# Carbonatation and Decarbonatation Kinetics in the La2O3-La2O2CO3 System under CO2 Gas Flows

Authors: Bahcine Bakiz; Frédéric Guinneton; Madjid Arab; Abdeljalil Benlhachemi; Sylvie Villain; Pierre Satre; Jean-Raymond Gavarri
Journal: Advances in Materials Science and Engineering
 (2010)

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## Abstract

The carbonatation of La2O3 oxide and the decarbonatation of lanthanum carbonate phase La2O2CO3 are investigated using thermal and thermogravimetry analyses under CO2 gas flow. The initial phase La2O3 is first elaborated from pyrolysis of a LaOHCO3 precursor. Then, thermal and thermogravimetry analyses are carried out under CO2 flow, as temperature increases then decreases. The carbonatation kinetics of La2O3 is determined at three fixed temperatures. Electrical impedance spectroscopy is performed to determine the electrical responses associated with ionic mobilities and phase changes, in the temperature range 25 to 900∘C. The electrical conduction during heating under CO2 gas flow should be linked to two regimes of ionic conduction of the carbonate ions. From these electrical measurements, the ionic mobility of carbonate ions CO32− is found to be close to 0.003 ·10−4 cm2 s−1 V−1 at 750∘C for the monoclinic La2O2CO3 phase.


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## Body

## 1. Introduction

The lanthanum-based system La2O3-CO2-H2O is characterized by successive phases LaOHCO3, La2O2CO3, and La2O3, stable in various temperature ranges [1–9], depending on the partial pressures of CO2 and H2O [10–15]. It has been established that the decomposition of the hydroxycarbonate LaOHCO3 under air generally gives the La2O2CO3 dioxycarbonate phase [6]. However, this last phase exists under three polymorphic structural varieties with tetragonal, hexagonal, and monoclinic crystal lattices [16–19]. The carbonatation of La2O3 under pure CO2 generally gives the main La2O2CO3 phase; however, the obtained system can be complex, with presence of several polymorphic structures depending on the experimental synthesis conditions [10, 18, 20]. In their work concerning the TG analysis of the La2O2CO3 phase under CO2 gas, the authors of [2] showed that a small amount of La2O(CO3)2 was probably formed as an additional phase. This phase was also studied by authors of [21].In room conditions, the lanthanum oxide is highly sensitive to environmental water. In a previous study [22], we have established correlations between the thermal decomposition and the electrical responses of compacted pellets of this LaOHCO3 phase, subjected to pyrolysis under air: we have shown that strong variations in conductances accompanied these phase changes.  We have also established that these LaOHCO3, La2O2CO3, and La2O3 phases have the capacity to convert carbon monoxide into CO2 at relatively low temperature: at 200–300°C, the L phase is a good catalyst converting CO into CO2, while it might be sensitive to CO2 only above 500°C.In the present study, we focus our attention on phase changes during carbonatation and decarbonatation processes, respectively, of the La2O3 phase and of the La2O2CO3 phase. The main objective of this approach should reside in connecting the weight variations due to these phase transformations with electrical responses, in order to appreciate their potential efficiency in gas sensing devices. These correlations between mass losses and electrical responses are not known, and they could deliver interesting information on the electrical sensitivity of such systems.


