Dyes and Pigments 156 (2018) 17–25

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Dyes and Pigments

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Study of applicability in an aqueous paint of the blue pigment T

YIn0.95Mn0.05O3
Myriam Y. Torres Ga, Mayerly K. Bravo La, Saúl A. Flórez Ma, Pardis Simonb, José J. Aguirre Pa,
Mario A. Macías La,c, Gilles H. Gauthiera,∗
a
Universidad Industrial de Santander, INTERFASE Group, Carrera 27, Calle 9, Ciudad Universitaria, Bucaramanga, Colombia
b
Université de Lille, CNRS, Centrale Lille, ENSCL, Université d´Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
c
Universidad de Los Andes, Departamento de Química, Carrera 1 No. 18A-12, 111711, Bogotá, Colombia

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

Keywords: This work evaluates the chemical stability of the composition YIn0.95Mn0.05O3, through exposure of the material
Inorganic pigment to different acidic, basic and neutral media and the incorporation into an aqueous base of white paint. A high
Chemical stability structural stability is evidenced for the different used media except for the acidic solvents, which causes a strong
Aqueous medium degradation of the optical properties of the material. The latter is due to the presence of a MnO2-type phase,
YInO3
possibly amorphous and/or in a low concentration, evidenced at the microscopic level and associated with an
Manganese
Chromaticity coordinates
oxidation of Mn3+ cation at the surface of the material. Nevertheless, the integration of the pigment into a water-
based paint presents suitable properties to the chemical attack of alkali and acid solvents, favouring the future
application of the material in the industrial sector of paints and coatings.

1. Introduction
Nowadays, the search for new, environmentally friendly, econom-
ically viable inorganic blue pigments with excellent physicochemical
characteristics has become a permanent challenge for the pigment in-
dustry. Excepting the vanadium-zirconium turquoise blue and ultra-
marine pigment (Na7Al6Si6O24S3), most inorganic pigments with a blue
hue are based on the incorporation of the cobalt chromophore into
different crystal structures such as cobalt aluminate (CoAl2O4), cobalt
orthosilicate (Co2SiO4), cobalt stannate (Co2SnO4), cobalt chromite
(CoCr2O4) and zinc silicate doped with Co(II) cations [(Co,Zr)2SiO4]
[1,2]. Although the existence of different pigmentary systems is evi-
dent, cobalt is currently considered a metal with a high degree of
toxicity, causing international environmental organisms to limit the
manufacture and use of this type of materials in the pigment market.
During 2010, an important discovery aroused the curiosity of aca-
demics and trade associations. Subramanian et al. obtained a material
with an intense blue colour when calcining at a temperature of 1300 °C
a mixture of Y2O3, In2O3 and Mn2O3 in different stoichiometric
amounts. Such shade was attributed to the introduction of Mn3+ ions
into the trigonal bipyramidal sites [InO5] of the hexagonal structure
YInO3 [3]. Several chemical methods of synthesis around this material
have recently been proposed, including solid-state, sol-gel and pyrolysis
of aerosols generated from solutions of Y, In and Mn nitrates [4,5]. A
clear variety in relation to its synthesis processes and the use of non-
toxic chemical species lead to classify this material as an interesting
alternative for the replacement of inorganic pigments based on cobalt.
Currently, there are very few studies reported on the chemical and
thermal stability of this material, as well as its performance in different
industrial applications. In particular, Ocaña et al.’s work evaluated the
performance of the YIn1-xMnxO3 pigments in the ceramic industry, by
the colouration of ceramic enamels [6]. They claim that the colour of
the ceramic is strongly influenced by the enamel annealing process and
the processing temperature, causing a possible reactivity between the
pigment and the enamel constituents above 800 °C. In 2016, Sheethu
et al. studied the solar reflectance index of coatings of YIn0.9Mn0.1O3-
ZnO in the form of paint on aluminium frames, obtaining favourable
results for their use as cool pigment in roofing materials in construc-
tions [5]. Likewise, in relation to the evaluation of the chemical sta-
bility of this new blue pigment, it is important to immerse the powder
in different aqueous solutions with different pH in short times, resulting
in insignificant changes in colour and weight of the material.
Considering the results of the previous researches and the need to
delve into the chemistry of this particular pigment for an application in
aqueous paints, this work presents a study of chemical stability in
aqueous medium of the YIn0.95Mn0.05O3 composition using prolonged
experimental times, in addition to the integration in an aqueous (white)
base of industrial painting and its interaction with some relatively

