Journal of Alloys and Compounds 970 (2024) 172503

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Journal of Alloys and Compounds

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

Enhancing colorant pigment properties of natural clinoptilolite zeolite

through thermal treatment: Comprehensive structural, optical, and
colorimetric analysis
Salar K. Fatah a, b, Mohsen Khajeh Aminian a, *, Milad Bahamirian c
a
Nano Pigments and Coatings Laboratory, Department of Physics, Yazd University, 89195–741 Yazd, Iran
b
Department of Physics, College of Education, University of Garmian, Kurdistan Region, Iraq
c
Department of Mining and Metallurgical Engineering, Yazd University, 89195–741 Yazd, Iran

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

Keywords: This study investigates the transformation of metastable zeolites, specifically clinoptilolite zeolite (CLNP), into
Clinoptilolite zeolite amorphous precursors for customized ceramics via ion-exchange and precipitation methods with Co and Zn ions,
Colorant pigment followed by thermal treatment in the temperature range of 700 ℃ to 1200 ℃. Analytical techniques including
Zeolite Modification
TGA/DTA, XRD, FE-SEM, UV-Vis, and Colorimetric analysis reveal that collapse into an amorphous CLNP phase
Thermal processing
Mineral colorants
occurs at 750–800 ℃, with subsequent thermal treatments reducing the CLNP phase’s weight fraction. Notably,
Co-willemite (Zn2− xCoxSiO4) recrystallization occurs at 800–900 ℃ without impurities. Morphological changes,
agglomeration, increased particle distribution, and crystallite size growth correlate with rising temperatures.
Different pigments emerge, such as brown (700 ℃), green (800 ℃), and blue (900 ℃), with stable Co-willemite
persisting post-treatment, yielding high-quality blue pigments. This research highlights the potential for tailored
ceramics via zeolite manipulation, offering stable and diverse pigment possibilities in the field.

1. Introduction the direct production of colored ceramics or powders that exhibit

Zeolites and other micro-porous materials have gained significant
attention for their intriguing metastable nature, which renders them
susceptible to collapse at elevated temperatures, leading to the forma­
tion of amorphous materials. These amorphous phases can serve as
precursors for the creation of new, denser phases through subsequent
heat treatment, presenting substantial potential for the development of
novel ceramics with tailored properties [1]. Among the fascinating ap­
plications of zeolites is their utilization, either in their original cation
form or after suitable pre-exchange [2,3], as precursors for ceramic
production [4–7]. The firing of zeolitic powders induces the breakdown
of the zeolite structure, resulting in the conversion into either amor­
phous or crystalline ceramic materials, depending on their chemical
composition. This non-traditional ceramic manufacturing process offers
numerous advantages over conventional methods, as extensively dis­
cussed in the literature [4,8,9].
A particularly interesting aspect of zeolites arises when transition
metal cations are introduced into their structure, imparting a distinctive
coloration that can be preserved even after heat treatment. This enables
ceramic pigment-like behavior [10]. The homogeneous distribution of
the extra-framework cations within the zeolite structure ensures a uni­
form distribution of coloring centers, leading to a more consistent and
stable coloration of the ceramic product after thermal treatment [4].
Of the various colorant pigments that have played a crucial role in
human civilization throughout history [11,12], one of the most
intriguing is the blue pigment achieved by doping zinc silicate with
cobalt, known as (Co, Zn)2SiO4 or willemite (Zn2SiO4) [13]. Willemite
possesses an orthosilicate structure with phenacite symmetry, where
zinc and silicon ions occupy three different fourfold crystallographic
sites of the tetrahedral framework [14]. The lattice parameters of
willemite result in rhombohedral symmetry. The substitution of cobalt
ions for zinc ions in the willemite structure is responsible for its more
intense blue coloration, similar to that observed in cobalt aluminates
[15].
Prior research has explored the co-adsorption of transition metal
cations within microporous and mesoporous structures [16,17]. Note­
worthy work by P.E. Riley and K. Seff investigated the Co (II) exchange
in fully hydrated zeolite A, and they reported the specific Co (II)

* Corresponding author.
E-mail address: kh.aminian@yazd.ac.ir (M. Khajeh Aminian).

