Journal of Non-Crystalline Solids 353 (2007) 20992103

www.elsevier.com/locate/jnoncrysol

Characteristics of colored inorganicorganic hybrid materials

K. Wojtach
a

a,*

, M. Laczka a, K. Cholewa-Kowalska a, Z. Olejniczak b, J. Sokolowska

AGH-University of Science and Technology, Faculty of Materials Science and Ceramics, Department of Glass Technology and Amorphous Coatings,
Avenue Mickiewicza 30, 30-059 Krakow, Poland
b
Institute of Nuclear Physics, ul. Radzikowskiego 152, 31-342 Krakow, Poland
c
_
Technical University of Lodz, Faculty of Chemistry, ul. Zeromskiego
116, 90-924 odz, Poland
Available online 24 April 2007

Abstract
Inorganicorganic hybrid glasses are relatively new nanometric materials of Ormosils group (organic modied silicates). There coexistence, on a molecular scale, exists between inorganic structures in the form of silica-oxide network and organic structures based on
carbon links. Properties of these materials are intermediate between those of inorganic glasses (hardness, chemical and thermal resistance) and organic polymers (low temperature of obtaining, elasticity of structure). The hybrid materials are compatible matrices for
organic compounds such as organic dyes, laser dyes, photo-chromic compounds, etc. Inorganicorganic hybrid glasses are usually produced in the form of thin coatings on various bases using a low-temperature sol-gel process. These coatings, depending on the kind and
amount of units, building their structure, show various properties: refractive index changing in a wide range, anti-static properties, antireection, corrosion protection, intensive color, luminescence and others. That is why these materials found application as protective and
colored covering of glass articles as well as in new technical areas. The aim of this paper is obtaining and characterizing colored inorganicorganic coatings on glass, considering both protective and colored properties. These materials have been produced from phenyltriethoxysilane (PhTES), 3-glycidoxypropyltrimethoxysilane (GPTMS), aluminium tri-sec-butylate (TBA); (PGT matrix). The structure of
PGT matrix was determined using the FTIR, 29Si MAS NMR and 27Al MAS NMR examinations. It has been found that chemical bonds
occur between structural units. The two groups of organic dyes were used for coloring the coatings. The rst group consisted of ORASOL dyes, chiey based on various metal complexes. These dyes have a wide range of commercial utilization. The second group included
the organic, intensive dyes obtained in the laboratory and are inaccessible for sale. The coloring coatings were coated on at glass using
the dip-coating method. The samples were submitted for thermal treatment at temperatures of 100 and 200 C. Investigation of chemical
resistance (boiling in water for 1 h) was made for coated materials after thermal treatment at 100 C. UVVIS transmission of colored
coatings was examined after each stage of thermal treatment and also after hydrolytic resistance examination. The quality of the coatings
and their thickness were estimated by SEM observations. The obtained, inorganicorganic coatings were characterized by good chemical
resistance and stability of color.
2007 Elsevier B.V. All rights reserved.
PACS: 81.07.Pr; 81.20.Fw
Keywords: FTIR measurements; NMR, MAS-NMR and NQR; Organicinorganic hybrids; Short-range order

1. Introduction
Recently, a new class of multifunctional materials has
emerged, i.e. inorganicorganic hybrids, being a unique
combination of inorganic structure in the form of a silicon

Corresponding author. Tel.: +48 12 6172455; fax: +48 12 6172509.

E-mail address: cholewa@agh.edu.pl (K. Wojtach).

0022-3093/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2007.02.032

oxide network and the organic structures based on carboncarbon chemical bonding. The properties of these
materials are intermediate between traditional ceramics
(hardness, chemical and thermal resistance) and organic
polymers (low preparation temperature, elastic structure).
It has been found that the hybrid materials are a compatible
matrix for numerous organic compounds, such as organic
dyes, laser dyes, and compounds that exhibit photo-chromic
behavior and many more [13]. Usually, inorganicorganic

