Review / Revisión bibliográfica
https://doi.org/10.17163/ings.n21.2019.01
pISSN: 1390-650X / eISSN: 1390-860X
Functionalized enamel of ceramic tiles
by sol gel technique (review)
Deposición de capas funcionales sobre
esmaltes cerámicos mediante la técnica
sol-gel (revisión)
Santiago Betancourt-Parra1,∗ , Manuel A. Domínguez-Ortiz1 , Diana M.
Mosquera-Palacio1 , Juliana Herrera-Guerra1 , Carlos M. Ríos-Rendón2 ,
Carlos E. Villa3
Abstract
Resumen
The function of enamels for the ceramic tile industry has been a research topic for the past 15 years.
Different researchers have focused their efforts on
achieving surfaces with functional attributes that increase product value and provide solutions for the
technological needs of our times. This article presents
a review of the scientific literature dedicated to obtaining functional surfaces by means of the sol-gel
technique, which provides a means for deposition and
formation of thin layers on traditional ceramic enamels in order to provide functional characteristics. The
document presents: typically used alcoxidic solutions,
the different deposition techniques emphasizing the
experimental findings obtained by the authors, and a
synthesis of the functional effects obtained by means
of the technique.
La funcionalización de esmaltes para la industria de
las baldosas cerámicas ha sido un frente de investigación importante en los últimos 15 años. Diferentes
investigadores han centrado sus esfuerzos en conseguir
superficies con atributos funcionales que incrementen
el valor agregado del producto y a su vez aporten
respuestas a las necesidades tecnológicas de nuestros
tiempos. El presente artículo se centra en hacer una
revisión de la literatura científica dedicada a la obtención de superficies funcionales por medio de la
técnica de sol-gel, la cual es apta para la fabricación
de soluciones que se depositan formando capas finas
sobre los esmaltes de cerámica tradicional con el fin
de aportar características funcionales al mismo. El
documento presenta las principales soluciones alcóxidicas usualmente empleadas, las diferentes técnicas
de deposición haciendo énfasis en los hallazgos experimentales obtenidos por los diferentes autores, y
presenta una síntesis de los efectos funcionales hasta
la fecha obtenidos por medio de la técnica.
Keywords: Ceramic enamel - Functional enamel –
sol gel - ceramic
Palabras clave: esmaltes cerámicos, esmaltes funcionales, sol-gel, cerámica.
1,∗
Research Group of New Materials (GINUMA), Universidad Pontificia Bolivariana (UPB), Colombia.
Corresponding author ✉: santiago.betancourt@upb.edu.co
http://orcid.org/0000-0003-4474-2447,
http://orcid.org/0000-0003-2167-7400,
http://orcid.org/0000-0003-0401-3557,
http://orcid.org/0000-0002-5636-7210
2
Product development management, Eurocerámica, Colombia,
http://orcid.org/0000-0001-6816-4296
3
http://orcid.org/0000-0002-4971-689X
Plant technical management, SENCO, Colombia,
Received: 16-11-2018, accepted after review: 13-12-2018
Suggested citation: Betancourt-Parra, S.; Domínguez-Ortiz, M. A.; Mosquera-Palacio, D. M.; Herrera-Guerra, J.;
Ríos-Rendón, C. M. and Villa, C. E. (2019). «Functionalized enamel of ceramic tiles by sol gel technique (review)».
Ingenius. N.◦ 21, (january-june). pp. 9-20. doi: https://doi.org/10.17163/ings.n21.2019.01.
9
INGENIUS N.◦ 21, january-june of 2019
10
1. Introduction
The ceramic enamel is a layer of glassy nature that is
deposited on the surface of different substrates, of ceramic nature in general, to provide beautiful attributes
and protect the surface due to its physical properties.
A vast field of enamel applications include ceramic
tiles, which are used for flooring and facing in the
construction sector [1, 2]. As shown in Figure 1, three
clearly defined layers can be distinguished in the tiles:
i) the bisque, which serves as support and has the highest thickness and body in the tile, ii) the engobe, which
has a thickness between 100 and 200 µm, and joins the
enamel and the bisque and iii) the enamel, which is a
layer of very low porosity, with a thickness between 75
a 300 µm and the aforementioned characteristics [3].
drolysis and condensation produce the transformation
of molecular precursors into oxide networks [11].
