Chemical Engineering Journal 171 (2011) 1178–1184

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Chemical Engineering Journal

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Cr-doped perovskite and rutile pigments derived from industrial by-products

W. Hajjaji a,∗ , C. Zanelli b , M.P. Seabra a , M. Dondi b , J.A. Labrincha a
a
Ceramics and Glass Engineering Department, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
b
Istituto di Scienza e Tecnologia dei Materiali Ceramici, CNR-ISTEC, 48018 Faenza, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In order to enhance the use of environment-friendly materials and to stimulate waste recycling, this work
Received 20 January 2011 has developed brown-maroon inorganic pigments belonging to rutile (TiO2 ) and perovskite (CaTiO3 )
Received in revised form 13 April 2011 structures. They were obtained by solid state reaction of industrial residues mixtures: tionite (i.e. insol-
Accepted 9 May 2011
uble residue of titania slag processing), Cr/Ni plating sludge and marble cutting/sawing sludge, for sake
of comparison, analogous formulations were prepared by using reagent-grade precursors. Chromium-
Keywords:
doped (0.04 mole of Cr2 O3 ) perovskite and rutile pigments were obtained at 1200 ◦ C and their phase
Sludges
composition, microstructure, optical properties and technological behaviour were characterized by XRD,
Pigments
Chromium doping
SEM, DRS and application in glazes, respectively. The presence of impurities (e.g. Fe, Ni, Al, Si) in the wastes
Perovskite induced the crystallization of secondary phases, like wollastonite (CaSiO3 ) and titanite (CaTiSiO5 ), whose
Rutile occurrence slightly shaded off the final colouration of the waste-based pigments; a further addition of
chromium is required to improve their colouring power in transparent glazes. The diffuse reflectance
spectroscopy shows that the colour development, in both structures, is due to the partial substitution of
titanium by chromium in octahedral coordination.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Incorporated in glazes for wall and floor tiles or in unglazed
porcelain stoneware, the ceramic pigments market is growing with
the huge production of ceramic products. As brown pigments,
the most used are based on hematite (DCMA 3-06-7) manganese
chrome antimony rutile (DCMA 11-46-7) and spinels (DCMA 13-
33-7, DCMA 13-37-7, DCMA 13-38-9, DCMA N. 13-48-7, DCMA
N. 13-51-7) [1,2]. The last two incorporate some toxic elements
(Co, Ni, Cr, Nb, . . .) that could be minimized or simply avoided by
investigation of new formulations, involving also technological and
economic concerns.
The use of industrial wastes as raw materials for the formula-
tion of brownish ceramic pigments based on titania is assessed with
the aim to improve the environmental sustainability of pigment
production by recycling hazardous residues. Such investigation is
within a research programme on waste-based ceramic colourants
[3] that already concerned the following structures: spinel [4,5],
malayaite-titanite [6,7], and hibonite [8,9]. It follows a general
interest in the literature on the valorization of heavy-metal bearing
residues into high added value products [10–14].
In the ceramic industry, brown pigments are mainly spinels
[15], but also rutile [16], perovskite [17], and pseudobrookite [18]
∗ Corresponding author. Tel.: +351 234370250; fax: +351 234370204.
E-mail address: w.hajjaji@ua.pt (W. Hajjaji).
can be utilized. Among Ti-bearing phases, rutile, TiO2 , and per-
ovskite, CaTiO3 , are promising structures which exhibit a brownish
colouration by doping with chromium, that can be tuned by further
addition of a counterion (W, Mo, Sb, Nb) to maintain the electrical
charge balance [19].
The perovskite structure, with the general formula ABO3 , is
built by a network of corner-linked BO6 octahedra and encloses
large cavities that accommodate the A-cations [20,21]. For tita-
nium dioxide, different polymorphs are found in nature: brookite
(orthorhombic symmetry), rutile and anatase (tetragonal symme-
try) [22,23]. The rutile structure is based on six oxygen atoms
surrounding each Ti ion, then forming tetragonally distorted TiO6
octahedra [23,24]. In this work, both perovskite and rutile struc-
tures are explored as inorganic pigments, using industrial wastes
as raw materials (or reagent-grade precursors as control), by inves-
tigating their structural and chromatic development as well as their
colouring behaviour in ceramic glazes.
2. Experimental procedure
Calcite (Calcitec), chromium (III) oxide (Riedel-de Haën), and
titanium dioxide (Kronos) were the reagent-grade precursors used
to prepare Cr-doped perovskite (PP) and rutile (PR) pigments. The
Cr2 O3 /TiO2 molar ratio was fixed equal to 0.04 (Table 1). The
pigments synthesis followed a conventional ceramic route. The
mixture of precursors was homogenized by ball milling (60 min),
dried at 100 ◦ C (24 h) then calcined in an electric kiln (Termolab) at

