Advanced Powder Technology 32 (2021) 3355–3363

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Synthesis of high color performance V-ZrSiO4 blue pigment with low

doping amount via inorganic sol–gel route
Wenjie Zhang a,1, Qikun Wang a,b,c,1,⇑, Xin Chen a,c, Xiaohong Li d, Qinghua Long a, Chao Wang a, Kun Liu a,
Yongqing Wang a, Qibing Chang a,⇑
a
School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, PR China
b
Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, PR China
c
Jingdezhen Ambitious Banding Materials Co., Ltd., Jingdezhen 333403, PR China
d
National Engineering Research Center for Domestic and Building Ceramics, Jingdezhen Ceramic University, Jingdezhen 333000, PR China

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

Article history: In this paper, high color performance vanadium ion (V4+) doped ZrSiO4 (V-ZrSiO4) blue pigment with low
Received 26 May 2021 doping amount has been successfully synthesized by inorganic sol–gel route. According to the phase evo-
Received in revised form 30 June 2021 lution and color behavior of the samples, the formation mechanism of the V-ZrSiO4 pigment was
Accepted 12 July 2021
revealed. Besides, due to the immobilization effect of the gel network and the high precursor reactivity,
Available online 31 July 2021
the reported synthesis route has extremely high vanadium utilization ratio (99.69%). Based on the results
of XPS and XRF analysis, it is found that the valence state of vanadium ion in the V-ZrSiO4 pigment is 4+,
Keywords:
meanwhile, the vanadium cations are heterogeneously distributed in the pigment particles and are
V-ZrSiO4 pigment
Sol-gel method
enriched within the outer layers. Compared with the previously reported V-ZrSiO4 pigments, the as-
Heterogeneously distribution prepared V-ZrSiO4 pigment shows a bright blue hue (b*=–22.01), in which the theoretical content of
Reaction mechanism V4+ is only 2 mol%. After applying on ceramic glaze, the V-ZrSiO4 pigment exhibited superior coloring per-
Color performance formance and high-temperature stability, indicating its potential application in ceramic decoration. This
work provides a facile strategy to synthesize high color performance ion-doping type pigment.
Ó 2021 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction doped YAlO3), (2) high energy consumption (e.g., CoZr4(PO4)6),

Ceramic pigment is a decorative material used for ceramic
products. As one of three-primary colors, a lot of blue ceramic pig-
ments would be consumed each year in ceramic industry [1].
Therefore, high color performance blue ceramic pigment has great
potential and market prospects. Over the past several decades, a
series of blue ceramic pigments with outstanding color perfor-
mance have been reported, such as CoAl2O4 [2], NaZn0.9Co0.1PO4
[3], V-ZrSiO4 [4], YIn1 xMnxO3 [5], a-LiZnBO3 [6], Sr1-xLaxCu1-
3+
yLiySi4O10[7], Tm doped YAlO3 [8], CoZr4(PO4)6 [9] and so on.
Nonetheless, some shortcomings persist about these blue pig-
ments: (1) high-cost (e.g., YIn1 xMnxO3, a-LiZnBO3 and Tm3+
⇑ Corresponding authors at: School of Materials Science and Engineering,
Jingdezhen Ceramic University, Jingdezhen 333403, PR China (Q. Wang).
E-mail addresses: 1099767147@qq.com (W. Zhang), 19B309004@stu.hit.edu.cn
(Q. Wang), 340195963@qq.com (X. Chen), 654391518@qq.com (Q. Long),
841438961@qq.com (C. Wang), nishiwodejia@126.com (K. Liu), wyq8248@126.
com (Y. Wang), changqibing@jci.edu.cn (Q. Chang).
1 compared with CoAl2O4 pigment, the color performance of
Co-first authors, these authors contributed equally to this study and share co-first
authorship.
(3) complex process, long production cycle and the crystal phase
control is difficult (e.g., Sr1-xLaxCu1-yLiySi4O10). Hence, these disad-
vantages would limit extensive use of the blue pigments. Due to
the excellent color performance, chemical stability and thermosta-
bility, CoAl2O4 pigment is currently the most consumed blue cera-
mic pigment. However, the price of cobalt has been rising with the
rapid development of new energy industry, which has put ceramic
enterprises under tremendous pressure [10–12]. Therefore, V-
ZrSiO4 has become the most promising candidate blue pigment
for its low-costs, simple process and energy saving.
V-ZrSiO4 is one of the zircon-based type pigments, which pre-
sents a sky-blue hue. The color mechanism of V-ZrSiO4 pigment
is vanadium ions enter into zircon lattice and occupy the Zr4+
and/or Si4+ site, resulting in the distortion of zircon lattice, and fur-
ther causing the V-ZrSiO4 particles show blue color [13,14]. Unfor-
tunately, due to the significant difference in ion radius between V4+
(0.58 Å) and Zr4+ (0.72 Å) or Si4+ (0.40 Å), the number of vanadium
ions that can enter into the zircon lattice is limited [15]. Therefore,
V-ZrSiO4 pigment is far from ideal, thereby would be restricted

