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Tabl
G.A. Rosales , T. Poirier1, J.P. Cosp2, J. Lira-Olivares1, J.B. Carda Castell3

High-Performance
Ceramics
Composition Modifications
on the Properties of Some
Bioactive Glasses and
Glass Ceramics
Titanium Nitride Coating
of Cobalt Chromium
Coronary Stents:
a SEM-EDS Analysis
Ceramic Based
Bio-Medical Implants
Preparation of Ca-_/`Sialon Powders by Microwave Reaction Nitridation
Ceramic Bricks Filling

Energy Saving
Development of Iron Oxide-Rich Frits and

Glazes for Application on Ceramic Tiles
Com
Building Materials
Effect of Bi2O3 on Cordierite Formation in Cordierite Based Bodies
TILE & BRICK
The Use of Residues in

the Manufacture of
Ceramic Tile Bodies
Hot-Pressed Gres
Porcellanato Body
Effect of Calcite on the
Brick Body Closing
Glossiness and Slipperiness of Polished Porcelain
Stoneware Tiles
Effect of Diaspore Addition
on Microwave-Assisted
Sintering of Floor Tile
U1_U4_IC_2_10.indd 2
Tile surface
Polished Porcelain
Stoneware Tiles
12.04.10 13:54
The authors
Gustavo A. Rosales-Sosa earned a Materials Engineering

degree at Simon Bolivar University of Caracas in 2008,
and is completing his MSc degree through collaboration
between his university and Jaume I University in the field
of glass and glass-ceramics for the tile industry. He is a
member of the Center for Surface Engineering at Universidad Simn Bolivar in Caracas since 2007 where he does
research in the field of wear and failure analysis.
The main author, Juan B. Carda Castell, earned a PhD in

Chemistry and became Full Professor at Jaume I University of Castelln in 1993. He is Cathedratic in Inorganic
Chemistry in the Department of Inorganic and Organic
Chemistry and co-founder of the Solid State Chemistry
Group, where he pursues his research interests. The focus of his extensive research activities and studies is on
new properties and applications of ceramic materials. He
has authored more than 150 articles in national and international Journals,
more than 400 scientific national and international contributions, and multiple books in the field of chemistry and materials.
Thierry Poirier earned a PhD in Ceramic Materials and

Surface Treatment and became Full Professor at Simon
Bolivar University of Caracas in 2000. He is a member of
the Surface Engineering Group in the Materials Science
Department, where he pursues his research interests in
ceramic processing, glass-ceramics and thermal spraying. He has authored 20 articles in national and international Journals, and contributed to 40 conferences and
meetings.
Joaqun Lira-Olivares, Emeritus Professor at Universidad

Simn Bolvar in Caracas (Venezuela), is director of the
Center for Surface Engineering at the same university.
He has published more than 100 articles in indexed journals and proceedings and has participated in the development of materials science books. His contributions to
Science and Technology in the last thirty years have concentrated on surface science, wear, coatings design and
characterization. His recent invited publications are Testing of coatings
for ASM (2001) and Designing a Surface for Endurance: Coatings Deposition Technologies in the Handbook of Metallurgical Process Design, Marcel
Dekker Inc. (2004).
Abstract
Keywords
In this study, different frit compositions were prepared in the SiO2CaOFe2O3 system. The amounts of Fe2O3 were varied between 10 mass-% and 40 mass-%. The frits were melted and characterized using several different techniques in order to study
the crystalline composition of the frits and glazes and assess their suitability for tile production processes. The characterization of the frits revealed the presence of multiple iron oxide forms. Finally, in order to confirm appropriate glaze maturity,
glaze slips were prepared and applied to tile bases. The final glazes displayed a glass-ceramic character and good adaptability
to the tile bases with defect-free surfaces. It is important to note that thermal kinetics affects the final properties of glazes.
These glazes could be optimized in the future for development of semiconducting glaze compositions for use in anti-static
coatings or radiation shielding.
1 Introduction
Glass-ceramic glazes for floor and wall tiles
have been of great importance to the ceramic industry thanks to the advantageous
properties they offer, such as high chemical
and wear resistance, fracture toughness, and
ability to adapt to polishing. Their technical
and aesthetic attributes generally tend to
exceed those of their glassy counterparts
[13]. Numerous properties have been de-
Department of Materials Science, Simon Bolivar University, Caracas, Venezuela.