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.05.021
 W. Hajjaji et al. / Chemical Engineering Journal 171 (2011) 1178–1184 1179

Table 1
Chemical composition of precursors and batch formulations of pigments.

Reagents Calcite Cr(III) nitrate Rutile M G T

Providers Calcitec Sigma–Aldrich Knoros Marble sludge Galvanizing sludge Tionite sludge
Chemical composition (wt.%)
SiO2 0.18 – – 1.12 0.20 28.19
TiO2 0.02 – 99.93 0.04 0.02 45.59
Al2 O3 0.18 – – 0.25 0.14 3.44
Cr2 O3 – 99.00 – – 20.60 0.05
Fe2 O3 0.12 – 0.03 0.42 0.36 2.05
MgO 0.36 – 0.54 0.38 2,18
CaO 99.11 – – 97.44 14.92 3.32
MnO – – – – – 0.39
NiO – – – – 29.71 –
CuO – – – – 17.97 0.01
Na2 O 0.02 – – – 1.29 –
K2 O 0.02 – – 0.19 0.04 0.40
SO3 – – 0.02 – 2.71 14.38
P2 O5 – – 0.02 – 11.66 –
Batch composition (wt.%)
PP 55.6 1.7 42.7 – – –
SP – – – 40.7 4.3 55.0
SP2 – – – 40.1 6.4 53.5
PR – 3.8 96.2 – – –
SR – – – 7.2 92.8
SR2 – – – – 7.3 92.7
T1200 – – – – – 100