∗
Corresponding author.
E-mail address: gilgau@uis.edu.co (G.H. Gauthier).

https://doi.org/10.1016/j.dyepig.2018.03.073
Received 6 January 2018; Received in revised form 7 February 2018; Accepted 29 March 2018
Available online 30 March 2018
0143-7208/ © 2018 Elsevier Ltd. All rights reserved.
M.Y. Torres G et al. Dyes and Pigments 156 (2018) 17–25

aggressive media. Table 1

Aqueous solutions conditions for stability tests.
2. Experimental procedure Aqueous solution Concentration pH

Deionised water – 7
2.1. Synthesis of the material
Hydrochloric acid (HCl) 2.5% w/w <1
Nitric acid (HNO3) 2.5% w/w <1
The solid solution YIn0.95Mn0.05O3 was synthesized by the poly- Sodium Hydroxide (NaOH) 2.5% w/w > 13
meric sol-gel method (citrate-nitrate). Stoichiometric amounts of Y2O3
(Alfa Aesar, 99.99%), In2O3 (Alfa Aesar, 99.99%) and MnCO3 (Sigma-
Aldrich, 99.9%) were dissolved in a mixture of deionised water and measured samples.
citric acid (Merck KGaA, 99.5%) in a molar ratio of H3Cit:cation = 3:1. Δa∗ = Difference of red/green coefficient between the reference and
Subsequently, nitric acid (Merck KGaA, 65%) was added in a molar the measured samples.
ratio of HNO3:Y2O3 = 6:1. The mixture was added to a Florence Flask Δb∗ = Difference of yellow/blue coefficient between the reference
connected to a reflux system, which was maintained at 150 °C and and the measured samples.
constant stirring at 200 rpm. After obtaining a homogeneous, translu-
cent solution, ethylene glycol (Panreac, 99%) was added in a molar 2.3. Chemical stability tests
ratio of H3Cit:EG = 3:2 while maintaining heating and stirring until gel
formation. This gel was then placed in a furnace with a vapour ex- The chemical stability of the pigment was evaluated by exposing the
traction system where two heat treatments were carried out, one at material to different acidic, basic and neutral aqueous solutions
300 °C for 2 h and the other at 500 °C for 3 h. Finally, dark brown (Table 1) during pre-established times. Stability tests were performed
powders were obtained and used to make pressed pellets at about 5000 using two methods:
psi, which were thermally treated on a plate of alumina with sacrificial
powder at 1000 °C, 1100 °C and 1200 °C for 12 h each, with a heating • Direct contact by immersion of powder: a pre-weighed amount of
ramp of 300 °C h−1, with intermediate grinding. the pigment in powder form was immersed in the solvents for
30 min, 1, 4 and 24 h with constant stirring and at room tempera-
ture. The samples were filtered on quantitative ashless filter paper
2.2. Structural and optical characterization of materials
(Boeco® grade 391, blue spot label), washed three times with deio-
nised water (in order to stop any reactions that might have oc-
The X-Ray Diffraction (XRD) technique was used to identify the
curred) and heat-treated in an oven at 575 °C for 5 h for complete
phases present in the material using a D8-AVANCE diffractometer
filter ignition. Finally, the resulting powders were weighed to de-
(BRUKER) operating in Bragg Brentano geometry, with Cu-Kα1,2
termine if any difference was found in relation to the initial weight.
(λ = 1,5406 Å, voltage = 40 KV, current = 40 mA) and linear detector
No difference was observed by XRD with a sample simply dried at
LinxEye. The data were obtained in a measuring range of 5–70° (2θ)
100 °C after filtration.
with a measuring step of 0.015° (2θ) and integration time of 2 s per
step. The structure of the material was refined by the LeBail method • Stability in the form of paint: Starting from a commercial aqueous
paint base with a TiO2 content ranging from 12 to 15 %w/w, the
using the DRX data, through the program Fullprof and its graphic in-
pigment was added in a percentage of 30 %w/w by means of an
terface WinPLOTR [7].
Ultra Turrax® stirrer at 3600 rpm for 10 min, obtaining a light blue
Diffuse reflectance spectra for all powder pigment samples were
fluid product. Subsequently, superboard graduated cylinders
recorded using a Shimadzu UV-2400 PC SERIES UV–Visible
(homogeneous cement mix, organic reinforcements and natural
Spectrophotometer equipped with an integrating sphere in a spectral
aggregates) were painted twice with the undiluted product, allowing
region of 200–900 nm with a mean scanning speed, and a sampling
to dry for 1 h under normal conditions, with a curing time of 5 days
interval of 1 nm. Each series of data were measured on a loose bed of
[10], giving a result as shown in Fig. 1. The surfaces were then
powder placed in a circular cavity with 4 cm diam. and 0.5 cm thick-
weighed and immersed in the media indicated above during periods
ness. A BaSO4 standard was used as a reference. The reflection data (R)
of 1, 4 and 24 h. Finally, they were washed with deionised water and
were converted into absorption data by applying the Kubelka-Munk
transformation [8], which allowed the determination of the di-
mensionless ratio K/S, where K is the absorption coefficient and S is the
diffusion coefficient of the material.

