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Dark brown Cr doped CaTiO 3 pigments with high NIR reflectance

Article  in  Materials Letters · April 2019

DOI: 10.1016/j.matlet.2019.04.031

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 Materials Letters 248 (2019) 173–176

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Dark brown Cr doped CaTiO3 pigments with high NIR reflectance

Jian Zou ⇑, Tingdong Zhang, Xianda He
School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China

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

Article history: Some brown CaTiO3 pigments have been synthesized by calcining the depositions of CaCO3 and Cr dopant
Received 25 January 2019 on the surface of TiO2 particles. The pigments have a pure phase composition of perovskite and a narrow
Received in revised form 19 March 2019 size distribution ranging from 0.5 to 1.5 lm. These pigments have a low lightness and exhibit dark brown
Accepted 8 April 2019
color due to the presence of Cr6+.The doped CaTiO3 pigment with 1% Cr has high NIR reflectance of 79.7%
Available online 9 April 2019
and high solar reflectance of 58%, and the doped pigment coating can lower 8.9 °C for the inner surface of
ceramic tiles.
Keywords:
Ó 2019 Elsevier B.V. All rights reserved.
NIR reflectance
Solar energy materials
Cool pigments
CaTiO3
Ceramics
Functional

1. Introduction 2. Experimental section

Solar heat accumulation in the hot season results in a significant
increase of the cooling energy consumption and a decrease of
indoor comfort. The near infrared irradiation (NIR, 700–2500 nm)
occupies 52% energy in the solar irradiance spectrum [1]. Thus,
some inorganic pigments with high NIR reflectance can be used
as the cool roofing products to reduce the heat build-up. White
pigments have better performances in reducing the solar heat
accumulation, but they have also some disadvantages of light pol-
lution, poor stain resistance, and monochrome etc. [2], and thus
the dark colored pigments are usually preferred [1].
Some colored pigments have been developed as the cool pig-
ments, but these pigments have the weakness of high lightness.
In fact, the solar reflectance tends to increase with higher lightness
[3], and the darker pigments tend to lower NIR reflectance [4,5]. A
dark brown BiFeO3 pigment has a low lightness (L* = 37.07), but its
NIR reflectance at 1100 nm is only 43% [6]. Although the NIR reflec-
tance of BiFeO3 can be enhanced to 71.8% by doping with 40% La,
the color becomes lighter (L* = 61.92) [2]. Previous researches indi-
cated that Cr doped perovskite products had some intense absorp-
tion in visible region [7–11], which hinted that these products
might have darker color, but there are no any results on their
NIR reflectance. In the current work, some darker Cr doped CaTiO3
pigments were synthesized, and these pigments exhibited high NIR
reflectance.
⇑ Corresponding author.
E-mail address: ezouj@swu.edu.cn (J. Zou).
1.6 g TiO2 powders were dispersed into 50 mL distilled water
under vigorous stirring. 2.22 g CaCl2 and some amounts of CrCl3
were dissolved in the suspension. Subsequently, 1 M Na2CO3 solu-
tion was added into the suspension drop by drop, and the pH value
of the suspension was adjusted to around 9. The precipitates were
obtained after several cycles of filtering and washing processes.
Some powders were obtained by drying the precipitates at 80 °C
for 2 h. Finally, some dark brown pigments were obtained by cal-
cining these powders at 1000 °C for 1 h. The CaTiO3 pigments
doped with different Cr contents were obtained by changing the
ratio of Cr/Ti. The characterizations are shown in Supporting
Information.
3. Results and discussions
The Cr-doped CaTiO3 samples were prepared by calcining the
depositions of CaCO3 on the surface of TiO2 particles. A pure and
highly crystalline perovskite CaTiO3 could be obtained when the
calcination temperature increased to 1000 °C (Fig. 1a and
Fig. S1a). All peaks of the XRD patterns of samples doped with
more Cr contents from 2.5 to 10% are also in good agreement with
those of CaTiO3 without other impurities at 1000 °C (Fig. S1b). The
previous study indicated that the high concentration of Cr would
result in some impurities in Cr doped CaTiO3, such as CaCrO4 [7].
These indicated that CaTiO3 pigments could be synthesized by
the current method at 1000 °C.