The following review is specifically focused in gathering scientific information, about the use of the sol-gel
technique for deposition of chemical solutions in glassy
enamels of ceramic tiles, in order to improve properties or provide functional attributes to the enameled
surface. Figure 2 presents a graphical report of the
yearly evolution of the publications about the subject,
in online scientific databases and specialized books
cited in the consulted literature, among which Google
Scholar, Science Direct, Wiley Online Library, Springer
Link, UN Institutional Repository, American Institute
of Physics, Taylor & Francis Online, ACS Publications
can be mentioned.
The review was carried out considering publications between 2000 and 2017, with the greater number
of works being reported in the period 2009-2017. First.
The report focuses on presenting the different types of
alkoxides typically used. Then, it describes the different
deposition techniques, emphasizing in the experimental findings obtained by different authors. At last, it
presents a synthesis of the functional effects.
Figure 1. Cross section of a ceramic tile
Besides providing aesthetic and decorative characteristics, the enamels on such tiles can be used for other
functional features. Some of the features that it is desired to improve or implement on these surfaces include:
self-cleaning, energy storage, photocatalytic, antibacterial, fungicidal, high scratch resistance, inhibiting ice
formation, absorb or emit substances, luminescent surfaces and even coating that can change properties when
subject to a certain stimulus [4]. Nevertheless, many of
the parameters which are necessary for an application
at industrial scale are not sufficiently stable yet, and
are still under research [5]. Therefore, this constitutes
a big challenge for industry, since incorporating new
technologies implies adaptation of production cycles
and of routine manufacturing conditions which entails
high economic investments.
To the best of our knowledge, there are various
techniques available to provide functional attributes
to the enamel, which include: i) modification of the
enamel composition by means of incorporating substances in the enamel mix prior to the burning, ii)
physical modification of the surface using plasma or
chemical deposition means in vapor phase, and iii)
chemical deposition of liquid solutions; the sol-gel technique is one of the most representatives of this family.
The sol-gel technique for material synthesis has
been extensively proven for obtaining glassy and ceramic materials [6–10]. Wet chemistry reactions of hy-
Figure 2. Report of publications per year.
2. Precursors
Table 1 presents the chemical precursors commonly employed for coating enamels using the sol-gel technique,
and their corresponding structures. The precursors
(starting reagent) are an alkoxide of typical chemical
formula R-O-M, which are compounds that comprise
a metallic ion (or another cation) represented by letter
M, an oxygen molecule represented by letter O and an
alkyl group R. The general reactions are expressed in
Table 2, according to [12].
Betancourt-Parra / Functionalized enamel of ceramic tiles by sol gel technique (review)
Table 1. Precursors
Name
Molecular formula
Titanium
Isopropoxide
11
becomes an alcogel, which can be removed from the
container and can stand by itself [13].
Figure 3 is a schematic representation made by [6].
The aerogels are obtained when the liquid-filled pore
is replaced by air, without altering the structure or
the volume of the gel body.
In the sol-gel process, the reactions depend upon
various parameters such as:
• Composition and concentration of the precursors
(alkoxide and solvent)
• Amount of water added
• Type and concentration of the catalyst employed
• Additional additives such as desiccants
Titanium
Ethoxide
• Sequence in which the components are added
• Mixing time
Zirconium
propoxide
• Aging time
Tetra-ethylorthosilicates
• Temperature
• Mixing conditions (efficiency of the mixture, agitation by ultrasound, atmosphere)
Table 2. General reactions of the sol-gel process
Hydrolisis
M-(OR)x + H-O-H → HO-M(OR)x-1 + H-OR
Condensation
Alcoxolation
(OR)x-1 –M-OH+RO-Me-(OR)x-1 → (RO)x-1
–Me-O-M-(OR)x-1 +ROH
Oxalation
(RO)x-1 –M-OH+HO-M-(OR)x-1 → (RO)x-1
–M-O-M-(OR)x-1 +HOH
Conventions:
M: Si, Ti, Zr, Hf, Ta, Nb, Al, Zn, etc.