## 2. Experimental Details

The LaOHCO3 hydroxycarbonate was first prepared via a specific route [22, 23] based on a thermal treatment at 80°C of three aqueous solutions of La(NO3)3·6H2O, urea CO(NH2)2, and polyvinyl-pyrrolydine (PVP) polymer. The La2O3 oxide was obtained by pyrolysis of this LaOHCO3 precursor.The various chemical steps can be summarized as follows:(i)
First initial decomposition processes under air as temperature increases (25–1200°C):
(1)LaOHCO3→La2O2CO3[1]+H2O+CO2,(1’)La2O2CO3[1]→La2O3[1]+CO2.(ii)
Carbonatation and decarbonatation under pure CO2 as temperature increases (25–1200°C):
(2)La2O3[1]+CO2→La2O2CO3[2],(2’)La2O2CO3[2]+CO2→La2O3[2]+2CO2.(iii)
Recarbonatation under pure CO2 as temperature decreases (1200 to 25°C):(3)La2O3[2]+CO2→La2O2CO3[3].In the previous equations, in bracket [1 to 3] we have designated phases obtained after a transformation process (decomposition, carbonatation, and decarbonatation). Theses phases have not the same characteristics (various morphologies and specific surfaces).The polycrystalline samples were systematically analyzed by X-ray diffraction, using a D5000 Siemens-Bruker diffractometer, equipped with a copper X-ray source (wavelengthλ=1.5410-10 m), and with a monochromator eliminating Kβ radiation. The experiments were carried out using classical θ-2θ configuration.Thermal and Thermogravimetric analyses (DTA-TG) were carried out using SETARAM DSC 92 equipment, with a thermal rate of10°C/minute, under CO2 pure gas (rate of flow of 33 cm3·s-1).Electrical measurements under CO2 gas flow were performed using a Solartron electrical impedance spectrometer working with a maximal tension of 1 V, in the frequency range 100 to 107 Hz. A reactive homemade cell was used to perform experiments under various gas flows (air, CO2) at various temperatures ranging between 25 and 900°C. The spectrometer delivers Nyquist representations of the resulting impedances recorded at fixed temperatures: the resistance value is classically obtained by extrapolation of the experimental Nyquist circles, and using electrical equivalent circuits (parallel R-C circuits) generated by the software. We have selected specific electrical circuits with a resistance (R) parallel to a constant phase element CPE=(jC*ω)n where the exponent n is comprised between 1 and 0, and C* is a term similar to a capacitance for n=1 (the unit of C* depends on n).To obtain electrical analyses of sample surfaces reacting with gas flows, the powder samples were first compacted under a pressure of 5 kbar in a cylindrical cell. Then, the obtained cylindrical pellet was cut in form of a rectangular plate, with platinum electrodes fixed on two parallel faces (dimensions 2.3× 8 mm). The distance between the electrodes is 9 mm. This configuration (adapted to the reactive cell) allows a determination of the electrical properties of a significant material surface exposed to gas action. In a later step, these results might be used to test a hypothetical gas sensor sensitive to CO2.


## 3. Results

### 3.1. Carbonatation-Decarbonatation Processes

#### 3.1.1. Heating Process under CO2 Flow

The La2O3 sample, initially obtained from thermal decomposition of LaOHCO3, has been subjected to thermal and thermogravimetry analyses under CO2 gas flow, with temperature increasing from 25 to 1200°C. The resulting TG-DTA curves are reported on Figure 1. A strong exothermic DTA peak is observed at 525°C: it is related to the carbonatation of La2O3 with formation of the La2O2CO3 phase. Then, at 960°C, we observe an endothermic feature corresponding with the decomposition of the carbonate phase.  Above 980°C the La2O3 phase stabilizes. A small endothermic feature is observed at 375°C: it might be associated with a partial dehydration of the sample due to the high sensitivity to environmental water of La2O3. The progressive mass evolution observed in the TG curve of Figure 1, as temperature increases, is directly associated with the classical buoyancy. A similar effect will be observed during the cooling process.Figure 1
Weight gain associated with carbonatation of La2O3 (first step): exothermic peak at 520°C linked with weight gain due to formation of the monoclinic La2O2CO3 phase; endothermic peak due to decarbonatation of La2O2CO3 phase and formation of final La2O3 (second step).


