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Redox behavior and transport properties of La0.5- 2xCexSr0.5+xFeO3- δ and La0.5+2yFe1- yNbyO3- δ perovskites

Identifieur interne : 000229 ( Russie/Analysis ); précédent : 000228; suivant : 000230

Redox behavior and transport properties of La0.5- 2xCexSr0.5+xFeO3- δ and La0.5+2yFe1- yNbyO3- δ perovskites

Auteurs : RBID : Pascal:07-0297918

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Abstract

The effects of doping the mixed-conducting (La,Sr)FeO3-δ system with Ce and Nb have been examined for the solid-solution series, La0.5_2xCe.rSr0.5+xFeO3-δ (x = 0-0.20) and La0.5-2ySr0.5+2yFe1-yNbyO3-δ(y = 0.05-0.10). Mossbauer spectroscopy at 4.1 and 297 K showed that Ce4+ and Nb5+ incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for L0.3Sr0.7Fe0.90Nb0.10-δ at 923-1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10-5-0.5 atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe4+ concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 x 10∼3 for La0.3Sr0.7Fe0.9Nb0.1O3-δcf. 1.3 x 10 for La0.5Sr0.5FeO3-δ at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0-21.2) x 10-6K-1 at 780-1080 K.

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Pascal:07-0297918

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<title xml:lang="en" level="a">Redox behavior and transport properties of La
<sub>0.5-</sub>
<sub>2x</sub>
Ce
<sub>x</sub>
Sr
<sub>0.5+x</sub>
FeO
<sub>3-</sub>
<sub>δ</sub>
and La
<sub>0.5+2y</sub>
Fe
<sub>1-</sub>
<sub>y</sub>
Nb
<sub>y</sub>
O
<sub>3-</sub>
<sub>δ</sub>
perovskites</title>
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<name sortKey="Kharton, V V" uniqKey="Kharton V">V. V. Kharton</name>
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<name sortKey="Patrakeev, M V" uniqKey="Patrakeev M">M. V. Patrakeev</name>
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<sZ>1 aut.</sZ>
<sZ>3 aut.</sZ>
<sZ>8 aut.</sZ>
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<name sortKey="Samakhval, V V" uniqKey="Samakhval V">V. V. Samakhval</name>
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<s1>Institute of Physicochemical Problems, Belarus State University', 14 Leningradskaya Street</s1>
<s2>220050 Minsk</s2>
<s3>BLR</s3>
<sZ>1 aut.</sZ>
<sZ>5 aut.</sZ>
<sZ>9 aut.</sZ>
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<date when="2007">2007</date>
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<idno type="RBID">Pascal:07-0297918</idno>
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<title level="j" type="main">Solid state sciences</title>
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<keywords scheme="KwdEn" xml:lang="en">
<term>Atmospheric pressure</term>
<term>Cerium</term>
<term>Charge carriers</term>
<term>Doping</term>
<term>Electrical conductivity</term>
<term>Electron delocalization</term>
<term>High temperature</term>
<term>Indium additions</term>
<term>Ionic conductivity</term>
<term>Iron</term>
<term>Lanthanum</term>
<term>Mixed conductivity</term>
<term>Moessbauer effect</term>
<term>Nonstoichiometry</term>
<term>P type conductivity</term>
<term>Partial pressure</term>
<term>Permeation</term>
<term>Perovskites</term>
<term>Pressure effects</term>
<term>Rare earth alloys</term>
<term>Solid solutions</term>
<term>Strontium</term>
<term>Superlattices</term>
<term>Thermal expansion coefficient</term>
<term>Thermoelectric power</term>
<term>Thermogravimetry</term>
<term>Transport processes</term>