Contact: gustavorosales@gmail.com
2
Department of Civil Engineering, Materials and Manufacturing, Malaga University, Malaga, Spain
3
Department of Organic and Inorganic Chemistry,
Jaume I University, Castelln, Spain
48-52_TB_Rosales_Sosa.indd 48
veloped by modifying their chemical components and microstructure through nucleation and growth of crystals in the glass. Examples of innovation in frit and glaze production include Joule-effect heating and
characteristics such as bactericidal, anti-slip
and anti-static properties [45]. In particular, iron rich compositions have been used
due to their aesthetic and technical properties. In numerous studies the SiO2CaO
Fe2O3 chemical system has demonstrated its
capacity to vitrify and to crystallize phases
in subsequent heat treatments. Among the
most interesting properties obtained using
these systems are ferrimagnetism and semiconduction, products of the crystallization
of magnetic phases, with medical and technological applications [610]. It is well
glass-ceramics, glazes,
frits, iron-oxide, tiles
Interceram 60 (2011) [1]
known that electrical conduction of glasses

rich in iron oxide and in crystalline phases
such as magnetite is due to the simultaneous presence of Fe+2 and Fe+3 valences and a
mechanism known as polaron hopping or
low mobility semiconduction [11]. Moreover, heat generation in iron-rich glass-ceramics with ferrimagnetic phases can be obtained by hysteresis loss in an alternating
magnetic field [89]. This phenomenon
may enable anti-static and/or heat-emitting
glazes to be manufactured in the future.
Furthermore, these glass-ceramics can be
used as aggregate in concrete to absorb
high-intensity electromagnetic waves [12].
The main objective of the present work is to
study the feasibility of developing iron oxide-rich frits and glazes for floor tiles when
27.01.11 18:43
subjec
the S
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[10].
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k is to
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Interceram 01/2011
INTERCERAM 59 (2010) No. 2 pp. 79166
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Table 1 Industrial raw materials used for the frits

Components
SiO2
Purity
99.0%
Table 2 Frits: chemical compositions in mass-%

High-Performance
Ceramics
Size distribution
35% residue, 40 mm sieve
CaCO3
99.2%
512 mm
Fe2O3
95.0%
0.30% residue, 44 mm sieve
Glass Ceramics
of Cobalt Chromium
Coronary Stents:
a SEM-EDS Analysis
Ceramic Based

Energy Saving
Sample
SiO2
CaO
Fe2O3
55
35
10
30
20
Building Materials
50
45
40
TILE & BRICK

the Manufacture of
Ceramic Tile Bodies
Hot-Pressed Gres
Porcellanato Body
Brick Body Closing
Stoneware Tiles
25
Tile surface
20
subjected to industrial firing processes in

the SiO2CaOFe2O3 system. Our studies
have focused on the formation of glass frits
with the purpose of understanding crystallization during subsequent heat treatments.
It should be noted that the heating kinetics
of a laboratory kiln differ greatly from an
industrial-scale kiln, which may have an effect on nucleation and crystallization in
glazes, thereby reducing the degree of crystallization in certain cases [13]. The use of
TiO2 as a nucleating agent in the SiO2CaO
Fe2O3 system has also been studied, but has
not been found to have a significant effect
on the kinetics of the devitrifying process
[10]. For the achievement of this objective,
the following tasks were performed:
Development of frits in the SiO2CaO
Fe2O3 chemical system,
Study and characterization of the frits,
Development of glass-ceramic glazes from
the frits, as well as study and characterization of these glass-ceramics materials.
2 Experimental
2.1 Synthesis of the frits
Based on previous studies, different compositions were proposed in order to study the
effect of Fe2O3 content on the final properties of frits and glazes [89]. The amount of
Fe2O3 in the composition was incremented
from 10 to 40 mass-%. Tables 1 and 2 list
the raw materials and theoretical compo
sitions studied. Industrially available raw
materials were used. The frits were produced
in a natural gas-fired industrial testing kiln
at a maximum temperature of 1450C for
2 hours before being quenched in water.
2.2 Development and application of
glass-ceramic glazes
The glass-ceramic glazes were obtained by
mixing frits ground to an average size of
10m with carboxymethylcelullose (CMC),
sodium tripolyphosphate (STPP), kaolin,
and sufficient water to generate a glaze slip
of 1.73 g/cm3 density. The glaze was applied
onto the porcelain stoneware body and then
fired in a porcelain tile thermal cycle. The
glazes were subjected to heat treatment at
1200C, common for porcelain tile, in an
industrial furnace.
Polished Porcelain
Stoneware Tiles
30
40
12.04.10 13:54
Table 3 Frits: experimental chemical composition in mass-% determined by XRF