https://doi.org/10.1016/j.apt.2021.07.018
0921-8831/Ó 2021 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
W. Zhang, Q. Wang, X. Chen et al.
the widespread application of V-ZrSiO4 pigment in ceramic decora-
tion, especially in ceramic ink-jet printing technology [16].
To improve the color performance, scholars have made a lot of
relevant research about V-ZrSiO4 pigment. As an example, Akdemir
et al., synthesized a V-ZrSiO4 pigment with the nominal doping
amount of V4+ is 7.3 mol% by solid-state method, which the
b*-value is 14.26[17]. Likewise, Monrós et al., were increased
the nominal doping amount of V4+ to 10 mol%, but the b*-value
of the as-synthesized pigment was merely optimized to 16.73
[14]. Therefore, it is not feasible to increase the chromatic value
of V-ZrSiO4 pigment by simply increasing the nominal doping
amount of V4+. This is because the excessive V4+ cannot enter into
the zircon lattice when the doping amount reached a higher level,
and the redundant V4+ will remain on the surface of the pigment as
oxides. Redundant vanadium oxides will be removed by pickling
process, however, in which the efficient recycle of vanadium ion
is difficult, thereby this will inevitably result in waste of vanadium
resources. Meanwhile, the unrecycled vanadium ions will pollute
the environment and pose a potential threat to human health
[18,19]. Based on the purpose of improving the color performance
of the V-ZrSiO4 pigment, Caselli et al., chose the Pechini method.
The results suggest that the b*-value of the obtained pigment
reached 20, when the nominal doping amount of V4+ is only
6 mol% [4]. Ardizzone et al., were prepared for the V-ZrSiO4 pig-
ment via organic sol–gel route, which the b*-value is up to –22.3.
Unfortunately, the nominal doping amount of V4+ is as high as
10 mol% [20]. Moreover, the other disadvantage of this method is
that the raw materials are expensive (such as Zr(OC3H7)4 and Si
(OC2H5)4). Compared with solid-state method, the liquid-phase
method is obviously more suitable for preparation of high color
performance V-ZrSiO4 pigment. It is because the pigment
particles prepared by liquid phase method have higher reactivity,
which is conducive to ion doped into matrix lattice [21]. In conclu-
sion, there is currently no ideal solution to the synthesis of V-
ZrSiO4 pigment with low V4+-doping amount with excellent color
performance.
In this paper, V-ZrSiO4 pigment was prepared using an inor-
ganic sol–gel approach, where ZrOCl2
8H2O as inorganic zirconium
source, commercial SiO2-sol as inorganic silicon source, NH4VO3 as
inorganic vanadium source, C6H12N4 as complexing agent and
hydrolysis agent. Furthermore, the effects of V4+-doping amount
and calcination temperature on chromatic parameters and phase
compositions of the as-synthesized pigments have been systemat-
ically investigated. Meanwhile, the formation mechanism of
V-ZrSiO4 pigment and the mechanism of high-efficient utilization
of vanadium ions were explained. Additionally, the distribution
behavior of vanadium ions in V-ZrSiO4 pigment was further stud-
ied by a series of characterization techniques. Finally, coloring
performance of V-ZrSiO4 pigment prepared by inorganic sol–gel
method in ceramic glaze was also considered.
2. Experimental procedure
2.1. Materials
Zirconyl chloride octahydrate (ZrOCl2
8H2O), ammonium
metavanadate (NH4VO3), hexamethylenetetramine (C6H12N4),
Oxalic acid dihydrate (C2H2O4
2H2O), Sodium fluoride (NaF),
sodium hydroxide (NaOH), hydrochloric acid (HCl), sulfuric acid
(H2SO4) and nitric acid (HNO3) all were purchased from Shanghai
Titan Scientific Co., Ltd. Silica sol (30 wt%) was obtained from
Jiangyin Xiagang Chemical Co., Ltd. The deionized water was
made by ultrapure water machine (Exceed-Cd, AK, China) in
our laboratory. All reagents were used as received without fur-
ther purification.
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Advanced Powder Technology 32 (2021) 3355–3363
2.2. Preparation