K (1 − R)2
=
S 2R (1)

The colour parameters of the material before and after the stability
tests were calculated using the Optrop computer tool of the MATLAB
software using the Roo2lab function, based on the standard light re-
flection data. A CIE standard illuminant D50 and a standard observer 2°
were used.
The colourimetry parameters were evaluated according to the
Commission Internationale de l'Éclairage (CIE) using the coordinates
L*a*b* [9]. In this system, L* is the colour clarity (L* = 0 for black and
L* = 100 for white), a* is the green (−)/red (+) axis and b* is the blue
∗
(−)/yellow (+) axis. The parameter ΔEab represents the difference of
the total colour in relation to the reference sample and is defined as:
∗
ΔEab = (ΔL∗)2 + (Δa∗)2 + (Δb∗)2 (2)

Where: Fig. 1. Photography of painted sample at 30% w/w of pigment content

ΔL∗ = Difference of colour clarity between the reference and the YIn0.95Mn0.05O3.

18
M.Y. Torres G et al.
taken to an oven at 40 °C for 1 h.
Before and after the chemical treatments, X-ray diffraction and
diffuse reflectance characterization were performed, as well as the de-
termination of the colour coefficients L*a*b* and the total colour dif-
ference (ΔE*ab) of the powder and of the painted surfaces with respect
to untreated material.
The XPS experiments were carried out with the XPS/ISS/UPS-
Acenteno surface characterization platform built by SPECS (Germany).
The platform is provided with a PHOIBOS 150, a 2D-DLD energy ana-
lyzer detector, and a FOCUS 500 X-ray source. For measurements,
monochromatic Al Kα radiation operated at 100 W was employed.
The pass energy of the hemispheric analyzer was set at 100 eV for
the survey spectra and at 60 eV for core level spectra. The surface
charge compensation was controlled by using a Flood Gun (device FG
15/40-PS FG500) operated at 58 μA to 2 eV. Particles of the oxide
precursors of the catalysts were mounted on a carbon conducting grid
on stainless steel metallic holders provided by the manufacturer.
Sample holders were electrically connected to the photospectrometer.
Spectra were analyzed using the CasaXPS program (Casa Software
Ltd.) [11]. For the decomposition of the spectra, Gaussian–Lorentzian
curves with a 30% Lorentzian contribution was used for each compo-
nent. The surface composition was determined from the area of C1s,
O1s, In3d, Y3d and Mn2p photopeaks after a Shirley background sub-
traction. Spectra were charge corrected to give the adventitious carbon
C 1s spectral component C-(C,H) a binding energy of 284.8 eV.
3. Results and discussion
3.1. Synthesis and structural characterization
The X-ray diffraction pattern of YIn0.95Mn0.05O3 as well as the result
of the structural refinement using the Rietveld/LeBail method is re-
presented in Fig. 2 and confirms the formation of a single hexagonal
phase with space group P63cm in the synthesis conditions described
above. The calculated cell parameter values for this composition
(a = 6.2675(2) Å, c = 12.2149(6) Å and V = 415.54(3) Å3) are similar
to those reported by Subramanian et al. (a = 6.2731 Å, c = 12.234 Å
and V = 416.928 Å3) [12], although a slight deviation is observed,
which is possibly due to small impurities in the detection limit of the
XRD technique.
3.2. Optical characterization of the reference material
Fig. 3 shows the absorption spectrum obtained from the Diffuse
Reflectance data of the composition YIn0.95Mn0.05O3 (powder) com-
pared to the material undoped with the chromophore ion Mn3+, YInO3.
