mixing TEOS and MTES (see Fig. 1c). Three degradation stages were detected in these thermograms. The rst was
assigned to the evaporation of water and ethanol again; with
weight losses below 160 C of the order 0.15.0%. The second degradation stage was attributed to volatile compounds produced in
condensation of Si OH and Si OR groups [19], at 160435 C, with
weight losses between 3.2 and 4.2%. The third stage associated to
the oxidation and degradation of methyl groups of MTES was produced between 435 and 600 C. This weigh loss was between 2.6
and 4.5%.
The DTA curves of Fig. 2d are also similar that those obtained
for the hybrid polysiloxanes synthetized from TEOS and MTES (see
Fig. 1d), which presented three minima at 3869 C, 248329 C and
462527 C for three weight losses. As the [TMOS]/[MTES] ratios
increases, the temperature decreases, suggesting a lower thermal
stability of formed hybrids. This behavior was opposite to that
depicted by polysiloxanes synthetized from TEOS and MTES. The
increase in the amount of TEOS and TMOS favored the inorganic

condensation, but TEOS favored the formation of a more stable

cross-linked structure.
The temperatures corresponding to second degradation step,
attributed to the scissions within the polymer chains, were different. The temperatures for [TEOS]/[MTES] system were lower than
those for [TMOS]/[MTES] system. This different behavior may be
due to the formation of a hybrid organicinorganic network, where
organic polymerization process is more favored than the formation
of the silica backbone [6].
3.2. FTIR characterization of the lms
Fig. 3 shows the FTIR spectra of four reagents used in reactions:
(a) 3-methacryloxypropyltrimethoxysilane (MPTS), (b) methyltriethoxysilane (MTES), (c) tetraethyl orthosilicate (TEOS) and (d)
tetramethyl orthosilicate (TMOS). The assignment of the different
vibration bands is given in four tables (supplementary data).
Fig. 3a shows the characteristic vibration bands of MPTS. Those
at 1703 and 1323 cm1 (signals 5 and 9) were assigned to the
asymmetric stretching of the C O bond and vibrations of ester C
( O) O groups [22,23]. The band around 1635 cm1 (signal 6) was
associated with vinyl groups [22,23]. The band at 1299 cm1 (signal
10) was assigned to Si C bonds [22,23]. This spectrum also shows
three vibrations corresponding to Si O C bonds: 1174, 1099 and
1029 cm1 (signals 11, 12 and 13) [24]. Finally, two bands detected
at 3671 and 919 cm1 (signals 1 and 14) were assigned to the

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

883

100

(a)

Temperature Difference ( C)

1,5

Weight loss (%)

80

60

R0
R0.5
R1
R2

40

1,0

R0
R0.5
R1
R2

(b)

0,5

0,0

-0,5

-1,0

-1,5

20
0

100

200

300

400

500

100

600

200

400

500

600

Temperature ( C)

Temperature ( C)
1,2

100

(c)

Temperature Difference/ C

0,8

Weight loss (%)

300
0

90

80

R0
R0.5
R1
R2

0,4

R0
R0.5
R1
R2

(d)

0,0
-0,4
-0,8
-1,2
-1,6

70
0

100

200

300

400

500

600

Temperature ( C)

100

200

300

400

500

600

Temperature ( C)

Fig. 2. TGA and DTA curves of the hybrid polysiloxanes synthetized with [TMOS]/[MPTS] (a and b) and with [TMOS]/[MTES] (c and d) in molar ratios of: 0 (R0), 0.5 (R0.5), 1
(R1) and 2 (R2).

vibrations of silanol (SiOH) [25], probably produced by hydrolysis

of MPTS in contact with the atmosphere.
Infrared spectrum of methyltriethoxysilane (MTES) (see Fig. 3b)
shows bending bands of Si C bonds at 1265 and 781 cm1 (signals 5
and 11) [22,23]. There are also ve characteristics vibration bands of
Si O C bonds at 1158, 1107 and 1074 (doublet), 995 and 815 cm1
(signals 6, 7, 8, 9 and 10) [24,26], and the bending band of O Si O
bonds at low wavenumbers (443 cm1 , signal 12) [26].
Infrared spectrum of tetraethyl orthosilicate (TEOS) (see Fig. 3c),
shows ve vibration bands of Si O C bonds at 1170, 1102 and
1079 (doublet), 961 and 787 cm1 (signals 6, 7, 8, 9 and 10) [24].
Finally, the bending band of O C C bonds (signal 11) was detected
at 477 cm1 [27].
Fig. 3d shows the characteristic vibration bands of tetramethyl
orthosilicate (TMOS) at 1198, 1092, 829 and 426 cm1 (signals 5,
6, 7 and 8). The rst three bands were associated with stretching
Si O C bands and the latter corresponded to the bending O Si O
bands [24,26].
After the characterization of the reagents, the FTIR study
was conducted in hybrid polysiloxanes synthetized via solgel
from mixtures of various reagents: [TEOS]/[MPTS], [TEOS]/[MTES],
[TMOS]/[MPTS] and [TMOS]/[MTES] (Fig. 4).
In general, mixtures of [TEOS]/[MPTS] and [TMOS]/[MPTS] promote thermal curing condensation of inorganic structures and also
induced the formation of an organic polymer interconnected by
opening double C C bond of MPTS.

