Ceramics International 49 (2023) 28824–28836

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

SrMn1-xFexO3-δ (x = 0–1) black ceramic pigment: Synthesis, color

properties, and application
Fanbing Lai a, 1, Wei Shi a, b, 1, Shuyun Hu c, Xiaohong Li a, b, Qibing Chang a, Yongqing Wang a, **,
Qikun Wang a, *
a
School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen, 333403, PR China
b
National Engineering Research Center for Domestic and Building Ceramics, Jingdezhen Ceramic University, Jingdezhen, 333000, PR China
c
Jingdezhen City Zhongrun Ceramics Co., Ltd, Jingdezhen, 333400, PR China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Dr P. Vincenzini In this work, SrMn1-xFexO3-δ (x = 0–1) black ceramic pigments were synthesized by the solid-state method. The
research explores the influence of calcination temperature and iron ion doping on the color properties of the
Keywords: pigments. Furthermore, the potential applications of SrMn1-xFexO3-δ pigments in ceramic glaze and heat-
SrMn1-xFexO3-δ absorbing materials are also discussed. The findings reveal that the synthesized SrMnO3 pigment exhibits the
Black pigment
lowest L*-value (22.30) at 1100 ◦ C, although it displays a slight blue hue. To optimize the color properties of the
Doping
SrMnO3 pigment, iron ion doping is employed. When the doping level of iron ions is 50 mol.% (i.e., x = 0.5), the
Color properties
Tinting performance L*-value of the SrMn0.5Fe0.5O3-δ pigment calcined at 1000 ◦ C significantly decreases to 19.77, while the a*- and
Sunlight absorption performance b*-values approach 0, resulting in a pure black color. This is attributed to the high surface roughness, low band
gap energy, and substantial oxygen vacancies present in the SrMn0.5Fe0.5O3-δ pigment. The tinting mechanism of
the SrMn1-xFexO3-δ pigment in the ceramic glaze is classified as "ion tinting", wherein the glaze color relies on the
concentrations of Mn and Fe ions. When the pigment content reaches 36 wt%, the L*-value of the glaze drops to
4.94, showing a deep black shade. Additionally, the SrMn0.5Fe0.5O3-δ pigment exhibits excellent sunlight ab­
sorption capabilities, with a near-infrared reflectance (R*) of only 5.04%. This research presents a black ceramic
pigment with various advantages, such as simplified processing, affordability, environmental friendliness, and
exceptional color performance.

1. Introduction and nickel raise concerns about potential environmental hazards.

Black ceramic pigments are highly valued in ceramic decoration due
to their ability to create a solemn and deep decorative effect [1–3].
Currently, two main material systems are used for black ceramic pig­
ments: encapsulated carbon black pigments (e.g., C@ZrSiO4 [4–6],
C@SiO2 [7,8]) and spinel-type black pigments (e.g., Co-Cr-Fe-Mn [9],
Fe-Cr [10], Ni-Fe-Cr [11]). However, these pigments have certain
drawbacks that are challenging to overcome. For instance, the encap­
sulation efficiency of C@ZrSiO4 pigments is too low (<12%), resulting in
unsatisfactory color performance [4,6]. The encapsulation layer (SiO2)
of C@SiO2 pigments is not stable in ceramic glaze [7,8]. Spinel-type
black pigments, containing heavy metals such as cobalt, chromium,
Moreover, the prices of cobalt and nickel have increased significantly
due to the rapid growth of the new energy industry, making it difficult to
control the production costs of cobalt- and nickel-containing pigments.
Cobalt prices have nearly tripled since 2015 due to increased demand
[12]. Consequently, researchers are interested in developing black pig­
ments with excellent color performance, high-temperature stability, and
environmental friendliness.
Perovskite materials are known for their structural simplicity [13],
ease of preparation, high-temperature stability [14,15], and corrosion
resistance [16,17]. SrMnO3, in particular, has significant applications in
catalysis [18–21] and as an electrode material [22–24], but its color
properties and potential use in ceramic decoration have received limited

* Corresponding author.
** Corresponding author.
E-mail addresses: 1436328003@qq.com (F. Lai), 034135@jci.edu.cn (W. Shi), 411916170@qq.com (S. Hu), lihong7178@163.com (X. Li), changqibing@jci.edu.
cn (Q. Chang), wyq8248@126.com (Y. Wang), 19B309004@stu.hit.edu.cn (Q. Wang).
1
Co-first authors, these authors contributed equally to this study and share co-first authorship.