An absorption band centred in 2 eV which absorbs in the region of the
red to green of the visible spectrum is clearly observed. The absence of
Fig. 2. Graphical result of LeBail analysis in P63cm symmetry of synthetized
YIn0.95Mn0.05O3 using XRD data.
19
Dyes and Pigments 156 (2018) 17–25
Fig. 3. Diffuse reflectance spectra for the YIn0.95Mn0.05O3 and YInO3.
absorption presented in the 2.5 eV and 3 eV range (blue region) results
in the characteristic colour of the material. Studies by Smith et al.
showed that the occurrence of the absorption band centred at 2 eV is
due to the transition between the higher energy occupied electronic
levels, which consists of states Mn-3dx2-y2, 3dxy hybridised with the O-
2px states, and the lowest unoccupied energy level, which at low doping
ratios corresponds to an acute band formed from the Mn-dz2 state found
in the energy gap of the YInO3 matrix [3].
3.3. Stability of the material by direct contact
Fig. 4 shows the absorption spectra of powders treated at different
times of experimentation and for all media tested. Notably, an ab-
sorption band around 2 eV similar to that obtained for the reference
sample is identified, as the absence of absorption in the 2.5–3 eV region
is responsible for the blue colour. In the case of the two acid media,
however, a greater difference in band intensities is observed compared
to alkali and water-treated powders and to the initial material curve
(without chemical treatment) for a submersion time equal to 24 h,
causing immersed samples to show a variation in their colorimetric
properties. This is evidenced by the change of tonality of the samples,
reflected in the coordinates L*a*b*, as shown in Table S1. For the
samples exposed to treatments with acid solvents, a considerable
change of the colour parameters was observed, compared to the values
of the initial sample and the treatments with H2O and NaOH. As it can
be seen in Fig. 5, for the case of HNO3, the luminance coefficient L*
decreases as the immersion time increases, as well as the chromatic
coordinate a*, which tends to reduce its value in the -a* direction,
causing a shift towards the green axis. On the other hand, the value of
b* increases in the b* direction, causing a change in the initial blue
tonality.
Fig. 6 describes the behaviour of the chromatic coordinates for the
material immersed in HCl, where most of the a* values present a de-
crease towards the -a* axis, causing a transition from red to green in the
space colour diagram. Although it is not visually perceptible, such
change is reflected in the variation of the saturation of the material,
turning into a paler colour than the original as the immersion time
increases. For the b* coordinate, a decrease of the absolute value ac-
cording to the -b* axis is observed, meaning a less blue colour, whereas
for L*, the luminosity, a significant reduction in values is observed,
starting from 44.83 (3) and ending at 33.06 (3) (in the case of 24 h),
causing the colour becomes darker.
Usually, the value ΔE*ab is very useful in many industrial processes
in which the problem is to guarantee the uniformity of the colour, but
not its reproducibility. To do this, a tolerance range that allows a
sample to be considered acceptable or unacceptable is usually selected.
For this case under study, the acceptability criteria (Table 2) is based in
that very same criteria which is generally used in industry and reported
M.Y. Torres G et al. Dyes and Pigments 156 (2018) 17–25