To follow the organic polymerization of the materials, the analysis was focused on 1730 and 1635 cm1 bands (signals 3 and 4)
assigned to C O and C C vibration modes, see Fig. 4a and c. A
decrease in the intensity of the C C band (1635 cm1 ) when adding
a larger amount of TMOS or TEOS, indicated that the organic polymerization have occurred. This reaction was accompanied by the
decrease and broadening of the C O band, produced by opening
of C C bonds as the polymerization increased, independently of
[TEOS]/[MPTS] and [TMOS]/[MPTS] ratios employed. The observed
broadening of the carbonyl group band should be associated with
the presence of two vibration modes at 1703 cm1 , assigned to
the stretching vibrations of C O conjugated with C C bonds, and
another mode at 1730 cm1 assigned to the stretching vibrations
of C O, produced during the organic polymerization [12,28]. The
presence of the 1730 cm1 band conrmed the polymerization
reaction in lms. In Fig. 4a and c, it was observed that the intensity of this band decreased with the increasing amount of TEOS and
TMOS. This modication may be due to the competition between
the organic and inorganic polymerization in the formation of hybrid
materials. If the growth of the organic chains happens when the
inorganic network is already formed, the mobility of the organic
groups is dramatically hindered and there is not enough free space
in the rigid framework to reach a larger degree of polymerization.
On the other hand, the formation of a connected silica backbone was accomplished not only through the reaction of Si OR
groups but also via the condensation of silanols. The condensation

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M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

(a)

(b)

12
1

7 8 10
6
9

4
3

4
14

56

23

1112

11
10

13

78

4000

3500

3000

2500

2000

1500

1000

500

4000

3500

3000

-1

2500

2000

1500

1000

500

-1

Wavenumber (cm )

Wavenumber (cm )

(d)

(c)
4

11

5
1
34

9 10

7
4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )

Fig. 3. FTIR spectra of four reagents studied: (a) MPTS, (b) MTES, (c) TEOS and (d) TMOS.

of silanols was conrmed by IR spectroscopy (Fig. 4a and c), where

a variation on the intensities and the wavenumber of SiOH bands
(3671 and 919 cm1 ) was detected along the reaction. The stretching Si OH band of pure MPTS was detected at 3671 cm1 (silanols
on the gel surface [25]). When this reagent was subjected to
thermal treatments (R0 molar ratio), this band shifted to lower
wavenumbers (3504 cm1 , signal 1) indicating that silanols reacted
(Fig. 4a and c). In IR spectra of materials with R0.5, R1 and R2 molar
ratios, the band at 3495 cm1 (signal 2) was ascribed to adsorbed
water [25], see Fig. 4a and c. By increasing the amount of TMOS
or TEOS, the intensity of the 919 cm1 band (signal 8) decreased
until disappearing and a new band was detected around 940 cm1
(signal 9), associated with vibrations of the Si O Si bonds.
Inorganic condensation reactions of polysiloxanes also occurred
through the reaction of Si OR groups, producing a series of bands
around 1167, 1122 and 1060 cm1 (signals 5, 6 and 7) which corresponded to both Si O Si and Si O C bonds for R0 and R0.5 molar
ratios (see Fig. 4a and c). Increasing the amount of TMOS or TEOS
only two bands were detected at 1169 and 1054 cm1 (asymmetrical stretching of Si O Si bonds). The intensity of 1054 cm1 band
increased with the addition of TMOS or TEOS, conrming inorganic
condensation reactions. These reactions were corroborated by the
appearance of two new bands at 692 and 600 cm1 (signals 10 and
11) probably due to O Si O ring siloxanes vibrations [25], which
were not observed in pure reagents.

Fig. 4b and d shows the FTIR spectra of hybrid materials

obtained in TEOS/MTES and TMOS/MTES mixtures. In these cases,
the inorganic condensation reactions occurred mainly through
Si OR groups. The spectra show Si O Si asymmetric stretching
vibrations (1130 and 1028 cm1 , signals 2 and 3), which were
shifted slightly to higher wavelength values while adding more
TMOS or TEOS to the mixture (1148 and 1059 cm1 ). The intensity
of the band at 1059 cm1 increases conrming the strengthening
of the siloxane network. This fact was conrmed by the appearance of two new bands, different to those found in pure reagents
(see Fig. 4b and d); the rst detected at 947 cm1 (signal 4), associated with the vibration modes of Si O Si bonds, and the second
at 579 cm1 (signal 6), associated to vibration modes of O Si O
bonds in cyclic siloxanes structures [25].
Fig. 4b and d shows a decrease in the intensity of the bands
at 1277 and 785774 cm1 (doublet) (signals 1 and 5), ascribed
to vibrations of Si C bonds, indicative of a lower proportion
of these groups in the polysiloxane structure. The condensation reactions increased the number of Si O Si bonds in hybrid
materials.
3.3. NMR-MAS characterization of the lms
29 Si spectra show one signal for each of the reactants (see
Fig. 5a). Chemical shift of MPTS and MTES signals, assigned to

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

885

(b)

(a)
R2
R2

8
R1
11

R0.5
2

10

R1

R0.5

R0

R0
1

4000

3500

3000

2500

2000

1500

56

23

1000

500

4000

3500

3000

2500

2000

1500

1000

500

-1

-1

Numero de onda (cm )

Wavenumber (cm )
(c)

(d)

R2

R2

R1

4
11

R1

R0.5
4

R0.5

10

R0

R0
1

1
56

3
4000

3500

3000

2500

2000

1500

1000

500

4000

3500

3000

-1

2500

2000

1500

5
23
1000

500

-1

Wavenumber (cm )

Wavenumber (cm )

Fig. 4. FTIR spectra of the hybrid polysiloxanes prepared with mixtures of the following reagents: (a) [TEOS]/[MPTS] (b) [TEOS]/[MTES] (c) [TMOS]/[MPTS] and (d)
[TMOS]/[MTES] in molar ratios of 0 (R0), 0.5 (R0.5), 1 (R1) and 2 (R2).