the maximum temperature of 1200 ◦ C (5 ◦ C/min heating rate and
3 h dwell time). The fired powders were manually ground and their
particle size distribution was determined by a Laser Coulter LS230
granulometer. Analogous formulations (SP and SR) were replicated
by using industrial wastes: (i) marble sawing sludge, (ii) Cr/Ni gal-
vanizing sludge and (iii) tionite, whose compositions are reported
in Table 1. In favour of comparison, the last sludge (tionite), under
the code T1200, was also calcined separately following the same
cycle.
The pigments were characterized by quantitative phase anal-
ysis (XRPD, D8 ADVANCE, fast detector LynkEye Bruker AXS,
Germany) under the following conditions: CuK␣ radiation in the
10–80◦ 2 range, scan rate 0.02◦ 2, 185 s equivalent per step.
The quantitative phase analysis was performed using GSAS-EXPGUI
software following RIR (Reference Intensity Ratio) and Rietveld
refinement techniques [25–27]. Each X-ray powder diffraction
pattern consists of approximately 5500 data points and 400
reflections. Up to 40 independent variables were refined: phase
fractions, zero point, 15–20 coefficients of the shifted Chebyschev
function to fit the background, unit cell parameters, profile coef-
ficients (one Gaussian, Gw, and one Lorentzian term, Lx). The
agreement patterns, as defined in GSAS, were found in the fol-
lowing ranges: 9.0% < Rp < 13.0%, 13.0% < Rwp < 16.5%, 6.0 < 2 < 11.0,
and 11.0% < R(F2) < 15.0%. The experimental uncertainty of phase
amount quantification is 5%.
A scanning electron microscope (SEM, Hitachi, SU 70) equipped
with XRF-EDS microprobe (Bruker AXS, software: Quantax) was
used to assess the microstructure and composition of pigment
particles. Inductively coupled plasma emission spectrophotome-
try (ICP) was carried out by a Horiba Jobin Yvon (Activa M model)
equipment to verify the chemical composition of pure obtained
pigments. The analytical solutions were obtained by microwave
assisted acid digestion. Their thermal behaviour was investigated
by DTA and TG simultaneous analyses (in air, 10 ◦ C min−1 heating
rate) performed on a Setaram apparatus.
The L*a*b* [L*: 0 = black/100 = white, green (−a*) to red (+a*)
and blue (−b*) to yellow (+b*)] chromatic parameters, measured
by a Konica-Minolta Chroma Meter CR-400 (D65 illuminant and
10◦ standard observer), were used to quantify the colour charac-
teristics of the pigments. The colouring mechanisms were studied
by UV–Vis–NIR absorption spectroscopy (Shimadzu UV-3100, step
interval 2 nm), using BaSO4 white as standard. These methods were
also applied to a lead-free transparent bright glaze (SiO2 , Al2 O3 ,
B2 O3 , CaO as main constituents >8%, 2–8% Na2 O, and <2% K2 O)
coloured with the perovskite or rutile pigment, which was added
to the glaze (1/20 weight ratio), homogenized and pelletized, then
fired at 1050 ◦ C (5 ◦ C/min heating and cooling rate and 30 min dwell
time).
3. Results and discussion
3.1. Pigment synthesis
Differences in the thermal behaviour between PP and SP are
detected at low-grade temperatures (<400 ◦ C). TG curves illustrate
a mass loss reaching 15% in waste based mixture related to dehy-
dration reactions. PP and SP show a large endothermic peak (Fig. 1),
at about 850 ◦ C, due to decarbonation of calcite in both the pure
reagent and the marble sawing sludge (25% weight loss in the TG
curves). Minor effects on the DTA curve are observed at temper-
atures higher than 1000 ◦ C, but no mass changes on the TG curve
were registered; they probably stem from the reaction of rutile with
calcium oxide to form perovskite [28]. These effects are less visible
in the SP formulation (Fig. 1). In the waste-based compositions, the
SO2 evolution was expected due to incomplete decomposition of
sulphates above 1200 ◦ C, as suggested by the weight loss registered
on TG. This reaction may be partially hidden by the exothermic
peak related to the perovskite formation (on DTA). The volatiliza-
tion of some sulphur oxide is not novel in the industrial practice,
because the pigment synthesis is usually promoted by mineralizers,
i.e. mostly alkaline and alkaline-earth halogenides and sulphates
[2,15], so that flue gas scrubbers are already in operation on kilns.
In the PR mixture, the total weight loss is less than 2% and it is
basically due to the release of physically adsorbed water. On the
DTA curve, the peaks occurring above 900 ◦ C are probably related
to the anatase-to-rutile transition, which allows the chromium
insertion into the lattice [29]. In contrast, the SR mixture under-
went to significant transformations upon heating, mostly caused
by decomposition of hydroxides (around 300 ◦ C) and sulphates
(around 1100 ◦ C) contained in the tionite sludge. The respective
weight loss measured up to 500 ◦ C reached about 15%; and is close
to 7% between 1000 and 1200 ◦ C.
1180 W. Hajjaji et al. / Chemical Engineering Journal 171 (2011) 1178–1184