In a special experiment, 1.00 g of C2H2O4
2H2O, 38.67 g of
ZrOCl2
8H2O and 0.28 g of NH4VO3 were firstly dissolved into
82.72 g of deionized water in one beaker. 13.46 g of C6H12N4 was
dissolved into 100.00 g of deionized water in another beaker.
And then, the C6H12N4 solution was dropped slowly into the
NH4VO3-ZrOCl2 solution under vigorous stirring at 10 °C. After
the end of the dropping, the as-prepared solution and 26.43 g silica
sol (n(Si)/n(Zr) = 1.1) were mixed at the speed of 300 rpm through
by magnetic stirring. Afterwards, the mixed solution was aged for
2 h at 25 °C to obtain the V2O5-ZrO2-SiO2 sol. The as-prepared sol
was firstly heated at 80 °C for 2 h to obtain wet gel, and further
heated at 150 °C for 12 h to obtain xerogel. The obtained xerogel
was calcined at 600 °C for 1 h, and then was mixed with 1 wt%
NaF to obtain precursor. Then, the precursor was calcined at
1100 °C for 1 h. Subsequently, the calcination product was dipped
in concentrated nitric acid for 30 min to remove undoped V4+, and
then washed with deionized water multiple times until the pH
value of the washing liquid was 7. Finally, the V-ZrSiO4 pigment
was achieved after drying.
For investigating the coloring performance of V-ZrSiO4 pigment
in ceramic glaze, 6 wt% of V-ZrSiO4 pigments add to base transpar-
ent glaze and calcined at 1200 °C for 20 min to obtain enameled
samples, and then test their color performance. The chemical com-
position of the base transparent glaze was listed in Table 1.
2.3. Characterization
A variety of test techniques were used to characterize the V-
ZrSiO4 pigment. The phase compositions in the pigment were ana-
lyzed by X-ray diffraction analysis (XRD, Bruker D8 Advance X-ray
diffraction) with a Cu Ka radiation source (k = 0.15418 nm). The
XRD data were collected using a step-scan mode with a step size
of 0.02° and a scanning range (2h) of 5-80°. The thermal evolution
process of the xerogel was studied by simultaneous thermo gravi-
metric and differential scanning calorimeter (DSC/TG, NETZSCH
STA 449C). Analysis was conducted from room temperature to
1300 °C at a rate of 10 °C/min in air using a-Al2O3 as a reference.
Fourier transform infrared (FT-IR) spectra of the xerogel were ana-
lyzed on Nicolet 5700 infrared spectrometer. Raman spectra of the
pigment were obtained with Raman spectrometer using a 532 nm
laser as the excitation source (in Via, Renishaw, UK). CIE lab param-
eters L*, a*, and b* were measured using a spectrophotometer
(Hunter Lab Miniscan MSXP 4000, 400–700 nm, white glazed tile
reference  = 31.5, y = 33.3). Here, L* is the lightness axis (black
(0) ~ white (1 0 0)), b* is the blue (-) ~ yellow (+) axis, and a* is
the green (-) ~ red (+) axis. The parameter C* (chroma) represents
saturation of the color. The chroma is calculated from the following
formula: C*=[(a*)2+(b*)2]1/2 [22]. DE is the hue variation and means
the color difference between two products. Hue variation can be
calculated by the following equation: DE = [(DL*)2+(Da*)2+(Db*)2]1/2
[23]. Visible light reflectance spectra of the samples were collected
by UV–vis light spectrophotometry (Lambda850, PerkinElmer,
USA) in the 200–900 nm range, with a step of 0.3 nm, and with
BaSO4 as a reference. Chemical compositions of the pigments and
transparent glaze were determined using an X-ray fluorescence
spectrometer (Shimadzu, XRF-1800, Japan) that was equipped with
a Rh target. The distribution and valence state of vanadium cations
in the pigment were determined by X-ray photoelectron spec-
troscopy (Escalab 250Xi; Thermo Fisher Scientific, Waltham, MA,
USA). The binding energy values were calibrated based on the
C1s peak that was measured at 284.8 eV. Inductively coupled
plasma mass spectrometry (ICP-MS, Optima 5300 DV-Perkin Elmer
Inc) was employed to measure the ion concentration of V4+ in the
separated water and the pickling solution.
W. Zhang, Q. Wang, X. Chen et al. Advanced Powder Technology 32 (2021) 3355–3363

