Dyes and Pigments 122 (2015) 368e381

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Dyes and Pigments

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Stability and coloring properties of Ni-qandilite green spinels

(Ni,Mg)2TiO4: The “half color wheel” of Ni-doped magnesium titanates
M. Llusar*, E. García, M.T. García, C. Gargori, J.A. Badenes, G. Monro

s

nica y Orga
Departamento de Química Inorga
nica, Universitat Jaume I, 12071, Castello

n, Spain

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

Article history: Solid solutions of Ni-doped qandilite spinel (Mg2
xNixTiO4, x ¼ 0e0.4) prepared by solid-state and
Received 16 June 2015 citrate-gel routes were investigated as potential ceramic pigments or dyes. Fired powders were char-
Received in revised form acterized by conventional solid-state and color-measurement techniques. The increase of Ni-doping
8 July 2015
favored qandilite decomposition in Ni-geikielite (Ni,Mg)TiO3 and Ni-periclase (Ni,Mg)O. In the ceramic
Accepted 13 July 2015
route, Ni-doped qandilite was stabilized at 1400  C, but still accompanied by small amounts of MgTiO3
Available online 18 July 2015
and MgO. Remarkably, the citrate-gel route enabled the formation of single-phase qandilite already at
1200  C (up to 10%mol Ni), and at 1400  C for all amounts of Ni-doping. Ni-doped qandilite developed
Keywords:
Nickel magnesium titanates
green colors due to Ni2þ ions allocated exclusively in octahedral sites of qandilite spinel, being the green
Qandilite colors of higher chroma in citrate-gel powders. Ni-qandilite powders were chemically instable in low-
Geikielite temperature (950e1050  C) ceramic glazes, acting only as yellow ceramic dyes. Optical properties of
Karrooite Ni-doped karrooite, geikielite and qandilite pigments were compared.
Green ceramic pigments © 2015 Elsevier Ltd. All rights reserved.
Citrates route

1. Introduction parameter of spinels may be considered as a disorder parameter

The spinel-type crystal structure (AB2O4 general formula for
oxide-based spinels, space group symmetry Fd-3m) represents one
of the archetype structures based on a cubic close packing of an-
ions, in which A and B cations occupy one-half and one-eigth of the
available octahedral and tetrahedral sites, respectively [1]. The
oxidation states of A and B cations can be þ2 and þ3 in the so-
called “2e3 spinels” and þ4 and þ2 in “4e2 spinels” (in the later,
a combination of pentavalent and trivalent instead of tetravalent
cations may also occur). Two extreme distributions of spinels
(normal and inverse) may be found, considering the allocation of A
and B cations among the available tetrahedral and octahedral sites.
In “normal spinels”, cations A and B occupy the tetrahedral and
octahedral sites, respectively ([A]tet[B2]octO4), while in completely
“inverse spinels” the B cations are equally partitioned among
tetrahedral and octahedral sites, with the A cations occupying
exclusively the octahedral sites ([B]tet[AB]octO4) [1,2]. However,
spinels may display variable degrees of inversion or disordering of
A and B cations over both sites. In this respect, the inversion
* Corresponding author. Departament de Química Inorg anica i Organica, Uni-
cnic, Av. Sos Baynat s/n, 12071, Castello

, Spain.
versitat Jaume I, Edifici Científico-Te
Tel.: þ34 964 728244; fax: þ34 964 728214.
E-mail address: mllusar@uji.es (M. Llusar).
(h), and thus the spinel formula may be expressed in terms of this
inversion or disorder parameter as [A1
hBh]tet[AhB2
h]octO4, where
h ¼ 0, 2/3 and 1 for normal, totally random and inverse or anti-
ordered spinels, respectively [1].
The inversion or disordering degree occurring in spinels is very
sensitive to temperature, occurring a tendency for both normal and
inverse spinels to disorder with the increase of temperature
reaching the random, maximum entropy (at x ¼ 2/3) [3]. For
instance, at high temperatures such as 1500  C, the inversion de-
gree can increase up to 0.35 for normal and decrease down to 0.70
for inverse spinels (see Ref. [4] and references therein). Moreover,
the inversion degree is also strongly affected by spinel composition,
attending mainly to considerations of crystal field stabilization
energy (CFSE) of the involved transition metals. In this respect,
those ions having high octahedral site preference energy (OSPE) are
expected to be allocated preferentially in octahedral sites of spinels.
The OSPE parameter is the difference between the octahedral and
tetrahedral CFSE, and may be regarded as a measure of the affinity
of a transition metal ion for octahedral coordination in an oxide
structure such as spinel [5]. According to these OSPE consider-
ations, it may be may well understood for instance that Cr3þ ions
occupy only octahedral sites and also the high affinity of Ni2þ and
Cu2þ ions for octahedral sites forming inverse spinels, while Mg2þ,
Fe2þ, Mn2þ or Co2þ exhibit preference for tetrahedral sites.

