Ceramics International 46 (2020) 2332–2343

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Synthesis and characterization of pigments based on copper-zinc aluminate T

(CuxZn1-xAl2O4) by combustion
Thais Cristine de Sousa Santosb, Darllan do Rosario Pinheiroc, Cristiane Maria Leal Costaa,
Diego Cardoso Estumanod, Nielson Fernando da Paixão Ribeiroa,∗
a
Faculty of Chemical Engineering FEQ/ITEC/UFPA, Rua Augusto Correa, 01, CEP 66075-110, Belém, PA, Brazil
b
Pos-graduation of Chemical Engineering PPGEQ/ITEC/UFPA, Rua Augusto Correa, 01, CEP 66075-110, Belém, PA, Brazil
c
Natural Resources Engineering PRODERNA/ITEC/UFPA, Rua Augusto Correa, 01, CEP 66075-110, Belém, PA, Brazil
d
Faculty of Biotechnology – ICB, Federal University of Pará - UFPA, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: New pigments with copper-zinc aluminate structures (CuxZn1-xAl2O4) were successfully produced by the com-
Pigments bustion method. The materials synthesized were evaluated by TGA, SEM, XRD, FT-IR and the CIELab method in
Spinel order to investigate the influence of chromophore ion content (x = 0, 0.1, 0.2, 0.4 and 1) and heat treatment
Aluminate temperatures of (600 °C, 800 °C and 1000 °C) on the structural, morphological and colorimetric properties of the
Copper
pigments. Thermogravimetric analysis showed less than 6% mass loss, indicating that the combustion reaction
was adequate. The XRD technique confirmed the presence of the spinel phase in all materials synthesized, except
for samples with x = 1 without heat treatment or treated at 600 °C or 800 °C. Infrared spectroscopy showed that
the addition of copper causes a small inversion in the assigned crystalline structure, verifying the presence of
aluminium ions in the tetrahedral sites through monitoring of the 805 cm−1 band. The colorimetric data ob-
tained from the dry powder pigments indicated coloration ranging from white (x = 0) to weak yellow (x = 0.1
and x = 0.2) and dark red (x = 1), which confirms the potential of copper-zinc aluminates in the production of
diversified colours. The colour differences between the dried and dispersed powders in varnish were considered
sharp. From the colorimetric experimental data, surface graphs were constructed, and empirical equations were
obtained to predict the values of L*, a* and b*.

1. Introduction
The aluminates are an essential class of materials composed of
metallic oxides having spinel-type structures [1]. For decades, complex
oxides with these structures have been investigated. These oxides pre-
sent a variety of relevant electrical, magnetic, catalytic, and optical
properties and have multiple applications and use as uses as magnetic
materials, semiconductors, catalysts, photocatalysts, pigments, and re-
fractories [2–9].
Spinels have cubic face-centered structures (fcc) and a general for-
mula of (A1-xBx) [AxB2-x] O4. They are classified as normal, inverse or
random. A is a divalent cation, B is a trivalent cation, and x is the in-
version parameter. In normal spinel (AB2O4), the trivalent cations oc-
cupy the octahedral sites, and the divalent cations are allocated to the
tetrahedral sites. In the inverse position, the cations are rearranged, and
the formula is B(AB)O4. Although the normal spinel is more stable,
some d-block elements have different affinities with the sites, which
causes the structure to reverse. Thus, the variation in cation distribution
between sites may lead to changes in the physical, chemical, and optical
properties [10–13].
Typically, ions of transition elements are responsible for the colours
of inorganic pigments and are characterized by incomplete d orbitals.
The electron transitions occurring in this orbital are of the same mag-
nitude as transitions occurring in the visible region of the spectrum. The
transitions absorb and emit radiation and are responsible for the
characteristic colours of transition metals. Furthermore, different col-
ours are influenced by the interactions produced by the crystalline field;
these interactions vary according to the transition element, oxidation
state, position geometry of the ion and crystalline field strength (anion
charge, bonding type, and polyhedron distortion coordination)
[10,14,15]. Therefore, the use of chromophore ions in spinels is inter-
esting for the pigment industry, giving rise to a range of different in-
termediate spinels with various properties.
Spinel synthesis has traditionally been carried out by the

∗
Corresponding author.
E-mail address: nielson@ufpa.br (N.F.d.P. Ribeiro).

https://doi.org/10.1016/j.ceramint.2019.09.224
Received 27 May 2019; Received in revised form 22 September 2019; Accepted 23 September 2019
Available online 24 September 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
T.C.d.S. Santos, et al. Ceramics International 46 (2020) 2332–2343

