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Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells
DISSERTATION for the degree of DOCTOR OF SCIENCES of the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH
presented by ERWIN POVODEN-KARADENIZ Mag. rer. nat. born on March 18, 1973 Citizen of Austria
accepted on the recommendation of Prof. Dr. Ludwig J. Gauckler, examiner Prof. John T.S. Irvine, co-examiner Dr. Ming Chen, co-examiner
Dedicated to my parents
Whatever creates or increases happiness or some part of happiness, we ought to do; whatever destroys or hampers happiness, or gives rise to its opposite, we ought not to do.
I am deeply grateful to my supervisor Professor Gauckler. He gave me a great chance by taking me into the boat: a boat that is not only sailed to scientific success. It took me away from an insecure float wobbling in the surf and approaches a promising future. Endless gratitude belongs to my wife who stays by my side throughout highs, downs, and distances, preventing me from losing the way; she is my firm anchor. I am greatly indebted to Nicholas Grundy for open doors, his patience of a saint, great teaching, and picky reviewing. He catalyzed my way into the field of thermodynamic modeling, airing the “modeling is fun” approach at any time. I would further like to thank Ming Chen for continuing scientific support and advising; he was often motivating me to spin the wheel of accurate and fast modeling and publishing. I owe thanks to Franc and Flavia Dugal-Borsari who saved me from an unintentional outdoor adventure in Zurich during a time when it was extremely difficult to find a new accommodation. It was a very pleasant time in Zollikon. I thank Brandon Bürgler and Jennifer Rupp for their pleasing office companionship at the beginning of my work: they facilitated my jump into the ETH waters. I would also like to thank Toni Ivas for abiding collegiality, cooperation, and friendship. I thank the rest of the office crew, Thomas Ryll and Rene Tölke, for always enjoyable working hours.
Zurich, December 2008
2 1.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.1.Table of Contents Table of Contents Summary Zusammenfassung 7 9 1 Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cralloy interconnects 1.1 1.3.1 1.3 Principles of SOFC The problem of chromium “poisoning” 11 11 11 13 14 17 17 22 24 24 27 28 36 36 37 45 46 46 47 47 48 49 Volatilization of Cr2O3 Literature survey 188.8.131.52 1.1.1 3.3.6 Degradation of SOFC caused by chromium from the interconnect The role of current load on electrical losses of degraded SOFC Impedance spectroscopy measurements and implications on the degradation process Microstructures in degraded SOFC Amounts of chromium in SOFC tested with and without current load Critical assessment of proposed mechanisms of chromium “poisoning” 1.1 3.2.1 Introduction 1.4.3 1.5 1.2 1.1 1.4.3 Stoichiometric solid oxides Solid solution phases – the Compound Energy Formalism (CEF) Vacancies and the concept of reciprocal reactions 4 .3.3.2 3.3.2 1.2 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC Thermodynamic modeling 3.2.2 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes New ways – alternative materials 2 3 Aim of study Method 3.
3 4 4.1 Technology 4.2 4.1.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials 4.2.1 Introduction 4.3 4.3.2 184.108.40.206 4.1 Calculation of defect chemistry using the Calphad approach 51 52 53 53 53 54 58 59 66 67 73 77 77 78 86 89 93 96 97 101 102 103 103 109 117 128 134 134 135 137 140 143 Optimization of model parameters Thermodynamic reassessment of the Cr-O system in the framework of SOFC research 4.4 4.5 4.3.6 Conclusions Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications 4.Table of Contents 3.4 Assessment of data from the literature Modeling and optimization Results and discussion 220.127.116.11 Experimental Thermodynamic modeling Optimization of parameters Results Discussion 4.4.3 4.5 4.3.4 Literature review of the La-Cr system Literature review of the La-Cr-O system Thermodynamic modeling and optimization Results and discussion 4.6 4.4.3 4.5 Conclusions 5 Thermodynamic calculations of impacts of chromium on Sr-doped 5 .18.104.22.168.6 Experimental data Previous assessments of the Cr-O System Thermodynamic modeling Optimization of parameters Results and discussion Thermodynamic assessments 22.214.171.124 3.2.4 4.1 Introduction 126.96.36.199 188.8.131.52.2 4.1 Introduction 4.7 Applications on SOFC Thermodynamic assessment of the La-Cr-O system 4.7 Conclusions 4.3 184.108.40.206.4 4.
8Sr0.9MnO3-δ contaminated by chromium Thermodynamic testing of LSM with Mn-deficiency Formation of Cr2O3 148 149 150 152 152 157 160 162 163 165 Discussion Conclusions Appendix Thermodynamic La-Cr database Thermodynamic La-Sr-Mn-Cr-O-(H) oxide database 170 169 172 Curriculum Vitae 190 6 .3 220.127.116.11 Thermodynamic calculations of La0.2 5.1MnO3-δ contaminated by chromium Thermodynamic calculations of (La0.2 5.2)0.9Sr0.1 5.3.1 5.4 5.3 Introduction Method Results 5.4 5.3.Table of Contents manganite (LSM) cathodes for SOFC 5.
even if the system is in a thermodynamic non-equilibrium state. and some are kinetically controlled. The chromium is known to deteriorate the electrical performance of the cathodes. Chapter 4 deals with the construction of the La-SrMn-Cr-O oxide database based on the assessments of subsystems. In chapter 1 the basics of planar SOFC are briefly explained. and the modeling approach used in this study is presented. Some of these processes are governed by thermodynamics. as well as the formation of a new spinel phase occur under thermodynamic control: decreasing concentrations of vacancies in LSM that contains chromium are calculated at decreased oxygen partial pressure reflecting SOFC operation at high current load. and the aim of this study (chapter 2) is to gather a deeper understanding of these unsolved problems by using thermodynamics. The new database is applied to the problem of chromium “poisoning” of Sr-doped lanthanum manganite cathodes ((La1−xSrx)1-yMnO3-δ or LSM) for Solid Oxide Fuel Cells (SOFC) stemming from gaseous Cr species from the high-Cr containing alloy of the interconnect. A key role is played by the adsorption of gaseous CrO3(g) (g = gaseous) and chromiumoxyhydroxides stemming from the interconnect on LSM and reaction of chromium with LSM. It is shown that chromium “poisoning” of SOFC cathodes is a rather complex process consisting of several steps. Furthermore spinel blocks pores and thus impedes the oxygen 7 . This has calamitous consequences for the electrochemical properties of the cathode. The new database is applied to the problem of chromium “poisoning” of SOFC with Cr-interconnects and LSM cathodes in chapter 5: a consistent phenomenological description of the process of chromium “poisoning” of SOFC cathodes is established that is in line with both experimental findings reported in the literature and thermodynamic calculations using the presented database. In the third chapter the reader learns. Based on the findings from the literature it gets clear that several questions about the key mechanisms of the chromium “poisoning” have not been answered yet. how thermodynamic calculations can lead to a better understanding of a system.Summary Summary The thermodynamic La-Sr-Mn-Cr-O oxide database is established by assessing oxide subsystems using the CALPHAD (Calculation of phase diagrams) approach. and previous findings of chromium “poisoning” of SOFC are critically reviewed. some of them probably occurring simultaneously. The associated chemical changes of the LSM phase.
With this contribution the prevailing question is resolved. 8 . which of the phenomena in a chromium-“poisoned” LSM cathode are governed by thermodynamics.Summary reduction required for the function of the cell. Appropriate measures can be foreseen preventing the long-term degradation of SOFC cathodes in combination with high-chromium containing interconnects. Cr2O3(s) (s = solid) that hampers the diffusion of oxygen into the electrolyte is a metastable phase in LSM contaminated by chromium.
Die thermodynamische La-Sr-Mn-Cr-O Oxid-datenbank wird basierend auf dem Assessment oxidischer Subsysteme mit dem CALPHAD-ansatz (Berechnung von Phasendiagrammen) aufgebaut. Die neue Datenbank wird auf das Problem der „Chromvergiftung“ von Srdotierten Lanthan-Manganit-kathoden ((La1−xSrx)1−yMnO3-δ oder LSM) für FestoxidBrennstoffzellen (SOFC) angewandt, welches von gasförmigen Cr spezies der hochgradig Crführenden Interkonnektor-Legierung herrührt. Es ist bekannt, dass das Crom die elektrische Leistung der Kathoden verschlechtert. In Kapitel 1 werden die Grundlagen von planaren SOFC kurz erklärt, und es wird ein kritischer Überblick über bisherige Erkenntnisse der „Chromvergiftung“ von SOFC gegeben. Basierend auf den Erkenntnissen aus der Literatur wird klar, dass einige Fragen, welche die Schlüsselmechanismen der „Chromvergiftung“ betreffen, noch nicht beantwortet wurden. Das Ziel dieser Studie (Kapitel 2) ist es, unter Verwendung der Thermodynamik ein tieferes Verständnis dieser ungelösten Probleme zu erlangen. Im dritten Kapitel lernt der Leser, wie thermodynamische Berechnungen zu einem besseren Verständnis eines Systems führen können, selbst wenn dieses System sich in einem thermodynamischen Ungleichgewichtszustand befindet, und der in dieser Studie verwendete Modellansatz wird vorgestellt. Kapitel 4 beschäftigt sich mit der Konstruktion der La-Sr-Mn-Cr-O OxidDatenbank, basierend auf den Assessments der Subsysteme. In Kapitel 5 wird die neue Datenbank auf das Problem der „Chromvergiftung“ von SOFC mit Cr-interkonnektoren und LSM-kathoden angewandt: Eine konsistente phenomenologische Beschreibung des Prozesses der „Chromvergiftung“ von SOFC-kathoden wird gegeben, welche sowohl im Einklang mit experimentellen Erkenntnissen in der Literatur als auch mit thermodynamischen Berechnungen unter Verwendung der präsentierten Datenbank steht. Es wird gezeigt, dass „Chromvergiftung“ von SOFC-kathoden ein ziemlich komplexer Vorgang mit mehreren, teilweise gleichzeitig in der Zelle ablaufenden Schritten ist. Manche dieser Prozesse sind thermodynamisch kontrolliert, und manche laufen unter kinetischer Kontrolle ab. Eine Schlüsselrolle spielt die Adsorbtion von gasförmigem CrO3(g) (g = gasförmig) und Chromium-oxyhydroxiden, welche vom Interkonnektor stammen, an LSM und die Reaktion von Chrom mit LSM. Die damit verbundenen chemischen Änderungen der LSM-phase und die Bildung einer neuen Spinellphase finden unter thermodynamischer Kontrolle statt. Die 9
Berechnungen ergeben abnehmende Konzentrationen der Leerstellen in Cr-hältigem LSM unter erniedrigtem Sauerstoffpartialdruck, und somit bei Betrieb von SOFC unter hohem Laststrom . Das hat katastrophale Konsequenzen für die elektrochemischen Eigenschaften der Kathode. Weiters blockiert Spinell Poren und behindert so die für die Funktion der Zelle notwendige Sauerstoffreduktion. Cr2O3(s) (s = fest), welches die Diffusion von Sauerstoff in den Elektrolyt erschwert, ist eine metastabile Phase in Cr-kontaminiertem LSM. Mit diesem Beitrag werden einige der vorherrschenden Fragen über „Chromvergiftung“ von SOFC geklärt, und geeignete Maßnahmen zur Verhinderung der Langzeitdegradation von SOFC-kathoden in Kombination mit hochgradig Chrom-führenden Interkonnektoren können vorhergesagt werden.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects
E. Povoden and L.J. Gauckler, to be submitted to Int. J. Mater. Rev. For the use of LSM cathodes in planar SOFC a comprehensive understanding of the mechanisms of the cell degradation caused by chromium diffusing from the interconnects into the cell is needed. This “poisoning” has been intensively investigated over the last decade. In this paper the affects of Cr on the degradation of SOFC with LSM cathodes and Cr-alloy interconnects are reviewed: the suggested models of chromium “poisoning” of planar SOFC with chromium-alloy interconnects and (La1-xSrx)1-yMnO3-δ (LSM) cathodes from the literature are critically assessed. Taking into account all available experimental findings on the affects of chromium on Sr-doped lanthanum manganite cathodes in planar solid oxide fuel cells, it can be concluded that several “poisoning” processes contribute to the deterioration of the cell performance. The review of all available experimental findings on the degradation of SOFC caused by chromium allows predictions, as to how the extent of degradation caused by chromium depends on the current load, operation temperature, operation time, as well as the amount of chromium diffusing from the interconnect.
1.1.1 Principles of SOFC A fuel cell directly converts chemical energy into electrical energy. A solid oxide fuel cell consists of two porous electrodes that are separated by a dense, oxygen ion-conducting electrolyte. A simple schematic of the electrochemical process is shown in Fig. 1.1.1 (next page).
White circles symbolize pores. All the components of the cell need to be matched in their thermal expansion in order to minimize mechanical stresses.7 to 1 V and power around 0. The electrodes are required to have high reactivity and the electrolyte must allow high oxygen ion diffusion. forming a cell stack to obtain higher voltage and power.2 (next page) for the widely used planar-design SOFC. 1. The materials for the cell components need to have a sufficient chemical and structural stability at rather high temperatures up to 1273 K that occur during cell production as well as during cell operation.5 to 1 W cm-2. e = electrolyte.1 Scheme of the electrochemical processes in a fuel cell with O2 oxidant and H2 fuel.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. 12 . as shown in Fig.1. c = cathode. 1. a = anode. At the anode the oxygen ions react with hydrogen of the fuel to form water and release electrons. A single cell produces a voltage of 0. and ceramicmetal composites are used for the anode. The direct-current electricity is produced by the electron flow through the external electric circuit. cathode and electrolyte consist of refractory solid oxide ceramics. supplied at the cathode reacts with electrons from the external electric circuit to form oxygen ions.1. The electrons flow from the anode through the external electric circuit to the cathode. These ions migrate through the electrolyte to the anode. In an SOFC. The oxygen. Normally many cells are electrically connected in series by an interconnect.