<term>Transport properties</term>
</keywords>
<keywords scheme="Pascal" xml:lang="fr">
<term>Propriété transport</term>
<term>Phénomène transport</term>
<term>Dopage</term>
<term>Conductivité mixte</term>
<term>Lanthanide alliage</term>
<term>Superréseau</term>
<term>Conductivité électrique</term>
<term>Solution solide</term>
<term>Effet Mössbauer</term>
<term>Délocalisation électronique</term>
<term>Porteur charge</term>
<term>Non stoechiométrie</term>
<term>Thermogravimétrie</term>
<term>Haute température</term>
<term>Perovskites</term>
<term>Cérium</term>
<term>Fer</term>
<term>Lanthane</term>
<term>Strontium</term>
<term>Perméation</term>
<term>Pouvoir thermoélectrique</term>
<term>Pression partielle</term>
<term>Effet pression</term>
<term>Conductivité type p</term>
<term>Conductivité ionique</term>
<term>Pression atmosphérique</term>
<term>Coefficient dilatation thermique</term>
<term>Addition indium</term>
<term>La</term>
<term>Sr</term>
<term>8233</term>
<term>7680</term>
</keywords>
<keywords scheme="Wicri" type="concept" xml:lang="fr">
<term>Dopage</term>
<term>Fer</term>
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<front>
<div type="abstract" xml:lang="en">The effects of doping the mixed-conducting (La,Sr)FeO
<sub>3-δ</sub>
system with Ce and Nb have been examined for the solid-solution series, La
<sub>0.5_2x</sub>
Ce.rSr
<sub>0.5+x</sub>
FeO
<sub>3-δ</sub>
(x = 0-0.20) and La
<sub>0.5-2y</sub>
Sr
<sub>0.5+2y</sub>
Fe
<sub>1-y</sub>
Nb
<sub>y</sub>
O
<sub>3-δ</sub>
(y = 0.05-0.10). Mossbauer spectroscopy at 4.1 and 297 K showed that Ce
<sup>4+</sup>
and Nb
<sup>5+</sup>
incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for L
<sub>0.3</sub>
Sr
<sub>0.7</sub>
Fe
<sub>0.90</sub>
Nb
<sub>0.10-δ</sub>
at 923-1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10
<sup>-5</sup>
-
<sup>0.5</sup>
atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe
<sup>4+</sup>
concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 x 10
<sup>∼3</sup>
for La
<sub>0.3</sub>
Sr
<sub>0.7</sub>
Fe
<sub>0.9</sub>
Nb
<sub>0.1</sub>
O
<sub>3-δ</sub>
cf. 1.3 x 10 for La
<sub>0.5</sub>
Sr
<sub>0.5</sub>
FeO
<sub>3-δ</sub>
at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0-21.2) x 10
<sup>-6</sup>
K
<sup>-1</sup>
at 780-1080 K.</div>
</front>
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<s1>Redox behavior and transport properties of La
<sub>0.5-</sub>
<sub>2x</sub>
Ce
<sub>x</sub>
Sr
<sub>0.5+x</sub>
FeO
<sub>3-</sub>
<sub>δ</sub>
and La
<sub>0.5+2y</sub>
Fe
<sub>1-</sub>
<sub>y</sub>
Nb
<sub>y</sub>
O
<sub>3-</sub>
<sub>δ</sub>
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<s1>KHARTON (V. V.)</s1>
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<s1>SAMAKHVAL (V. V.)</s1>
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<fA14 i1="01">
<s1>Department of Ceramics and Glass Engineering, CICECO, University of Aveiro</s1>
<s2>3810-193 Aveiro</s2>
<s3>PRT</s3>
<sZ>1 aut.</sZ>
<sZ>3 aut.</sZ>
<sZ>8 aut.</sZ>
</fA14>
<fA14 i1="02">
<s1>Institute of Physicochemical Problems, Belarus State University', 14 Leningradskaya Street</s1>
<s2>220050 Minsk</s2>
<s3>BLR</s3>
<sZ>1 aut.</sZ>
<sZ>5 aut.</sZ>
<sZ>9 aut.</sZ>
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<fA14 i1="03">
<s1>Chemistry Department, ITNICFMC-UL, Estrada Nacional 10</s1>
<s2>2686-953 Sacavem</s2>
<s3>PRT</s3>
<sZ>2 aut.</sZ>
<sZ>7 aut.</sZ>
</fA14>
<fA14 i1="04">
<s1>institute of Ceramics and Glass, CSIC, Cantoblanco</s1>
