See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/294122419

TiO2 @ CoTiO3 Complex Green Pigments with

Low Cobalt Content and Tunable Color
Properties

Article in Ceramics International February 2016

DOI: 10.1016/j.ceramint.2016.02.029

CITATIONS READS

0 77

2 authors, including:

Jian Zou
Southwest University in Chongqing
10 PUBLICATIONS 131 CITATIONS

SEE PROFILE

All in-text references underlined in blue are linked to publications on ResearchGate, Available from: Jian Zou
letting you access and read them immediately. Retrieved on: 09 October 2016
 Ceramics International 42 (2016) 81988205

Contents lists available at ScienceDirect

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

TiO2@CoTiO3 complex green pigments with low cobalt content

and tunable color properties
Jian Zou n, Wei Zheng
School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China

art ic l e i nf o a b s t r a c t

Article history: Green complex pigments with TiO2@CoTiO3 coreshell structure were prepared through calcination of
Received 30 December 2015 precursors obtained from the precipitation of Co2 on TiO2 particles. The synthesized pigments were
Received in revised form characterized by colorimetry, near-infrared diffuse reectance spectroscopy, X-ray diffraction (XRD),
31 January 2016
scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ultravioletvisible
Accepted 4 February 2016
Available online 10 February 2016
(UVvis) spectroscopy. The pigments were found to consist of a rutile TiO2 core and outer ilmenite
CoTiO3 shell. The green pigments with good color properties could be obtained via calcination of the
Keywords: precursors at 800 C. The pigments with Co/Ti ratio of 0.4 had the highest green component value and
Complex pigments exhibited good color properties (L* 49.51, a*  34.58, b* 5.53). The color properties could be tuned by
Coreshell
just changing the Co/Ti ratio. The as-prepared complex pigments exhibited an enhanced near-infrared
Green
reectance compared with pure CoTiO3 pigments and also exhibited better color properties than the
Low content
NIR reectance mixed pigments of TiO2 and CoTiO3. Further, the complex pigments had much lower consumption of
cobalt compared to pure CoTiO3 and Co2TiO4 pigments. The special coreshell structure was found to be
responsible for the enhanced near-infrared reectance and good color properties.
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

1. Introduction
Inorganic green pigments are widely used in ceramics, plastics,
paints, building materials, and glass coatings. For these applica-
tions, many inorganic green pigments have been developed. Most
of the currently available green pigments consist of chromium (Cr)
based compounds [17], such as chromium oxide [13], the green
spinel of cobalt chromate [5,6], and pyrophosphate BaCr2(P2O7)2
[7]. However, these pigments contain the metal element Cr, which
have hazardous effects on the environment [8,9]. Recently, some
rare-earth based pigments have been proposed as viable alternates
to traditional toxic pigments due to their low toxicity [810]. These
pigments showed good color properties and high near-infrared
(NIR) reectance [8,10].
Due to its excellent performance in green color, durable che-
mical stability and corrosion resistance, inverse spinel Co2TiO4 is
often used as a green pigment [8,11,12]. Another particular aspect
of this pigment is its high color stability which makes it to be the
only green pigment (except for chromium oxide pigment) that
meets color stability requirements for building materials based
upon cement and/or lime [13]. However, cobalt (Co) is scarce and
expensive. Furthermore, serious environmental problems may
n
Corresponding author.
E-mail address: ezouj@swu.edu.cn (J. Zou).
arise from the manufacture of Co-based ceramic pigments [14]. So,
the consumption of cobalt should be reduced for these green
pigments. Replacing Co element with nontoxic and cheaper ele-
ments is an efcient method to reduce the usage of Co for cobalt
based pigments [15,16]. However, this doping technology resulted
in diminishing the intensity of the color for the doped pigments
[6]. The cobalt based pigments could be reduced efciently by
mixing them with light pigments, but these mixed pigments often
exhibit light color hue [17,18]. Besides, it seemed that coating the
colored pigments on mica could reduce the consumption of co-
lored pigments, and a similar color hue as of colored pigments
could be obtained [12,19,20]. tengla et al. [19] obtained a variety
of colored pigments by coating different colored pigments on
mica. Liu et al. [12] also prepared green complex Co2TiO4 based
pigments by coating the mica. However, such complex pigments
presented much lower color intensity than the pure Co2TiO4 pig-
ments [8].
It has been observed that the ilmenite CoTiO3 has similar ab-
sorption spectra as of spinel Co2TiO4 in the visible region
[12,21,22]. This means that ilmenite CoTiO3 probably presents
green hue in color. In fact, Yadav et al. [22] observed the as-pre-
pared CoTiO3 presented green color. Peng et al. [23] also conrmed
that CoTiO3 contributed to the brilliant green color of Co doped
TiO2 particles. By comparing the formulae of CoTiO3 and Co2TiO4, it
can be observed that the preparation of CoTiO3 needs lesser
amount of Co. Furthermore, CoTiO3 could be obtained within a

http://dx.doi.org/10.1016/j.ceramint.2016.02.029
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205 8199

