materials

Article
Synthesis and Characterizations of (CoxMg(2−x))SiO4
Forsterite Ceramic Pigments from Mirror Waste
Niti Yongvanich ID
, Kullada Supanichwatin, Jitat Penglan and Narit Triamnak *
Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology,
Silpakorn University, Nakhon Pathom 73000, Thailand; niti.yongvanich@gmail.com (N.Y.);
kang.kullada@gmail.com (K.S.); chaingather_kub@hotmail.com (J.P.)
* Correspondence: triamnak_n@su.ac.th; Tel.: +66-3421-9363




Received: 10 June 2018; Accepted: 11 July 2018; Published: 13 July 2018


Abstract: Ceramic pigments have been widely used in a variety of industries because of their excellent
properties, such as high thermal stability, low-cost productions, and simple manufacturing processes.
Re-use of mirror waste, which consists of silicon dioxide greater than 70%, is a method that can reduce
raw materials cost. In this work, ceramic pigment with forsterite structure, Mg2 SiO4 , was synthesized
via conventional solid state reaction by using mirror waste as a precursor. Solid solutions of
Co-doped forsterite pigment, Cox Mg(2−x) SiO4 where x = 0.02–1.6, were calcined at 1000 ◦ C for 2 h.
The calcined powders were characterized by X-ray diffraction technique (XRD), Fourier-transform
infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray photoelectron spectroscopy
(XPS), UV-Vis spectrophotometer, and color measurement (CIEL*a*b*). XRD results confirmed that
forsterite phase was found as a main phase in the ceramic powder. However, the forsterite phase
decreased with increased concentration of Co to x = 0.8–1.6. This could be because of the solubility
limit of Co in solid solution. In addition, the use of mirror waste as a raw material was able to reduce
calcination temperature compared to the use of oxide reagents. Color measurements or CIEL*a*b*
color space of forsterite pigments were located in red-blue quadrant for Co-doped pigment.

Keywords: ceramic pigment; forsterite; mirror waste

1. Introduction
Ceramic pigments have been used extensively in decorative industries as a coloration component
due to their advantages such as low-cost productions, stability, longevity, and mass-producibility.
Even though ceramic pigments possess many advantages, the reduction of raw materials cost is still
needed to compete in the market. Re-use of industrial waste is the current trend to lower the cost of
raw materials. Traditionally, this waste is disposed of in landfill. It includes glass and mirror waste.
The advantage of these wastes for re-use is their amorphous structure. Such structure could lead to
a lower reaction temperature. However, this might cause a variation in pigment properties, such as
firing formula and color tone, due to the composition differences between the waste and pure reagents.
In addition, this variation could be seen between wastes of similar chemical compositions, such as glass
and mirror, as well. Even though the secondary processing of glass is common, the aluminum film in
mirror waste might deviate the final product properties. Practically, if the desirable pigment phase can
be obtained as well as excellent chromatic quality in term of both stability and color tone, then the
waste can be used. This method could be optimized and could lead to benefits both economically
and environmentally.
Generally, the pigments are used as a dispersed phase in media such as glaze, ceramic body,
and porcelain enamels causing the desirable color in applications. Such applications usually involve
high-temperature processes. Therefore, the synthesized pigments must exhibit excellent thermal

Materials 2018, 11, 1210; doi:10.3390/ma11071210 www.mdpi.com/journal/materials

Materials 2018, 11, 1210 2 of 11

and chemical stability. There have been researches into the synthesis, phase formation, and thermal
stability in Co olivines and related compounds such as CaCoSi2 O6 , Ca2 CoSi2 O7 , and CaCoSiO4 [1–3].
Forsterite [4,5], with the chemical formula Mg2 SiO4 , is a crystalline magnesium silicate and seems to
be usable as the ceramic pigment due to its fabulous refractoriness. It shows high thermal stability
with a melting temperature of 1890 ◦ C as well as high chemical stability. In contrast, the common
way to synthesize forsterite also requires very high temperatures. It is usually fired at a temperature
of approximately 1500 ◦ C. Therefore, it is crucial to lower the synthesized temperature which also
means lowering productions cost. In addition, the thermal stability of forsterite pigment needs to be
investigated simultaneously to understand and optimize the pigment preparation processes.
This study aims to synthesize the forsterite pigment and characterize its properties by using
mirror waste as a raw material and cobalt oxide as a chromophore of the pigment. Phase evolution
and chromatic properties of the pigment are investigated with the different chromophore contents.