a thermal expansion coefficient close to that of the cathode and the anode. 1. It is the most demanding component in a planar SOFC as it should have a high electronic conductivity.1.1. 1. low permeability for oxygen and hydrogen to minimize direct combination of oxidant and fuel during cell operation. and chemical compatibility (no reactions) with other cell materials.2 Planar design of SOFC The interconnect separates the fuels and oxidants in adjacent cells. and their thermal and redox-stability is satisfying. the electronic conductivity of several LaCrO3-based ceramics under SOFC operating conditions is high. However high costs of these materials. stability in both oxidizing and reducing atmospheres at the high cell operating temperature (from about T = 973 K to 1273 K). 13 .2 The problem of chromium “poisoning” In the 1990is LaCrO3-based ceramics were intensively investigated for interconnect applications in SOFC. as chromium alloys come close to all desired properties. Nowadays the state-of-the-art interconnect is commonly a chromiumcontaining metal plate[3-5]. as the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. However high-valent gaseous Cr-oxide and Cr-oxyhydroxides diffuse from the Cr2O3(s) scale covering the interconnect into the cathode up to the cathode-electrolyte interface and cause the degradation that results in the strong deterioration of the electrical performance of SOFC. a low ionic conductivity. difficulties in sintering and manufacturing and low mechanical strength required the development of alternative interconnect materials.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects In the last decade a lot of effort was made to elucidate the degradation mechanisms.2 Volatilization of Cr2O3 Early investigations[6-9] revealed that oxidation of Cr-containing alloys at high temperatures leads to the redeposition of Cr2O3(s) crystals at cooler parts of the experimental apparatus from the gas phase. The volatilization in wet oxygen was significantly higher after 20 h at the same gas flow rate: 2.1 mg at T = 1373 K and 5. A known volatile oxide of Cr is CrO3. the volatile species must be a higher oxide of chromium. The observation that no loss of Cr2O3(s) occurs in argon confirms that volatilization does neither occur by dissociation of the oxide nor as Cr2O3(g) vapor.6 mg at T = 1473 K at a gas flow rate of 200 ml min-1 after 20 h. as the film of Cr2O3(s) covering the alloy specimen would have been expected to act as a diffusion barrier preventing the migration of Cr that has a high vapour pressure from the alloy through the Cr2O3 layer.2. the weight loss being 0. in the absence of metal. and at T = 1373 and 1473 K in flowing dry and wet oxygen as well as in dry and wet argon. Volatilization of Cr2O3(s) was neither observed in dry nor in wet argon. but its formation by the reaction Cr2 O3(s) + 3 2O2(g) → 2CrO3(g) (1. But when it was learned that Cr2O3(s).1) 14 .6 mg at T = 1473 K. it became evident that a volatile Cr-oxide was being formed. Appreciable volatilization occurred in dry oxygen. This was a surprising result. and it was suggested that high-valent gaseous Cr-oxide and Cr-oxyhydroxides detrimentally affect the O2 -adsorbtion. and -diffusion processes. Because of the high vapour pressure of Cr it was thus first considered that the metal itself would diffuse along oxide grain boundaries of the barrier film.3 mg at T = 1273 K after 72 h. lost weight when heated in oxygen.6 mg at T = 1373 K and 2. Caplan and Cohen investigated the evaporation of Cr2O3(s) by measuring the weight loss when Cr2O3(s) pellets with 1. or at discontinuities such as fractures in the film and would then evaporate. In stagnant air the volatilization was 0. 1. Furthermore.2 cm in diameter and height were heated at T = 1273 K in stagnant air. Since weight loss takes place under oxidizing conditions.3-2. neither the vapour pressure of Cr2O3(s) nor its dissociation pressure is high enough to account for the quantities of deposits observed. -reduction.
and Δ°G of reaction 1.2) Cr2 O3(s) + 1 2O2(g) + H 2 O(g) → 2CrO2 (OH)(g) (1.2. and Ebbinghaus. Δ°G of Eq. data for O2(g) from Dinsdale. 1. 1.3 is calculated to be +134 kJ at T = 1273 K using combined data from Kim and Belton and Ebbinghaus.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects is thermodynamically unfavourable at high temperatures. and for CrO3(g) from Ebbinghaus. μ(O) being −300 J mol-1 referred to pure oxygen gas result from combined thermodynamic data[11-14.2.1 (next page): the calculated amounts of main Cr-species in the gas phase as a function of temperature in humid air of pH2O = 2000 Pa at constant chemical potential of oxygen. 15 . Ebbinghaus estimated a significantly higher partial pressure of CrO2(OH)2(g) compared to CrO3(g) in wet atmosphere up to T = 1600 K based on available thermodynamic data of gaseous Cr-species. This tendency is shown in Fig.2.2 is calculated to be −158 kJ at T = 1273 K using combined data from Opila et al. The existence of gaseous Cr-oxyhydroxides as oxidation products (Eqs. 1.18] cited above. These findings are supported by the higher volatilization of Cr2O3(s) in wet air.2. in a recent combined experimental and modeling study these earlier findings are rejected for high temperatures: in wet atmosphere CrO2(OH)2(g) is predominant in the gas from T ≤ 1173 K. Their formation by oxidation of Cr2O3 in wet air reads: Cr2 O3(s) + 1 2O2(g) + 2H 2 O(g) → 2CrO2 (OH)2(g) (1.3) in wet atmosphere was experimentally proven in several studies[14-17].1 is calculated to be +321 kJ at T = 1273 K using assessed thermodynamic data for Cr2O3(s) from Povoden et al.2 and 1. and this was affirmed by thermodynamic modeling. whereas at higher temperatures the gas phase mainly contains CrO3(g) and CrO2OH(g).3) Δ°G of reaction 1. As gaseous CrO3(g) was detected experimentally by mass spectrometry when Cr2O3(s) was heated under oxidizing conditions..2. However. the formation of CrO3(g) occurs under kinetic control.
57x10-3 Pa at T = 1223 K. and the 16 .3 μg h-1 for 25 mol% H2O in air at T = 1073 K.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. and 18.1 Calculated amounts of gas molecules in Cr-gas as a function of temperature for constant pH2O = 2000 Pa at μ(O) = −300 J mol-1 referred to 100000 Pa O2(g) Transpiration experiments of Cr2O3(s) from T = 673 K to 1223 K resulted in the following partial pressures of Cr at a flow rate of 150 m min-1: pCr = 2.6 μg h-1 for 3 mol% H2O in air at T = 973 K. Mass loss of Cr2O3(s) at T = 973 K and 1073 K was measured in air with different amounts of water. to measure the vaporization rate of Cr from Cr5Fe1Y2O3 (Ducrolloy) and Crofer22APU (high-Cr ferritic steel).12x10-5 Pa at T = 673 K and increases as a function of increasing temperature. two high-chromium alloy interconnects widely used in SOFC. at T = 1073 K for a time period of about 500 h.2. the mass loss being higher at higher water content and higher temperature: the constant rate of mass loss was 0. Cr-vaporization in SOFC: Konysheva et al. used a transpiration method proposed by Gindorf et al. The Cr-vaporization rate of Cr5Fe1Y2O3 exceeds that of Crofer22APU by about a factor of 3 in the temperature range from T = 1023 K to 1173 K. reaching pCr = 4.2 μg h-1 for 3 mol% H2O in air at T = 1073 K. 1. 3.
 mentioned significant amounts of deposited Cr2O3(s) in the air exhaust of the cell. With increasing humidity the difference in the vaporization rates between the two alloys increases.32.3 Literature survey 1. However. pp.3. 17 .1. Badwal et al.3. and the chromium problem is restricted to the interconnect-cathodeelectrolyte region of SOFC. Experimental results[21-29. for an SOFC setup with a Cr5Fe1Y2O3 interconnect plate. The amount of Cr in these degraded cells was 140 μg cm-2 with Cr5Fe1Y2O3.1 Degradation of SOFC caused by chromium from the interconnect Considering the experimental data from Caplan and Cohen. an LSM cathode. thus quantitative chromium “poisoning” rates affecting the cathode are difficult to determine. 1.5 higher than with Crofer22APU. this value being by about a factor of 2.34. This is in line with the experimental observation that only a fraction of the chromium deposited at the cathode side contributes to the strong degradation of SOFC with LSM cathodes and Cr-alloy interconnects that were tested under a current load of 200 mA cm-2 for 393 h.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects vaporization rate increases with increasing temperatures for both alloys. the volatilities of gaseous CrO3(g) and gaseous Cr-oxyhydroxides are negligible under the low oxygen partial pressure at the fuel side of the cell. an yttriumstabilized zirconia (YSZ) electrolyte and a Ni-zirconia cermet (ceramic-metallic composite) anode operated at T = 1173 K and 1273 K.31.35] of the degradation of SOFC with LSM cathodes caused by chromium are listed in Table 1. 18-21.
1 Results of chromium poisoning of SOFC with and without Cr-containing interconnects with LSM cathodes collected from the literature 18 .3.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Table 1.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 19 .
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 20 .
In a test of the same setup under open circuit conditions for 21 .Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects The degrading effect of gaseous chromium species that form at the Cr2O3 scale under oxidizing conditions and diffuse into the cathode on the cell performance was first reported in 1995 by Taniguchi et al. a YSZ electrolyte and a NiO/YSZ anode with a piece of a Ni-Cr-Fe-alloy (Inconel 600) attached on top of a Pt mesh used as current collector. The cell voltage decreased over this time from initially about 0.7 V to about 0. The cell was electrochemically tested at T = 1273 K under a current load of 300 mA cm-2 for 400 h. These authors measured an increase of cathode polarization and decrease of cell voltage in an SOFC consisting of an LSM cathode with the compositions La0.9Sr0. and intensity measurements using electron probe microanalysis showed that Cr was concentrated at the cathode-electrolyte interface.1 V.1MnO3-δ..
whereas ohmic losses (resistance to 22 . an LSM cathode. the voltage drop being 0. the power density being 0. ascribed the voltage decrease to increasing losses of cathodic overpotential. The cell performance without interconnect plate deteriorated only little by less than 0.4 V after only 16 h. a Sm2O3-CeO2 interlayer between cathode and electrolyte. Simner et al. its power density decreasing from a maximum of 0.7 V: without the interconnect steel. an LSM cathode.1 V during an operation time of 2500 h. A comparison of measurements of the overpotentials of SOFC with LSM cathode and high-Cr alloy interconnect with measurements without interconnect[24-27] or LaCrO3-based interconnect led to the following results: the overpotentials without interconnects or with LaCrO3-base interconnects consistently became less negative with time. All these experimental studies[22-29] unambiguously proved that chromium stemming from the alloy interconnect causes the degradation of SOFC. presented cell performance data of an SOFC with LSM cathode. and to chromium deposited at the LSM-YSZ interface filling pores.05 W cm-2 after 110 h. holding the cells at 0. the cell started to degrade severely after 20 h of testing. and Cr was randomly distributed across the cathode. Later these results were confirmed by Badwal et al.: these authors tested the cell performance of an SOFC with a Cr5Fe1Y2O3 interconnect plate.2 The role of current load on electrical losses of degraded SOFC Badwal et al. a YSZ electrolyte and a Ni-zirconia cermet anode at T = 1273 K and a current density of 250 mA cm-2. reported that the degradation rate of SOFC with a Cr5Fe1Y2O3 interconnect plate. 1. thus linked the cell degradation to the time that the discharge current was applied. On the other hand the voltage of the cell with Cr-Fe-alloy interconnect decreased rapidly as a function of operation time.3. the cell performance was stable for 110 h.48 W cm-2. whereas the opposite was observed for SOFC with Cr-alloy interconnect. Taniguchi et al.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 300 h no deterioration of the cell performance was observed. Experiments without a Cr-based interconnect plate with Pt mesh serving as current collectors were conducted at T = 1205 K and 188 mA cm-2 current density using the same electrodes and electrolyte.2 W cm-2 to 0. a YSZ electrolyte and a Pt counter electrode (in the following SOFC with Pt counter electrode are denoted as half-cell) with and without Crofer22APU interconnect at T = 1073 K. a YSZ electrolyte and a Ni-zirconia cermet anode at T = 1173 K and T = 1273 K was more related to the period of current passage and was less dependent on the time when no current was flowing through the cell: Badwal et al. hindering the supply of oxygen gas and decreasing the number of reaction sites for the oxygen reduction. But using a Cr-Fe-alloy interconnect.
At the beginning of the cell tests.5 V potential. A plateau of degradation was reached after about 400 h of testing.07 V.[24. Konysheva et al. tested the reversibility of degradation in a half-cell setup with CrFe-alloy interconnect. with a tendency of stabilization of the cell performance after this testing period at much lower magnitude of output current.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects flow of electrons through the cathode) increased only insignificantly during the cell tests. Konysheva et al. losses increased sharply and reached their maximum values after only 15 h of cell operation.28. Paulson and Birss reported rapid deterioration of the performance of a half-cell setup with a stainless steel disk containing 15. The polarization behavior of SOFC with Crcontaining interconnect was explained by the strong inhibiting effect of gaseous Cr-species on the oxygen reduction in LSM. In earlier studies using the same setup a rapid decrease from −360 to −560 mV after 10 minutes[25. in agreement with earlier findings[22.2)0.21 % Cr on top of a (La0. whereas at 280 mA cm-1 the voltage dropped by 0. using a half-cell with a Cr5Fe1Y2O3 interconnect.33].65Sr0. La0.25.6 V. However the cell degraded rapidly again when the current was switched on again.3MnO3-δ/LSM+YSZ double layer cathode and a YSZ electrolyte confirmed the strong dependence of the voltage drop on the current density during 450 h cell tests at T = 1073 K: at 70 mA cm-1 the voltage decrease was 0.23.98MnO3-δ cathode and a YSZ electrolyte over 5 to 10 h at T = 1073 K applying a −0. The overpotential losses were higher and the cell deterioration was faster at higher current density. in general agreement with Jiang et al.8Sr0. In reference tests without Cr-Fe-alloy interconnect the results were opposite to the tests with Cr-Fe-alloy interconnects: the polarization increased from −550 to −300 mV or −420 to −170 mV [24. measured a rapid decrease of cell polarization from initially −350 to −750 mV after only 10 minutes in a half-cell with Cr-Fe-alloy (RA446) interconnect.4MnO3-δ cathode and a YSZ electrolyte at 300 mA cm-2 current density. The total polarization resistance (Rpol) of a half-cell setup using a Cr-Fe-alloy interconnect.26] was observed. LSM cathode and YSZ at a current density of 100 mA cm-2 at T = 1073 K and found that the rapid degradation was reversible and disappeared after switching off the current load.32. Zhen et al. LSM cathode and a YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2. Rpol being 0. a La0. Matsuzaki and Yasuda measured an overpotential loss from initially −500 mV to −2000 mV after 14 h in a half-cell setup with an Inconel 600 interconnect.5 Ohm cm2 for a thickness of 23 .31].25] at 1173 K and a current density of 200 mA cm-2.6Sr0.. an LSM/LSM-YSZ cathode double layer and a YSZ electrolyte tested for 400 h was markedly dependent on the thickness of the LSM-YSZ layer.