temperature range of 5001000 C [24,25], but pure Co2TiO4 was sphere (Hatachi U-4100); BaSO4 was used as a reference sample. The
synthesized at a temperature above 850 C [26]. Meanwhile, the color of the pigments was evaluated by measuring L*a*b* parameters
formation of Co2TiO4 depended on Co/Ti ratio, and no Co2TiO4 was with a spectrophotometer NS810 (Shenzhen 3nh technology Co. Ltd.).
obtained even though the Co/Ti ratio was 1.9 [22]. On the contrary,
CoTiO3 could be obtained for a Co content as low as only 1 wt%
TiO2
[27]. These results indicated that the manufacture of CoTiO3 is
1400 CoTiO3
more feasible on technological grounds. Therefore, it is possible to (104)
use ilmenite CoTiO3 as a green pigment having low Co content.
1200 Co3O4
In order to reduce Co consumption in green pigments, a com-
plex pigment with a TiO2@CoTiO3 coreshell structure has been 1000 o

Intensity (a.u.)
synthesized in this study. It was expected that this pigment would 900 C
not only have lower Co consumption but would also exhibit good 800
color properties. Due to the introduction of rutile TiO2, which has a o
800 C
high NIR reectance [28], this complex pigment was expected to 600
have an enhanced NIR reectance, so that it can be used in the
eld of solar reection paints in the buildings. 400 700 C
o

200 o
2. Experimental 600 C
0
2.1. Materials 20 30 40 50 60 70
2
CoCl2  6H2O and NH3  H2O (2528%) were purchased from the
Chuandong Chemical Co. Ltd., China. All reagents were analytically 2500 TiO2
pure. Other reagents, such as polyethylene glycol (PEG 10000),
CoTiO3
titanium tetrachloride (TiCl4, Sinopharm Chemical Reagent Co.
Ltd., China.) and polyurethane (PU) paint (D Fang, Acryl PU-Kla- 2000
lack) were used as received. 1
Intensity(a.u)

2.2. Synthesis of TiO2@CoTiO3 complex pigments 1500

0.6
The TiO2 powder was synthesized according to a process si-
milar to the one reported in references [28,29]. In a typical 1000 0.4
synthesis, 20 mL of TiCl4 was added to the ice blocks under vig-
orous stirring. After the ice blocks melted completely, the solution 0.2
was diluted to approximately 1 M precursor solutions by deio- 500
nized water. Subsequently, 1 wt% of PEG 10000, which acted as a
dispersant, was added to the solution. After reuxing the solution 0.1
at 100 C for 4 h, the pH value of the suspension was adjusted to 0
about 6 by using 10% aqueous ammonia. The TiO2 powder was 20 30 40 50 60 70
obtained by ltering and washing the suspension several times 2
followed by a drying process at 90 C for 4 h. Fig. 1. XRD pattern of products calcined at different temperatures and with a Co/Ti
The as-prepared TiO2 powder was re-dispersed in the distilled ratio of 0.4 (a), and calcined at 800 C and with different Co/Ti ratio (b).
water to obtain 5 wt% suspension under vigorous stirring. Cobalt
chloride was dissolved in this suspension. Then, 2 M sodium hy-
610
droxide solution was used to adjust the pH value to 10, after
which, the precipitate was formed. The precipitate was subjected 100000 445
to several cycles of ltering and washing processes. The resulting
powder was obtained by drying the precipitate at 105 C for 4 h.
The complex pigment was obtained by calcination of the powder 80000
at different temperatures ranging from 600 C to 1000 C for 1 h.
237 695
The contents of cobalt chloride were determined by Co/Ti ratio
Intensity

which was 0.05, 0.1, 0.2, 0.4, 0.6, and 1.0 respectively. The Co/Ti 60000
ratios refer the molar ratio of Co/Ti in this paper. The mixed pig- 266 335
383
ment, which had the same Co/Ti ratio as of the complex pigment,
was acquired by direct mixing of CoTiO3 and TiO2 powder. None of 40000
the as-synthesized pigments were further milled or sieved. a)

2.3. Characterization techniques 20000 b)

c)
The phases of the products were characterized by XRD using CuKa
0
radiation in an XD-3 diffractometer (Beijing Pgeneral). Morphological
200 300 400 500 600 700 800
analyses were performed by scanning electron microscopy (Quanta
x50 FEG). Raman spectra were recorded on a Bruker SENTERRA spec- cm-1
trometer by using 532 nm light as the excitation source. UVvisNIR Fig. 2. Raman patterns of synthesized pigments with different Co/Ti rations. (a) 0.1,
spectra were recorded on a spectrophotometer with an integrating (b) 0.4, (c) 1.
8200 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205