https://doi.org/10.1016/j.ceramint.2023.06.145
Received 1 March 2023; Received in revised form 23 May 2023; Accepted 15 June 2023
Available online 16 June 2023
0272-8842/© 2023 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
F. Lai et al.
attention. SrMnO3 powder is generally black, suggesting its potential as
a black pigment. Therefore, investigating the color properties and ap­
plications of SrMnO3 is of great practical importance.
Doping is an effective technique for controlling and optimizing the
color performance of ceramic pigments [25–27]. For instance, the
introduction of iron ions caused the transition of Co0.5Mg0.5Al2O4
pigment from blue to black, reducing its L*-value from 55.04 to 29.55
[28]. In the field of photocatalysis, the introduction of iron ions reduces
the band gap of the powder, enhancing its ability to absorb natural light
energy and improving photocatalytic efficiency [29,30]. Consequently,
incorporating iron ions into the structure of SrMnO3 is expected to
enhance the color performance by increasing visible light absorption.
Apart from its use as a ceramic glaze colorant, SrMnO3 shows
promise as a heat-absorbing material due to its exceptional light ab­
sorption properties. Effective heat-absorbing materials can enhance the
efficiency of solar energy collection, thus, increasing the power gener­
ation capacity of solar thermal power systems [31]. Among the crucial
properties of heat-absorbing materials, solar reflectance is of particular
interest, as low reflectance minimizes heat loss from convection and
irradiation [32]. However, current research focuses more on materials
with high near-infrared reflectance, as they can be employed as cool
pigments to mitigate the urban heat island effect [33]. Unfortunately,
the materials reported in existing literature generally exhibit
near-infrared reflectance greater than 10%, which is not optimal for
highly efficient solar thermal power systems [28,34–37].
This study aimed to synthesize SrMnO3 pigment using the solid-state
method and investigate its thermal evolution and color performance.
Additionally, the influence of iron ions on the color performance of
SrMnO3 was examined to examined to optimize its characteristics.
Finally, the potential applications of SrMn1-xFexO3-δ pigment in ceramic
glazes and heat-absorbing materials were discussed.
2. Experiment
2.1. Materials
Strontium carbonate (SrCO3, 99%), manganese monoxide (MnO,
99%), ferric oxide (Fe2O3, 99.9%), and ethanol (CH3CH2OH, 99.7%)
were procured from Shanghai Aladdin Technology Co., Ltd. These re­
agents were of analytical grade and employed without additional
purification.
2.2. Synthesis of SrMn1-xFexO3-δ (x = 0–1) pigment
To prepare SrMn1-xFexO3-δ (x = 0–1) pigment, a typical experiment
was conducted as follows: 14.76g of SrCO3, 20g of ethanol, and a spe­
cific amount of MnO and Fe2O3 were mechanically ground together
using an agate mortar. Detailed recipes are given in Supplementary
Materials Table S1. During the grinding process, the ethanol volatilized,
resulting in the formation of the SrMn1-xFexO3-δ precursor. It is impor­
tant to note that there were no strict requirements regarding the
grinding time or speed in this mixing process. The evaporation of
ethanol indicated the completion of the mixing process. Subsequently,
the precursor was calcined at various temperatures for 1h to produce the
SrMn1-xFexO3-δ pigment.
2.3. Application of SrMn1-xFexO3-δ (x = 0–1) pigment in ceramic glaze
To investigate the colorant efficacy of the SrMn1-xFexO3-δ pigment
within the ceramic glaze, enameled specimens containing varying de­
grees of pigment admixture (6 wt%, 12 wt%, 24 wt%, 36 wt%, 48 wt%)
were prepared. The procedure to create these enameled specimens is as
follows. Initially, a glaze slurry was produced by subjecting the base
transparent glaze (comprising 50 wt% solid content) and the SrMn1-
xFexO3-δ pigment to a ball milling operation at a speed of 200 rpm for a
duration of 10 min. The base transparent glaze was obtained
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Ceramics International 49 (2023) 28824–28836
commercially, and its chemical composition is given in Supplementary
Materials Table S2. Subsequently, the glaze slurry was employed on the
test piece using a dipping technique. This test piece constructed of high-
white clay through a pressing and preliminary firing process (800 ◦ C),
had dimensions of 1 cm in thickness and a 5 cm diameter. Once dry, the
glaze slurry formed a layer the top of the test piece, which was then
polished using abrasive paper to make a controlled glaze layer thickness
of approximately 1.0 mm. The polished test pieces were then heated
from room temperature to 1200 ◦ C at a heating rate of 5 ◦ C/min in an air
atmosphere and held for 20 min. Finally, the specimens were allowed to
cool down ambiently to room temperature. After cooling, the enameled
specimens were collected and subjected to color performance
examinations.
2.4. Application of SrMn1-xFexO3-δ (x = 0–1) pigment in heat-absorbing
material
In order to investigate the application of SrMn1-xFexO3-δ pigment in
heat-absorbing material, a SrMn1-xFexO3-δ coating was prepared. Firstly,
the SrMn1-xFexO3-δ paint was obtained by mechanically blending 5 g of
SrMn1-xFexO3-δ pigment with 5 g of a polyvinyl alcohol (PVA) solution
(with a 1 wt% concentration) using an agate mortar. In the subsequent
phase, the newly produced SrMn1-xFexO3-δ paint evenly applied onto a
glass slide and subjected to a drying process within an oven maintained
at 80 ◦ C for a duration of 12 h. This culminated in the successful pro­
duction of the desired SrMn1-xFexO3-δ coating.
2.5. Characterization
Several analytical techniques were employed to evaluate the prop­
erties of the SrMn1-xFexO3-δ black pigment and the associated enameled
and coating specimens. XRD information for both the pigments and
enameled specimens were analyzed by X-ray diffraction analyzer (XRD,
Bruker D8 Advance X-ray Diffraction) with a Cu Kα radiation source (λ
= 0.15418 nm). The XRD data of the SrMnO3 and SrMn0.5Fe0.5O3-δ
pigments produced under various temperatures, along with the enam­
eled specimens, was procured employing the standard scan mode, with
parameters of 0.02◦ 2θ per step, 0.2 s per step and a scan range (2θ) from