Fig. 4. Diffuse reflectance spectra of YIn0.95Mn0.05O3 pigments (powder) after chemical resistance tests with (a) H2O (b) NaOH (c) HNO3 y (d) HCl.

in the literature [13].
The variation of the magnitude ΔE*ab as a function of the immersion
time and according to the different chemical treatments applied to the
study material is shown in Fig. 7. Except for samples immersed in acid
solvents, the tests in H2O or in alkali media are within the limit of
acceptability, which proves the chemical stability of the pigment
against this type of solvents. The opposite is observed for HNO3 and HCl
acids for which, regardless of the exposure time, the critical colour
degradation of the material is notorious, even in short experiment
times, confirming the instability of the material in such environment.
In addition to the degradation of the material's hue, the mass var-
iation of each sample was evident during the stability tests. Fig. 8 shows

Fig. 5. Evolution of the colour coordinates as a function of the exposure time after chemical resistance test with HNO3.

20
M.Y. Torres G et al. Dyes and Pigments 156 (2018) 17–25

Fig. 6. Evolution of the colour coordinates as a function of the exposure time after chemical resistance test with HCl.

Table 2
The industrially acceptable limits of ΔE*ab.
Grade Difference Level

ΔE*ab < 1 Imperceptible

ΔE*ab < 2 Minimal
ΔE*ab < 3 Acceptable
ΔE*ab < 5 Almost Acceptable
ΔE*ab≥5 Unacceptable

Fig. 8. Evolution of the mass as function of exposure time for the samples
YIn0.95Mn0.05O3 after chemical resistance tests by direct contact. The lines are
only a guide to the eye.

3.3.1. Presence of a second phase

Fig. 7. Variation ΔE*ab as a function of exposure time for the samples
YIn0.95Mn0.05O3 after chemical resistance tests by direct contact. The lines are
only a guide to the eye.
the evolution of the samples' mass as a function of the experimentation
time for each treatment. In the case of H2O and NaOH, the mass loss is
low, ranging from 3% to 10%, due to the different manipulations during
the tests. In contrast, for acidic solvents, there is a noticeable variation
that increases with the immersion time, reaching up to 95% dissolution
of the material in the medium, which shows that the materials have
suffered a chemical attack.
Based on the latter result, two possible origins for the change of
YIn0.95Mn0.05O3 hue in acid medium can be proposed: i) the presence of
a secondary phase and/or ii) the change of oxidation state or co-
ordination of elements at the surface of the material. To validate or
discard each of both hypotheses, different characterization techniques
were used: X-ray diffraction (XRD), Scanning Electron Microscopy
(SEM) and finally X-ray Photoelectron Spectroscopy (XPS).
A first structural characterization using X-Ray Diffraction was per-
formed on the material after chemical treatment. The diffraction pat-
terns are shown in Figure S1. Regardless of the immersion time and the
nature of the solvents, the material remains stable at the structural
level, retaining the same hexagonal phase with the P63cm space group
as the initial sample. It calls into question the possible formation of
other crystalline species, which would be responsible for the colour
change (and in particular in the case of exposure to acids). Using the
SEM technique, it was possible to obtain high resolution images of the
materials' surface in order to definitely verify the first hypothesis. The
morphology of the material surface before and after the stability tests is
shown in Figure S2. For both the pigment in its initial state and the
samples treated with NaOH, HNO3 and HCl in a time of 24 h, the pre-
sence of grains of different sizes with irregular shapes, uniformly dis-
persed on most of the surface, was identified. At higher magnification,
for the material exposed to acid solvents (especially to HCl), we can
observe white areas and certain light grey or opaque areas, which are
marked with red and yellow, respectively, and which are no present in
the base material (Fig. 9). These regions were identified at the edges of
the grains and evidence the attacked surface of the grains. The identi-
fication of these zones is probably linked to (i) the formation of another
amorphous and/or low-proportion manganese oxide-type secondary
phase, not observed by XRD, corresponding to opaque areas, and (ii)

