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Solid State Sciences 38 (2014) 150e155

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Solid State Sciences


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Review

Study of the formation of the apatite-type phases


La9.33x(SiO4)6O23x/2 synthesized from a lanthanum oxycarbonate
La2O2CO3
chade a, *, I. Julien a, O. Masson a, P.M. Geffroy a, R. Mayet a,
A. Pons a, J. Jouin a, E. Be
a
b
P. Thomas , K. Fukuda , I. Kagomiya b
a
Science des Proc
ed
es C
eramiques et de Traitements de Surface, UMR CNRS 7315, Centre Europ
een de la C
eramique e Facult
e des Sciences et Techniques e
ENSCI, 12 Rue Atlantis, 87068 Limoges Cedex, France
b
Department of Environmental and Materials Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan

a r t i c l e i n f o

a b s t r a c t

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.

In this context, lanthanum silicates of general formula


La9.33x(SiO4)6O23x/2 and with apatite-type structure appeared as
attractive ionic conductors and are considered as potential candidates to operate as electrolyte for SOFC in intermediate temperatures (700e900  C) [5e11]. Their structure is based on a 3dimensional organization of isolated silica tetrahedra, forming
large lanthanum oxide channels oriented along c-axis [12e14]. This
explains that they can exhibit high anisotropic conductivity in the c
direction increasing with the incorporation of interstitial oxygen
inside large channel (formula with x > 0) [6e8,10,13e16]. For
example, highly oriented La9.5(SiO4)6O2.5 apatite crystals of a few
micrometers have been prepared from La2Si2O7 and La2SiO5 with a
long time heating at 1650  C and exhibit a high conductivity value
along c-axis of 7.9  102 S cm1 at 800  C with a low activation
energy value of 0.35 eV [13]. This conductivity is higher than the
2.39  102 S cm1 measured at 800  C on a c-oriented apatite
polycrystal of La9.33(SiO4)6O2 [6]. No difference in activation energy
values between these compositions is observed. It suggests that
both materials present the same oxygen interstitial mechanism
along the channel [6,13,16].

A. Pons et al. / Solid State Sciences 38 (2014) 150e155

Studies performed on the synthesis of apatite-type lanthanum


silicates by solid state reactions have indicated that thermal treatments at high temperatures and long time are required to prepare
pure apatite-type lanthanum silicate when starting from La2O3 and
SiO2 precursors [17e20]. These high temperatures present some
disadvantages such as a low control of the particle morphology and
material density. Recent works [21e25] have shown that bulk and
grain boundary conductivities may highly depend on the microstructure of the apatite sample, especially porosity and grain size. It
was previously demonstrated that pure apatite-type structure
could be synthesized at a lower temperature of 1200  C using an
appropriate thermal treatment and synthesis process [21].
This paper deals with the synthesis of pure oxyapatites using
lanthanum oxycarbonate La2O2CO3 as a new reagent. Compositions
La9.33x(SiO4)6O23x/2 (0.2 < x < 0.27) were synthesized for the
present study. La9.33(SiO4)6O2 composition was used as a reference material because of its oxygen stoichiometry. The others
were oxygen under- and over-stoichiometric (x < 0 and x > 0
respectively) in order to study phase diagram compositions and to
characterize evolution of electrical properties in relation to the
oxygen stoichiometry (or x) in apatite phase.
2. Materials and methods
2.1. Reagents
All the samples were elaborated by solid state reaction using
high purity powders of La2O3 (Aldrich, 99.9%) and SiO2 (Prolabo,
>99.5%) as starting reagents. The synthesis procedure is discussed
in the results section.
2.2. Characterization
X-ray powder diffraction (XRPD) patterns of the calcined powders were recorded with CuKa radiation in the 2q range 20e50 on
a q/2q diffractometer (Siemens D5000, Germany) with a step of
0.04 and exposure time of 2.8 s per step. The crystalline phases
were identied from a comparison of the registered patterns with
the International Center for Diffraction Data (ICDD) powder
diffraction les (PDF).
A D8 advance diffractometer (Bruker, Germany) with CuKa1 radiation was used to characterize sintered samples at room temperature and to study the in-situ evolution of La2O3 reagent under
CO2 ux as a function of temperature. For the former experiment,
patterns were recorded in the 2q range 10e60 with a step of 0.014
and exposure time of 87 s per step. For the latter experiment, an
exposure time of 350 s per step and Anton Paar HTK1200N Furnace
with a controlled CO2 ow were used.
The carbonatation of lanthanum oxide was also investigated by
thermogravimetric and differential thermal analysis (TGeDTA, TA
instruments STD2960) from room temperature to 1200  C in platinum crucible with a heating/cooling rate of 10  C min1 and a CO2
ow rate of 20 mL min1. The sample mass was about 40 mg.
Microstructural aspects of sintered pellets were revealed by
scanning electron microscopy (Philips XL30 SEM microscope).
Surfaces of the pellets were treated before observation by polishing
with SiC paper and thermal etching at 1500  C for 15 min. The
relative density of the sintered samples was evaluated by image
analysis using ImageJ software [26].
In order to perform electrical characterization, metallic electrodes were deposited on the pellets using platinum paint (Ferro,
6402-1001) calcined at 1000  C for 1 h with 5  C/min heating rate
and 2  C min1 cooling rate. Electrical properties were measured
using a Solartron 1260 Impedance/Gain Phase Analyzer. The samples have been characterized in static air by the complex