Table 1
The chemical composition of base transparent glaze.

SiO2 Al2O3 K2O Na2O CaO MgO BaO ZnO total

66.41 11.80 4.17 1.06 13.26 0.90 1.05 1.35 100.00

3. Results and discussion

Fig. 1 exhibits the gelation process of V0.02-ZrSiO4 sol. It can be

observed that the sol is yellowish green and clear, which indicates
the Zr, Si and V ions reach homogeneous mixing via inorganic sol–
gel method in macroscopic viewpoint. After heated at 80 °C for 1 h,
the liquid sol transforms into a solid gel due to the coupling effect
of C6H12N4 [24]. As heating time goes on, the gel network gradually
shrinks, at the same time, free water also gradually overflows from
in it. Significantly, the separated free water is colorless and clear,
instead of yellowish green. The result of ICP test manifests that
the concentration of vanadium ion in the separated free water is
only 0.227 mg/L, suggesting that 99.98% of vanadium are immobi-
lized in the gel network structure.
In order to understand the entanglement patterns between Zr,
Si, and V species, the valence bond composition of the xerogel
was analyzed by Fourier infrared spectrum instrument. Fig. 2
shows the FT-IR spectra of the ZrSiO4 and V0.02-ZrSiO4 xerogels,
respectively. The broad band at around 3130 cm 1 and the peak
at 1683 cm 1 are related to the O-H stretching and bending vibra-
Fig. 1. Images captured at different stages of the gelation process: (a) Sol, (b) Wet
tions, respectively, which are assigned to the solvents and hydrox-
gel, (c) Xerogel, (d) Separated water.
ide in the xerogels [25,26]. The weak band detected at 2360 cm 1
can be attributed to the stretching vibration mode of the C = O
bonds of CO2 in testing atmosphere [27]. The band at 1579 cm 1
and the sharp peak at 1404 cm 1 correspond to the band vibrations
of the N-H and C-H bands, respectively, indicating the complexa-
tion between ZrO(OH)2, Si(OH)4 and C6H12N4 [15,28,29,30]. Bands
appearing at 1114, 981, 451 cm 1, which are attributed to different
vibration modes of Si-O-Si or O-Si-O bands [13,15,31]. The weak
band observed at 798 cm 1 is attributed to the vibration of Si-O-
Zr bond for the ZrSiO4 xerogels, which indicates the xerogel reach
homogeneous mixing at the atomic level via inorganic sol–gel
method [25]. However, the presence of V-O band (at around
1020, 820, 600, and 410 cm 1) is not detected in the IR spectrum
with x = 0.02, probably because the V content in the xerogel is very
low [32]. With the increase of vanadium content (x = 0.04), bands
at 820 and 1020 cm 1 are detected, attributed to V-O and V = O
stretching vibration [13,32,33]. Meanwhile, the peaks detected at
the wavenumber around 1040 and 1140 cm 1 can be related to
C = O and N-H stretching vibration, which come from Fig. 2. FI-IR spectra of the Vx-ZrSiO4 xerogels with different V4+ contents.
(NH4)2(VO)2(C2O4)3 [2NH4VO3 + 4C2H2O4?(NH4)2(VO)2(C2O4)3 + 2-
CO2 + 4H2O] [33,34]. This means that vanadium element exists in
the form of a coordination compound in this sol system. Obviously, mic peaks in the range 300–600 ℃ of DSC curves, which are
(NH4)2(VO)2(C2O4)3 is a macromolecule, and its radius is much lar- mainly attributed to the degradation and combustion of organics,
ger than that of V4+, which is conducive to the immobilization of such as C6H12N4, C2H2O4 and (NH4)2(VO)2(C2O4)3. Besides, the crys-
the V4+ by the gel network. Based on the above analysis, the advan- tallization of amorphous gel and the initial formation of tetragonal
tages of the inorganic sol–gel route in this work can be confirmed: ZrO2 take place at around 300 ℃ [35]. When the temperature
(1) the raw materials can be evenly mixed at the atomic level; (2) exceeds to 600 ℃, the mass loss is delayed (less than 2%). Mean-
vanadium species can be efficiently immobilized in the gel net- while, DSC curves of the ZrSiO4 and V0.02-ZrSiO4 xerogel present
work structure, which reduces the waste of vanadium. a sharp exothermic peak at 973 and 944 ℃, which are associated
Fig. 3 presents the DSC-TG curves of ZrSiO4 and V0.02-ZrSiO4 with the initial formation of zircon [14,36]. Due to the mineraliza-
xerogels from room temperature to 1300 ℃. There is obvious that tion of vanadium, the synthesis temperature of V0.02-ZrSiO4 pig-
only minor differences arose as a result of the introduction of vana- ment is lower than the pure ZrSiO4 [25]. As the temperature
dium ion. The total weight loss of ZrSiO4 and V0.02-ZrSiO4 xerogel is higher than 1000 ℃, there is almost no mass loss of the samples,
49.0% and 50.7% after heating to 1300 ℃, respectively. On the basis suggesting not any chemical reaction took place at a high
of the TG curves, when the temperature reaches about 600 ℃, the temperature.
xerogels show a major weight loss of more than 47% are related to Fig. 4 shows the XRD patterns of V0.02-ZrSiO4 pigment calcined
the dehydration of water molecules (80–250 ℃) and the oxidiza- at temperatures ranging from 200 to 1300 ℃ for 1 h. At 200 ℃, the
tion of organics (250–600 ℃) [2,21]. Specifically, several exother- xerogel is amorphous. Besides, the diffraction peaks of NH4Cl

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W. Zhang, Q. Wang, X. Chen et al. Advanced Powder Technology 32 (2021) 3355–3363

Fig. 3. DSC-TG curves of ZrSiO4 (a) and V0.02-ZrSiO4 xerogel (b).

Fig. 4. XRD patterns of V0.02-ZrSiO4 pigments prepared by different temperatures.