5 to 80◦ . Similarly, XRD information for SrMn1-xFexO3-δ pigments with
various x-values was procured using the slow scan mode, with param­
eters of 0.01◦ 2θ per step, 0.6 s per step and a scan range (2θ) from 5 to
80◦ . The thermal evolution of the SrMnO3 precursor was examined
utilizing a by simultaneous thermogravimetric and differential thermal
analyzer (DTA/TG, NETZSCH STA 449C). This analysis was performed
from room temperature to 1300 ◦ C at a temperature increase rate of
5 ◦ C/min in the air using α-Al2O3 as a reference. CIE lab parameters L*,
a*, and b* were measured using a spectrophotometer (Hunter lab Min­
iscan MSXP 4000, 400–700 nm, white glazed tile reference x = 31.5, y =
33.3). Here, L* is the lightness axis (black (0) ~ white (100)), b* is the
blue (− ) ~ yellow (+) axis, and a* is the green (− ) ~ red (+) axis.
Visible light reflectance spectra of the pigments were captured using
a UV–vis light spectrophotometer (Lambda850, PerkinElmer, USA) in a
range of 200–900 nm, with a step size of 0.3 nm, and with BaSO4 as a
reference. The band gap energy (Eg) of the pigments was deduced from
the Tauc relation [38].
(αhv) n = A(hv-Eg)
where hv is the incident photon energy, A is a constant and α is the
absorption coefficient. n is the value between 2 and 1/2 depending on
the direct and indirect allowed electronic transitions, respectively [38].
SrMnO3 is a direct band gap semiconductor, so n is 2 in this work [19]. α
can be calculated from the Kubelka-Munk (K-M) equation, which rep­
resents the relation between the absorption coefficient (α) and the
reflectivity (R) [39]:
F. Lai et al.
Fig. 1. XRD patterns of SrMnO3 pigments synthesized at different calcination
temperatures.
(1 − R)2
α = F(R) =
2R
where R is the reflectivity value measured at UV–vis region.
The UV–Vis–NIR diffused reflectance spectra of the SrMn1-xFexO3-δ
pigments were captured utilizing a UV–Vis–NIR spectrophotometer
(Shimadzu UV-3600i Plus). A BaSO4 standard white plate was used as a
reference, and a 2 nm step was applied in the scanning wavelength range
of 200–2500 nm. The NIR reflectance (R*) within the wavelength scope
of 700–2500 nm was computed using by the subsequent equation:
∫ 2500
R∗ = 700
r(λ)ⅈ(λ)d(λ)
∫ 2500
700
ⅈ(λ)d(λ)
where r(λ) is the spectral reflectance (W⋅m− 2), obtained experimentally,
and i(λ) is the solar spectral irradiance (W⋅m− 2 nm− 1), obtained from
ASTM standard G159-98 [33].
The microstructure of the sample was analyzed using a scanning
electron microscope (SEM, model SU8010, Hitachi). The content and
valence state of Sr, Mn, Fe, and O ions on the pigment surface were
determined through X-ray photoelectron spectroscopy (XPS) using an
Escalab 250Xi instrument (Thermo Fisher Scientific, Waltham, MA,
USA). The binding energy values were calibrated based on the C1s peak
measured at 284.8 eV. Infrared thermal imaging photos of the SrMn1-
xFexO3-δ coating and the corresponding temperature rise were captured
using an infrared thermal imager (FLIR Systems, Inc., USA). The imager
utilized a xenon lamp (Zolix LHX150 Arc Lamp) as its light source, with
a wavelength range of 200–2500 nm and a light source power of 0.285
W. The distance between the light source and the sample was main­
tained at 30 cm.
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Ceramics International 49 (2023) 28824–28836
Fig. 2. DTA-TG curves of SrMnO3 precursor.
3. Results and discussion
3.1. Synthesis of SrMnO3 pigment
Fig. 1 presents the XRD patterns of the SrMnO3 pigment synthesized
at various calcination temperatures. At 400 ◦ C, the sample showed
diffraction peaks corresponding to the raw materials, MnO and SrCO3,
indicating that no chemical reaction had occurred at this stage. At
500 ◦ C, portion of MnO underwent oxidation to form Mn2O3, which was
completely oxidized at 600 ◦ C. Subsequently, Mn2O3 and SrCO3
remained as the dominant crystalline phases until the calcination tem­
perature reached 800 ◦ C. Upon increasing the calcination temperature
to 900 ◦ C, weak diffraction peaks associated with manganese-strontium
compounds, such as SrMn3O6-x, Sr7Mn4O15 and SrMnO3, were detected.
With further temperature escalation, the intensity of Mn2O3 and SrCO3
diffraction peaks gradually diminished, while the intensity of the
diffraction peaks of manganese-strontium compounds gradually
increased. At 1100 ◦ C, the diffraction peaks of Mn2O3 and SrCO3 dis­
appeared completely. At 1200 ◦ C, the diffraction peaks of Sr7Mn4O15
and SrMn3O6-x also vanished, leaving only the diffraction peak corre­
sponding to hexagonal SrMnO3 [40]. The thermal evolution of SrMnO3
pigment synthesized by solid-state method using SrCO3 and MnO as raw
materials revealed that the minimum synthesis temperature of SrMnO3
pigment is 1100 ◦ C, and Sr7Mn4O15 and SrMn3O6-x are the intermediate
phases for the synthesis of SrMnO3 pigment.
Fig. 2 presents the DTA-TG curve of the SrMnO3 precursor. The
heating process up to 1300 ◦ C revealed four distinct stages of weight
change in the precursor. It should be noted that there is a certain level of
hysteresis between the DTA-TG and XRD results. This can be attributed
to the continuous heating in the DTA-TG test, while the XRD analysis
was performed on samples that were held for 1 h after calcination. Stage
I (room temperature to 700 ◦ C) corresponds to a weight gain process,
which aligns with the oxidation of MnO to Mn2O3 as indicated by the
XRD results [41]. The oxidation temperature, according to the DTA
curve, is 609.6 ◦ C. Stage II (700–900 ◦ C) represents a relatively stable
process, as observed in the TG curve. A weak exothermic peak was
identified at 774.5 ◦ C in the DTA curve, which may be associated with
the enhanced crystallinity of SrCO3. This conclusion is supported by the
gradual increase in diffraction peak intensity of SrCO3 within the tem­
perature range of 400–800 ◦ C. Stage III (900–1060 ◦ C) involves a weight
loss process, accompanied by a sharp endothermic peak at 931.0 ◦ C in
the DTA curve. This peak corresponds to the decomposition of SrCO3
[42,43]. In stage IV (1060–1300 ◦ C), a slight weight rebound is
observed. An exothermic peak at 1079.6 ◦ C in the DTA curve signifies
the formation of SrMnO3, SrMn3O6-x, and Sr7Mn4O15. Additionally, the
F. Lai et al. Ceramics International 49 (2023) 28824–28836

