Mechanochemical Synthesis of High Crystalline Cerium Hexaboride Nanoparticles from CeO2-B2O3-Mg Ternary System

Article abstract of DOI:10.1002/jccs.201500479

High crystalline cerium hexaboride (CeB₆) nanoparticles (NPs) were synthesized using mixture of magnesium (Mg), cerium oxide (CeO₂) and boron oxide (B₂O₃) via the mechanochemical process at room temperature. Based on the results, magnesiothermic reduction of B₂O₃ occurred after about 2 h of milling in a mechanically induced self-sustaining reaction (MSR). The significant amount of heat produced by the reduction reaction resulted in CeO₂ reduction to elemental Ce which finally reacted with elemental B and formed CeB₆ compound. According to XRD analyses, the degree of crystallinity and lattice parameter of the product was calculated about 93 % and 4.1458 ?, respectively. The morphology observations revealed that the synthesized CeB₆ had semi-cubic shape with the range of size 25-60 nm. The synthesis of CeB₆ during the thermal treatment was studied by simultaneous thermal analysis (STA) technique. It was found that the reduction of B₂O₃ took place after melting of Mg meanwhile, no CeB₆ phase achieved even up to 1100 °C.

Full text of DOI:10.1002/jccs.201500479

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Mechanochemical Synthesis of High Crystalline Cerium Hexaboride Nanoparticles
from CeO -B O -Mg Ternary System
2
2
3
a
b
a
a
Omid Torabi, Sanaz Naghibi, * Mohammad-Hossein Golabgir and Amin Jamshidi
Young Researchers and Elite Club, Najafabad Branch, Islamic Azad University, Najafabad, Iran
a
b
Young Researchers and Elite Club, Shahreza Branch, Islamic Azad University, Shahreza, Iran
(Received: Nov. 25, 2015; Accepted: Feb. 23, 2016; Published Online: Apr. 5, 2016; DOI: 10.1002/jccs.201500479)
High crystalline cerium hexaboride (CeB
nesium (Mg), cerium oxide (CeO ) and boron oxide (B
perature. Based on the results, magnesiothermic reduction of B
mechanically induced self-sustaining reaction (MSR). The significant amount of heat produced by the re-
duction reaction resulted in CeO reduction to elemental Ce which finally reacted with elemental B and
formed CeB compound. According to XRD analyses, the degree of crystallinity and lattice parameter of
the product was calculated about 93% and 4.1458 Å, respectively. The morphology observations revealed
that the synthesized CeB had semi-cubic shape with the range of size 25-60 nm. The synthesis of CeB
during the thermal treatment was studied by simultaneous thermal analysis (STA) technique. It was found
that the reduction of B took place after melting of Mg meanwhile, no CeB phase achieved even up to
100 °C.
6
) nanoparticles (NPs) were synthesized using mixture of mag-
) via the mechanochemical process at room tem-
occurred after about 2 h of milling in a
2
2 3
O
2
O
3
2
6
6
6
2
O
3
6
1
Keywords: Mechanochemistry; Cerium hexaboride; Formation mechanism; XRD; TEM.
INTRODUCTION
CeB is an engineering ceramic with excellent elec-
In this regard, Dou et al. prepared CeB
by high-temperature self-propagating synthesis (SHS) me-
thod. They milled the powder mixture (including CeO
, Mg and KClO ) for 12 h and then pressed and placed
in a combustion chamber. Their results showed that the sin-
gle phase CeB powder with particle size of less than 150
6
nanopowder
6
tronic and magnetic characteristics, such as high thermal
stability, low volatility, low work function (2.5 eV), high
stability in vacuum and high melting point (> 2000 °C). It
owns one of the highest electron emissivity which has been
found to use in high-tech equipment such as cathodes for
electron microscopy, high current applications in micro-
wave tubes, electron-beam welders, X-ray sources and
2
,
B
2
O
3
3
6
3
nm was achieved by the SHS method. Due to the general
restrictions in thermal techniques such as high required
temperature, non-uniform phase, large particle size and so
on, the main aim of this work was to find an effective tech-
1
etc.