(JCPDS 07–0007), NaCl (JCPDS 05–0628) and NaF (JCPDS 36–1455)

are results from the hydrolysis by-product in the sol–gel process
and the mineralizer added before calcination, respectively [24].
When the calcination temperature increased to 300 ℃, the crystal-
lization of t-ZrO2 (JCPDS 50–1089) phase from the amorphous gel
network, which is consistent with the result in DSC curves. After
calcined at 400 ℃, the diffraction peak of NH4Cl disappeared
because of thermal decomposition. Subsequently, the NaF phase
disappeared at 500 ℃, which is attributed to the reaction between
NaF and SiO2[4]. And the disappearance of the NaCl phase at 600 ℃
is due to the separation from the sample after being melted into
liquid at a high temperature [37]. When the calcination tempera-
ture is below 1000 ℃, the crystallinity of t-ZrO2 phase increases
with the calcination temperature gradually increases. Meanwhile, Fig. 5. XRD patterns of Vx-ZrSiO4 pigments with different x-values, and magnified
the ZrSiO4 phase (JCPDS 06–0266) is detected at 1000 ℃, which view of (2 0 0), ( 1 1 1), (0 1 1) and (1 1 1) peaks. (Note: the calcination temperature
is in good agreement with DSC-TG analysis in Fig. 3. As the calcina- is 1100 ℃.)
tion temperature is more than 1100 ℃, the main crystalline phase
of the specimens is changes into ZrSiO4. Besides, the cristobalite
phase (JCPDS 27–0605) is also observed arose as a result of crystal- phase is t-ZrO2 phase and ZrSiO4 phase is not detected when the
lization of excess SiO2 [38]. Meanwhile, it is worth noting that a x-value of 0. With the x-value increased to 0.01, the diffraction
small amount t-ZrO2 phase is still detected, even though the SiO2 peaks of ZrSiO4 phase are observed. With the increase of vanadium
is the majority one. The similar phenomenon has also been content, the intensity of ZrSiO4 phase diffraction peaks gradually
reported in other papers [39,40]. The reason is that the t-ZrO2 increases and the intensity of ZrO2 phase diffraction peaks gradu-
can be dimensionally stable and undoped as long as the zirconia ally decreases. Obviously, ZrSiO4 is the main crystalline phase in
grain size is smaller than a critical value of around 10–40 nm the specimens containing vanadium. Besides, the introduction of
[41,42]. Obviously, it is easy to obtain t-ZrO2 particles with a grain vanadium results in a slight shift of the (2 0 0) peak toward smaller
size of smaller than 10–40 nm by sol–gel method. diffraction angles in comparison with the matrix oxide, because
To investigate the influence of vanadium ion on phase evolution the smaller Si4+ (0.40 Å) was replaced by the larger V4+ (0.58 Å)
behavior of the Vx-ZrSiO4 pigment, XRD measurement was per- and then resulted in a slight expansion in unit-cell volume of
formed to the samples with different vanadium contents. Fig. 5 Vx-ZrSiO4 [43,44]. It is important to note that the V4+ occupies pref-
presents the XRD patterns of Vx-ZrSiO4 (x = 0–0.04) pigments cal- erentially the Si4+ site rather than the Zr4+ site for the system of low
cined at 1100 ℃ for 1 h. It can be seen that the main crystalline amount of vanadium [15].

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W. Zhang, Q. Wang, X. Chen et al.
Fig. 6. Raman spectra of Vx-ZrSiO4 pigments with different x-values.
Raman spectroscopy can be used to effectively analyze the crys-
talline form of Vx-ZrSiO4 samples [44]. The Raman spectra of the
Vx-ZrSiO4 pigments with different x-values calcined at 1100 ℃
are displayed in Fig. 6. In the sample with x = 0, five weak peaks
located at approximately 145, 267, 315, 460 and 647 cm 1 were
observed, which are assigned to the Raman active modes of
t-ZrO2 [45,46]. When the x-value great than 0.01, the bands
appearing at 200, 213, 221, 355,436, 973, 1006 cm 1, are attributed
to Raman active modes in ZrSiO4, suggesting that the ZrSiO4 phase
is formed [47,48]. At the same time, two weak characteristic peaks
assigned to V-O band at 390 and 915 cm 1 appeared in the doped
samples, which indicate the vanadium ion have entered into ZrSiO4
lattice [49,50]. Obviously, the results of Raman spectra are consis-
tent with the XRD analysis in Fig. 5. To sum up, vanadium is not
Fig. 7. XPS spectra of the V0.02-ZrSiO4 pigment (a), high resolution XPS spectra of Si 2p (b), Zr 3d (c) and V 2p (e) of the pigment.
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Advanced Powder Technology 32 (2021) 3355–3363
only acting as a colorant in the SiO2-ZrO2-V2O5 ternary system,
but also a mineralizer.
The V0.02-ZrSiO4 pigment was analyzed by XPS spectra to gain
information on the distribution and valence state of vanadium
cations in the zircon matrix, as seen in Fig. 7. The survey spectrum
is shown in Fig. 7(a), indicating the existence of Zr, Si, O and V ele-
ments in the pigment, and no peaks related to other elements is
detected. The peaks located at approximately 101, 182, and
517 eV were observed, which correspond to the Si 2p, Zr 3d and
V 2p levels, respectively. Moreover, Fig. 7(d) demonstrates that
the V 2p core level spectrum consists of two peaks locating at
516.4 and 523.5 eV, corresponding to V 2p1/2 and V 2p3/2 [51].
According to the previous reports, these signals could be assigned
to V4+ [52,53]. Therefore, it can be concluded that the valence state
of vanadium ion in the V-ZrSiO4 pigment is 4 + .
To investigate the content and distribution of V4+ in the V-
ZrSiO4 pigment, the V/Zr ratio was measured by XPS and XRF, as
shown in Fig. 8. According to the results of XRF, the measured V/
Zr ratio of V-ZrSiO4 pigment is slightly lower than the theoretical
stoichiometric ratio. Furthermore, according to the vanadium con-
tent in the pickling solution measured by ICP, the effective doping
rate of vanadium is calculated to be 99.69%, which is attributed to
the precursor prepared by the inorganic sol–gel method have
highly reactive. Therefore, due to the immobilization effect of gel
network structure and the highly reactive precursor, the proposed
synthesis route in this contribution has extremely high vanadium
utilization ratio, which means that the product cost of V-ZrSiO4
pigment can be remarkably reduced (including raw material cost
and wastewater treatment cost). Noticeably, the V/Zr ratio mea-
sured by XPS is significantly greater than the V/Zr ratio measured
by XRF and theoretical value, indicating the vanadium cations are
heterogeneously distributed in the pigment particles and are
enriched within the outer layers [54]. The enrichment behavior
W. Zhang, Q. Wang, X. Chen et al. Advanced Powder Technology 32 (2021) 3355–3363