conventional method (solid-state reaction) [16,17], but alternative
routes have already been discovered, which produce pigments with
better characteristics and lower environmental impacts. The majority of
unconventional methods use water: sol-gel processing, co-precipitation,
the polymer precursors method (Pechini), and the combustion method
[18–22]. The combustion method is a low-cost, easy, and efficient route
for the production of pure and homogeneous nanometric-scale mate-
rials. It is based on exothermic and self-sustaining reactions between
the reducing propellant and the oxidizing element [23,24]. The amount
of gas released in the synthesis depends on the fuel used and the molar
ratio of fuel to nitrates. Furthermore, the gas is essential for the mate-
rial's nanometre size [25,26].
Zinc aluminate has a standard structure and is a material of low
toxicity, chemical and thermal stability, mechanical resistance, rapid
cation diffusion, and potential as a receptor structure for different d
ions groups. The characteristics matrix make this compound a coveted
material, and it can be used in the synthesis of compounds with less
toxicity while maintaining the original characteristics. In the pigmented
area, aluminate can be used with low doping of transition metals, such
as nickel, iron, copper, and cobalt, to produce dyes with pleasing aes-
thetics and intense colours [27,28]. Copper is a transition metal that
has nine electrons in its d orbital and may assume different states of
oxidation, depending on the material. In the literature, few papers are
applying it as a pigment, while most are related to properties for cat-
alysis, photocatalysis, and semiconductors [29–32].
Works using copper as a pigment include that of Dohnalová et al.
[33], who studied the colour possibilities of CuAl2-xLnxO4 materials
with x = 0 to 2 and Ln = I, Sm, Nd, Y, La, and Tm. They found that the
resulting colour was related to the rare earth cations. Furthermore,
trivalent ions with ionic radii greater than 0.092 nm (Sm, Nd, Eu, and
La) caused the formation of black pigments, whereas a turquoise colour
was obtained with ionic radii lower than 0.092 nm (Y, Tm). Zhang et al.
[34] synthesized inorganic Cu and In doped pigments in ZnSxSe1-x by a
co-precipitation method to investigate the morphological, structural,
chromaticity, NIR, and thermal reflective properties. They obtained
pigments in different colours (red, yellow and others) and found the
surface temperature of aluminum plates coated with the yellow and red
synthesized pigments to be reduced by 4.2–7.9 °C, which shows a NIR
reflective potential and possible application as “cool pigments."
To study the use of copper as a pigment and to consider that zinc
aluminate is non-toxic and can be used as an ion support, this paper
describes the preparation of CuxZn1-xAl2O4 spinels by combustion
method using glycine as fuel. The structural, morphological, and col-
orimetric properties were measured as functions of copper concentra-
tion and the heat treatment temperature. In addition, a mathematical
model is proposed to describe the dynamics of the L*, a* and b* CIELab
variables and thus estimate the final color of the pigment to be formed.
After that, to investigate the influence of the heat treatment on the
final properties, the materials were separated into four portions and
calcined in a muffle furnace at three different temperatures (up to
600 °C, 800 °C and 1000 °C) for 6 h. The solid calcined materials were
ground with an agate mortar and pestle. Finally, the powders were
stored for further characterization and application.
The amount of fuel and nitrates used in the preparation of alumi-
nates was based on stoichiometric balance calculated by the following
equation: ∑ ni vi = 0 , where ni represents the mole number of each
reactant and vi is the oxidation number, so that the fuel/oxidizer ratio
corresponds to the stoichiometric ratio. The combustion reactions is
described as follows:
x Cu(NO3)2.3H2O + (1-x) Zn(NO3)2.6H2O + 2 Al(NO3)3.9H2O + 4.4
NH2CH2COOH → CuxZn1-xAl2O4 + (35.1-3.x) H2O + 8.9 CO2 + 6.2 N2
The powders were prepared with nominal compositions of x = 0;
0.1; 0.2; 0.4 and 1. Likewise, the prepared spinels will be identified
based on the composition of copper (x) and the calcination temperature
(y) as CuxZny. That is, Cu0.1Zn600 is the sample containing 0.1 copper
calcined at 600 °C. Furthermore, the samples without thermal treatment
are designated as “SC”.
2.2. Thermodynamic calculation of the flame temperature
To calculate the diabatic flame temperature of combustion, Eqs.
(1)–(3) were used [35]. The flame temperature is the highest tem-
perature achieved during the combustion reaction.
ΔHo = ∑ nΔHPo − ∑ nΔHRo (1)
T
ΔHo = ∫ nCP dT
To (2)
CP
= A+ BT + CT 2 + DT−2
R (3)
where n is the number of moles; ΔHRoand ΔHPo
are the standard en-
thalpies of the formation of the reactants and products, respectively; T
is the adiabatic flame temperature; and To is the starting temperature
(298 K). Cp is the heat capacity of the products at constant pressure.
The thermodynamic data of reactants and products, available from the
literature [35,36], are listed in Tables 1 and 2. Due to a lack of ther-
modynamic properties of spinels, the heat capacity of MgAl2O4
(1.90613 cal mol−1 K−1) was used because this is an isostructural
compound and the divalent metallic radii [Cu2+, Zn2+ and Mg2+] are
nearly identical [37–39].

2. Experimental section Table 1

Thermodynamics data required for calculation of adiabatic flame temperature
[36].
In the synthesis of the colourful aluminate pigments, the chemical
reagents were purchased from commercial sources: copper nitrate [Cu Compound Entalphy of formation (kcal.mol−1)
(NO3)2.3H2O, Vetec-Brazil], zinc nitrate [Zn(NO3)2.6H2O, Synth-
Cu(NO3)2.3H20(c) −290.21
Brazil], aluminium nitrate [Al(NO3)3.9H2O, Synth-Brazil], and glycine Zn(NO3)2.6H20(c) −551.30
[NH2CH2COOH, SIGMA-Brazil]. All materials were used as received, Al(NO3)3.9H20(c) −897.57
and experiments were carried out with distilled water (Quimis). NH2CH2COOH(c) −126.31
ZnAl2O4(c) −493.26
CuAl2O4(c) −433.00
2.1. Sample preparation Cu0,1Zn0,9Al2O4(c)a −487.2
Cu0,2Zn0,8Al2O4(c)a −481.21
The spinels (CuxZn1-xAl2O4) were synthesized by combustion Cu0,4Zn0,6Al2O4(c)a −469.16
method: the metal nitrates and fuel were dissolved in water and heated H2O(g) −57.80
CO2(g) −94.05
up to 80 °C under constant stirring, in order to evaporate all the water
N2(g) 0
and fully form a gel. When the gel was prepared, the temperature of the
hot plate was increased to reach the ignition temperature of the pro- (c): crystalline; (g): gas.
pellant. The combustion reaction started at approximately 140 °C, a
The entalphy of formation was calculated in the appropriate stoichiometric
lasted 10 s until the high flame temperature. proportions of pure spinel: CuAl2O4 and ZnAl2O4.