TEM and HRTEM images were obtained using an FEI Tecnai G2 F20
transmission electron microscope with an acceleration voltage of
200 kV. The colored paint was acquired by mixing 0.2 g of pigments in
10 g of polyurethane (PU) paint with ultrasonic treatment for 2 min.
A circular colored lm was obtained by curing the paint in a 9 cm Petri
dish. The photographs of paint lms and pigments were obtained di-
rectly by Nikon d7000 camera. The micrographs were obtained using
an Olympus CX31 instrument.
3. Results and discussions
In order to obtain green pigment, cobalt titanate ilmenite phase
was expected to occur in the complex oxide pigment. The calci-
nation temperature was a key factor for the formation of ilmenite
CoTiO3. A high temperature beneted the formation of CoTiO3
[24,25]. As shown in Fig. 1a, no other peaks of CoTiO3 could be
detected except the weak (104) plane peak at 600 C. Obviously,
the pigments mainly consisted of rutile TiO2 and Co3O4. As the
calcination temperature increased, the peaks corresponding to
planes of ilmenite CoTiO3 became more intense, while the
intensity of Co3O4 peaks decreased and eventually disappeared
above 800 C. A few differences between the diffraction spectra for
pigments calcined at 800 and 900 C could be observed. These
indicated that 800 C was adequate for the formation of CoTiO3.
This temperature was much lower than the temperature required
(41000 C) for thermal decomposition method [25] and the tra-
ditional solid state reaction method [30].
The controllable content of CoTiO3 was expected to be obtained
only by changing the Co/Ti ratio. Fig. 1b shows that as the Co/Ti
ratio increased from 0.1 to 1, the intensity of peaks corresponding
to ilmenite CoTiO3 increased gradually. However, within the same
range of Co/Ti ratio, opposite changes were observed for one of the
TiO2 peaks, and ultimately a pure phase composition of ilmenite
CoTiO3 was obtained. Obviously, the pigments with different
CoTiO3 contents could feasibly be prepared by adding different
amounts of Co precursor. Besides, no conclusion concerning the
spinel structured Co2TiO4, which generally was used as a green
pigment [8,11,12], could be drawn for all synthesized pigments,
though it was a highly competitive phase with the ilmenite CoTiO3
in the solid-state reaction [31], thermal decomposition method
[25] and co-precipitation reaction [12].

Fig. 3. SEM results of synthesized samples with different Co/Ti ratios. (a) 0.1, (b) 0.4, (c) 1.

Fig. 4. TEM (a and b) and HRTEM (c) images of the as-prepared complex pigments with Co/Ti ratio of 0.4.
 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205 8201

The phase compositions of pigments are further investigated by
Raman scattering. The spectra of as-synthesized pigments with
different Co/Ti ratio are comparatively shown in Fig. 2. For the
product having low Co/Ti ratio, two evident peaks, located at 445
and 610 cm  1, can be observed. These two peaks along with the
peak at 237 cm  1 can be attributed to rutile TiO2 [29]. Obviously,
the band corresponding to rutile TiO2 gradually decreases with an
increase in Co/Ti ratio, especially for 445 and 610 cm  1, which, for
the products with Co/Ti ratio of 1, moved to 456 and 604 cm  1
respectively. These two peaks along with the ones at 208, 237, 266,
335, 383 and 695 cm  1 corresponded to CoTiO3 ilmenite phase
[32]. In addition, for all products, no conclusion could be drawn
concerning Co2TiO4, which did not exhibit any Raman active band
in the spectral range between 200 and 800 cm  1 [33]. Hence, the
pigments with Co/Ti ratio below 1.0 presented rutile and ilmenite
phases, and pure ilmenite CoTiO3 could be obtained for pigments
with Co/Ti ratio of 1.0. These results are consistent with the XRD
results shown in Fig. 1.
Fig. 3 shows the images of the synthesized pigments with
different Co/Ti ratios. All pigments presented a spherical mor-
phology. The pigments had a narrow size distribution, ranging
from 0.5 mm to 3 mm, and most of them had the particle size of
approximately 1.5 mm. In addition, as shown in Fig. 3, all pigments
presented good dispersion, especially for the pigments with Co/Ti
ratios of 0.4 and 1.0. For the traditional solid-state reaction
method, the as-prepared pigments often exhibit irregular mor-
phology and big size distribution [15]. Therefore, the calcined
products must be milled and sieved further to adjust the grain size
and dispersion of the inorganic pigments synthesized by solid-
state reaction method [34,35]. However, we previously reported
that the synthesized pigments presented good dispersion and
at 600 C, no characteristic band of CoTiO3 could be observed. This
was a characteristic spectra of Co3O4 [22] and indicated that
CoTiO3 was not formed. When the calcination temperature was
increased to 700 C, the characteristic bands of CoTiO3 became
evident, and were accompanied with the characteristic band of
Co3O4. CoTiO3 pigments enriched in Co3O4 exhibited black hue
[22], which resulted in loss of color properties. For the samples
calcined at more than 800 C, these bands accorded completely
with the characteristic bands of CoTiO3, which meant that pure
ilmenite CoTiO3 was obtained. Obviously, the expected phase
composition of pigments could be obtained at a temperature of
800 C.
The optical spectra determined by chemical compositions are
shown in Fig. 5b. Similarly, all samples showed the characteristic
absorption band of CoTiO3 phase. The difference can be dis-
tinguished only in the intensity of absorption band. It could be
concluded from Fig. 5b that the absorption band in the range of
500700 nm became more intense with the increase of Co con-
tent, while the most intense absorption was observed for sample
with the Co/Ti ratio of 0.6. The shoulder band around 760 nm, by
which Co2TiO4 and CoTiO3 might be identied [33], was observed
for all samples, and the band decreased gradually with an increase
in the Co content. This hinted that all absorption came from the
CoTiO3, and not from Co2TiO4. In fact, it was difcult to obtain pure
Co2TiO4 at 800 C. Although pure Co2TiO4 could be prepared at
1.0
800
900
0.8
Absorbance (a.u)