organic matter have not been completely oxidized at this temper-

ature [58]. With the calcination temperature exceeds to 500 ℃, the
organics is completely oxidized, therefore, the L*-value of the spec-
imens soar to about 70. As the calcination temperature below 1000
℃, the a*-value decreases to a negative number, and the b*-value
gradually increases. The chromatic parameters manifest the
specimens show pale yellow-green hue [59]. When the calcination
temperature reaches 1100 ℃, the optimal b*- and C* -value of
V0.02-ZrSiO4 pigment is –22.01 and 24.56, respectively, thus the
pigment shows the brightest blue hue [16]. To the pigments cal-
cined at 1200 and 1300 ℃, their chromatic values are barely differ-
ent from the pigment calcined at 1100 ℃. Meanwhile, the same
color evolution can also be observed from the chromatic coordi-
nates, as shown in Fig. 9(a). Therefore, we believe that the optimal
calcination temperature for the synthesis of V-ZrSiO4 pigment is
1100 ℃ in this work.
Fig. 8. Atomic ratios of V/Zr in the V-ZrSiO4 pigment with different x-value. Despite the vast amount of research into V-ZrSiO4 pigment over
the decades, however, the formation mechanism (including reac-
Table 2 tion kinetics and doping behavior) remains controversial. As an
Chromatic parameters of V0.02-ZrSiO4 pigment with different calcination example, Valentín et al., believed that the whole process of V-
temperatures. ZrSiO4 pigment formation occurs through three steps: (1) V4+ dis-
Temperature/℃ L* a* b* C* solves in t-ZrO2 to form a tetragonal V-ZrO2 solid solution, (2)
the tetragonal V-ZrO2 transform to monoclinic phase, (3) mono-
300 28.01 7.84 11.06 13.56
400 37.67 8.83 13.74 16.33 clinic V-ZrO2 reacts with amorphous SiO2 to form V-ZrSiO4 pig-
500 70.86 3.03 18.95 19.19 ment [13]. In this opinion, the V4+ occupies the Zr4+ site in ZrSiO4
600 69.93 4.96 19.39 20.01 lattice. However, Torres et al., deemed that the V4+ occupies prefer-
700 67.00 6.87 20.57 21.69 entially the Si4+ site [14,15]. Meanwhile, Valentín et al., also found
800 63.84 7.01 16.21 17.66
900 69.60 6.63 10.68 12.57
that the V4+ replaces Si4+ in tetrahedral site [13]. Obviously, these
1000 73.24 12.45 4.24 13.15 analyses and explanations of the formation mechanism of V-
1100 66.98 12.50 21.35 24.42 ZrSiO4 pigment are contradictory.
1200 65.75 9.54 21.94 23.92 Combined with the experimental analysis in this article and the
1300 70.32 9.73 21.01 23.15
former research findings, a reasonable explanation could be given
to the reaction kinetics and V4+ doping behavior of the V-ZrSiO4
pigment. In the system with low vanadium doping amount (＜4
of coloring ion in the outer layers was also observed in the Pr- mol.%), the V4+ first dissolves in amorphous SiO2 to form V-SiO2
ZrSiO4 pigment [55,56]. solid solution, and then reacts with t-ZrO2 to form V-ZrSiO4 pig-
Table 2 presents the chromatic values of V0.02-ZrSiO4 pigment ment. It is to be noted that the V4+ did not be dissolved in the t-
with different calcination temperature (the photographs of the ZrO2 crystalline. Based on the previous research, V4+ can only dope
V0.02-ZrSiO4 pigment calcined at different temperatures are pre- into m-ZrO2 lattice, not t-ZrO2 lattice. Meanwhile, the temperature
sented in the supporting information). When the calcination tem- at which the monoclinic V2O5- ZrO2 solid solution is formed
perature less than 400 ℃, the L*-value of the samples is about 30, exceeds 800 ℃ [60]. Besides, there is currently no report on tetrag-
and the a*- and b*-value is both about 10, indicating the samples onal zirconia solid solutions in the V2O5-ZrO2 binary system. On
show brown hue [57]. According to the DSC-TG analysis in Fig. 3, the other hand, the V2O5 is yellow, and the vanadium doped glass
it can be known that the reason is the degradation products of is green [61,62]. Therefore, the specimen calcined at low tempera-

Fig. 9. Chromatic coordinates of the V-ZrSiO4 pigment with different calcination temperatures (a) and different x-values (b).