2. Materials and Methods

Forsterite powder was prepared via a conventional solid state reaction method by
stoichiometrically mixing reagent-grade silicon dioxide (SiO2 ) and magnesium oxide (MgO) as
precursors. The mixture was wet ball-milled for 24 h with ethanol followed by calcination in an
alumina crucible at temperatures between 800 and 1200 ◦ C for 2 h. The as-calcined powder was
then ground in a mortar prior to structural characterization by X-ray diffraction technique (XRD,
LabX XRD-6100 Diffractometer, Shimadzu, Kyoto, Japan) with Cu-Kα radiation at λ = 1.5406 Å.
Cobalt-doped forsterite pigment (Cox Mg(2−x) SiO4 , when x = 0–1.6) was synthesized by mixing
mirror waste (as the SiO2 source) instead of reagent-grade SiO2 , MgO and cobalt oxide (Co2 O3 ),
stoichiometrically. The mixed powder was subjected to the previous preparation method as the reagent
grade forsterite powder. Phase evolution of the pigment powder from mirror waste was comparatively
investigated by XRD technique.
Fourier transformation infrared spectroscopy (FTIR, Vertex70, Bruker, Billerica, MA, USA) was
performed as a complement study for pigment structural investigation.
X-ray fluorescence (XRF, Minipal-4, PANalytical, Almelo, The Netherlands) was used to
characterize mirror waste composition, as shown in Table 1. The morphology and elemental
distribution of the powder were examined by scanning electron microscope (SEM, TM3030, Hitachi,
Tokyo, Japan) and energy dispersive spectroscopy (EDS, TM3030, Hitachi).

Table 1. Compositions of oxides from mirror waste.

Oxides Mol %
SiO2 71.11
Na2 O 12.68
CaO 11.38
MgO 3.52
Etc. 1.31

Optical properties of the pigment were investigated by using the Uv-Vis spectroscopy technique
(UV-1800, Shimadzu) to study light reflection character and the CIELab method by colorimeter
(Color Reader CR-10, Minolta, Osaka, Japan) was used to examine chromatic values. The color is
defined as the three parameters, L*, a* and b*, where they represent the brightness, change from green
(negative value) to red (positive value), and change from blue (negative value) to yellow (positive
value), respectively.
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3. Results
Results and
and Discussion
Discussion
The possibility
possibilityofofusing
usingmirror
mirrorwaste to synthesize
waste forsterite
to synthesize pigment
forsterite via the
pigment viacommon route
the common
preparation, such assuch
route preparation, using
as reagent-grade SiO2 asSiO
using reagent-grade the2 precursor, neededneeded
as the precursor, to be investigated. Phase
to be investigated.
evolution of this of
Phase evolution composition is illustrated
this composition in Figure
is illustrated 1.
in Figure 1.

Figure 1. X-ray diffraction (XRD)

(XRD) patterns
patterns of as-calcined forsterite powder at various temperatures
between 800
between 800 and 1200 °◦CC by
and 1200 by mixing
mixingreagent-grade
reagent-gradeSiO
SiO2:2 :(a)(a)Without
WithoutNaF
NaFmineralizer;
mineralizer;(b)(b) Added
Added 5
5 wt.
wt. %%ofof NaF.
NaF.

It
It is
is clearly
clearly shown
shown in in Figure
Figure 1a1a that
that the
the forsterite
forsterite phasephase could
could not
not bebe observed
observed even even ifif the
the
calcination temperature was increased to 1000 °C. With further temperature
calcination temperature was increased to 1000 C. With further temperature increase to 1200 ◦ C,
◦ increase to 1200 °C, there
was
thereawas small peak peak
a small pattern of forsterite
pattern phasephase
of forsterite occurrence. On the
occurrence. Onother hand,hand,
the other the main phase
the main of this
phase of
powder remained as SiO 2 (labeled with “S”) which identified with JCPDF 00-046-1045. This results
this powder remained as SiO2 (labeled with “S”) which identified with JCPDF 00-046-1045. This results
confirmed
confirmed the the difficulty
difficulty of forsterite synthesis
of forsterite synthesis at moderate temperature
at moderate temperature by by conventional
conventional solid solid state
state
reaction
reaction because
becauseof ofits
itsexcellent
excellentrefractoriness
refractoriness [6].[6].
Therefore,
Therefore, the the
addition of a of
addition mineralizer,
a mineralizer,NaF, NaF,
was
performed to increase the raw materials diffusion rate leading
was performed to increase the raw materials diffusion rate leading to a reduction of the reaction to a reduction of the reaction
temperature.
temperature. The The XRDXRDpattern
patternofof NaF-added
NaF-added powder
powder is shown
is shown in Figure
in Figure 1b. Forsterite
1b. Forsterite structure
structure peaks
peaks (labeled with “F”) were observed with small intensity when
(labeled with “F”) were observed with small intensity when the powder was calcined at temperatures the powder was calcined at
temperatures as
◦ low as 800 °C which was matched to JCPDF 00-034-0189.
as low as 800 C which was matched to JCPDF 00-034-0189. The peak pattern intensity increased The peak pattern intensity
increased
clearly when clearly when the temperature
the temperature increased toincreased
1000 ◦ C. to In 1000 °C. In
addition, addition,
there was anthereabruptwas an abrupt
decreased of
decreased of SiO 2 precursor peaks. The single phase of forsterite structure was obtained when the
SiO2 precursor peaks. The single phase of forsterite structure was obtained when the calcination
calcination
temperaturetemperature
increased up increased
to 1100 up ◦ C.to 1100 °C. According
According to data1, in
to data in Table theTable
second1, the second
highest highest
elemental
elemental
concentration concentration
of mirror waste of mirrorwas waste
sodium was sodium
which could which
play could play
a role in a role in
forsterite forsteriteasformation
formation a similar
as a similar mineralizer,
mineralizer, NaF [6–9]. NaF [6–9].
XRD pattern of of as-calcined
as-calcined powder
powderCo CoxxMg
Mg(2−x)SiO 4, when x = 0, synthesized from mirror waste
XRD pattern (2−x) SiO4 , when x = 0, synthesized from mirror waste
are
are shown
shown in in Figure
Figure 2. 2. The
The forsterite
forsterite peaks
peaks can
can bebe clearly
clearly seen
seen when
when the
the powder
powder was was calcined
calcined atat the
the
temperature of 800 °C,
◦ and their intensity significantly increased with
temperature of 800 C, and their intensity significantly increased with the calcination temperature the calcination temperature
increase.
increase. ItIt was was observed
observed that that using
using mirror
mirror waste
waste as as the
the SiO
SiO22 source
source could
could reduce
reduce the the forsterite
forsterite
formation
formation temperature [10]. This could be because of the disorder-structure within mirror waste from
temperature [10]. This could be because of the disorder-structure within mirror waste from
industrial
industrial post-processes.
post-processes. In In addition,
addition, other
other oxides
oxides components, especially Na
components, especially Na2O, could behave as the
2 O, could behave as the
mineralizer.
mineralizer. It It needs
needs to to be
be noted
noted that
that the
the secondary
secondary phases phases appeared
appeared in in all
all preparation
preparation conditions.
conditions.
This
This is because of the high impurities content in mirror waste which is very difficult to eliminate and
is because of the high impurities content in mirror waste which is very difficult to eliminate and
control.
control. However,
However, comparedcompared to to the
the main
main phase,
phase, thethe number
number of of secondary
secondary phases
phases appears
appears to to be
be small
small
and
and influences
influences on on the
the pigment
pigment properties
properties areare correspondingly
correspondingly small. small.
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2. XRD patterns
Figure 2. patterns of as-calcined
as-calcined forsterite powder from mirror waste
waste at
at various
various temperatures
temperatures
Figure 2. XRD patterns of as-calcined forsterite powder from mirror waste at various temperatures
◦ C.
between 800 and 1200
1200 °C.
between 800 and 1200 °C.