151

impedance method in the frequency range from 1 Hz to 5 MHz with


an ac signal of 300 mV. Curve tting and resistance calculations
were done using Z-live software [27]. The total conductivities were
calculated using the Equation (1):

l
S:R

(1)

where l is the sample thickness, S is the electrode area of the sample


surface and R is the total bulk resistance. Activation energies (Ea)
were calculated by tting the conductivity data using the Arrhenius
relation for thermally activated conduction, which is given by
equation (2).



Ea
s,T s0 ,exp
k,T

(2)

where s, s0, Ea, k, T are the conductivity, pre-exponential factor,


activation energy, Boltzmann constant and absolute temperature,
respectively.
3. Results and discussion
3.1. Preparation and characterization of La2O2CO3 precursor
Previous work revealed that La2O3 reagent was unstable and led
to the formation of La(OH)3 and La2(OH)4CO3 phases at ambient
atmosphere. These two phases decompose when temperature raises above 300  C leading to the formation of LaOOH and hexagonal
La2O2CO3 respectively, as shown in Fig. 1.
When the La2O3/SiO2 mixture was calcined to obtain apatite,
La2Si2O7 impurity was observed at 450  C; the formation of this
secondary phase during the thermal treatment is likely due to the
existence of LaOOH phase according Equation (3).

2LaOOH 2SiO2 /La2 Si2 O7 H2 O

at 450  C

(3)

A preliminary La2O3 treatment (800  C) and furnace pre-heating


at 450  C was necessary in order to use lanthanum oxide as a reagent and to avoid LaOOH phase formation above 300  C.
As La2O2CO3 reagent is more stable in this range of temperature,
the direct use of this reagent is a good solution to simplify the
synthesis procedure. Moreover, Kobayashi et al. [29] reported that
the formation of lanthanum silicate apatite was in good agreement
with the decomposition of hexagonal lanthanum oxycarbonate
during solegel synthesis.

Fig. 1. Thermal reaction of the La2O3 secondary phases in air according to Bernal et al.
[28].

152

A. Pons et al. / Solid State Sciences 38 (2014) 150e155

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

La2 O2 CO*3 La2 O3 CO2 !


2La2 O2 CO3

(4)

(5)

In-situ X-ray diffraction as a function of the temperature was


performed under a ow of CO2 using La2O3 as starting reagent, in
order to understand the main reactions occurring during thermal
treatments. The maximum temperature of the experiments was
either 900  C (Fig. 3) or 1100  C (Fig. 4).
The rst cycle, represented in Fig. 3, was used to understand the
mechanism of the carbonatation occurring with increasing temperature and the stability of the obtained lanthanum carbonate.
The second one (Fig. 4) follows the second carbonatation observed
from La2O3 during the temperature decrease, especially the feature
observed at 485  C on the DTA curve.
La2O3 is highly sensitive to atmospheric water and leads to the
formation of La(OH)3 which weak peaks are visible on starting
room temperature diffractograms.

Fig. 2. TGeDTA analyses of La2O3 precursor calcined under CO2.

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.

A. Pons et al. / Solid State Sciences 38 (2014) 150e155

stable hexagonal phase can be synthesized at lower temperature as


show in Fig. 3. The thermal stability of this phase is crucial to avoid
formation of La2Si2O7 secondary phase [17] as reported in equation
(3).