7 V. reported the existence of a high frequency and a low frequency arc in impedance spectra of a half-cell with Cr-Fe-alloy interconnect. 0. This finding was confirmed 24 . reflecting increasing cathode resistance. LSM cathode and YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2. 1. observed an increased size of the high frequency arc during the current passage in half-cell tests using a Cr5Fe1Y2O3 interconnect plate.4 Microstructures in degraded SOFC Cathodic polarization: Taniguchi et al.3.3 Impedance spectroscopy measurements and implications on the degradation process Badwal et al. an LSM cathode and a YSZ electrolyte as a function of operation time. Influence of temperature on the degradation: SOFC with LSM cathodes and high-chromium 430 stainless steel were tested at T = 973 K and 1073 K for 300 h. were the first who reported the occurrence of Cr-Mn-spinel in Cr“poisoned” SOFC with an LSM cathode by using XRD analysis. it deteriorated from 500 mA to 350 mA at T = 1073 K and from 300 mA to 150 mA at T = 973 K over the testing time of 200 h and then remained constant. Mazusaki and Yasuda concluded from the interpretation of impedance spectra of a half-cell with an Inconel 600 interconnect.26. Jiang et al. The total polarization resistance was also higher at higher current load. a La0. 1.4MnO3-δ cathode and a YSZ electrolyte operated at T=1073 K and 300 mA cm-2 current load that the degradation in the electrode caused by chromium was due to the increase in both charge-transfer resistance and surface diffusion resistance. and 2 Ohm cm2 for 7 μm.[24.3.6Sr0. and from −800 to −1120 mV at T = 973 K after 10 minutes. Zhen et al.75 Ohm cm2 for 13 μm.33] and Jiang et al. The degradation was higher at higher temperatures at 0.32]. from −900 to −1200 mV at T = 1073 K. observed less overpotential losses at lower temperatures in a half-cell with CrFe-alloy interconnect. LSM cathode and a YSZ electrolyte: they measured an overpotential change from initially −300 mV to −650 mV after 10 minutes at T = 1173 K. but not due to the increase in ohmic resistance. The increase of both arcs over the testing time was ascribed to the affect of Cr on the oxygen diffusion processes in the LSM cathode and across the LSMelectrolyte interface and is in line with the interpretations from Jiang[25.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 50 μm.
In a half-cell setup with a Cr-Fe-alloy interconnect. an LSM/LSM-YSZ cathode double layer and a YSZ electrolyte chromium-deposits were only found in the LSM layer under open circuit conditions. in some of the experiments forming a dense layer of several microns at the cathode-electrolyte interface. observed dense Cr-Mn spinel-deposits exclusively at the LSM-YSZ interface after a half-cell test of an SOFC with Cr-Fe-alloy interconnect operated for 20 h at T = 1173 K and a current density of 200 mA cm-2. In some cases these authors also observed Cr2O3(s) at the cathode-electrolyte interface. and the cell-degradation was weak. a YSZ electrolyte and a Nizirconia cermet anode at T = 1173 and 1273 K under current load.36]. no Cr-deposits formed after 50 h of testing under open circuit conditions[25. and the cell degradation was strong.05 μm) of Cr2O3 towards the cathode-electrolyte interface. For the same setup large quantities of spinel had formed after 2000 to 2500 h of cell operation. Jiang et al.36] documented spinel formation at the LSM-YSZ interface already after 4 h. Badwal et al. The zone of these large faceted crystals was followed by a zone of very fine grains (about 0. further observed spinel in the contact region between interconnect and cathode. Zhen et al. Using the same setup as above. Using a half-cell setup with Inconel 600. but under anodic polarization very fine grains of Cr2O3 were forming exclusively at the LSM-YSZ interface. LSM cathode and YSZ electrolyte Matsuzaki and Yasuda reported the formation of a dense layer of Cr-deposit at the LSM-YSZ interface after a cell test at T = 1073 K and a current density of 300 mA cm-2 over 100 h of polarization. unfortunately the specific conditions for its formation were not given in more detail. The grain size of spinel was about 0.7 μm after 50 h. but further details on their spatial distribution and composition were not given. On the other hand Cr-Mn spinel formed already at 25 . an LSM cathode. The deposition zone broadened as the polarization time increased from about 60 μm after 50 h to 89 μm after 129 h.[25. Very small grains of Cr-deposits formed at T = 1373 K under open circuit conditions. Using the same setup.17 μm after 4 h of cell testing and increased to about 0. In the same setup without LSM-YSZ functional layer no chromium-deposits were detected without current at T = 1073 K over 393 h.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects by Badwal et al. On the other hand chromiumdeposits were also found in the LSM-YSZ layer and on the surface of the YSZ electrolyte on increasing the current density up to 280 mA cm-2. who detected small amounts of Cr-Mn spinel after 100 h of operation of SOFC with a Cr5Fe1Y2O3 interconnect plate. Under the same testing conditions as above. The amount of spinel at the cathode-electrolyte interface was much larger than within the LSM cathode particularly after a period of current load.
5 V and T = 1073 K.72Sr0. Paulson and Birss investigated the microstructures in a half-cell setup with a stainless steel disk containing 15. and the density and size of deposits increased by time. Transmission electron microscopy analyses revealed the layered structure of the composites: a 0.98MnO3-δ cathode that rested on a 144 mm2 square YSZ electrolyte. Cr2O3 was also found inside YSZ. The morphology of the particles was different than the morphology of the deposits under cathodic polarization. Cr2O3 completely filled gaps between YSZ grains. dense Cr2O3-layers at the edge of LSM on the YSZ surface.8Sr0. reported the formation of very fine particles of Cr2O3..Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects very low current load of 2 mA cm-2 on the surface of the electrolyte and near the LSMelectrolyte contact. Influence of temperature: Microstructural changes during half-cell tests of a setup consisting of a Cr-Fe-alloy interconnect. Anodic polarization: After a half-cell test of an SOFC with Cr-Fe-alloy interconnect operated for 6 h at T = 1173 K and a current density of 200 mA cm-2. up to 10 μm away from the LSM-YSZ interface after 160 h of testing.18MnO3-δ cathode and a YSZ electrolyte were systematically investigated as a function of time and temperature at a current load of 200 mA cm-2 by Jiang et al. a La0. after the half-cell was tested by a sequence of 8 chronoamperometry experiments at −0.5 μm thick layer directly adjacent to the YSZ containing mainly Cr2O3 is covered by a spinel layer. and spinel crystals were found on the surface of a thin Cr2O3-layer adjacent to the electrolyte. and 30 μm from the LSM-YSZ contact after 940 h. These authors observed the formation of a 500 μm broad zone of 8 individual. In direct contact with YSZ about 500 nm large Cr2O3-grains were detected. exclusively covering the YSZ surface. Cr-deposits consisting of Cr2O3 and Cr-Mn-spinel were concentrated in an about 2 μm broad region at the LSM-YSZ interface. and the deposition was less pronounced at T = 1073 K and 973 K. A reference test without polarization did not lead to these features.2)0. After 5 minutes of testing at T = 1173 K very fine Cr-deposits (< 100 nm) already formed on the YSZ-surface. No spinel formation was observed in these experiments.21 % Cr attached on top of a 4 mm2 square (La0. Jiang et al. large gaps between YSZ grains formed. After 20 h spinel formation was observed forming a 40 to 50 μm wide band at the LSM-YSZ interface. almost completely 26 . After 160 h of testing at 100 mA cm-2 current load.
1. a Sm2O3-CeO2 interlayer between cathode and electrolyte and a YSZ electrolyte with a Crofer22APU interconnect operated at T = 1073 K.5 wt. Krumpelt et al. holding the cell at 0.% at 14 μm distance from the contact to the electrolyte. compared the total amounts of chromium in half-cells with Cr-Fe-alloy interconnects. In SOFC with LSM cathodes and a Cr-Fe-steel interconnect that were tested at T=1073 K for 300 h at 0. although the degradation of the polarized cell was remarkably higher. 27 . By using molecular dynamics simulation techniques it was stated recently that only 890 ppm Cr3+ in LSM significantly increase the formation energy of O2. The Cr-content dropped to about 0. The decreasing degradation at lower temperatures was ascribed to slower diffusion and lower partial pressure of gaseous Cr-species.65Sr0.7 V.3.8 wt. The amount of Cr-deposits was significantly smaller after 20 h of testing and 200 mA cm-2 current load at T = 973 K: isolated fine particles (about 100 to 200 nm) were detected on the YSZ surface. It further decreased slightly towards the interconnectcathode interface. a La0. comm. This was explained by the following: only under current load chromium deposits are concentrated in the functional region of LSM close to the contact to YSZ where they inhibit oxygen reduction and diffusion processes.5 Amounts of chromium in SOFC tested with and without current load Konysheva et al. and under 200 mA cm-2 current density showing strong degradation as a function of testing time at T = 1073 K.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects covering the YSZ surface. associated with large grains (about 1 μm) of spinel. This may lead to a dramatic drop of the oxygen diffusion coefficient in LSM by about 60% and pers.7 V for 120 h.% Cr in the Sm2O3-CeO2 interlayer. Simner et al. In a half-cell with LSM cathode.vacancy within about 10 Å around Cr3+.3MnO3-δ/LSM+YSZ double layer cathode and a YSZ electrolyte after tests without current showing very small degradation. measured about 2. The amounts of chromium in the half-cell operated under a current was 100 μg cm-2 after 150 h and 150 μg cm-2 after 500 h. measured 5 at. this is only 15 to 20 % higher than in the cell operated without current. but no Cr in LSM using energy dispersive scanning electron microscopy.% of Cr at 10 μm distance from the cathode-electrolyte interface.
2. X(Mn)= 2X(Cr): La1− xSrx MnO3−δ + 1 2 y Cr2 O3(s) → La1− xSrx Mn1− 2 y Cry O3−δ + yMn 2 CrO4 + 5 4 y O 2(g) (1.33]. 1) Several authors[21-23.2) 28 . This reduction reaction would compete with the oxygen reduction and would lead to blocking of the active sites at the TPB and subsequent formation of Cr-Mn spinel by the reaction of Cr2O3(s) with LSM.3.2 is a possible reaction for the formation of spinel with a higher amount of Mn. Badwal et al. ascribe a key role for the late stages of cell degradation to the formation of Cr-Mn spinel that would block pores and lead to substantial decrease of the TPB area.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. and gas. including changes of the chemical composition of the LSM surface.1.30-31. Cr-Mn spinel is interpreted by these authors to form in a solid-solid reaction between Cr2O3(s) and LSM that may have the simplified form of Eq. electron-donating LSM and oxygen-accepting YSZ are available.33] ascribe the mechanism of chromium “poisoning” to the reduction of gaseous CrO3(g) and Cr-oxyhydroxides at the cathode-electrolyte interface. YSZ.1) Eq. X(Cr) = 2X(Mn): La1− xSrx MnO3−δ + 3 2 y Cr2 O3(s) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2 O4 + 1 4 y O2(g) (1. Badwal et al.3.6 Critical assessment of proposed mechanisms of chromium “poisoning” For the mechanisms of chromium “poisoning” two models have been proposed: 1) Reduction of gaseous Cr-species under polarization[21-23.33. emphasized that chromium “poisoning” would consist of several processes.3. In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary (TPB) between LSM. and blocking of pores by Cr-Mn spinel and Cr2O3(s).3. In particular they suggest the tight intercalation between changes of the chemical composition at the surface of LSM particles and the oxygen adsorption and surface diffusion kinetics in the early stage of chromium “poisoning”. where the reaction partners for the reduction. 1. 1.32.31. 1.1 when solid solubility of Cr in LSM is considered and spinel contains the molar fraction of Cr.3. and 2) Chemical dissociation of Crspecies on the LSM surface[24-26.230. reduction of CrO3(g) at the cathode-electrode interface competing with the normal oxygen reduction reaction. Both reduction and chemical dissociation processes reflect non-equilibrium conditions. described by inverse Eq.37].
3.1 is a simplified illustration of possible reaction paths that lead to the end product Cr-Mn spinel. Fig. reactions of direct formation of spinel by the interaction between Cr-gas and LSM can be formulated (Eqs. As it is not assured if spinel in fact forms in a solid-solid reaction. more oxygen is produced. Fig. 1. The true shape of the curves depends on the activation energy Ea and is thus not known. 1.2 less Cr2O3 is needed for the formation of Mn2CrO4. Such gas-solid reaction can be split into two reaction steps: formation of 29 . On the other hand it may last a long time for the Cr2O3(s) that was formed by the reduction reaction to transform into spinel in the solid-solid reaction with LSM. These assumptions would mean that fast reduction of Cr-gas to Cr2O3(s) occurs as one process.3. Ea of the concerning reaction.3.5) considering the main chromium molecules that interact with LSM for spinel with X(Cr) = 2X(Mn). depends on the activation energy. thus assuming a lower activation energy for the LSM-Cr-gas reaction. 1. and the LSM-Cr-gas reaction occurs as a parallel process leading to the formation of spinel. Oxygen production stems from the reduction of Mn3+ in perovskite to Mn2+ in spinel.3. The shape of the curves in Fig.3 to 1. Which of the possible reaction paths is realized. and the mobility of the gas phase is high.1 and 1. sp-form = spinel formation.1 was chosen based on the consideration that the diffusionless reduction of Cr-gas may have a lower activation energy than the solid-solid reaction between LSM and Cr2O3(s). 1.3. and this is not known.3. and LSM gets more deficient in Mn.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects For equal y in Eqs.3. red = reduction. 1.1 Possible reaction paths for the spinel formation as a function of Gibbs energy. However the formation of spinel can also be interpreted as a direct solid-gas reaction.
3. The ionic conductivity was lower at lower oxygen partial pressures.32. 1. and consequently to Cr-Mn spinel and Cr2O3(s). It can be seen from Eqs.5 that oxygen is produced during the formation of spinel.33.37] oxygen diffusion is inhibited by the nuclei-formation. opposite to the trend that would be expected under the control of the vacancy diffusion mechanism. Huang et al.3.3. On the other hand the measured oxygen tracer diffusion coefficient in LSM strongly increases when the oxygen partial pressure is decreased from pure oxygen to pO2 = 200 Pa. As Mn2+ is associated to vacancy formation in LSM that is necessary for the oxygen diffusion.33.37]: Mn2+ on the surface of LSM at reduced oxygen partial pressure close to the cathode-electrolyte interface would react with gaseous Crspecies to Cr-Mn-O nuclei.5) 2) The chemical dissociation of gaseous Cr-species on the LSM surface for the cell degradation was proposed as the key process for the degradation of SOFC caused by chromium by another research group[24-27.4) La1− xSrx MnO3−δ + 3 yCrO2 (OH)(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2 O4 + 3 2 y H 2 O(g) + 3 4 y O2(g) (1.32.1 to 1.3. confirmed these early suggestions by evaluating the ionic conductivity of LSM from pure oxygen to pO2 = 300 Pa at temperatures from 953 K to 1153 K using YSZ as blocking electrode.3) La1− xSrx MnO3−δ + 3 yCrO2 (OH)2(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2O4 + 3 yH 2O(g) + 5 2 y O2(g) (1.3. Thus the pO2 at the locations of the spinel formation is expected to increase. The role of the oxygen vacancy diffusion mechanism in an LSM cathode has been considered controversially: Mogensen and Skaarup concluded from the low oxygen self-diffusion coefficients of the order of 4×10-14 cm2 s-1 at T = 1173 K that long range bulk migration of oxygen ions cannot play a significant role for the cathode performance.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Cr2O3(s) from the gas and subsequent spinel formation from Cr2O3 + LSM. This in turn will also lead to less Mn2+ in LSM and consequently lower oxygen diffusion in LSM. concluded that 30 . The differences of oxygen contributions to respective reactions stem from the reaction step of Cr2O3(s) formation: La1− xSrx MnO3−δ + 3 yCrO3(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2 O4 + 5 2 y O2(g) (1. Yasuda et al.[24-27. However they did not discuss the dependence of oxygen diffusion upon pO2 .