(a)

(b)

14

-79

-82

TMOS
13

12

-44

TEOS

11

TMOS

10

-43

TEOS

MTES
8

MTES

5 4

2
1

MPTS

MPTS
-20

-40

-60

-80 -100 -120 -140

Chemical shift (ppm)

200

160

120

80

40

Chemical shift (ppm)

Fig. 5. (a) 29 Si and (b) 13 C MAS-NMR spectra of four pure reagents.

-40

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M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

(a)

(b)

12
2

T
2

5 7`
13
4

8`8

R2

76

R2
R1

R1

R0.5

R0.5
8`

7`

6`

R0

R0
-20

-40

-60

-80 -100 -120 -140

200 160 120

Chemical shift (ppm)

80

40

-40

Chemical shift (ppm)

(c)

(d)

Q
3

13
11

Q
2

12
10

T
R2

R2

R1

R1

R0.5
R0.5
R0
R0
-20

-40

-60

-80 -100 -120 -140

Chemical shift (ppm)

200 160 120

80

40

-40

Chemical shift (ppm)

Fig. 6. 29 Si MAS and 13 C CPMAS-NMR spectra of hybrid polysiloxanes synthetized from [TEOS]/[MPTS] (a and b) and from [TEOS]/[MTES] (c and d) in molar ratios of 0 (R0),
0.5 (R0.5), 1 (R1) and 2 (R2).

RCH2 -Si(OR)3 environments, appeared about 43/44 ppm,

whereas the signal of TMOS and TEOS, assigned to Si-(OR)4
environments, were between 79 and 82 ppm.
Fig. 5b shows 13 C CPMAS-NMR spectra of the various reagents.
MPTS spectrum consisted of 8 signals, where rst carbon linked to
the silicon appear at 5 ppm (signal 1), carbon in the methyl terminal
group at 18 ppm (signal 2), second carbon close to the silicon at
22 ppm (signal 3), carbon in the methyl close to oxygen at 50 ppm
(signal 4), third carbon close to the silicon at 66 ppm (signal 5),
vinyl group carbons (CH2 = C) at 124 and 136 ppm (signals 6 and
7, respectively) and carbonyl group at 166 ppm (signal 8) [28]. In
MTES spectrum three signals detected at 8, 18, 57 ppm (signals 9,
10 and 11), correspond to CH3 groups directly bonded to silicon,
CH3 groups attached to CH2 and CH2 groups. The TEOS spectrum
showed two carbon signals: one of CH3 groups (18 ppm, signal
12) and other of CH2 groups (58 ppm, signal 13). The spectrum of
TMOS was constituted only by a signal of CH3 groups at 50 ppm
(signal 14).

29 Si spectra corresponding to hybrid polysiloxanes synthetized

from [TEOS]/[MPTS] are given in Fig. 6a and b. The spectrum of
Fig. 6a, shows three signals at 49, 58 and 67 ppm, assigned to
T1 units ( CH2 Si(OSi)(OR)2 , R = H or CH3 ), T2 ( CH2 Si(OSi)2 (OR))
and T3 ( CH2 Si(OSi)3 ) [6,12,29], which were related to the condensation of the organic material. In the absence or presence of a
small amount of TEOS (R0 and R0.5) T2 units predominated, indicating that the hybrids formed were mainly linear siloxane structures.
Increasing the amount of TEOS the percentage of T3 units and
therefore the degree of polycondensation increased giving more
branched siloxanes structures.
If attention is focused on the condensation reactions of the inorganic part of the hybrid, the 29 Si spectra show, in presence of TEOS
(R0.5), three additional signals at 91, 101 and 109 ppm, associated with Q2 (Si(OSi)2 (OR)2 ), Q3 (Si(OSi)3 (OR)) and Q4 (Si(OSi)4 )
species [6,12,29]. For R1 and R2 ratios, the intensities of Q3 and Q4
units increased considerably, becoming the percentage of Q4 units
similar to that of Q3 units.

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

(a)

887

(b)

R2

8
8`

7
6

5
6` 7`
4

R2
R1
R1
R0.5

R0.5

R0

R0

-20

-40

-60

-80 -100 -120 -140

200 160 120

Chemical shift (ppm)

(c)

80

40

(d)

10

Q
2

-40

Chemical shift (ppm)

11
R2

T
R2

R1

R1
R0.5
R0.5
R0

R0
-20

-40

-60

-80 -100 -120 -140

Chemical shift (ppm)

200 160 120

80

40

-40

Chemical shift (ppm)

Fig. 7. 29 Si MAS and 13 C CPMAS-NMR spectra of hybrid polysiloxanes synthetized from [TMOS]/[MPTS] (a and b) and from [TMOS]/[MTES] (c and d) in molar ratios of 0 (R0),
0.5 (R0.5), 1 (R1) and 2 (R2).