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K. Wojtach et al. / Journal of Non-Crystalline Solids 353 (2007) 20992103

hybrid glasses are obtained in the form of thin coatings on

dierent substrates by means of a low-temperature sol-gel
process. Since the properties of the hybrids depend on the
kind and amount of the units building their structure, the
coatings are characterized by various properties, e.g. a
refractive index changing within a wide range, anti-static
and anti-reectivity, corrosion protection, intensive color,
and luminescence [4,5]. For this reason the hybrid materials
have found application as protective and decorative, colored
coatings for glass items, as well as in new technical branches.
Colored hybrid coatings are relatively low cost method
for modifying the glass materials with a sophisticated shape
and high surface area. A matrix based on aluminium tri-secbutylate (TBA), phenyltrimethoxysilane (PhTMS) and 3glycidoxypropyltrimethoxysilane (GPTMS) seems to be
particularly suitable for these applications. Kron et al. demonstrated that the coatings based on this matrix possess the
best mechanical parameters when TBA:PhTMS:GPTMS
ratio was 20%:10%:70%. Such coatings were characterized
by an increased hydrophobicity of the glass surfaces, as well
as a very good adhesion and abrasion resistance, when
applied onto a soda-lime glass [6]. Also, it was found by
Chu et al. that introducing GPTMS during the synthesis
led to increased density and layer thickness, as well as the
enhanced adhesion on the polymer substrate [7]. The inuence of the GPTM presence during the synthesis on the corrosion resistance of the obtained coatings was investigated
by Metroke et al., who showed that the coatings can be used
for protection of the aluminium-based alloys against corrosion [8]. The structure of the materials in GPTMS/PhTMS/
TEOS group was studied by Peeters et al. by means of 29Si
MAS NMR. They reported that in the presence of GPTMS,
an increase in condensation of the tetrafunctional silicon
atoms (Q) is related to the presence of the trifunctional silicon atoms (T), while the number of bondings within the
three dimensional lattice of T atoms decreases with an
increasing size of the organic tail [9]. According to Peeters
and Kentgens, when aluminium originating from TBA is
introduced in the composition of the PhTES/GPTMS/
TEOS system, the Al atoms occur in tetrahedral and octahedral surrounding. While the amount of the atoms in a
given position depends on the hybrid synthesis route, a
low water content during synthesis favors the tetrahedral
Al position [10].
The aim of this paper was to obtain the colored inorganicorganic coatings on glass substrates, based on PGT
matrix (phenyltriethoxysilane (PhTES), 3-glycidoxypropyltrimethoxysilane (GPTMS), and aluminium tri-sec-butylate (TBA)), and characterize their structure, optical
transmission, as well as the chemical resistance and thermal
stability of color.

(GPTMS), and aluminium tri-sec-butylate Al(OCH(CH3)C2H5)3 (TBA). The solutions were prepared at room
temperature according to the scheme given in Fig. 1. The
molar ratio of particular substrates was 0.5:0.3:0.2. The
mixing times were selected empirically. The organic dyes
used in the experiment fall into two classes. The rst group
consisted of ORASOL dyes, chiey based on various metal
complexes: Red BL (chrome complex), Orange G (cobalt
complex), Orange RG (chrome complex), Blue GN (Cuphthalocyanine), Yellow 4GN (metal-free monoazo), Black
RLI (chrome complex). These dyes have a wide range of
commercial applications. The second group included
organic dyes of high color intensity, obtained from the
University of Lodz laboratory. They also represented various metal complexes, but their composition is patented
and they are not commercially available. The color and
the symbols of these dyes are as follows: R9 (brownred),
R12 (yelloworange), R16 (violet), PAS (pink), B1
(orange), B2 (blackviolet), CzE6B (brown), and ZGGW
(yellow). The dyes in the form of powder were added to
the solutions. The amount of the dye was kept constant,
at 12% of the wet gel weight. The synthesis time did not
exceed 2 h. Finally, the coatings were applied from the previously prepared solutions on the microscopic glass plates
by means of dip-coating technique. The immersion-withdrawal rate was identical for all the samples and was equal
to about 4 cm/min. The coatings were then dried at room
temperature and subsequently in the dryer at 40 C for
1021 days. Next, the samples were treated thermally.
Some of the samples heated at 100 C were boiled in water
at 98 C for 1 h.
In order to determine the hybrid structure, the FTIR
examinations for all gels were performed, using DIGILAB
spectrophotometer. Also, for the gels treated thermally at
100, 200, 300 and 400 C, 29Si MAS NMR and 27Al

Ethyl
alcohol

PhTES

GPTMS
Stiring at
ambient
temperature

TBA

H2O+HCl

Organic
dye

2. Experimental
The materials have been produced from phenyltriethoxysilane (C6H5)Si(CH3CH2O)3 (PhTES), 3-glycidoxypropyltrimethoxysilane
(OCH3)3Si(CH2)3OCH2CHOCH2

Final
solution
Fig. 1. Scheme of hybrids preparation.