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W. Zhang, Q. Wang, X. Chen et al. Advanced Powder Technology 32 (2021) 3355–3363

Table 3
Chromatic parameters of Vx-ZrSiO4 pigments with different x-values. (Note: the
calcination temperature is 1100 ℃.)

x-value L* a* b* C*
0 86.77 4.30 0.83 4.38
0.005 79.66 8.79 8.38 12.14
0.010 74.99 12.04 15.67 19.76
0.015 70.74 11.88 20.82 23.97
0.020 66.98 12.50 21.35 24.42
0.025 69.51 11.85 19.52 22.83
0.030 68.30 13.43 11.79 17.87
0.040 72.23 11.73 7.54 13.94

ture (500–1000 ℃) show yellow-green hue (as shown in Fig. 1S),

which may be derived from V-SiO2 solid solution and unreacted
V2O5, instead of the V4+ doped ZrO2 yellow pigment. As for the
phase transformation of tetragonal to monoclinic ZrO2, it is not
observed in this work (as can be seen in Fig. 4). Hence, despite
the presence of m-ZrO2 is kinetically favorable to the zircon forma-
tion, the formation of the monoclinic phase is not essential, which
is consistent with the point of Tartaj et al [32]. To sum up, the V4+
occupies the Si4+ site rather than in the Zr4+ site in the zircon
matrix in this work.
Table 3 presents the chromatic parameters of V-ZrSiO4 pigment
with different x-values calcined at 1100 ℃ for 1 h. The specimen
without V4+ is of course white, while the vanadium-containing
specimens have a comparatively strong coloration, which can be
seen in the lower L*- and b*-value. As the x-value increases from
0 to 0.04, the L*- and b*-value of the V-ZrSiO4 pigments was
decreased and then reached a minimum value at x = 0.02
(L*=66.98 and b*=-21.35). Meanwhile, the C*-value reached a
maximum value of 24.42. C* represents the purity of pigment, a
considerable value indicates high purity [60]. In the specimens
with x-value greater than 0.02, the L*- and b*-value is increased
with the increase of V4+content, which means it is useless to
increase the blue hue of the V-ZrO2 pigment by adding excessive
vanadium. Fig. 9(b) illustrates the chromatic coordinates for
Vx-ZrSiO4 pigment with x-values. The results show that the color
coordinate for specimen in the absence of V4+ falls in the white
color region, and the color coordinates of vanadium-containing
specimens correspond to the blue color region. In summary, the
V-ZrSiO4 pigment with x-value of 0.02 shows the brightest blue
hue than other specimens.
The chromatic parameters of the V-ZrSiO4 pigment obtained by
different methods are summarized in Table 4 [4,14,17,20,32,63]. It
can be seen that the blue hue of the V-ZrSiO4 pigment obtained by
this work is superior to the commercial and the previously
reported V-ZrSiO4 pigments. It should be emphasized that the dop-
ing amount of V4+ is as low as 2 mol.%, which is the minimum
reported in the literature.
Fig. 10. UV–vis reflection spectra of the Vx-ZrSiO4 (x = 0 ~ 0.04) and CoAl2O4
pigment.
To further understand the effect of V4+ content on the color
behavior of the V-ZrSiO4 pigment, UV–vis reflection characteristic
of the series Vx-ZrSiO4 (x = 0 ~ 0.04) pigment was also investigated,
as shown in Fig. 10. The undoped sample is a continuous band with
strong reflection in the range of visible light wavelengths, reflect-
ing its white coloration. In contrast, the Vx-ZrSiO4 pigments show
a strong reflection band at 380–500 nm (blue band) and a weak
reflection band at 500–780 nm (yellow band) [2,20]. Specifically,
the weak reflection band (i.e., strong absorption band) at 500–
780 nm is related to d-d (2B1?2E) electronic transition of tetrahe-
dral V(Ⅳ) coordination [13,14,20]. The reflectance difference
between these two wavelengths indicates that the Vx-ZrSiO4 pig-
ments show a blue hue. The reflectance intensity of the samples
in the full visible wavelength range gradually decreases with the
increases of the x-value, indicating the high V4+ content is con-
ducive to obtain a darker hue. However, the reflectance intensity
at 380–500 nm gradually decreases and the reflectance intensity
at 500–780 nm gradually increases when the x-value greater than
0.02, suggesting that the deterioration of blue hue of the V-ZrSiO4
pigment [43,60]. In short, due to the difference value in reflectance
between blue and yellow band is the largest and the reflectance
intensity is the lowest, the V0.02-ZrSiO4 pigment has the most vivid
blue color [25]. Besides, the visible light reflection behavior of
Vx-ZrSiO4 and CoAl2O4 pigment was compared [2,44]. Obviously,
two pigments demonstrate a similar UV–vis reflection curve, sug-
gesting that they both exhibit a blue hue. Nevertheless, compared
with CoAl2O4 pigment, V-ZrSiO4 pigment shows stronger visible
light reflection intensity in the range of 380–680 nm. Therefore,

Table 4
Comparison of the chromatic parameters of V-ZrSiO4 pigment obtained by several methods.