https://doi.org/10.1016/j.jallcom.2023.172503
Received 13 August 2023; Received in revised form 20 September 2023; Accepted 10 October 2023
Available online 13 October 2023
0925-8388/© 2023 Elsevier B.V. All rights reserved.
S.K. Fatah et al.
locations in the crystal structure using 3-dimensional X-ray diffraction
data [18]. Another research group focused on utilizing Na-A [LTA]
zeolite to synthesize cobalt-based inorganic pigments, emphasizing the
potential to control the zeolite precursor’s composition at the micro­
scopic level through ion-exchange mechanisms. By varying the tem­
perature and/or cobalt concentrations in the solution, they successfully
achieved a diverse range of chromatic effects [4]. Furthermore, W.
Mozgawa employed the FTIR characterization technique to study zeo­
lites incorporating heavy metal cations, observing changes in the zeolite
structure after cobalt incorporation [19]. In the context of clinoptilolite
zeolite, Wenbo Wang et al. explored changes in surface area, pore vol­
ume distribution, and cation exchange to remove ammonia nitrogen
from water [17]. Another research group focused on preparing alumi­
nate ceramics using zeolite X as a precursor, successfully obtaining
transparent aluminate microcrystals through heat-induced collapse with
ion exchange [20]. Colyer et al. investigated the presentation of tran­
sition metal ions in aluminosilicate structures formed from collapsed
zeolites, while F. Davar et al. conducted a similar study using zeolite Y
[1,21]. Moreover, investigations have revealed that Co ion-exchanged
zeolites undergo several transformations, including dehydration,
amorphization, and eventual formation of a spinel crystal structure [22].
Additionally, authors have utilized natural chabazite and stilbite zeo­
lites, characterized by low silicon content, to produce blue
sodalite-structured products. The color of the samples could be further
modified by employing different polysulfides and adjusting the calci­
nation process [23].
Despite the abundance of research on zeolites, there remains a sig­
nificant knowledge gap regarding the structural, optical, and chromatic
properties of Co and Zn-ion exchanged natural CLNP zeolite. Compre­
hensive studies on the thermal treatment process, starting from raw
materials to ion exchange and subsequent calcination at different tem­
peratures and stages, are scarce in the literature. Hence, this study aims
to fill this critical gap by thoroughly examining each step of the thermal
treatment process, with a particular focus on the structural and chro­
matic changes induced by the incorporation of Co and Zn ions in the
CLNP zeolite structure. By investigating the morphological and optical
properties of the pigments at each thermal treatment stage, this research
endeavors to provide valuable insights into the fascinating interplay
between Co and Zn-doped natural CLNP zeolite and the resulting blue
pigmentation. The study will contribute significantly to the under­
standing of the chromatic properties and color alterations observed at
different stages of the process, offering novel perspectives on the utili­
zation of zeolites as potential ceramic colorants.
2. Experimental details
2.1. Materials
In this study, the primary material employed was a natural cli­
noptilolite zeolite (CLNP) obtained from Semnan Zeolite Corporation in
Iran. The zeolite had the chemical formula (Ca3.16Si33.60Al2.40O93.80)
and was used in its raw form without undergoing any purification pro­
cesses. A total of 2 g of this zeolite was utilized for the experiments.
Additionally, we utilized the following chemicals: Zinc oxide (ZnO) [24]
with a purity of 98.5%, obtained from Shahin Rouy Sepahan Co. in Iran.
A quantity of 1 g of ZnO was used. A 1-gram quantity of Cobalt chloride
hexahydrate (CoCl2⋅6 H2O) was utilized. The source of it was Darmstadt,
Germany, and it was identified by the Cas-No: 7791–13–1. The experi­
mental medium consisted of 50 mL of water.
2.2. Preparation of the pigments
The pigment preparation in this study followed a method similar to
that described in previously published papers [13,25]. The procedure
involved an ion-exchange and precipitation route to synthesize the
desired materials. The preparation process can be outlined in the
2
Journal of Alloys and Compounds 970 (2024) 172503
following steps:
Step 1: All the raw materials were combined with distilled water,
serving as the aqueous media. The mixture was placed on a magnetic
stirrer and stirred for 5 h at a heating temperature ranging between 100
and 110 ℃.
Step 2: After the initial mixing and reaction, the obtained materials
underwent a precipitation process. The precipitates were subsequently
filtered and washed repeatedly with distilled water to eliminate any
undesired mineral impurities present in the samples.
Step 3: The filtered materials were then dried overnight at a tem­
perature of approximately 110 ℃ to remove any remaining moisture
and to stabilize the prepared samples.
Step 4: The final stage involved subjecting the dried samples to a
calcination process. Various temperatures were tested during this step,
and the details of the specific temperatures used can be found in the
following section. For a visual representation of the entire pigment
preparation process, one can refer to the diagram in Fig. 1, which il­
lustrates all the steps involved in synthesizing the pigments using the
ion-exchange and precipitation method. The process aimed to create
stable and pure pigment samples suitable for subsequent analysis and
experimentation.
2.3. Calcination process
In order to achieve thermal treatment of the dried powder, referred
to as the "ion-exchange sample," we conducted a calcination process at
various temperatures. The calcination process was carried out using an
electric kiln tube furnace in a static air environment. To hold the samples
during the calcination, alumina crucible boats were used as sample
holders. The calcination temperatures were set at 700 ℃, 800 ℃,
900 ℃, 1000 ℃, 1100 ℃, and 1200 ℃, respectively. The temperature
was increased at a controlled rate of 6 ℃/min. Once the desired calci­
nation temperature was reached, the samples were allowed to soak at
that temperature for 1 h to ensure complete thermal treatment and
stabilization. For clarity, we designated the samples as follows:
• Ion-exchange sample: This refers to the sample that did not un­
dergo any calcination.
• Calcinated samples: These are the samples that underwent calci­
nation at specific temperatures, namely 700 ℃, 800 ℃, 900 ℃,