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T.C.d.S. Santos, et al.
Table 2
Constants of equation (5) [35].
Chemical Species A 103 B 106 C 10−5 D
CO2 5.457 1.045 – −1.157
N2 3.280 0.593 – 0.04
H2O 3.470 1.450 – 0.121
2.3. Characterization
The thermal behavior of aluminates in powder form was determined
by using thermogravimetric analysis (NETZSCH-STA 449 F3 Jupiter
model) at a heating rate of 10 °C/min from 25 °C to 700 °C in an alu-
mina crucible (sample holder) under a nitrogen atmosphere at a flow
rate in 50 mL/min.
The crystalline phases were determined by X-ray diffraction (XRD)
using the powder method. The diffraction patterns were determined
using a D8 ADVANCE Bruker diffractometer equipped with a goni-
ometer (theta/theta) and Cu anode ceramic X-ray tube (Kα1 = 1.54058
A), model 10190376 (2 kW/60 kV). The diffractograms used a detection
range of 10°≤2 θ ≤80° with a step size of 0.02° and a speed of
0.01°s−1. The crystallite sizes were calculated using the Scherrer
equation. The quantification of the phases and the lattice parameters
were calculated by the Rietveld methodology.
Scanning electron microscopy (SEM) with a VEGA3 System coupled
to dispersive energy detector (EDS) from Shimadzu investigated the
microstructure of the powders. The secondary electron beam was used,
and samples were previously metalized by the deposition of gold film.
Infrared spectra were recorded in the 400–4000 cm−1 spectral re-
gion with a Shimadzu (IRPrestige-21). The analyses were performed on
self-supporting pellets diluted with KBr.
The CIELab chromaticity coordinates were taken directly from the
calcined powders by means of a Konica Minolta Color Reader CR-10
portable colorimeter, using D65 illumination and the 10° standard ob-
server. To verify the paint formulations and properties, the synthesized
powders were sifted through a 200-mesh sieve and dispersed in col-
ourless acrylic varnish (ACRILEX) at a proportion of 10%. The CIELab
parameters were measured after 48 h of drying at room temperature.
Finally, the colour differences between dry and dispersed powders were
calculated using Eq. (4), which is the simple distance between two
points in the three-dimensional colorimetric space.
Δ E= ΔL2 + Δa2 + Δb2 (4)
In the CIELab system, L* is the degree of lightness or darkness of the
color, ranging from white (L* = 100) to black (L* = 0). Positive values
of a* correspond to red, and negative values correspond to green.
Finally, positive values of b* correspond to yellow, while negative va-
lues correspond to blue.
3. Results and discussion
3.1. Synthesis
To obtain nanometric materials, it is necessary to have a high
temperature during preparation and a significant amount of gas re-
leased that disintegrates agglomerates and large particles, increasing
contact between the particles and minimizing the sintering process
[25,26].
The materials obtained in this work had a spongy, fragile, and
porous appearance, as can be seen in Fig. 1. The yellowish coloration
observed is from the addition of copper ions to the spinel structure, and
the dark area corresponds to combustion residue during synthesis. This
deposition is a consequence of the irregular combustion reaction, which
generates an incomplete burning of fuel, and in turn, promotes residue
deposits on the surface of the material. The quantity and thermal
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Ceramics International 46 (2020) 2332–2343
Fig. 1. Material synthesized by the combustion method.
behavior of these residues were evaluated by thermal analysis, with the
results presented in the 3.2 sessions.
The extreme release of gases not only affects the nucleation and
growth of the particles but also decreases the maximum flame tem-
perature during the firing, thereby reducing the energy produced by the
system and leading to the appearance of secondary crystalline phases
(see XRD results). In this context, heat treatment is an essential step for
obtaining a pure crystalline phase [40].
Table 3 shows the theoretical adiabatic flame temperature data,
calculated based on the enthalpies of reaction through equations
(1)–(3). The values are consistent with the literature data [39] and
present a temperature variation of 100 °C depending on the synthesis
conditions. However, there were no significant changes in the visual
appearance of the produced spinels observed. This can be attributed to
the small-time duration at the maximum peak temperature (~10 s) in
the combustion process.
3.2. Synthesis residues characterization
To evaluate the thermal behavior of the materials and to confirm the
presence of residue deposited on the surfaces, thermogravimetric ana-
lyses on the Cu0ZnSC, Cu0.4ZnSC and Cu1ZnSC samples and FT-IR
analysis in CuxZn800 series were performed, with the results obtained
shown in Fig. 2a and b, respectively. The mass loss may be due to the
removal of organic residuals in the form of nitrogenous and carbonac-
eous compounds. The Cu1Zn sample showed the lowest mass loss. As
shown in Table 3, this sample had the highest flame temperature
(1070 °C), which left little nitrogenous and carbonaceous material to be
evaporated. The small mass loss (< 6%) can be evaluated by following
the calculated maximum flame temperature values (Table 3), which are
all above 900 °C. Based on the fact that deposited residue is a side effect
of irregular combustion and that the adiabatic flame temperature va-
lues are high, it can be inferred that the small loss of mass indicates that
the combustion reactions were practically complete. In addition, as
verified by TGA analysis above 600 °C all residue was eliminated,
Table 3
The theoretical adiabatic flame temperature of the copper series.
x Theoretical adiabatic flame temperature Total number of gaseous
(°C) moles
0 967.0 50.2
0.1 976.9 49.9
0.2 986.9 49.6
0.4 1007.3 49.0
1 1070.7 47.2
T.C.d.S. Santos, et al.
Fig. 2. a) Thermal analysis of the prepared powders and b) IR spectra of CuZn800 series.
indicating that the calcined samples have a clean surface.
To confirm the presence or absence of residues on the pigment
surface, Fig. 2b shows the full FT-IR spectrum of the CuZn800 series;
the other samples synthesized in the work had the same behavior. There
was no significant presence of bands attributed to organic-only bands
with significantly reduced intensity around 1700 and 3500 cm−1, cor-
responding to the stretching vibrations –OH groups, the result of phy-
sically adsorbed water and hydroxyl water superficial. In addition, the
small band around 2300 cm−1 can be attributed to the OfCfO stretch
vibration mode. According to Wei and Chen [41], the high surface area
of these materials results in the rapid absorption of water and carbon
dioxide from the atmosphere. Hassanzadeh-Tabrizi et al. [42] studied
the synthesis of nanostructured CuAl2O4 particles by a co-precipitation
process with the aid of diethylamine as a precipitating agent. The
presence of peaks attributed to organic residues as intense as those that
characterize the spinel structure are observed, as follows: around
1380 cm−1 due to vibration of NO3 groups confirming the presence of
Cu(NO3)2 and Al(NO3)3 species and 1042 cm−1 by the presence of the
C–N stretching vibration of aliphatic amine.
3.3. Microstructure and porosity characterization
The evaluation of the heat treatment effects on morphological
properties was performed by SEM analysis. Fig. 3 shows the
Fig. 3. SEM of Cu0.4Zn samples: a) not-calcined; b) calcined at 600 °C; and c) calcined at 1000 °C.
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Ceramics International 46 (2020) 2332–2343