http://dx.doi.org/10.1016/j.dyepig.2015.07.014
0143-7208/© 2015 Elsevier Ltd. All rights reserved.
 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
Nevertheless, these CFSE and OSPE arguments (based on the d-
electron configuration of transition metal) fail to explain for
instance the preference of Al3þ (d0) and Zn2þ ions (d10) for octa-
hedral and tetrahedral sites, respectively. Owing to these discrep-
ancies, other factors such as the relative sizes of s and p atomic
orbitals governing the s-type interactions between metal cations
(M) and oxide anions [6], the covalence degree of M
O bonds as
well as the lattice flexibility [7] have been also reported to influence
the cation exchange between tetrahedral and octahedral sites [8].
This cation order/disorder becomes especially important in spinels
since it may influence many of its chemical and physical properties
and it also determines its thermodynamic stability. Indeed, a more
randomized (disordered) distribution involves a higher (more
positive) entropy, resulting in a lower free energy and thus in a
higher stability for spinel formation [3].
In comparison with the more common family of “2e3 spinels”,
the “4-2 spinels” are rarer or less abundant as mineral species.
Indeed, only a few mineral species are included in this family, such
as ringwoodite (SiMg2O4), ahrensite (SiFe2O4), brunogeierite
(GeFe2O4), ulvo €spinel (TiFe2O4), filipstadite ((Sb0.5Fe0.5)Mn2O4),
and the rare mineral qandilite (TiMg2O4) [1]. Mg2TiO4 qandilite
crystallizes in the cubic Fd-3m spatial group and is a completely
inverse spinel ([Mg]tet[MgTi]octO4), with Mg2þ ions being equally
partitioned between both octahedral and tetrahedral sites [3,9,10].
Although a slight cation disorder (lower anti-ordered state; h < 1)
has been observed at high temperatures (4% of Ti in tetrahedral
sites by 1416  C), the kinetics of reordering is so fast upon cooling
that this disorder cannot be preserved at room temperature [3],
recovering its fully inverse or anti-ordered state. Mg2TiO4 is one of
the three intermediate magnesium titanates of the MgOeTiO2
system, along with MgTiO3 ilmenite (geikielite), the most stable
phase in terms of formation enthalpy, and MgTi2O5 pseudobrookite
(karrooite). Both MgTi2O5 karooite and Mg2TiO4 qandilite are sta-
bilized only at high temperatures (above about 1200e1300  C)
because of the configurational entropy arising from cation disorder
[9e11]. Mg2TiO4 qandilite remains stable at high temperatures,
melting incongruently at 1756  C, and although it should decom-
pose at or slightly below 1000  C in a mixture of MgTiO3 geikielite
and MgO periclase [10,12], this transformation does not occur upon
cooling due to kinetic limitations. However, Mg2TiO4 qandilite may
undergo a phase transition from the cubic to a metastable tetrag-
onal modification of the spinel structure (with space group P4122)
after long time annealing at temperatures about 933 ± 20 K
(660  C) [10,13] or even below (753 K) [9,14], involving this
tetragonal form a long-range ordering of Mg2þ and Ti4þ cations on
the octahedral sublattice (two nonequivalent octahedral sites).
Apart from these prolific investigations concerning crystal
chemical and thermodynamic properties of Mg2TiO4 qandilite and
related Mg titanates [3,9e14], this structure has received recently
increasing attention due to its potential technological properties
and applications. In this respect, Mg2TiO4 qandilite is an insulating
dielectric material and a semiconducting behavior below room
temperature has been reported for related stoichiometric
Mg1þxTi2
xO4 and nonstoichiometric spinels [15]. Moreover, recent
studies have analyzed the DC-conduction mechanism and curious
spiral-like morphology features of Mg2TiO4 qandilite [16,17], being
also postulated as a promising microwave dielectric resonator
[18,19]. Mg2TiO4 may also be used in optical applications as thin
films (optical modulation and protective layer of plasma display
panels) [20], as a heat resistor [21] and as a novel substrate for
epitaxial growth of high temperature superconducting thin films,
due to its high stability, low microwave loss and well-defined
surface structure [22]. On the other hand, only a few reports may
be found in the literature regarding solid solutions of Mg2TiO4 with
other metals. Some examples include crystal chemical studies on
369
ulvo€spinel-qandilite series (Fe2TiO4eMg2TiO4), which belongs to
the Fe2TiO4eMg2TiO4eFeFe2O4eMgFe2O4 spinel quadrilateral
(utilized as petrogenic indicators of temperature and pressure for
geological processes) [4], magnesioferrite-qandilite
(MgFe2O4eMg2TiO4) solid solutions [23], Al-doped qandilite [24],
and also Ni- and Sn-codoped Mg2TiO4 solid solutions and Co-doped
Mg2TiO4eCaTiO3 composite systems investigated for microwave
dielectric applications [18,19].
Recently, we reported the potential use as ceramic pigment or
dye of Ni-doped MgTi2O5 pseudobrookite (karrooite) prepared by
solid-state method and also through a citrate-gel metalorganic
decomposition route. Ni-doped karrooite pigments exhibited nice
orange colorations only partially stable in low-temperature ceramic
glazes fired at 1000e1050  C, where rather yellowish colors were
developed [25]. Aiming to obtain much purer yellow colors, it thus
occurred to us it could be interesting to analyze the effect of ac-
commodating Ni2þ ions replacing Mg2þ in the single octahedral
sites of closely-related Mg titanates of the MgOeTiO2 system,
namely MgTiO3 ilmenite (geikielite) and Mg2TiO4 spinel (qandilite).
The relatively distinct (Mg,Ni)eO distances should give rise to
variations in crystal field strength and intensities exerted on Ni2þ
ions and result in a substantial and perhaps useful color change. In
effect, in a second study the synthesis and coloring properties
NieMgTiO3 (geikielite) pigments [26] were investigated, and Ni-
doped geikielite pigments were found to produce much more
intense yellow colors associated to the resulting narrower absorp-
tion bands and to the slight variation of crystal field energy (with
respect to Ni-karrooite). An increase of the orange hue with
increasing temperature was associated to an increased distortion of
octahedral environments. In addition, in the same investigation a
preliminary test on Ni-doped (10 mol %) Mg2TiO4 qandilite
composition prepared by solid-state reaction (from MgCO3 and
TiO2 anatase precursors) and fired under rapid industrial-like
conditions (1000 and 1200  C with 3 h soaking) showed only a
poorly-advanced reaction yield at the used firing conditions.
Indeed, the Ni-doped qandilite spinel phase was still present only
as a secondary phase at 1200  C, being mostly decomposed in a
mixture of MgTiO3 ilmenite and MgO periclase. Accordingly, this
previous study revealed the necessity of using still higher firing
temperatures or more reactive alternative synthesis routes to
obtain single-phase solid solutions of Ni-doped qandilite. Never-
theless, the minor presence of Ni-doped qandilite observed in
1200  C-fired pigments resulted in a subtle and interesting color
change giving rise to a nice greenish-yellow “pistachio” color.
Therefore, these preliminary studies pointed towards the possi-
bility to obtain greenish colorations by incorporating Ni2þ ions in
Mg2TiO4 qandilite. The color change could arise from the smaller
(Mg,Ni)eO octahedral distances and the associated increase of
crystal field strength with respect to those found in MgTiO3 gei-
kielite and MgTi2O5 karrooite. In Ni-doped qandilite, Ni2þ ions are
expected to replace preferentially Mg2þ occupying octahedral sites
of the fully inverse or anti-ordered spinel ([Mg]tet[Mg1
x NixTi]octO4)
due to its high octahedral site preference energy (OSPE) [5].
Therefore, in order to complete these prospects and complete
the investigation, in this third report of the series the formation by
solid-state and citrate-gel routes of Ni-qandilite greenish solid so-
lutions (Mg2
xNixTiO4) were scrutinized more in detail, analyzing