Fig. 3. Chromatic parameters and photographs (a), and UV–vis reflection spectra (b) of SrMnO3 pigments synthesized at different calcination temperatures.

intermediate phases, Sr7Mn4O15 and SrMn3O6-x, react with O2 to

generate SrMnO3, which occurs during this stage [44]. The weight
rebound can be attributed to the reaction of the intermediate phase with
O2 to form SrMnO3. Based on the combined analysis of XRD and
DTA-TG, the possible chemical reactions involved in the synthesis of the
SrMnO3 pigment are presented below.

4MnO + O2→2Mn2O3 [Occurs at about 600◦ C] ———— (1)

◦
4SrCO3+2Mn2O3+O2→4SrMnO3+4CO2 [Occurs at about 1000 C]
———— (2)
◦
7SrCO3+2Mn2O3+O2→Sr7Mn4O15+7CO2 [Occurs at about 1000 C]
———— (3)
◦
4SrCO3+6Mn2O3+(1-2x) O2→4SrMn3O6-x+4CO2 [Occurs at about 1000 C]
———— (4)

2SrMn3O6-x+4SrCO3+(1 + x) O2→6SrMnO3+4CO2 [Occurs at about

1100◦ C] ———— (5)

2Sr7Mn4O15+2Mn2O3+3O2→14SrMnO3 [Occurs at about 1100◦ C]

———— (6)

Fig. 3(a) presents the chromatic parameters and photographs of

SrMnO3 pigments calcined at various temperatures. The L*-value of the
SrMnO3 pigment steadily decreased as the calcination temperature
increased from 400 to 1200 ◦ C, reaching its minimum value of only
22.30 at 1100 ◦ C.The corresponding a*- and the b*-values were 0.98 and
− 5.05, respectively. The photographs also demonstrate that the SrMnO3
pigment synthesized at 1100 ◦ C exhibits the darkest black hue. Unfor­
tunately, this black SrMnO3 pigment displays a blue-green tinge (the
absolute value of b*-value is larger), indicating it is not pure black. To Fig. 4. XRD patterns of SrMn0.5Fe0.5O3-δ pigments synthesized at different
more objectively characterize this issue, UV–vis reflection analysis was calcination temperatures.
performed, as shown in Fig. 3(b). Compared with other visible wave­
lengths, the SrMnO3 pigment exhibits stronger light reflection in the red-
was chosen to modulate the color properties of the SrMnO3 pigment.
orange light region (620–780 nm), suggesting that the pigment displays
Fig. 4 displays the XRD patterns of SrMn0.5Fe0.5O3-δ pigments synthe­
its complementary color, namely blue-green. Furthermore, the SrMnO3
sized at different calcination temperatures. At 700 ◦ C, the sample
pigment synthesized at 1100 ◦ C exhibits the weakest reflection intensity
comprises SrCO3, Fe2O3, and Mn2O3. A weak diffraction peak ascribed to
in the full visible light region (380–780 nm) compared to the other
the SrMn0.5Fe0.5O3-δ phase is detected at 800 ◦ C, which is 100 ◦ C lower
samples, indicating its deepest black hue. The broad absorption bands
than the temperature required for the formation of the SrMnO3 phase.
observed in the full visible region for SrMnO3 pigments can be attributed
When the calcination temperature reaches 900 ◦ C, the generation of
to the 6A1g→4A1g and 6A1g→4T2g crystal field transitions of octahedral
multiple Sr–Mn–Fe–O compounds, including SrMn0.5Fe0.5O3-δ,
Mn4+ sites [45,46]. Based on the reflection curve, it can be observed that
Sr7Mn4O15, SrMnO3, and SrMn3O6-x, is detected. As the calcination
when the calcination temperature is either lower or higher than 1100 ◦ C,
temperature exceeds 1000 ◦ C, SrMn0.5Fe0.5O3-δ becomes the predomi­
the reflection intensity of the pigment toward light is enhanced,
nant crystalline phase, with the intensity of its diffraction peak gradually
resulting in unsatisfactory color performance.
increasing. Concurrently, Sr7Mn4O15, SrMnO3, and SrMn3O6-x gradually
disappear, indicating that they serve as intermediate phases in the for­
mation of SrMn0.5Fe0.5O3-δ. Notably, with the introduction of 50 mol.%
3.2. Effects of calcination temperature on Fe-doped SrMnO3 pigment
Fe ions, the crystal structure of SrMnO3 transitions from hexagonal to
cubic [40,47].
To address the issue of the blue hue, the incorporation of iron ions

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F. Lai et al.
Fig. 5. Chromatic parameters and images of SrMn0.5Fe0.5O3-δ pigments syn­
thesized at different calcination temperatures.
Compared to SrMnO3, the incorporation of iron ions lowers the
temperature required for the formation of the perovskite phase. This is
attributed to the smaller ionic radius of Mn ions, which necessitates a
higher temperature to expand the volume of the Mn–O cubic lattice to
accommodate Sr ions. In contrast, iron ions possess a larger ionic radius,
enabling the formation of a larger sized cubic lattice structure at a lower
temperature [48]. Therefore, the introduction of Fe ions facilitates the
formation of cubic SrMn0.5Fe0.5O3-δ at lower temperatures [49,50].
Fig. 5 illustrates the chromatic parameters and photographs of
SrMn0.5Fe0.5O3-δ pigments prepared at different calcination tempera­
tures. Similar to the SrMnO3 pigment, the L*-value gradually decreases
and reaches its minimum value of 19.77 at 1000 ◦ C as the calcination
temperature ranges from 700 to 1200 ◦ C. Importantly, the a*- and b*-
Fig. 6. SEM images of the SrMn0.5Fe0.5O3-δ pigment synthesized at 900 ◦ C (a), 1000 ◦ C (b), 1100 ◦ C (c), and 1200 ◦ C (d).
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Ceramics International 49 (2023) 28824–28836
values of the SrMn0.5Fe0.5O3-δ pigment synthesized at 1000 ◦ C are close
to 0, with values 0.15 and 0.70, respectively. Consequently, the
SrMn0.5Fe0.5O3-δ pigment exhibits a purer and deeper black hue
compared to the SrMnO3 pigment.
Based on the XRD analysis in Fig. 4, it is evident that the main
crystalline phases of the synthesized pigment are all SrMn0.5Fe0.5O3-δ
when the calcination temperature exceeds 1000 ◦ C. However, the L*-
values of the samples synthesized at 1000 ◦ C, 1100 ◦ C, and 1200 ◦ C
exhibit significant difference. To understand the underlying mechanism
of how the calcination temperature effects the color properties, an
investigation was conducted on the microstructure and surface element
state of the SrMn0.5Fe0.5O3-δ pigment. Fig. 6 illustrates the SEM images
of the SrMn0.5Fe0.5O3-δ pigments synthesized at 900 ◦ C, 1000 ◦ C,
1100 ◦ C and 1200 ◦ C. As depicted in Fig. 6(a) and (b), the pigments
synthesized at 900 ◦ C and 1000 ◦ C exhibit a rough particle surface. In
contrast, the pigments synthesized at 1100 ◦ C and 1200 ◦ C displays a
relatively smooth particle surface, as shown in Fig. 6(c) and (d).
To obtain a more precise examination of the surface roughness of the
SrMn0.5Fe0.5O3-δ pigments, atomic force microscopy (AFM) was
employed. Supplementary Fig. S1 presents the 3D AFM images and
roughness parameters (Ra and Rq) of the SrMn0.5Fe0.5O3-δ pigments
synthesized at 900 ◦ C, 1000 ◦ C, 1100 ◦ C and 1200 ◦ C. In general, surface
roughness can be characterized by Ra or Rq, which respectively repre­
sent the arithmetic average and root mean square value of the absolute
values of the profile height deviations from the mean line [51]. It is
evident that the Ra and Rq values of the pigment synthesized at 1000 ◦ C
are higher than those of the other pigments, indicating that the pigment
exhibits the greatest surface roughness at a synthesis temperature of
1000 ◦ C. Meanwhile, Ra and Rq gradually decrease with an increase in
the calcination temperature, suggesting a reduction in the surface
roughness of the pigments. This observation aligns consistent with the
results of the SEM analysis shown in Fig. 6.
Combining the XRD and SEM findings, it is evident that increasing
the calcination temperature results in enhanced crystallinity and parti­
cle size of the pigment. In general, the brightness of black objects is
particularly influenced by surface roughness due to the specular
component of selectively reflected light [52–54]. In comparison to the
diffuse component, the specular component contributes less to the
F. Lai et al. Ceramics International 49 (2023) 28824–28836