2. as Δ°G of the reduction being the inversion of reaction Eq. and η = −0. as well as Konysheva et al. Based on the findings from the literature it can be summarized that in LSM oxygen diffuses through grain boundaries at high pO2 .Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects oxygen ions in the bulk of LSM diffuse by the vacancy diffusion mechanism.336 V. Contradictory interpretations from the dependence of the ionic conductivity on pO2 need to be judged with care due to the difficulty of controlling the numerous factors that can influence the results of the blocking electrode method used.1CoO3-δ in which oxygen ions are transported by the vacancy mechanism. This strong tendency for the precipitation of Cr2O3(s) makes a rejection of the reduction of CrO3(g) as a possible process contributing to the cell degradation doubtful. observed the extension of dense Cr2O3layers into YSZ.4x10-6. Paulson and Birss. η = −0.33.090 V) using isotopic oxygen exchange and secondary ion mass spectrometry it was found that oxygen ions can only diffuse through dense LSM at the high overvoltage of η= − 0. compared to δ = 3.336 V corresponding to pO2 = 10-4 Pa. as oxygen vacancies are simply not available under these conditions. This phenomenon was well explained by continuous feeding of an initial 31 . We believe that the oxygen vacancy diffusion mechanism contributes to the oxygen diffusion under high current loads.32. It was also mentioned in the early paper of Caplan and Cohen that substantial precipitation of Cr2O3(s) from CrO3(g) occurred in the cooler part of the experimental setup.2MnO3-δ at 973 K and pO2 = 10-4 Pa is δ = 2. as it was directly proven by isotopic and tracer diffusion experiments. The activation energy for the diffusion of oxygen for LSM is in the range of 250 to 300 kJ mol-1. when the oxygen partial pressure at the cathode-electrolyte interface is decreased significantly.9Sr0. This is close to 270 kJ mol-1 for La0. The calculated amount of oxygen vacancies (δ) in La0.94x10-9 in air. Reduction of CrO3(g) to Cr2O3(s) was such predominant as to make sampling of gaseous CrO3(g) difficult. It is necessary to test the arguments for this claim of exclusive validity: a strong tendency exists for CrO3(g) to get reduced to Cr2O3(s) at the TPB. 1. This indicates that a vacancy diffusion mechanism also applies to LSM.185 V. The electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach[24-27.8Sr0.1 has a large negative value. In an investigation of active sites for the oxygen reduction at the O2/LSM/YSZ interface for three different overvoltages of cathode polarization (η = −0.37]. This confirms the suggestion that the formation of oxygen vacancies in LSM contributes to the oxygen diffusion at high current loads.
Thus it is obvious that the explanation of the “poisoning” process by the chemical dissociation approach alone is not without doubt. which does not seem to be the case for the spinel phase.23.37] and subsequent formation of spinel. and the degradation can be associated to the dissociation process[24-27. partly layered structures. Also two different diffusion processes were distinguished.30.32. The region of spinel formation extends several microns from the TPB into the cathode. This explanation is in line with the microstructural features of tested cells both under open circuit voltage and under current load. which both seemed to be inhibited by chromium poisoning. which is increasing as a function of increasing polarization. Some indications for two independent chromium poisoning mechanisms can be found in the work from Jiang et al. This is in contrast with the complicated mechanism for the formation of Cr2O3(s) under anodic 32 .28. But how can one explain the strictly localized deposition of Cr2O3 that also occurs under anodic polarization? Under oxidizing conditions little Mn2+ is expected to be present in LSM. thus the formation of nuclei by the proposed LSM-Cr interaction won’t occur. Cr2O3(s) deposition should also occur under open-circuit conditions. whereas in a polarized cathode the reduction of CrO3(g) takes place and competes with the oxygen reduction leading to Cr2O3(s) deposition.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Cr2O3-layer with CrO3(g). In this case no chromium will be deposited at the cathode-electrolyte interface under open-circuit conditions. In this case the contribution of reduction to the Cr-“poisoning” has to be rejected. From the occurrence of finegrained Cr2O3 the existence of a large number of nuclei for its formation is concluded. which was definitively not observed.26. whereas an explanation by the chemical dissociation approach is not satisfying. and the normal charge transfer can take place by switching it on again. one with a lower rate on the LSM surface. whereas the phase that was most likely identified as Cr2O3 occurs in fine-grained. from impedance spectra analyses it was in fact possible to distinguish two distinctive depositions of Cr-species.31]: by switching off the polarization the competing reduction of CrO3(g) no longer occurs. and it is also in line with the observed temporary reversibility of the cell deterioration[22. However the situation changes if the reduction of CrO3(g) is under the main control of the oxygen partial pressure gradient towards the cathode-electrolyte interface.33.37]: the two phases formed in the scope of a polarized LSM cathode exhibit distinctive microstructures: spinel forms large grains. whereas Cr2O3 is always located directly at the cathode-electrolyte interface. and the second with a higher rate on the YSZ electrolyte surface. If CrO3(g) is electrochemically reduced to Cr2O3(s) in a cell. Furthermore. the latter becoming reduced at the new TPB consisting of YSZ and electron-donating Cr2O3(s)[21.[24.34].
if both the chemical dissociation as well as the reduction of gaseous Cr-species is occurring with different proportions. LSM cathode and a YSZ electrolyte at T = 1173 K and a current density of 200 mA cm-2 from Zhen et al. the number of the latter being less than under cathodic polarization. and in LSM a pO2 gradient is expected under polarization. but several processes may lead to the deterioration of cell 33 . opposite to the situation with a platinum cathode. and thus under these conditions LSM has no tendency at all to accept oxygen. Oxygen deficiency is negligible in LSM under high pO2 . the following simple explanation for strictly localized Cr2O3(s) formation under anodic polarization can be given: in an LSM cathode the reduction of gaseous Cr-species is expected to be localized at the triple phase boundary. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. are particularly interesting: the slope of the cathode polarization curve (Fig. In cell tests of a polarized platinum electrode using a Cr-containing interconnect no Cr was observed. this apparent antagonism is abolished. This is a simple and consistent explanation for a strict localization of Cr2O3(s) formed by reduction of gaseous Cr-species even under anodic conditions. and thus lack of spinel formation. This is an indication against one unique “poisoning” mechanism. This different behavior of Pt and LSM electrodes under Cr-poisoning was used as an evidence for the exclusive validity of the dissociation approach. It was further mentioned that the existence of Cr-containing products away from the TPB would be in disagreement with the reduction approach. This once again may favor the reduction of CrO3(g) and gaseous Croxyhydroxide resulting in Cr2O3(s) deposition at the cathode-electrolyte interface in LSM. 4 b) as a function of time reveals an inflection point after about 6 1/2 h. vacancies are expected to form in LSM under increasing polarization.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects polarization established by Jiang et al. In this context experimental results of a half-cell test with Cr-Fe-alloy (RA446) interconnect. based on an early finding that LSM behaves like a metallic electrode at low polarization potentials that was not quantified. where the reaction partners for the reduction. However. Alternatively. contrary to an LSM electrode. that includes diffusion of Mn3+/Mn2+ driven by the oxygen evolution reaction at the cathode/electrolyte interface. This is indeed true for the case of CrO3(g) and Cr-oxyhydroxide reduction being the only Cr-poisoning mechanism. which is indeed not the case in a platinum cathode. again with Mn2+ acting as agent for the formation of Cr-Mn-O nuclei. However this conclusion was not tested in the light of the oxygen partial pressure gradient towards the electrode-electrolyte interface: contrary to platinum. contrary to the situation of a strong pO2 gradient under cathodic polarization.
Reduction already takes place at higher pO2 at the beginning of the current load operation. The small area close to the new TPB that was strongly depleted of oxygen under current load is filled with air leaking through remaining pores between LSM and Cr2O3. even though the decrease is expected to be less due to less LSM/YSZ active sites caused by the first degradation. This results in a lower oxygen partial pressure at the interface as compared to that in air. give the following explanation. why the strong oxygen partial pressure gradient in the LSM cathode under high current densities plays a key role for the degradation: the LSM cathode has a low electrochemically active area (TPB) near the interface with the electrolyte only. thereby still more decreasing the oxygen partial pressure at a newly formed Cr2O3(s)/electrolyte interface: the TPB between LSM and YSZ diminishes more and more by the blocking of Cr2O3(s). Applying a current load. Oxygen is mainly reduced at the new TPB between Cr2O3(s) and YSZ. Under polarization.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects performance. the oxygen ions from this new. as electronic conductivity of Cr2O3 is significantly higher at higher pO2 (1. The higher the current density under SOFC operation. the lower is the oxygen partial pressure at the contact between LSM and YSZ. under open circuit the LSM-Cr interactions occur randomly throughout the cathode. From the considerations in this chapter we conclude that no sustainable arguments exist for the rejection of the reduction of gaseous Cr-species as one of the controlling mechanisms of Cr-“poisoning” of SOFC. As Cr2O3(s) has a small electronic conductivity of 0. The deposition of chromium followed by its reduction near this interface blocks direct oxygen access to the electrochemically active sites. 34 . and the chemical activity of the cell is furthermore deteriorating due to the lack of oxygen supply through the rather dense Cr2O3 layer to the new TPB. thus the remaining TPB/YSZ active sites are almost unaffected under open current circuit.. the oxygen ions formed at this interface are transported from the cathodeelectrolyte interface through the electrolyte. The temporary reversibility of the deterioration by switching the cell off and on again can also be explained: in contrast to current load operation.8 S m-1 at T = 1282 K and pO2 = 1 Pa. weak catalytic reaction diffuse into YSZ. and their respective influence on the cell deterioration may vary as a function of time. Konysheva et al.8 S m-1 in air). and oxygen cannot access the TPB. the LSMCr interaction is again favored in the region close to YSZ as pO2 decreases at the TPB. The important role of decreased oxygen activity at the LSM-YSZ interface under current load for the cell degradation was already suggested by Taniguchi et al.
1. followed by diffusion of the gaseous products into the cathode.3 occurs. 1.2 denotes the interconnect-cathode interface region where oxidation of Cr2O3(s) to gaseous Cr-oxides and Cr-oxyhydroxides by Eqs. and chromium content is schematized in the picture.2. or gas-solid reaction. 1.3. and the degradation increases as a function of time. 1.1 to 1.5.3 to 1. Numbers refer to locations of processes that are decisive for the degradation Number 1 in Fig.2. 35 .2 Model of chromium poisoning of an SOFC with Cr-interconnect and LSM cathode based on the findings in the literature. 1. Eqs. and number 3 denotes the reduction of gaseous Cr-species by the reverse of Eq.3.3. Active LSM/YSZ sites further diminish by ongoing formation of spinel and Cr2O3 deposits.2. The reported dependence of structural features of the degraded cell on the operation temperature.2 is a visualisation of the microstructural consequences of chromium in an LSM cathode.3.3.3. 1. Eqs.2.1 leading to the redeposition of Cr2O3(s) at the cathode-electrolyte interface. Fig. current load. Number 2 denotes the region of interactions between LSM and chromium leading to spinel formation by solid-solid reaction.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Oxygen ions diffuse into YSZ. 1.1 to 1. Fig. but new oxygen is not supplied to the new TPB.3.
However.65Sr0. La0. La0. or Mn2CrO4.Al)N.4. thereby improving the electrical conductivity of the interconnect-cathode interface[49-69]. Application of the following coatings upon the interconnect has been shown to considerably reduce the diffusion of chromium into the cathode thus decreasing the cell degradation: Electroplated metallic Co[49.54].2O3.4Co0. La0.3MnO3[58. La.5O3.05Mn1.15MnO3-δ. Ce0.65]. Several promising materials for coating applications were developed in the following years that act as chromium diffusion barrier and hinder growth of chromia scale at the alloy surface.85Sr0.475Co1.5Co0. La0. Co3O4. Mn.67Sr0. Co-Mn.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.475O4. (La.6Sr0. sputtered Co.8Fe0.2Mn0. Ni. coating alone does not solve the problems associated to chromium poisoning completely.33MnO3. as well as (Ti. as Cr in the ppm range significantly influences the oxygen diffusion in the LSM cathode. or Cu-Mn.8Sr0. more active sites for the oxygen reduction will result in a higher Cr-tolerance. The formation of a dense electrically isolating Cr2O3 layer is probably preventable by using electrolyte materials or a functional layer between LSM cathode and YSZ electrolyte that can incorporate Cr in solid solution without affecting the electrical conductivity.2Mn0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. but a combination of the quoted strategies is advisable to further improve the long-time stability of SOFC performance.50].1 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes More than ten years ago Badwal et al.8Sr0.8Sr0.Co)3O4. However.Sr)CoO3. La0. This was recently shown for a cell with a YSZ-LSM functional layer: a functional LSM-YSZ layer adjacent to the YSZ electrolyte led to a lower cell degradation: increasing the ionic conductivity of the LSM cathode that is predominantly electronically conducting down to pO2 = 10-7 Pa by admixture of YSZ results in an 36 .5Co0. Cu1.4Mn1. La0. La0. proposed that coating of the Cr-interconnect with a protective electrically conductive dense layer would be an effective strategy against the diffusion of Cr-species into the cathode. or Cu. two-segment Cr-Al-Y-O nanocomposite and (Mn. Furthermore such a buffer layer may act as a sink for CrO3(g) thus diminishing nuclei formation on LSM.5O3-δ.6O4[53.2FeO3-δ. MnCo2O4[54-61]. If the buffer layer contains an ionic conductor. so far volatilization could not be suppressed completely.
4. Effects of Cr upon the degradation of La1-xSrxCo1-yFeyO3-δ (LSCF)[26.73].72]. and (La. In recent time it was found that new cathode materials such as La1-xSrxCo1-yFeyO3-δ (LSCF). Based on these findings they predicted that highly Cr-tolerant cathodes can be developed.Ba)(Co. Besides. Matsuzaki and Yasuda concluded from insignificant Crdeposits in tested SOFC with Cr-Fe-alloy interconnect.Fe)O3-δ (LNF). The highest tolerance against the effects of chromium under SOFC operating conditions combined with high electrical conductivity has been reported recently for (La.Fe)O3-δ (LBCF)[71.75] cathodes were investigated using impedance spectroscopy. 1.71.Fe)O3-δ (LNF)[71. whereas no proper nuclei were reported for LBCF. As for LSM these authors concluded that the mechanism of Cr poisoning can be explained by chemical dissociation of CrO3(g) to the perovskite-structured materials and nuclei formation in the cases of LSCF and LNF. which makes this material a promising candidate for a steady long-term SOFC performance.2Fe0. particularly LSCF and LNF show rather high ionic contributions to the total electrical conductivity. La(Ni. leading to the formation of more scattered reduction products instead of a dense layer: thus the block of oxygen diffusion into the electrolyte can be avoided.8O3-δ (LSCF) cathode and Ce0.9 electrolyte that the ratio of the reduction of gaseous CrO2(OH)2(g) to that of O2(g) at the electrode/electrolyte interface is controlled by the electrochemical properties of the interface.Ba)(Co. contrary to LSM. Thus the number of active sites is increased.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects expanded area of active sites for the oxygen reduction away from the TPB. the reduction of gaseous chromium will not be restricted to the small area at the TPB due to a smaller oxygen partial pressure gradient.8Sm0. La(Ni. In all these cathodes Cr-deposition was observed throughout the cathode both under polarization and without polarization. LNF and LBCF revealed extraordinary high tolerance against chromium poisoning.2O1. All these perovskites are mixed electronic-ionic conductors. and (La. The amount of Cr- 37 . Ideally the selected dopants decrease the mobility of Mn2+ and thus prevent the formation of nuclei for the adsorption of CrO3(g) without influencing the formation of vacancies.6Sr0.74]. already considered alternative cathode materials to reduce or stop the formation of the spinel phase. La0.2 New ways – alternative materials Badwal et al.Fe)O3-δ (LBCF) are more tolerant against chromium “poisoning”.Ni)FeO3-δ [71. and the cell is more tolerant against chromium. The ionic conductivity can be increased by doping the B-site of ABO3 perovskite with reducible cations.4Co0.