for the first time the effect of firing temperature (1200 and
1400  C), Ni doping (10, 20 and 40 mol%) and preparation method
(solid-state vs. citrate-gel routes) on its reactivity, optical properties
and technological performance as ceramic pigments or dyes for the
coloration of conventional low-temperature ceramic glazes. Higher
amounts of Ni-doping above 40 mol % were not analyzed taking
into account that Ni is a rather scarce and toxic element [27] and,
similarly to the previous studies, the more homogenous and
370 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
reactive citrate-gel metalorganic decomposition (MOD) route was
employed as an alternative to the ceramic method [25,28e31]. A
comparison of UVeviseNIR absorption spectra and optical prop-
erties (crystal field energy, interelectronic repulsion Racah B
parameter and nephelauxetic ratio) of selected orange Ni-karrooite,
yellow Ni-geikielite and green Ni-qandilite pigments is also shown.
2. Materials and methods
2.1. Samples preparation (ceramic and MOD routes)
Solid solutions of Ni-doped MgeTi qandilite spinel (Mg2
xNix-
TiO4, with x ¼ 0.1, 0.2 and 0.4) were prepared firstly by the con-
ventional solid-state ceramic route, using MgCO3 (98%, Al-Farben),
NiO (99%, SigmaeAldrich) and TiO2 (anatase, 99e100.5%, Panreac)
as precursors. In this method, mixtures of each composition were
homogenized in planetary mills (20 min) using acetone as disper-
sant. The dried powders were then directly calcined in an electrical
furnace up to 1200 and 1400  C, with heating rate of 5  C/min, a
soaking time of 3 h and with free cooling to room temperature.
These rapid conditions emulate the firing schedules employed in
the industrial manufacture of ceramic pigments.
On the other hand, qandilite Mg1
xNixTiO3 compositions (x ¼ 0,
0.1, 0.2 and 0.4) were also prepared in aqueous media by a citrate-
gel metalorganic decomposition route (MOD) [28e31], following
the same preparation steps previously reported for (Ni,Mg)Ti2O5
and (Ni,Mg)TiO3 pigments [25,26]. Mg(NO3)2.6H2O (98%, Panreac),
Ni(NO3)2.6H2O (99%, Aldrich) and Ti n-butoxide (Ti[O(CH2)3CH3]4,
97%, Aldrich) were used as precursors, and citric acid (C6H8O7,
99.5%) was added as chelating agent with a 3:1 M ratio (citric
acid:qandilite) prior to Ti n-butoxide addition. The formed dark-
green citrate wet gels (after 24 h-drying at 110  C) turned into
dark brown xerogels after further drying (48 h). These xerogels
were homogenized (micronized) with mortar and pestle and the
resulting dried powders were directly calcined up to 600, 800,
1000, 1200 and 1400  C, using the same rapid firing conditions.
2.2. Sample characterization
Simultaneous differential thermal and thermo-gravimetric
analysis (DTA-TGA) was carried out (with MOD dried xerogels)
using a Mettler Toledo thermal analyzer (Pt crucibles with a con-
stant 10  C/min heating from 20 up to 1400  C). Crystal chemical
characterization of calcined samples was performed by X-ray
diffraction (XRD) in a D4 Endeavor (Bruker-AXS) powder diffrac-
tometer with Cu-Ka radiation (from 10 to 70 2q, with steps of
0.05  2q and a counting time of 2 s per step). The diffractometer was
equipped with a graphite secondary monochromator to eliminate
Kb and fluorescence signals. When necessary, the obtained powder
diffraction patterns were compared with powder diffraction files
(PDF) of the ICDD collection. The cell parameters were also deter-
mined by indexing and least-squares refinement of XRD patterns of
selected powder compositions mixed (50 wt%) with Al2O3
corundum as internal standard and measured under slower con-
ditions (steps of 0.02 2q and a counting time of 4 s per step), using
the POWCAL and LSQC programs (Department of Chemistry, Uni-
versity of Aberdeen, UK).
On the other hand, the microstructure and morphology of
NieMg2TiO4 fired samples was examined by scanning electron
microscopy (SEM) with a JEOL 7001F electron microscope
(following conventional preparation and imaging techniques). The
chemical composition and homogeneity of the samples was
determined by semi-quantitative elemental analysis with an EDX
analyzer (supplied by Oxford University) attached to the
microscope.
In order to analyze the stability and optical or coloring proper-
ties (pigmenting performance) of NieMg2TiO4 solid solutions
within conventional low-temperature ceramic glazes, the fired
powders were 5 wt-% enameled within three different commercial
transparent glazes of relatively low-temperature onto conventional
ceramic biscuits: glaze A of the SiO2eCaOeZnO system (high Ca and
Zn content), glaze B of the SiO2eAl2O3ePbOeCaOeNa2OeK2O
system (low Ca content, free of Zn but Pb-containing) and glaze C of
the SiO2eAl2O3eK2O eCaOeZnO system (low Ca and Zn content,
and free of Pb). Enameled samples were fired following fast-firing
schemes (52 min of duration from cool to cool at a maximum
temperature of 1050, 1000 or 980  C for glazes A, B and C respec-
tively). The optical properties of fired powders and enameled
samples were then analyzed by diffuse reflectance spectroscopy
(UVeviseNIR) performed with a Jasco V670 spectrophotometer.
The color parameters (L*a*b*) were also measured using a standard
lighting C, following the CIE-L*a*b* colorimetric method recom-
mended by the CIE (Commission Internationale de l'Eclairage) [32],
using an 8/d geometry (diffused illumination of 8 ), with the
observer at 10 and a standard lighting D65. On this method, L* is
the lightness axis (black (0) / white (100)), a* is the green (
)/
red (þ) axis, and b* is the blue (
) / yellow (þ) axis.
3. Results and discussion
3.1. Reactivity (XRD) and color characterization of (Mg,Ni)2TiO4
ceramic samples
XRD analysis of fired powders prepared by the ceramic route
enabled to elucidate the evolution with firing temperature (1200
and 1400  C) and Ni-content (10, 20 and 40 mol %) of the formation
and stabilization of Ni-qandilite solid solutions (Mg2
xNixTiO4)
under the fast-firing conditions herein employed. The XRD patterns
of ceramic compositions fired at 1200  C (see Fig. 1a) showed in all
cases only a minor presence of spinel phase (Mg2TiO4 qandilite, PDF
025e1157), predominating a mixture of MgTiO3 ilmenite (geikielite,
PDF 006e0494) and MgO periclase (PDF 045e0946) or (Mg,Ni)O
(PDF 024e0712). This result is in agreement with previous reports
indicating that mixtures of conventional magnesia and titania
powders may form or stabilize the qandilite spinel only when
heating above 1200e1300  C [33], becoming this phase entropy-
stabilized at high temperatures [10]. As it may be also appreci-
ated, at 1200  C the increase of Ni-doping (especially from 20 to
40 mol %) resulted in a much lower stabilization of Ni-doped
qandilite, being this phase more extensively decomposed in
ilmenite and periclase compounds. Thus, the increase of Ni-doping
does not enable the stabilization of qandilite spinel at 1200  C, but
it seems rather to have the opposite effect, favoring its decompo-
sition in ilmenite and periclase compounds. This would also agree
with the increased geikielite ilmenite stabilization with Ni-doping
recently reported [26].
Attending to the color properties, these ceramic powders fired
at 1200  C (consisting of a mixture of Ni-doped ilmenite, spinel and
periclase solid solutions, since Ni may enter as solid solution in all
these three structures) gave rise to quite intense yellowish color-
ations. The color aspect and L*a*b* color parameters of fired pow-
ders are shown in Fig. 2 (above). As it may be appreciated, the
yellow component increases with Ni-doping (more positive b*
value, from 15.9 to 32.1), and compositions with x ¼ 0.2 and x ¼ 0.4
present also a higher green hue (negative a*, between
5.4
and
5.9) giving rise to nice greenish-yellow “pistachio” colors. The
greenish hue could be associated to the minor presence of Ni-
qandilite solid solution, still present as secondary phase in
1200  C-fired powders.
 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381 371