Fig. 7. High-resolution XPS spectra of elements of SrMn0.5Fe0.5O3-δ pigments synthesized at different calcination temperatures (a) Sr, (b) Mn, (c) Fe, (d) O; (1)
900 ◦ C, (2) 1000 ◦ C, (3) 1100 ◦ C.

were fitted using Origin 2018 software, and Table 1 provides the
Table 1
element species and their corresponding percentages on the surface of
Percentage of each element on the surface of SrMn0.5Fe0.5O3-δ pigment synthe­
the SrMn0.5Fe0.5O3-δ pigment synthesized at 900 ◦ C, 1000 ◦ C and
sized at different calcination temperatures.
1100 ◦ C.
Element 900 ◦ C 1000 ◦ C 1100 ◦ C
The high-resolution spectrum of the Sr element in Fig. 7(a) reveals
Species that the surface of the SrMn0.5Fe0.5O3-δ pigment synthesized at 900 ◦ C
Sr Surface Sr 21.07 100 19.78 76.21 17.14 40.75 only exhibits the “surface Sr” species, whereas the surfaces of the pig­
Lattice Sr 0 23.79 59.25 ments synthesized at 1000 ◦ C and 1100 ◦ C contain both “surface Sr” and
Mn Mn3+ 2.44 46.93 4.55 55.99 6.29 50.38 “lattice Sr” species. Moreover, the percentage of lattice Sr increases with
Mn4+ 53.07 44.01 49.62 the rise in calcination temperature. SrO and the cubic perovskite
Fe Fe2+ 1.47 23.24 5.35 40.29 5.93 27.93
structure can form a limited solid solution, commonly known as the
Fe3+ 40.76 32.53 41.06 “Ruddlesden-Popper (RP)” phase [56]. In this model, the surface region
Fe4+ 36.00 27.18 31.01 possesses an unusually high dislocation density, where these extended
O Adsorbed O 75.04 85.84 70.31 80.86 69.64 48.02 defects not only act as fast diffusion pathways for Sr ion segregation at
Lattice O 14.16 19.14 51.98 the crystal surface, but are also accompanied by a mechanical strain.
Total (%) 100 100 100 Kinetic stratification driven by mechanical strain gradients can be
considered as the relevant driving force for surface Sr segregation [57].
The increased surface roughness of the SrMn0.5Fe0.5O3-δ pigment may be
“dilution” of the visible light reflected from an object. Therefore, black a macroscopic manifestation of this strain, which is consistent with the
pigments with a rough surface reflect less visible light, leading to lower SEM image in Fig. 6 [58].
brightness. In other words, the roughness of the particle surface is Fig. 7(b) displays the XPS spectra of Mn 2p, comprising four peaks
inversely proportional to the L*-value of the SrMn0.5Fe0.5O3-δ pigment. with binding energies of 640.48 eV, 641.68 eV, 651.98 eV and 653.23
In summary, the change in particle surface roughness is one of the eV. According to previous literature, the signals at 640.48 eV and
mechanisms by which the calcination temperature affects the color 651.98 eV were assigned to trivalent Mn cations (Mn3+), while the
properties of the SrMn0.5Fe0.5O3-δ pigment. signals at 641.68 eV and 653.23 eV were assigned to tetravalent Mn
Our previous research has demonstrated that the surface element cations (Mn4+) [59,60]. Consequently, it can be inferred that the Mn
states, including valence and element distribution, have a significant cations in the SrMn0.5Fe0.5O3-δ pigment exhibit two valence states:
impact on the color properties of ceramic pigments [55]. To investigate trivalent (+3) and tetravalent (+4). At 1000 ◦ C, the atomic ratio of Mn3+
the surface information of the SrMn0.5Fe0.5O3-δ pigment, XPS analysis to Mn4+ is 1.27, representing the maximum value among the three
was conducted, and the results are presented in Fig. 7. The XPS spectra calcination temperatures. The increased percentage of Mn3+ on the