#### 3.1.2. Cooling Experiments under CO2 Flow

Using cooling experiments, we have analyzed the carbonatation of La2O3 from 1200°C to 25°C. The results are represented on Figure 2. The formation of La2O2CO3 starts from 820°C and is maximum at 750°C. The exothermic peak associated with the crystallization of La2O2CO3 carbonate is observed at 790°C. This temperature of carbonatation is strongly different from the one obtained during the heating process.Figure 2
Evolution of La2O3 weight during cooling process, under CO2 flow: formation of La2O2CO3 phase (exothermic peak) then relative stabilization of this phase as temperature decreases.At each step involving a stabilized phase, we have carried out X-ray diffraction analyses to identify the obtained phases. We have confirmed that, in the case of thermal decomposition under air of LaOHCO3 phase, two different tetragonal and hexagonal La2O2CO3 structures are simultaneously observed. In the case of carbonatation of the La2O3 phase in the temperature range 500 to 700°C, we observe the formation of the La2O2CO3 phase. The La2O(CO3)2 phase was not observed in our experiments. This fact was previously reported by other authors [10, 18]. On Figure 3, we have reported the X-ray diffraction pattern characteristic of the monoclinic La2O2CO3 phase heated at 520°C under CO2 flow, during 3 hours. The refined cell parameters are a=0.4073±0.0003 nm; b=1.3503±0.0008 nm; c=0.4079±0.0005 nm; β=90.89°. In the pattern, a weak trace of the hexagonal phase (noted as *) is observed.Figure 3
X-ray diffraction pattern of La2O2CO3 (monoclinic) obtained by heating La2O3 at 520°C under CO2 flow. Trace of hexagonal phase (noted *).


### 3.2. Kinetics Study of Carbonatation of La2O3 at Fixed Temperatures

We have performed a weight analysis of the La2O3 powder, obtained from the thermal decomposition of the initial LaOHCO3 phase, under CO2 gas flow at three constant temperatures. The CO2 gas flow rate was 33 cm3·s-1. In the SETARAM equipment, a fast temperature increase is first applied to the sample, and then, the temperatures are successively fixed to 450, 480, and 500°C. The three initial masses of La2O3 are successively (at T=450, 480, and 500°C) m0=74.36 mg, 70.73 mg, and 39.26 mg. The data evolutions have been interpreted in terms of an elemental Avrami’s model [24] (using a single mechanism approach):
(4)Δm=Δm0[1-exp(-k·tp)],(i)
t is the reaction time;(ii)
Δm0 is the  limit mass of CO2 involved in the carbonate formation La2O2CO3 from a mass m0 of La2O3;(iii)
Δm is the CO2 mass having reacted with La2O3 at the time t;(iv)
k is a kinetics parameter depending of temperature;(v)
p is the exponent characteristic of the reaction mechanism (p>2 for complex mechanisms, p<1, for example, for mechanisms involving diffusion barriers).To test the degree of validity of this Avrami’s model, we have reported the functionY versus ln(t) on Figure 4:
(5)Y=ln[-ln(Δm0-Δm)Δm0]=ln(k)+pln(t).
For a single crystal growth mechanism, the variation of Y versus ln(t) should have been linear.  Presently, the representation of Figure 4 is not linear: this should be mainly due to the existence of at least two different crystal growth mechanisms, with two periods of mass gain corresponding to two behaviors.Figure 4
Test of Avrami’s model validity: the representation ofY=ln[-ln(Δm0-Δm)/Δm0] versus ln(t) (t in mn) shows that two main types of behaviors can be observed as time increases.In Table1, we have reported the values of the kinetics parameters k1 and k2 and exponents p1 and p2, corresponding with the two different behaviors in which a linear correlation might be observed. The parameters k1, p1 are relative to the first period depending on temperature, and the parameters k2, p2 are relative to the second period. The k1 and k2 are thermally activated with activation energies of, respectively, 7.6 and 2.8 eV. The p1 exponent is quasi-constant, while the p2 exponent is close to 1 at 450°C and becomes very weak at higher temperatures.Table 1
Parameters extracted from Avrami’s model:k1 and k2 kinetics parameters and p1 and p2 exponents, respectively, associated with the fast and slow regimes (1st and 2nd periods).
1st period2nd periodT (°C)Time range (min)k1p1Time range (min)k2p245045→1121.5 10-73.3167→3200.020.94806→171.4 10-53.930→900.540.35003→71.2 10-33.430→901.100.2Activation energiesE1 (k1)7.6 (eV)Activation energiesE2 (k2)2.8 (eV)The first growth regime should be associated with a fast carbonatation of grain surfaces associated with complex diffusion mechanisms. During this period, a carbonate shell enveloping oxide grains probably should be formed. The second growth regime should be associated with reaction and diffusion in grain cores, with a decrease of the reaction rate due to the carbonate shell: the resulting slow diffusion regime could govern the global reaction speed.