micrographs of samples Ni0.4Zn0 (Fig. 3a), Ni0.4Zn600 (Fig. 3b) and
Ni0.4Zn1000 (Fig. 3c). The three samples are porous and do not have
definite shape structures. Isolated particles have not been identified,
only aggregates. The formation of these large aggregate systems is
characteristic of nanostructured particles as a result of the Van der
Waals attraction forces between particles [43].
The morphological aspects presented in the sample without calci-
nation (Cu0.4ZnSC) are a result of pore obstruction by carbonaceous
material. The heat treatment at 600 °C promotes a small change in the
material's morphological properties with an increase in the quantity
and size of pores, which may be a result of pore clearance [44]. The
micrograph of the Cu0.4Zn1000 sample, in comparison with other
samples, presents a smaller number of pores, which can be attributed to
the continuation of the sintering process at high temperatures. With
excessive temperature increase, the pores tend to collapse due to the
compacting of the material that negatively affects its surface area and
consequently worsens the dispersion of the pigment. In addition, a
particular behavior was observed in the micrograph of the Cu0.4Zn0
with increasing magnification (Fig. 4). The numerous spherical parti-
cles on the surface of the structure, attributed to the presence of CuO,
segregated, as seen by the diffractogram (Fig. 5d).
T.C.d.S. Santos, et al.
Fig. 4. SEM of the Cu0.4Zn not-calcined sample.
3.4. Crystallography phase formation
The diffractograms used to identify the crystalline phases formed
through the synthesis and subsequent heat treatment of copper-zinc
pigments are shown in two forms: as a function of temperature at each
composition (Figs. 5 and 6), and as a function of composition at each
temperature (Fig. 7).
Fig. 5 confirms the development of the cubic spinel structure at all
temperatures evaluated for x = 0, 0.1, 0.2 and 0.4, including the not-
Fig. 5. XRD with varying calcination temperature: a) Cu0Zn; b) Cu0.1Zn; c) Cu0.2Zn; and d) Cu0.4Zn.
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Fig. 6. XRD with varying calcination temperature for the Cu1Zn sample.
calcined samples (ICSD-9559 and ICSD-40023 for ZnAl2O4 and
Cu0.6Zn0.4Al2O4, respectively). This shows that the combustion method
is suitable for producing copper-doped zinc aluminates. In contrast, for
x = 1 (Fig. 6), only heat treatment at 1000 °C was found to give the
CuAl2O4 spinel structure (ICSD-9558), revealing that the method pre-
sents difficulties in producing copper aluminate, and therefore, the
subsequent heat treatment is essential.
The diffractograms of copper-zinc aluminate samples showed dif-
ferent behaviours depending on doping and temperature, revealing that
spinel formations with pure phases are very unstable. Analysing the
results for the Cu0Zn and Cu0Zn600 samples (Fig. 5a and b), in addition
T.C.d.S. Santos, et al.
Fig. 7. XRD with varying copper ion content: a) not-calcined; b) 600 °C; c) 800 °C; and d) 1000 °C.
to the spinel phase, a ZnO segregated phase (ICSD-26170) was identi-
fied, indicating that the energy of the synthesis and heat treatment up
to 600 °C were not sufficient to complete the reactions and incorporate
the Zn2 into the structure. These data are in agreement with the lit-
erature data in which the ZnO and ZnAl2O4 phases are obtained for
thermal treatments at temperatures above 700 °C [41].
For x = 0.1 (Fig. 5b), the pure spinel was identified in the samples
at 800 °C and 1000 °C, while for x = 0.2 (Fig. 4c), it was only found in
the sample at 800 °C. For samples with x = 0.1, 0.2 and 0.4, not-cal-
cined and calcined at 600 °C, copper oxide not accommodated in the
structure (CuO ICSD-16025) was identified. In samples with x = 0.2
and 0.4 calcined at 1000 °C, alumina was identified as the secondary
phase (Al2O3 AMCSD-0010593). The phase equilibrium diagram of the
CuO/Al2O3 system confirms this instability [45].
Different from other samples under the same conditions, in the
materials with x = 1 (Fig. 6) not-calcined or calcined at 600 °C and
800 °C, the spinel phase was not formed, and only alumina and copper
oxide phases were identified. Furthermore, especially in the Cu1Zn
sample, the Cu2O phase was identified, and with heat treatment at
1000 °C, the spinel phase was formed, but still with alumina.
To support the XRD analysis, the Rietveld method was used to
quantify the phases and unit cell parameters. The obtained values are
shown in Table 4 as well as the approximate chemical composition data
of each sample obtained by EDS analysis. In Table 4, the crystallite
sizes, obtained by the Scherrer equation, are shown. The highest values
of the pure spinel phase were found at the temperature of 800 °C in all
copper doping, except for the Cu1Zn series, which exhibited spinel
formation only at 1000 °C and was quantified at 94.11%. The heat
treatment at 1000 °C promotes the incorporation of copper into the
structure. This incorporation is carried out in two stages: first, Cu2O
becomes CuO, and second, CuO is added into the spinel structure. This
fact is verified by the quantification of the crystalline phases of the
Cu1Zn group samples applying the Rietveld method. It is observed that
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Ceramics International 46 (2020) 2332–2343
concerning secondary phases for samples Cu1Zn0 and Cu1Zn600, the
increase in heat treatment temperature caused the phase change of
Cu2O to CuO. Comparing the Cu1Zn600 and Cu1Zn800 quantifications,
there was a slight increase in the amount of CuO and a decrease in the
amount of Al2O3. In addition, by evaluating the Cu1Zn800 and
Cu1Zn1000 samples, it is noted that this temperature increase pro-
moted the majority formation of the spinel phase, with the copper ions
and most of the aluminum entering the spinel structure, leaving only
5.89% segregated Al2O3.
In the series Cu0.2Zn and Cu0.4Zn, comparing the values at 600 °C
and 800 °C, total incorporation of the segregated copper oxide in the
spinel structure was observed. For samples calcined at 800 °C and
1000 °C, alumina segregation occurred with increasing temperature and
copper content. The values of 8.066% and 13.99% for Cu0.2Zn1000
and Cu0.4Zn1000, respectively, were found, as presented in Table 4.
Fig. 7 shows the diffractograms of the samples for each temperature,
varying the composition of the chromophore ion. The approximation
was made in the most intense peak at position (I311), for better vi-
sualization. At all temperatures, a small displacement of the peak at
position (I311) 2θ - 37° to the right was observed with increasing
copper concentration, which can indicate the substitution of Zn2+ ions
for Cu2+ ions in structure, due to their different ionic radii. The copper
radius (0.73 Å) is slightly smaller than that of zinc (0.74 Å), which
causes the discrete displacement to the right [46,47]. In addition, this
displacement confirms the formation of solid solutions with the gradual
replacement of ions.
Based on the fact that peaks indicate planar directions, changes in
the cation distributions due to the inversion of the structure can modify
the planar density and planar directions, causing peaks to appear and/
or disappear in the diffractograms. No peaks emerged/disappeared
when compared to the data for standard ZnAl2O4 (ICSD-9559), in-
dicating that the addition of copper ions causes little or no change in
the distribution of cations in the structure. It is worth mentioning that
T.C.d.S. Santos, et al. Ceramics International 46 (2020) 2332–2343