Sample
SiO2
CaO
Fe2O3
Al2O3
Na2O
MgO
K2O
52.70
31.00
8.10
3.20
0.20
0.40
0.50
49.30
27.40
19.00
2.10
0.90
0.10
0.10
44.80
24.00
23.60
4.00
0.10
0.20
0.30
39.20
19.00
33.50
5.10
<0.05
0.10
0.20
2.3 Characterization of frits and glazes

For detailed characterization of the materials developed in our laboratory work, the
following instrumental techniques were
used:
Chemical composition of as-quenched
frits was determined by X-ray Florescence
(XRF) in a Bruker AXS S4 Pioneer XRF
spectrometer.
In order to assess phase identification in
the frits and glazes, X-ray Diffraction
(XRD) patterns were produced (via a
Bruker AXS D4 ENDEAVOR diffractometer) with Cu-Ka radiation in the range of
2q from 10 to 70 at an intensity of 20 mA
and a voltage of 40 kV.
Surface chemical nature of frits was determined by X-ray Photo-Electron Spectroscopy (Physical Electronics ESCA 5701
system).
Crystalline character of frits was studied
by Transmission Electron Microscopy
(Philips CM-100 Microscope).
Microstructure and elemental analysis of
frits and glazes were measured with Scanning Electron Microscopy (LEO 440i
SEM) and Energy Dispersive Spectroscopy (Oxford Link ISIS was used for the
EDS micro-analysis unit), respectively.
Glass characteristic temperatures of frits
were determined using differential dilato
metry (Bahr Thermo-analyze DIL80IL)
using a heating rate of 5C/min from
25C to 1250C for each sample. The experimental dilatometric coefficients were
compared with calculated values using
Appens formula [14].
Hot stage microscopy (Misura 3.32 hot
stage microscope) was used to measure the
glaze characteristic temperatures using a
thermal cycle between 600C and 1400C,
at a heating rate of 20C per minute.
3 Results and discussion

3.1 Frit characterization
3.1.1 Chemical analysis
Table 3 shows the XRF chemical analysis on
the frits. Significant deviation is observed
from the theoretical composition values for
all frits due to preferential introduction of
Al2O3, possibly from the melting crucibles.
The increasing content of alumina with increasing proportion of Fe2O3 in the composition suggests a higher reactivity of ironrich melts. This is indicative of the corrosive
nature of these chemical systems at high
temperatures. Furthermore, one can also see
that the SiO2/CaO ratio remains approximately within the pseudo-wollastonite
range ( 12).
3.1.2 Crystallinity of frits
The XRD diffractograms of frits A, B, C and
D revealed an amorphous nature. However,
composition D displays small peaks of crystallinity that are possibly associated with
magnetite, according to the results of the
diffraction tests [15]. In the SEM studies
(Fig. 1), composition D clearly reveals the
presence of crystalline phases with a dendrite structure typical of magnetite in iron
oxide-rich glass where crystallization forms
these structures during cooling. Sample C,
similar to A and B, appeared to display a
glassy nature because of surface homogeneity. The EDS patterns revealed homogenous
patterns that were similar in each of the experimental compositions. Generally, magnetite crystallization during cooling in these
glasses is enhanced when iron immiscibility
occurs in the melt. This causes the precipitation of iron-based crystalline phase nuclei
with dendrite morphologies, typical of
strong undercooling [16]. Preliminary TEM
tests, not presented in this paper, indicated a
27.01.11 18:43
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IPB 2009, China
Ceramics Forum

EU Today a Survey
High-Performance
Ceramics
Glass Ceramics
of Cobalt Chromium
Coronary Stents:
a SEM-EDS Analysis
Ceramic Based