### 3.3. Electrical Analyses under CO2 Gas Flows

To correlate the phase modifications to electrical behaviors, we have analyzed compacted powder samples in the electrical cell. In this experiment, a rectangular compacted sample resulting from the total decomposition of the initial LaOHCO3 sample has been subjected to a progressive heating, under pure CO2 gas flow. Between 600 and 700°C, carbonatation occurs, thus involving a strong increase in conductance mainly due to the ionic mobility of CO32- carbonate ions. Then, above 750°C decarbonation occurs, involving a decrease of conductance due to CO32- carbonate ions elimination and formation of La2O3.  This oxide should be formed at 950°C.On Figure5, we have reported the ln(Σ) values versus temperature (total Σ values). We observe a strong decrease of ln(Σ) between 450°C and 750°C: the carbonatation of La2O3 should start from 450°C, with a first regime up to 600°C and a second regime up to 750°C. Two activation energies for the conduction behavior can be determined: 2.5 (first regime) and 1.4 eV (second regime). In this carbonatation domain, the ionic conduction plays a major role with mobile species CO32-.Figure 5
Evolution ofln(Σ) versus 103/T of initial La2O3 sample during its carbonatation and decarbonatation, in the temperature range 300 to 950°C, under a constant CO2 gas flow: (a) starting step of carbonatation between 450 and 750°C with two conduction regimes; (b) decarbonatation step above 750°C.Above750°C, we observe a strong decrease in the ln(Σ) values: in this temperature range, decarbonatation occurs in a continuous way, with the elimination of CO32- ions. As La2O3 phase stabilizes, the resistance reaches a stabilized value.Using the observed valueΣ=1.7·10-4 Ω-1 at 750°C (on Figure 5: maximum value of Σjust before decomposition), and considering as negligible the conductance of La2O3 at the same temperature (close to 10-8 to 10-9 Ω-1 at 750°C), we have evaluated an ionic conductance due to CO32- ions to ΔΣ=1.7·10-4 Ω-1. From this evaluation of ΔΣ, we have determined the order of magnitude of the carbonate ion mobility u(CO32-) at 750°C. Other values could be derived from the data obtained in the temperature range 450 to 700°C. The concentration of carbonate ions Cion has been calculated from the effective density of the sample μ=5.1 g·cm-3 (for a theoretical crystal density of 6.51 g.cm-3) and using the sample volume V=0.1656 cm3. A value of Cion=0.0155 mol·cm-3 has been obtained. To determine the mobility, we have used the classical relations:
(6)ΔΣ=σSL,σ=Q·Cion·u(ion),
where σ is the conductivity, S and L are the surface and separation distance of the two electrodes, and where Q=193000 C·mol-1. The relation giving the conductivity assumes an activity coefficient of 1: it only delivers an order of magnitude for the mobility.We have obtained an order of magnitude ofu(CO32-) = (0.003±0.001) 10-4 cm2 s-1 V-1 for a carbonate ion moving at 750°C mainly along grain boundaries (or grain surfaces), and partly in the grain cores. This relatively high mobility can be associated with the activation energy of 1.4 eV (in the temperature range 600 to 750°C) as calculated above.


## 3.1. Carbonatation-Decarbonatation Processes

### 3.1.1. Heating Process under CO2 Flow

The La2O3 sample, initially obtained from thermal decomposition of LaOHCO3, has been subjected to thermal and thermogravimetry analyses under CO2 gas flow, with temperature increasing from 25 to 1200°C. The resulting TG-DTA curves are reported on Figure 1. A strong exothermic DTA peak is observed at 525°C: it is related to the carbonatation of La2O3 with formation of the La2O2CO3 phase. Then, at 960°C, we observe an endothermic feature corresponding with the decomposition of the carbonate phase.  Above 980°C the La2O3 phase stabilizes. A small endothermic feature is observed at 375°C: it might be associated with a partial dehydration of the sample due to the high sensitivity to environmental water of La2O3. The progressive mass evolution observed in the TG curve of Figure 1, as temperature increases, is directly associated with the classical buoyancy. A similar effect will be observed during the cooling process.Figure 1
Weight gain associated with carbonatation of La2O3 (first step): exothermic peak at 520°C linked with weight gain due to formation of the monoclinic La2O2CO3 phase; endothermic peak due to decarbonatation of La2O2CO3 phase and formation of final La2O3 (second step).