triangle (Fig. 3) where further phases are stable. A similar phe-

nomenon contributed to the appearance of titanite (CaTiSiO5 ) in
the SR powder [30,35]. The presence of Fe in the Ti-rich sludge
is responsible for the formation of a pseudobrookite-like phase
(Fe,Mg)Ti2 O5 .
The morphology of pigments obtained from pure-grade
reagents is characterized by micrometric, rounded particles (Fig. 4).
The micrographs show that the Cr-doped rutile has a more uniform
particle aspect then the Cr-doped perovskite, since less thermal
energy (no endothermic decomposition) is required than in the per-
ovskite formation. The normalized EDS results are shown in Fig. 4;
some quantification discrepancies associated to the effect of light
elements, particularly when using powder samples (e.g. surface
irregularities) [35], required the correction of the atomic number of
oxygen (3 oxygens for perovskite and 2 oxygens for rutile). For both
compositions, a similar Cr2 O3 /TiO2 ratio was estimated (between
0.03 and 0.04) that is close to the expected value (0.04). Concerning
the same ratio, ICP analysis (Fig. 4) gave a slight difference of 0.01. It
was not possible to get a reliable crystallochemical composition of
sludge-based pigments because of their chemical complexity and
the occurrence of secondary phases, like wollastonite (CaSiO3 ) and
titanite (CaTiSiO5 ).
Fig. 5 shows the grain size distributions of the prepared pig-
ments; the mean particle size is between 1 ␮m and 20 ␮m, as
also supported by the morphological study (Fig. 4). The rutile pig-
ments are coarser (4.7–5.9 ␮m), and this is coherent with their
mentioned faster sintering rate. Since SEM micrographs (Fig. 4)
revealed a homogeneous grain size (especially in the PR pigment),
the measured fraction between 20 and 40 ␮m is likely to result
from particles agglomeration in the aqueous suspension used in the
granulometric analysis. The existence of fine (inferior to 1 ␮m) and
coarse particles (superior to 20 ␮m) could induce important varia-
tions in the final glaze colouration. The fines tend to dissolve in the
Fig. 1. Thermal behaviour (DTA/TG curves) upon heating of perovskite (top) and
glaze matrix, while the coarse particles create hue heterogeneities
rutile (bottom) dried mixtures: based on pure reagents (in black), and formulated
from wastes (in grey). [2]. Differences in grain size distribution between reagent-grade
and sludge-based pigments are small and less relevant than varia-
tions related to compositional changes (perovskite vs. rutile).
3.2. Microstructure and phase composition
3.3. Colour and technological properties
The pigments obtained from commercial reagents are
monophasic and the expected perovskite and rutile structures
Measured L*a*b* coordinates of pigments are given in Table 3.
were obtained, while the composition of pigments prepared from
Cr-doped perovskite prepared from pure reagents (PP) exhibits
sludges is complex (Fig. 2 and Table 2). Although the expected
a higher red chroma (a* = 4) than the pigment SP based on
perovskite (44 wt.%) and rutile (42 wt.%) phases are abundant in the
wastes. Moreover, PP is darker (i.e. lower L* value) implying a
SP and SR pigments, respectively, the presence of impurities in the
stronger colouring power. This is confirmed by the UV–Vis–NIR
sludges (see Table 1) led to the formation of secondary crystalline
spectra (Fig. 6) where SP exhibits an absorbance in the visible
phases. In SP, the occurrence of a high amount of silica in the tionite
range lower than PP. In both cases, the brownish colour results
sludge is responsible for the formation of calcium silicates as Wol-
from the combination of three bands in the visible range at
lastonite (CaSiO3 ), Melilite (Ca2 (Al,Mg,Fe)(Si,Al)2 O7 ) and larnite
about 450 nm (∼22,200 cm−1 ), 580 nm (∼17,200 cm−1 ) and 640 nm
(Ca2 SiO4 ), along with calcium sulphate. This denotes a competition
(∼15,600 cm−1 ). The first and the second band are attributable to
between TiO2 and SiO2 to react with CaO, as predicted by the phase
spin-allowed transitions of Cr3+ in octahedral coordination (d3 elec-
diagram of the CaO–TiO2 –SiO2 system [30–34]. The point of the
tronic configuration) from the 4 A2g ground state to the excited
SP formulation falls in the CaTiO3 –CaSiO3 –Ca2 SiO4 compatibility 4 T (F) and 4 T (F) states, respectively, which correspond to a crys-
2g 1g
tal field strength around 17,000 cm−1 and a Racah B parameter
Table 2 around 500 cm−1 [36]. The third band has an energy too low and an
Phase composition of pigments.
absorbance too high to account any Cr3+ transition; it might be due
(wt.%) PP SP PR SR to the occurrence of impurities or a minor amount of Ti3+ [37]. A
Perovskite 100 64.2 ± 0.3 – – similar behaviour was recognized in some other structures, namely
Melilite – 22.1 ± 0.2 – – titanite (CaTiSiO5 ) [7], malayaite (CaSnSiO5 ) [6,38] and corundum
Anhydrite – 7.7 ± 0.2 – – (Al2 O3 ) [39]. The electrical charge balance is likely to be ensured
Wollastonite – 4.2 ± 0.1 – – by anionic vacancies, e.g. 2Ti4+ → 2Cr3+ + O2− vacancy, which are
Larnite – 1.8 ± 0.1 – –
Rutile – – 100 44.3 ± 0.3
known to occur in perovskite systems [40,41].
Titanite – – – 26.1 ± 0.2 The use of wastes seems not to affect the mechanism
Pseudobrookite – – – 20.1 ± 0.2 responsible for the colour development of rutile and perovskite
Corundum – – – 8.6 ± 0.1 pigments, despite the compositional differences with reagent-
Cristobalite – – – 0.9 ± 0.1
grade precursors discussed before. Colorimetric coordinates of
 W. Hajjaji et al. / Chemical Engineering Journal 171 (2011) 1178–1184 1181