Table 4
Phase quantification, lattice parameter and crystallite size.
Sample Chemical Composition by EDS Phases (%) Lattice Parameter (Ȧ ) Crystallite Size (nm)

Spinel ZnO CuO Al2O4 Cu2O

Cu0ZnSC Cu0Zn1.1Al2O4 97.1 2.93 – – – 8.087 22.808

Cu0Zn600 Cu0Zn1.1Al2.1O4 97.3 2.73 – – – 8.087 23.197
Cu0Zn800 Cu0Zn1.1Al2O4 100 – – – – 8.087 28.535
Cu0Zn1000 Cu0Zn1.1Al1.9O4 100 – – – – 8.085 45.278
Cu0.1ZnSC Cu0.08Zn0.92Al2.1O4 96.5 – 3.5 – – 8.085 25.615
Cu0.1Zn600 Cu0.09Zn0.91Al2.2O4 97.3 – 2.7 – – 8.072 25.431
Cu0.1Zn800 Cu0.08Zn0.92Al2.2O4 100 – – – – 8.074 30.168
Cu0.1Zn1000 Cu0.09Zn0.91Al2.2O4 100 – – – – 8.074 33.716
Cu0.2ZnSC Cu0.21Zn0.79Al2.1O4 83.6 – 16.3 – – 8.042 18.081
Cu0.2Zn600 Cu0.2Zn0.8Al2.2O4 87.8 – 12.2 – – 8.051 19.181
Cu0.2Zn800 Cu0.2Zn0.8Al2.0O4 100 – – – – 8.064 27.447
Cu0.2Zn1000 Cu0.21Zn0.79Al2.0O4 91.9 – – 8.0 – 8.071 38.493
Cu0.4ZnSC Cu0.41Zn0.59Al2.2O4 77.9 – 22.1 – – 8.037 18.037
Cu0.4Zn600 Cu0.37Zn0.63Al2.1O4 79.8 – 20.1 – – 8.039 18.872
Cu0.4Zn800 Cu0.4Zn0.6Al2.2O4 96.2 – – 3.7 – 8.067 35.522
Cu0.4Zn1000 Cu0.39Zn0.61Al2.0O4 86.0 – – 13.9 – 8.072 51.078
Cu1ZnSC Cu1Zn0Al2.2O4 – – 39.6 57.0 3.25 – –
Cu1Zn600 Cu1Zn0Al2.2O4 – – 47.0 52.9 – – –
Cu1Zn800 Cu1Zn0Al2.18O4 – – 48.6 51.3 – – –
Cu1Zn1000 Cu1Zn0Al2.14O4 94.1 – – 5.8 – 8.073 67.414

dp → crystallite size by Scherrer equation.