13 C spectra provide information about the polymerization of the

MPTS methacryloxy groups (see Fig. 6b). These spectra showed the
presence of two signals at 126 and 136 ppm (signals 6 and 7), associated with CH2 = C carbons, and one signal at 167 ppm associated
with carbonyl groups (signal 8) of unpolymerized methacryloxy
groups. The polymerization of the organic part of hybrids was conrmed by the detection of the quaternary carbon at 45 ppm (signal
7 ), the CH2 -groups of polymerized hydrocarbon chains (56 ppm,
signal 6 ) and the C O groups located near aliphatic carbons, after
the C C opening (176 ppm, signal 8 ) [28], not detected in pure
MPTS. The increment of signals 12 and 13 suggested the presence
of a large amount of TEOS in the medium.
Fig. 6c and d shows 29 Si and 13 C NMR spectra of hybrid materials obtained by mixing MTES and TEOS. 29 Si MAS-NMR spectra
of hybrids show three signals at 55, 59 and 66 ppm, assigned
to T1 , T2 and T3 units (see Fig. 6c). T3 units predominated even in
hybrids with low ratios, R0 and R0.5, suggesting the formation of
highly branched organic structures. The addition of TEOS promoted

the condensation reaction of the inorganic part as seen in the spectra of Fig. 6c. In this case, Q2 , Q3 and Q4 species (93, 101 and
109 ppm) were formed whose intensities increased with the TEOS
content.
Fig. 6d shows the 13 C NMR spectra of hybrid polysiloxanes with
different R ratios. It could be observed in all cases the presence of
three signals at 4, 18 and 58 ppm, assigned to the carbon bonded
directly to Si (signal 9), CH3 group (signal 10) and CH2 groups (signal
11) of MTES. In this system, the organic condensation could not
occur through the organic vinyl group, since none of the starting
reagents presented this organic group. However, it can be seen that
the intensity of the signals 10 and 11 increased with the addition
of TEOS to the system, conrming that these signals correspond to
this reagent (signals 12 and 13, see Fig. 6d).
29 Si spectra conrm that the condensation reactions occurred
in hybrid materials (see Fig. 7a). If the analysis focused on the
organic polymerization, it could be observed that spectra are initially dominated by T2 units, indicating that polysiloxanes had

888

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

linear structures. When adding a larger amount of TMOS, the number of T3 units increased, suggesting that the structure of the
organic part displays higher connectivity.
With respect to the inorganic condensation, NMR spectra of
Fig. 7a show that in the absence of TMOS, Qn units were not
detected, but in the presence of this reagent, reaction occurred
between TMOS and MPTS, detecting Q2 , Q3 and Q4 units. The percentage of Q3 and Q4 units increased with the amount of TMOS,
mainly Q3 units.
Through 13 C CPMAS-NMR spectra of Fig. 7b it is possible to
check if the organic condensation reactions is produced through
MPTS methacryloxy groups. In this case, signals at 176 ppm (C O,
signal 8 ), 55 ppm ( CH2 -carbonyl, signal 6 ) and 45 ppm (quaternary carbon, signal 7 ) should be detected [28]. These signals
were observed in all NMR spectra, but their intensities decreased
with increasing TMOS (R2), indicating that under these conditions organic condensation was not favored via methacryloxy
group.
Fig. 7c and d shows the 29 Si MAS and 13 C CPMAS-NMR spectra
of hybrid materials obtained by mixing TMOS and MTES in different molar ratios. 29 Si spectra show three signals at 55, 59 and
66 ppm, assigned to T1 , T2 and T3 units. In all cases, T3 units were
predominant and the hybrids formed displayed branched structures. The addition of TMOS favored the inorganic condensation
reactions as demonstrated by the presence of Q2 , Q3 and Q4 units
(92, 100 and 109 ppm), see Fig. 7c. The intensities of these signals increased with the addition of TMOS, mainly increasing the
percentage of Q3 units.
Finally, Fig. 7d shows the 13 C spectra of hybrid materials
obtained with different [TMOS]/[MTES] ratios. In these spectra only
three signals were observed corresponding to carbons of MTES (6,
16 and 59 ppm of signals 9, 10 and 11) but any signal associated with
carbons of the OCH3 group of TMOS (50 ppm), indicating that this
reagent had reacted with MTES. In this system organic condensation through the vinyl group was not possible.
3.4. Organicinorganic condensation
The local structure of hybrid organicinorganic materials
results from organic and inorganic polymerizations, which are not

independent in investigated hybrids. The proportions of Tn and Qn

species, strongly related to the formation of Si O C and Si O Si
bonds, can be deduced from 29 Si MAS-NMR spectra using a standard
Gaussian lineshape deconvolution. Qn /Tn ratios were found to be
practically equal to nominal 0, 0.5, 1 and 2 values used in the synthesis, conrming the NMR spectral t goodness.
From deduced values, the degree of condensation of T and Q
species was calculated from Tn and Qn values, according to expressions [30]:


Dc (T) =

(T1 + 2T2 + 3T3 )