R: CH3 , C2 H5 , C3 H: 7, etc.
Once the reaction has occurred, the precursors form
colloids, which are suspensions with a small dispersed
phase (1-1000 nm), negligible gravitational forces and
interactions being dominated by short range forces
(Van der Waals attraction forces and surfaces loads).
The sol is a colloidal suspension with solid particles
inside a liquid.
The gel point is the moment in which the oxide
bounded particles spread through the vessel that contains the colloid. During the gelation reaction, the viscosity increases until constituting a solid which adopts
the form of the mold. At this point, the pore fluid
mainly comprises alcohol and water, and the colloid
Figure 3. Schematic representation of the sol-gel process [6].
3. Deposition techniques
Regarding the deposition techniques, this sections
presents the remarkable findings reported in the reviewed literature, which are complemented with the
information presented in Table 3 that summarizes characteristics of the reported techniques.
12
3.1. Spin
This technique is based on the deposition of small
amounts of solution on the surface of a substrate that
spins at a high speed, such that the solution disperses
due to the centrifugal force, forming a homogeneous
liquid film. The solution quickly evaporates the solvent
and the oxide molecules are deposited on the substrate.
The thickness of the film directly depends on the following variables: speed of rotation, viscosity, contents
of solvent and its properties when evaporating.
There are mathematical models of the variation of
the thickness, which are described in detail in [12–17].
Thin layer coatings, with a thickness between 0,1 and
10 µm, can be obtained with this technique [18].
This technique has been extensively used in applications which require the formation of uniform films,
namely with homogeneous thickness and low rugosity [19]. For this reason, it is employed in manufacturing electronic micro components and has been of
interest to obtain highly glossy enamels for tiles, since
a reduction of the rugosity of a surface increases its
gloss [2].
3.2. Dip
The dip coating deposition technique involves totally
immersing the substrate in the solution, and further
removing it at a controlled speed [20, 21] under environmental conditions. According to some researchers,
it is considered the simplest technique to deposit films
on the surface of a substrate, which may be either
flat or curved [11]. Indeed, they state that it can be
implemented on surfaces with areas in the order of
square meters.
The thickness of the film directly depends upon
the velocity of substrate retraction and the viscosity of
the solution; low velocities are appropriate to obtain
thin films, with a thickness between 0.3 and 3 µm, and
rugosity between 60 and 690 nm [18].
In 2007, Kuisma et al. [22] studied the cleaning
capacity of ZrO2 and TiO2 thin films, deposited using
the dip coating technique on the surface of enameled
ceramic tiles of dimension 3.0 x 3.0 cm. Using topographic measurements, this work showed that for
higher roughness of the ceramic enamel, more organic
material gets adhered to the surface.
On the other hand, Piispanen et al. [23] characterized the effects of the resistance to a chemical attack
(stained) and cleaning of two tiles, one with dull finish
and the other with glossy finish, with TiO2 and ZrO2
films deposited using the dip coating technique. It was
determined that the TiO2 coating has greater cleaning
and self-cleaning capacity after being exposed to UV
light. The authors indicated that the cleaning capacity
of glossy glassy surfaces was not steep, and the zirconium coatings could negatively affect the enamels
INGENIUS N.◦ 21, january-june of 2019
self-cleaning capacity.
Hofer et al. [24] studied the thermal stability and
the active photocatalytic property of titanium, deposited on ceramic surfaces (enameled substrates and
non-enameled corundum substrates) with a coated
area of dimension 2.5 × 4.0 cm, using a dip coating
process. It was found that the thermal stability reduction depends on the composition of the substrate,
thus making evident a slight variation on the electronic structure of the titanium, which indicated weak
interactions between the silica and the titanium.
Similar results were reported in a study of the
coating of ceramic tiles and window glasses with thin
films of nano TiO2 , using dip and spray deposition
techniques, showing a good self-cleaning performance
of the coatings [25].