https://doi.org/10.1016/j.matlet.2019.04.031
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
174 J. Zou et al. / Materials Letters 248 (2019) 173–176
Fig. 1. XRD pattern (a), Uv–Visible absorption spectra (b), the plots of (Ahv)2 versus hv (c) and XPS spectra of the Cr2p (d) of pure CaTiO3 and CaTiO3 samples doped 1% Cr.
Fig. 1b shows the results of UV–Vis absorption of the samples.
The Cr doped pigment has an absorption band located at around
520 nm, which can be assigned to the Cr4+ [7,9] or Cr6+ [12]. The
absorption has a distinct red shift to 700 nm relative to the pure
CaTiO3 and Cr-Sb co-doped TiO2 in previous work [13,14]. The
energy gap can be estimated to 1.93, 3.39 eV for 1% Cr doped and
undoped CaTiO3, respectively, according to the plots of (Ahv)2 ver-
sus hv in Fig. 1c. The colorimetric parameters are 42.5, 9.7 and 11.3
corresponding to the luminosity (L*), the red component (a*) and
the yellow component (b*), respectively. Obviously, this pigment
has a low L* value, which is much lower than that of previous
reports [7,9]. This also resulted in a dark brown colour in the set
of Fig. 1b. The absorption band and energy gap can be further reg-
ulated by increasing the Cr contents. As shown in Fig. S2, the
absorption at 520 nm increases with the increase of Cr contents
while the absorption band edge shift to the longer wavelength,
which results in reduced energy gaps of 1.92, 1.89 eV for the
increased Cr contents of 2.5 and 5%, respectively. And the colori-
metric parameters also decrease with the increase of Cr contents.
It is noteworthy that the luminosity (L*) is reduced to 34.29 when
the Cr contents increased to 5%. This indicates that the darker
brown CaTiO3 pigments could be feasibly synthesized by increas-
ing the Cr content.
Figure 1d shows the XPS spectra of the Cr2p of CaTiO3 doped
with 1% Cr. The Cr2p spectrum shows not only a shoulder Cr
2p3/2 peak at 576.7 eV assigned to Cr (III) [8,13] but also a sharper
peak at 580.1 eV assigned to Cr (VI) [8]. This indicates that two oxi-
dation states of Cr co-existed in Cr doped CaTiO3 pigments. The
Ti2p spectrum shows a sharper peak at 458.1 eV (Fig. S3), which
can be assigned to Ti4+ [15]. This indicated that no low valent tita-
nium existed in CaTiO3. Therefore, the low luminosity and dark
brown color of the Cr doped CaTiO3 pigments might stem from
the Cr (VI). Previous research indicated that the existence of only
Cr (III) resulted in a yellow color and higher L* value for Cr doped
CaTiO3 [10]. And Stoyanova et al. [11] also observed that the exis-
tence of higher valent Cr resulted in a brown color for Cr doped
CaTiSiO5 pigments.
The microstructure and size of pigment observed by SEM and
TEM are shown in Figs. 2 and S4. Some spherical particles with
the particle distribution between 0.5 and 2 lm can be observed
in all as-synthesized pigments regardless of the doped
contents (Fig. 2a and S4). It can be further observed that the
spherical particle consists of some small particles with the size
of 100–200 nm in Fig. 2b and c. These small particles exhibit a
good crystalline structure (Fig. 2d). The interplanar spacing is
calculated at about 0.27 nm, which is in good agreement with
the distance between two (1 2 1) crystal planes of the cubic
CaTiO3.
Results above indicated that the doped pigments had low lumi-
nosity (<45), but this pigment has a high NIR reflection (Fig. 3a).
For pure CaTiO3, the reflectance in visible and NIR region is beyond
90%. The doped CaTiO3 has only 30% reflectance in visible region,
which is resulted from the visible absorption of Cr dopant in
CaTiO3 lattice. It is well known that the visible absorption is also
necessary for color pigments. NIR irradiation (700–2500 nm)
accounts for 52% of energy in the solar irradiance spectrum [1].
Hence, the solar reflection of color pigments depends basically on
their NIR reflection. It is noted that the reflectance increases dra-
matically up to about 80% in NIR region for the Cr doped CaTiO3
in Fig. 3a. The Cr doped CaTiO3 pigment has lower the solar irradi-
 J. Zou et al. / Materials Letters 248 (2019) 173–176 175