Various techniques have been reported to prepare
nique to prepare CeB
gree of crystallinity.
6
NPs with high purity and high de-
CeB
CeB
6
. The two conventional methods for synthesizing
are (i) direct reaction of B and Ce at an elevated tem-
6
Mechanochemistry is the simultaneous mechanical
and chemical reactions in a molecular scale; including me-
chanical breakage and chemical reactions. This is an in-situ
solid-state method in which the starting powders mixture
reacts at room temperature or at least much lower tempera-
ture. This phenomenon is related to the mechanical break-
age and cold deformation of the particles during high en-
ergy milling. This method may decrease reaction time, save
2 2 3
perature and (ii) carbothermal reduction of CeO -B O
2
mixture. These methods require high temperature and lead
to produce a powder with low purity and poor sinterabi-
3
lity; therefore, it is important to develop the methods to
achieve high-quality products.
Sahadev et al. have synthesized CeB
6
single crystals
4
by the floating zone route. CeB
6
thin film was prepared by
5
8
using a molecular beam epitaxy (MBE) method. Kushkhov
energy and produce high purity of products; therefore, the
et al. used electroreduction of Ce ions with fluoroborate
mechanochemical is a promising approach for the synthe-
6
9-10
ions to prepare CeB
6
nanotube. The high cost of the equip-
sis of advanced materials processing such as carbides,
1
1-12
13
14
ment needed, is the main disadvantage of these techniques
nitrides,
intermetallics and borides. This method has
7
14
15
16
which limits its applicability.
been applied to synthesize TiB
2
,
NbC-NbB
2
,
2
CrB ,
*
Corresponding author. Tel: +98 31 53292060; Fax: +98 31 53502701; Email: naghibi@iaush.ac.ir
J. Chin. Chem. Soc. 2016, 63, 379-384
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379

Article
Torabi et al.
1
7
18
19
Mo
2
B, Al
2
O
3
-BN by this research team. During the
state into its amorphous. In this case, only the main peaks
of Mg [JCPDS: 35-821] and CeO [JCPDS: 75-390] were
observed. The sharp peaks of products (CeB and MgO)
milling process, the exothermic reduction of the metal
oxides by Al or Mg releases large amount of heat and then,
the generated elemental metals react with B and/or C to
2
6
were clearly observed in the sample milled for 2 h. The
abrupt phase transformation in the XRD pattern and the
calculated Tad (~2773 °C) reveals that the type of reaction
1
4-18
synthesize borides and/or carbides.
Akgun et al. have been prepared CeB
chemical method. The powder mixture (including CeO
and Mg) was milled for long time of 30 h. The ob-
tained powder was a mono-phase CeB with the particle
6
by mechano-
2
,
2 3 2
in the stoichiometric mixture of Mg–B O –CeO was
B
2
O
3
MSR. A loud voice of explosive reactions which was rec-
ognized after 2 h of milling confirms this fact. As can be
6
7
8
size of about 240 nm. It is well determined that the level
of contamination significantly increases if the as-received
powder mixture is milled for long times, hence, it is advan-
tageous that the products would be obtained in short dura-
tions.
2
seen, a negligible trace of CeO was still remained. This
can be explained by following reasons: (i) the accumula-
tion of starting materials in the dead regions of the milling
pot and (ii) the insufficient mixing of the reactants at short
time. The presence of negligible unreacted materials after
the ignition is a typical characteristic of MSR type of reac-
The purpose of this research is to investigate the for-
2
0
mation of CeB
the high energy ball mill. Fundamental aspects of reaction
path in CeO -B -Mg ternary system as well as the influ-
ences of B content were studied. Afterward, the system
6
NPs by using CeO
2
, Mg and B
2
O
3
during
tions.
By prolonging the milling time for another 2 h (4 h),
2
2
O
3
the unreacted powders were exposed to the ball hits and
high temperature, thus the required energy for completion
2
O
3
will be described in view point of thermodynamic and
thermal treatment.
of reactions was supplied and the remaining trace of CeO
2
was removed from the XRD pattern. It must be noted that,
the explosion did not occur in this step, because the amount
of unreacted powder was negligible and hence the heat re-
leased by reactions were not as high as enough to explode.