Energy Saving
Building Materials
TILE & BRICK

the Manufacture of
Ceramic Tile Bodies
Hot-Pressed Gres
Porcellanato Body
Brick Body Closing
Stoneware Tiles
Tile surface
Polished Porcelain
Stoneware Tiles
12.04.10 13:54
Fig. 1 SEM images of frits C and D, in the back-scattered electron mode and EDS patterns
Fig. 2 TEM imaging, EDS patterns and electron diffraction patterns for the frits being studied
predominantly amorphous glass with a similar composition to the formulated compositions. However, a semi-crystalline character was detected in several frits particles. As
seen in the TEM images (Fig. 2), the material is predominantly amorphous, although
in samples A, B and D, a slightly crystalline
character is present in the ring electron diffraction patterns. EDS chemical analysis of
samples A and B revealed a high percentage
of Al and O, which could be associated with
the presence of alumina from the melting
crucibles. Furthermore, in samples C and D
(which are richer in Fe2O3), small crystals,

possibly magnetite, can be observed, though
the crystalline nature of C is not as visible as
in samples A, B and D. The presence of magnetite is suggested by the high iron content
of samples C and D in the EDS analysis and
the difference in the ring patterns compared
to samples A and B.
3.1.3 Surface characterization of the frits
XPS is a surface spectroscopy technique that
enables one to determine how the atoms in
the surface are bonded together, providing
additional data for the study of crystallinity

in this type of glass. Generally, iron ions at
the surface in glass are sensitive to the atmosphere and tend to oxidize in the presence of high temperature and oxygen. The
deconvolutions of the Fe2p3/2 XPS spectrum
for the three compositions (Fig. 3) shows
that all of them, except B (which also contains Fe0), display:
Fe+2, which corresponds to 709.6 eV, characteristic of FeO;
possibly Fe+3, corresponding to 711711.2
eV, in a state affected by the coordination
environment;
Fe2O3 and Fe3O4 (Fe+3 in Fe2O3/Fe3O4
environment), which corresponds to
715.03 eV.
The FeO is indicated by lines 707 eV and
720.1 eV, characteristic of metal iron [17].
One of the most significant observations in
this spectrum is the possible presence of Fe,
FeO, Fe2O3 and Fe3O4 surface crystalline
phases, which generally induce crystallization in iron oxide-rich glasses. Although the
XRD spectra do not reveal the presence of
such crystal phases, the results of the TEM,
electron diffraction and XPS tests all appear
to confirm their presence, albeit incipient, in
the initial frits. This would confirm that,
even with low Fe2O3 content and high
quenching speeds, the crystallization of iron
oxides is inevitable. This has been verified by
Kamaranov et al. [15]. Recent results in this
system suggest a strong tendency of Fe2O3 to
crystallize in the quenched glasses and in the
glazes with decreasing melting temperature
and time, due in part to incomplete dissolution of iron oxide in the glass matrix at low
temperature (1350C). This could be explained in terms of the oxidation state of the
iron ions. Above 1350C, Fe+3 tends to reduce to Fe+2 and form magnetite [9].
3.1.4 Dilatometry and hot stage microscopy
testing of the frits
Table 4 provides a summary of the dilatometric properties of the glasses. The table
shows that in samples A and B, transition
temperature Tg tends to decrease as Fe3 is increased. This is understandable bearing in
mind that in silicate glasses, the Fe+3 is generally inserted into the glass partly in octahedral coordination (modifying oxide),
which reduces glass refractoriness. However,
at 30 mass-% Fe2O3, refractoriness increases,
which does not match the trend observed in
samples A and B. The possible presence of
crystalline phases in C and D may delay the
glass transformation. This same phenomenon is observed with the glass softening
temperature. On the other hand, the linear
dilatometric coefficients measured between
27.01.11 18:43
Fig. 3
Fig. 4
were n
50 to
and li
and 7
values
glazes
the co
therm
betwe
shoul
values
and d
and D
ably h
therm
ence o
ously
show
point
Tabl
linea
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llinity
ons at
he atpresn. The
ctrum
shows
o con-
Ceramics Forum
EU Today a Survey
High-Performance
Ceramics
Glass Ceramics
of Cobalt Chromium
Coronary Stents:
a SEM-EDS Analysis
Ceramic Based