Fig. 2. SEM (a, b), TEM (c) and HRTEM (d) of CaTiO3 pigment doped with 1% Cr.
Spectral irradiance W m -2 nm-1

100 (b)
(a) 1.5 700 nm Global title
80 Pure CaTiO3
Reflectance (%)

1.2 CaTiO3 doped

60 with 1.0% Cr
CaTiO3 doped 0.9
with 1% Cr
40 0.6
Pure CaTiO3

20 0.3

0 0.0
500 1000 1500 2000 2500 500 1000 1500 2000 2500
Wavelength/nm Wavelength/nm

60
c)
50
Temperature/oC

40
PU Blank Film
30 Pure CaTiO3 Film
Cr doped CaTiO3 Film

20

0 5 10 15 20 25 30
Time/minutes

Fig. 3. UV–Vis-NIR diffuse reflection spectrum (a), solar irradiance reflective spectrum based on AM 1.5 solar spectrum w/37° global title (b) and inner surface temperatures
of ceramic tiles vary with irradiation time based on the undoped and doped CaTiO3 pigments with 1% Cr.
176 J. Zou et al. / Materials Letters 248 (2019) 173–176
ance reflective spectrum relative to pure CaTiO3 and the standard
of global tilt (Fig. 3b) at the wavelength of 700 nm, which can
be attributed to the visible absorption of Cr doped CaTiO3 in
Fig. 1b and 3a; at the wavelength of 700–2500 nm, some slight dif-
ferences of spectra are observed, indicating that Cr doped CaTiO3
pigments have also high NIR solar irradiance reflection.
The NIR (700–2500 nm) solar reflectance value (RNIR ) of 1% Cr
doped CaTiO3 pigment can be estimated to 79.7% based on NIR
solar reflectance spectrum, and this pigment has also a high solar
reflectance value (Rsol , 280–2500 nm) of 58%.The NIR reflectance
would be depressed by increasing of Cr dopant (Fig. S5). TheRNIR
decreases to 52.3% from 67.1% when Cr content increases to 5%
from 2.5%, while Rsol decreases also to 40% from 51.7%. These values
are higher than some dark pigments in previous reports [3,6].
This hinted that Cr doped CaTiO3 pigments might have high solar
reflective properties. Fig. 3c shows that the inner surface
temperatures of tiles vary with irradiation time. After 30 min of
irradiance, an even temperature is reached for the blank tile and
the tiles coated doped and pure CaTiO3 PU film, and the corre-
sponding temperature are 56.8, 47.9 and 47.4 °C, respectively.
The pigment coat can remain approximately up to 8.9 °C cooler
than pure PU coating although its temperature is slightly higher
than one of pure CaTiO3.
4. Conclusions
Some dark colour pigments of the doped CaTiO3 were prepared
by calcining the depositions of CaCO3 and Cr dopant on the surface
of TiO2 particles. The as-prepared pigments have an intense visible
absorption and exhibit a dark brown-red colour. These pigments
have also high NIR reflection, and the coating based on the doped
CaTiO3 pigments could lower efficiently the temperature of 8.9 °C
of the ceramic surface.
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Conflicts of interest
The authors declared that they have no conflicts of interest to
this work.
Acknowledgments
This research was funded by Chongqing Research Program of
Basic Research and Frontier Technology (cstc2016jcyjA0027).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2019.04.031.
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