21
M.Y. Torres G et al. Dyes and Pigments 156 (2018) 17–25

Fig. 9. SEM micrographs of YIn0.95Mn0.05O3 powder pigments after chemical resistance tests by direct contact with (b) NaOH (c) HNO3 y (d) HCl. In (a) the material
without treatment.

the effect of intergranular corrosion of material due to the H+ ions in Another possibility could be a variation of the oxidation states of
the acid solution of HCl, the first being a possible cause of the de- Mn3+ cations on the surface of the material, but they would require the
gradation of the colour. use of more advanced techniques such as X-ray photoelectron spectro-
scopy (XPS) in order to be confirmed.
XPS survey spectra in the 1200-0 eV energy range (Figure S3) pre-
3.3.2. Change of oxidation state or coordination of elements on the surface
sent a series of photopeaks which binding energy allow to identify the
of the material
constituent elements at the surface of the material, Y, In, Mn O and C, as
The pH changes affect the redox equilibrium of certain transition
expected.
elements and hence the optical properties thereof according to the
The surface relative atomic concentrations were determined from
crystalline field theory (where the transition metal complexes present
the XPS spectra and are shown in Tables 3 and 4. We can note that a
different transitions according to the nature of the metal, the metal
significant increase of the Mn relative concentration is observed at the
oxidation state and/or the geometric arrangement of the ligands). In
surface of the sample after chemical treatment.
this sense, immersion of the pigment in acidic solvents may have pro-
The In3d spectra for both samples (with or without chemical
moted a change of oxidation state (initially Mn3+), resulting in new
treatment) exhibit a doublet peak corresponding to In3d5/2 and In3d3/2
electronic transitions corresponding to Mn2+ or Mn4+ in the visible
orbitals (Figure S4). The peak attributed to In3d5/2 is symmetric and
spectrum compared to the reference sample. It is worth noting that such
localized at 444.6 eV which indicates that indium is in the 3 + oxida-
hypothesis of the change of oxidation number could occur in the vo-
tion state.
lume of the material or only in its surface.
The Y3d spectra for both samples are decomposed into two doublets
At the experimental level, a slight displacement of the diffraction
peak. Both doublet is attributed to Y3d5/2 and Y3d3/2 orbitals and
peaks of the exposed material to acidic solvents can be associated to a
possible change in the cell volume, generally caused by defects or
structural modifications created in the crystal structure, in particular, Table 3
by redox modifications from Mn3+ to Mn2+ or Mn4+. As a con- Elemental quantification of powder pigment YIn0.95Mn0.05O3
sequence, the possible change in unit cell volume was examined by before chemical resistance test.
refinement of the cell parameters (Table S2) for materials which ex-
Sample without chemical treatment
hibited a greater degradation of the hue, i.e. the samples exposed to
acidic solvents for immersion during 1, 4 and 24 h (difference ΔE*ab Name Approximate at.% (all elements)
above the allowed threshold). As observed in Table S2, similar values of C 40.4
cell parameters were obtained for both samples treated with HNO3 and O 35.3
In 10.0
HCl compared to the reference sample, concluding that there was no
Y 14.0
drastic change in the oxidation state of manganese in the bulk of the Mn 0.2
material.

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M.Y. Torres G et al. Dyes and Pigments 156 (2018) 17–25