Energy Saving
Building Materials
TILE & BRICK

the Manufacture of
Ceramic Tile Bodies
Hot-Pressed Gres
Porcellanato Body
Brick Body Closing
Stoneware Tiles
Tile surface
Polished Porcelain
Stoneware Tiles
12.04.10 13:54
char-
711.2
nation
Fe3O4
ds to
V and
[17].
ons in
of Fe,
talline
allizagh the
nce of
TEM,
ppear
ent, in
that,
high
f iron
ied by
n this
2O3 to
in the
rature
ssoluat low
be exof the
to re-
opy
dilatotable
sition
is inng in
s genoctaxide),
wever,
eases,
ved in
nce of
ay the
nomeening
linear
tween
Fig. 3 Deconvolution of Fe2p3/2 XPS spectra for compositions A, B and D
Fig. 4 Sintering (S), softening (A), and melting (F) points for samples A, B and D determined by hot stage microscopy; half-sphere (ME) and sphere (E) points
were not calculated as they could not be observed
50 to 300C and 50 to 500C are similar

and lie in the ranges of 73.6 85.6 107 K1
and 77.887.4 107 K1, respectively. These
values are generally high for use in porcelain
glazes (70 107 K1); however, in the future
the composition could be altered to reduce
thermal expansion and thus prevent stresses
between the glaze and the base material. It
should be noted that the theoretical Appen
values were similar in compositions A and B
and differed significantly in compositions C
and D, where the crystal content is presumably higher. Similar variations in theoretical
thermal expansion coefficients in the presence of crystalline phases have been previously reported [18]. Sintering curves (Fig. 4)
show the softening, melting and sintering
points observed by hot stage microscopy for
frits A, B and D. In all compositions, melting

occurs at approximately 1200C. Sintering
is achieved at approximately 850C in all
compositions, although it is later in sample
D, with a sintering point of nearly 900C, as
a result of the crystallinity of the sample.
The significant expansion noted in A and B
(also observed in C) at around 1150C is
due to presumed reduction of Fe2O3 type
iron oxides nucleated during heat treatment
and release of O2 in the frit. In glass D, no
such expansion is observed at 1150C,
which may be due to a low Fe+2 concentration, which may have combined with the
magnetite or strongly bonded to the glassy
network, restricting the formation of Fe2O3.
It should be noted that in iron oxide-rich
glasses, the Fe+2 ions tend to oxidize superfi-
cially and switch to an Fe3+ state, which may

be the cause of the effects observed in samples A, B and C. Laboratory examination revealed the presence of surface pinholes in
samples A, B and C, which is in line with the
observed results.
3.2 Characterization of the glazes
3.2.1 XRD crystalline study of the glazes
As can be seen from the Fig. 5, the glazes are
able to develop a glass-ceramic character
after being subjected to industrial firing
cycles. According to the XRD patterns, the
crystalline phase in sample A is parawollastonite; however, the more stable phase according to the SiO2-CaO-Fe2O3 phase diagram was pseudowollastonite. Moreover, in
glaze B, no crystalline phases can be ob-
Table 4 Frits characteristic points: Ta dilatometric softening temperature, Tg glass transition temperature, experimental
linear dilatometric coefficients* and Appen formula coefficients**
*a / 107 K1
Characteristic points
**a / 107 K1
Sample
Tg /C
Ta /C
50300C
300500C
20400C
713
787
78.2
79.7
72.8
657
1044
73.6
77.8
73.0
791
1121
72.1
79.7
58.5
742
1090
85.6
87.4
63.9
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High-Performance
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Glass Ceramics
of Cobalt Chromium
Coronary Stents:
a SEM-EDS Analysis
Ceramic Based