RESULTS AND DISCUSSION
Mechanochemistry of Mg/CeO
2 2 3
/B O system
The theoretical chemical reaction taking place during
6
By comparing the intensities of CeB and MgO peaks
the synthesis of CeB
scribed by Eq. (1).
6
in CeO
2
-B
2
O
3
-Mg system can be de-
after 2 and 4 h of milling, it can be concluded that increas-
ing the milling time slightly decreases the height of XRD
peaks, due to plastic deformation, particle size reduction
and amorphization.
CeO
2
+ 3B
2
O
3
+ 11Mg = CeB
6
+ 11MgO
(1)
DH 298 = -2062.9 KJ/mol, DG 298 = -1999.9 KJ/mol,
ad » 2773 °C
0
0
Figure 2 shows the phase component of sample mil-
led for 4 h after leaching. As can be observed, the charac-
T
According to the theoretical thermodynamic calcula-
tions, the reaction of stoichiometric amount of starting ma-
terials is highly exothermic and favorable at room tempera-
ture. The adiabatic temperature of Eq. (1) met the critical
value of 1800 K, suggesting the reaction type is MSR. In
this type of reactions, the minimum amount of energy is
needed to start a self-propagating combustion reaction. The
activation energy is provided by the milling of mixture,
then the combustion reactions occur and the vessel temper-
8
ature increases.
The XRD patterns of the stoichiometric powder mix-
ture milled for 1.5, 2 and 4 h are shown in Figure 1. The
XRD pattern of the sample after 1.5 h of milling illustrates
that no considerable phase changes occurred. The peaks of
Fig. 1. XRD patterns of the stoichiometric powder
mixture after 1.5, 2 and 4 h of milling.
B
2
O
3
disappeared due to the transformation from crystal
380
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
6
Mechanochemical Synthesis of High Crystalline CeB NPs
teristics traces of MgO are completely removed and CeB
6
corners. This phenomenon can be explained by the me-
chanical damage during milling process.
[
JCPDS No. 38-1455] appears as a unique phase. Miller in-
dexes are provided for the cubic CeB
6
with a space group of
The SEM micrographs of the as-synthesized CeB
6
Pm3m. The standard lattice parameter is 4.1412 Å, whereas
the estimated value data from the XRD analysis is 4.1458
Å. This deviation can be related to the strain, defects and
NPs are illustrated in Figure 4. The powder agglomeration
can be seen before and after the leaching. The agglomera-
tion is an inevitable phenomenon in the preparation of NPs
via mechanochemical systems due to the higher specific
surface area.
2
1
chemical compound. The less deviation is measured, the
higher quality of crystals is achieved. Degree of crystal-
linity of the prepared CeB
6
was calculated about 93%. In
The sequence and mechanism of chemical reactions
addition, the allocated score of profile fitting via the
search/match software (PANalytical X’Pert HighScore)
was 95%. Therefore, according to (i) tiny difference be-
tween the standard and calculated lattice parameter values,
6
The mechanism for the preparation of CeB in the
stoichiometric mixture of Mg-B
as follows.
2
O
3
-CeO
2
can be explained
(
ii) the high degree of crystallinity and (iii) high score of
2 3
B O + 3Mg = 2B + 3MgO
(2)
0
0
profile fitting, it can be concluded that this method can be a
very effective technique to synthesize high-crystalline and
DH 298 = -531.3 KJ/mol, DG 298 = -513.5 KJ/mol,
ad » 2240 °C
CeO + 2Mg = Ce + 2MgO
T
high-quality CeB
6
NPs.