Fig. 8. a) Lattice parameter as a function of copper ion content; b) particle size as a function of copper ion content; c) lattice parameter as a function of calcination
temperature; and d) particle size as a function of calcination temperature.

when analyzing the Cu1Zn1000 sample, wherein total substitution of
zinc ions by copper occurs, the same peak positions present in the
normal spinel structure are observed, which can confirm the similarity
between the copper and zinc ions in terms of preference for tetrahedral
sites and a greater tendency to form normal or slightly inverted spinels
[10].
The copper influence on the lattice parameter (a0) was investigated,
with the results presented in Fig. 8a. For samples calcined at 800 °C and
1000 °C, a tendency to stabilize the lattice parameter from x > 0.2 to
reach a final value of 8.067 and 8.079 (Ȧ ), respectively, was observed.
This behavior was also observed by Arean et al. [48], who studied the
substitution of zinc for copper ions in spinel structures. The authors
found a slight decrease in a0 with increasing copper content, with the
portion of copper cations with tetrahedral coordination increasing from
1/2 to 2/3 with the increase in x from 0.2 to 1. For samples not-calcined
and calcined at 600 °C, a continuous and pronounced decrease in a0
with increasing copper content was observed, which can be related to
the lower stabilization of the material structure. Thus, the energy ori-
ginating from synthesis processing (combustion energy) and heat
treatment up to 600 °C was not sufficient for complete incorporation
and stabilization of the Cu2+ ions in the spinel structure. It is important
to note that the heat treatment is a fundamental process in obtaining
pure and well-ordered structures, and the maximum flame temperature
has the potential to reach approximately 1070 °C. This temperature is

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T.C.d.S. Santos, et al.
Fig. 9. FT-IR of samples: a) Cu0Zn; b) Cu0.1Zn; c) Cu0.2Zn; and d) Cu0.4Zn with varying calcination temperature.
Fig. 10. FT-IR of the Cu1Zn sample with varying calcination temperature.
maintained for only a few seconds, an insufficient time to promote the
complete incorporation and stabilization of the ions. The temperature
effect on the lattice parameter is shown in Fig. 8c. For the Cu0Zn
samples, no significant variation in a0 was observed, as it remained
practically constant at all temperatures studied. For Cu0.1Zn samples,
a0 decreased with the increase in temperature, and the inverse behavior
occurred for the Cu0.2Zn and Cu0.4Zn samples. This was attributed to
the different stabilizations of the spinel structure.
The crystallite sizes varying with copper content and temperature
are shown in Fig. 8b–d, respectively. There was no significant change in
crystallite size between not-calcined and calcined samples at 600 °C
(Fig. 8d), indicating again that the energy generated at this temperature
is not sufficient to modify the material structure. In addition, by ana-
lyzing the theoretical adiabatic flame temperature (Table 3), it can be
seen that in the synthesis, temperatures above 1000 °C are reached, if
only for a few seconds; however, the large volume of gas released and
its rapid expansion during synthesis dissipate the heat and limit the
temperature rise, which affects the nucleation of the crystals,
2339
Ceramics International 46 (2020) 2332–2343
substantially decreasing their growth and stabilizing the structure. For
samples calcined at 800 °C and 1000 °C (Fig. 8d), an almost linear
crystallite growth is observed, due to material sintering caused by the
high heat treatment temperature.
Fig. 8b shows the chromophore ion effect on crystallite size. The
not-calcined and calcined at 600 °C samples showed a similar beha-
viour, with a slight decrease in crystallite size caused by the increase in
the copper amount in the chemical composition of materials, which
implies that the energy generated in synthesis and the use of heat
treatment at 600 °C are not sufficient to cause change or ordering in the
material structure. Distinct behavior was seen for the other samples,
calcined at 800 °C and 1000 °C; with 0 < x < 0.1, a reduction in
particle size occurred, and from x = 0.1, growth occurred with in-
creasing copper content. This decrease can be the result of atomic re-
arrangement in the crystalline structure, reducing the defects and
consequently the system entropy, making the particle sintering process
difficult. The increase in copper content promotes the inversion of the
structure, which destabilizes the material, causing crystal growth from
x = 0.1 for the sample calcined at 1000 °C and x = 0.2 for the sample
calcined at 800 °C.
3.5. Infrared spectroscopy
FT-IR analysis was completed to investigate the structural mod-
ifications caused by variations of the variables in the synthesis method.
Fig. 9 shows the results obtained for samples with x = 0, 0.1, 0.2 and,
0.4 as a function of the increase in the heat treatment temperature. All
spectra showed bands in the range of 500–900 cm−1 associated with
the M − O, Al–O and M-O-Al vibrations that are characteristic of the
spinel structure [49], confirming the XRD analysis (Fig. 5).
The bands between 750 and 450 cm−1 are characteristic of alu-
minum at an octahedral site (AlO6), and the bands between 750 and
950 cm−1 are attributed to aluminum at a tetrahedral site (AlO4) [50].
Thus, the absence of bands above 750 cm−1 in the samples with x = 0
shows that the ZnAl2O4 spinel is of normal type (bivalent metal ions at
tetrahedral sites and trivalent metal ions at octahedral sites). This be-
havior is often seen in Visinescu et al. [51]. The discrete band at
805 cm−1 present in samples with x = 0.1, 0.2 and 0.4 can indicate a
T.C.d.S. Santos, et al. Ceramics International 46 (2020) 2332–2343