Improved inhibition of the reduction of CrO3(g) is predicted for LNF. As an alternative to the complicated nuclei mechanism. Stimming. the following considerations can be made using the reduction model: For the reduction reaction of CrO3(g) the presence of both an electron donor and oxygen ion acceptor is necessary.W. nuclei might form in addition. However under strong polarization one can expect that LSCF gets more and more ionic conducting towards the electrode-electrolyte interface. despite rapidly developing processing techniques it is not clear at the moment if the obstacles of sinterability and low mechanical strength as well as difficult manufacturing correlated with high costs can be coped. J. Advances. J. 1-15. H. aging mechanisms and lifetime in solid-oxide fuel cells. as this phase has a particularly high ionic conductivity.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects poisoning of LSCF was considerable. pp. 2004. pp. which was explained by a removing effect of nuclei for the chromium deposition under polarization conditions. J. pp. Fergus.W. Fergus. Solid State Ionics. 284-93. but their influence on the Cr deposition compared to the reduction of CrO3(g) cannot be decided yet. Metallic interconnects for solid oxide fuel cells. 3. 38 . most likely resulting in retarding or inhibiting of the reduction reaction. 397. Materials Science and Engineering A. Even if the reduction reaction is considered to be the dominant mechanism of chromium poisoning. However. that is towards lower oxygen partial pressures. Opposite to the case of LSM no driving force for CrO3(g) to migrate to the triple phase boundary exists due to the mixed ionic-electronic conducting behaviour of the regarding cathodes. The higher the contribution of the ionic conduction the less complete reduction is expected due to prolonged lack of an electron donator. and a typical mixed ionic-electronic conductor such as LSCF can take over both functions. U. In recent years research activities for LaCrO3-base ceramic interconnector materials were revitalized by several groups[76-78] to circumvent the problems of chromium “poisoning”. 2005. The amount of deposited Cr in LSCF was even larger without polarization than under polarization. Thus reduction of CrO3(g) takes place inside the whole cathode even without being promoted electrochemically by polarization of the cell. 127. 2004. 2. References 1. Power Sources. Tu. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. 271-83. 171.
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101-13. Solid St.P.Y. 2008.5O3-δ. Arakawa. Int. G. S. L. J. pp. X.. 177. Diwu.-H. 75. Jiang. V. Tsipis. J. Komatsu. Wang. Tok. Y. M.Y. Kim.75Sr0. pp. T. Developing TiAlN coatings for intermediate temperature solid oxide fuel cell interconnect applications. J. Electroceram. B42-6.Fe)O3 cathodes of solid oxide fuel cells. 176. J. Shin. J. Electrochem.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. Irvine. Electrochem. SolidState Lett. Dong. pp. A9-12. K. Development of Cr-tolerant cathodes for solid oxide fuel cells. Liu. T. Power Sources. J.V.-Y. C.P. Zhang. Zhen. 61-6.-R. 2007.I. 77. S. Cr Poisoning suppression in solid oxide fuel cells using LaNi(Fe)O3 electrodes. Johnson. 451-56. Arai. Peck.S. 70.Ba)(Co.T. 11.-H. and D. pp. Y. R. pp. E.Fe)O3 as a cathode material with high tolerance to chromium poisoning for solid oxide fuel cells.-H.25)0. Lim.P. Y. Ni. 82-89. X. Chiba. 2006.C. 2008. S. Jiang. 71. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. Lee.. Characterization and performance of (La. and V doped-LaCrO3 interconnect materials prepared by Pechini..D. S. A127-A134. 189-96. pp.Y. J. Power Sources. Cross.I. J. pp. J.D. 33. Jiang. Boey. S. J. J. Song. Wu.95Cr0. S. Zhen. 2008. 2008.Y. Hydrogen Energ. Solid State Ionics.P. Power Sources. Soc. Y. Tok.-G. L. 73. P. G.. Y. Power Sources. Kharton. F. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. 2007. Shul. D. J. Marozau. Viskup. Ong. pp. A. Xu. I. K. Properties of Cu.P.P. 170. Jiang.Sr)(Co. Zhen. 78. Sato. 178. C. Li. 76. Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells. Electrochem. 723-27. Frade. 695-703. Liu. H. D. 44 . J. K.P.D.P. 72. A. Deposition of Cr species at (La. 9. Li. Zhen. pp. S. 2006.C. C. Liu.. 153. Liu.V. J. Jiang. F. 74. Zhao. La(Ni.-H. Pu. 2006. 17. M. Meng.5Mn0. Boey. A. 2008. pp. Mixed conductivity and electrochemical behavior of (La0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 69.R. R. 180. Nozawa.
Reduction of CrO3(g) at the TPB leads to the formation of electrically low conducting Cr2O3. Mn2+ in LSM plays an important role for the adsorption of gaseous CrO3(g) and Croxyhydroxide on LSM resulting in blocked oxygen transport from the cathode to the electrolyte. Previous experiments have shown that the following factors: -) High temperature -) Decrease of oxygen partial pressure at the TPB under current load of SOFC and processes: -) Interaction of chromium with LSM leading to Mn-Cr-O nuclei and/or spinel formation -) Reduction of CrO3(g) to Cr2O3(s) at the TPB -) Blocking of pores at the TPB by Cr2O3 and/or spinel govern the degradation of SOFC caused by chromium. So far it was not possible to define unambiguously. However. it seems that strategies against the cell degradation have been mostly established in a rather random way so far. severe degradation has been observed after several hours of testing under current load at state-of-the-art SOFC operating temperatures: from the literature findings it is obvious that the degradation of SOFC caused by chromium starts immediately after starting SOFC tests under current load. but the effects of chromium would be observed only after thermodynamic equilibrium is obtained.Aim of study 2 Aim of study Chromium poisoning of planar SOFC with LSM cathodes and Cr-alloy interconnects is a complex process consisting of several steps that may occur simultaneously inside the cell. this behaviour would not be expected. For a more systematic and thus more efficient combination of strategies a strong knowledge about the mechanisms of chromium poisoning of SOFC is required. and some strategies against cell degradation caused by chromium have already been successfully applied. This means that the kinetic control on the mechanisms of chromium 45 . The causes and consequences of chromium poisoning are clear. which further retards the diffusion process of oxygen into the electrolyte. which of these processes play a dominant role for the degradation and which don’t. If the process of chromium “poisoning” were completely governed by thermodynamics. In fact it was shown that without sufficient protection against the diffusion of chromium into the cathode the degradation of SOFC caused by chromium is not a long-term phenomenon.
The following questions have remained unsolved so far: -) Does spinel form by a solid (LSM)-solid (Cr2O3) reaction or directly in a solid (LSM)-gas (gaseous Cr) reaction? -) Can the concentration of deposits at the cathode-electrolyte interface under current load be explained by thermodynamics? -) How does the LSM phase chemically change due to the interaction with chromium. and several studies can be found regarding the degradation of LSM cathodes caused by chromium. In particular LSM cathodes have been intensively investigated over the last decade. and can this change be explained by thermodynamics? -) Which of the phases observed in LSM contaminated by chromium form under thermodynamic control. and as LSM cathodes are still considered to serve as promising cathodes due to their high electrical conductivity and stability at SOFC operating conditions. 3 Method 3. Therefore the thermodynamic La-Sr-Mn-Cr-O oxide database needs to be established based on the assessments of low-order subsystems.Aim of study is high. and a degrading cell is in a non-equilibrium state particularly at the early stages of the degradation. As a degrading cell is in a non-equilibrium state. and what are the conditions that favour their formation? This work aims to answer these questions by the application of thermodynamic calculations. In recent times many materials have been tested for SOFC cathodes. Thus. the obvious question why the results of thermodynamic calculations should be feasible for a deeper understanding of the mechanisms 46 .1 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC A thermodynamic La-Sr-Mn-Cr-O oxide database is highly desirable to enable fundamental understanding of the mechanisms of chromium “poisoning” of LSM cathodes for SOFC. in this study the author focuses on the effects of Cr on the degradation of SOFC with LSM cathodes.
3.1) By calculating thermodynamic equilibria for a LSM cathode that is affected by chromium (A) in the relation above. a with the positive electrical charge r and b with the positive electrical charge q. composition of LSM. including the operating temperature. and for solid solution phases as a function of temperature and composition. 47 . 3.1 Stoichiometric solid oxides The stoichiometric ternary phase α. temperatures.1. can be calculated using the thermodynamic La-Sr-Mn-Cr-O oxide database: C non . and oxygen partial pressures. the theoretical final state of chromium poisoning after a very long time is found by thermodynamic equilibrium calculations (B). Over time the system LSM + Cr will change from its nonequilibrium state at the beginning of the Cr-“poisoning” process towards the calculated equilibrium state. Hence. using the thermodynamic database one can calculate the expected thermodynamic equilibrium. by choosing the starting conditions composition of LSM and defined amount of Cr at a specific temperature. C can be predicted for changing cathode compositions. one can draw conclusions on the evolution of the phase chemistry of degraded LSM cathodes.2 Thermodynamic modeling 3. From A and B. It contains the optimized Gibbs energy functions of solid oxide phases: for stoichiometric phases as a function of temperature. for instance under reducing oxygen partial pressures reflecting the situation at the TPB under current load. and the rate of chromium diffusion the equilibrium state of chromium “poisoning”.1 reflects the path the system takes towards its equilibrium state.1.equilibrium (A) ⎯⎯ equilibrium (B) → (3. C in Eq.2. The presented thermodynamic database of the La-Sr-Mn-Cr-O oxide system is constructed using the CALPHAD approach. containing m and n moles of two different sorts of cations.Method of chromium “poisoning” needs some explanation: from the conditions of the non-equilibrium state at the beginning of the degradation process. The optimization of model parameters is based on the accurate assessment of experimental thermodynamic and phase diagram data of oxide subsystems. For instance. taking into account experimental data on the chromium “poisoning” of SOFC and using a thermodynamic La-Sr-Mn-Cr-O oxide database.
3.1) α The molar Gibbs energy of α.) p = q )v (O2. D.)u and Ox2: (b q )v (O2. c with the negative electrical charge s. 3. bq can sit in the same sublattice as a.2. and p moles of one sort of anions. can be described by the sublattice formula (a r )m (b q )n (c s ) p .) w ( t .5 is the criterion for charge neutrality: 48 . E. 3.2.2) A. the three types of ions sitting in three distinctive crystallographic sublattices.2. A and B are optimized by thermodynamic and phase diagram data.4: m ° ( a )t (O2. For oxides c = O and charge s = −2. Eq. v.3) α C. and F are model parameters to be optimized by thermodynamic and phase diagram data. mr + nq + 2 p = 0 (3. 3. b q )t (O2.)u n ° (b G + Gm t m v r ° α Gm = °Gm ( a r )m (bq )n (O2.2.)u . As Cp(α) is defined by C p = −C − 2 DT − 6 ET 2 − 2 FT −2 (3. Eq. D.2. E and F are optimized to heat capacity data only. To account for the charge neutrality criterion.2 Solid solution phases – the Compound Energy Formalism (CEF) If in the binary oxide Ox1: (a r )t (O2.1 is true. C.2. another sort of cation with the positive charge q. °Gm at constant pressure is given by ° α Gm = A + BT + CT ln T + DT 2 + ET 3 + FT ( −1) (3.4) ° α Gm is the Gibbs energy of formation of the phase α relative to the oxide components.2.2. the sublattice formula of the resulting solid solution phase β(ss) reads (a r . if it is assumed that the heat capacity of the ternary oxide composed by the two binary oxides is simply the sum of the heat capacities of the composing oxides as shown in Eq. °Gm can be based on the molar Gibbs energies of existing binary oxides Ox1: (a r )t (O2. w ∈ N ).)w + ptv − muv − nwt ° O (g) Gm + A + BT 2tv 2 (3. B.)u containing cation a with the positive charge r. u.Method respectively.