The crystal
The crystal structure characterization
characterization of forsteriteforsterite mirror waste waste pigment with with increasing
The crystal structure
structure characterization of of forsterite mirror
mirror waste pigmentpigment with increasing
increasing
concentration
concentration of Co chromophore is depicted in Figure 3. This investigation was designed to study
study
concentration of of CoCo chromophore
chromophore is is depicted
depicted in in Figure
Figure 3.3. This
This investigation
investigation was was designed
designed to to study
structural
structural stability based on the content of chromophore ion. The concentration of Co ion was varied,
structural stability
stability based
based onon the
the content
content of of chromophore
chromophore ion. The concentration
ion. The concentration of of Co
Co ion
ion was
was varied,
varied,
xxx =
= 0–1.6,
0–1.6, with
with aa constant
constant calcination
calcination temperature
temperature of 1000
of 1000 ◦°C.C. This
This temperature
temperature
= 0–1.6, with a constant calcination temperature of 1000 °C. This temperature was enough to obtain
was enough
was enough to to obtain
obtain
forsterite
forsterite phase
phase in in the
inthe pigment
thepigment as noted
pigmentasasnoted noted in previous XRD results. It was found that the increase of Co
forsterite phase in in previous
previous XRDXRD results.
results. It wasIt was
found found thatincrease
that the the increase
of Co
ion content from x = 0 to x = 0.4 caused the shifting of the peaks pattern towards a smaller diffraction
ofionCo ion content
content from x from = 0 toxx== 00.4tocaused
x = 0.4the caused theofshifting
shifting the peaksof the peaks
pattern patterna towards
towards a smaller
smaller diffraction
angle. It could
diffraction angle. beItimplied
could bethat the d-spacing
implied of unit cell
that the d-spacing increased
of unit because because
cell increased of the greater Co ion
of the greater
angle. It could be implied that the d-spacing of unit cell increased because of the greater Co ion
diffusion
Co ion into
diffusion the structure.
into the The
structure.changes
The of unit
changes cell
of volume
unit cell with different
volume with Co content
different Co were observed
content were
diffusion into the structure. The changes of unit cell volume with different Co content were observed
in related in
observed compounds
related such as CaCoSi
compounds such 2OCaCoSi
as 6 pyroxenes [11,12] as well. However, when
2 6 [11,12] as well. However, when the contentthe
O pyroxenes [11,12] as well. However,the content
when of
in related compounds such as CaCoSi2O6 pyroxenes of
Co was of
content increased
Co was to x = 0.8–1.6,
increased to x the XRD patterns
= 0.8–1.6, the XRDexhibit
patternstheexhibit
Co2SiO 4 phase
the Co2 SiOwhich matched
4 phase whichto JCPDF
matched
Co was increased to x = 0.8–1.6, the XRD patterns exhibit the Co2SiO 4 phase which matched to JCPDF
00-015-0865,
to labeled “CS”
JCPDF 00-015-0865, in Figure
labeled “CS”3d. In addition,
in Figure 3d. Inpeak intensity
addition, peak ofintensity
this phase ofreduced.
this phase It might
reduced. be
00-015-0865, labeled “CS” in Figure 3d. In addition, peak intensity of this phase reduced. It might be
because
It might the
be excess Co theinteracted
excess Cowith the other oxides within the mixture resulting inresulting
an increase of
because thebecause
excess Co interacted interacted
with the otherwith the other
oxides withinoxides within the
the mixture mixture
resulting in an increase in an
of
secondary
increase of phases
secondary and decrease
phases and of the main
decrease phase
of the [8,13].
main phase [8,13].
secondary phases and decrease of the main phase [8,13].