### 3.1.2. Cooling Experiments under CO2 Flow

Using cooling experiments, we have analyzed the carbonatation of La2O3 from 1200°C to 25°C. The results are represented on Figure 2. The formation of La2O2CO3 starts from 820°C and is maximum at 750°C. The exothermic peak associated with the crystallization of La2O2CO3 carbonate is observed at 790°C. This temperature of carbonatation is strongly different from the one obtained during the heating process.Figure 2
Evolution of La2O3 weight during cooling process, under CO2 flow: formation of La2O2CO3 phase (exothermic peak) then relative stabilization of this phase as temperature decreases.At each step involving a stabilized phase, we have carried out X-ray diffraction analyses to identify the obtained phases. We have confirmed that, in the case of thermal decomposition under air of LaOHCO3 phase, two different tetragonal and hexagonal La2O2CO3 structures are simultaneously observed. In the case of carbonatation of the La2O3 phase in the temperature range 500 to 700°C, we observe the formation of the La2O2CO3 phase. The La2O(CO3)2 phase was not observed in our experiments. This fact was previously reported by other authors [10, 18]. On Figure 3, we have reported the X-ray diffraction pattern characteristic of the monoclinic La2O2CO3 phase heated at 520°C under CO2 flow, during 3 hours. The refined cell parameters are a=0.4073±0.0003 nm; b=1.3503±0.0008 nm; c=0.4079±0.0005 nm; β=90.89°. In the pattern, a weak trace of the hexagonal phase (noted as *) is observed.Figure 3
X-ray diffraction pattern of La2O2CO3 (monoclinic) obtained by heating La2O3 at 520°C under CO2 flow. Trace of hexagonal phase (noted *).


## 3.1.1. Heating Process under CO2 Flow

The La2O3 sample, initially obtained from thermal decomposition of LaOHCO3, has been subjected to thermal and thermogravimetry analyses under CO2 gas flow, with temperature increasing from 25 to 1200°C. The resulting TG-DTA curves are reported on Figure 1. A strong exothermic DTA peak is observed at 525°C: it is related to the carbonatation of La2O3 with formation of the La2O2CO3 phase. Then, at 960°C, we observe an endothermic feature corresponding with the decomposition of the carbonate phase.  Above 980°C the La2O3 phase stabilizes. A small endothermic feature is observed at 375°C: it might be associated with a partial dehydration of the sample due to the high sensitivity to environmental water of La2O3. The progressive mass evolution observed in the TG curve of Figure 1, as temperature increases, is directly associated with the classical buoyancy. A similar effect will be observed during the cooling process.Figure 1
Weight gain associated with carbonatation of La2O3 (first step): exothermic peak at 520°C linked with weight gain due to formation of the monoclinic La2O2CO3 phase; endothermic peak due to decarbonatation of La2O2CO3 phase and formation of final La2O3 (second step).


## 3.1.2. Cooling Experiments under CO2 Flow

Using cooling experiments, we have analyzed the carbonatation of La2O3 from 1200°C to 25°C. The results are represented on Figure 2. The formation of La2O2CO3 starts from 820°C and is maximum at 750°C. The exothermic peak associated with the crystallization of La2O2CO3 carbonate is observed at 790°C. This temperature of carbonatation is strongly different from the one obtained during the heating process.Figure 2
Evolution of La2O3 weight during cooling process, under CO2 flow: formation of La2O2CO3 phase (exothermic peak) then relative stabilization of this phase as temperature decreases.At each step involving a stabilized phase, we have carried out X-ray diffraction analyses to identify the obtained phases. We have confirmed that, in the case of thermal decomposition under air of LaOHCO3 phase, two different tetragonal and hexagonal La2O2CO3 structures are simultaneously observed. In the case of carbonatation of the La2O3 phase in the temperature range 500 to 700°C, we observe the formation of the La2O2CO3 phase. The La2O(CO3)2 phase was not observed in our experiments. This fact was previously reported by other authors [10, 18]. On Figure 3, we have reported the X-ray diffraction pattern characteristic of the monoclinic La2O2CO3 phase heated at 520°C under CO2 flow, during 3 hours. The refined cell parameters are a=0.4073±0.0003 nm; b=1.3503±0.0008 nm; c=0.4079±0.0005 nm; β=90.89°. In the pattern, a weak trace of the hexagonal phase (noted as *) is observed.Figure 3
X-ray diffraction pattern of La2O2CO3 (monoclinic) obtained by heating La2O3 at 520°C under CO2 flow. Trace of hexagonal phase (noted *).


