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Article history:
Received 27 May 2014
Received in revised form
13 October 2014
Accepted 23 October 2014
Available online 24 October 2014
Lanthanum silicated apatites with nominal composition La9.33x(SiO4)6O23x/2 (0.2 < x < 0.27) have
been successfully synthesized by solid state reaction using a new reagent La2O2CO3 and amorphous SiO2
precursors. The formation mechanism of La2O2CO3 reagent, which cannot be purchased, has been followed by in-situ temperature depend XRD of La2O3 under CO2 atmosphere. The stability of this reagent
during the synthesis step allowed to limit the formation of secondary phase La2Si2O7 and made the
weighting of the reagent easier. High purity powders could be synthesized at the temperature of 1400 C.
Dense pellets (more than 98.5%) were obtained by isostatic pressing of powders calcined at 1200 C and
then sintered at 1550 C. Traces of La2SiO5 secondary phase present in synthesized powder disappeared
after densication and pure oxyapatite materials were obtained for all the compositions. Electrical
measurements conrmed that conductivity behaviors of the sintered pellets were dependent to the
oxygen over-stoichiometry. Indeed, a relatively high conductivity of 1 102 S cm1 was exhibited at
800 C for the nominal composition La9.60(SiO4)6O2.405 with low activation energy around 0.79 eV. The
ionic conductivity properties were comparable with that of the earlier obtained materials.
2014 Elsevier Masson SAS. All rights reserved.
Keywords:
Oxyapatite
Powders-solid state reaction
Lanthanum carbonate
Ionic conductivity
Fuel cells
1. Introduction
Over the last three decades, solid oxide fuel cell (SOFC) has been
attracting considerable interest because of their low emission of
pollutants and high energy conversion efciency [1e3]. An
important number of oxide ion conductor materials have been
developed for an application as SOFC's solid electrolytes. At present,
the most common materials for this kind of fuel cells are oxide ion
conducting yttria-stabilized zirconia (YSZ) [2e4]. However, the
need of using SOFC at lower temperatures, from 600 to 800 C,
requires new oxide ions conductors with equivalent conductivity
values than YSZ at 1000 C (above 0.1 S cm1).
* Corresponding author.
E-mail addresses: aenor.pons@uniliom.fr (A. Pons), jenny.jouin@unilim.fr
chade), isabelle.julien@unilim.fr
(J. Jouin), emilie.bechade@unilim.fr (E. Be
(I. Julien), olivier.masson@unilim.fr (O. Masson), pierre-marie.geffroy@unilim.fr
(P.M. Geffroy), richard.mayet@unilim.fr (R. Mayet), philippe.thomas@unilim.fr
(P. Thomas), fukuda.koichiro@nitech.ac.jp (K. Fukuda), kagomiya@nitech.ac.jp
(I. Kagomiya).
http://dx.doi.org/10.1016/j.solidstatesciences.2014.10.013
1293-2558/ 2014 Elsevier Masson SAS. All rights reserved.
151
l
S:R
(1)
Ea
s,T s0 ,exp
k,T
(2)
at 450 C
(3)
Fig. 1. Thermal reaction of the La2O3 secondary phases in air according to Bernal et al.
[28].
152
La2O2CO3 reagent cannot be purchased and has to be synthesized at the laboratory. The transformation from La2O3 to La2O2CO3
was followed by TGeDTA analysis under CO2 atmosphere as shown
in Fig. 2.
An endothermic feature is observed at 370 C. It is associated
with a small weight loss and corresponds to a partial dehydratation
of the sample due to its high sensitivity towards water. Then, a
progressive carbonatation of the sample occurs from 470 C to
700 C and results in the formation of La2O2CO3 phase [30].
This is related to a broad exothermic peak and a weight gain of
12%. This carbonate phase is stable until 950 C, and the decarbonatation leads to La2O3 phase at 1025 C. This decarbonatation is
associated with a sharp endothermic peak. Upon decreasing of the
temperature, the lanthanum oxide is carbonated again from 815 C
to 660 C with a strong exothermic effect. Finally, a last exothermic
feature is observed at 485 C without any mass change. This is due
to the allotropic transformation of monoclinic to hexagonal
lanthanum carbonate as shown below.
According to Belous et al. [31], the carbonatation and decarbonatation processes occur into two steps as proposed in the
following equations. This explains the slight deformation/asymmetry of corresponding DTA peaks.
550 C
2La2 O3 CO2 !
La2 O2 CO*3 La2 O3
650 C
(4)
(5)
Fig. 3. In-situ temperature dependent XRD of La2O3 under CO2 atmosphere at the
maximum temperature of 900 C.
The study of the rst in-situ XRD, Fig. 3, shows that La(OH)3
dehydrated at 370 C as seen in DTA (Fig. 2). Indeed, a mixture of
La2O3 and La(OH)3 is observed on XRD diagram measured at room
temperature and only La2O3 can be seen at 400 C. Single phase
hexagonal La2O2CO3 (PDF No 037-0804) detected at 900 C conrms the total carbonatation of our compound. This phase is well
crystallized and remains stable during cooling.
The second in-situ XRD reveals that after heating at higher
temperature than 1000 C, La2O2CO3 decarbonate to form La2O3 as
observed at 1100 C (Fig. 4). During the cooling step toward 600 C,
recarbonatation of La2O3 isn't completed due to low kinetic of the
carbonation reaction. At 600 C, a mixture of three phases La2O3,
monoclinic La2O2CO3 and hexagonal La2O2CO3 is detected. Peaks
are much broader than in the rst cycle, which suggests a much
smaller crystallite size. At 400 C, La2O3 phase is totally transformed
into monoclinic and hexagonal oxycarbonate phases. The intensity
of the hexagonal phase is higher at 400 C than 600 C in agreement
with the DTA peak observed at 485 C (without mass change,
Fig. 2).
Carbonatation from temperature higher than 1000 C leads to a
mixture of hexagonal and monoclinic La2O2CO3. However, pure and
Fig. 4. In-situ temperature dependent XRD of La2O3 under CO2 atmosphere at the
maximum temperature of 1100 C.
(6)
(7)
153
154
Fig. 7. SEM micrographs of (a) La9.13(SiO4)6O1.7, (b) La9.33(SiO4)6O2, (c) La9.53(SiO4)6O2.3 and (d) La9.60(SiO4)6O2.405 synthesized at 1200 C for 4 h and sintered at 1550 C for 8 h.
Conductivity
at 320 C
(S cm1)
La9.13(SiO4)6O1.7
La9.33(SiO4)6O2
La9.53(SiO4)6O2.3
La9.60(SiO4)6O2.4
YSZ
1.3
7.3
1.3
1.8
8.9
106
106
105
105
106
155
References
and
activation
Extrapolated
conductivity
at 800 C
(S cm1)
0.3
0.5
1.1
1.0
6.7
102
102
102
102
102
energy
values
for
Activation
energy (eV)
0.95
0.83
0.84
0.79
1.08
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