1000 ℃, 1100 ℃, and 1200 ℃.
The calcination process aimed to bring about structural and chemical
transformations in the ion-exchange sample, allowing us to investigate
the impact of different calcination temperatures on the material’s
properties.
2.4. Characterization techniques
2.4.1. TGA and DTA analysis
The characterization of the samples involved Thermogravimetric
Analysis (TGA) and Differential Thermal Analysis (DTA), which were
performed using a state-of-the-art NETZSCH 409 PC/PG equipment,
renowned for its precision and reliability. The instrument allowed us to
obtain valuable insights into the thermal behavior of the sample in an
accurate and controlled manner. The parameters of the equipment were
set as follows: Accuracy for mass change was ± 0.2 μg, for voltage
± 0.06 μV, and for temperature ± 0.1 ◦ C. The weight of the powder
sample used for analysis was 10.37 mg, and the rate of temperature
increase was set at 10 ◦ C/min, ranging from 25 ◦ C to 1200 ◦ C. The
analysis was conducted in an air atmosphere. The combination of TGA
and DTA in this equipment allowed us to study both the mass changes
and the corresponding thermal effects of the sample as it was subjected
to controlled temperature conditions. These measurements were essen­
tial in understanding the sample’s decomposition, phase transitions, and
other thermal events, which were crucial for the comprehensive analysis
S.K. Fatah et al.
Cobalt Mixing with
chloride distilled
Zinc CLNP
hexahydrate oxide water
zeolite
1gram
1gram 2gram
Before ion-exchange
1200˚C 1100˚C 1000˚C 900˚C
Heat treatment
Before ion-exchange Ion-exchange
Ca3.16Si33.60Al2.40O93.80 + CoCl2 Ca(3.16-x)CoxSi33.60Al2.40O93.80 + xCa+2 + 2Cl- +(1-x)Co+2
Ca(3.16-x)CoxSi33.60Al2.40O93.80 + ZnO
Heat treatment
Fig. 1. Illustrates sample preparation through ion-exchange and precipitation, including raw material conversion, final calcination, and varying thermal treatments.
Process reactions are depicted pre-ion-exchange, post-ion-exchange, and after heat treatment.
of our study.
2.4.2. XRD analysis
X-ray diffraction (XRD) analysis was carried out to investigate the
crystallographic properties of the sample pigments. The measurements
were performed using a Philips X′pert X-ray diffractometer, known for
its high precision and reliability in obtaining crystallographic data. The
2θ range for the analysis was set from 10◦ to 80◦ , with a step size of 0.01
and a time per step of 1 s, ensuring fine resolution and accurate data
collection. The X-ray source used was λCukα with a wavelength of
1.540598 Å. The instrument was operated at 40 kV and 40 mA, while
the analysis was conducted at a stable temperature of 25 ◦ C.
2.4.3. Modulating and structural refinement
The collected XRD data were refined structurally using the Rietveld
Refinement technique with the assistance of the GSAS II software [26].
This method enabled us to accurately determine the crystal structure of
each sample by comparing the experimental data with theoretical
models. The crystallographic information for each sample was gathered
and input into the GSAS II program for the refinement process. This step
provided us with detailed insights into the precise arrangement of the
pigment’s crystals, enhancing our understanding of its structural char­
acteristics. Additionally, we utilized the VESTA software to modulate
the crystal structures of both the CLNP zeolite and the samples subjected
to thermal treatment [27].
2.4.4. FE-SEM analysis
Field-Emission Scanning Electron Microscopy (FE-SEM) analysis was
conducted to investigate the surface morphology. The measurements
were performed using a high-performance QUANTA FEG-450 FE-SEM
from FEI, renowned for its exceptional imaging capabilities and
analytical precision. The FE-SEM was operated at a high voltage of
25.00 kV to achieve optimal imaging resolution and sensitivity to sur­
face features. The analysis was carried out under high vacuum condi­
tions to ensure the accurate detection and characterization of the
sample’s surface without interference from atmospheric gases or
contaminants.
Journal of Alloys and Compounds 970 (2024) 172503
Filter
and
Dry
wash Ion-exchange
Ion-exchange
800˚C 700˚C
Calcination in furnace
Zn(2-x)CoxSiO4 +CaO+SiO2+Al2O3
2.4.5. Colorimetric analysis
In the study, reflectance spectra within the UV/visible range for all
samples were meticulously recorded spanning 250–1000 nm using a
UV-Vis spectrometer, namely, the Ocean Optic HR400-USA. Addition­
ally, colorimetric parameters were ascertained using the same UV-Vis
device, which was equipped with the CIE L* a* b* color coordinate
system. The L* parameter is indicative of the color pigment’s white
(lightness) and black, represented by scaled values of 100 and 0,
respectively. On the other hand, the a* parameter manifests itself with
(-) and (+) values, corresponding to green and red colors, respectively,
while the b* values signify yellow (+) and blue (-) colors. The pigment’s
Chroma, denoted as C* , is a measure of the richness and saturation of its
color and can be derived from C* = [(a*)2 + (b*)2]1 /2. Additionally, the
hue angle, represented as h◦ , describes the color’s position around a
color wheel and can be calculated as (h◦ =tan-1(b*/a*)). Depending on
the signs of a* and b* , the hue angle h◦ is positioned in one of the four
quadrants: 0◦ − 90◦ (first quadrant, red to yellow) if both b* and a* are
positive, 90◦ − 180◦ (second quadrant, yellow to green) if b* is positive
and a* is negative, 180◦ − 270◦ (third quadrant, green to blue) if both
b* and a* are negative, and 270◦ − 360◦ (fourth quadrant, blue to red) if
b* is negative and a* is positive. This comprehensive colorimetric
analysis allows for a detailed examination of the samples’ color char­
acteristics and provides valuable insights into their visual attributes.
3. Results and discussion
3.1. Thermal treatment analysis
The ion-exchange sample, referred to as the prepared sample, was
subjected to thermal treatment. The treatment involved TGA, which was
conducted by gradually raising the temperature from 25 ℃ to 1200 ℃ at
a rate of 10 ℃/min. Fig. 2 displays the TGA/DTA results for all samples,
with the blue curve representing the TGA data and results, and the red
curve depicting the DTA results.
The dehydration process initiates at temperatures between 25 and
200 ℃, as evident from the DTA curve, which shows an endothermic
peak around 120 ℃. This observation is consistent with literature
3
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