+ yVa ln yVa + EGma ( ) ( ) . (a 2 + )2 (O 2. and B denoting the anion sublattice.)u and (bq )t (O2.ln yO2.°Gma 3+ )2 (O2. The molar Gibbs energy of the phase at constant pressure reads 3+ ° A ( Gm 2 O3−δ = °Gma 2+ .7) Once again the molar Gibbs energies of all the 4 endmember compounds (a3+ )2 (O2.)3 . (a 3+ )2 (Va)3 . and (a 2 + )2 (Va)3 of the phase are required for the molar Gibbs energy 49 .6) where yar is the site fraction of cation a on the cation sublattice.2. The last term describes the excess Gibbs energy of mixing due to interactions of ions in the mixture that can be accounted for by introducing interaction parameters. and ybq is the site fraction cation b on the cation sublattice.2. The second-last term accounts for the configurational entropy of mixing of t moles of a and b. In the sublattice form the phase can be written as (a3+ .)3 ( + ya3+ yVa °Gma 3+ )2 (Va )3 3+ ( + ya2+ yVa °Gma )2 (Va )3 ( + 2 RT ya3+ ln ya3+ + ya2+ ln ya2+ + 3RT yO2. a 2+ )2 (O2. Charge neutrality under such reducing conditions can be remained by the formation of zero-charged vacancies (Va) in the anionic sublattice resulting in the phase becoming oxygen-nonstoichiometric.)u .5) Using the Compound Energy Formalism (CEF)[2-4].)3 .31451 J mol-1 K-1. The Gibbs energy of β(ss) at constant pressure reads ° β Gmss = yar °G ( a r) t (O2. R=8.3 Vacancies and the concept of reciprocal reactions Let us consider the case of a binary oxide phase (A)2(B)3. Va)3 ..Method u= t ( ya q + yb q ) 2 (3.Va )3 (3. with only one cation a accepting the charge 3+ or 2+ in the cation sublattice. The oxygen nonstoichiometry is denoted “O3-δ”. the molar Gibbs energy of the solid solution phase contains the Gibbs energies of the compounds. a 2+ )2 (O2. A standing for the cation sublattice.°Gma 2+ )2 (O2. the charge neutrality criterion is no longer obeyed by an anionic sublattice that is completely filled with oxygen.)u β + tRT yar ln yar + ybq ln yar + EGmss ( ) (3.)u + ybq °G (b q )t (O2. a 2+ )2 (O2.. For β(ss) the two compounds read (a r )t (O2. 3.Va )3 ( = ya3+ yO2.)3 ( + ya2+ yO2.2.2.. If the cation is reduced.
plotted above the composition square. 3.2.3 2 Va)3 . the only neutral endmember is (a3+ )2 (O2. The three other endmembers are charged and cannot exist.)3 and (a 2 + )2 (Va)3 or (a3+ )2 (Va)3 and (a 2 + )2 (O 2. and its molar Gibbs energy can be defined by optimization of model parameters by experiments.)3 . for instance oxygen nonstoichiometry data. thus far off neutral compositions that can really exist..2. For the example of the reciprocal solid solution phase (a3+ . Va)3 the 6+ charged compound (a3+ )2 (Va)3 is chosen as reference. but a line of neutral compositions connects (a3+ )2 (O2.)3 .1 The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . a 2+ )2 (O2. and (a3+ ..2.1. 3..Va)3 . (a3+ a 2+ )2 (3 2O2. The composition square of the phase can be seen in Fig.Method of the phase. a 2+ )2 (O2. However. It thus can exist. is theoretically obtained by mixing equal amounts of either (a3+ )2 (O 2.)3 with the reduced compound (a 2+ )2 (2 3O2. with the neutral line and the reduced compound. A system that obeys this relation is called a reciprocal system.1 that is redrawn from Hillert. As the chosen molar Gibbs energy of the reference is unlikely the true value. For an unambiguous definition of the molar Gibbs energy of the reciprocal phase it is necessary to give an arbitrary molar Gibbs energy to a reference. included. Va)3 approximating its overall Gibbs energy for Δ°Grec > 0 and Δ°Grec = 0. and its Gibbs energy can be optimized with experiments that are related to the reduction of the phase. a 2+ )2 (O2. 50 . Fig. denoted with A in Fig. Va)3 is a reciprocal phase. 3. The 2+ charged center composition of the square. denoted with R. the reference should favorably be a highly charged compound.
)3 − (a 2 + )2 (Va)3 : Δ °G rec = °G ( a 3+ ) 2 (Va)3 + °G ( a 2+ ) 2 (O 2. 3. the Gibbs energy surface is curved. c3+ .) 3 − °G ( a 3+ ) 2 (O 2.2.4 Calculation of defect chemistry using the Calphad approach The Calphad approach is very powerful for the calculation of the defect chemistry of highorder nonstoichiometric reciprocal solid solution oxide phases such as (A)(B)O3-δ perovskite with a complex sublattice formula. Va)(c 2 + . and no experiments define a proper value of the reciprocal reaction parameter. c 4 + .1 (page 50) and approximates the whole Gibbs energy of the phase. b 2 + .. a 2+ )2 (O2. d 3+ . the Gibbs energies of the remaining endmembers are significantly different for Δ°Grec > 0 and Δ°Grec = 0. d 4+ . as long as these endmembers are charged and away from the existing composition range of the phase. For this purpose model parameters of the reduced and oxidized compounds are optimized with experimental information on charge carriers. site fractions and oxygen content. when the Gibbs energies of the endmember (a 3+ )2 (O 2. On the other hand. Δ°Grec is positive.8) If Δ°G of the reciprocal reaction. This is not a problem for the description of a reciprocal oxide phase. In Fig.)3 − (a3+ )2 (O 2. 51 . Va)3 at very low temperatures (to make the configurational entropic contribution negligible). Va)3 for a Cr-doped LSM perovskite as a function of composition. The morphology of the Gibbs energy surface depends on Δ°G of the reciprocal reaction (a3+ )2 (Va)3 + (a 2 + )2 (O 2.2. the true surface shape of a reciprocal oxide phase with charged endmembers is not known.2.)3 and (a 2+ )2 (Va)3 by only slightly oxidizing or reducing it..)3 and the reference (a 3+ )2 (Va)3 are fixed. and without excess terms for the Gibbs energy is visualized in Fig.1 (page 50) only the edge of this plane is seen as bold line. it is legitimate to define Δ°Grec = 0.2. Note that in order to obtain the same Gibbs energy of the reduced compound R for Δ°Grec > 0 and Δ°Grec = 0. Va)(O 2. and oxygen partial pressure. As no tendency of demixing was reported for the nonstoichiometric oxide solid solutions that are treated in this study. for instance (a 3+ .Method The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . if Δ°Grec is zero. Anyway. and the theoretic compound A will tend to demix to (a3+ )2 (O2.) 3 − °G ( a 2+ ) 2 (Va)3 (3. temperature. the Gibbs energy surface is flat and no tendency of demixing of A exists. 3. 3.
Grundy. 33-41. 1998.3 Optimization of model parameters The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system. 6. 3. Jansson. 437-445. 34..-O. Vol. 1. L. 4. 2. Cmpd. J. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously. Pergamon Materials Series.J. 2006. Sundman. Calculation of Defect Chemistry Using the CALPHAD Approach. The program minimizes the sum of squared errors between calculated and experimentally determined phase diagram and thermodynamic data. A. 5. The Thermo-Calc databank system. 2001. E. M. A. B. 9(2). pp. Sundman. B. 479 p. M.. Andersson. pp.. 79(2). Sundman. Hillert. B. 320. Jansson. This weighting process is based on the accurate assessment of experimental thermodynamic and phase diagram data. Andersson. pp. 30. 1988. Calphad.Method 3.F. B. Alloy. Jansson. Application of the Compound-Energy Model to Oxide Systems.. the authors selectively adjusted the relative weight of each experimental data point and excluded data that were inconsistent with the majority of the data points during the optimization procedure. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. pp. 1986. References 1. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. Ivas. T. Hillert. J. 52 .O. Elsevier Science Ltd. Z.N. B. Guillermet. N. J. Hillert. Miodownik. Povoden. Gauckler. M. Calphad. 153-90.P. 81-87. Acta Metall. pp. The Compound Energy Formalism. A. 161-76. 1985. Calphad Calculation of Phase Diagrams. B. Metallkd. Saunders.
thus substantially reducing the triple- 53 . which block active sites as well as pores. Nonstoichiometry of eskolaite (Cr2+xO3) is described using the compound energy model. and the liquid is described using the two-sublattice model for ionic liquids. For the planar design SOFC. due to the high operating temperature (>1173 K). 5 wt. 2006.1. Loss of performance caused by the migration of Cr originating from the alloy interconnect is well documented by several investigators. Grundy. and L. the use of this alloy as an interconnect material in SOFC leads to the degradation of the fuel cell performance especially on the cathode side of the fuel cell. which offers low fabrication costs. Gauckler J. a consistent set of thermodynamic model parameters is optimized based on new experiments.% Fe and 1 wt. ceramic and metal interconnect materials have been tested and evaluated over the years. However. pp.Thermodynamic assessments 4 Thermodynamic assessments 4.J. Microstructural analyses of the cathode of SOFC show the formation of Cr2O3 and (CrMn)3O4..N. 27.% Y2O3 developed jointly by Plansee and Siemens with satisfying material properties has been promoted as a suitable alternative to the earth alkaline-doped LaCrO3 ceramics interconnect.and power-generation capability.1 Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research E. Cr3O4 is described as a stoichiometric compound. combined heat. by application of the CALPHAD method. low manufacturing costs and high thermal conductivity.1 Technology SOFC offers high fuel conversion efficiencies and. Phase Equilib. A. Namely a Cr5Fe1Y2O3 oxide dispersion strengthened alloy with the composition 94 wt. A comprehensive compilation and evaluation of experimental and thermodynamic data for the Cr-O system is presented and. 353-62. 4. Also the magnetic transition in Cr2O3 and the oxygen solubility in Cr are modeled. Diff. Meanwhile the use of Cr-based alloy interconnect materials has gained popularity due to their relative ease of fabrication. Povoden.% Cr.
These authors document the existence of a large miscibility gap between the metallic and the oxide melt. tectic T (K) ----T (K) ----Reference Kanolt experimental Wilde and Rees experimental McNally et al.1. Eskolaite (Cr2O3) is the dominating stable oxide phase over a wide temperature range. X(O) ----Cr3O4 detected ----Stability range Mono- of Cr3O4.1 Special points in the Cr-O system Eutectic Melting of Cr2O3 in Eutectic composition.1.1.2 Experimental data Phase diagram data: Experimental investigations of phase diagrams in the Cr-O system were made by Ol’shanskii and Shlepov and Toker. Table 4.1.Thermodynamic assessments phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. The influence of Cr from the interconnect alloy on the strontium-doped lanthanum manganite (LSM) cathode can be modelled in terms of an equilibrium thermodynamic view to contribute to strategies for reducing the SOFC chromium poisoning process by optimizing SOFC operating conditions and refining SOFC material compositions. experimental Bunting experimental air. Results of special points in the Cr-O phase diagram from several studies are summarized in Table 4. 4. T (K) T (K) 2257 2317 2603 ---- 2543 ± 25 -- 54 .
Lam reported the existence of molten chromium with oxygen impurities of 1400 ppm at T = 2133 K.496 0. whereas Toker et al.Thermodynamic assessments --2571 ---2539 1933 1918 1941 1929 1937 1938 ± 2 1938 0.497 0. experimental This work.499 0. calculated Note: Itallicized data were used for optimization The melting temperatures of eskolaite in air reported from Kanolt and Wilde and Rees can be discarded as being too low. concluded from microstructural observations and a discontinuity in the slopes of the temperature-oxygen pressure curves for univariant equilibria involving metallic Cr and various chromium oxide phases that a Cr3O4 phase exists in a narrow temperature range between T = 1923 K and 1978 K. Ol’shanskii and Shlepov and Johnson and Muan did not find Cr3O4 up to the eutectic temperature of chromium oxide. Investigations made by Hilty et al.% Cr2O3 lowers the melting point of metallic Cr from T = 2163 K to between T = 2043 K and 2063 K. experimental Johnson and Muan experimental Degterov and Pelton calculated Kowalski and Spencer calculated Taylor and Dinsdale calculated Toker et al. and Hook and Adair led them to postulate the existence of a crystalline Cr3O4 phase in the Cr-Fe-O system.513 0. The question of the existence of a crystalline Cr3O4 phase was discussed controversially by several authors.497 no no yes yes yes yes yes --1923 1978 1918 1974 1923 1978 1923 ± 2 – 1978 ± 3 1918 1973 – – – – 2083 2083 -2160 2130 2083 2117 Ol’shanskii and Shlepov. This value significantly deviates from the result of Bunting. who measured T = 2543 ± 25 K also in air.523 0. Concerning the pure Cr-O system. Microstructures of a quenched 55 . Mc Nally measured a melting temperature of 2603 K in air using an induction furnace.52 0. Grube and Knabe found that 1 wt. The monotectic reaction of Cr (bcc) metal and liquid was found at T = 2083 K by Grube and Knabe and by Ol’shanskii and Shlepov.
1273 K. Pugliese and Fitterer. and Tretjakow and Schmalzried were assigned to possible electronic conduction in the zirconia electrolyte used by the latter authors. The independent results of corrected cell potentials of the two measurement series are excellent.. days for T < 1100 K. as well as the importance of sufficient time to attain equilibrium. Novokhatskii and Lenev studied the equilibrium of the reduction of Cr2O3 to Cr with hydrogen from T=1493 K to 1893 K. Thus in this study the authors accept the findings of Toker et al. The obtained 56 . causing transfer of oxygen through the cell. and Lam. At T ≥ 1573 K they were confronted with the loss of a quarter of Cr in the case of oxidation. thus at these temperatures log( pO2 ) values were determined solely from the reduction of Cr2O3. measured log( pO2 ) values of Cr2O3 by equilibrating Cr and Cr2O3 in H2-CO2 mixtures of known oxygen potentials at temperatures from T = 1773 K to 2098 K..Thermodynamic assessments chromium melt with maximum oxygen impurities of about 2930 ppm lately investigated by Lam document an inner Cr3O4 phase and an outer Cr2O3 phase in dispersed oxides in large chromium grains and grain boundaries.. Appreciable sublimation of metallic chromium was not observed. Davies and Smeltzer determined log( pO2 ) values of Cr2O3 at T=1173 K. using an electrochemical cell with a calcia-zirconia electrolyte and a Fe/FeO reference electrode. that is. Pehlke et al. Applying the same technique as Pehlke et al. used two separate series of emf measurements employing the solid oxide electrolyte galvanic cell technique from T = 1148 K to 1548 K. Thermodynamic data: Oxygen Potentials: Grube and Flad measured log( pO2 ) values for the Cr-Cr2O3 equilibrium between T = 1053 K and 1573 K by both oxidizing Cr to Cr2O3 and reducing Cr2O3 to Cr in a flowing H2-H2O atmosphere. This indicates that the first phase to crystallize on solidification is Cr3O4 giving strong evidence for the stability of this phase. and 1373 K. as well as transport of oxygen ions from the cathode to the Cr/Cr2O3 anode. Disagreement between the emf results from Pehlke et al. The reversibility and accuracy of the yttria-doped thoria electrolyte and the electrode was tested by measurements of a standard iron-chromium alloy at 1326 K. Toker et al. The data are in close agreement with the gas-solid equilibrium measurements by Jeannin et al. Holzheid and O’Neill noted a deviation from the well-established trend from T = 900 K to 1300 K for high-temperature data caused by finite electronic conductivity at elevated temperatures. These authors used a flow method where thermal diffusion problems were suppressed by inserting corundum bushes into the reaction tube.
Bruce and Cannell applied a two-dimensional temperature wave method using a single crystal of Cr2O3 to calculate specific heat in the temperature range 290.10 ×10−3 T 2 + 3.68 ≤ T ≤ 323. Resulting Cp data correspond nicely to the most recent calorimetric results from Klemme et al. and entropies: Anderson’s calorimetric data set of Cp-values lacks detailed documentation of the experimental procedure.7 % for Cp (T < 20 K) were estimated.2 results in C p = 28. The latter authors measured a consistent data set of heat capacities of synthetic eskolaite from T = 1. relied on the calculated results from heat content measurements performed by Kelley et al. Heat Capacities. heat Contents.53 + 2.. The latter authors fitted their data measured from T = 400 K to 1800 K by H T − ° H 298K = aT + b T 2 + cT −1 + d 2 ° (4. The accuracy of this study is evident from excellent data reproduction by performing two runs in the entire temperature range.2) Temperature derivation of Eq.Thermodynamic assessments dissociation pressures of Cr2O3 are in agreement with average values derived from emf studies using an yttria-doped thoria electrolyte worked out by Jacob and a very high temperature gas-mixing study of Toker et al.736 ×105 T −2 (4.84 J K-1mol-1 by a graphical method of plotting the heat capacity against the logarithm of the temperature and modeling the heat capacity curves with Debye 57 .1.37 J mol-1 K-1 at T = 298.5 K to 340 K with mean increments of 0.53T + 1. and fitting procedure are worked out very carefully. 4.17 ± 0. Documentation of the experiments.736 ×105 T −1 − 9759 (4. For Cp(Cr2O3) = 120. who calculated ° S298K (Cr2O3) = 81..56 K.1.1.. relied on the results from Anderson.3) For ° S298K (Cr2O3) Chase et al. data presentation.4 % for Cp (20 K < T < 200 K) and 0.1) yielding ° H T − ° H 298K = 28.20 ×10−3 T − 3.1.43 K.15 K Chase et al. Uncertainties of 0. and fitted the data to the heat of diffusion equation that considers some material properties employing a least-mean-squares fit.