3


Dc (Q) =


100

(Q1 + 2Q2 + 3Q3 + 4Q4 )

4

(1)


100

(2)

where Dc (T) is the degree of condensation of T species, Tn describing

the relative amount of T species; Dc (Q) is the degree of condensation of Q species, Qn describing the relative amount of Q species.
Values obtained in these calculations are given in Table 1.
Table 1 Degrees of condensation of T and Q species deduced from
29 Si MAS-NMR spectra of hybrid organicinorganic materials.
Regarding the condensation of TEOS or TMOS with MPTS, the
evolution of T and Q species, deduced from 29 Si MAS-NMR spectra, was analyzed. The ts of 29 Si spectra for all R2 ratios were
represented in Figs. 6 and 7; similar ts were obtained for the
rest of spectra (not shown). T2 units were present in signicant
concentrations at low molar ratios (R0 and R0.5) while T3 groups
predominated at R1 ratio (see Table 1). The addition of a higher
amount of TEOS or TMOS (R2 ratio) favored the decrease of the
relative concentration of T3 groups, making this percentage more
similar to those of T1 and T2 groups. The presence of T1 groups indicated that only part of T species had participated in condensation
reactions (see Table 1).
The 29 Si MAS-NMR spectra show that hybrid materials are
mainly cross-linked by Q3 and Q4 species independently of the
molar ratio employed. In general, the increment of TEOS or TMOS
favored the presence of Q4 groups, in [TEOS]/[MPTS] mixtures.
Therefore, the degree of condensation of the Q species increases
as the molar ratio R increases (see Table 1).

Table 1
The degrees of condensation of the T and Q species of the hybrid organicinorganic systems from the 29 Si MAS-NMR spectra.
Samples

Ratios

Proportionsa (%)

Dc (T) (%)

T1

T2

T3

Q2

Q3

Q4

Dc (Q) (%)

Ratiob (%)
Tn

Qn

TDc c (%)

d(T)

d(Q)

dtotal

[TEOS]/[MPTS]

0
0.5
1
2

11.1
3.5
12.0
9.6

58.6
37.7
14.4
12.2

30.3
30.3
27.8
14.9

6.2
4.5
4.1

13.6
23.6
30.9

8.7
17.7
28.3

73.1
79.2
76.4
71.5

0.0
77.2
82.2
84.5

100.0
71.5
54.2
36.7

0.0
28.5
45.8
63.3

73.1
78.6
79.0
79.7

2.19
2.37
2.29
2.14

3.09
3.29
3.38

2.19
2.58
2.75
2.93

[TMOS]/[MPTS]

0
0.5
1
2

11.1
4.7
10.1
14.4

58.6
40.1
21.5
9.5

30.3
27.3
25.1
15.4

4.3
3.6
5.9

15.0
24.1
34.7

8.6
15.6
20.1

73.1
77.1
75.5
67.5

0.0
78.9
82.0
80.9

100.0
72.1
56.7
39.3

0.0
27.9
43.3
60.7

73.1
77.6
78.3
75.6

2.19
2.31
2.26
2.02

3.15
3.28
3.23

2.19
2.55
2.70
2.76

[TEOS]/[MTES]

0
0.5
1
2

9.9
8.8
7.3
5.6

14.1
7.6
7.4
5.2

76.0
50.0
34.5
22.8

2.2
4.2
9.0

16.0
27.2
37.6

15.4
19.4
19.8

88.7
87.4
85.0
83.7

0.0
84.8
82.5
79.0

100.0
66.4
49.2
33.6

0.0
33.6
50.8
66.4

88.7
86.5
83.8
80.6

2.66
2.62
2.55
2.51

3.39
3.30
3.16

2.66
2.88
2.93
2.94

[TMOS]/[MTES]

0
0.5
1
2

9.9
7.7
5.0
4.5

14.1
7.7
5.5
4.4

76.0
48.0
38.2
23.1

2.9
4.7
6.4

21.7
29.3
42.0

11.9
17.3
19.6

88.7
87.9
89.4
86.1

0.0
81.2
81.1
79.8

100.0
63.4
48.7
32.0

0.0
36.6
51.3
68.0

88.7
85.4
85.2
81.8

2.66
2.64
2.68
2.58

3.25
3.25
3.19

2.66
2.86
2.97
2.99

Proportions (%) were calculated by the deconvolution technique. Errors are 1%.
Ratio (%): Tn = [total T species/(T species + Q species)] 100%, Qn = [total Q species/(T species + Q species)] 100%.
Dc (T) and Dc (Q) are the degrees of condensation of the T and Q species respectively.
c
Total degree of condensation, TDc (%): (Dc (T) Tn ratio (%) + Dc (Q) Qn ratio (%))/100.
d(T) = [(T1 + 2T2 + 3T3 )/Tn ] and d(Q) = [(Q1 + 2Q2 + 3Q3 + 4Q4 )/Qn ].
dtotal = (Tn d(T) + Qn d(Q))/(Tn + Qn ).
a