In addition, it has been used to obtain antibacterial effects on glassy substrates of ceramic tiles against
Escherichia coli y Staphylococcus aureus, using solutions of Ag/SiO2 [26] deposited on the enameled surface of the tiles by means of a dip coating technique.
They achieved an excellent antibacterial performance
against both types of bacteria related to a high synthetizing temperature of the deposited layer, since after
this treatment the silver ions are constantly released,
which generates variations in their concentrations thus
inhibiting the growth of these bacteria.
Soares et al. [27] used the sol-gel technique for producing thick coatings of silica and silica/zirconium
colloidal particles, on glassy-ceramic substrates of the
system Li2 O-Al2 O3 -SiO2 , in order to increase if resistance to scratch and wear. The deposition was carried
out at a retraction speed of 5 cm/min. Compared with
the results obtained with the substrate without coating, it was found an improvement in the final look of
the surface for the functional coatings; nevertheless,
the resistance to wear kept constant compared with
the samples without coating.
In addition, Zhang et al. [28] studied the effects
of incorporating titanium nano particles to solutions
of tetraethyl orthosilicate (TEOS) deposited on commercial white glassy ceramic tiles (25 × 25 × 5 mm),
by means of a dip coating technique in which the substrates were submerged during 3 minutes and further
removed at 1 mm/s. This research verified a better
dispersion for the particles of P25-TiO2 /TEOS, with a
greater surface area and rugosity, and a smaller particle size compared to the particles of P25-TiO2 , which
produced a better hydrophilicity and a greater photocatalytic activity, under irradiation of visible light.
López et al. [29] examined the effect of different
types of substrate, on the morphology of the surface
and the photocatalysis of a great scale TiO2 film. The
impregnation was carried out by dip coating; specifically, for the cases of a glassy substrate of soda-lime
ground with acid (12 × 21.5 cm), a SiO2 barrier layer
was deposited with a retraction velocity of 5 cm/min.
Betancourt-Parra / Functionalized enamel of ceramic tiles by sol gel technique (review)
On the other hand, the substrates (12 × 21.5 cm) of
sodium-lime glazed with acid, glassy soda-lime glazed
with acid previously coated with a SiO2 barrier layer,
enameled ceramic tile and 6061 aluminum alloy, were
impregnated with a TiO2 film. These tests determined
that the phase and microstructure of the TiO2 film are
exclusively anatase. Additionally, it was found a significant variation in the growth of the TiO2 crystals and
the morphology and thickness of the film with respect
to the substrate being used, which in turn affects the
photocatalytic activity.
The studies carried out by Hazmaliza et al. [30]
showed the antibacterial performance of the anatase
mixed with enamel applied on ceramic tiles, using two
different sizes of anatase powder (micrometric and
nano). For conducting these experiments, the concentration by weight of the anatase powder in microns
was varied, while the size nano anatase was established
on a fixed value. The results obtained show a slight
variation in the color of the manufactured tile, which
becomes more yellowish as the anatase composition
increases. Similarly, it is evident that the antibacterial
properties increase when the composition of nanometric anatase is greater compared to the micrometric, due
to larger area of antibacterial agents on the tile. Likewise, as the composition of anatase powder is greater,
the enamel viscosity will be larger.
It is important to note that research has been also
conducted related to the application of this technique,
in the TiO2 self-cleaning coating of clay roof tiles (1
× 1 × 0.8 cm) [31]. The authors demonstrated that a
TiO2 photocatalytic coating in the anatase nanocrystalline phase applied under industrial conditions for
thin film (0,399 mg of suspension/tile surface cm2 ), has
a better photocatalytic activity in the decomposition
of methylene blue, hydrophilicity and antimicrobial
activity, than a thick (0.885 mg suspension/ cm2 ) photocatalytic coating.
13
to the glassy surface creating a thin layer coating with
a thickness between 0.1 and 3 µm [18].