narrow size distribution even without any milling and sieving [28]. 1000
In the current work, TiO2 cores of the complex pigments were also 700
prepared by the same method, and it was likely that their mor- 0.6 600
phology and dispersion were inherited to the complex pigments,
which resulted in good dispersion and narrow size distribution
although no milling and sieving were performed on them. 0.4
The microstructures of the obtained complex pigments are
further shown in Fig. 4. The as-prepared pigments were mainly
around 1.5 mm (Fig. 4a), which was consistent with the SEM results 0.2
shown in Fig. 3. The complex pigments' powder was of typical
coreshell structure with a relatively smoothed out layer of ap- 0.0
proximately 25 nm thickness (Fig. 4a and b). The high-resolution 400 500 600 700 800
TEM (HRTEM) image of the particle edge provided information on
nm
the phase of the shell of the complex pigments. As shown in
Fig. 4c, the outer layer exhibited crystalline structures and clear
lattice fringes. The inter-planar spacing was calculated to be
around 0.27 nm, which was consistent with the distance between 1.0
two (104) crystal planes of ilmenite CoTiO3. Combined with the Co/Ti
results of XRD and Raman, it could feasibly come to a conclusion 1
0.8
Absorbance(a.u.)

that the complex pigments' particles consisted of outer CoTiO3 0.6

shell and inner TiO2 core.
0.4
The XRD results in Fig. 1 showed that the phase composition of
0.6 0.2
the complex pigments depended on the calcined temperature and
chemical compositions. The difference in phase compositions can 0.1
also be distinguished from optical absorption of the samples. The 0.4 0.05
optical absorption spectra of the pigments are shown in Fig. 5. For
ilmenite CoTiO3, there are mainly two characteristic absorption
bands in the range of 300700 nm. The absorption in the range of 0.2
300500 nm could be assigned to octahedral Co2 -Ti4 inter-
valence charge transfer in CoTiO3 [22,32]. Another band in the
0.0
region of 500700 nm with maximum value at around 612 nm
400 500 600 700 800
could be attributed to 4A2 (F)-4T1 (F) and 4A2 (F)-4T1
(P) transitions, indicating the presence of tetrahedral Co2 species nm
[22]. A shoulder band around 760 nm could also be assigned to Fig. 5. UVvis absorption spectra of products with Co/Ti ratio of 0.4 calcined at
octahedral Co2 [33]. As shown in Fig. 5a, for the sample calcined different temperatures (a) and with different Co/Ti ratio at 800 C (b).
8202 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205

850 C, however the pigment presented worse color properties Co3O4 phase existed in the as-prepared pigments below 800 C. As
[26]. And Co2TiO4 phase depended greatly on the Co/Ti ratio, while shown in Fig. 6a, the pigment calcined at 700 C exhibited lower
pure Co2TiO4 could not be obtained even though the Co/Ti ratio values for luminosity (L*) and green component (  a*) than the
was increased up to a value of 1.9 [22]. However, the formation of corresponding values for other pigments. The difference was at-
CoTiO3 was prone to occur for the composition containing oxides tributed to the existence of Co3O4 phase in the pigment calcined at
of Co and Ti. As shown in Fig. 5b, the characteristic absorption 700 C. This indicated that the unexpected Co3O4 phase would
band of the CoTiO3 could evidently be observed for sample with have resulted in the loss of color properties, and that the CoTiO3
Co/Ti ratio of 0.05. Even CoTiO3 could be detected in titania doped pigments enriched in Co3O4 exhibited black hue [22]. Minor dif-
with 1 wt% Co [27]. This indicated that samples with low Co ference in the color properties are presented for all pigments
content exhibited good green hue. above 800 C. These pigments had high L* value of around 49 and
The colorimetric parameters of the as-prepared pigments are a* value of around 35. These results suggested that these pigments
shown in Fig. 6. The above XRD and UVvis results showed that may be presenting bright green color.