<s2>28049 Madrid</s2>
<s3>ESP</s3>
<sZ>4 aut.</sZ>
</fA14>
<fA14 i1="05">
<s1>Institute of Solid State Chemistry, Ural Division of RAS, 91 Pervomaiskaya Street</s1>
<s2>Ekaterinburg 620219</s2>
<s3>RUS</s3>
<sZ>6 aut.</sZ>
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<fC01 i1="01" l="ENG">
<s0>The effects of doping the mixed-conducting (La,Sr)FeO
<sub>3-δ</sub>
system with Ce and Nb have been examined for the solid-solution series, La
<sub>0.5_2x</sub>
Ce.rSr
<sub>0.5+x</sub>
FeO
<sub>3-δ</sub>
(x = 0-0.20) and La
<sub>0.5-2y</sub>
Sr
<sub>0.5+2y</sub>
Fe
<sub>1-y</sub>
Nb
<sub>y</sub>
O
<sub>3-δ</sub>
(y = 0.05-0.10). Mossbauer spectroscopy at 4.1 and 297 K showed that Ce
<sup>4+</sup>
and Nb
<sup>5+</sup>
incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for L
<sub>0.3</sub>
Sr
<sub>0.7</sub>
Fe
<sub>0.90</sub>
Nb
<sub>0.10-δ</sub>
at 923-1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10
<sup>-5</sup>
-
<sup>0.5</sup>
atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe
<sup>4+</sup>
concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 x 10
<sup>∼3</sup>
for La
<sub>0.3</sub>
Sr
<sub>0.7</sub>
Fe
<sub>0.9</sub>
Nb
<sub>0.1</sub>
O
<sub>3-δ</sub>
cf. 1.3 x 10 for La
<sub>0.5</sub>
Sr
<sub>0.5</sub>
FeO
<sub>3-δ</sub>
at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0-21.2) x 10
<sup>-6</sup>
K
<sup>-1</sup>
at 780-1080 K.</s0>
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<fC02 i1="02" i2="X">
<s0>001C01A02</s0>
</fC02>
<fC03 i1="01" i2="X" l="FRE">
<s0>Propriété transport</s0>
<s5>01</s5>
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<fC03 i1="01" i2="X" l="ENG">
<s0>Transport properties</s0>
<s5>01</s5>
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<s5>01</s5>
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<s5>02</s5>
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<s0>Transport processes</s0>
<s5>02</s5>
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<s0>Dopage</s0>
<s5>03</s5>
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<s0>Doping</s0>
<s5>03</s5>
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<s0>Doping</s0>
<s5>03</s5>
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<s0>Conductivité mixte</s0>
<s5>04</s5>
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<fC03 i1="04" i2="3" l="ENG">
<s0>Mixed conductivity</s0>
<s5>04</s5>
</fC03>
<fC03 i1="05" i2="3" l="FRE">
<s0>Lanthanide alliage</s0>
<s5>05</s5>
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<s0>Rare earth alloys</s0>
<s5>05</s5>
</fC03>
<fC03 i1="06" i2="3" l="FRE">
<s0>Superréseau</s0>
<s5>06</s5>
</fC03>
<fC03 i1="06" i2="3" l="ENG">
<s0>Superlattices</s0>
<s5>06</s5>
</fC03>
<fC03 i1="07" i2="3" l="FRE">
<s0>Conductivité électrique</s0>
<s5>07</s5>
</fC03>
<fC03 i1="07" i2="3" l="ENG">
<s0>Electrical conductivity</s0>
<s5>07</s5>
</fC03>
<fC03 i1="08" i2="3" l="FRE">
<s0>Solution solide</s0>
<s5>08</s5>
</fC03>
<fC03 i1="08" i2="3" l="ENG">
<s0>Solid solutions</s0>
<s5>08</s5>
</fC03>
<fC03 i1="09" i2="3" l="FRE">
<s0>Effet Mössbauer</s0>
<s5>09</s5>
</fC03>
<fC03 i1="09" i2="3" l="ENG">
<s0>Moessbauer effect</s0>
<s5>09</s5>
</fC03>
<fC03 i1="10" i2="X" l="FRE">
<s0>Délocalisation électronique</s0>
<s5>10</s5>
</fC03>
<fC03 i1="10" i2="X" l="ENG">
<s0>Electron delocalization</s0>
<s5>10</s5>
</fC03>
<fC03 i1="10" i2="X" l="SPA">
<s0>Deslocalización electrónica</s0>
<s5>10</s5>
</fC03>
<fC03 i1="11" i2="3" l="FRE">
<s0>Porteur charge</s0>