Figure 3. Cont.
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Figure
Figure 3.3. XRD
XRD patterns
patterns ofof CoCoxMg (2−x)SiO4 sample synthesized by mirror waste calcined at 1000 °C
◦ for
x Mg(2−x) SiO4 sample synthesized by mirror waste calcined at 1000 C for
22 h:
h: (a,b) x ==0–0.1; (c,d)
(c,d) xof
x ==Co
0.2–1.6.
Figure 3. xXRD
(a,b) 0–0.1;
patterns 0.2–1.6.
xMg(2−x)SiO4 sample synthesized by mirror waste calcined at 1000 °C for

2 h: (a,b) x = 0–0.1; (c,d) x = 0.2–1.6.

FTIR was studied as the supplementary structural characterization and is illustrated in Figure 4.
FTIR was studied as the supplementary structural characterization and is illustrated in Figure 4.
The results exhibited small peaks at wave number 2800–3600 cm−1 which refer to the vibration of O-H
FTIR was
The results studiedsmall
exhibited as thepeaks
supplementary structural
at wave number 2800–3600 cm−1 which
characterization and refer
is illustrated in Figureof
to the vibration 4.
stretching mode. These peaks were probably a result of humidity that KBr absorbed while the
The results exhibited small peaks at wave number 2800–3600 cm −1 which refer to the vibration of O-H
O-H stretching mode. These peaks were probably a result of humidity that KBr absorbed while the
measurement was being conducted. In addition, the peak of O-H bending was observed at wave
stretching mode.
measurement wasThese
being peaks were In
conducted. probably
addition, a result of humidity
the peak that KBr
of O-H bending wasabsorbed
observedwhile the
at wave
number of 1454 cm− −1 which is also the evidence of water molecule existence. After that, peaks of Si-O
1 which
measurement
number of 1454was
cm being conducted.
is also the In addition,
evidence of the peak
water of O-H
molecule bending
existence. was
After observed
that, peaks at
ofwave
Si-O
bonding were seen at−1894 and 999 cm−1 which are Si-O-Si stretching [14,15]. Finally, Si-O-Si bending peaks
number of
bonding 1454
were cm atwhich
seen 894 andis 999
alsocmthe−evidence
1 which are of Si-O-Si
water molecule
stretchingexistence.
[14,15]. After
Finally,that, peaksbending
Si-O-Si of Si-O
were observed at 521 and 620 cm−1. As−1the−content 1
of Co ion increased both Si-O-Si stretching and bending
bonding
peaks were
were seen at 894
observed andand
at 521 999620
cm cm which arethe
. As Si-O-Si stretching
content [14,15].
of Co ion Finally,
increased Si-O-Si
both bending
Si-O-Si peaks
stretching
peaks broadened [16]. The appearance of peak broadening was evidence of structural distortion because
werebending
and observedpeaks
at 521broadened
and 620 cm[16].
−1. As the content of Co ion increased both Si-O-Si stretching and bending
The appearance of peak broadening was evidence of structural
of the diffusion of Co ion in the structure. These results are in agreement with XRD data.
peaks broadened
distortion because [16].
of The appearance
the diffusion ofofCo
peak
ionbroadening was evidence
in the structure. of structural
These results are indistortion
agreement because
with
of thedata.
XRD diffusion of Co ion in the structure. These results are in agreement with XRD data.

Figure 4. Fourier transformation infrared spectroscopy (FTIR) Spectrum of CoxMg(2−x)SiO4 (x = 0.1, 0.4,
0.8, 1.6) samples synthesized by mirror waste calcined at 1000 °C for 2 h.
Figure 4. Fourier transformation infrared spectroscopy (FTIR) Spectrum of CoxMg(2−x)SiO4 (x = 0.1, 0.4,
Figure 4. Fourier transformation infrared spectroscopy (FTIR) Spectrum of Cox Mg(2−x) SiO4 (x = 0.1,
0.8, 1.6) samples synthesized by mirror waste calcined at 1000 °C for ◦C 2 h.
To
0.4,predict
0.8, 1.6)the behavior
samples of Co ion,
synthesized Co0.4Mg
by mirror 1.6SiO
waste 4 powder
calcined at was
1000 then analyzed
for 2 h. by X-ray photoelectron
spectroscopy technique (XPS). The result of Co-2p binding energy is shown in Figure 5. It was found that
To predict the behavior of Co ion, Co0.4Mg1.6SiO4 powder was then analyzed by X-ray photoelectron
there were peaks split into Co-2p1/2 and Co-2p3/2 at 797 eV and 781 eV, respectively. This result
spectroscopy technique (XPS). The result of Co-2p binding energy is shown in Figure 5. It was found that
described the existence of divalent cobalt (Co2+) which could mean the substitution of Co ion at the
there were peaks split into Co-2p1/2 and Co-2p3/2 at 797 eV and 781 eV, respectively. This result
described the existence of divalent cobalt (Co2+) which could mean the substitution of Co ion at the
Materials 2018, 11, 1210 6 of 11