2
100 weight loss %
DTA 0
-2
80

TGA (weight loss %) mg

-4

DTA (mg/µV)
-6
60
-8
-10
40
-12
-14
20
-16
-18
0
0 200 400 600 800 1000 1200
Temperature (°C)

100 weight loss %

TGA (weight loss %) mg

95

90

weight loss=15%
85

weight loss=3.36%

80
0 200 400 600 800 1000 1200
Temperature (°C)

Fig. 2. Presents TGA/DTA results for the ion-exchange sample, highlighting the zeolite colorant’s weight loss curve. These findings reveal thermal stability,
decomposition behavior, and temperature-induced weight changes.

findings [28]. The dehydration continues until temperatures reach
600 ℃, likely due to the release of water and hydroxy species [29]. The
weight loss of approximately 15% from the powder, as observed in the
enlarged TGA blue curve, can be attributed to desorption and hydroxy
groups, as mentioned earlier [30].
Beyond 600 ℃ and up to 800 ℃, exothermic peaks are discernible,
indicating the commencement of structural collapse in the CLNP zeolite.
This phenomenon is substantiated by XRD results, which will be dis­
cussed later. Temperatures above 800 ℃ lead to the emergence of new
structures and phases, as evident from exothermic peaks in the DTA
curve at 800 ℃, marking the collapse of the CLNP zeolite structure.
Subsequently, recrystallization and the formation of new phases occur,
as indicated by the DTA curve from 800 ℃ to 1000 ℃ [30].
An additional weight loss of about 3.36% is observed in the DTA
curve from 450 ℃ to 1000 ℃. Consequently, the total weight loss from
the original powder, beginning from the initiation of thermal treatment
until its conclusion, amounts to approximately 18.36%.
At temperatures exceeding 1000 ℃, the resulting phase is Co-
willemite, as corroborated by XRD analysis, which will be presented
in the subsequent section. This phase remains stable and persists until
1200 ℃, accompanied by observable exothermic peaks in the DTA
curve. The thermal treatment process induces changes in crystal struc­
tures, leading to alterations in color for each calcination temperature.
The colors of the new structures at various temperatures are displayed in
the TGA and DTA graphs.
3.2. X-ray diffraction analysis
The XRD data for the various samples are presented in Fig. 3.
Experimental peaks are accompanied by reference bars, aiding in phase
identification, and reference codes for each phase are provided in
Table 1.
During the sample preparation process conducted at a temperature of
110 ℃, significant structural alterations were observed upon the ion-
exchange of the CLNP zeolite framework with Zn and Co atoms. This
phenomenon can be attributed to the substitution of Co+2 ions for atoms
located within the internal voids or on the external surface of the zeolite
lattice. Concurrently, zinc, primarily in the form of ZnO or Zn(OH)2
particles, manifested itself through surface adsorption. It is this dual
mechanism of ion replacement and surface adsorption that underlies the
observed structural transformations within the zeolite framework. Fig. 3
(b) reveals the emergence of new phases, namely zincite ZnO and Ca-
CLNP, alongside a discernible reduction in the intensity of the Ca-
CLNP phase, indicative of its weakening. Subsequent thermal treat­
ment of the ion-exchanged sample significantly influenced the phases
and structures. At a calcination temperature of 700 ℃, SiO2 phases were
observed in conjunction with Ca-CLNP and zincite (Fig. 3(c)). The
further weakening of the CLNP-Ca phase was confirmed through anal­
ysis of the enlarged figure.
Upon raising the temperature to 800 ℃, a significant transformation
in the zeolite structure occurred, leading to the disappearance of zeolite-
related peaks and the transition to an amorphous phase (Fig. 3(d)). At

4
S.K. Fatah et al.
Fig. 3. Displays XRD results. Panels show: (a) Ca-CLNP zeolite, (b) Pre-calcination ion-exchange, and subsequent panels at varied calcination temperatures: (c)
700 ℃, (d) 800 ℃, (e) 900 ℃, (f) 1000 ℃, (g) 1100 ℃, and (h) 1200 ℃.
this stage, only two phases were discernible: ZnO and SiO2. These
findings align with the outcomes of TGA/DTA analyses mentioned
earlier. Notably, at 900 ℃, a new phase, Co-willemite, emerged, indi­
cating a distinct recrystallization of the CLNP zeolite structure (Fig. 3
(e)). This phase marked a transitional state between the amorphous
phase and the zeolite’s recrystallization. All observed diffracted peaks
were exclusively associated with the new phase of Co-willemite, devoid
of any trace elements.
Subsequent temperature increases to 1000 ℃ and 1200 ℃ exhibited
no further changes in the Co-willemite phase or its associated peaks,
suggesting a stable crystal structure for the obtained powder at these
temperatures (Fig. 3(f, g, and h)). However, it was evident that the
crystallization process was confirmed through the sharpening of peaks
and increased intensity at specific positions. This observation was
reinforced by the analysis of crystallite size particles as described in
5
Journal of Alloys and Compounds 970 (2024) 172503
below paragraphs. The TGA and DTA results, which indicated
exothermic peaks after 1000 ℃, were in concurrence with the afore­
mentioned observations. Additionally, the colorimetric properties of the
achieved powder provided further support for these findings.
To demonstrate the congruence between the obtained phases and
XRD experimental data, the General Structure Analysis System-II (GSAS-
II) software was employed for refining the crystal structure phases in the
samples [26]. The refinement process encompassed multiple parame­
ters, including the maximum number of cycles (15), instrument type
(Bragg-Brentano), background function (Chebyshev-1), instrument pa­
rameters (U, V, W), phase fraction, unit cell, residual weight for each
phase (wR%), and goodness of fit (GOF). During the Rietveld refinement
using GSAS-II, meticulous considerations were given to factors such as
optimizing instrument parameters and peak shapes, background
modeling, and the application of constraints and restraints. The
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