Fig. 1. XRD patterns of qandilite compositions (Mg2
xNixTiO4) prepared by the ceramic route and fired directly at 1200  C/3h (a) and 1400  C/3h (b). Crystalline phases: S ¼ Spinel
(qandilite) Mg2TiO4 or (Mg,Ni)2TiO4; I ¼ Ilmenite (geikielite) MgTiO3 or (Mg,Ni)TiO3; M ¼ MgO periclase or (Mg,Ni)O.

As it was to expect, the Ni-doped qandilite solid solutions the incorporation of Ni2þ as solid solution in Mg2TiO4 qandilite
became stabilized as the major crystalline phase when firing the crystal lattice induces and interesting shift from orange-yellow to
raw ceramic compositions at 1400  C/3h (see XRD patterns in green color. This may be explained by the variation in crystal field
Fig. 1b). Nevertheless, this phase was still accompanied by very intensity and energy arising from the distinct Ni2þ octahedral en-
small amounts of residual MgTiO3 geikielite and MgO periclase, vironments (see detailed discussion in section 3.6).
which were present in rather similar amounts irrespective of Ni-
doping (perhaps a slightly smaller amount of residual ilmenite
3.2. Thermal analysis, reactivity (XRD) and color characterization of
was present for x ¼ 0.4 composition). Remarkably, the prospects
MOD citrate-gel samples
suggesting the possibility of obtaining green pigments by doping
Mg2TiO4 qandilite with Ni ions were fully confirmed (Fig. 2), and
For comparison reasons, Ni-qandilite solid solutions (Mg2
xNix-
Ni-doped qandilite powders fired at 1400  C developed relatively
TiO4, x ¼ 0, 0.1, 0.2 and 0.4) were also prepared by a more ho-
intense (low L*) and nice yellowish green colors (more negative b*
mogenous and reactive metalorganic decomposition (MOD) route
values, between
10 and
12). Therefore, differently to the orange
of citrate gels [25,28e31]. The XRD patterns of the obtained raw
and yellow colors of Ni-doped karrooite and geikielite pigments,
xerogels (see supplementary Fig. A.1, Appendix A) showed only
372 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
Fig. 2. Color aspect of Mg2
xNixTiO4 fired powders (1200 and 1400  C/3h) obtained by the ceramic route, and of their corresponding enameled samples (5 wt%, glaze A for 1200  C-
fired pigments, and glaze B and C for 1400  C-fired pigments). The measured color parameters (L*/a*/b*) are also indicated. (For interpretation of references to color in this figure the
reader is referred to the web version of the article).
intense diffraction peaks associated to ammonium nitrate (PDF 00-
008-0452) crystallized upon drying. The absence of any other fea-
tures in the diffractogram indicates the amorphous nature of the
accompanying heterometalic NieMgeTi citrates, a quite common
occurrence for xerogels. The thermal analysis curves of these
xerogels presented similar features in all samples, irrespective of
the amount of Ni-doping. These decomposition features were also
quite similar to those previously reported for Ni-doped MgTi2O5
(karrooite) and MgTiO3 (geikielite) precursor citrate xerogels
[25,26], with the logical differences arising from the variable
amount of organics (citrates and Ti alkoxide) and magnesium and
Ni nitrates content (the metal nitrate:alkoxide ratio was 1:2 in Ni-
karrooite, 1:1 in Ni-geikielite and 2:1 in Ni-qandilite). The DTA-TG
curves of a representative xerogel composition (x ¼ 0) are shown
in Fig. 3.
As it may be appreciated, the DTA-TG curves showed three main
decomposition regions, apart from the very small weight-loss
(8.5 wt %) below 150  C associated to removal of adsorbed water
(drying). Firstly, a very sharp and two-step weight-loss
(26.1 þ 35.9 wt %) takes place between 150 and 280  C, with an
associated endothermic effect (around 227  C) subsequently fol-
lowed by a very sharp and intense exothermic signal (262  C). Both
Fig. 3. Differential thermal-thermogravimetric analysis (DTA-TG curves) of a repre-
sentative qandilite spinel xerogel composition (Mg2TiO4; x ¼ 0).
effects could be assigned to the melting and subsequent decom-
position of ammonium nitrate (which melts at 169.6  C and de-
composes exothermically at around 200e300  C) [34,35]. This
endothermic effect was also related to dehydration of the citrate
ligand by YF Deng et al. [29], and this additional process could
explain the two-step weight loss occurring in this first decompo-
sition region. The second and complex two-step weight-loss of ca.
16 wt % (6.8 þ 9.2 wt %) between 278 and 580  C, with two asso-
ciated broad exothermic effects partially overlapped and centered
around 377 and 481  C, corresponds to other two important
decomposition processes taking place subsequently at these tem-
peratures: the first step (300e450  C) could be ascribed to the
combustion reaction between nitrates and citrates, as it has been
already observed in citrate-nitrate xerogels prepared under similar
conditions, followed by elimination of residual citrates. Subse-
quently, the second weight-loss step (450e580  C) could be asso-
ciated to decomposition of remaining alkoxides (from Ti n-butoxide
precursor). Finally, a last and very small weight-loss (ca. 2 wt%) may
be observed at higher temperatures between 580 and 790  C
(which was also found in previous studies on the decomposition of
complex MgeTi ammonium citrates [29]).
These assignations and the relative weight of decomposition
steps in the DTA-TG curves are in good correspondence with the
different content of nitrates, citrates and alkoxides in Ni-doped
qandilite xerogels in comparison with related Ni-doped karrooite
and geikielite samples, previously reported [25,26]. Effectively, the
exothermic signal associated to ammonium nitrate decomposition
is much more intense and sharp in Ni-qandilite xerogels (due to the
higher amount of employed nitrate salts and crystallized ammo-
nium nitrate), while the last weight-loss between 400 and 580 (and
the associated endothermic peak) is much less intense in these
xerogels, in agreement with the lower amount of Ti alkoxide
employed in the spinel formulation.
These raw xerogels were then calcined using the same fast-
firing conditions (3 h soaking) up to different temperatures (600,
800, 1000, 1200 and 1400  C; always direct calcination from raw
xerogels). Previous investigations on the formation and stability of
non-doped Mg2TiO4 qandilite spinels and related magnesium ti-
tanates from coprecipitated xerogels or nanometric systems
[33,36,37] found that nanocrystalline qandilite already forms at
about 600  C, although only as a metastable phase since from about
700 to 1200  C Mg2TiO4 spinel decomposes almost completely into
MgTiO3 geikielite and MgO periclase (extensive decomposition at
 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381 373

900e1100  C); then, at higher temperatures (at about 1300  C) the
qandilite phase becomes entropy-stabilized and reappears again. A
very similar behavior and evolution of crystalline phases with firing
temperature occurred in the present investigation upon calcination
of the heterometalic (Mg,Ni,Ti) citrate-nitrate xerogels. At 600  C
the XRD patterns showed broad and low-intensity peaks (see
supplementary Fig. A2, Appendix A) associated to the incipient
formation of qandilite spinel with nanometric crystallite sizes. Also
noteworthy, the increase of Ni doping resulted in a lower stabili-
zation of qandilite spinel at this low temperature (especially for
x ¼ 0.4 sample), being this phase accompanied by a mixture of
geikielite and periclase phases.
The XRD patterns of xerogels fired at 800e1400  C are shown in
Fig. 4. In agreement with previous reports mentioned above, the
spinel became destabilized at 800  C and it was partially decom-
posed into geikielite and periclase (Fig. 4a). Noteworthy, we found
that this decomposition was more extended the higher the Ni-
doping (for x ¼ 0.4 only traces of qandilite spinel were detected).
This result confirms once again that Ni doping induces a lower
stability of Ni-qandilite spinel against its decomposition into Ni
geikielite ilmenite and periclase. This decomposition proceeded
more extensively with increasing firing temperature, and it was
complete at 1000  C (Fig. 4b) for all compositions (only negligible
traces of spinel were detected for x ¼ 0 and 0.1 samples). Inter-
estingly, when firing at 1200 and 1400  C the spinel phase reap-
peared again (Fig. 4c and d), confirming that qandilite spinel
becomes entropy-stabilized at these higher temperatures. It must
be highlighted that at 1200  C/3h the spinel formed almost as a
single-phase for x ¼ 0 and 0.1 compositions (only with traces of
residual geikielite), while for higher amounts of Ni-doping (20 and
40 mol%) the spinel became completely destabilized or fully
decomposed into geikielite and periclase.
As two important remarks, this result evidences on the one
hand the possibility to obtain Mg2TiO4 (or 10 mol% Ni-doped)
spinel almost as single phase already at 1200  C by direct calcina-
tion of citrate xerogels (MOD route), being not necessary the use of
higher temperatures (about 1300  C) as reported in previous
studies [33,36,37]. On the other hand, it is evident once again that
Ni-doping has a detrimental effect on the thermodynamic stabili-
zation of qandilite spinel (decomposing in geikielite and periclase),
and this “destabilization effect” proceeds in a more abrupt or
sudden manner (being the extension of the decomposition more
sensitive to Ni-doping) in citrate-gel samples than in ceramic
compositions, where the decomposition increased with Ni-doping
more progressively (see corresponding XRD spectra in Fig. 1a). This
distinct behavior in both synthesis routes (ceramic vs. citrates-gel)