Table 5
Colourimetric properties of powdered pigments – CuxZn1-xAl2O4.
Sample Powder dry Powder dispersed in varnish colorless

Visual Aspect L* a* b* Aspecto Visual L* a* b* ΔE

aa aa aa
Cu0Zn 28.83 1.07 7.17 12.60 0.00 4.80 8.77

Cu0Zn 43.70ba 0.77aa 5.50ba 30.57 0.10 15.23 5.87

Cu0Zn 46.23ca −0.83ca 5.77ca 30.83 0.37 15.77 7.92

Cu0.1Zn600 20.97ab 0.93aa** 7.27aa 12.63 −0.27 3.77 6.26

Cu0.1Zn800 36.30bb 0.43aa** 14.00bb 28.37 3.83 18.43 4.34

Cu0.1Zn1000 38.63cb 0.43aa** 14.40cb 18.70 8.73 19.07 16.10

Cu0.2Zn600 18.57ac 0.63ac 5.53ac 11.80 0.70 4.27 3.32

Cu0.2Zn800 32.67bc 3.23bc 18.53bc 24.77 8.80 15.73 6.06

Cu0.2Zn1000 34.20cc 4.40cc 19.63cc 27.53 5.70 20.10 4.31

Cu0.4Zn600 13.03ad 1.40ad 7.27aa 12.60 0.00 4.80 8.77

Cu0.4Zn800 27.77bd 8.00bd 20.93bd 30.57 0.10 15.23 5.87

Cu0.4Zn1000 29.67cd 9.13cd 21.60cd 30.83 0.37 15.77 7.92

Cu1Zn600 Dark – – – – –

Cu1Zn800 Dark – – – – –

Cu1Zn1000 18.13ce 12.90ce 18.67ce 19.77 8.13 9.67 10.31

a, b, c, d, e
= mean values following the same set of letters and same column no differ from each other by Tukey 5% test.

small reversal of the structure; its intensity increased with increased structure, making the spinel partially inverted. Similar results were also
copper doping and decreased with heat treatment, as seen in Fig. 9b–d. obtained by Buvaneswari et al. [52], who described CuAl2O4 synthe-
Thus, the copper ion causes a partial inversion in the structure, and the sized as inverted based on their FTIR analyses.
calcination process promotes better allocation of aluminum ions at the
tetrahedral sites and copper at the octahedral sites. Fig. 9b–d shows a
3.6. Colorimetry
band around 660 cm−1 attributed to Cu+2 in a tetrahedral site [3],
whose intensity is greater than that of the band around 805 cm−1 (at-
The visual appearance and the mean values of the CIELab colori-
tributed to tetrahedral aluminum). It is believed that the copper-zinc
metric coordinates of all pigments produced and dispersed in colourless
spinel is partially inverted, tending more to the normal-type spinel,
lacquer are presented in Table 5, along with their color differences.
which corroborates the non-appearance and/or disappearance of peaks
Each variable was measured in triplicate, and the mean values were
in the diffractograms containing copper (Fig. 7).
assessed via the Tukey test at the 5% probability level to evaluate if the
Fig. 10 shows the FT-IR spectrum for samples with x = 1 varying
obtained colours were statistically different. In this manner, it could be
with temperature. The spectra of samples without heat treatment
determined if changes in the chromophore copper ion content and heat
(Cu1Zn), at 600 °C (Cu1Zn600) and 800 °C (Cu1Zn800), are different
treatment significantly influenced the coloration of the formed pig-
from those obtained for samples calcined at 1000 °C (Cu1Zn100). A
ments. The test was performed on samples with the same content of
band is observed around 444 cm−1, characteristic of α-Al2O3 [50], with
chromophore ion but varying calcination temperatures, and on samples
bands near 587 and 637 cm−1 attributed to copper present in a tetra-
with the same calcination temperature but varying contents of chro-
hedral site and aluminum in an octahedral site. In the Cu1Zn1000
mophore ion.
spectrum, there was no clear definition of bands—only the discrete
Analyzing the visual appearance of pigments in Table 5 with x = 0,
bands at 730 and 805 cm−1 indicate a small inversion of structure.
it is noted that the pigment at temperatures of 800 °C and 1000 °C tends
Arean et al. [48], from the quantification of the occupancy factor and
toward white. This color was expected, because zinc is a transition
cation distribution at the different sites, described that Zn2+ occupies
element that has all d orbitals filled, and thus, it is not colored. Pig-
only tetrahedral sites independent of the copper composition in the
ments with 0 < x < 1 at 800 °C and 1000 °C showed different colours
CuxZn1-xAl2O4 spinel, while the Cu2+ ion changes its position in the
ranging from yellow to orange and red, while samples calcined at