Fig. 2. XRD results observed (+), calculated (line) and difference (below) for pigments.

chromium-doped rutile pigments denote lower brightness (L*) and
red component (+a*), when compared with perovskite, even if the
resultant colour for both PR and SR pigments is a dark brown. The
brightness (L*) and yellow component (+b*) of the SR pigment are
approximately twice of the PR ones and a green component (−a*)
arises. In SR, the titanite, being present as the second major phase
(29 wt.%), is responsible for the strong deviation from the PR col-
orimetric values. In fact, chromium bearing titanite also develops
a brown colour, but its hue is less intense than that obtained now
for Cr-doped rutile [7].
The optical spectra of rutile-based formulations (Fig. 7) exhibit,
in the visible region, three bands at about 460 nm (∼21,700 cm−1 ),
590 nm (∼16,900 cm−1 ) and 680 nm (∼14,700 cm−1 ) which are
characteristic of Cr-doped rutile [19]. The first two bands are
due to the sixfold coordinated Cr3+ transitions 4 A2g → 4 T2g (F) and
4 A → 4 T (F) [7], leading to crystal field strength and a Racah
2g 1g
B parameter values that are slightly lower than in Cr-doped per-
ovskite (around 16,900 cm−1 and 460 cm−1 , respectively). As in the
case of perovskite, the occurrence of Cr3+ in substitution of Ti4+
implies a mismatch of the electrical charge of the rutile structure,
that is thought to be balanced through oxygen vacancies, already
known in the literature for doped rutile [42,43]. The UV–Vis–NIR
spectra denote relevant discrepancies between PR and SR pigments,
concerning the absorbance level, in the red region of the visible
range, as already observed and discussed for L*a*b* parameters.
The optical spectrum of the SR pigment is analogous to that of tion-
ite calcined at 1200 ◦ C (Fig. 7 and colour coordinates in Table 3);
this is not surprising since the tionite sludge represents ∼98 wt.%
of the SR pigment composition. Impurities, such as iron (∼3 wt.% in
the sludge), may justify the colour deviation, as the Fe-doped rutile
also develops a similar brown colouration [17].
When used to colour the transparent glaze, pink-brown or
orange-brown shades are obtained with perovskite and rutile,
respectively (Fig. 8). The mentioned colorimetric differences

Table 3
L*, a* and b* colorimetric values of pigments and transparent glazes.

Pigments Transparent glaze (G-)