Fig. 4. XRD patterns of qandilite powders Mg2
xNixTiO4 prepared by MOD-citrate route and fired at 800  C/3h (a), 1000  C/3h (b), 1200  C/3h (c) and 1400  C/3h (d); Crystalline
phases: S ¼ Spinel (qandilite) Mg2TiO4 or (Mg,Ni)2TiO4; I ¼ Ilmenite (geikielite) MgTiO3 or (Mg,Ni)TiO3; M ¼ MgO or (Mg,Ni)O.
374 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
was also found in Ni-doped karrooite solid solutions (also entropy-
stabilized), in which karrooite decomposition into a mixture of
geikielite and rutile was much more effectively triggered by Ni-
doping in citrates samples than in solid-state compositions [25].
Following with the thermal evolution of fired samples, compo-
sitions fired at 1400  C (Fig. 4d) consisted of well-crystallized Ni-
doped qandilite spinel solid solutions. Surprisingly, very small and
almost negligible traces of residual geikielite were this time
observed in compositions with a lower Ni-doping (x ¼ 0 and 0.1),
being stabilized the qandilite spinel as single phase for higher Ni-
doping (x ¼ 0.2 and 0.4). Thus, the negative effect of Ni-doping
on qandilite stabilization probes to be much more important or
critical at 1200 than at 1400  C, being at this higher temperature
the qandilite phase more entropy-stabilized.
As it may be seen in Fig. 5 above (which also includes the
measured L*/a*/b* color parameters), the obtained fired powders
exhibited a varied and nice gamut of greenish-yellow, yellowish-
green or pure green colors, as a result of the distinct amounts of Ni-
doped geikielite (yellow-colored) and Ni-doped spinel (green-
colored) solid solutions present in the fired pigments depending on
firing temperature (800e1400  C) and Ni-doping (x value). Logi-
cally, the green hue (negative a*) increased with the amount of
stabilized spinel phase, while the yellow hue (positive b*) increased
with geikielite content. Also noteworthy, in comparison with fired
pigments obtained by ceramic route, the “citrate-gel” pigments
having well-crystallized Ni-doped qandilite spinel (x ¼ 0.1 at
1200  C, and all samples from x ¼ 0.1 to 0.4 at 1400  C) exhibited
much more vivid green colors than ceramic samples (b* values
between
17 and
30 for “citrate” pigments and between
10
and
12 for “ceramic” pigments). The green color of citrate samples
were also brighter (higher L* values). In section 3.5 we tested if
these green colors could be maintained in conventional low-
temperature (1000e1050  C) ceramic glazes, thus behaving Ni-
doped qandilite powders as “true” ceramic pigments, or if the co-
lor changed due to chemical reactions within the glaze, actuating in
this case as ceramic dyes.
3.3. Cell parameters measurement in Mg2
xNixTiO4 geikielite
pigments
The cell parameters of selected Mg2
xNixTiO4 fired pigments
were measured to have a more direct confirmation of the successful
formation of Ni-doped qandilite spinel solid solutions. In principle,
replacement of Mg2þ (72 pm) by the slightly smaller Ni2þ ions
(69 pm) [38] should result in an almost linear decrease of cell pa-
rameters, irrespective of the substitution taking place either in
tetrahedral or in octahedral sites of the fully inverse spinel
([Mg]tet[MgTi]octO4). As it was already mentioned, the most prob-
able situation is that Ni2þ ions replace preferentially Mg2þ occu-
pying octahedral sites of the fully inverse or anti-ordered spinel
([Mg]tet[Mg1
x NixTi]octO4), considering its high octahedral site
preference energy (OSPE) [5]. Nevertheless, in the case that Ni-
doping could induce a slight Mg2þ/Ti4þ cation disordering at high
temperatures (and that this disordering could be maintained at
room temperature), thus displacing a small fraction of the smaller
Ti4þ cations to tetrahedral sites instead of the larger Mg2þ ions, this
effect would have also some influence on cell parameters, taking
into account that <M-O> distances are considerably shorter in
tetrahedral (~1.98 Å) than in octahedral sites (~2.02 Å) of qandilite
spinel [9].
Table 1 summarizes the determined values of cell parameter
and volume for Mg2
xNixTiO4 ceramic and citrate-gel (MOD)
compositions fired at 1400  C/3h depending on Ni-doping (x). The
evolution of cell parameter (a) with Ni-doping (x) is also shown in
Fig. 6 for samples prepared by MOD-citrates route. In citrate-gel
samples the unit cell parameters and cell volume of (Mg,Ni)2-
TiO4 qandilite pigments were found to decrease quite linearly with
the increase of Ni-doping (x value) in nominal formulations (the
reported value for a non-doped Mg2NiTiO4 qandilite is 8.4409 Å
according to PDF 00-025-1157). As it was previously stated, this
variation of cell parameters would be in accordance with the
replacement of Mg2þ by the smaller Ni2þ ions in qandilite spinel.
In the case of ceramic compositions, however, the variation of cell
parameters with Ni-doping was rather anomalous (the cell
parameter decreased considerably for x ¼ 0.2, and then increased
for x ¼ 0.4). Nevertheless, in these ceramic samples the measured
cell parameters must be only considered as approximate values,
since these compositions did not contain single phase of Ni-
qandilite, and therefore a non-negligible amount of Ni could be
also incorporated as solid solution in residual geikielite and peri-
clase phases.
3.4. Microstructure and morphology characterization (SEM/EDX)
SEM/EDX characterization was performed with selected ceramic
and citrate-gel fired pigments, in order to gain further information
about the morphology, homogeneity and composition of pigment
powders at the microscale. SEM observations of representative
Mg2
xNixTiO4 ceramic and “citrate” powders calcined at 1200 and
1400  C are shown in Fig. 7.
Regarding to the ceramic route, only the pigments fired at
1400  C were analyzed by SEM, since qandilite spinel was not
stabilized as major phase below this temperature. As it may be
appreciated, Ni-doped qandilite “ceramic” powders fired at 1400  C
consisted of very compact and sintered aggregate particles (Fig. 7b,
for x ¼ 0.4) of irregular shapes and sizes (from a few to ca. 50 mm).
These aggregates were formed by smaller grain-like particles with
variable sizes (around 2e6 mm) and with more or less rounded
morphologies (Fig. 7a, for x ¼ 0.1). The increase of Ni doping was
not observed to affect substantially the morphology, which was
very similar in all samples. In contrast, the qandilite fired pigments
obtained from citrate-gel (MOD) samples were found to consist at
1200  C (Fig. 7c and d) of aggregate particles with a finer grain-like
texture conformed by submicron grains having more rounded
morphologies and forming in some cases interconnected macro-
porous cavities (Fig. 7c). Similarly to ceramic samples, these grains
became much larger (between 3 and 10 mm) at 1400  C having a
much more compact (less porous) or sintered aspect (Fig. 7e and f).
Again, the increase of Ni doping did not produce any substantial
change in the morphology or microstructure.
On the other hand, aiming to determine the chemical compo-
sition and homogeneity of Ni-doped qandilite solid solutions,
semiquantitative EDX analyses were performed in different regions
of the samples. In general terms, the average sample compositions
determined by EDX analyses (not shown) were in good correlation
with the nominal formulations for both ceramic and citrate-gel
samples. However, more localized (point) EDX analyses per-
formed within the aggregates indicated a slight dispersion in the
molar Mg:Ni:Ti:O ratios, indicative of some chemical heterogeneity,
especially in the case of samples prepared by the solid-state
(ceramic) route.
3.5. UV-VIS-NIR spectroscopy and technological performance as
ceramic pigments or dyes
The UVeviseNIR absorption spectra of Ni-qandilite (Mg2
xNix-
TiO4) pigments (powders) prepared by both ceramic and citrate-gel
routes and fired at 1400  C/3h are shown in Fig. 8a and c, respec-
tively. As it may be appreciated, the absorption profiles of Ni-
qandilite fired pigments fit perfectly with the spectral features of
 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381 375

Fig. 5. Color aspect of Qandilite Mg2
xNixTiO4 fired powders (800, 1000, 1200 and 1400  C/3h) obtained by MOD route (above), and of their corresponding samples enameled (5 wt
%) within glaze B or C (below). The measured color parameters (L*/a*/b*) are also indicated. (For interpretation of references to color in this figure the reader is referred to the web
version of the article).