## 3.2. Kinetics Study of Carbonatation of La2O3 at Fixed Temperatures

We have performed a weight analysis of the La2O3 powder, obtained from the thermal decomposition of the initial LaOHCO3 phase, under CO2 gas flow at three constant temperatures. The CO2 gas flow rate was 33 cm3·s-1. In the SETARAM equipment, a fast temperature increase is first applied to the sample, and then, the temperatures are successively fixed to 450, 480, and 500°C. The three initial masses of La2O3 are successively (at T=450, 480, and 500°C) m0=74.36 mg, 70.73 mg, and 39.26 mg. The data evolutions have been interpreted in terms of an elemental Avrami’s model [24] (using a single mechanism approach):
(4)Δm=Δm0[1-exp(-k·tp)],(i)
t is the reaction time;(ii)
Δm0 is the  limit mass of CO2 involved in the carbonate formation La2O2CO3 from a mass m0 of La2O3;(iii)
Δm is the CO2 mass having reacted with La2O3 at the time t;(iv)
k is a kinetics parameter depending of temperature;(v)
p is the exponent characteristic of the reaction mechanism (p>2 for complex mechanisms, p<1, for example, for mechanisms involving diffusion barriers).To test the degree of validity of this Avrami’s model, we have reported the functionY versus ln(t) on Figure 4:
(5)Y=ln[-ln(Δm0-Δm)Δm0]=ln(k)+pln(t).
For a single crystal growth mechanism, the variation of Y versus ln(t) should have been linear.  Presently, the representation of Figure 4 is not linear: this should be mainly due to the existence of at least two different crystal growth mechanisms, with two periods of mass gain corresponding to two behaviors.Figure 4
Test of Avrami’s model validity: the representation ofY=ln[-ln(Δm0-Δm)/Δm0] versus ln(t) (t in mn) shows that two main types of behaviors can be observed as time increases.In Table1, we have reported the values of the kinetics parameters k1 and k2 and exponents p1 and p2, corresponding with the two different behaviors in which a linear correlation might be observed. The parameters k1, p1 are relative to the first period depending on temperature, and the parameters k2, p2 are relative to the second period. The k1 and k2 are thermally activated with activation energies of, respectively, 7.6 and 2.8 eV. The p1 exponent is quasi-constant, while the p2 exponent is close to 1 at 450°C and becomes very weak at higher temperatures.Table 1
Parameters extracted from Avrami’s model:k1 and k2 kinetics parameters and p1 and p2 exponents, respectively, associated with the fast and slow regimes (1st and 2nd periods).
1st period2nd periodT (°C)Time range (min)k1p1Time range (min)k2p245045→1121.5 10-73.3167→3200.020.94806→171.4 10-53.930→900.540.35003→71.2 10-33.430→901.100.2Activation energiesE1 (k1)7.6 (eV)Activation energiesE2 (k2)2.8 (eV)The first growth regime should be associated with a fast carbonatation of grain surfaces associated with complex diffusion mechanisms. During this period, a carbonate shell enveloping oxide grains probably should be formed. The second growth regime should be associated with reaction and diffusion in grain cores, with a decrease of the reaction rate due to the carbonate shell: the resulting slow diffusion regime could govern the global reaction speed.