2
(3)
(4)
0
0
Figure 3 shows TEM micrographs of the as-synthe-
sized NPs before and after leaching process. According to
Figure 3-A, the un-leached powder contains some semi-
spherical particles in the range of 10-20 nm as well as some
semi-cubic particles in the range of 30-60 nm. Figure 3-B
shows only semi-cubic particles with particle size of 25-60
nm in the leached sample. By comparing these Figures
DH 298 = -112.8 KJ/mol, DG 298 = -111.6 KJ/mol,
ad » 960 °C
Ce + 6B = CeB
T
6
0
0
DH 298 = -351.5 KJ/mol, DG 298 = -342.3 KJ/mol,
ad » 3701 °C
T
(
Figures 3-A and B), it can be concluded that semi-spheri-
cal MgO NPs were removed via leaching. On the other
hand, in accordance to XRD result (Figure 2) and TEM im-
age (Figure 3-B), the phase component of the semi-cubic
6
particles is CeB . It can be seen that these NPs have curved
Fig. 2. XRD pattern of the 4 h milled sample after the
leaching process.
Fig. 3. TEM micrographs of the as-synthesized NPs.
(A) un-leached sample, (B) leached sample.
J. Chin. Chem. Soc. 2016, 63, 379-384
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381

Article
Torabi et al.
tion of CeO
In order to further evaluate the proposed mechanism
and to identify the effect of B content on the boride for-
mation phenomena, the value of B in the B -CeO
2
(Eq. 3) is a progressive reaction.
2
O
3
2
O
3
2
O
3
2
-
Mg mixture was changed according to the following gen-
eral reaction:
CeO
2
+ (3 - x)B
2 3
O + (11 - 3x)Mg => (x/3)Ce +
(
1 - x/3)CeB
6
+ (11 - 3x)MgO
(5)
When x = 0, the stoichiometric portion of the reac-
tants was achieved. The XRD pattern of the leached sample
milled for 4 h was shown in Figure 5-a, approving the for-
mation of CeB
content decreased about 10%, which means that the re-
leased energy from the reduction of B decreased, which
affected the reduction of CeO . In this reason, the traces of
CeO were reminded in XRD pattern of this sample (Figure
-b). Further decrease in the B content (x = 2) resulted
in more decrease in CeB peaks intensities and more in-
crease in the remaining CeO peaks height (Figure 5-c). In
other words, in non-stoichiometric conditions, the B O
3
6 2 3
as a unique phase. When x = 1, the B O
2
O
3
2
2
5
2 3
O
6
2
2
content is not as high enough to provide required energy
via reduction reaction to complete the Eq. (4). It seems that
6
when x is equal to two, the amount of synthesized CeB de-
ceased rigorously, due to the insufficient heat generated to
overcome barrier energy.
Thermal analysis
Fig. 4. SEM micrographs of the as-synthesized NPs.
A) un-leached sample, (B) leached sample.
STA analysis was utilized to investigate the reaction
sequence of this system during heat treatment (Figure 6).
As can be seen, there are three endothermic peaks (at 120,
170 and 645 °C) and an exothermic event at 707 °C. The
(
By considering thermodynamic evaluations, it can be
predicted that, in the presence of Mg, B and CeO , mag-
nesium initially reduces B (due to higher negative
2
O
3
2
2
O
3
0
0
values of DG and DH ) in MSR manner (Eq. 2) and pro-
duces boron as well as significant amount of heat. This heat
can provide enough energy to active magnesiothermic re-
duction of CeO
quently, CeB can be synthesized by reaction between the
generated B and Ce during a high exothermic reaction (Eq.
). It worth mentioning that all these reactions occurred at
the same time; therefore, the only the peaks of MgO and
CeB was observed in XRD pattern of sample just after ex-
plosion. The presence of remaining CeO peaks (see Figure
) confirmed the suggested reaction mechanism. Regard-
ing the calculated adiabatic temperatures, the Eq. (2) and
4) can be considered as the MSR type, whereas the reduc-
2
to form elemental Ce (Eq. 3). Conse-
6
4
6
2
1
Fig. 5. XRD patterns of samples a (x = 0), b (x = 1) and
c (x = 2) after 4 h of milling.
(
382
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6
Mechanochemical Synthesis of High Crystalline CeB NPs
chromium steel container with a balls-to-powder ratio of 20. To
prevent oxidation, the milling pots were filled with high-purity
argon gas and the mill was stopped and allowed to cool for 15 min
after each 1 h of grinding.