To predict the behavior of Co ion, Co0.4 Mg1.6 SiO4 powder was then analyzed by X-ray
photoelectron spectroscopy technique (XPS). The result of Co-2p binding energy is shown in Figure 5.
It was found that there were peaks split into Co-2p1/2 and Co-2p3/2 at 797 eV and 781 eV, respectively.
This result described the existence of divalent cobalt (Co2+ ) which could mean the substitution of
Materials
Co ion at the 2018,
Mg 11,position
x FOR PEERin
REVIEW
the forsterite structure. Characterized data from XRD, FTIR,6 of 11 XPS
and
confirm that Co-doped forsterite pigment was successfully synthesized by using mirror waste as the
Mg position in the forsterite structure. Characterized data from XRD, FTIR, and XPS confirm that Co-
SiO2 doped
source.forsterite pigment was successfully synthesized by using mirror waste as the SiO2 source.

Figure 5. X-ray photoelectron spectroscopy (XPS) spectra of Co0.4Mg1.6SiO4 samples showing binding
Figure 5. X-ray photoelectron spectroscopy (XPS) spectra of Co0.4 Mg1.6 SiO4 samples showing binding
energy of Co 2p.
energy of Co 2p.
The morphology and elemental distribution of the Co0.4Mg1.6SiO4 powder obtained from SEM
and EDS
The techniquesand
morphology are elemental
shown in Figure 6. It wasoffound
distribution the Cothat
0.4the
Mgparticle
1.6 SiO4 shape
powder of the pigmentfrom
obtained was SEM
irregular.
and EDS In addition,
techniques particleinsize
are shown was non-uniform.
Figure 6. It was found It could be aparticle
that the result ofshape
the non-uniformity
of the pigment of was
mirror waste structure. The majority elements of the pigment were Si and Mg as expected.
irregular. In addition, particle size was non-uniform. It could be a result of the non-uniformity of mirror Moreover,
the other elements such as Co, Na and Ca were observed with small concentrations which agreed
waste structure. The majority elements of the pigment were Si and Mg as expected. Moreover, the other
with XRF data listed in Table 1. However, distribution of Co, which was doped into the forsterite
elements such as Co, Na and Ca were observed with small concentrations which agreed with XRF
pigment, was uniform.
data listed in Table
UV-Vis 1. However,
spectroscopy spectradistribution
are illustrated ofinCo, which
Figure 7. Itwas dopedthat
was found intothethe forsterite
absorption pigment,
spectra
was uniform.
were at the wavelength of 550–700 nm. Such absorbed wavelength range is due to the excitation of
UV-Vis spectroscopy
electron from spectra
4T1(F) to 4T1(P) andare illustrated
2T1(G) to 2T2(G)instates
Figure
of Co7.2+ chromophore
It was found whichthatlocated
the absorption
at the
spectra were atsites
octahedral theofwavelength of 550–700
the forsterite structure nm.There
[17,18]. Suchareabsorbed wavelength
three absorption peaks inrange is duenmto the
the 550–700
range of
excitation (absorbing
electronyellow, orange,to
from 4T1(F) and red). The
4T1(P) andobserved
2T1(G) tocolor, according
2T2(G) statestoofthe 2+ chromophore
Cocomplimentary colorwhich
theory, is mainly green and blue (430–560 nm) which was clearly reflected
located at the octahedral sites of the forsterite structure [17,18]. There are three absorption peaksby dramatic changes in
in theboth a and nm
550–700 b color parameters
range in Table
(absorbing 2. The
yellow, a parameter
orange, remained
and red). The in the redness
observed regime
color, whereasto the
according
the b parameter displayed blueness. Upon increasing the amount of cobalt doping, slight increases
complimentary color theory, is mainly green and blue (430–560 nm) which was clearly reflected by
in the intensity of the absorption peaks were observed as the peaks became more prominent. This
dramatic changes in both a and b color parameters in Table 2. The a parameter remained in the redness
phenomenon was also confirmed by an enhancement of more than double for both a and b
regime whereaswhen
parameters the bincreasing
parametercobalt
displayed blueness.
concentration fromUpon
x = 0.2increasing
to x = 0.4.theThisamount
result isoflikely
cobaltto doping,
be
slightassociated
increaseswithin the intensity
the absence of of
freethe absorption
cobalt peaks by
oxide observed wereXRDobserved
and the XRD as the
peak peaks became
shift as a resultmore
prominent. This phenomenon
of successful was also
cobalt incorporation intoconfirmed by an
the Mg lattice. Asenhancement
the content of of Comore than to
increased double for both a
x = 0.8–1.6,
and babsorption
parameters whenappeared
strongly increasing cobaltthe
through concentration from x = 0.2
full range of measured to x = 0.4.
wavelength This result
leading to darkisgray
likely to
color which is shown in Figure 8 [17].
be associated with the absence of free cobalt oxide observed by XRD and the XRD peak shift as a result
of successful cobalt incorporation into the Mg lattice. As the content of Co increased to x = 0.8–1.6,
absorption strongly appeared through the full range of measured wavelength leading to dark gray
color which is shown in Figure 8 [17].
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Figure 6. Scanning electron microscope (SEM) micrograph and energy dispersive spectroscopy (EDS)
Figure 6. Scanning electron microscope (SEM) micrograph and energy dispersive spectroscopy (EDS)
data of6.Co 0.4Mg1.6SiO4 powder: (a) morphology; (b) silicon; (c) magnesium; (d) cobalt; (e) sodium; and
data ofFigure
Co0.4 Mg Scanning electron microscope (SEM) micrograph and energy dispersive spectroscopy (EDS)
1.6 SiO4 powder: (a) morphology; (b) silicon; (c) magnesium; (d) cobalt; (e) sodium;
(f) calcium.
data of Co0.4Mg1.6SiO4 powder: (a) morphology; (b) silicon; (c) magnesium; (d) cobalt; (e) sodium; and
and (f) calcium.
(f) calcium.