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Fig. 8. XRD patterns of SrMn1-xFexO3-δ pigments with different x-values, and
magnified view of (110) peak. (Note: the calcination temperature is 1000 ◦ C).
pigment surface theoretically requires more oxygen vacancies to main­
tain balance [61]. In perovskite-based photocatalytic materials, surface
oxygen vacancies can sever as photoinduced charge traps and adsorp­
tion sites, enhancing the absorption and utilization of visible light and
improving their photocatalytic performance [62].
Fig. 7(c) displays the XPS spectra of Fe 2p, which exhibits six peaks
with binding energies of 709.68 eV, 710.63 eV, 712.98 eV, 723.38 eV,
724.68 eV and 726.73 eV. The corresponding satellite peaks have also
been observed. In general, the signals at 709.68/723.38 eV, 710.63/
724.68 eV and 712.98/726.73 eV can be assigned to Fe2+, Fe3+ and
Fe4+, respectively [63,64]. This indicates that the Fe cations on the
surface of the SrMn0.5Fe0.5O3-δ pigment possess three valence states. As
shown in Table 1, the percentage of Fe2+ is the highest, while the per­
centage of Fe4+ is the lowest at a calcination temperature of 1000 ◦ C.
Similar to Mn ions, an increase in Fe2+ leads to an increase in oxygen
vacancies on the pigment surface, thereby enhancing the absorption of
visible light. Consequently, the SrMn0.5Fe0.5O3-δ pigment exhibits a
lower L* value.
Fig. 7(d) shows the XPS spectra of O 1s, which consists of two peaks
with binding energies of 527.68 eV and 530.38 eV. The signal at 527.68
Fig. 9. Chromatic parameters and photographs (a), and UV–vis reflection spectra (b) of SrMn1-xFexO3-δ pigments with different x-values. (Note: the calcination
temperature is 1000 ◦ C).
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Ceramics International 49 (2023) 28824–28836
eV is assigned to “lattice oxygen”, while the signal at 530.38 eV is
assigned to “adsorbed oxygen”. The presence of adsorbed oxygen is
determined by defects such as oxygen vacancies and chemical adsorp­
tion [65]. It can be observed that the percentage of adsorbed oxygen
decreases with increasing calcination temperature, which in turn re­
duces the absorption of visible light by the SrMn0.5Fe0.5O3-δ pigment.
3.3. Effect of Fe doping amount on SrMn1-xFexO3-δ pigment
Fig. 8 illustrates the XRD patterns of SrMn1-xFexO3-δ (x = 0–1) pig­
ments calcined at 1000 ◦ C. The results show that the incorporation of
iron ions promotes the formation of Sr–Mn–Fe–O compounds. When x is
greater than 0.5, the diffraction peaks corresponding to raw materials
such as SrCO3, Fe2O3, and Mn2O3 become barely detectable. Addition­
ally, the introduction of iron results in a slight shift of the (110) peak
towards smaller diffraction angles compared to the matrix oxide. This
shift occurs because the smaller Mn4+ ions (0.530 Å) are replaced by the
larger Fe3+(0.645 Å), resulting in a slight expansion of the unit-cell
volume of SrMn1-xFexO3-δ [55].
The chromatic values of SrMn1-xFexO3-δ pigments with different x-
values are depicted in Fig. 9(a). As the x-value increases from 0 to 1, the
L*-value of the SrMn1-xFexO3-δ pigment decreases and reaches its mini­
mum at x = 0.5 (L* = 19.77). Surprisingly, both the a*- and b*-values of
the SrMn0.5Fe0.5O3-δ pigment are closest to 0. This indicates that the
optimal doping amount of iron ions is 50 mol.%. To visually demon­
strate the color purity of the SrMn0.5Fe0.5O3-δ pigment, UV–vis reflection
analysis was conducted, as shown in Fig. 9(b). Apparently, the light
reflection intensity of the SrMn1-xFexO3-δ pigment is significantly
reduced across the entire visible spectrum compared to the SrMnO3
pigment. Moreover, the doping of iron ions effectively diminishes the
light reflection intensity of the SrMn1-xFexO3-δ pigment in the red-orange
light region, which is crucial for enhancing the color purity of the
SrMnO3 pigment.
The improvement in the color properties of the SrMn1-xFexO3-δ
pigment can be attributed to the alteration of the band gap energy
resulting from the introduction of iron ions. This, in turn, affects the
reflection behavior of the SrMnO3 pigment. As shown in Fig. 10, the
band gap energy (Eg) of SrMn1-xFexO3-δ pigments with different x-values
was determined using the Tauc plot method. As expected, the Eg value of
SrMnO3 decreased upon doping with iron ions. Specifically,
SrMn0.5Fe0.5O3-δ (i.e., x = 0.5) exhibited the minimum Eg value of 2.06
eV. The narrowing of the band gap can be attributed to charge transfer
[2p(O2− ) → 3d(Fe3+)] [34] and Fe3+ d-d intramolecular transitions
(6A1g → 4T1g and 6A1g → 4T2g) [66]. A smaller band gap, enables better
absorption of natural light and facilitates the absorption of energy from
valence band electrons. This leads to enhanced electron jumps and
increased light absorption, resulting in lower reflection intensity. After
x > 0.5, the band gap energy gradually increases, which can be
F. Lai et al. Ceramics International 49 (2023) 28824–28836

Fig. 10. Band gap energy (Eg) of SrMn1-xFexO3-δ pigments with different x-values.

explained by the Burstein-Moss and bandgap renormalization effects
arising from heavy doping [67,68].
Fig. 11 illustrates the SEM images of SrMn1-xFexO3-δ pigments with
different x-values. The images reveal that the introduction of iron ions
does not bring about significantly changes in the microscopic
morphology of the pigments. All pigments consist of irregular particles
with an approximate size of 1 μm.
To further investigate the influence of surface element states on the
color properties of SrMn1-xFexO3-δ pigments, XPS analysis was con­
ducted on SrMnO3 and SrFeO3-δ pigments synthesized at 1000 ◦ C. The