Table 1
Summarizes Rietveld refinement for all samples, including phases, COD code references, weight fractions, lattice parameters, wR% residuals, and GOF metrics for both
experimental and reference data.
Samples Phases COD code Weight fraction Lattice constant alpha beta gamma wR% GOF

a b c

CLNP zeolite Ca-CLNP 900–9578 1 17.670 17.916 7.425 90 116.356 90 16.82 0.54
Ion-exchange Ca-CLNP 900–5428 0.46 17.670 17.945 7.411 90 116.278 90 7.60 1.26
ZnO 900–8877 0.54 3.249 3.249 5.206 90 90 120
700◦ C Ca-CLNP 900–9578 0.18 17.653 17.889 7.403 90 116.45 90 7.36 1.18
ZnO 900–4181 0.80 3.249 3.249 5.205 90 90 120
SiO2 101–0944 0.02 7.083 7.083 7.083 90 90 90
800◦ C ZnO 900–4181 0.73 3.250 3.250 5.204 90 90 120 6.39 1.02
SiO2 101–0944 0.27 7.097 7.097 7.097 90 90 90
900◦ C Co-willemite 046–1316 1 13.948 13.948 9.288 90 90 120 7.53 1.24
1000◦ C Co-willemite 046–1316 1 13.930 13.930 9.311 90 90 120 8.52 1.37
1100◦ C Co-willemite 046–1316 1 13.935 13.935 9.315 90 90 120 7.69 1.17
1200◦ C Co-willemite 046–1316 1 13.933 13.933 9.313 90 90 120 8.15 1.30

outcomes of the Rietveld refinement for all samples are depicted in
Fig. 4. It is essential to note that the observed peaks correspond to the
experimental XRD data, while the calculated peaks align with theoret­
ical reference data. Moreover, the (Obs-Calc) peaks correlate to the
discrepancies between the XRD data and the theoretical reference data.
It is evident from the results that the XRD data for all samples, encom­
passing different phases, exhibit strong conformity with the theoretical
data. Detailed information, such as lattice constants, weight fractions for
each phase in each sample, residual weight wr%, and goodness of fitness
GOF, is summarized in Table 1.
The analysis of the results demonstrates that, with the exception of
the CLNP zeolite sample, the residual weight (wR%) for all samples
remains below 10%. The elevated wR% value for the CLNP zeolite
sample is attributed to potential noise interference within the peak data.
Notably, the Ca-CLNP phase exhibits distinct alterations concerning
lattice constants and weight fractions as the thermal treatment pro­
gresses from the pristine CLNP zeolite to 700 ℃. Specifically, the weight
fraction of Ca-CLNP diminishes from its initial value of 1 in Ca-CLNP to
0.18 at 700 ℃, a phenomenon attributed to the emergence of alternative
phases. Concomitantly, lattice parameters b and c experience notable
deviations from the Ca-CLNP sample to the ion-exchanged counterpart.
However, as the thermal treatment escalates to 700 ℃, lattice parame­
ters a, b, and c all exhibit a trend of contraction, as evidenced in the
tabulated data. The ion-exchange process, involving the replacement of
ions both on the surface and within the porous structure of the zeolite as
mentioned earlier, induces distortions and deviations in the crystal
structure. These phenomena accelerate the ultimate collapse of the
zeolite structure, with the ion-exchange further driving the trans­
formation towards the development of a novel crystal structure during
thermal treatment. This observation aligns with the outcomes of thermal
treatment analysis and X-ray diffraction (XRD) peak data, conclusively
indicating the deformation and subsequent collapse of the CLNP zeolite,
ultimately resulting in the appearance of an amorphous phase upon
reaching 700 ℃ in XRD analysis. It is noteworthy that additional pa­
rameters, such as beta, are also affected by this calcination process.
Furthermore, at temperatures exceeding 800 ℃, the Ca-CLNP phase
becomes undetectable, marking the culmination of its structural
disintegration.
At 800 ℃, a new phase emerges, comprising ZnO and SiO2, with no
apparent presence of Co ions due to their amorphous nature. However,
further calcination results in the appearance of the Co-willemite phase
(Zn2− xCoxSiO4) in conjunction with willemite structure. As indicated in
the literature, Co ions occupy the position of Zn1 site in the willemite
structure [14,25]. This assertion is corroborated by the change in color
from green to blue, as willemite itself is white, but the introduction of a
small amount of Co ions alters its color to blue, as will be discussed in the
forthcoming colorimetric analysis section [25]. At 900 ℃, a single phase
is present without any impurities. When reaching 900 ℃, a singular
phase emerges, untainted by impurities. However, it’s worth high­
lighting that the lattice dimensions a, b, and c display a somewhat more
pronounced expansion when contrasted with the temperatures that
follow.
The crystalline structures of the Ca-CLNP zeolite, along with thermal
treatments at 700 ℃ and within 900–1200 ℃, are presented in Fig. 5.
Data for modifying these structures are acquired through Rietveld
refinement for each sample and visualized using VESTA software. The
CLNP zeolite exhibits a 3D arrangement of silicate minerals comprising
aluminum oxide (AlO4) and silicon oxide (SiO4) tetrahedra [9]. Calcium
ions are variably positioned within the CLNP structure, bonding with
oxygen and water ions. Upon heating to 700 ℃, dehydration eliminates
water molecules, facilitating the entry of Co and Zn ions that replace Ca
ions post-CLNP amorphization. At 900 ℃, a new Co-willemite phase
emerges, featuring an orthosilicate structure with phenacite symmetry.
Cobalt, zinc, and silicon ions occupy distinct tetrahedral framework sites
[14].
The determination of crystallite size for each phase in the samples
was carried out using the Debye-Sherrer method with the assistance of
OriginPro software. This involved fitting each peak with Lorentzian
fitting system to obtain the Full Width at Half Maximum (FWHM) and
peak position 2θ, as comprehensively presented in Table 2. Notably, the
crystallite size of the Ca-CLNP phase exhibited a relatively small value in
its pure zeolite structure without calcination. However, this size
increased significantly after undergoing ion-exchange and even at
700 ℃, aligning with the concurrent changes in the lattice constant of
the structure throughout these processes. Subsequently, following the
structural collapse and the emergence of the new Co-willemite phase,
the crystallite size demonstrated further improvement and growth with
increasing thermal treatment temperatures, as evident from the range of
900 ℃ to 1200 ℃. Additionally, the peaks’ intensity and sharpness were
also observed to increase, as visually depicted in Fig. 3. These findings
collectively indicate the evolution of crystallite characteristics and
structural improvements during the thermal treatment stages.
3.3. Morphology and particle size distribution analysis
The morphology and particle size distribution of the samples were
analyzed using FE-SEM imaging, and the results are presented in Fig. 6
and Fig. 7. For each case, a small table is included within each figure,
providing details such as the total number of particles considered for
measurement, the mean size (average size) distribution, as well as the
minimum and maximum particle size distribution. The determination of
these values and tables was conducted using Image J and Origin Lab
software.
From the examination of Fig. 6, it can be observed that the CLNP
zeolite has undergone a transformation, though it has not yet collapsed
after undergoing ion exchange, as evident in the comparison between