L* a* b* L* a* b*

PP 48.3 4.4 9.3 48.3 5.9 13.7

SP 65.4 1.7 11.9 67.2 −0.9 12.8
PR 37.1 0.6 8.1 39.8 9.7 17.8
SR 62.7 −0.9 16.4 60.3 1.5 26.7
SP2 41.5 2.2 9.2 49.7 4.1 11.3
SR2 40.1 2.0 10.5 44.8 3.5 17.7
T1200 59.3 0.3 14.0 54.7 −0.5 22.3
Fig. 3. Representation of prepared mixtures in the CaO–SiO2 –TiO2 ternary diagram.
1182 W. Hajjaji et al. / Chemical Engineering Journal 171 (2011) 1178–1184
Fig. 4. SEM micrographs and EDS, ICP quantitative analyses of pigments prepared from pure-grade reagents (PP and PR).
Fig. 5. Particle size distribution of the pigments after calcination.
Fig. 6. Optical spectra of Cr-doped perovskite pigments.
between G-PP and G-PR are also easily noticed, especially in terms
of brown shade. The brightness shown by the glaze is rather stable
and close to that developed by the pigments, but red and yellow
components tend to increase in the coloured glaze. This improve-
ment is more significant when PR is used (see Table 3).
The use of waste-based pigments to colour of the transpar-
ent glaze results in distinct features. SP is stable in the glaze and
the changes on L*a*b* coordinates between the pigment and the
coloured glaze are small. However, the use of SR tends to increase
considerably the yellow component (+b*), as shown in Fig. 8 and
Table 3. This tendency is similar to that obtained with T1200. This
change is caused by both the presence of secondary phases in the SR
pigment, such as titanite and wollastonite, and the impurities pro-
vided by residues, especially Ni and Fe. At this stage, the secondary
phases present in SP and SR pigments apparently did not react with
the glaze, as suggested by the diffraction patterns of glazes (Fig. 9).
Similarities in the pattern’s framework of pure (GPP and GPR) and
waste based (GSP and GSR) products are noted. This is a good point
Fig. 7. Optical spectra of Cr-doped rutile pigments and of calcined tionite.
 W. Hajjaji et al. / Chemical Engineering Journal 171 (2011) 1178–1184
Fig. 8. Visual aspect of coloured transparent glazes.
in favour of the chemical stability of the pigments and their inert-
ness in the glaze. The same Fig. 9 evidenced the presence of rutile
peaks (for GPR and GSR) while perovskite ones (for GPP and GSP)
seem to act as a dye. This consideration is clarified by the incom-
plete reaction of the studied perovskite-based pigments described
in XRD and TDA-TG interpretations (previous Section 3.2). As a con-
sequence of the interference of wastes in colorimetric properties,
the final colour developed by the pigments produced from the sec-
ondary raw materials slightly shades off, and further addition of
chromium is required to improve their colouring power in glazes.
In order to overcome this drawback, other formulations were
prepared having 0.06 Cr2 O3 /TiO2 molar ratio (instead of 0.04), just
by increasing the amount of Cr/Ni galvanizing sludge in the mixture.
The major disadvantage of this solution might be risks of colour
changes due to the presence of Ni in the sludge, fortunately not
observed. The obtained pigments, SP2 and SR2, exhibit a brown
colour and L*a*b* coordinates much closer to the pigments based
on pure-grade reagents (PP and PR, see Table 3). In comparison
to SP and SR formulations, the brown hue in the coloured glazes
1183
Fig. 9. XRD patterns of coloured transparent glazes.
was considerably enhanced, mostly due to the L* decrease. Nev-
ertheless, the b* value of the coloured glaze diminished from 26.7
(G-SR) to 17.7 (G-SR2), while the original yellow-red hue evolved
to a deepest brownish colouration.
4. Conclusions
Pigments prepared from pure-grade reagents calcined at
1200 ◦ C showed the desired single phases, perovskite (PP) and rutile
(PR). By contrast, wastes-based formulations (SP and SR) show sec-
ondary phases due to the complex chemical composition of the
precursors. The percentages of perovskite and rutile phases are
∼44 wt.% and ∼42 wt.%, respectively, for the SP and SR pigments.
The secondary phases are silicates (titanite, wollastonite, melilite
and larnite) implying a competition between Si and Ti during the
synthesis process. This complex phase composition induces colour
changes on the waste-based pigments, when compared to standard
formulations. In particular, the measured brightness (L*) and yel-
low hue (+b*) are stronger in those pigments, while a slight green
component (−a*) becomes visible. In all cases, the optical spec-
1184 W. Hajjaji et al. / Chemical Engineering Journal 171 (2011) 1178–1184
troscopy reveals a similar pattern of absorbance bands that are
responsible for the brown colouration. They are ascribed to octahe-
drally coordinated Cr3+ transitions. Nevertheless, the brown hue of
waste-based pigments is not exclusively related to the perovskite
and rutile structures hosting the trivalent chromium, because of
the complexity of the systems, containing several chromophores
(at least Cr3+ , Ni2+ , Fe3+ ). Each one may be accommodated in differ-
ent crystal phases (perovskite and melilite in P; rutile and titanite
in R) and no reliable attribution of optical bands, further than those
of Cr3+ , may be attempted.
Once applied in transparent glazes, colour differences between
waste and pure reagents based pigments are visible, mostly in
the brown hue. A slight opacification, observed with waste-based
pigments, is likely due to crystallization promoted by secondary
phases. To overcome this problem, the amount of chromium oxide,
in the perovskite and rutile hosting structures, was increased from
0.04 to 0.06 mole, simply by enhancing the amount of Cr/Ni galva-
nizing sludge. This way, we assured a brown hue in the transparent
glaze that is similar to that obtained by using reagent-grade pig-
ments.
Acknowledgments
The work was supported by FCT (Project
PTDC/CTM/72318/2006) and FCT-CNR joint project 2011–2012
“Ceramic pigments from industrial wastes”.
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