74 ± 1.2 ± 0.3 J K-1 mol-1 from their measurements. This procedure was critically documented by other authors. Shirokov estimated Δ f.7 ± 8. Navrotsky cited Garrels and Christ for Δ f.86 J K-1 mol-1. for example. Klemme et al.5 kJ mol-1 (el=elements) by applying a calorimetric technique.06 kJ mol-1.. were used.72 kJ mol-1 from Wagman et al.16 K. which is in good agreement with an early finding by Bunting who measured T = 2543 ± 25 K.el° H 298K (Cr2O3) = –1128.el° H 298K (Cr2O3) = –1122. This was circumvented by heating the combustion products to T = 1323 K. adopted their ° S298K (Cr2O3) value from Wagman et al. 4.7 kJ mol-1. adopted Δ f. Degterov and Pelton reassessed the CrO-Cr2O3 subsystem for the molten slag database using a modified quasi-chemical model for the liquid phase.3 Previous assessments of the Cr-O system Banik et al. Enthalpies of Formation: Roth and Wolf found Δ f.Thermodynamic assessments functions.. The latter authors proposed a 58 . Dellien et al. recommend ° S298K (Cr2O3) = 83.el° H 298K (Cr2O3) = –1125. Their calculated liquidus temperature of Cr2O3 in air is T = 2571.el° H 298K (Cr2O3) = –1128. using a bomb calorimetric combustion technique at 1323 K and 30 atm oxygen pressure. and thermodynamic estimates for CrO from Shirokov.4 kJ mol-1 by evaluating emf data from Holzheid and O’Neill.1 J K-1mol-1 by reevaluating emf data from Holzheid and O’Neill. Klemme et al.el° H 298K (Cr2O3) the heat content data given by Kelley et al. evaluated Δ f. established a phase diagram for the Cr-O system based on a subregular solution model that is in good agreement with experimental data obtained by Ol’shanskii and Shlepov. recommended Δ f. Chase et al. Kowalski and Spencer used the associated solution model for the liquid phase based on the experimental data used by Taylor and Dinsdale. calculated Δ f.4 kJ mol-1 from several earlier studies.42 kJ mol-1. while Dellien et al. Ramsey et al.el° H 298K (Cr2O3) = –1134. Shirokov estimated ° S298K of a metastable CrO phase to be 46. who calculated ° S298K (Cr2O3) = 85. thermodynamic data for Cr-Cr2O3 from Fromm and Gebhardt.el° H 298K (Cr2O3) =–1140.1. used heat capacity and entropy data from tabulations of Coughlin to obtain Δ f.el° H 298K (CrO) = –305.98 ± 1. Klemme et al. Mah.4 kJ mol-1 for metastable CrO.8 ± 2.el° H 298K (Cr2O3) = –1139. For the calculation of Δ f. Some difficulty caused by moisture adsorption was encountered in weighing the combustion products..
especially as their miscibility gap does not close on increasing temperature. Toker. This is reflected by significant variations of the position of the eutectics. and only few thermodynamic data of the Cr3O4 phase and the liquid phase exist. Eskolaite shows an antiferromagnetic to paramagnetic transition at T = 305. and simplified by Hillert and Jarl. space group R3c . 4. at elevated temperatures as a sum of magnetic and nonmagnetic contributions. the stability field of Cr3O4. Experimental information on phase relations for their assessment was taken from Ol’shanskii and Shlepov. using the same thermodynamic models as the authors use in this work.4 Thermodynamic modeling Solid phases: The crystal structure of eskolaite is α-Al2O3 type.. Taylor and Dinsdale fitted Cp data from Anderson close to the antiferromagnetic to paramagnetic transition and data from Chase et al.5 K. The use of six parameters for the description of the Cr3O4 phase is somewhat incommensurate with the scanty experimental information of this phase. In this model. a magnetic contribution to the Gibbs energy is added to the nonmagnetic part of the Gibbs energy given as: MAG ΔGm = RTln(β +1) f ( τ ) (4.1.4) 59 . which are the two-sublattice ionic model for the liquid and the compound energy model for the Cr2+xO3 phase.Thermodynamic assessments phase diagram in good agreement with the experimental data obtained by Toker.1. There is a large uncertainty concerning the exact melting point of Cr2O3. The heat capacity of Cr3O4 was taken as 7/5 times the nonmagnetic value for Cr2O3 according to Neumann and Kopp’s rule. Their optimization of one of the charged endpoints in their compound energy model for eskolaite and the use of six interaction parameters to describe the liquid may lead to problems on extrapolation to higher-order systems. Their calculated values for the enthalpy of formation and the entropy of Cr3O4 are in agreement with an estimate done by Chipman. and the temperature of the monotectic reaction of Cr(bcc) and liquid between the assessments of the Cr-O system. The magnetic properties of eskolaite can be described using a magnetic ordering model proposed by Inden. and Grube and Knabe. Kelley et al.
The following other interstitial defects could be assumed: Cri•• giving a slope of pO2 −1 4 .1. Both are unlikely: the former because it is unlikely to get Cr4+ on reduction.Va)1 (O2-)3 can be modeled using experimental data from Matsui and Naito. Inserting this ' into Eq.5 and 4.1. however. 4.5) giving the equilibrium constant ' x [CrCr ]3 2 [Cri••• ]1 2 [Va ix ]1 4 [OO ]9 4 pO x x [CrCr ]2 [Va ix ][OO ]3 38 2 Kr = (4. and τ = T/Tc.1. it is important to submit the experimental data to a defect-chemistry analysis.7) 60 .Thermodynamic assessments where β is a parameter related to the total magnetic entropy. The defect chemistry of Cr2+xO3 with the sublattice occupation (Cr2+.28. their equation violates the fundamentals of defect chemistry and must be rejected in favor of the defect reaction given above (Eqs.6 gives the proportionalities [Cri••• ] ∝ pO2 −3 16 and [CrCr ] ∝ pO2 −3 16 . When modeling nonstoichiometry in an oxide phase.1. the latter because of the large size of Cr2+. and Cri•••• giving a slope of pO −3 20 2 . Tc is the critical temperature for magnetic ordering.Cr3+)2 (Cr3+. In the case of Cr2+xO3 modeled with interstitial Cr3+ the defect reaction reads x x ' x 2CrCr + Va ix + 3OO → 3 2CrCr + 1 2Cri••• + 1 4 Va ix + 9 4OO + 3 8O 2(g) (4. which is in agreement with Young et al.1.6).. Tc and β are both dependent on the composition.1.6) ' Assuming small defect concentrations all concentrations except [CrCr ] and [Cri••• ] are ~ 1 and ' can be ignored. Due to charge neutrality the relation [Cri••• ] = 3[CrCr ] must hold. Assuming the defect reaction that describes the formation of oxygen vacancies: x x ' CrCr + 1 2OO → CrCr + 1 2 Va •• + 1 4O2(g) O (4. The magnetic parameter p equals 0. 4. This means that reduction is accomplished by the formation of interstitial Cr3+ and not by the formation of oxygen vacancies. To explain their experimental results Matsui and Naito proposed a defect reaction that leads to the same proportionality.
where each corner of the composition square represents a °G parameter. Fig. Fig. In contrast to Matsui and Naito who explain this assuming that neutral Cr forms interstitially. The corner Cr3+:Va:O2corresponds to stoichiometric Cr2O3. Also the defects cannot explain the electrical properties measured by Young et al. As the most reasonable way to model reduction is to use the reduced neutral endpoint 61 .1. Only compounds along the neutral line can exist on their own. as it would make the description quite complex. 4. the present authors believe that the different slopes are caused by a competing defect reaction. 4. The present authors didn’t consider this by their defect chemistry model. Cr3+ → Cr2+ + Cr4+. similar to the case of LaMnO3 perovskites..1.Thermodynamic assessments ' leads to a proportionality of [Va •• ] ∝ PO2 −1 6 and [CrCr ] ∝ PO2 −1 6 .1 is a graphic representation of the model the authors use to describe the oxygen nonstoichiometry of eskolaite.1 Compound energy model for the Cr2+xO3 phase The four corner compositions represent all possibilities to express the Cr2+xO3 phase according to the above formula for the sublattice occupation. The low nonstoichiometry data from Matsui and Naito show a different slope than their higher nonstoichiometry data. The three other corner compositions present charged compounds. This slope does not correspond O to the experimental findings of Matsui and Naito. for example charge disproportionation.
2. The expressions for all °Gs at the corners resulting from Eq. 4. which leads to ° G Cr3+ :Cr3+ + °G Cr 2+ :Va − °G Cr3+ :Va − °G Cr 2+ :Cr3+ =0 (4.1.1.Thermodynamic assessments (Cr2+)2 (Cr3+2/3Va1/3)1 (O2-)3.1. 62 . The function to model the reduction then reads ° GCr2+ 3+ 2− 2 (Cr 2 3Va1 3 )(O )3 = °GCr O + 2 3 °GCrSER + A + BT + RT ( 2 3ln 2 3+1 3ln1 3) 2 3 (4.10 are listed in Table 4.1. This is done by using the two equations for the stoichiometric and the reduced endpoints.8) The last term describes the configurational entropy due to mixing of Cr3+ and Va on the interstitial site.9) In order to avoid the inevitable formation of miscibility gaps if the energy of the reciprocal relation is large we set this energy zero. °G of the 3+ charged endmember (Cr3+)2 (Cr3+)1 (O2-)3 is chosen as reference and given the value °GCr3+ :Cr3+ .1. one has to find functions of °G of three charged corners expressed solely in terms of the neutral compositions. 4.1.63-64.8 to 4. labeled A in Fig.1. pp. Then the reciprocal relation reads ° G Cr3+ :Cr3+ + °G Cr 2+ :Va = °G Cr3+ :Va + °G Cr 2+ :Cr3+ = ΔGr (4.10) This means that without introducing interaction parameters one gets an ideal description between Cr2O3 and Cr2+xO3. by choosing an arbitrary reference.1. and by defining a reciprocal reaction giving four equations with which all °Gs at the corners can be expressed.
− H Cr = GCR_L L SER GCr3+ :Va q.6 β = 3.5 p = 0.= 0 LCr3+ :O2.2923T 3 p = 0.+ qyVa .28 Tc = 308.)3 ° ° ° ° Cr 3 SER SER GCr 2O:Va:O 2.− 2 H Cr − 2H O = 2GCR1O1_L Reference Cr (bcc_A2) 1 2 Mass 51.Va)3 ° ° bcc SER GCr:Va − H Cr = GHSERCR  bcc SER SER GCr:O − H Cr − 3H O = GHSERCR + 3GHSEROO + 243T 0 bcc Cr:O.= 121000 Solid Cr (bcc_A2) (Cr)1 (O.52 mol O2 0 LCr 2+ :O2.− 3H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.1.2923T 3 Cr O3 SER SER GCr 22+ :Va:O 2.− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.2 Thermodynamic description of the Cr-O System Element Element Cr O Liquid (Cr 2+ .Cr 3+ ) p (O 2. q = 2 yCr 2+ + 3 yCr3+ ° ° ° ° L SER GCr 2+ :Va q.0 S298 23.Va L = −709542 Tc = −311.0 Cr3O4 ° Cr3O SER SER GCr:O 4 − 3H Cr − 4 H O = GCR3O4 Functions 63 .Va)1 (O 2.)q p = 2 yO2.996 15.Thermodynamic assessments Table 4.008 CrO ° Cr1O SER SER GCr:O1 − H Cr − H O = GCR1O1 Cr2O3 (Cr 2+ .− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L L SER SER GCr3+ :O2...Va q.− 2 H Cr − 3H O = GCR2O3_L L SER SER GCr 2+ :O2. Cr 3+ ) 2 (Cr 3+ .− 3H Cr − 3H O = GCR2O3 + GHSERCR  3+ Cr O3 SER SER GCr 22+ :Cr3+ :O 2.999 H298 .Va q.543 102..0 4341.H0 4050.Va q.− 2 H Cr -3H O = GCR2O3 3+ Cr 3 SER SER GCr 2O:Cr3+ :O 2.4 β = −0.
The descriptions for solid and liquid chromium metal and gaseous O2 are from Dinsdale. literature data from Caplan and Fraser are used.Va that must of course be negative. For the optimization of model parameters.5GCR2O3 − 0.5GHSEROO + 339673 − 121.2 (next page) is a graphic expression of the model. and gaseous O are from Dinsdale In contrast to Taylor and Dinsdale.31451 J mol-1 K-1. 0 LCr2+ :O2. The oxygen solubility in solid Cr(bcc) can be described by an interstitial solution model of the form (Cr)1(O.5GHSEROO + 255269 − 53. Parameters for solid Cr. It was not possible to model the oxygen solubility using the endmember °GCr:O as this endmember turned out to be too stable and CrO3 appeared in the stability diagram at high oxygen partial pressures. Fig. who needed 4 parameters to model the Cr2O3 phase and had to arbitrarily equate the °G of (Cr2+)2 (Va)1 (O2-)3 to stoichiometric Cr2O3.4T Note: All parameters are in SI units: J.76T GCRO0 = 108305 + GCR2O3 + 2 GHSERCR  3 GCR2O3_L = GCR2O3 + 439078 − 169T GCR1O1_L = 0.5GCR2O3 − 0.Cr2+)p(O2-. the number of parameters is kept as low as possible. The sublattice occupation (Cr3+. K. and one can reduce the number of parameters to only two. The Cr3O4 phase is based on the eskolaite phase. With this expression one is able to obtain reasonable results for the liquid phase using the positive interaction parameters. 64 . the latter constraint is not needed in the model.Vaq-)q is chosen.82T GCR3O4 = 1.Va that are required to give the miscibility gap.5GHSEROO + 280045 − 93...56T − 119.Thermodynamic assessments GCR2O3 = −1164542 + 728. Metastable CrO is described in the same way. Its heat capacity is given by Neumann and Kopp’s rule. mol.1. where each corner of the composition square represents a °G parameter of the liquid phase. Pa: R = 8. Ionic liquid: The two-sublattice ionic liquid model[50.51] is selected to describe the ionic liquid.Va)3. As the experimental data on the liquid phase are scarce.Va and 0 LCr3+ :O2. Therefore a large value is given to the endmember °GCr:O (in this case 0 was a large number) and the oxygen stability is modeled with the temperature dependence of °GCr:O and a regular interaction parameter 0 LCr:O. 4. liquid Cr.97 × 10-3T 2 + 1050000T -1 GCR1O1 = 0.8T ln T −4.5GCR2O3 − 0.