For removing the produced by-products such as MgO, the
powder after milling was leached with 18% hydrochloric acid
(
HCl) for 1 h. The solution was filtered and the purified products
were repeatedly washed by distilled water to eliminate extra HCl
until the pH value reached a value of about 7. The residue on the
filter was dried at 90 °C for 2 h.
The thermodynamic studies were conducted base on ther-
0
0
modynamic data (DH 298, DG 298 and Tad) that were collected from
2
3
Kubaschewski’s book.
The thermal behavior of this system was characterized by
means of simultaneous thermal analysis (STA) in an instrument
(
BAHR THEMOARALYSE, 503, Germany). 50 mg of the pow-
der mixture was weighted and held in an alumina crucible and
-
1
Fig. 6. STA curve of the as-blended mixture of the
CeO -B -Mg system.
heated under argon flow at a heating rate of 10 °C×min up to
100 °C.
The powder mixtures after milling and after leaching were
2
2 3
O
1
first weak endotherm, corresponding to the decrease region
in the TG curve, is ascribed to vaporization of the water ab-
characterized by XRD (D8 advance spectrometer, Bruker, Ger-
many) with Cu radiation (Ka = 1.540598 Å) and a Ni filter. The
diffraction patterns were analyzed using PANalytical X’Pert
HighScore software by comparison with the JCPDS database.
The degree of crystallinity of the NPs was quantitatively
evaluated. In this method, ‘sum of net area’/ ‘sum of total area’in
PANalytical X’Pert High Score software was the criterion for the
degrees of crystallinity. To calibrate the results, backgrounds of
2 3
sorbed to boron oxide. Usually B O particles adsorb water
on their surfaces and lose it during heating. There is a peak
at about 650 °C in STA curve, which can be related to the
melting of Mg. The exothermic peaks at approximately 700
°
C without any weight changing can be ascribed to the ini-
tiation of the magnesiothermic reaction of boron oxide as
predicted in thermodynamic calculations. This temperature
peaks were determined by considering 100% crystallinity for the
2
2
24
is too low for the reduction of CeO
2
. Low intensity of this
commercial CeO
As the CeB
interplanar d-spacing (d), miller indices (h k l) and lattice parame-
2
. This method has been reported elsewhere.
peak indicates that this reaction didn’t occur completely.
On the other hand, increasing the temperature to 1100 °C
had no effect on DTA curve. This means that the reduction
6
is a cubic crystal, the relation between the
2
2
2
2
2
ter is described by a = d / (h + k + l ). The interplanar d-spacing
of CeO
Based on the thermal analysis, melting of Mg and
lack of the required energy for reduction of CeO are obsta-
cles of SHS reaction. It seems that CeB production from
CeO is not possible via direct heating. The similar results
2
by Mg needs higher temperature.
and miller indices are determined by XRD software for each
2
1
peak; therefore, the lattice parameter could be achieved.
2
The microstructures of the samples were observed by SEM
(LEO, 435 VP, Germany, at 18 kV) and TEM (Philips CM200
FEG, Netherlands, at 200 kV).
6
2
2
2
2 2 3
were reported by Jalaly et al in the Mg/ZrO /B O system.
CONCLUSIONS
EXPERIMENTAL
The mechanochemical method was successfully ap-
plied to synthesize high crystalline cerium boride nano-
For synthesis of CeB
rium oxide (CeO : Merck Co., > 99%, ~3 mm), magnesium (Mg:
Merck Co., 99.7%, 40 ± 5 mm) and boron oxide (B : Merck Co.,
9.9%, 30 ± 5 mm) were mixed.
Powder blends were milled in a planetary mill at 500 rpm
with hardened carbon steel balls (F = 10 mm, n = 5) in a hardened
6
, the stoichiometric amounts of ce-
2
2 2 3
powder from a mixture of Mg-CeO -B O at room temper-
2
O
3
ature. As predicted by thermodynamic evaluations, the re-
action mode in this system was MSR with an ignition time
of 2 h. According to the experimental findings, at first,
9
2 3
magnesium reduced B O in a self-sustaining manner and
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Article
Torabi et al.
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2
. The
2 3
B O
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