<s5>11</s5>
</fC03>
<fC03 i1="11" i2="3" l="ENG">
<s0>Charge carriers</s0>
<s5>11</s5>
</fC03>
<fC03 i1="12" i2="3" l="FRE">
<s0>Non stoechiométrie</s0>
<s5>12</s5>
</fC03>
<fC03 i1="12" i2="3" l="ENG">
<s0>Nonstoichiometry</s0>
<s5>12</s5>
</fC03>
<fC03 i1="13" i2="3" l="FRE">
<s0>Thermogravimétrie</s0>
<s5>13</s5>
</fC03>
<fC03 i1="13" i2="3" l="ENG">
<s0>Thermogravimetry</s0>
<s5>13</s5>
</fC03>
<fC03 i1="14" i2="X" l="FRE">
<s0>Haute température</s0>
<s5>14</s5>
</fC03>
<fC03 i1="14" i2="X" l="ENG">
<s0>High temperature</s0>
<s5>14</s5>
</fC03>
<fC03 i1="14" i2="X" l="SPA">
<s0>Alta temperatura</s0>
<s5>14</s5>
</fC03>
<fC03 i1="15" i2="3" l="FRE">
<s0>Perovskites</s0>
<s5>15</s5>
</fC03>
<fC03 i1="15" i2="3" l="ENG">
<s0>Perovskites</s0>
<s5>15</s5>
</fC03>
<fC03 i1="16" i2="3" l="FRE">
<s0>Cérium</s0>
<s2>NC</s2>
<s5>16</s5>
</fC03>
<fC03 i1="16" i2="3" l="ENG">
<s0>Cerium</s0>
<s2>NC</s2>
<s5>16</s5>
</fC03>
<fC03 i1="17" i2="3" l="FRE">
<s0>Fer</s0>
<s2>NC</s2>
<s5>17</s5>
</fC03>
<fC03 i1="17" i2="3" l="ENG">
<s0>Iron</s0>
<s2>NC</s2>
<s5>17</s5>
</fC03>
<fC03 i1="18" i2="3" l="FRE">
<s0>Lanthane</s0>
<s2>NC</s2>
<s5>18</s5>
</fC03>
<fC03 i1="18" i2="3" l="ENG">
<s0>Lanthanum</s0>
<s2>NC</s2>
<s5>18</s5>
</fC03>
<fC03 i1="19" i2="3" l="FRE">
<s0>Strontium</s0>
<s2>NC</s2>
<s5>19</s5>
</fC03>
<fC03 i1="19" i2="3" l="ENG">
<s0>Strontium</s0>
<s2>NC</s2>
<s5>19</s5>
</fC03>
<fC03 i1="20" i2="X" l="FRE">
<s0>Perméation</s0>
<s5>29</s5>
</fC03>
<fC03 i1="20" i2="X" l="ENG">
<s0>Permeation</s0>
<s5>29</s5>
</fC03>
<fC03 i1="20" i2="X" l="SPA">
<s0>Permeación</s0>
<s5>29</s5>
</fC03>
<fC03 i1="21" i2="3" l="FRE">
<s0>Pouvoir thermoélectrique</s0>
<s5>30</s5>
</fC03>
<fC03 i1="21" i2="3" l="ENG">
<s0>Thermoelectric power</s0>
<s5>30</s5>
</fC03>
<fC03 i1="22" i2="3" l="FRE">
<s0>Pression partielle</s0>
<s5>31</s5>
</fC03>
<fC03 i1="22" i2="3" l="ENG">
<s0>Partial pressure</s0>
<s5>31</s5>
</fC03>
<fC03 i1="23" i2="3" l="FRE">
<s0>Effet pression</s0>
<s5>32</s5>
</fC03>
<fC03 i1="23" i2="3" l="ENG">
<s0>Pressure effects</s0>
<s5>32</s5>
</fC03>
<fC03 i1="24" i2="X" l="FRE">
<s0>Conductivité type p</s0>
<s5>33</s5>
</fC03>
<fC03 i1="24" i2="X" l="ENG">
<s0>P type conductivity</s0>
<s5>33</s5>
</fC03>
<fC03 i1="24" i2="X" l="SPA">
<s0>Conductividad tipo p</s0>
<s5>33</s5>
</fC03>
<fC03 i1="25" i2="3" l="FRE">
<s0>Conductivité ionique</s0>
<s5>35</s5>
</fC03>
<fC03 i1="25" i2="3" l="ENG">
<s0>Ionic conductivity</s0>
<s5>35</s5>
</fC03>
<fC03 i1="26" i2="3" l="FRE">
<s0>Pression atmosphérique</s0>
<s5>36</s5>
</fC03>
<fC03 i1="26" i2="3" l="ENG">
<s0>Atmospheric pressure</s0>
<s5>36</s5>
</fC03>
<fC03 i1="27" i2="X" l="FRE">
<s0>Coefficient dilatation thermique</s0>
<s5>37</s5>
</fC03>
<fC03 i1="27" i2="X" l="ENG">
<s0>Thermal expansion coefficient</s0>
<s5>37</s5>
</fC03>
<fC03 i1="27" i2="X" l="SPA">
<s0>Coeficiente dilatación térmica</s0>
<s5>37</s5>
</fC03>
<fC03 i1="28" i2="3" l="FRE">
<s0>Addition indium</s0>
<s5>38</s5>
</fC03>
<fC03 i1="28" i2="3" l="ENG">
<s0>Indium additions</s0>
<s5>38</s5>
</fC03>
<fC03 i1="29" i2="3" l="FRE">
<s0>La</s0>
<s4>INC</s4>
<s5>46</s5>
</fC03>
<fC03 i1="30" i2="3" l="FRE">
<s0>Sr</s0>
<s4>INC</s4>
<s5>47</s5>
</fC03>
<fC03 i1="31" i2="3" l="FRE">
<s0>8233</s0>
<s4>INC</s4>
<s5>65</s5>
</fC03>
<fC03 i1="32" i2="3" l="FRE">
<s0>7680</s0>
<s4>INC</s4>
<s5>71</s5>
</fC03>
<fN21>
<s1>197</s1>
</fN21>
</pA>
</standard>
</inist>
</record>

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