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

In light of these results, the total degree of condensation

depends on the amount of TEOS or TMOS. A higher amount of
these reagents (ratio of 1) did not favor the organic polymerization through C C bonds, because steric hindrance generated by
the high number of side chains. The organic condensation took
place through SiOR groups ( CH2 Si(OR)3 ) and generated branched
structures favors T3 species. For R2, the inorganic condensation
was favored, the mobility of the organic groups is hindered and
the degree of polymerization decreases. The values obtained for
[TEOS]/[MPTS] hybrids prepared with ratios of 0.5, 1 and 2 are 79%,
79% and 80%. For hybrids prepared with [TMOS]/[MPTS] ratios of
0.5, 1 and 2, these values were 78%, 78% and 76%.
On the other hand, the evolution of T bands with the condensation of TEOS or TMOS with MTES was similar (see Table 1). In these
cases, T3 groups were predominant and relative concentrations of
these species decreased with the molar ratio. The incorporation of a
higher amount of TEOS or TMOS produced a decrease of the organic
condensation degree (see Table 1). However, the values of condensation degrees were higher than those obtained for hybrid materials
prepared with [TEOS]/[MPTS] or [TMOS]/[MPTS], so the percentage of T3 species was signicant greater in former ones (degree of
condensation upper 84%).
Regarding the evolution of Q bands with the condensation of
TEOS or TMOS with MTES, practically no differences were detected,
see Table 1. These materials were mainly constituted by Q3 and Q4
species, the amount of Q3 units increasing with the amount of TEOS
or TMOS, while the amount of Q4 groups remains independent of
the molar ratio. The degree of inorganic condensation of hybrids
prepared with [TEOS]/[MTES] ratios 0.5, 1 and 2 was 85%, 82%
and 79% and that of hybrids prepared with [TMOS]/[MTES] ratios
0.5, 1 and 2 was 81%, 81% and 80% respectively (see Table 1). The
degree of inorganic condensation was similar to that obtained for
hybrid materials prepared with [TEOS]/[MPTS] or [TMOS]/[MPTS]
mixtures (between 79 and 85%).
In light of these results, the total degree of condensation is
dependent of the amount of TEOS or TMOS, the incorporation of
these reagents leading to a decrease of the total degree of condensation. The relative amount of T3 species clearly decreased and that
of Q4 species remained practically constant. The heterocondensation reactions are less favored between T and Q units. The values
obtained for hybrids prepared with [TEOS]/[MTES] ratios of 0.5, 1
and 2 were 86%, 84% and 81% respectively and for hybrids prepared with [TMOS]/[MTES] ratios 0.5, 1 and 2 were 85%, 85% and
82%. The values of total degree of condensation were higher than
those obtained for hybrid materials prepared with [TEOS]/[MPTS]
or [TMOS]/[MPTS], indicating that the condensation of the species
in former systems was more favored.
On the other hand, MTES had no double C C bonds and
the organic polymerization took place through SiOR groups

889

( CH2 Si(OR)3 ), favoring structures with a higher degree of T

polymerization (T3 groups display important concentrations, see
Table 1).
As it has been previously mentioned, the hybrid network formation is inuenced by organic polymerization through methacryloxy
groups, which can be monitored by using 13 C CPMAS-NMR spectroscopy. The presence or absence of TEOS and TMOS precursors
had a great inuence on the extension of vinyl polymerization
and the utilization of TEOS or TMOS affects in different way the
development of the reaction. Table 2 shows relative intensities
of species detected in 13 C CPMAS-NMR spectra of [TEOS]/[MPTS]
and [TMOS]/[MPTS] mixtures. Estimated values should only be
considered in a semiquantitative way, because cross polarization
efciency in CPMAS experiments can differs considerably for different environments.
In absence of TEOS or TMOS, the relative intensity of the quaternary carbons (signal 7 , at 45 ppm), carbons of polymerized
hydrocarbon chain CH2 (signal 6 , 58 ppm) and carbonyl groups
close to aliphatic carbons, after C C opening (signal 8 , 177 ppm)
are 16, 4 and 12% respectively, conrming that the organic polymerization is produced by C C opening in MPTS. The presence of
TEOS or TMOS (R = 0.5) produced a decrement in the area of 7 and
8 peaks, indicating the existence of some competition between
the vinyl polymerization and the SiOR polymerization through the
(R = CH3 ) (signal 4, at 51 ppm). In the specic case of TEOS, a higher
amount of this reagent (R = 1) increased slightly the intensity of
7 and 8 peaks, supporting the vinyl polymerization. When R = 2,
these signals decreased, indicating that the organic polymerization via methacryloxi groups was not favored, probably because
the formation of voluminous side chains, which generated steric
hindrance. These results agree with earlier works, where the proportions of Tn and Qn species were deduced from 29 Si MAS-NMR
spectra.
The 6 signal seemed to have different behavior than 7 and 8
signals with composition. The presence of a higher amount of TMOS
(R = 1 and 2) decreases the intensity of area of these three peaks
(signals 6 , 7 and 8 ), being more visible for a ratio of 2. The vinyl
polymerization was not favored and the organic condensation took
place through SiOR groups (important decrease of the signal 4 and
increment of signals 6, 7 and 8, associated to CH2 = C groups and
carbonyl groups respectively). These results support those deduced
from 29 Si MAS-NMR spectra.
Therefore, based on these latter ndings, it can be concluded
that the organic polymerization occurs via opening the C C double bond in lms prepared with [TEOS]/[MPTS] and [TMOS]/[MPTS]
mixtures. This is also conrmed by IR spectroscopy, where a strong
decrease of the intensity of 1630 cm1 band associated with C C
bonds and the formation of a new band at 1730 cm1 , assigned to
the stretching vibration of C O not conjugated with C C bonds.