3.2. Synthesis of oxyapatite powders


Powders with the nominal composition La9.33x(SiO4)6O23x/2
(x 0.2, 0, 0.2 and 0.27) were synthesized using stoichiometric
amounts of La2O2CO3 and SiO2 in accordance with Equation (6).

9:33 x=2 La2 O2 CO3 6 SiO2 /La9:33x SiO4 6 O23x=2


9:33 x=2 CO2

(6)

In order to obtain our reagent, La2O3 was calcined at 900  C


under CO2 for 2 h with a heating and cooling rate of 10  C/min, on
platinum sheets under a continuous ux of 0.5 L h1 of CO2 in order
to be carbonated into La2O2CO3 phase according to the reaction
following.

La2 O3 CO2 /La2 O2 CO3

(7)

In opposite to La2O3, the La2O2CO3 precursor is not hygroscopic


and the lanthanum molar ratio could be precisely determined.
Stoichiometric amounts of SiO2 and La2O2CO3 (see Equation (6)),
were attrition milled in ethanol (2 h 30 min, 180 rpm) using a Union
Process 01-Lab Attritor. Then, the ethanol was evaporated under
vacuum at 45  C (P 100 mbar). During this step, hexagonal
La2O2CO3 was stable and was not transformed into La(OH)3 phase
as observed with La2O3 reagent.
Then these mixtures were calcined at different temperatures
from 1000 to 1500  C during 4 h with a heating and cooling rate of
10  C/min and phases were identied by XRD (example of
La9.33(SiO4)6O2 in Fig. 5).
It can be observed that the powders calcined at 1000e1200  C
presented apatite crystalline phase and traces of La2O3 and La2SiO5
impurities. No trace of La2Si2O7 is observed, which conrms the
inuence of lanthanum oxycarbonate on the synthesis. Moreover,
traces of secondary phase La2SiO5 are no longer detected from
1300  C for stoichiometric phase and from 1400  C for the other
samples. La2O3 reagent is no longer observed from 1300  C.

Fig. 5. XRD patterns of synthesized La9.33(SiO4)6O2 powders after calcination at


1000  C, 1100  C, 1200  C, 1300  C, 1400  C and 1500  C for 4 h.

153

Apatite powders, without La2SiO5 or La2Si2O7 secondary phases


and with the nominal composition La9.33x(SiO4)6O23x/2 (x 0.2,
0, 0.2 and 0.26), are synthesized at 1400  C for 4 h. This synthesized
temperature is signicantly lower than the ones previously reported in literature (1750  C/4 h for Yoshioka [11] or 1700  C/2 h for
Sansom [18] for example). Actually, according to ref [8,9], La10(SiO4)
O3 were synthesized, but no data on the relevant atomic positions
were published up today. In our laboratory, the experimental attempts in that direction were unsuccessful.
3.3. Microstructural and electrical characterizations
The La9.13(SiO4)6O1.7, La9.33(SiO4)6O2, La9.53(SiO4)6O2.3 and
La9.60(SiO4)6O2.405 powders calcined at 1200  C were manually
grinded and isostatically pressed at 2000 bar for 1 min. Then the
samples were sintered on platinum sheets at 1550  C for 8 h with a
heating rate of 10  C min1 and natural cooling down to room
temperature. The obtained pellets were ~6 mm in diameter and
~2 mm thickness.
X-ray diffraction patterns of the crushed sintered samples are
presented in Fig. 6. Although traces of La2SiO5 phase in the powders
calcined below 1300  C were observed, samples sintered at 1550  C
were single oxyapatite phase without any other impurity.
SEM micrographs obtained for the four pellets of different
composition are presented in Fig. 7. It can be seen that some pores
exists in the sintered body; all of them are located at the grain
boundaries or at the triple points. When the composition is overstoichiometric in oxygen, the pores quantity is more important
which lead to a small decrease of the relative density. The relative
density of these samples, calculated from SEM image analysis, was
over 98.5% after sintering at 1550  C for 8 h (Fig. 7). Although no
optimization of the sintering time was performed, it seems that
oxygen vacancies lead to a signicant increase of the grain size
(6.2 mm average) as compared to stoichiometric or over-stoichiometric compositions, due to higher ion mobility.
3.4. Electrical conductivity
Electrical characterizations were carried out on pellets obtained
from the experimental procedure presented below. Complex
impedance spectra were analyzed using the program Z-live
developed by S. Georges [26], in order to quantitatively estimate
the total conductivity of the samples. Fig. 8 shows an example of
complex impedance plan plot obtained for the composition
La9.13(SiO4)6O1.7 at 320  C. The contributions of grain bulk, grain
boundaries and electrodes were deconvoluted by using a parallel
equivalent circuit. The deconvolution of the different contributions

Fig. 6. XRD patterns of La9.13(SiO4)6O1.7, La9.33(SiO4)6O2, La9.53(SiO4)6O2.3 and


La9.60(SiO4)6O2.405 sintered at 1550  C for 8 h from powders synthesized at 1200  C.