Method Composition L* a* b* Ref

Polyol x= 0.020 69.4 3.7 14.0 59
Polyol x= 0.065 50.3 2.6 13.2 59
Solid-state x= 0.073 76.36 13.32 14.26 17
Solid-state x= 0.100 65.38 12.78 16.73 14
Colloidal gel x= 0.040 74.93 12.65 5.19 14
Pechini x= 0.060 70 12 20 4
Pechini x= 0.480 63 15 20 4
Aerosols Hydrolysis x= 0.320 81.2 9.5 10.7 32
Organic Sol-gel x= 0.100 66.2 24.9 –22.3 20
Inorganic sol–gel x= 0.020 66.98 12.50 21.35 This work
Commercial — 65 13 20 4
Commercial x= 0.063 67.78 14.18 15.47 17

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W. Zhang, Q. Wang, X. Chen et al.
Table 5
Chromatic values of V0.02-ZrSiO4 pigment after water, acid and alkali tests
Acid/Alkali V0.02-ZrSiO4
L* a* b*
In air 66.98 12.50 21.35
H2O 66.18 12.36 21.33
HNO3 66.76 12.88 –22.24
HCl 66.74 13.06 –22.21
H2SO4 66.55 12.93 21.70
NaOH 65.65 12.46 21.51
Fig. 11. Photographs of enameled samples with V-ZrSiO4 pigment.
V-ZrSiO4 pigment presents a sky-blue, while CoAl2O4 pigment pre-
sents a dark-blue that contains a purple hue.
In summary, the V-ZrSiO4 pigment with high vanadium utiliza-
tion ratio, low vanadium doping amount and excellent color per-
formance was prepared by inorganic sol–gel method.
Based on the analysis of the preceding context, it can be seen
that the V-ZrSiO4 pigment with excellent color performance is pre-
pared by inorganic sol–gel method. To survey the chemical stabil-
ity, the acid and alkali resistance of the V-ZrSiO4 pigment was
tested. The weight loss was neglected for all the acids and alkalis
tested, which means that the pigments are stable and resistant to
the different mineral acids and alkalis. Chemical stability testing
is very important to know the pigment application of prepared
samples. The color difference (DE) is a common way for measuring
the color difference between two pigments. The difference
between two colors can be differentiated by the human eye when
the value of the color difference is larger than 1 [64]. Table 5
demonstrates the color difference of V-ZrSiO4 pigment after trea-
ted by water, alkali and acid. Small values of DE mean that the syn-
thesized V-ZrSiO4 pigment has outstanding chemical stability [65].
It is widely known that the pigment used for ceramic glaze
must have excellent coloring performance and high-temperature
stability [25]. For this purpose, enameled sample was prepared
with V0.02-ZrSiO4 pigment, and the photograph of the sample is
shown in Fig. 11. Obviously, the enameled sample shows bright
sky blue, and its chromatic parameters is L*=69.32, a*=-13.50,
b*=-21.97, C*=25.79, respectively, which indicates the V-ZrSiO4
pigment synthesized by inorganic sol–gel method has outstanding
coloring performance and high-temperature stability [60].
4. Conclusions
To summarize, this article reported a facile strategy for the syn-
thesis of V-ZrSiO4 pigment, and its formation mechanism was
investigated. The main conclusions are as follows:
(1) High color performance V-ZrSiO4 pigment was successfully
prepared by inorganic sol–gel method, which the doping
Advanced Powder Technology 32 (2021) 3355–3363
amount of V4+ was as low as 2 mol%. The chromatic
parameters of the optimal sample are L*=66.98, a*=-12.50,
b*=-21.35, respectively.
DE (2) The vanadium utilization ratio of this strategy is as high as
99.69%, which is attributed the immobilization effect of the
–
0.81
gel network and the as-prepared precursor has highly
0.99 reactive.
1.05 (3) The valence state of vanadium ion in the V-ZrSiO4 pigment is
0.70 4+, and vanadium cations are not homogeneously dis-
1.34
tributed in the pigment particles and are enriched at their
outer layers.
(4) In this work, the formation mechanism of V-ZrSiO4 pigment
is the V4+ first dissolves in amorphous SiO2 to form V-SiO2
solid solution, and then reacts with t-ZrO2 to form
V-ZrSiO4 pigment. In addition, the V4+ occupies the Si4+ site
rather than in the Zr4+ site in the zircon matrix.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the financial support by the
National Natural Science Foundation of China (Nos. 21761015,
51772136).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.apt.2021.07.018.
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