This deposition technique does not have limitations
in terms of the substrate size, since the aperture angle
of the application gun can be adjusted. It requires a
small amount of solution because the deposition is carried out only on the enameled surface, thus reducing
costs and minimizing the environmental impact since
it is not necessary to use a vacuum to eliminate the
gases emerging from the process [33–35].
Bondioli et al. [36] studied the functionalization
of the surfaces of industrial ceramic tiles by means of
the sol-gel technique, to improve the cleaning capacity
of non-enameled thin porcelain stoneware, preparing
TiO2 -SiO2 coatings with different concentration of titanium that were deposited using an airbrush. This
work reports that films are transparent, they do not
modify the stoneware gloss and show good adhesion.
In addition, they yield a greater catalytic effect at
high synthetizing temperatures, which produces a selfcleaning and self-sterilizing ceramic surface that may
also degrade various organic contaminants in the surrounding environment.
Savvova et al. [37] developed TiO2 coatings on ceramic enamels, determining the multi-functionality of
this material by reporting its substantial (70-90 %)
antibacterial and antifungal properties. Once again
Bondioli et al. [38, 39] reported the functionalization
of the surfaces of ceramic tiles, but this time focusing on soluble salts (alternative coloring processes of
ceramic materials without enamel) to improve mechanical properties (resistance to scratch and wear) and
the conductivity.
For that purpose, solutions with different concentrations of zirconium, titanium and silver were prepared,
and 300 g/cm2 were applied with airbrush on green
unfired bisque. It was visualized that the addition of
zirconium soluble salts increased the scratch resistance,
while simultaneously maintaining the final aesthetic
appearance of the ceramic tiles. The results obtained
3.3. Spray
for titanium and silver were similar to the results alThis deposition technique consists of a process of spray ready mentioned for zirconium, with the difference
or vertical atomization of a stationary liquid solution that a multi-functional layer is generated.
or in linear movement, where a fluid beam driven by
compressed air is fragmented into disperse drops that 3.4. Screen
collide on a substrate. There are many variables associated to the correct operation of the spray, namely The serigraphy or screen imprinting enables the realizaflow of solution, pressure of the compressed air, type tion of two-dimensional designs, which makes it useful
of nozzle and nozzle-substrate distance, among oth- in industrial processes [40]. The serigraphic processes
ers [32]. Such variables influence on the size, shape, require a knitting material, that may be synthetic fiber
velocity and drop strength of collision; these are also of steel mesh tensioned and bonded to a frame, which
related to fluid properties (surface tension, density and is covered with an emulsion that is impermeable to
the coating solution in the area in which no printing
viscosity).
After the collision, a heat transfer occurs between should appear.
the drops and the surrounding air, thus evaporating
It is a technique that virtually does not cause losses
the solvent through the boundary layer around each of the coating solution during printing, because the
drop. At the end of the evaporation, the drops adhere frame goes across the screen at a constant velocity,
14
and after performing the application it goes backwards
in order to repeat the procedure.
Due to its versatility, this method has been utilized
for 50 years in the ceramic industry to deposit enamels
and decorate tiles [18]. For this type of substrates,
processes that generate a TiO2 thin layer using the
sol-gel technique, produce thicknesses between 5 and
35 µm, taking into account that both the thickness
and the amount of applied material can vary according to the application percentage of the screen, which
includes the volume between the screen threads and
the thickness of the emulsion [40].
Since not all the material is deposited on the screen,
the thickness of the wet layer also depends on the
strength and the trawl speed of the frame, the screensubstrate distance, and the viscosity of the deposited
solution [40].
In 2008, São Marcos et al. [41] studied the TiO2
layers deposited by means of serigraphy (55 and 136
µm sifting) at 25 and 50 g/m2 on enameled single-pore
tiles. They determined that the layers gave more than
90% efficiency 6 to 8 h after performing the Orange
II discoloration, under visible artificial light without
layer deactivation; this yielded acceptable levels of
discoloration in reasonable periods of time.