Table 4 3.4. Stability in the form of paint

Elemental quantification of powder pigment YIn0.95Mn0.05O3 after
chemical resistance test by direct contact with HCl for 24 h. Stability tests of the pigment diluted in a base paint were carried
Sample chemical treatment by direct contact out, taking into account that the different additional components con-
tained in the paint (resins, wetting agents, dispersants, etc.) can provide
Name Approximate at.% (all elements)a protection to the material and suffer low colour damages when in
C 35.8
contact with acidic substances. Fig. 11 shows the absorption spectra for
O 40.5
In 8.3 the painted samples as a function of time for each treatment.
Y 9.0 A band of intense absorption around 2 eV can be seen, which is
Mn 6.4 related to the absorption of yellow-red visible spectrum responsible for
a
the perception of complementary blue colour characteristic of surfaces.
The atomic composition was determined taking into account all
This behaviour is similar for all surfaces exposed to different media and
elements, including "adventitious carbon" or carbon of contamina-
strongly agrees with the shape of the pigment powder spectrum (Fig. 4).
tion as well as the oxygen bound to it.
Unlike the tests by direct contact of the powdered pigment with the
acids, the difference of intensity of absorption with relation to the base
present a spin orbit splitting of 2.05 eV (Figure S5). The first doublet
sample is very small, which suggests that the pigment, when in-
which present a Y3d5/2 line with binding energy of 156.5 eV is attrib-
corporated in a matrix has more tolerant properties to chemical attack.
uted to the presence of yttrium oxide in its 3 + oxidation state. The
Table 5 shows the evolution of the colour coordinates of the plates
second doublet which present a Y3d5/2 line with binding energy of
in the different immersion media. In the case of treatment with H2O and
158.3 eV is attributed to the presence of yttrium carbonates. The for-
NaOH, it can be seen that the coordinates L* and a* slightly decrease
mation of yttrium carbonates is quite common for such basic oxides that
over time whereas the value of b* remains approximately constant,
is in contact at room temperature with the atmosphere.
reflecting a similar appearance in the colour of the samples before and
Fig. 10 shows the Mn2p and In3p3/2 XPS spectra for YIn0.95Mn0.05O3
after chemical treatment. As with the direct contact test, a colour dif-
before and after the chemical attack with HCl for 24 h, i.e. the sample
ference ΔE*ab was established. As it can be seen, in the case of H2O and
which presented more hue degradation. In the case of the Mn2p core
NaOH treatments, changes in the colour coordinates do not appear to be
level spectrum, a doublet peak with binding energies of ≈640
significant, which is evidenced by the very small values of ΔE*ab being
and ≈ 654 eV is attributed to Mn2p3/2 and Mn2p1/2 lines respectively,
within the limits of acceptability. On the other hand, under treatments
in a relative intensity ratio of 2:1. Mn2p spectra were decomposed
with acid solvents, the luminance parameter L* tends to increase no-
based on Biesinger et al. work in order to identify the oxidation states
tably whereas the parameters a* and b* decreases and increase, re-
with their respective atomic concentrations present on the surface of
spectively, as the immersion time is higher (a similar behaviour to that
the material [14].
obtained in the direct contact test). In terms of colour, it corresponds to
For the chemically treated sample, the presence of manganese in
a displacement towards the green axis and a distance of the blue axis in
two different oxidation states is evidenced: Mn3+, with a main con-
the chromatic diagram. The variations of the L*a*b* coefficients for
tribution localized at 641.2 eV, and Mn4+, whit a main peak localized
acid media are again more noticeable in relation to water and basic
at 642.0 eV. This result is consistent with the spectra reported in surface
media, and although the ΔE*ab value does not exceed the permitted
studies of lanthanum manganites, where the presence of mixed states
threshold, an extrapolation of the tendency to longer times would ex-
Mn2+//Mn3+ and Mn3+/Mn4+ is indicated [15,16]. After decom-
ceed such limit in the case of HCl test (see Fig. 12).
position, the amount of Mn4+ species is found equal to around 66%.
Taking into account the previous quantification and SEM results, it
is inferred that some Mn3+ cations showed surface oxidation after the 4. Conclusion
acid treatment, leading to the formation of an additional amorphous or
of low crystallinity MnO2 phase and in low proportion. The presence of Blue inorganic pigments of composition YIn0.95Mn0.05O3 were ob-
this phase explains the darkening of the material, since usually MnO2 tained by the polymeric citrate/nitrate method with a high degree of
oxide exhibits a dark colour, which would explain the degradation of purity. A study of chemical stability by immersion of powders in dif-
the blue colour of the material YIn0.95Mn0.05O3 in acid media. ferent aqueous media showed that this type of ceramic material has a
stable behaviour against the different media except for acid solvents,
which caused a strong degradation of the colour of the pigment.