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Fig. 11. SEM images of SrMn1-xFexO3-δ pigments with different x-values, (a) x = 0, (b) x = 0.1, (c) x = 0.3, (d) x = 0.5, (e) x = 0.7, (f) x = 1.0.
high-resolution spectra of the detected elements and the percentages of
different element species are presented in Fig. S2 and Table S3,
respectively. The results reveal that the evolution of surface element
states in SrMn1-xFexO3-δ pigments with different x-values follows the
pattern described in Fig. 7 and Table 1. Specifically, pigments with
higher percentages of surface Sr, Fe2+, Mn3+, and adsorbed oxygen tend
to exhibit a darker color.
In summary, a pure deep black SrMn0.5Fe0.5O3-δ pigment was ob­
tained by doping 50 mol.% of iron ions into SrMnO3 and calcining at
1000 ◦ C. The dark black hue of this pigment arises from the combination
of several factors: (1) a high surface roughness resulting from the
segregation of surface Sr and low crystallinity; (2) the introduction of
iron ions significantly reduces the band gap energy of SrMnO3; and (3) a
high percentage of low-valence manganese and iron ions on the particle
surface leads to an abundance of oxygen vacancies. The high surface
roughness reduces the reflection of visible light by the pigment, while
the low band gap energy and the presence of oxygen vacancies enhance
the absorption of visible light by pigment. Collectively, these factors
contribute to the deep black color exhibited by the SrMn0.5Fe0.5O3-δ
pigment.
3.4. Application of SrMn0.5Fe0.5O3-δ pigment in ceramic glaze
High-temperature ceramic color glazes represent a significant
application area for ceramic pigments. Therefore, it is crucial to inves­
tigate the tinting performance of the SrMn0.5Fe0.5O3-δ black pigment in
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Ceramics International 49 (2023) 28824–28836
ceramic glazes. Fig. 12 presents photographs and chromatic parameters
of enameled samples with varying additions of SrMn0.5Fe0.5O3-δ pig­
ments. The control group, without any pigment, appears white, while
the samples containing SrMn0.5Fe0.5O3-δ exhibit pronounced coloration,
evident from their lower L*-values. As the pigment addition increased
from 0 to 48 wt%, the L*-values of the enameled samples progressively
decreased, and reached a minimum value of only 4.94 at an addition of
36 wt%. In other words, enameled samples with pigment additions
below 12 wt% displayed a brownish yellow hue, while enameled sam­
ples with pigment additions exceeding 24 wt% appeared black.
Furthermore, all enameled samples exhibited excellent surface gloss,
with no observed defects, indicating the outstanding compatibility of the
SrMn0.5Fe0.5O3-δ pigment with transparent glazes.
The color of the enameled glaze may not always match that of the
SrMn0.5Fe0.5O3-δ pigment, indicating the involvement of a tinting
mechanism. The XRD patterns of enameled samples with varying addi­
tions of SrMn0.5Fe0.5O3-δ pigment are depicted in Fig. 13. It can be seen
that all samples exhibit an amorphous nature. The control group dis­
plays a weak peak corresponding to quartz, suggesting that the addition
of SrMn0.5Fe0.5O3-δ pigment promotes the melting of quartz. Crucially,
no diffraction peak attributed to SrMn0.5Fe0.5O3-δ is detected in the
samples containing the pigment, indicating that the SrMn0.5Fe0.5O3-δ
pigment has dissolved into the base transparent glaze. Hence, it can be
concluded that the tinting mechanism of SrMn0.5Fe0.5O3-δ pigment is
based on “ion tinting”, whereby the coloration in SrMn0.5Fe0.5O3-
δ-containing glazes originates from the Mn and Fe cations that have
F. Lai et al. Ceramics International 49 (2023) 28824–28836

Fig. 12. Photographs and chromatic parameters of the enameled samples with different additions of SrMn0.5Fe0.5O3-δ pigment.

melted into the glass phase, rather than from SrMn0.5Fe0.5O3-δ crystals
[69].

3.5. Application of SrMn1-xFexO3-δ pigment in heat-absorbing material

In addition to its use as a coloring agent in ceramic glazes, the

Fig. 13. XRD patterns of enameled samples with different additions of
SrMn0.5Fe0.5O3-δ pigment.
pigment SrMn0.5Fe0.5O3-δ can also function as a material for absorbing
heat. Solar electromagnetic radiation consists of ultraviolet radiation (λ
= 200–400 nm), visible light radiation (λ = 400–780 nm) and near-
infrared radiation (λ = 780–2500 nm), which account for 5%, 42%,
and 52% of the total energy, respectively [70]. Therefore, the reflec­
tance properties of the SrMn1-xFexO3-δ black pigment can be evaluated
by examining the reflectance of light waves in the visible-near infrared
region.
Fig. 14(a) illustrates the NIR reflectance spectra of the SrMn1-xFexO3-
δ pigment with various x-values. As the value of x increases, the R* of the
SrMn1-xFexO3-δ pigment gradually decreases. According to the Drude
theory, reflectance is influenced by the concentration of free carrier. A
lower concentration of free carrier leads to lower reflectance. Ion doping
introduces lattice defects that attract free carriers for repair, resulting in
a reduced concentration of free carrier in the crystal [71]. Additionally,
the d-d intramolecular transitions and charge transfer from oxygen to
iron also contribute to the reduction in R* [72]. At an x-value of 0.5, the
R* of the pigment reaches a minimum of less than 10% in the wave­
length range of 0–2500 nm. Beyond 50 mol.% iron ion doping, the R* of
the SrMn1-xFexO3-δ pigment remains nearly constant. Fig. 14(b) presents
the solar irradiance reflection spectra based on the NIR reflectance
spectra. The energy of solar irradiance reaches its maximum around 900
nm and then decreases as the wavelength increases, suggesting a higher
proportion of energy in the shorter NIR range. In the wavelength range

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Fig. 14. (a) NIR reflectance spectra and (b) solar irradiance reflection spectra of SrMn1-xFexO3-δ pigments with different x-values.