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T.C.d.S. Santos, et al.
Fig. 11. Effect of temperature and chromophore ion content on the colourimetric variables of pigment powder.
600 °C showed dark colouring, tending to brown or black. Therefore,
increasing the temperature from 600 °C to 800 °C makes the samples
lighter visually, and increasing from 800 °C to 1000 °C allows the tones
to become more identifiable and pronounced. In particular, the sample
series Cu1Zn shows coloration identifiable only at 1000 °C, with a
reddish hue.
The Tukey, 5% analysis, indicated that all mean values of L* are
statistically different. As for the variable a*, only samples with x = 0
and 0.1 at 600 °C and 800 °C presented the same mean values. The
variable b* presented the same mean values for x = 0, 0.1 and 0.4 at
600 °C. Although some values are statistically equal, it is sufficient to
say that the color is different even if only one of the CIELab variables
presents different mean values. Thus, the variation in copper content
and calcination temperature caused significant changes in the color of
zinc-copper pigments, which confirms the visual analysis of materials in
Table 5.
Furthermore, most of the samples showed an evident visual differ-
ence in coloration between the dry powder and that dispersed in var-
nish. The values of ΔE (equation (4)) did not show a trend, and no
sample had a colour difference between 0 and 1.5 (almost identical
coloration) [53]. Only samples Cu0.2Zn800, Cu0.4Zn600, and
Cu0.4Zn1000 showed ΔE values in the range of 1.5–5, which indicates a
noticeable difference in colour. The others presented ΔE values above 5,
indicating that the colour difference is evident [53], confirming the
visual analysis.
Fig. 11 presents the CIELab parameters varying with the calcination
temperature and copper content. When analyzing the luminosity (L*),
its increase with the increase in the temperature for all the values of
copper is verified. When the effect of copper addition is evaluated, the
decrease in the L* variable is observed for all temperatures. As the
ZnAl2O4 base is white, when the chromophore dopant is added, the
samples tend to take on a different shade of white and therefore darken
(L* decreases). The copper has an incomplete d orbital, and electronic
transitions in this orbital give origin to the colours present in these
pigments.
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Ceramics International 46 (2020) 2332–2343
The Cu1Zn600 and Cu1Zn800 samples were identified as dark
bodies, a fact attributed to the non-formation of the spinel phase and
the significant presence of CuO discrete phase, which is black. This is
evidenced through the quantification of phases by the Rietveld method,
where CuO levels between 39% and 48% were found (see Table 4).
Furthermore, increasing of temperature to 1000 °C originates the
CuAl2O4 phase, resulting in a dark red pigment. According to Dohna-
lová et al. [33], this coloration is directly linked to the material phase
composition, which in this case is predominantly spinel. Bolt et al. [54]
reported that samples of CuAl2O4 treated at 1000 °C for a relatively
short period (3 h) were brown, but after more extended periods, they
became orange. The samples of the present work were calcined for 6 h,
which could influence the lighter coloration of the Cu1Zn1000 sample
compared to that found in the literature of dark brown. The increasing
copper doping at 800 °C and 1000 °C increased a* and b*, which in-
dicates a trend toward yellow-red. The origin of colour is the d-d
transition within the copper ion (which is a d9 species), and these
modifications in the coloration occur due to the ordering of the energy
level of the d orbitals caused by the environment of the binder field
surrounding the metal [50]. The indication of the formation of the
partially inverted spinel (Figs. 9 and 10) suggests changes in positions
of the ions from tetrahedral to octahedral sites. It modifies its binding
field, and consequently, its coloration also changes; thus, several col-
ourations were observed. This variety of shades obtained through
copper doping in zinc is advantageous for the pigment industry, as it
can give several colourations to meet increasingly different and specific
demands.
In order to predict the CIELab parameters and consequently, the
final colour of pigments formed under different synthesis conditions,
surface graphs were constructed from the colourimetric data obtained
experimentally. Fig. 12 shows the surface profiles followed by Equa-
tions (5)–(7) for L*, a* and b*, respectively. It is observed that the
equations satisfactorily describe the experimental data and can thus be
used to predict the colour behaviour of the materials.
T.C.d.S. Santos, et al.
Fig. 12. a) Variable luminosity (L*); b) variable chromaticity a*; and c) variable chromaticity b* as a function of heat treatment temperature and copper content.
L = −95.39 − 37.86LCu + 0.3CT + 27.06LCu2 − 0.015LCuCT
− 0.0002CT 2
a ∗ = −12.15 − −23.07LCu + 0.035CT − 19.26LCu2 − 0.0572LCuC
− 2.48x10−5CT 2
b ∗ = −52.35 − 30.69LCu + 0.14CT − 55.74LCu2 + 0.09LCuCT
− 9.09x10−5CT 2
CT represents the calcination temperature and LCu represents the
copper content in the spinel structure.
4. Conclusion
The CuxZn1-xAl2O4 aluminates were synthesized by combustion
using glycine as a propellant at stoichiometric ratios, and the results
showed this route of synthesis to be suitable for the production of na-
nometric spinel powders. However, to obtain a pure phase, a heat
treatment is required. The morphological properties were not affected
by the amount of the chromophore ions but only by heat treatment. The
zinc spinel presents a normal structure, and the increase in copper
content causes the partial inversion of the structure.
The pigments produced showed colourations ranging from yellow to
orange and red, showing the potential of copper in the synthesis of new
colours, although phase instability was found in XRD. The colouri-
metric data of ΔE indicated that the dilution of the pigment powder in
the colourless matrix acrylic lacquer caused significant changes in the
colouring of all samples, but yellow, orange and red shades similar to
Ceramics International 46 (2020) 2332–2343
the dry powders were seen. The proposed model for calculating L*, a*
(5) and b* based on different conditions of the calcination temperature and
copper ion content proved to be effective at reproducing the experi-
mental data.
(6)
Declaration of interests
(7) The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors acknowledge LEVAP, FINEP, LABNANO-AMAZON/
UFPA network and Laboratory of Nanotecnologia Farmacêutica –
Nanofarm-UFPA for the support to the facilities used in this work. This
work has been mainly supported by CNPq, FAPESPA, CAPES in Procad
Amazônia 2018 process number 88881.200618/2018-01.
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