Table 2
The peak areas of the signals in the 13 C MAS-NMR spectra of the mixtures [TEOS]/[MPTS] and [TMOS]/[MPTS].

Samples

Ratios

Signals
1

[TEOS]/[MPTS]

[TMOS]/[MPTS]

0
0.5
1
2
0
0.5
1
2

7`

6`

(9
ppm)

(18
ppm)

(22
ppm)

(45
ppm)

(51
ppm)

(58
ppm)

(67
ppm)

(126
ppm)

(136
ppm)

(168
ppm)

(177
ppm)

13.7
17.3
14.6
14.2
13.7
11.4
13.5
12.7

12.2
12.2
9.5
16.3
12.2
8.3
11.7
21.7

19.0
17.8
22.7
18.3
19.0
22.7
18.6
13.8

16.1
14.1
14.4
12.5
16.1
15.5
13.7
4.3

3.1
2.9
1.9
1.9
3.1
4.9
4.5
0.8

4.1
5.6
4.9
5.4
4.1
4.7
4.2
1.7

11.3
10.5
10.9
13.0
11.3
11.2
11.2
10.9

3.3
4.1
4.2
3.6
3.3
4.6
5.0
9.4

3.0
3.2
3.0
2.6
3.0
4.1
5.0
9.7

2.6
4.0
3.6
3.3
2.6
3.4
4.9
11.1

11.7
8.3
10.1
8.9
11.7
9.2
7.4
3.9

Colour emphasized the new signals that are formed when organic polymerization has been produced through methacryloxy groups.

890

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

3,1
3,0
2,9

"dtotal" values

2,8
2,7
2,6
2,5
2,4

[TEOS]/[MPTS]
[TMOS]/[MPTS]
[TEOS]/[MTES]
[TMOS]/[MTES]

2,3
2,2
2,1
0

0.5

Molar ratios
Fig. 8. Evolution of the total dimensionality (dtotal ) parameter of all hybrid materials
synthetized with the different molar ratios employed.

during condensation reactions between Si OH and Si OR (R: CH3

and C2 H5 ) in [TEOS] or [TMOS]/[MTES] mixtures. The third loss was
associated to the dehydration of silanol groups, or to the oxidation
or degradation of MTES methyl groups.
FTIR spectra showed that the formation of hybrids materials
from [TEOS]/[MPTS] and [TMOS]/[MPTS] mixtures was produced
through the reaction of Si OR groups, the condensation of silanols
(inorganic condensation) and the formation of an interconnected
organic polymer via C C opening of MPTS. FTIR spectra showed
that the formation of the hybrids prepared from [TEOS]/[MTES]
and [TMOS]/[MTES] mixtures was mainly produced through the
reaction of Si OR groups.
29 Si MAS NMR spectra showed that a higher amount of TEOS or
TMOS in the mixture with MPTS favored the inorganic condensation; however, the organic polymerization (through methacryloxy
groups), the mobility of the organic groups and the degree of
organic polymerization were less favored. The total condensation
degrees in [TEOS] or [TMOS]/[MTES] hybrids were higher than
those obtained in [TEOS] or [TMOS]/[MPTS], so MTES favors the
formation of branched organic structures.
Acknowledgment

Finally, the dimensionality of the hybrid materials synthetized

was studied through d parameter, which provides information
about the nal structure achieved in lms (see Table 1). The d
parameter values are between 0 and 4, when d = 0 the structure
is formed by isolated tetrahedra; when d = 1, it is constituted by
dimeric units; when d = 2, linear chains are formed; when d = 3 or 4,
the structure is bidimensional or tridimensional, respectively. The
inorganic dimensionality (d(T)), the organic dimensionality (d(Q))
and the total dimensionality (dtotal ) parameters of hybrid materials
are depicted in Table 1. These parameters were obtained from 29 Si
NMR-MAS spectra of the four hybrid organicinorganic systems. In
Fig. 8 dtotal parameters of all studied mixtures are depicted. In samples with R = 0, hybrids with linear chains are formed in [TEOS] or
[TMOS]/[MPTS] mixtures (dtotal = 2.19) and more condensed structures, between linear and planar structures, were developed in
[TEOS] or [TMOS]/[MTES] mixtures (dtotal = 2.66). The rst reagent
(MPTS or MTES) provides the base structure of hybrids; the second
reagent (TEOS or TMOS) reacts with free Si O R bonds of T units,
lling the holes and giving a nal structure with lower porosity and
probably greater thickness.
An increase of the amount of TEOS or TMOS in all studied mixtures involved a higher dtotal value (see Fig. 8), indicating that a
more complex and polymerized structure was formed. For example, when a ratio R = 2 was used, dtotal values were between 2.76
and 2.99, that favors the formation of planar structures. In general,
it is observed that hybrids synthetized from MTES present a higher
dtotal parameter than those synthetized from MPTS. This tendency is
logical taking account that mixtures with MTES presented a higher
degree of condensation (see Table 1).
The organicinorganic coatings prepared with the mixtures [TEOS]/[MTES] and [TMOS]/[MTES] mixtures can be good
alternatives for metal protection against corrosion in reinforced
concrete structures (ratio of 1), because higher degree of condensation and dimensionality, display a bigger thickness and lower
porosity.
4. Conclusions
TG thermograms of prepared [TEOS] or [TMOS]/[MPTS] hybrid
showed three types of weight losses. The rst one visible below
160 C was due to the evaporation of ethanol and water. The second one produced between 160 C and 470 C, was attributed to
scissions within polymer chains or to volatile compounds produced