6
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

Observed Calculated Background (Obs-Calc) Observed Calculated Background (Obs-Calc)

Ca-CLNP ZnO CLNP-Ca SiO2 ZnO

Intensity (Arbitrary units)

Intensity (Arbitrary units)
Ion- exchange 700˚C

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2θ (°) 2θ (°)
Observed Calculated Background (Obs-Calc) Observed Calculated Background (Obs-Calc)
SiO 2 ZnO Co-willemite
Intensity (Arbitrary units)

900˚C

Intensity (Arbitrary units)

800˚C

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2θ (°) 2θ (°)

Observed Calculated Background (Obs-Calc) Observed Calculated Background (Obs-Calc)

Co-willemite Co-willemite
Intensity (Arbitrary units)
Intensity (Arbitrary units)

1000˚C 1100˚C

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2θ (°) 2θ (°)

Fig. 4. Shows Rietveld refinement outcomes for ion-exchange and calcination samples at temperatures from 700 ℃ to 1100 ℃. Excludes 1200 ℃ due to similarity to
1100 ℃ result, differing only in peak sharpness and intensity.

Fig. 6(a) and (b). Furthermore, the particle size distribution has reaching 900 ℃, a transition phase to a new phase of Co-willemite oc­
increased during this transformation, as shown in Fig. 7(a) and (b). curs. This transition is accompanied by a change in the morphology of
Subsequent thermal treatments ranging from 700 ℃ to 1200 ℃ are particle distribution, with particles appearing smaller and agglomer­
illustrated in Fig. 6(c) to (h). Notably, even at 700 ℃ (Fig. 6(c)), the ating to form groups. These observations are apparent in Fig. 6(e) and
CLNP structure still exists in the powder, and the particle size distribu­ Fig. 7(e).
tion continues to rise. This indicates that the CLNP zeolite structure has Throughout the thermal treatment range from 900 ℃ to 1200 ℃, the
not yet collapsed, which is corroborated by TGA/DTA and XRD results. morphology of the particle size distribution remains relatively consis­
At 800 ℃, the CLNP zeolite enters an amorphous phase, leading to tent. However, with increasing temperature, particle agglomeration
the collapse of its structure, as previously mentioned. The appearance of becomes more pronounced, leading to an increase in the particle size
other phases, such as SiO2 and ZnO, contributes to a change in the distribution. This behavior may be attributed to the aggregation of
morphology of the distribution particles. Consequently, the particle size particles, resulting in the formation of larger particles. These findings
distribution decreases during this stage, as evident in Fig. 7(d). Upon are consistent with the crystallite size results obtained from the XRD

7
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

Fig. 5. Demonstrates the dynamic changes in the crystal structure of Ca-CLNP that includes thermal treatments at both 700 ℃ and within the range of 900 ℃ to
1200 ℃. At 700 ℃, the structure undergoes dehydration, allowing the infiltration of Co and Zn ions into the pores and surface of the CLNP zeolite structure. A new
Co-willemite phase is observed between 900 ℃ and 1200 ℃. Notably, the red spheres in the figure represent water ions.