Figure 7. Diffuse reflectance spectra of CoxMg(2−x)SiO4 (where x = 0.02–1.6) synthesized by mirror

Figure calcined
waste at 1000
7. Diffuse °C for 2spectra
reflectance h. of CoxMg(2−x)SiO4 (where x = 0.02–1.6) synthesized by mirror
7. Diffuse
Figure waste reflectance
calcined 2 h. of Cox Mg(2−x) SiO4 (where x = 0.02–1.6) synthesized by mirror
spectra
at 1000 °C for
waste calcined at 1000 ◦ C for 2 h.
Materials 2018, 11, 1210 8 of 11

Table
Materials CIEL*a*b*
2. 11,
2018, x FOR PEERdata of
REVIEW as-calcined Cox Mg(2−x) SiO4 (where x = 0.05–1.6) powder.
8 of 11

Table 2. CIEL*a*b* data of as-calcined CoxMg(2−x)SiO4 (where x = 0.05–1.6) powder.

Cox Mg(2−x) SiO4 (x) L* a* b*
CoxMg(2−x) SiO4 (x) L* a* b*
0.05 79.9 0.8 −1.9
0.05 79.9 0.8 −1.9
0.1
0.1
71.1
71.1 0.3
0.3 −2.5
−2.5
0.2
0.2 64
64 0.7
0.7 −2.4
−2.4
0.4
0.4
52.9
52.9 1.7
1.7 −6.4
−6.4
0.8
0.8 32.8
32.8 1.61.6 −1.8
−1.8
1.6
1.6 25.5
25.5 1.61.6 −0.1
−0.1

(c)

(a) (b) (d)

Figure 8. Chromatic tone and CIEL*a*b* diagram of CoxMg(2−x)SiO4 (where x = 0.05–1.6): (a,c) As-
Chromatic
Figure 8. calcined toneMixing
powder; (b,d) and glaze
CIEL*a*b* diagram of Cox Mg(2−x) SiO4 (where x = 0.05–1.6):
fired powder.
(a,c) As-calcined powder; (b,d) Mixing glaze fired powder.
Chromatic characteristics of CoxMg(2−x)SiO4 with various content of Co are illustrated in Figure
8. Parameters L*, a* and b*, which were measured by CIELab method, are listed in Table 2. Brightness,
Chromatic characteristics
L*, decreased of Coxincreased
as the Co content Mg(2−x)leading
SiO4 with various
to a darker content
tone and wasof Coinare
seen theillustrated
similar trendin Figure 8.
ParametersofL*, a* and
UV-Vis b*, which
spectra. wereCo
In addition, measured
xMg(2−x)SiO4by CIELab
pigments method,
tended are listed
to exhibit in Table
their color 2. Brightness,
in positive a* L*,
decreasedand
as negative
the Co b* coordination
content as shown
increased in Figure
leading to8ba which
darker showed
tonevioletish
and was color [19,20].
seen As pigment
in the similar trend of
application is generally dispersed in glaze, its glazed chromatic properties were investigated and are
UV-Vis spectra. In addition, Cox Mg(2−were
shown in Figure 8b,d. Pigments x) SiO 4 pigments
mixed
tended to exhibit their color in positive a* and
with low-temperature glaze powder (1000 °C firing
negative b* coordination
glaze) with 10:90 wt.as% shown
ratio and in Figure
followed by 8b which
firing at 1000showed
°C for 2 h.violetish color
After firing, [19,20].were
the mixtures As pigment
application is generally
ground to a fine dispersed
powder beforein glaze, its glazed chromatic
color measurement. It was found properties were
that the color investigated
of the mixtures and are
changed8b,d.
shown in Figure and exhibited
Pigments more
werevioletish
mixedthan withas-calcined pigments as
low-temperature shown
glaze in Figure
powder 8a,c.◦ C
(1000 The
firing glaze)
with 10:90 wt. % ratio and followed by firing at 1000 ◦ C for 2 h. After firing, the mixtures were ground
to a fine powder before color measurement. It was found that the color of the mixtures changed and
exhibited more violetish than as-calcined pigments as shown in Figure 8a,c. The parameters a* and b*
showed a greater value in the identical quadrantal coordination as shown in Figure 8d. The differences
in pigment color quality are listed in Table 3 which are calculated by an equation as follows:
q
∗
dE = dL∗2 + da∗2 + db∗2 (1)
Materials 2018, 11, 1210 9 of 11