63.64
60 60 56.33
Colorimeter Parameter Values

Colorimeter Parameter Values

49.51
50.46 48.05 49.51 47.85
43.60
45 38.93 L* L*
40
30
20 11.62
15 8.12 5.53
5.38 5.53 4.55 3.82 3.61 1.93
b* 0 b*
0

-15 -15.13
-20 -27.81 -26.58
-30 -34.58 -34.88 -33.84 -32.82 -34.58 -32.45 a*
a*
-40
700 800 900 1000 0.0 0.2 0.4 0.6 0.8 1.0
Temperature/ oC Co/Ti

80 76.34
72.38 51.3
68.88 50
Co2TiO4
Colourimetric parameter valus

58.04
60 51.05 40
Content of Co (wt.%)

L*
38.1
40 CoTiO3
30
28.3
20 20 ts
8.83 21.4 en
1.39 1.09 1.11 ig m
1.39
0 b*
10
12.4 xp
-10.15 -12.87 6.7 ple
-16.73 C om
-20.16 3.5
-20 -22.99 a* 0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.0 0.2 0.4 0.6 0.8 1.0 2.0
Co/Ti Co/Ti
Fig. 6. Colorimetric parameters of the complex pigments calcined at different temperatures (a) and doped with different dopant contents (b), and the mixed pigments
(c) based on the CIELAB system. (, and symbols denoted as the complex pigments with Co/Ti ratio of 0.05); the contents of Co for pigments with different Co/Ti ratio (d).