154

A. Pons et al. / Solid State Sciences 38 (2014) 150e155

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.

is shown as dashed-line semicircle for the sample La9.13(SiO4)6O1.7


presented in Fig. 8. The grain boundary contribution for the sample
La9.13(SiO4)6O1.7 is higher than the grain bulk contribution, as reported in previous works [17]. However, it is not possible to
distinguish the contribution of grain bulk and grain boundaries for
other samples. Further studies are required to distinguish the effect
of oxygen over or under-stoichiometry compositions on the grain
bulk and grain boundary conductivities of apatite.
Total electrolyte resistance was calculated by addition of the
resistances at high frequency (RHF) and at medium frequency (RMF),
corresponding respectively to the bulk and the grain boundary
contributions. Fig. 9 shows an Arrhenius plot of total conductivities

Fig. 8. Example of deconvolution, using Z-live software, of complex impedance plan


plot measured under air atmosphere at 320  C for La9.13(SiO4)6O1.7.

versus temperature. Extrapolated conductivities at 800  C and


activation energy values are reported in Table 1.
The high temperatures conductivity values for apatite material
were lower than that reported for YSZ [4]. This was probably due to
a small grain size in our pellets. The microstructures and thus
properties of our materials were not optimized but can be modied
with an appropriate thermal treatment.
The conductivity is directly correlated with the amount of oxygen in the apatite structure. The activation energy is the highest
(0.95 eV) for the composition with the lowest oxygen content
(corresponding to oxygen under-stoichiometry composition). For
stoichiometric and over-stoichiometric compositions, the activation energy (~0.8 eV) is similar, suggesting that the conduction
mechanism is similar. This value is measured on polycrystalline

Fig. 9. Total ionic conductivity for the La9.13(SiO4)6O1.7, La9.33(SiO4)6O2, La9.53(SiO4)6O2.3


and La9.60(SiO4)6O2.405 compositions. Data on polycrystalline YSZ (8% mol Y2O3) [4] are
shown for comparison.

A. Pons et al. / Solid State Sciences 38 (2014) 150e155


Table 1
Conductivities at 320  C, 800  C
La9.33x(SiO4)6O23x/2 materials and YSZ.
Composition

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

material, and is higher than what can be obtained on oriented or


monocrystalline material. However these results are in good
agreement with what is reported in literature [11,13,17,32] and assume that the oxide-ionic conductivity in this apatite-type structure is due to interstitial oxide ions [10,15,16,23]. This new
elaboration route has no damaging effect on the ionic conductivity.
4. Conclusions
Homogeneous apatite-type La9.13(SiO4)6O1.7, La9.33(SiO4)6O2,
La9.53(SiO4)6O2.3 and La9.60(SiO4)6O2.405 have been prepared successfully by a new process consisting in hexagonal La2O2CO3 and
SiO2 solid state reaction. The use of lanthanum dioxycarbonate as
reagent makes the weighting step easier. Moreover, the formation
of La2Si2O7 secondary phase, which appears by chemical reaction
between LaOOH and SiO2, can be completely eliminated by using
La2O2CO3 instead of La2O3. Pure dense pellets were prepared by
sintering at 1550  C of isostatically-pressed powders calcined at
1200  C. The oxygen content dependence of electrical properties is
in good agreement with conduction mechanisms previously
observed. The highest ionic conductivity s800 C 1.102 S cm1 and
lowest activation energy 0.79 eV were obtained for the composition
La9.60(SiO4)6O2.405 with the highest oxygen content. This new
experimental procedure for elaboration of pure apatite dense pellets using lanthanum carbonate reagent seems to have no
damaging effect on the electrical properties of this series of
materials.
Investigations are in progress to improve the microstructure of
the pellets and study the effect of the grain size and density on the
conductivity.
Acknowledgments
The authors wish to thank R. Kaneko and Y. Shimono for their
help during the synthesis process. Limousin Region is gratefully
acknowledged for its nancial support.

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