Table 2 analysis, where it was observed that the crystallite size increased with
Displays crystallite size analysis outcomes for all studied samples, including higher thermal treatment temperatures. The correlation between the
values for each phase. morphology and distribution of particles and the crystallite size further
Sample Names Phases Crystallite size (nm) supports the validity of the results obtained in this study.
Ca-CLNP zeolite Ca-CLNP 28.89
Ion-exchange Ca-CLNP 46.05
ZnO 71.77 3.4. Optical and colorimetric analysis
700◦ C Ca-CLNP 71.92
ZnO 69.58 Based on the UV–vis reflected results, a comprehensive examination
SiO2 26.90
of the optical properties of each powder sample was conducted, as
800 C
◦
ZnO 67.21
SiO2 11.90 illustrated in Fig. 8. This figure displays the reflected curves obtained
900◦ C Co-willemite 28.69 during the ion-exchange process and subsequent thermal treatment
1000◦ C Co-willemite 39.79 ranging from 700 ℃ to 1200 ℃. During the ion-exchange process, co­
1100◦ C Co-willemite 51.97 balt (Co) ions are found to occupy both the tetrahedral (Td) and octa­
1200◦ C Co-willemite 61.79
hedral (Och) coordination positions within the dehydrated zeolites and

8
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

Fig. 6. FE-SEM images of samples: (a) CLNP zeolite, (b) ion-exchange; samples heated at (c) 700 ℃, (d) 800 ℃, (e) 900 ℃, (f) 1000 ℃, (g) 1100 ℃, and (h) 1200 ℃.

9
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

20 N total Mean Minimum Maximum

N total Mean Minimum Maximum 60
18 84 49.173 19.945 114.938 122 63.675 18 306.894
16 50
14 [a] Ca-CLNP [b] Ion-exchange
40
12
Count

Count
10
30
8
6 20
4
10
2
0 0
20 40 60 80 100 120 0 50 100 150 200 250 300 350
Particle size distribution (nm) Particle size distribution (nm)
N total Mean Minimum Maximum
30 60 N total Mean Minimum Maximum
112 66.304 19 251.078 117 61.789 13.454 290.759

25 50
[c] 700˚C [d] 800˚C
20 40

Count
Count

15 30

10 20

5 10

0
0 0 50 100 150 200 250 300
0 50 100 150 200 250 Particle size distribution (nm)
Particle size distribution (nm)
35 N total Mean Minimum Maximum
60
N total Mean Minimum Maximum 128 49 19.313 115.395
121 50.125 19.698 286.819
30
50
[f] 1000˚C
40
[e] 900˚C 25
Count

Count

20
30
15
20
10
10
5
0
0 50 100 150 200 250 300 0
Particle size distrubution (nm) 0 20 40 60 80 100 120
Particle size distribution (nm)
16 N total Mean Minimum Maximum 18
N total Mean Minimum Maximum
63 61.41 26 150.266
16 63 71.11 46.53 112.432
14
14
12 [g] 1100˚C [h] 1200˚C
12
10
Count
Count

10
8
8
6
6
4 4

2 2

0 0
0 20 40 60 80 100 120 140 160 40 50 60 70 80 90 100 110 120
Particle size distribution (nm) Particle size distribution (nm)

Fig. 7. Shows particle size histogram for samples: (a) CLNP zeolite, (b) ion-exchange, and (c-h) various heating temperatures. Tables provide particle count, mean
size, and range for each case.