Fig. 7. Photographs of synthesized pigments with different Co/Ti ratios (top row) and the corresponding polyurethane paint lms (bottom row). (For interpretation of the
references to color in this gure, the reader is referred to the web version of this article.)
 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205
As the Co content increased, the CoTiO3 phase also increased.
The change of phase composition also resulted in difference of
color properties. The color performance could feasibly be tuned by
just changing the Co/Ti ratio. As shown in Fig. 6b, the L* values of
pigments decreased evidently from 63.64 to 43.60 as the Co con-
tent was increased. The yellow component (b*) also presented a
similar change, however the change was smaller (from 11.62 to
1.93). It was noted that the yellow component was low relative to
other green pigments [3,7,9], especially for pigments with high
content of Co. This meant that the pigments presented more of the
pure green color. The green component exhibited the maximum
value (a* 34.58) when the Co/Ti ratio reached a value of 0.4.
Additionally, all pigments had high green hue. Even the pigment
with Co/Ti ratio of 0.1 also had a high green component
(a*  27.81). This value was higher than of the corresponding
value for Co2TiO4 coated mica pigments [12]. The most green
pigment with Co/Ti ratio of 0.4 also presented higher a* value than
70
60
50
Reflectance (R%)
40
30
20
10
0 maintain good color performance while the content of Co could
750 1000 1250 1500 1750 2000 2250 2500
nm
Fig. 8. NIR reectance spectra of the as-prepared pigments.
Fig. 9. Formation scheme for TiO2@CoTiO3 particles (ac) and Interaction of pigments with light (d, e).
8203
the corresponding values for other green pigments [3,10]. These
results indicated that the as-prepared pigments would present
vivid green color.
As a comparison, the colorimetric parameters of the mixed
pigments are shown in Fig. 6c. For the mixed pigments, the lu-
minosity values (L*) decreased with an increase in Co content. An
opposite trend was observed for the green component (  a*).
Additionally, the variations in yellow component were negligible.
Obviously, the mixed pigments had higher L* values relative to the
complex pigments with the same Co content. However, the green
component (  a*) was lower than the complex pigments, even in
the case when the complex pigments contained much less Co
content. As shown in Fig. 6c, the complex pigment with Co/Ti ratio
of 0.05 showed higher green component than the mixed pigment
having Co/Ti ratio of 0.6. This suggested that the color properties
of pigments would greatly be diluted if the CoTiO3 pigments were
mixed with white pigments.
The usage of Co was expected to be decreased due to its en-
vironmental impacts and high cost for the Co based inorganic
colored pigments [15]. The substitution of Co with other metal
ions could decrease the consumption of cobalt, but often the color
properties were evidently changed [6]. The mixed pigments di-
luted with white ones, as shown in Fig. 6c and reported in other
works [17,18], exhibited only light color hue. However, in this
work, the as-prepared pigments exhibited high green hue and the
Co:Ti complex pigments consumed lesser Co. As shown in Fig. 6d, the
0.1 commercial Co2TiO4 pigments with Co/Ti ratio of 2.0 contained
0.4 51.3 wt% of Co, while the as-prepared pure CoTiO3 pigments had
0.6 38.1 wt% Co. The Co content in complex pigments could further be
1 reduced to 3.5 wt%. More importantly, the color properties of the
complex pigments did not decrease, even though white TiO2 was
introduced and their green components were higher than that of
the pure CoTiO3 (except for the complex pigment with Co/Ti ratio
of 0.05). Obviously, the as-prepared complex pigments could
substantially be reduced.
Photographs of the pigments and polyurethane (PU) lm co-
lored with the corresponding pigments are shown in Fig. 7. All
8204 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205
Fig. 10. Micrograph of the samples. (a) Complex pigments with Co/Ti ratio of 0.4, (b) mixed pigment with the same content of Co. The bar is 20 m. (For interpretation of the
references to color in this gure, the reader is referred to the web version of this article.)
pigments exhibited vivid green color. As the Co/Ti ratio increased,
the pigments presented yellow green to dark green color. These
results were in agreement with the colorimetric values presented
in Fig. 6b. All colored PU lms showed similar, homogenous colors
indicating that the pigments could homogeneously be dispersed
directly in the organic matrix. This meant that the as-prepared
pigments could be applied in paint eld.
52% of the solar energy is contained in the NIR spectrum (700
2500 nm) [11,36]. The surface temperature of the building mate-
rials rises under solar irradiation due to the NIR absorption, which
reduces the comfort of inner rooms and hence, increases the en-
ergy consumption due to the need for air conditioning. This part of
solar energy is expected to be reected back as much as possible,
so that the heat built-up on the building material's surface can be
cut down. Therefore, an enhanced NIR reectance is always ex-
pected for color inorganic pigments because they often are used as
the surface coating for building materials [37]. Fig. 8 shows the NIR
reectance spectra of the as-prepared pigments. For pure green
CoTiO3 pigments, a characteristic absorption band at around
1500 nm was observed, which resulted in a depressed NIR re-
ectance. However, an evident improvement of NIR reectance
could be observed for the complex pigments. The enhancement
was more pronounced for the pigments with lower Co content.