K. Wojtach et al. / Journal of Non-Crystalline Solids 353 (2007) 20992103

MAS NMR measurements were carried out. Optical transmission of coatings was measured within UV and visible
ranges using a UVVIS spectrophotometer HP 8453. These
measurements were performed for the samples after a complete thermal treatment, as well as for the ones boiled in
water.

29

Si N M R
4 kH z M AS

PGT
Q

100 C

200 C

3. Results and discussion

The PGT matrix represents hybrid material composed
of inorganic and organic units. In this structure each silicon
atom, besides the links with oxygen SiOR (R@CnHm)
(trifunctional silicon atoms), forms SC bond representing
a link either with the phenyl group (PhTES precursor) or
with carbon chain ended with an epoxide group (GPTMS
precursor). The inorganic network is additionally modied
by the tetrahedral [AlO4] (TBA precursor). Such type of
hybrid structure has been conrmed by the results of FTIR
and 29Si MAS NMR examinations (Figs. 24). In the FTIR
spectra of the PGT gels the bands derived from vibrations
of both inorganic and organic structural units occurred
(Table 1) [14]. However, in the spectra of samples heated
to a temperature of 200 C, the bands characteristic for
the symmetric stretching vibrations (about 800 cm 1) and
bending vibrations (about 440 cm 1) of SiOSi bridges
do not appear, while a distinct band derived from SiO
C bonds at about 11101133 cm 1 (stretching vibrations)
is observed. It indicates that in this structure the bridging

2101

300 C

400 C
0

-20

-40

-60

-80

-100 -120 -140 -160 -180

ppm from TMS

Fig. 3. 29Si MAS NMR spectra of PGT gels, after treatment at 100, 200,
300 and 400 C.

27

Al NMR
8 kHz MAS

PGT

[AlO4]
[AlO6]

100 C

200 C

300 C

400 C
200

150

100

50

-50

-100

ppm from Al(NO3)3

Fig. 4. 27Al MAS NMR spectra of B class gels, after treatment at 100,
200, 300 and 400 C.

Fig. 2. FTIR spectra of PGT gels after heat treatment at various

temperatures (40, 100, 200, 300 and 400 C).

oxygen between two silicon atoms SiOSi does not

occur at all. This same conclusion results from NMR
examinations. In the 29Si MAS NMR spectra of PGT gels
heated to a temperature 200 C (Fig. 3), the signals derived
from Q units are not observed, which is an indication that
there are no tetrahedral [SiO4] in which the Si ion would be
combined by an oxygen bridge. On the other hand, there
occur two distinct group eects at about 70 and 80 ppm
derived from T units, in which besides SiO bonds there
occurs SiC bond [9,13]. Separation of the peaks is
undoubtedly connected with the fact that through the

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K. Wojtach et al. / Journal of Non-Crystalline Solids 353 (2007) 20992103

Table 1
Characteristic bands appearing in FTIR spectra of obtained hybrid gels
and their interpretations on the base of [14]
Origin

487

OSiO bend

701

Si

oop Ring bend

In phase, oop 5 adjacent H

Si

Si

70
60
50
o

40

PGT_OrBlue GN_40 C
o
PGT_OrBlue GN_100 C
o
PGT_OrBlue GN_200 C
o
PGT_OrBlue GN_100 C_H
o
PGT_base_100 C

30
20
10

11101133

80

Structural units

742

90

Transmitance [%]

Band

100

0
200

Si

m SiOSi
SiOC

Si O C

12001201

COC

COC in GPTMS

1460
1595
2937

Ring
CH

3429

OH, H

HOH

300

400

500

600

700

800

900

1000 1100

Wavelength [nm]

Fig. 5. UVVIS spectra of base lm and Orasol Blue GN dyed lms after
treatment at various temperatures (40, 100 and 200 C) and after boiling in
water (H).