10
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

samples. Higher thermal treatment temperatures lead to increased par­

ticle size distribution due to enhanced particle agglomeration, contrib­
uting to the intensified blue coloration. These observations establish a
connection between the thermal treatment steps and the development of
the desired blue hue. Notably, the lightness of the powders consistently
decreases with each temperature increase.
The Co-willemite structure exhibits superior color stability and
quality at higher temperatures, leading to the achievement of a near-
perfect blue color with b* − 30.90, a* − 2.25, and L* 43.41.
Additionally, Fig. 9(c) provides the CIE 1976 model, illustrating the
uꞌ and vꞌ diagram to precisely indicate the color position of each sample.
The analysis confirms the progression of the powders toward a blue hue.
Apart from the L* , a* , and b* values, Table 3 also includes the
C* chroma and h* (hue angle) properties for each sample. C* chroma
represents the colorfulness or saturation of a color, calculated based on
the a* and b* components. Higher C* chroma values correspond to more
vivid and saturated colors. On the other hand, h◦ denotes the color’s
position on the color wheel, ranging from 0◦ to 360◦ , with specific de­
Fig. 8. Displays UV–vis reflection data across the experimental range, starting
grees corresponding to distinct colors on the color spectrum. Specif­
with ion-exchange and progressing through sequential thermal treatments from
ically, 0◦ corresponds to red, 120◦ to green, and 240◦ to blue. The hue
700 ◦ C to 1200 ◦ C.
angle determines the color’s hue and direction of movement around the
color wheel. A positive hue angle indicates clockwise movement, while a
willemite structure [31].
negative hue angle indicates counterclockwise movement.
Notably, distinct peaks within the range of 570–580 nm are
In our study, the results reveal a blue color from 900–1200 ℃ when
observed, corresponding to the presence of Co ions within the structure.
considering the third quadrant where -a* and -b* values are located,
Subsequently, as the thermal treatment commences at 700 ℃ and con­
consistent with the counterclockwise movement on the color wheel.
tinues beyond 800 ℃, three prominent peaks of lower reflectance
These findings reaffirm the progression of the samples toward a blue
become evident, confirming the presence of Co ions in the structure. This
hue, in line with the thermal treatment steps and crystal structure
observation aligns with the energy level diagram of Co in Td coordi­
modifications.
nation, wherein it undergoes three spin-forbidden transitions [16]. The
Co ions, occupying the Td coordination position in zeolite structures and
4. Conclusion
spinals, exhibit a split in the Co 4 F ground state energy into spin orbital
levels, transitioning from double degenerate (e) to triply degenerate (t2)
In conclusion, this study explored the collapse of metastable zeolite
[31].
under elevated temperatures, resulting in amorphous precursor forma­
Moreover, the results are further substantiated as the zeolite struc­
tion. By employing natural clinoptilolite zeolite (CLNP) and Co/Zn ion
ture collapses at temperatures of 800 ℃ and above, where the peaks
exchanges via thermal treatment, the research aimed to create varied
remain consistent from 900 ℃ to 1200 ℃. This consistent behavior
color pigments. Utilizing techniques like TGA/DTA, XRD, FE-SEM, UV-
suggests the presence of a singular phase of Co-willemite throughout
Vis, and Colorimetric analysis, the investigation tracked structural,
these thermal treatments, accounting for the similarity in observed
morphological, and color changes during ion-exchange, amorphization,
patterns. An essential observation is the gradual reduction in reflectance
and CLNP recrystallization. The outcomes revealed collapse occurring at
after ion-exchange, which persists throughout the subsequent thermal
750–800 ℃, leading to an amorphous CLNP phase. We validate that the
treatment from 900 ℃ to 1200 ℃. However, it is noteworthy that there
weight fraction of the CLNP phase diminishes during each sequential
is a noticeable shift in the positions of the peaks. The color changes from
thermal treatment phase until the structure ultimately undergoes
light blue to dark blue below, which will be corroborated through color
collapse. Transition to Co-willemite (Zn2− xCoxSiO4) and its recrystalli­
wheel analysis and photographic evidence.
zation happened at 800–900 ℃, impurity-free. Subsequent thermal
The colorimetric analysis results for the ion-exchange and thermal
treatments slightly affected the phase, intensifying crystallization.
treatment of samples, ranging from 700–1200 ℃, are presented in
Morphological shifts aligned with temperature changes, indicating
Fig. 9. A color wheel is employed to illustrate the CIE L* , a* , and
particle distribution growth and crystallite enlargement. Pigments
b* values, as depicted in Fig. 9(a), and a comprehensive summary of all
emerged: brown (700 ℃, CLNP retained), green (800 ℃, structural
outcomes is provided in Table 3.
change), and blue (900 ℃, Co-willemite). Co-willemite’s stable presence
During the ion-exchange process, noticeable alterations in color and
improved blue pigment quality (L* = 43.41, a* = − 2.25, b* = − 30.9).
L* , a* , and b* values are observed. The color transforms from a beige or
This study underscores zeolite manipulation’s potential for ceramics,
cream hue with a lightness value of approximately L* 90.49 to a
yielding stable, varied pigments. The multi-technique approach en­
somewhat brown tint upon 700 ℃ calcination during thermal treat­
hances our understanding and opens doors for broader applications and
ment. Subsequently, at 800 ℃, the color shifts to green, accompanied by
advancements.
a gradual decrease in lightness across all powder samples. These changes
are directly related to the stepwise modification of the crystal structure
CRediT authorship contribution statement
of CLNP zeolite, as the phases and crystal structures evolve, thus influ­
encing the observed color shifts. To provide visual evidence, photo­
Salar K. Fatah: Conceptualization, Validation, Writing – original
graphic images for each thermal treatment step are included in Fig. 9(b).
draft. Mohsen Khajeh Aminian: Conceptualization, Validation,
Continuing the thermal treatment from 800 ℃ to 900 ℃, it has been
Writing – review & editing. Milad Bahamirian: Visualization, adviser,
previously verified that a new phase, Co-willemite, is formed. The
Investigation, characterization.
photographic evidence aligns with this finding, demonstrating a blue
coloration as the amorphous phase undergoes recrystallization into Co-
Declaration of Competing Interest
willemite. Furthermore, the XRD results confirm the presence of a single
phase from 900–1200 ℃, with morphological similarities across the
The authors declare that they have no known competing financial

11
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

Fig. 9. Presents colorimetric outcomes. (a) Color wheel with L* , a* , and b* values. (b) Photographic images of each case. (c) CIE 1976 uꞌ and vꞌ diagram for
all samples.

12
S.K. Fatah et al. Journal of Alloys and Compounds 970 (2024) 172503

Table 3 U, Fxc kernel for LRC model, and BSE approaches. Part II: CoSiO3 and Co2SiO4
presents the colorimetric results for all samples, including the L* , a* , and pigments, Powder Technol. 397 (2022) 50–61, https://doi.org/10.1016/j.
powtec.2021.11.043.
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800◦ C 67.57 -5.45 0.24 5.46 177.40 heulandite zeolite, Ceram. Int. 48 (2022) 21954–21966, https://doi.org/10.1016/
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