Energy Saving
Building Materials
TILE & BRICK

the Manufacture of
Ceramic Tile Bodies
Hot-Pressed Gres
Porcellanato Body
Brick Body Closing
Stoneware Tiles
Tile surface
Polished Porcelain
Stoneware Tiles
12.04.10 13:54
Fig. 5 XRD surface spectra of the glass-ceramic glazes obtained on porcelain
Fig. 6 Back-scattered electron SEM imaging and EDS spectra of the surface
stoneware; Parawollastonite (CaSiO3) 760925, Cristobalite (SiO2) 790940,
and cross-section for glazes A and D
Hematite (Fe2O3) 79094.
served, which would seem to indicate that the

increase in the quantity of Fe2O3 prevents
crystallization of the pseudowollastonite in
the firing cycle. Finally, in glazes C and D, the
presence of hematite is observed as the predominant phase. This concurs with the predictions of the phase diagram and with the
fact that in iron oxide-rich glass powders, the
predominant surface phase is hematite when
heating is carried out in air [1415].
3.2.2 SEM study of the resulting glazes
The surfaces and cross-sections of glazes A
and D may be observed in Fig. 6. The SEM
images for glazes B and C indicated surface
properties similar to those of A and D,
respectively, and were therefore omitted.
Pseudowollastonite crystals were not observed in the surface with back-scattered
electron scanning on glaze A. However, the
crystals may merge with the substrate due
to their compositional similarity with the
glass, bearing in mind that the iron content
is low (see EDS spectrum). The cross-section of sample A exhibits good bonding
with the engobe and the substrate, showing
no closed porosity, chipping or cracking. In
sample D, numerous Fe2O3 crystals are observed in the XRD and EDS spectra. As in
glaze A, the cross section of composition D
appears free of defects. The absence of pinholes or defects in D, which was to be expected in view of the sintering curves obtained by hot stage microscopy, indicates
that the high speed of the firing cycles
could delay the reduction of hematite and
thus prevent surface defects. Furthermore,
it is important to note that these industrial
firing cycles were carried out at a heating
rate of approximately 150C/min, which
prevents hematite decomposition in the

frits, as observed in the hot stage micros
copy curves taken at 20C/min. Crystalline
phase-rich glazes could exhibit higher fracture toughness. These glazes open up new
prospects for the future development of
iron oxide-based glazes with useful technical attributes.
Acknowledgments
The authors wish to express their gratitude
for the help and support provided by the
staff of Servei Central dInstrumentaci
Cientfica of Universitt Jaume I of Castelln and to the staff of the Centro de Ingeniera de Superficies at Universidad Simn
Bolvar in Caracas (Venezuela), as well as to
all the staff of quimiCer S.A and Colorobbia
S.A, who have participated in the development of this study, without explicitly appearing as authors of this paper.
References
[1] Tichell, M., Fontanet, E., Pascual, A., Bakalii, J.,
Monrs, G., Escribano, P., Carda, J.B.: Estudio del
desarrollo de aplicacin de esmaltes de naturaleza
vitrocristalina en orden a mejorar las propiedades
tecnolgicas de los esmaltes convencionales. Qualicer 1996, Conference Proceedings, 209238
[2] Quinteiro, E., Ortega Boschi, A., Leonelli, C., Manfredini, T., Siligardi, C.: Sistemas vitrocermicos
compatibles con las condiciones de coccin utilizadas en la industria cermica. Qualicer 2002, Conference Proceedings, 301311
[3] Martinez, J., Ario, M., Marinova, I.T., Peir, M.C.,
Nuez, I., Carda, J.B.: Desarrollo de nuevos esmaltes para soportes de gres y gres porcelnico
adaptado a los procesos de pulido y que representan buenas prestaciones tcnicas y estticas, Qualicer 2004, Conference Proceedings, 137152
[4] Nuez, J., Pedra, J.M., Peir, M.C., Gmez, J.J.,
Chiva, L., Carda, J.B.: Investigaciones de inters industrial sobre baldosas cermicas. Cermica Industria 252 (2002) 2635
[5] Snchez-Muoz, L., Marinova, I.T., De la Fuente,