## 3.3. Electrical Analyses under CO2 Gas Flows

To correlate the phase modifications to electrical behaviors, we have analyzed compacted powder samples in the electrical cell. In this experiment, a rectangular compacted sample resulting from the total decomposition of the initial LaOHCO3 sample has been subjected to a progressive heating, under pure CO2 gas flow. Between 600 and 700°C, carbonatation occurs, thus involving a strong increase in conductance mainly due to the ionic mobility of CO32- carbonate ions. Then, above 750°C decarbonation occurs, involving a decrease of conductance due to CO32- carbonate ions elimination and formation of La2O3.  This oxide should be formed at 950°C.On Figure5, we have reported the ln(Σ) values versus temperature (total Σ values). We observe a strong decrease of ln(Σ) between 450°C and 750°C: the carbonatation of La2O3 should start from 450°C, with a first regime up to 600°C and a second regime up to 750°C. Two activation energies for the conduction behavior can be determined: 2.5 (first regime) and 1.4 eV (second regime). In this carbonatation domain, the ionic conduction plays a major role with mobile species CO32-.Figure 5
Evolution ofln(Σ) versus 103/T of initial La2O3 sample during its carbonatation and decarbonatation, in the temperature range 300 to 950°C, under a constant CO2 gas flow: (a) starting step of carbonatation between 450 and 750°C with two conduction regimes; (b) decarbonatation step above 750°C.Above750°C, we observe a strong decrease in the ln(Σ) values: in this temperature range, decarbonatation occurs in a continuous way, with the elimination of CO32- ions. As La2O3 phase stabilizes, the resistance reaches a stabilized value.Using the observed valueΣ=1.7·10-4 Ω-1 at 750°C (on Figure 5: maximum value of Σjust before decomposition), and considering as negligible the conductance of La2O3 at the same temperature (close to 10-8 to 10-9 Ω-1 at 750°C), we have evaluated an ionic conductance due to CO32- ions to ΔΣ=1.7·10-4 Ω-1. From this evaluation of ΔΣ, we have determined the order of magnitude of the carbonate ion mobility u(CO32-) at 750°C. Other values could be derived from the data obtained in the temperature range 450 to 700°C. The concentration of carbonate ions Cion has been calculated from the effective density of the sample μ=5.1 g·cm-3 (for a theoretical crystal density of 6.51 g.cm-3) and using the sample volume V=0.1656 cm3. A value of Cion=0.0155 mol·cm-3 has been obtained. To determine the mobility, we have used the classical relations:
(6)ΔΣ=σSL,σ=Q·Cion·u(ion),
where σ is the conductivity, S and L are the surface and separation distance of the two electrodes, and where Q=193000 C·mol-1. The relation giving the conductivity assumes an activity coefficient of 1: it only delivers an order of magnitude for the mobility.We have obtained an order of magnitude ofu(CO32-) = (0.003±0.001) 10-4 cm2 s-1 V-1 for a carbonate ion moving at 750°C mainly along grain boundaries (or grain surfaces), and partly in the grain cores. This relatively high mobility can be associated with the activation energy of 1.4 eV (in the temperature range 600 to 750°C) as calculated above.


## 4. Discussion-Conclusions

The carbonatation kinetics of La2O3 has been determined at various temperatures. In the case of mass gain analyses, an elemental Avrami’s approach has allowed determining a complex two-step mechanism of growth: (i) a fast surface carbonatation with carbonate shell formation and (ii) a diffusion mechanism in grain cores with slower kinetics. The electrical analyses argue in favor of two different conduction mechanisms: during carbonatation at increasing temperature, the first activation energy (2.5 eV) should be associated with ionic conduction at grain surfaces, and the second activation energy (1.4 eV) should due to an increasing contribution of the conduction in the bulk. Correlatively, it should be remarked that, in thermal analyses, the stability range is observed from 500 to 850°C, while in electrical analyses, this stability range is observed from 500 to 750°C. This can be explained by the two different heating kinetics conditions used in the two experiments.Finally, we observe a relatively high ionic mobility mainly due to theCO32- ions in La2O2CO3 at 750°C. In our evaluation, we have neglected the ionic conduction of oxygen ions.It should be concluded that these phase modifications associated with high ionic conduction might be used as electrical sensitive material to detect CO2, provide temperatures that could be fixed close to 400–550°C (carbonatation of La2O3 phase) and 750°C to restore the initial La2O3 phase.



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*Source: 360597-2010-09-16.xml*