In the following year, these researchers [42] characterized and determined the photocatalytic degradation
INGENIUS N.◦ 21, january-june of 2019
of Orange II, for active ZnO layers deposited at 25 and
50 g/m2 by means of different sifting screens (55 and
135 µm), using single-pore tiles with glossy enamel
(20 × 10 cm from Revigrés, PT); in this case, results
revealed a considerable discoloration performance of
Orange II (more than 50% efficiency after 6 to 8 h,
with a maximum attenuation degree of 72%), under
artificial visible light or by direct exposure to sun
light. For this effect, the TiO2 and ZnO layers avoid
the elimination of the photocatalyst at the end of the
process.
For the same year, Rego et al. [43] used the materials previously described to determine the photocatalytic degradation of the Orange II coloring in aqueous
solutions, under direct exposure to sun light. For this
purpose, TiO2 and ZnO layers were deposited with 50
g/m2 on ceramic tiles of single-pore glossy commercial
enamels (20 × 20 cm from Revigrés, PT) by means of
a serigraphic process where sifting screens were used
(136 µm).
This layers exhibited a greater performance for the
TiO2 , besides a maximum degree of color attenuation
of 90%. On the other hand, in 2011 Seabra et al. [44]
evaluated the photocatalytic behavior of titanium layers deposited by spray and serigraphy, and the former
gave a better coverage with small rugosity levels.
DIP
SPRAY
SCREEN
0,1-10 µm
0,3-3 µm
0,1-3 µm
5-55 µm
[26, 30]
[45–47]
[21–25, 28, 29, 31]
[25, 35, 36, 48–58]
[27]
[36–39]
Graphic representation
Typical curve of behavior of thickness
as a function of the
process variables
Thickness range
AntibacteriaL
Photocatalysis
Scratch resistence
[29]
[40–44, 48]
Betancourt-Parra / Functionalized enamel of ceramic tiles by sol gel technique (review)
SPIN
Table 3. Characteristics and publications per deposition technique
Technique
15
16
4. Applications
INGENIUS N.◦ 21, january-june of 2019
the aerobic activity of the microorganism, due to the
absence of oxygen in the medium.
This application has been of great interest in public places highly exposed to conditions of growth of
microorganisms, such as health facilities (clinics, hospitals, surgery rooms), schools and colleges, as it has
been proposed in [62].
Figure 4 illustrates the distribution of the consulted
literature according to the desired application. It is
clearly seen that the applications associated to photocatalysis and antibacterial effect have mainly received
the attention. Less than 10% of these researches have
focused in increasing the scratch resistance of the surfaces. A brief description of this type of applications
4.3. Scratch resistence
is presented in the following.
4.1. Photocatalysis
The absorption of photons coming with light with
enough energy (equal or greater than the energy band
of the catalyst), promotes catalytic reactions in the
surface of the material, generating excitons (pairs e−
– h+ ). Such excitons can be used to produce redox
reactions [59].
Behind the improvement of this property, underlie aspects related with the improvement in other properties
such as the useful life of the surfaces and their attributes, namely: gloss, color, texture, hardness, among
others, which are affected by the wear due to friction
phenomena to which the ceramic products are subjected.
The possibility of forming nano and micrometric
ceramic layers with crystalline structure, instead of the
amorphous structure typical of the glassy enamels, has
demonstrated notorious increments in the response of
the surface regarding scratch resistance [63].
5. Conclusions
After conducting this revision, it was found that the solgel technique has been employed for manufacturing solutions that are deposited in thin layers on traditional
ceramic enamels, in order to provide it with functional
characteristics. The reported literature mainly corresponds to researchers located in Italy, Brazil and Portugal. The surfaces with photocatalyst (self-cleaning)
functional attributes have been a major axis that has
motivated the research works in this area. In addition,
the broad market and the potential positive effect have
driven innovations for the industry.
Even though this is a research topic from 2000,
Figure 4. Distribution of research works according to with a strong boost from 2007, the researches in other
applications.
functionalities seem to be susceptible of being studied,
because it is possible to coat enamels with alkoxidic
The main purpose of obtaining coatings with cat- solutions using the sol-gel technique.
alytic functions using titanium and its variations on
enameled ceramic surfaces, is the self-cleaning such
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