Ni2þ (3d8 ion) in octahedral coordination [5,39e42]. However, in
comparison with the optical spectra previously reported for Ni-
doped karrooite (orange-colored) [25] and geikielite pigments
(yellow-colored at 1200  C, with an increased orange tan at
1400  C) [26], the absorption bands found in Ni-doped qandilite
spectra appear strongly shifted to lower wavelengths or higher
energies (see a detailed comparative analysis of the three related
magnesium titanates on next section 3.6).
Indeed, the highest energy band associated to n3 spin-allowed
transition (3A2g (3F) / 3T1g (3P)) is centered at ca. 400 nm (or
below), almost in the near-UV region and highly overlapped with
the typical O2
eTi4þ and O2
eNi2þ charge transfer transitions
376 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381

Table 1
Cell parameter (a) and volume (V) of Mg2
xNixTiO4 qandilite (cubic) spinels prepared by the ceramic and MOD-citrate routes and fired at 1400  C/3h.

Mg2
xNixTiO4 composition (x) / 0 0.1 0.2 0.4

a (Å) Ceramic route 8.4409a 8.4339 (3) 8.4156 (6) 8.4224 (4)
MOD-citrate route 8.4392 (1) 8.4392 (1) 8.4350 (6) 8.4292 (8)
V (Å3) Ceramic route 601.40 (6) 599.91 (6) 596.01 (13) 597.46 (8)
MOD-citrate route 601.04 (2) 601.04 (2) 600.14 (13) 598.91 (17)
a
Reported value for Mg2TiO4 qandilite (fired at 1380  C) in PDF 00-025-1157.

Fig. 6. Evolution of cell parameter (a) with Ni doping (x) in Mg2
xNixTiO4 qandilite
spinels prepared by MOD-citrate route and fired at 1400  C/3h.
(around 250e400 nm). The spin-forbidden transitions to 1T1g (1G),
1
T2g (1G) and 1Eg (1G) would be also contributing to the absorbance
in this near UV region (see deconvolution of x ¼ 0.4 spectrum later
in Fig. 10c). Then, the second spin-allowed transition (n2: 3A2g
(3F) / 3T1g (3F)) is responsible for the broad band extending from
the yellow (560e590 nm), through the orange (590e630 nm) and
red (630e750 nm) regions of the visible, and extinguishing in the
near-IR (900 nm). Finally, the third spin-allowed transition (n1: 3A2g
(3F) / 3T2g (3F)) results in a still broader band falling in the near IR
region from 900 to 1400 nm (and centered around 1150 nm).
Moreover, some absorption shoulders are also discernible at
around 450e500 and 750 nm, which would correspond to spin-
forbidden transitions to 1A1g (1G) þ 1T2g (1D) and 1Eg (1D) terms,
respectively.
As it may be appreciated, the optical transitions occur at very
similar wavelength or energy values, irrespective of the amount of
Ni-doping, and this fact indicates that NieO distances do not
change substantially with Ni-doping. Also logically, the increase of
Ni-doping is accompanied by an increase of the intensities or op-
tical density of absorption bands (more evident correlation in MOD
than in ceramic samples), which correlates perfectly with the in-
crease in the saturation or vividness of the green color of fired
pigments with Ni-doping. Of course, in agreement with the
observed greenish color of the pigments, the position of the
maximum reflectance (or minimum absorption) takes place within
the green region of the visible spectrum (480e560 nm), especially
in the case of MOD samples, which exhibit more vivid or better
defined green colors. In this respect, the position of the maximum
reflectance becomes slightly shifted to lower wavelengths
becoming greener the color with the increase of Ni-doping: in the