Fig. 10. XPS spectra of the Mn2p and In3p3/2 core level for YIn0.95Mn0.05O3 (a) without treatment and (b) after chemical resistance tests by contact direct with HCl
for 24 h.

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M.Y. Torres G et al. Dyes and Pigments 156 (2018) 17–25

Fig. 11. Diffuse reflectance spectra for painted surfaces after chemical resistance tests with (a) H2O (b) NaOH (c) HNO3 y (d) HCl.

Table 5 the Mn3+ ion (which is responsible for the origin of the blue colour) on
The colour coordinates for painted samples after chemical resistance tests. the surface of the material. The formation of this phase comes from the
Aqueous solution Exposure time (h) L* a* b* ΔE*ab
dissolution of a large part of the material demonstrated by the loss of
mass in acid medium. The application of such blue pigment has been
- 0 64.33(1) −0.40(3) −31.71(2) – evaluated by incorporating it into an aqueous-based industrial paint,
H₂O 1 64.29(2) −0.76(7) −31.37(3) 0.5 resulting in properties that are tolerant to chemical attack of alkaline
4 63.42(2) −0.95(5) −30.51(7) 1.6
24 64.04(2) −0.5(1) −31.9(1) 0.38
agents and strong acids but for short times of exposition, allowing them
NaOH 1 63.93(2) −0.65(5) −31.87(3) 0.5 to become an attractive alternative that can relegate the use of cobalt-
4 63.25(2) −0.74(3) −31.48(9) 1.16 based toxic pigments that are commonly used in this field.
24 64.77(8) −0.45(7) −31.2(1) 0.69
HNO₃ 1 63.55(1) −0.56(4) −31.72(3) 0.79
Acknowledgements
4 63.44(2) −1.01(4) −30.82(2) 1.4
24 64.30(2) −1.01(4) −30.10(3) 1.61
HCl 1 63.47(2) −0.55(8) −31.7(1) 0.88 This work was developed with the financial support (i) of the Banco
4 64.05(1) −0.85(6) −30.4(1) 1.42 de la República (national bank) through the Fundación para la
24 65.14(4) −1.09(4) −29.78(6) 2.2
Promoción de la Investigación y la Tecnología, (FPIT) (Foundation for
the Promotion of Research and Technology), which approved the ex-
ecution of the project entitled "Preparation and testing of chemical
Possibly, this change of material hue is due to the formation of an
stability of new non-toxic inorganic pigments "(# 3639) and (ii) the
amorphous MnO2 phase and/or in low concentration to be detected by
Vicerrectoría de Investigación y Extensión de la Universidad Industrial
XRD, evidenced at microscopic level and associated to the oxidation of
de Santander (University's Vice-rectory of Research and Extension)

24
M.Y. Torres G et al.
Fig. 12. Variation ΔE*ab as a function of exposure time for painted samples
after chemical resistance tests.
within the framework of the internal project # 5465 entitled" Synthesis
and characterization of new materials belonging to the systems YIn1-
xAxO3 (A = V, Cr, Mn, Fe, Co, Ni and Cu) and (Y1-xScx) (Mn0.1In0.9-yA´y)
O3 (A' = Ga, Al) with potential application as inorganic pigments or
luminophores.
The authors would also like to thank to the X-ray diffraction la-
boratory and Microscopy (UIS) for the services they provided, as well as
to the Instrumental Laboratory of Chemical Analysis, the School of
Chemistry (UIS) and in particular the Professors Enrique Mejía Ospino
and Jader Enrique Guerrero for their collaboration in optical mea-
surement equipment and guidance in the treatment of optical data. UIS'
Central Laboratory of Surface Science (SurfLab-UIS) is also acknowl-
edged for supporting this work carrying out the XPS measurements.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://dx.
25
Dyes and Pigments 156 (2018) 17–25
doi.org/10.1016/j.dyepig.2018.03.073.
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