G., Nez, I., Rodrguez, M.A., Sanz, J., Carda, J.B.:
I+D+I para las baldosas cermicas del siglo XXI:
competencia, diversidad y funcionalidad. Qualicer
2010, Conference Proceedings
[6] ES-Pat. 2 161 193 A1 (2001)
[7] ES-Pat. 2 161 193 B1 (2002)
[8] Ebisawa, Y., Sugimoto, Y., Hayashi, T., Kokubo, T.,
Ohura, K., Yamamuro, T.: Crystallization of (FeO,
Fe2O3)CaOSiO2 glasses and magnetic properties
of their crystallized products. Nippon Seramikkusu
Kyokai Gakujutsu Rombunshi 99 (1991) [1] 713
[9] Yong-Keun, L., Se-Young, C.: Crystallization and
properties of Fe2O3CaOSiO2 glasses.Journal of the
American Ceramic Society 79 [4] (1995) 992996
[10] Poirier, T., Labrador, N., Alvarez, M.A., Lavelle, C.,
Enet, N., Lira-Olivares, J.: Formation of crystalline
phases in (SiO2CaOFe2O3)TiO2 based glasses.
Materials Letters 59 (2005) 308312
[11] Moulson, A.J., Herbet, J.M.: Electroceramics, 2nd
edition. Wiley, New York (2003), 452
[12] Francis, A.A.: Crystallization kinetics of magnetic
glass-ceramics prepared by the processing of
waste materials. Materials Research Bulletin 41
(2006) 11461154
[13] Froberg, L., Kronberg, T., Huppa, L., Huppa, M.: Influence of firing parameters on phase composition
of raw glazes. Journal of the European Ceramic Society 27 (2007) 16711675
[14] Bou, E., Gazulla, M.F., Orts, M.J., Sanchez, E.,
Sanz, V., Viciano, F.: Manual para el control de
calidad de materias primas empleadas en la preparacin de los vidriados cermicos, 1st edition.
Instituto de Tecnologia Ceramica ITC (2000), 319
pages
[15] Kamaranov, A., Pelino, M.: Crystallization phenomena in iron-rich glasses. Journal of Non-Crystalline
Solids 281 (2001) 139151
[16] Karamanov, A., Pisciella, P., Pelino, M.: The crystallisation kinetics of iron rich glass in different atmospheres. Journal of the European Ceramic Society 20 (2000) 22332237
[17] Mekki, A., Holland, D., Mcconville, C.F., Salim, M.:
An XPS study of iron sodium silicate glass surfaces.
Journal of Non-Crystalline Solids 208 (1996) 267
276
[18] Rasteiro, M.G., Gassman, T., Santos, R., Antunes,
E.: Crystalline phase characterization of glass-ceramic glazes. Ceramics International 33 (2007)
345354.
Received: 28.05.2010
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0210 APRIL VOL.

Including Special TILE & BRICK

Tile & Brick

Trade Fairs &

G.A. Rosales , T. Poirier1, J.P. Cosp2, J. Lira-Olivares1, J.B. Carda Castell3

Ceramic Bricks Filling

Development of Iron Oxide-Rich Frits and

Effect of Bi2O3 on Cordierite Formation in Cordierite Based Bodies

TILE & BRICK

The Use of Residues in

Gustavo A. Rosales-Sosa earned a Materials Engineering

The main author, Juan B. Carda Castell, earned a PhD in

Thierry Poirier earned a PhD in Ceramic Materials and

Joaqun Lira-Olivares, Emeritus Professor at Universidad

Department of Materials Science, Simon Bolivar University, Caracas, Venezuela.

known that electrical conduction of glasses

INTERCERAM 59 (2010) No. 2 pp. 79166

0210 APRIL VOL. 59

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Table 1 Industrial raw materials used for the frits

Table 2 Frits: chemical compositions in mass-%

0.30% residue, 44 mm sieve

Ceramic Bricks Filling

Effect of Bi2O3 on Cordierite Formation in Cordierite Based Bodies

TILE & BRICK

subjected to industrial firing processes in

Table 3 Frits: experimental chemical composition in mass-% determined by XRF

2.3 Characterization of frits and glazes

3 Results and discussion

0210 APRIL VOL. 59

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The Glass Industry in the

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(which are richer in Fe2O3), small crystals,

additional data for the study of crystallinity

0210 APRIL VOL. 59

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Fig. 3 Deconvolution of Fe2p3/2 XPS spectra for compositions A, B and D

50 to 300C and 50 to 500C are similar

frits A, B and D. In all compositions, melting

cially and switch to an Fe3+ state, which may

0210 APRIL VOL. 59

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Fig. 5 XRD surface spectra of the glass-ceramic glazes obtained on porcelain

stoneware; Parawollastonite (CaSiO3) 760925, Cristobalite (SiO2) 790940,

and cross-section for glazes A and D

Hematite (Fe2O3) 79094.

served, which would seem to indicate that the