Fig. 7. SEM images (x5000 or x1000 magnification) of selected qandilite spinel pigment compositions (Mg2
xNixTiO4) prepared by ceramic (a and b) and MOD (c to f) routes and
fired at 1200 or 1400  C/3h, as indicated for each composition. The length of the bar is also given.
 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
Fig. 8. UVeviseNIR absorption spectra of qandilite spinel powders (Mg2
xNixTiO4) fired at 1400  C/3h and prepared by the ceramic (a) and MOD (c) routes, and of their corre-
sponding samples enameled within glaze B (b and d, respectively).
case of ceramic samples the peak of maximum reflectance shifts
from 565 nm (x ¼ 0.1) to 560 nm (x ¼ 0.2) and 550 nm (x ¼ 0.4),
while in MOD pigments this maximum reflectance changes from
549 nm (x ¼ 0.1) to 539 nm (x ¼ 0.2) and 533 nm (x ¼ 0.4). These
values of maximum reflectance explain that the yellowish hue
(positive b*) predominates over the green hue (negative a*) in
qandilite pigments obtained by the ceramic route (which still
contain residual Ni-geikielite), while the green hue becomes much
more predominant in pigments obtained by MOD-citrates route
(the color parameters are shown in Figs. 2 and 5 for ceramic and
MOD samples, respectively).
Finally, the potential application of these greenish Ni-doped
qandilite solid solutions as ceramic pigments or dyes for the
coloration of low-temperature ceramic glazes was also tested. With
this aim, in order to evaluate their stability and coloring perfor-
mance, we enameled the fired pigments within three conventional
transparent ceramic glazes (5 wt% of pigment) of relatively low
firing temperature compressed between 980 and 1050  C (the
composition details were given in section 2.2). The color aspect and
measured colored parameters (L*a*b*) of glazed samples may be
seen in Fig. 2 in the case of pigments prepared by the ceramic route,
and in Fig. 5 for citrate-gel pigments. As the first an important
remark, the pigments were not stable enough to withstand the
chemical attack within the employed ceramic glazes during enamel
firing (980e1050  C), since in all cases the green colors of pigment
powders disappeared almost completely. However, the resulting
glazed samples developed relatively intense and nice yellowish
377
colors. Accordingly, the obtained Ni-doped qandilite solid solutions
could be used as yellowish colorants or dyes in the coloration of
ceramic glazes, but they could not be used as true ceramic pig-
ments, since they do not remain stable or insolubilized in the glassy
matrix.
Noteworthy, qandilite pigments showed a lower stability in
glaze A (more CaO and ZnO-enriched, and fired at 1050  C), giving
rise in this case to less intense yellowish colors of considerably
lower chromaticity. For this reason the images and color parame-
ters of fired pigments enameled within glaze A have not been
included in Figs. 2 and 5 (except in the case of ceramic pigments
fired at 1200  C, which still contained Ni-doped geikielite as the
major phase). Comparatively, Ni-doped qandilite pigments devel-
oped more saturated or intense yellow colors (higher chromaticity)
once enameled within ceramic glazes B and C (fired at 980 or
1000  C) which contained a much lower amount of CaO and ZnO.
This is in agreement with previous reports on related Fe pseudo-
brookite pigments, which were found to be less stable in more
aggressive ceramic glazes containing higher amounts of CaO and
ZnO oxides [43].
In both glazes, the increase of Ni-doping in pigments formula-
tion gave rise to more intense colors (lower L*) with more vivid
yellow hues (higher and positive b* values), and in all cases the
color of the glazes possessed also a very slight reddish cast (very
low and positive a* values). The obtained yellow colors were very
similar in both glazes B and C, although with a slightly higher
chromaticity (higher a* and b* values) in the case of glaze B which
378 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
contained a small amount of PbO (5.4 wt %). Stablishing a com-
parison between the two synthesis routes (ceramic vs. MOD-
citrates), glazed samples with Ni-doped qandilite pigments pre-
pared by MOD-citrates route developed yellow colors of slightly
higher chromaticity (higher yellow hue), although the colors did
not differ substantially to those of the ceramic route (for instance,
the L*/a*/b* values in glaze B for x ¼ 0.4 composition were 59/3/36
for “ceramic” pigments and 60/4/37 for “citrate-gel” pigments). The
best yellow colors were obtained with pigments fired at 1200  C
and with a high Ni-doping (x ¼ 0.2 and 0.4), although these pig-
ments consisted of a mixture of geikielite and periclase (L*/a*/
b* ¼ 65/4/42 in glaze B for x ¼ 0.4). Indeed, Ni-doped geikielite and
karrooite pigments give rise to yellower colors in glazed samples
[25,26] than Ni-doped qandilite dyes.
A complementary confirmation of the instability of Ni-doped
qandilite pigments in the employed ceramic glazes (already
evident taking into account the substantial color change) was ob-
tained by optical spectroscopy. The absorbance spectra of 1400  C-
fired pigments prepared by both synthesis methods and once
enameled within glaze B are shown in Fig. 8b and d (for ceramic
and MOD pigments, respectively). These spectra of glazed samples
exhibit also the same features associated to the three spin-allowed
transitions of Ni2þ in octahedral environment, with increased ab-
sorption intensity (optical density) the higher the Ni doping.
However, a substantial difference was observed in all samples with
respect to the absorption spectra of the corresponding Ni-doped
qandilite powders (Fig. 8a and c). As it may be appreciated, all
the transitions were largely shifted to higher wavelengths (lower
energies) in glazed samples, with the position of the bands being
very similar to those previously reported for Ni-doped karrooite
and geikielite pigments [25,26]. For instance, the three spin-
allowed transition bands were centered at around 430 (n3),
720e880 (n2) and 1200e1240 nm (n1) for samples enameled in
glaze B. A similar shift was observed when enameling the pigments
in glazes A and C (not shown). As a result, the reflection window
(minimum absorption) of glazed samples becomes centered mostly
in the yellow region at around 560e600 nm, in agreement with
their yellowish coloration. Again, this important shift in the ab-
sorption bands of glazed samples with respect to Ni-doped qan-
dilite powders confirms that a strong modification or distortion of
Ni2þ coordination environment in qandilite pigments must occur
upon enamel firing, thus behaving Ni-doped qandilite composi-
tions as ceramic dyes and not as stable ceramic pigments.
3.6. Optical properties comparison of Ni-doped karrooite, geikielite
and qandillite pigments
As the final part of the investigation, a comparative analysis was
performed of the optical spectra and optical properties of the three
related and Ni-doped (40 mol%) magnesium titanates of the
MgOeTiO2 system: an orange-colored karrooite pseudobrookite
(Mg0.6Ni0.4Ti2O5 fired at 1400  C) [25], a yellow-colored geikielite
ilmenite (Gei, Mg0.6Ni0.4TiO3 fired at 1200  C) [26] and a green-
colored qandilite spinel (Qan, Mg1.6Ni0.4TiO4 fired at 1400  C).
With this aim, the reflectance (R∞) was previously converted to K/S
absorbance by the KubelkaeMunk equation (K/S ¼ 2(1
R∞) x
2R
1
∞ ). The corresponding KubelkaeMunk (K/S) absorption spectra
are shown for comparison reasons in Fig. 9 (the abscissa axis has
been set in wavenumber units).
As a consequence of the different position, intensity and
broadness of absorption bands in optical spectra (especially n2 þ 1Eg
(1D) and n3), the complementary reflection window (minimum
absorption) falls in the case of Ni-doped qandilite pigment at
around 550 nm (18,200 cm
1), which is included in the green re-
gion of visible spectrum (480e560 nm). In contrast, this maximum
Fig. 9. UVeviseNIR KubelkaeMunk absorption spectra of related Ni-doped (40 mol%)
Mg titanates: an orange karrooite pseudobrookite (Kar-0.4, Mg0.6Ni0.4Ti2O5 fired at
1400  C), a yellow geikielite ilmenite (Gei-04, Mg0.6Ni0.4TiO3 fired at 1200  C), and a
green qandilite spinel (Qan-0.4, Mg1.6Ni0.4TiO4 fired at 1400  C). The color of the pig-
ments is shown as inset at the left side of the legends. The octahedral Ni2þ absorption
bands appear strongly shifted to higher energies in qandilite spinel with respect to
ilmenite and pseudobrookite structures. (For interpretation of references to color in
this figure the reader is referred to the web version of the article).
reflection becomes shifted to ca. 580 nm (17,240 cm
1; in the yel-
low region) for Ni-doped geikielite pigment and to ca. 617 nm
(16,200 cm
1; in the orange region) for Ni-doped karrooite
pigment. Thus, an interesting color tuning is observed accompa-
nying the shift of the maximum reflectance from lower energies
(higher wavelengths) in Ni-karrooite (orange color), through in-
termediate values in Ni-geikielite (yellow color) and up to higher
energies (lower wavelengths) in Ni-qandilite (green color). The
obtained smart color modulation, from orange (karrooite) through
intense yellow (geikielite) and up to green (qandilite), must arise
from the slight differences in NieO distances (and polyhedral
distortion) occurring when accommodating Ni2þ ions in the
distinct octahedral sites of the three related magnesium titanates
(MgTi2O5 karrooite, MgTiO3 geikielite and Mg2TiO4 qandilite),
along with the consequent variation in crystal field energies and
intensities exerted by oxide ligands onto Ni2þ ions. Of course, the
effects of structural relaxation or changes in the covalence nature of
M
O bonds may be also affecting the optical spectra [7].
In order to determine the optical properties (crystal field
strength D0, interelectronic repulsion Racah B parameter, and
nephelauxetic b parameter) [41] and also to stablish a comparison
between the three Ni-doped magnesium titanate pigments, we
fitted the optical spectra of the selected pigment compositions
(prepared by the ceramic route) to component bands by the least-
squares method using Gaussian product functions. Table 2 sum-
marizes the results of optical properties for the studied pigments
(energies of experimental bands and optical parameters according
to the fitting of spin-allowed transitions to d8 TanabeeSugano di-
agram). The fitting of the K/S spectra corresponding to the selected
pigments are shown in Fig. 10. The different component bands
(obtained by deconvolution analysis) and its assignment to the
different spin-allowed and spin-forbidden transitions of octahedral
Ni2þ are indicated in the spectra. As it may be appreciated in Fig. 10,
the energy position of spin-allowed (n1, n2 and n3) transitions is very
similar for Ni-doped karrooite (above) and geikielite (middle)
pigments, although these bands are considerably broader in the
former (karrooite), due to the fact of the partial disordering of Ni2þ
ions in two distinct and non-equivalent octahedral sites (M1 and
M2) [25]. As a result, the n3 band becomes broadly overlapped with
 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381
Table 2
Optical properties of orange pseudobrookite pigment (karrooite Mg1
xNixTi2O5; x ¼ 0.4), yellow ilmenite pigment (geikielite Mg1
xNixTiO3; x ¼ 0.2) and green spinel pigment
(qandilite Mg1
xNixTi2O5; x ¼ 0.4) fired at 1200 or 1400  C: energies (cm
1) of spin-allowed and spin-forbidden bands (from deconvolution analysis), and optical parameters
according to TanabeeSugano fitting (crystal field strength D0, interelectronic repulsion Racah B parameter, and nephelauxetic ratio b ¼ B/B0, where B0 is the B value of free Ni2þ
ion, 1041 cm
1 [41]).
NieO charge transfer (peaking at around 27,000 cm
1) in Ni-doped
karrooite, while both contributions are perfectly differentiated in
Ni-doped geikielite.
Also noteworthy, the absorption contribution associated to spin-
forbidden 1T2g (1D) and 1A1g (1G) transitions is much more
important in Ni-doped karrooite than in geikielite; as a result, the
karrooite pigment has a much higher absorption of the yellow re-
gion of the visible (560e590 nm; 17,860-16,950 cm
1) resulting
orange-colored, while Ni-geikielite pigment fired at 1200  C is
yellow-colored. In the case of Ni-doped qandilite pigment, it may
be also clearly appreciated (as in Fig. 9) that all the transitions are
shifted to higher energies (or wavenumbers), with the exception of
the shoulder associated to spin-forbidden 1Eg (1D) transition, which
remains almost in the same position in the spectra of the three
magnesium titanates. This fact is in agreement and fits perfectly
with the corresponding d8 TanabeeSugano diagram, in which the
energy of 1Eg (1D) term remains almost constant or unaffected by
the increase of crystalline field. Thus, in the spectrum of Ni-doped
qandilite an inversion occurs in the position of n2 and 1Eg (1D)
transitions (with respect to spectra of Ni-doped karrooite and
geikielite). Owing to the broad and blue-shifted n2 absorption,
extending from the red, through the orange and yellow region, the
Ni-doped qandilite pigment becomes green-colored, as it was
previously discussed.
As it may be appreciated in Table 2, the values of crystal field
strength (D0) determined for Ni-doped karrooite (orange) and
geikielite (yellow) pigments do not differ substantially (7373 and
7330 cm
1, respectively), and the values of interelectronic repul-
sion Racah parameter (B) are also very similar (768 and 763 cm
1),
resulting in a coincident D0/B ratio (9.6) and in a very similar
covalence degree (expressed by the nephelauxetic ratio b ¼ B/B0;
0.74 and 0.73 for karrooite and geikielite). This fact is indicating that
<NieO> bond length distances may not differ substantially in Ni-
karrooite and Ni-geikielite pigments. Indeed, the reported
average <M
O> distances for an ordered karrooite (corresponding
379
to M1 sites, which is the position mostly occupied for Ni2þ in Ni-
karrooite pigments [25]) and for geikielite are around 2.08 [44]
and 2.11 Å [9], respectively. Comparatively, the green Ni-qandilite
spinel presents a much higher crystal field strength
(D0 ¼ 8960 cm
1) and an increased Racah parameter (786 cm
1),
which is associated to a slightly increased ionicity or lower cova-
lence of NieO bonds (higher nephelauxetic ratio b ¼ 0.76). Taking
into account that the octahedral crystal field splitting D0 follows
and inverse fifth-power dependence on the metal oxygen distance
[5], the considerable increase of crystal field strength determined in
Ni-qandilite spinel is in good agreement with the smaller <M-O>
distances occurring in the octahedral sites of qandilite spinel
(around 2.02 Å according to previous reports [9]), with respect to
those found in related karrooite and geikielite magnesium tita-
nates. The values for the crystal field strength exerted on Ni2þ ions
have been reported to be between 8500 and 10,500 cm
1 in several
oxide structures with regular or distorted octahedral sites [5,45].
The D0 value obtained for the green Ni-qandilite pigment herein
investigated (8960 cm
1) falls within this range, but a considerably
lower D0 splitting was obtained for Ni-doped orange karrooite and
yellow geikielite pigments (7330-7373 cm
1). However, these
lower crystal field values for karrooite and geikielite are in good
accordance with other investigations reporting an even much
lower crystal field strength (around 6900 cm
1) for Ni2þ ions in a
yellow-colored Ni-doped clinoenstatite (Mg0.95Ni0.05SiO3; P21/c
structure), although a much higher ionicity was determined in this
structure (B ¼ 1039, b ¼ 1) [46].
4. Conclusions
Solids solutions of Ni in Mg2TiO4 qandilite spinel (Mg2
xNix-
TiO4; from x ¼ 0 to 0.4) have been successfully prepared by the
conventional ceramic method and also by a citrates gel metal-
organic decomposition route (MOD) using rapid industrial-like
firing conditions (3h soaking), and their technological application
380 M. Llusar et al. / Dyes and Pigments 122 (2015) 368e381