The pigments with Co/Ti ratio of 0.4 had an enhancement of more
than 10% in NIR reectance. Even the enhancement of reectance
value exceeded 20% at 1500 nm for the pigment having Co/Ti ratio
of 0.1. This enhancement was different from the mixed pigments
prepared by coloring white pigments having high NIR reectance
by the colored pigments. The enhancement of NIR reectance for
the mixed pigments was at the expense of color intensity [17,18],
and the results shown in Fig. 6 also conrm the loss of color in-
tensity for the mixed pigments. However, for the complex pig-
ments, the above results indicated that the color intensity was
considerably improved. Hence, the complex pigments could ex-
hibit good color properties and high NIR reectance as expected.
The above results indicated that the as-prepared pigments
exhibited good color performances, and required lesser Co content
than the commercial Co2TiO4 pigments. For the complex pigments,
which also showed good color properties, the Co content could
even be reduced to 3.5 wt%. This was completely different from
the mixed pigments, which often resulted in fading of colored
pigments [17,18,38]. In this work, as shown in Fig. 9ac, Co ions
were precipitated on the surface of rutile TiO2, and the subsequent
calcination resulted in the formation of CoTiO3 by the reaction of
Co oxide and TiO2. This meant that the CoTiO3 always existed on
the surface of the complex pigments' particles if the Co/Ti ratio
was below 1.0. This means that the complex pigments consisted of
CoTiO3 on the surface with inner core consisting of the rutile TiO2
(Fig. 9c). As shown in Fig. 10a, the micrograph of complex pigment
exhibited almost a uniform green hue. However, for the mixed
pigments with the same compositions, a completely different
micrograph was obtained (see Fig. 10b). The mixed pigments
consisted of aggregates of green CoTiO3 and yellow rutile TiO2. The
vast majority of rutile TiO2 could reect the light and shielding
part of CoTiO3 to absorb some of the visible light (Fig. 9e). This is
why lighter green hue was observed for the mixed pigments (see
Fig. 6c). However, the special coreshell structure could maximize
the visible absorption of CoTiO3 on the surface of the complex
pigments (Fig. 9d), which would result in the green hue of the
complex pigment particles. Besides, a lesser CoTiO3 phase would
also reduce the absorption of NIR, while the introduction of rutile
TiO2 (which has a high NIR reectance) [28] would promote the
NIR reection of complex pigments. As the ratio of Co/Ti increased,
the shell of CoTiO3 also thickened while rutile TiO2 core would
decreased, so the interface between CoTiO3 and TiO2 would also
shrink, which would result in decrease of NIR reection on the
interface of the different phases, that is, the Ref 2. would decrease
in Fig. 9e. So the NIR reectance of pigment would decrease with
the increase of Co/Ti ratio as shown in Fig. 8. In our previous re-
search [38], an enhanced NIR reectance and a brilliant blue color
for CoAl2O4/TiO2 complex pigments were observed. Consequently,
the complex pigments with the coreshell structure retained the
good color performance although lesser Co was used. Simulta-
neously, these complex pigments had an enhanced NIR reectance
relative to the pure CoTiO3 phase.
4. Conclusion
In this study, green complex pigments were prepared by pre-
cipitating Co ions on the rutile TiO2 particles and performing
subsequent calcination. The complex pigments presented a core
shell structure, which consisted of rutile TiO2 core and CoTiO3
shell. The color of pigments was tunable from light green to dark
green by changing the Co/Ti ratio. The complex pigments ex-
hibited good color properties and an enhanced NIR reectance.
Meanwhile, the complex pigments could substantially reduce the
Co consumption. The special coreshell structure was responsible
for the enhanced NIR reectance and good color properties. Hence,
these complex pigments are environmentally friendly and can be
manufactured at a relatively lower cost.
Acknowledgments
The work described in this paper was supported by a grant
from China Postdoctoral Science Foundation funded project
(2013M531925) and Fundamental Research Funds for the Central
Universities (XDJK2014C038).
 J. Zou, W. Zheng / Ceramics International 42 (2016) 81988205
References
[1] G.Y. Wei, J.K. Qu, Z.H. Yu, Y.L. Li, Q. Guo, T. Qi, Mineralizer effects on the
synthesis of amorphous chromium hydroxide and chromium oxide green
pigment using hydrothermal reduction method, Dyes Pigments 113 (2015)
487495.
[2] Y.X. Zhou, X.L. Weng, L. Yuan, L.J. Deng, Inuence of composition on near in-
frared reectance properties of M-doped Cr2O3 (M Ti,V) green pigments, J.
Ceram. Soc. Jpn. 122 (2014) 311316.
[3] S. Sangeeth, R. Basha, K.J. Sreerama, S.N. Sangilimuthu, B.U. Nair, Functional
pigments from chromium(III) oxide nanoparticles, Dyes Pigments 94 (2012)
548552.
[4] G.X. Gayo, F. Troncoso, A.E. Lavat, Application of LnCrTeO6 oxides as new
ceramic pigments of the type green chromium, Ceram. Int. 40 (2014)
611617.
[5] S.A. Elizirio, J.M. Andrade, S.J.G. Limac, C.A. Paskocim, L.E.B. Soledade,
P. Hammer, E. Longo, A.G. Souzab, I.M.G. Santos, Black and green pigments
based on chromiumcobalt spinels, Mater. Chem. Phys. 129 (2011) 619624.
[6] H.R. Hedayati, A.A.S. Alvani, H. Sameie, R. Salimi, S. Moosakhani, F. Tabatabaee,
A.A. Zarandi, Synthesis and characterization of Co1  xZnxCr2  yAlyO4 as a near-
infrared reective color tunable nano-pigments, Dyes Pigments 113 (2015)
588595.
[7] Z.X. Tao, W.Q. Zhang, Y.L. Huang, D.L. Wei, H.J. Seo, A novel pyrophosphate
BaCr2(P2O7)2 as green pigment with high NIR solar reectance and durable