where dE* identified as the color stability of the pigments after glaze which is calculated
from the differences of the L*, a*, and b* parameters from prior to and after being glazed.
Generally, the acceptable value of dE* should be less than 1. It was discovered that the calculated value
of the pigments was greater than 1 in every doping compositions, shown in Table 3. The unsteady
color changes also tend to increase as the Co content increased. It is probably because of the excess
Co ions’ outward diffusion from the forsterite pigments. This prediction was confirmed by the EDS
results which are depicted in Figure 9. The interface between as-calcined powder and low-temperature
Materials 2018, 11, x FOR PEER REVIEW 9 of 11
glaze powder (CG466) was created by cold isostatic compression to pellet form. Then it was subjected
parameters
to the identical a* and b* showed
temperature profileaas
greater value in
previous the identical The
procedures. quadrantal coordination
elements as shown
existences at thein interfacial
Figure 8d. The differences in pigment color quality are listed in Table 3 which are calculated by an
vicinity were then investigated by EDS technique and are illustrated in Figure 9. It is clearly seen
equation as follows:
that Co ion diffused and leaked from the pigment region and spread homogeneously across the
interface. The ready dissolution of Co was dE * =thedorigin
L*2 + daof
*2
+ db*2 changes of the pigments and
color (1) exhibited

insufficient stability
where withinasthe
dE* identified theglaze. This instability
color stability might
of the pigments afterbe improved
glaze by further
which is calculated frominvestigations,
the
such as temperature profile adjustment in processing or co-dopings into the pigments. the
differences of the L*, a*, and b* parameters from prior to and after being glazed. Generally,
acceptable value of dE* should be less than 1. It was discovered that the calculated value of the
pigments was greater than 1 in every doping compositions, shown in Table 3. The unsteady color
Table 3. Color stability dE*of Cox Mg(2−x) SiO4 (where x = 0.05–1.6) pigments after being glazed.
changes also tend to increase as the Co content increased. It is probably because of the excess Co ions’
outward diffusion from the forsterite pigments. This prediction was confirmed by the EDS results
which are depicted in Figure 9. TheCo x Mg(2−
interface x) SiO4as-calcined
between (x) dE*powder and low-temperature glaze
powder (CG466) was created by cold isostatic 0.05compression to 8.6 pellet form. Then it was subjected to
the identical temperature profile as previous 0.1procedures. The11.8elements existences at the interfacial
vicinity were then investigated by EDS technique
0.2 and are illustrated
14.1 in Figure 9. It is clearly seen that
Co ion diffused and leaked from the pigment0.4 region and spread homogeneously across the interface.
12.4
The ready dissolution of Co was the origin of0.8
color changes of the
15.9pigments and exhibited insufficient
stability within the glaze. This instability 1.6
might be improved 21.3by further investigations, such as
temperature profile adjustment in processing or co-dopings into the pigments.

Figure 9. EDS mapping of the interface between Co0.1Mg1.9SiO4 pigment and low-temperature glaze:
Figure 9. EDS mapping of the interface between Co0.1 Mg1.9 SiO4 pigment and low-temperature
(a) existing elements; (b) morphology of inter-layer between pigment and glaze; (c) silicon; (d)
glaze: (a) magnesium;
existing elements; (b)(f)morphology
(e) cobalt; and calcium. of inter-layer between pigment and glaze; (c) silicon;
(d) magnesium; (e) cobalt; and (f) calcium.
Materials 2018, 11, 1210 10 of 11

4. Conclusions
The pigments with Co-doped forsteritre structure were successfully synthesized from mirror
waste. The phase evolution of the pigments was investigated, and it was found that mirror waste
could decrease the calcination temperature. It was because of the other oxides within mirror waste,
such as Na2 O. FTIR and XPS measurements confirmed the existence of Co2+ ion in the pigment
structure. The Co doping caused the forsterite pigment to color violetish. Color tone was darker
as the concentration of doping ion increased which was illustrated by UV-Vis spectroscopy and the
CIELab method. However, the forsterite pigments showed low stability in glaze which was because of
the diffusion of Co chromophore. The stability of this mirror waste pigment could be enhanced by
further investigation.