reflectance (R*) values with various black pigments, as outlined in

Table 2
Table 2 [28,34–37,74]. The SrMn1-xFexO3-δ pigment exhibits lower L*
Chromatic parameters and NIR reflectance of different black pigments.
and R* values in comparison to other black pigments, indicating its
Pigment L* a* b* R*(%) Ref. broader range of potential applications.
Co0.5Mg0.5Al1.2Fe0.8O4 40.84 − 3.74 6.92 43.0 [28] Heat-absorbing black coatings were formulated with SrMnO3 and
CuCr2O4 21.21 1.96 − 2.65 19.0 [34] SrMn0.5Fe0.5O3-δ pigments, serving as the thermal absorption elements.
Ce0.8Gd0.2VO4 22.2 5.71 2.77 66.3 [35]
These are portrayed in Fig. 15(b) and (c). Concurrently, heat-absorbing
Ca2MnO4 20.9 0.60 3.30 45.9 [36]
CaMnO3 28.3 1.24 1.61 9.92 [74] coatings were developed with MnTiO3 pigment [75] and a commercial
Ca2Mn0.77Ti0.15Zn0.08O3.92 23.2 2.81 0.83 74.6 [37] black pigment from the Co–Cr–Fe system, serving as the control groups,
SrMnO3 26.66 − 0.18 4.00 29.26 This work respectively. In terms of the pigments’ color properties, the coating
SrMn0.9Fe0.1O3-δ 25.11 1.57 2.13 18.02 derived from SrMn0.5Fe0.5O3-δ appears darker compared to that of
SrMn0.7Fe0.3O3-δ 23.05 1.0 1.21 8.69
SrMn0.5Fe0.5O3-δ 19.77 0.15 0.70 5.04
SrMnO3. Moreover, the produced coatings exhibited a smooth and sur­
SrMn0.3Fe0.7O3-δ 23.56 0.30 − 1.97 5.29 face without any observable flaws, implying the ease of fabrication for
SrFeO3-δ 22.28 − 0.14 − 2.46 5.17 SrMn1-xFexO3-δ-based coatings. Experiments to simulate sunlight ab­
sorption were performed on these four coatings. The efficiency of sun­
light performance was evaluated through infrared thermography, which
measures the temperature fluctuations of the coatings [76–78]. It can be
inferred from the temperature alteration curves in Fig. 15(a) that the
SrMn0.5Fe0.5O3-δ coating demonstrates a higher equilibrium tempera­
ture and a more rapid temperature rise rate in comparison to the
SrMnO3, MnTiO3, and Co–Cr–Fe system coatings. After an exposure
duration of 150 s to the xenon lamp, the SrMn0.5Fe0.5O3-δ coating ach­
ieved thermal equilibrium, and the temperature of the coating stabilized
at around 78.9 ◦ C. These results provide evidence that the
SrMn0.5Fe0.5O3-δ coating possesses superior solar energy collection ca­
pabilities [31].

4. Conclusion

To summarize, this study involved the synthesis of SrMn1-xFexO3-δ

(where x ranges from 0 to 1.0) black pigments using the solid-state
method, and a systematic investigation was conducted to understand
the impact calcination temperature and iron ions on the pigments’ color
characteristics. In addition, the potential applications of SrMn1-xFexO3-δ
pigments in ceramic glazes and heat-absorbing coatings were explored.
The principal conclusions derived from this work can be summarized as
follows.
Fig. 15. (a) Temperature curves of coatings fabricated with MnTiO3, SrMnO3,
SrMn0.5Fe0.5O3-δ and commercial pigments under xenon lamp irradiation, 1. The SrMnO3 pigment, when calcined at 1100 ◦ C, exhibits the lowest
photographs of the SrMnO3 coating (b) and SrMn0.5Fe0.5O3-δ coating (c). L*-value, characterized by chromatic parameters of L* = 22.30, a* =
0.98, and b* = − 5.05. However, the larger absolute value of b* im­
of 700–2500 nm, the energy proportion is dominant in the 700–1150 nm parts a slightly blue hue to the pigment, indicating that the SrMnO3
fraction [73]. Similar to Fig. 14(a), the solar reflectance of the pigment is not completely black.
SrMn1-xFexO3-δ pigments decreases gradually as the x-value increases. 2. A black pigment, SrMn0.5Fe0.5O3-δ is achieved when iron ion doping
For x ≥ 0.5, the solar irradiance of the SrMn1-xFexO3-δ pigments drops is at 50 mol.% (i.e., x = 0.5) and the calcination temperature is set to
below 0.05 W m− 2 nm− 1 and remains relatively constant from 700 to 1000 ◦ C. This pigment displays a pure, deep black hue with chro­
2500 nm. Fig. 14(a) and (b) demonstrate that SrMn1-xFexO3-δ pigments matic parameters of L* = 19.77, a* = 0.15, and b* = 0.70. The
with x ≥ 0.5 exhibit excellent sunlight absorption performance. incorporation of iron ions not only decreases the synthetic
To emphasize the merits of the SrMn1-xFexO3-δ pigment investigated
in this study, we conducted a comparison of chromatic parameters and

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temperature of the SrMnO3 pigment but also eradicates the blue hue
inherent to the SrMnO3 pigment.
3. The influence of iron ions on the SrMnO3 pigment operates via two
mechanisms: band gap energy (Eg) reduction and an increase in
oxygen vacancies. The Eg of SrMnO3 is 2.45 eV, while that of
SrMn0.5Fe0.5O3-δ is merely 2.06 eV. This decrease in the forbidden
bandwidth for the SrMnO3 pigment can be attributed to charge
transfer [2p(O2− ) → 3d(Fe3+)] and Fe3+ d-d intramolecular transi­
tions (6A1g → 4T1g and 6A1g → 4T2g).
4. The SrMn0.5Fe0.5O3-δ pigment manifests a pure, deep black hue, the
result of a conjunction of several factors: (1) a high roughness par­
ticle surface arising from the segregation of surface Sr and low
crystallinity; (2) the introduction of iron ions notably decreases the
band gap energy of SrMnO3; (3) a high proportion of low-valence
manganese and iron ions on the particle surface leads to a high
content of oxygen vacancies. High surface roughness can diminish
the reflection of visible light by the pigment, whereas low band gap
energy and a high percentage of oxygen vacancies can augment the
absorption of visible light by the pigment.
5. The tinting mechanism of the SrMn0.5Fe0.5O3-δ pigment in the
ceramic glaze is referred to as "ion tinting", and the coloring effect of
the glaze is determined by the Mn and Fe ion concentrations in the
glass phase. When the pigment added amounts to 36 wt%, the glaze
surface appears dark black, with an L*-value of just 4.94.
6. The SrMn0.5Fe0.5O3-δ pigment demonstrates excellent sunlight ab­
sorption performance, with an R* of only 5.04%, suggesting poten­
tial applications with appealing prospects.
Declaration of competing interest
The authors declare that they have no known competing financial
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), the Key project of Natural Science Foundation of Jiangxi
Province (Grant No. 20212ACB204011), Science Foundation of Jiangxi
Provincial (P. R. China) Department of Education (Nos. GJJ211317), the
Science and Technology Program of Jingdezhen City (20224GY008-09).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ceramint.2023.06.145.
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