chemical stability, Solid State Sci. 34 (2014) 7884.
[8] T. Masui, N. Takeuchi, H. Nakado, N. Imanaka, Novel environment-friendly
green pigments based on rare earth cuprate, Dyes Pigments 113 (2015)
336340.
[9] V. Sivakumar, U.V. Varadaraju, Environmentally benign novel green pigments:
Pr1  xCaxPO4 (x 0 0.4), Bull. Mater. Sci. 28 (2005) 299301.
[10] S. Jose, A. Prakash, S. Laha, S. Natarajan, M.L. Reddy, Green colored nano-
pigments derived from Y2BaCuO5: NIR reective coatings, Dyes Pigments 107
(2014) 118126.
[11] R. Levinson, P. Berdahl, H. Akbari, Solar spectral optical properties of pig-
mentsPart II: survey of common colorant, Sol. Energy Mater. Sol Cells 89
(2005) 351389.
[12] C.L. Liu, M. Ye, A.J. Han, J. Li, Structural analysis and characterization of doped
spinel Co2  xMxTiO4 (M Mg2 , Mn2 , Ni2 , Cu2 and Zn2 ) coated mica
composite pigments, Ceram. Int. 41 (2015) 55375546.
[13] G. Buxbaum, G. Pfaff, Industrial Inorganic Pigments, 3rd ed., 2005, P115.
[14] L.K.C. Souza, J.R. Zamian, G.N.R. Filho, L.E.B. Soledade, I.M.G. Santos, A.G. Souza,
T. Scheller, R.S. Anglica, C.E.F. Costa, Blue pigments based on CoxZn1  xAl2O4
spinels synthesized by the polymeric precursor method, Dyes Pigments 81
(2009) 187192.
[15] A. Fors, M. Llusar, J.A. Badenes, J. Calbo, M.A. Tena, G. Monrs, Cobalt mini-
misation in willemite (CoxZn2  xSiO4) ceramic pigments, Green Chem. 2
(2000) 93100.
[16] M. Llusar, A. Fors, J.A. Badenes, J. Calbo, M.A. Tena, G. Monrs, Colour analysis
of some cobalt-based blue pigments, J. Eur. Ceram. Soc. 21 (2001) 11211130.
[17] L. Jiang, X. Xue, J. Qu, J. Qin, J. Song, Y. Shi, W. Zhang, Z. Song, J. Li, H. Guo,
T. Zhang, The methods for creating energy efcient cool gray building coat-
ingsPart II: preparation from pigments of complementary colors and tita-
nium dioxide rutile, Sol. Energy Mater. Sol. Cells 130 (2014) 410419.
[18] X. Xue, J. Qin, J. Song, J. Qu, Y. Shi, W. Zhang, Z. Song, L. Jiang, J. Li, H. Guo,
T. Zhang, The methods for creating energy efcient cool gray building coat-
ingsPart I: preparation from white and black pigments, Sol. Energy Mater.
8205
Sol. Cells 130 (2014) 587598.
[19] V. tengla, J. ubrta, S. Bakardjieva, A. Kalendova, P. Kalenda, The preparation
and characteristics of pigments based on mica coated with metal oxides, Dyes
Pigments 58 (2003) 239244.
[20] J. Chen, X.B. Shi, B. Han, The preparation and characteristics of cobalt blue
colored mica titania pearlescent pigment by microemulsions, Dyes Pigments
75 (2007) 766769.
[21] M.W. Li, X.M. Gao, Y.L. Hou, C.Y. Wang, Characterization of CoTiO3 Nanocrys-
tallites prepared by homogeneous precipitation method, J. Nano- Electron.
Phys. 5 (2013) 0302203025.
[22] M.K. Yadav, A.V. Kothari, V.K. Gupta, Preparation and characterization of bi-
and trimetallic titanium based oxides, Dyes Pigments 89 (2011) 149154.
[23] B. Peng, X.W. Meng, F.Q. Tang, X.L. Ren, D. Chen, J. Ren, General synthesis and
optical properties of monodisperse multifunctional metal-ion-doped TiO2
hollow particles, J. Phys. Chem. C 113 (2009) 2024020245.
[24] S.H. Chuang, R.H. Gao, D.Y. Wang, H.P. Liu, L.M. Chen, M.,Y. Chiang, Synthesis
and characterization of ilmenite-type cobalt titanate powder, J. Chin. Chem.
Soc. 57 (2010) 932937.
[25] M.A. Gabal, S.A. Hameed, A.Y. Obaid, CoTiO3 via cobalt oxalateTiO2 precursor
synthesis and characterization, Mater. Charact. 71 (2012) 8794.
[26] S. Khanahmadzadeh, M. Enhessari, Z. Solati, A. Mohebalizadeh,
A. Alipouramjad, Synthesis, characterization and optical bandgap of the
Co2TiO4 nanoparticles, Mater. Sci. Semicond. Process. 31 (2015) 59603.
[27] I. Ganesh, A.K. Gupta, P.P. Kumar, P.S.C. Sekhar, K. Radha, G. Padmanabham,
G. Sundararajan, Preparation and characterization of Co-doped TiO2 materials
for solar light induced current and photocatalytic applications, Mater. Chem.
Phys. 135 (2012) 220234.
[28] J. Zou, P. Zhang, C. Liu, Y. Peng, Highly dispersed (Cr, Sb)-co-doped rutile
pigments of cool color with high near-infrared reectance, Dyes Pigments 109
(2014) 113119.
[29] J. Zou, Low temperature preparation of Cr-doped rutile pigments with good
colour properties, Dyes Pigments 97 (2013) 7176.
[30] P.S. Anjana, M.T. Sebastianw, Synthesis, characterization, and microwave di-
electric properties of ATiO3 (A Co, Mn, Ni) ceramics, J. Am. Ceram. Soc. 89
(2006) 21142117.
[31] Y.K. Sharma, M. Kharkwal, S. Uma, R. Nagarajan, Synthesis and characteriza-
tion of titanates of the formula MTiO3 (M Mn, Fe, Co, Ni and Cd) by co-
precipitation of mixed metal oxalates, Polyhedron 28 (2009) 579585.
[32] G.W. Zhou, D.K. Lee, Y.H. Kim, C.W. Kim, Y.S. Kang, Preparation and spectro-
scopic characterization of ilmenite-type CoTiO3 nanoparticle, Bull. Korean
Chem. Soc. 27 (2006) 368372.
[33] Y. Brik, M. Kacimi, M. Ziyad, F. Bozon-Verduraz, Titania-supported cobalt and
cobaltphosphorus catalysts: characterization and performances in ethane
oxidative dehydrogenation, J. Catal. 202 (2001) 118128.
[34] W. Hajjaji, C. Zanelli, M.P. Seabra, M. Dondi, J.A. Labrincha, Cr-doped titanite
pigment based on industrial rejects, Chem. Eng. J. 158 (2010) 167172.
[35] A. Atkinson, J. Doorbar, D.L. Segal, P.J. White, Solgel ceramic pigments, Key
Eng. Mater. 150 (1998) 1520.
[36] A. Libbra, L. Tarozzi, A. Muscio, M.A. Corticelli, Spectral response data for de-
velopment of cool coloured tile coverings, Opt. Laser Technol. 43 (2011)
394400.
[37] R. Levinsona, H. Akbaria, J.C. Reilly, Cooler tile-roofed buildings with near-
infrared-reective non-white coatings, Build. Environ. 43 (2007) 25912605.
[38] W. Zheng, J. Zou, Synthesis and characterization of blue TiO2/CoAl2O4 complex
pigments with good colour and enhanced near-infrared reectance properties,
RSC Adv. 5 (2015) 8793287939.