M. Criado expresses her gratitude to the Spanish Ministry of

Science and Innovation for the Juan de la Cierva (Ref. JDC-2010)
contract.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.porgcoat.
2014.01.019.
References
[1] C. Sanchez, F. Ribot, New J. Chem. 18 (1994) 10071047.
[2] C. Sanchez, B. Julin, P. Belleville, M. Popall, J. Mater. Chem. 15 (2005)
35593592.
[3] R. Nass, E. Arpac, W. Glaubitt, H. Schmidt, J. Non-Cryst. Solids 121 (1990)
370374.
[4] A. Bordoli, N.T. Mathew, F. Lefebure, S.B. Halligudi, Microporous Mesoporous
Mater. 115 (2008) 345355.
[5] D. Wang, G.P. Bierwagen, Prog. Org. Coat. 64 (2009) 327338.
[6] V.H.V. Sarmento, M.G. Schiavetto, P. Hammer, A.V. Benedetti, C.S. Fugivara,
P.H. Suegama, S.H. Pulcinelli, C.V. Santilli, Surf. Coat. Technol. 204 (2010)
26892701.
[7] M.L. Zheludkevich, R. Serra, M.F. Montemor, I.M. Miranda Salvado, M.G.S. Ferreira, Surf. Coat. Technol. 200 (2006) 30843094.
[8] T.L. Metroke, R.L. Parkhill, E.T. Knobbe, Prog. Org. Coat. 41 (2001)
233238.
[9] M.L. Zheludkevich, I.M. Miranda Salvado, M.G.S. Ferreira, J. Mater. Chem. 15
(2005) 50995111.
[10] S.K. Medda, D. Kundu, G. De, J. Non-Cryst. Solids 318 (2003) 149156.
[11] G. Kickelbick, Prog. Polym. Sci. 28 (2003) 83114.
[12] S.A. Pellice, R.J.J. Williams, I. Sobrados, J. Sanz, Y. Castro, M. Aparicio, A. Durn,
J. Mater. Chem. 16 (2006) 33183325.
[13] Y. Wei, D. Yang, L. Tang, J. Mater. Res. 8 (1993) 11431152.
[14] Y. Abe, Y. Honda, T. Gunji, Adv. Organomet. Chem. 12 (1998) 749753.
[15] J. Mndez-Vivar, A. Mendoza-Bandala., J. Non-Cryst. Solids 261 (2000)
127136.
[16] D. Massiot, F. Fayon, M. Capron, I. King, S. Le Calv, B. Alonso, J.-O. Durand, B.
Bujoli, Z. Gan, G. Hoatson, Magn. Reson. Chem. 40 (2002) 7076.
[17] L. Jianguo, G. Gaoping, Y. Chuanwei, Surf. Coat. Technol. 200 (2006)
49674975.
[18] T.C. Chang, Y.T. Wang, Y.S. Hong, Y.S. Chiu, J. Polym. Sci. A: Pol. Chem. 38 (2000)
19721980.
[19] X. Chen, S. Zhou, B. You, L. Wu, Prog. Org. Coat. 74 (2012) 540548.
[20] D.Y. Nadargi, A. Venkateswara Rao, J. Alloys Compd. 467 (2009)
397404.
[21] G. Li, M. Kanezashi, T. Tsuru, J. Membr. Sci. 379 (2011) 287295.
[22] E.E. Pretsch, P. Bhlmann, C. Affolter, A. Herrera, R. Martnez, Determinacin
estructural de compuestos orgnicos, Barcelona, Springer, 2001.
[23] R.M. Silverstein, F.X. Webster, Spectrometric Identication of Organic Compounds, sixth ed., John Wiley and Sons, New York, 1998.

M. Criado et al. / Progress in Organic Coatings 77 (2014) 880891

[24] J. Habsuda, G.P. Simon, Y.B. Cheng, D.G. Hewitt, D.A. Lewis, H. Toh, Polymer 43
(2002) 41234136.
[25] J.R. Martnez, F. Ruiz, Rev. Mex Fs 48 (2002) 142149.
[26] M. Lavorgna, L. Mascia, G. Mensitieri, M. Gilbert, G. Scherillo, B. Palomba, J.
Membr. Sci. 294 (2007) 159168.
[27] M.C. Matos, L.M. Ilharco, R.M. Almeida, J. Non-Cryst. Solids 147148 (1992)
232237.

891

[28] P. Innocenzi, G. Brusatin, S. Licoccia, M.L. Di Vona, F. Babonneau, B. Alonso,

Chem. Mater. 15 (2003) 17974790.
[29] S.-R. Zhai, Y. Song, B. Zhai, Q.-D. An, C.-S. Ha, Microporous Mesoporous Mater.
163 (2012) 178185.
[30] Y.-H. Han, A. Taylor, M.D. Mantle, K.M. Knowles, J. Sol-Gel Sci. Technol. 43 (2007)
111123.