CH
100
90
80

Transmitance [%]

SiC bond, various units combine with silicon [12]. Increase

of the temperature of the gels treatment up to 300400 C
causes a distinct change in the 29Si MAS NMR spectra
(Fig. 3), indicating the decomposition of the SiC bond
and formation of inorganic network composed only of
the Q units. These results are also conrmed by FTIR spectra of gels heated at 300 and 400 C (Fig. 2), in which the
bands characteristic for vibrations of SiOSi groups
appeared. In the 27Al MAS NMR spectra (Fig. 4), there
occur two peaks situated at about 5 and 50 ppm, which
may be connected with the occurrence of Al in the hybrid
structures in the tetrahedral (55 ppm) and octahedral
(5 ppm) coordinations [10,11].
The coatings, obtained on the base of PGT matrix, containing Orasol dyes, were of a highly intensive color, characteristic for the applied dyes. A similar behavior was
observed for the coatings from the second group, except
for those dyed with B2, CzE6B and ZGGW, where the
color intensity was much lower. Interestingly, after addition of the R9, PAS or CzE6B, the observed color of the
matrix was dierent in comparison to the dye itself, i.e.
coatings were redpink, yellow and red, probably due to
the interaction between the dye molecules and the matrix.
The UVVIS spectra reveal the bands originating from
the applied dyes. Taking into account the high intensity
of the coloring, it is likely that the absorption bands
observed in the spectra result from the allowed electronic
transitions in the dye molecules. The UVVIS spectra for
all the coatings dried at 40 C and heated at 100 C are
almost identical (Figs. 5 and 6). After heating at 200 C
the coloring intensity of the coatings with Orasol dyes is
slightly decreased, while for the coatings containing the
dyes from the second group bleaching is observed, probably causing decomposition of the dye. It is most likely connected with the lower thermal resistance of these dyes, as

70
60
50
o

PGT_R12_40 C
o
PGT_R12_100 C
o
PGT_R12_100 C_H

40
30
20
10
0
200

300

400

500

600

700

800

900

1000

1100

Wavelength [nm]

Fig. 6. UVVIS spectra of the R12 dyed lms obtained from PGT matrix
after heat treatment at various temperatures (40 and 100 C) and after
boiling in water (H).

compared to Orasol dyes. The coloring stability and a high

integrity of the coatings were also conrmed by boiling the
samples in a water bath, indicating the dye stability within
the matrix. Exceptionally, for the coatings with R12 and
R16 dyes there was a decrease in the coloring intensity
(washing away of the dye), followed by the decreased integrity of the coating. However, for the coating with R9 the
integrity remained unaected by the bleaching process.
The SEM observations conrmed a high quality of the
coatings. The layers were smooth, no inclusions or cracks
were observed (Fig. 7). Also, they showed a high adhesion
to the substrate. The fracture images served for estimating
the layer thickness, which was about 1520 lm (Fig. 8).
4. Conclusions
The PGT hybrid materials are compatible matrices for
organic dyes. Furthermore, the obtained color coatings

K. Wojtach et al. / Journal of Non-Crystalline Solids 353 (2007) 20992103

2103

ature of 200 C. The behavior of no-commercial dyes

obtained in the laboratory was diverse. Part of them
behave similar as Orasol dyes, however, some of them
showed low intensity as well as low chemical and thermal
resistance. Therefore, the coatings with Orasol dyes can
be easily applied for decorative and protective layers and
second group of dyes requires further examinations.
Acknowledgement

Fig. 7. SEM image of the Orasol Orange RG dyed lm obtained from

PGT after heat treatment at 100 C.

This investigation is nancially supported by the Polish

State Committee for Scientic Research Project No. 3
T08D 41 29.
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Fig. 8. SEM image of the fracture of Orasol Blue GN dyed lm obtained

from PGT after heat treatment at 100 C.

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However, the intensity, as well as thermal stability of color
and chemical resistance, depends on the kind of the introduced dyes. The application of the commercial Orasol dyes
leads to obtaining intensive dyed coatings with good chemical resistance and thermal stability of color up to a temper-

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