solutions of Ni-doped qandilite only stabilized at 1400  C, although

still accompanied by considerable amounts of MgTiO3 and MgO
phases. In contrast, in the citrate-gel MOD route the qandilite spinel
already crystallized at 600  C as metastable (and nano-crystalline)
phase, partially and fully decomposing in a mixture of Ni-doped
geikielite and periclase at 800 and 1000  C, respectively, and
reappearing again at higher temperatures (1200 and 1400  C).
The increase of Ni-doping had and important and detrimental
effect on the stabilization of the qandilite spinel phase, favoring its
decomposition in geikielite and periclase compounds. This
decomposition was much more sensitive to the increase of Ni-
content in samples prepared by the citrate-gel route (between
600 and 1200  C). In this method, the qandilite spinel was already
stabilized as almost single phase at 1200  C (only up to a 10 mol%
Ni-doping) and at 1400  C for all the investigated amounts of Ni-
doping (10, 20 and 40 mol%).
The successful incorporation of Ni2þ ions replacing for Mg2þ in
qandilite lattice was accompanied by a decrease of unit cell
parameter (a) and volume of the cubic spinel, and the resulting Ni-
doped qandilite solid solutions developed green colorations of
higher vividness and green chromaticity in the case of pigments
prepared by the citrate-gel route, intensifying also the green hue
with Ni doping.
By UVeviseNIR spectroscopy, the green color was associated to
electronic transitions of Ni2þ allocated exclusively in octahedral
sites of qandilite inverse spinel ([Mg]tet[Mg1
x NixTi]octO4). Thus, the
relatively distinct <NieO> distances resulting from the accom-
modation of Ni2þ ions in the distorted octahedral sites of related Mg
titanates enables a smart color modulation from the orange color
found in Ni-karrooite pseudobrookite, through the yellow in Ni-
geikielite ilmenite and to the green in Ni-qandilite spinel. The
smaller octahedral distances occurring in Ni-doped qandilite spinel
are in good accordance with the higher values determined for the
crystalline field strength (8960 cm
1) and interelectronic repulsion
Racah B parameter (786 cm
1), relative to those in Ni-doped gei-
kielite (7330 and 763 cm
1) and karrooite (7373 and 768 cm
1),
being the covalence degree of NieO bonds very similar in the three
structures (nephelauxetic ratio b ¼ 0.73e0.76).
The synthesized Ni-doped qandilite green solid solutions were
chemically unstable in the three tested low-temperature
(950e1050  C) commercial ceramic glazes (especially in a CaO-
and ZnO-enriched glaze), although glazed samples gave rise to
relatively intense yellow colorations (very similar in both synthesis
routes). Therefore, Ni-doped qandilite solid solutions could act as
yellowish ceramic dyes but not as true pigments in the coloration of
ceramic glazes.

Acknowledgements

The authors acknowledge the Spanish “Ministerio de Economía

y Competividad” (Project MAT2012-36988-C02-01) for financial
support. The technical assistance provided by the Scientific
Instrumentation Central Services (SCIC) of the University Jaume I is
also fully acknowledged.
Fig. 10. Fitting of KubelkaeMunk (K/S) absorption spectra of selected pigments
(x ¼ 0.4): an orange karrooite (Kar, Mg0.6Ni0.4Ti2O5) fired at 1400  C (top), a yellow Appendix A. Supplementary data
ilmenite (Gei, Mg0.6Ni0.4TiO3) fired at 1200  C (middle), and a green spinel (Qan,
Mg1.6Ni0.4TiO4) fired at 1400  C (bottom).
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2015.07.014.
as potential ceramic pigments or dyes for the coloration of low-
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