Author Contributions: N.T. planned the experimental activities, performed the data analysis and interpretation,
and wrote the paper. N.Y. planned the experimental activities, supported raw materials, and interpreted the results
of the color characterizations. K.S. and J.P. performed the materials synthesis and structural characterizations.
Funding: This research was funded by Silpakorn University Research and Development Institute (Fiscal
Year 2017).
Acknowledgments: The authors also would like to acknowledge the Department of Materials Science and
Engineering, Faculty of Engineering and Industrial Technology, Silpakorn University.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Mukhopadhyay, S.; Jacob, K. Phase Equilibria in the System CaO-CoO-SiO2 and Gibbs Energies of Formation
of the Quaternary Oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4. Am. Mineral. 1996, 81, 963–972.
[CrossRef]
2. Mimani, T.; Ghosh, S. Combustion synthesis of cobalt pigments: Blue and pink. Curr. Sci. 2000, 78, 892–896.
3. Navrotsky, A.; Coons, W.E. Thermochemistry of some pyroxenes and related compounds.
Geochim. Cosmochim. Acta 1976, 40, 1281–1288. [CrossRef]
4. Svryru, J.R.; lNp RonBnt, M.H. The Crystal Structures of Forsterite and Hortonolite at Several Temperatures
Up to 900"C. Am. Mineral. 1973, 58, 588–593.
5. Hazen, R. Effects of temperature and pressure on the crystal structure of forsterite. Am. Mineral. 1976, 61,
1280–1293.
6. Cheng, L.; Liu, P.; Chen, X.; Niu, W.; Yao, G.; Liu, C.; Zhao, X.; Liu, Q.; Zhang, H. Fabrication of nanopowders
by high energy ball milling and low temperature sintering of Mg2 SiO4 microwave dielectrics. J. Alloys Compd.
2012, 513, 373–377. [CrossRef]
7. Sedel’nikova, M.B.; Pogrebenkov, V.M.; Liseenko, N.V. Effect of mineralizers on the synthesis of ceramic
pigments from talc. Glass Ceram. 2009, 66, 223–226. [CrossRef]
8. El Hadri, M.; Ahamdane, H.; El Idrissi Raghni, M.A. Sol gel synthesis of forsterite, M-doped forsterite
(M=Ni, Co) solid solutions and their use as ceramic pigments. J. Eur. Ceram. Soc. 2015, 35, 765–777.
[CrossRef]
9. Tavangarian, F.; Emadi, R. Synthesis of nanocrystalline forsterite (Mg2 SiO4 ) powder by combined mechanical
activation and thermal treatment. Mater. Res. Bull. 2010, 45, 388–391. [CrossRef]
10. Esteves, D.; Hajjaji, W.; Seabra, M.P.; Labrincha, J.A. Use of industrial wastes in the formulation of olivine
green pigments. J. Eur. Ceram. Soc. 2010, 30, 3079–3085. [CrossRef]
11. Mantovani, L.; Tribaudino, M.; Dondi, M.; Zanelli, C. Synthesis and color performance of CaCoSi2 O6
pyroxene, a new ceramic colorant. Dyes Pigment 2015, 120, 118–125. [CrossRef]
12. Gori, C.; Tribaudino, M.; Mantovani, L.; Gatta, G.D.; Delmonte, D.; Gilioli, E.; Mezzadri, F.; Calestani, G.
Synthesis and crystal structure of C2/c Ca(Co,Mg)Si2 O6 pyroxenes: Effect of the cation substitution on cell
volume. Mineral. Mag. 2017, 81, 1129–1139. [CrossRef]
13. Ianoş, R.; Lazău, R. Chromium-doped calcium zirconate—A potential red shade pigment: Preparation,
characterization and testing. Dyes Pigment 2014, 105, 152–156. [CrossRef]
Materials 2018, 11, 1210 11 of 11

14. Eliziário, S.A.; de Andrade, J.M.; Lima, S.J.G.; Paskocimas, C.A.; Soledade, L.E.B.; Hammer, P.; Longo, E.;
Souza, A.G.; Santos, I.M.G. Black and green pigments based on chromium–cobalt spinels. Mater. Chem. Phys.
2011, 129, 619–624. [CrossRef]
15. Kharaziha, M.; Fathi, M.H. Synthesis and characterization of bioactive forsterite nanopowder. Ceram. Int.
2009, 35, 2449–2454. [CrossRef]
16. López-Navarrete, E.; González-Elipe, A.R.; Ocaña, M. Non-conventional synthesis of Cr-doped SnO2
pigments. Ceram. Int. 2003, 29, 385–392. [CrossRef]
17. Llusar, M.; Forés, A.; Badenes, J.A.; Calbo, J.; Tena, M.A.; Monrós, G. Colour analysis of some cobalt-based
blue pigments. J. Eur. Ceram. Soc. 2001, 21, 1121–1130. [CrossRef]
18. Leite, A.; Costa, G.; Hajjaji, W.; Ribeiro, M.J.; Seabra, M.P.; Labrincha, J.A. Blue cobalt doped-hibonite
pigments prepared from industrial sludges: Formulation and characterization. Dyes Pigment 2009, 81,
211–217. [CrossRef]
19. Maslennikova, G.N.; Pishch, I.V.; Radion, E.V. Current classification of ceramic silicate pigments. Glass Ceram.
2006, 63, 281–284. [CrossRef]
20. Pogrebenkov, V.M.; Sedel’nikova, M.B.; Vereshchagin, V.I. Talc-based ceramic pigments. Glass Ceram. 1997,
54, 351–353. [CrossRef]

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