One derives the °GL functions of the oxide compositions (Cr3+:O2-) and (Cr2+:O2-) from the eskolaite phase. 4. in his original assessment of the Cu-O system. If the reciprocal energy of the system is large there will be a tendency to form miscibility gaps as pointed out by Hillert and Sundman. One way of doing this would be to simply say that Cr3+:Va equals Cr2+:Va plus a large positive term. In this model description of the liquid phase metallic Cr-liquid can be described by both the corners Cr2+:Va and Cr3+:Va. This considerably improved the description of the Cu-O liquid and removed the inverted 65 . Cr3+:Va must be metastable compared to Cr2+:Va.2 Two-sublattice ionic liquid model for the Cr-O system The four corner compositions represent all possibilities to express the liquid phase according to the above formula. This is however problematic for reciprocal systems.Thermodynamic assessments Fig. The °GL of liquid Cr is taken from Dinsdale. 4.2.1. Hallstedt and Gauckler recently reoptimized the Cu-O liquid. obtaining the parameter °GCu2+ :Va from the reciprocal relation and giving it a reciprocal energy of 0. The liquid composition changes along the hyperbolic curves in Fig. A special feature of the Cr-O system is the occurrence of a eutectic very close to the composition of CrO. for example +600000 as given to °GCu2+ :Va by Hallstedt et al.1. The eutectic temperature is mainly determined by the value of the corner Cr2+:O2-.
 close to the antiferromagnetic to paramagnetic transition temperature.. The melting temperature of eskolaite in air was taken from Bunting. the authors selectively adjusted the relative weight of each experimental data point and excluded data that were inconsistent with the majority of the data points during the optimization procedure.el° H 298. and experimental data on the liquidus at the oxygen rich side of the miscibility gap from Ol’shanskii and Shlepov. using experimental phase equilibria data from Toker et al. with low relative weight. ΔGr = 0 (4.11) 4.The ° G L 3+ Cr :Va = 2 °G L 2+ Cr :Va + °G L 3+ Cr :O2- − 3 °G L 2+ Cr :O2- + ΔGr . They assessed Cr3O4 and the liquid simultaneously.2 (pp.1. experimental data on the liquidus at the oxygen poor side from Toker et al. high temperature emf data from Holzheid and O’Neill  . PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously.16 and ° S298. 63-64). and Toker et al.1.16 data from Holzheid and O’Neill were used. An identical strategy is employed here. Δ f. Thus metallic liquid is given by the corner L parameter °GCr3+ :Va is obtained by the reciprocal reaction given as ° G LCr2+ :Va . at T = 290 K and from T = 335 K to 338 K with a low relative weight.1. and Cp data from Klemme et al. The program minimizes the sum of squared errors between the calculated and experimentally determined phase diagram and thermodynamic data. and. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. In principle. The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system. The authors optimized Tc and β using Cp data from Klemme et al. The first parameters to be optimized were the Cp-parameters of Cr2O3. These parameters were then kept fixed during the rest of the optimization. The data used were heat content data from Kelley et al. Finally the solubility of O in solid Cr was optimized using data 66 .Thermodynamic assessments miscibility gap found at high temperatures in the original assessment..5 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Cr-O system is given in Table 4. To determine the parameters describing the enthalpy and entropy of Cr2O3 log( pO2 ) data from Jeannin et al.. In the next step the authors optimized the nonstoichiometry of Cr2+xO3 using data from Matsui and Naito.
4. logarithmic) given.1.6 Results and discussion Phase diagram: The calculated phase diagram with oxygen isobars is shown in Fig.Thermodynamic assessments from Caplan and Fraser. 67 .1 (p.1. 4.4 (next page).3 Calculated Cr-O phase diagram with oxygen isobars (Pa. The gas phase was not included in the calculation An enlargement of the phase diagram close to the CrO composition is presented in Fig.1. 4. 54-55) values that were used for our optimization are written in italic letters.1. Fig. 4.3. In Table 4.1.
4. logarithmic) included The shape of the liquidus at the oxygen poor side of the miscibility gap resulting from the authors’ optimization relying on a single experimental datum from Toker et al. 2 68 .497 it decomposes in a peritectic reaction at T = 1973 K forming Cr2O3 and liquid.Thermodynamic assessments Fig. Cr3O4 is formed at T = 1918 K by the eutectoid reaction Cr2 O3 + Cr + 1 2O2 → Cr3O4 .497. in good agreement with the measurement from Bunting. 4. with experimental data and oxygen isobars (Pa.1. and an earlier experiment from Ol’shanskii and Shlepov is slightly deviating from former optimizations. and for the eutectic one gets T=1938 K at a mole fraction of oxygen of 0. For the monotectic temperature of the reaction of Cr (bcc) and liquid the present authors calculate T = 2117 K.1. At a mole fraction of oxygen > 0. Fig.4 Enlargement of the calculated Cr-O phase diagram close to the CrO composition. The calculated liquidus temperature of eskolaite in air is T = 2539 K.5 (next page) shows the calculated oxygen potential phase diagram of the Cr-O system with experimental log( pO ) data included.
5 Calculated oxygen potential phase diagram of the Cr-O system.6 Stability of Cr3O4 in the log( pO2 ) versus temperature diagram 69 . 4.Thermodynamic assessments Fig. with experimental log( pO2 ) data as a function of temperature from different studies The experimentally determined phase stabilities from Toker et al. The stability of Cr3O4 is shown in the log( pO2 ) versus temperature diagram in Fig. 4. 18.104.22.168. The shape and size of the miscibility gap is speculative due to the lack of experimental data. Fig.1. are particularly well reproduced by the authors’ optimization.
The cation overstoichiometry resulting from the presented optimization might seem somewhat high. logarithmic) included For the maximum solubility of oxygen in Cr(bcc) one calculates 0. 4.098 at T = 1918 K.1. 4.% at T=1938 K.1.8 (next page). If the commonly used – however grubby – notation “Cr2O3-δ” is applied.1. but it results simply from the extrapolation of experimental data from Matsui and Naito on excess Cr as a function of pO down to the oxygen partial pressure at the Cr-Cr2O3 2 equilibrium following the proportionality given by the defect chemistry analysis in section 4.08 at.7. The comparison of the calculated nonstoichiometry in Cr2+xO3 with the experimental data by Matsui and Naito is given in Fig.4.Thermodynamic assessments The solubility of oxygen in Cr(bcc) is shown in Fig.1. The maximum calculated δ = 0. 4. 70 .7 Calculated oxygen solubility in Cr(bcc) with experimental data and oxygen isobars (Pa. the total charge of Cr is given by 6+2δ. Fig.
1. as the introduction of an additional defect species would be required to reproduce these. The data at low oxygen nonstoichiometries were not used. The low nonstoichiometry data show a different slope than the higher nonstoichiometry data. Considering a temperature dependence for the reduced neutral endpoint of the phase Cr2+xO3 gives values of GCRO0 = −202130 + 235T + GCR2O3 + 2 3GHSERCR (dotted lines in Fig. and due to existing data at only three different temperatures from a single author it was decided not to optimize a temperature dependence giving GCRO0 = 108305 + GCR2O3 + 2 3GHSERCR .8 Optimized nonstoichiometry of Cr2+xO3 with the only available experimental data from Matsui and Naito included. Solid lines result from our accepted optimization without considering temperature dependence. 4.8) and leads to the reduced neutral endpoint being too stable at low temperatures.1. Optimization of a temperature dependence is represented by dotted lines. Obviously the calculated results show a temperature dependence that is significantly stronger compared to the experiments. 71 . Therefore. 4.Thermodynamic assessments Fig. The solid lines correspond to the optimization that is accepted in this work.
which is in particularly good agreement with the data from Ramsey et al.555 J K-1 mol-1.el° H 298K (Cr3O4) we calculate –1402 kJ mol-1. Cp. of the solid Cr2O3 phase (Fig.1. Fig. and ° S298K = −79 J K -1 mol-1 based on the estimates of Shirokov.0. 4.1.685 kJ mol-1. These values for Cr3O4 deviate significantly from the results of Taylor and Dinsdale who calculated Δ f ° H 298K (Cr3O4) = –1447..el° H 298K (Cr2O3) we calculate –1123 kJ mol-1. and ° S298K (Cr3O4) = 150. and for Tc we get 308. which is very close to the results from Holzheid and O’Neill.9) are well represented by our assessment. and for ° S298K (Cr2O3) we get 85 J K-1mol-1. For a metastable CrO phase we calculate Δ f.9 Comparison of calculated heat capacities of Cr2O3 with experimental data For the magnetic parameter β we calculate 3. 72 .el° H 298K = −306 kJ mol-1 .Thermodynamic assessments Thermodynamic Data: The heat capacities. For Δ f. 4. For Δ f. and for ° S298K (Cr3O4) we get 175 J K-1mol-1.6.
203(2). Bur. R. Ol’shanskii. 6(6). V. J. Toker. 99. 2000. 1961..Y. Y. Ceram. pp. Acad. P. 1997. it must be kept in mind that experimental data on the liquid miscibility gap are largely missing. Shlepov. McNally. Bunting. Grube. 1936.. Ribbe. and that a large variation of the measured melting points of eskolaite exists.F. Ceram. I. 10. pp. 3. 793-804 (in German). 1913. pp. J.K.W. Sistema Cr-Cr2O3. 315-18. The system palladium–chromium. Solid State Ionics. R.. Trans. Lam. Melting points of some refractory oxides. Elektrochem. 42(11). 1978. However.C. C. 3. D. G. Kanolt. SSSR.L.T. 7. 297-310.. pp. pp. 5. N.P. Min. 73 . Melting and casting of high purity chromium with controlled oxygen content. Nat.N. Hilty. Phase equilibria in the system Cr2O3-Al2O3. melting points of MgO in a N2 atmosphere and of Cr2O3 in N2 and in air atmospheres. R. 491-93. W. Ramprakash. W. 4. T. Wilde. Rees.7 Conclusions With the presented reassessment of the Cr-O system the authors are able to excellently describe available thermodynamic and phase diagram data with as few optimizing parameters as possible. Wash. Res. 561-64. 1953.H. Zhang.. E. 947-49. R. Deller. W. pp. Metall. Folkman.I. Knabe. Eng. Stand. J. 42(7). United States Patent 6039788. 44(10).D.N. Foger. K. 8. Laboratory furnace for studies in controlled atmospheres. The ternary system MgO-Al2O3-Cr2O3.1. Brit.P. Badwal. 91(3). Forgeng. Sci. 123-55. R. F.Thermodynamic assessments 4. 1955. References 1. pp. Akad. Pennsylvania State University. 6.S.J. 1931. 2. Thesis. Equilibrium phase relations and thermodynamics for the systems Cr-O and Fe-Cr-O in the temperature range 1500 to 1825 °C.K. Y.. Soc. Nauk.I. 9. pp. Am. 1943. J. Z. Dokl. S. Oxygen solubility and oxide phases in the FeCr-O system. J. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. 253-68. Peters.
227(2). Chem.T.M. 4451-59. 1975. E. Lenev. 59(3). Geochim. 22. 1(7). 15. Metall. 24. R. A. 1977.. FeCr2O4. 19. C. Darken. 300-5. Anderson. J. pp. Phys. F. Trans. Mannerskantz. Soc. Pugliese.D. The heat capacities of chromium. R. Jacob. Bunsen Gesell. 1964. Geochim. F. J. 488-91. Smeltzer. 1827-31. pp. pp.S. Thermodynamic properties of Cr2O3 and FeCr2O4 at high temperatures. Schmalzried.D. Adair. 1974. The formation and dissolution of chromium oxides in chromium.. 1970. Muan. 51(8). pp. O’Neill.. 22(2). J. 14.H.E. Soc. Activities and phase boundaries in the Cr–Ni system using a solid electrolyte technique. Ac. Soc. Specific heat of Cr2O3 near the Neel temperature. Aime. and Cr2O3 at low temperatures and derived thermodynamic properties.R.D. 15(9). pp. Ceram.E.Y.S. Muan. 20. chromous chloride and chromic chloride at low temperatures. Rev.. Affinity and enthalpy of the solid solution in the system Cr-Ni. Soc. O’Neill. L. Ac. Tretjakow. L. H. 11(9). R. W. Hook. Cannell. Trans. Mazandarany. 1686-93. Richardson. Z. Am.N. 2000.Thermodynamic assessments 11. pp.S. Flad. Metall. pp.. Am. 69(5).. Holzheid. Soc. Electrochem. 12. Ceram. R. Bruce. 1937. 13. G. J. pp. chromic oxide. K. Metall. B. 1997-2002.. B. 1942. 23. 1977. Russ. 21. Klemme. R. 59. 39. Grube. aluminate). A. Phase diagrams for the systems Si-O and Cr-O. 25. Y. 225-32. Jeannin. Cosmochim. Electrochem. Fitterer. 17. Johnson. 377-89 (in German).. Solid oxide electrolyte emf cell determination of the standard free energy of Cr2O3 and applications to chromium–bearing mineral systems. The heat capacity of MgCr2O4.A. pp.S. T.T.M. 430-33.. 124. 18. A. 121(4). Oxygen and metal activities of the chromium–nickel–oxygen system between 900° and 1100°C. 1278-83. H. Soc. 396-402 (in German). Berich. Metall. J. 48(7). pp. 1995. Cosmochim. 230(6). 475-79. Elektrochem. Pehlke. pp. Gmelin. 1991. 74 . pp. Mineral. Am. T. 1078-80. Davies. 85.W. pp. D. N. H. Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites. Inorg. 1965. Equilibrium phase relations and thermodynamics of the Cr-O system in the temperature range of 1500 °C to 1825 °C. Toker. 1966.H. Activities in iron–chromium alloys. 1963. Radzilowski. H. L. 16.. pp. J. ferrite. C.. A. S. M. Novokhatskii. The thermodynamics of spinel phases (chromite. W. 833-45. pp. Aime. 543-49. The Cr-Cr2O3 oxygen buffer and the free energy of formation of Cr2O3 from high-temperature electrochemical measurements. 1968. G. A. Schnelle.
pp. Gebhardt: Gases and Carbon in Metals. 102. U. I. B.M. 2. J. Chem. 270(4).H. Evans. Caplan. Banik. D. Thermodynamic properties of chromous oxide. 1940. I. Ref. Metallkd. Paper. pp. Berlin. 45-46 (in German). 410. Chem. Mines Tech. 1980. 940-42. Harper & Row. Pelton. 1976. SSSR. E.N. Downey. F. 17(6). 135-38. Z.. 71(10): pp. J. 1965.H. 76(13).S.Thermodynamic assessments 26. C. J. Metal.A. and standard potentials. Data. Kelley. 28. Cosmochim. 3363-65. Chase. The heat of formation of chromium oxide. p. Nauk.D.D. R. Bur. 542. D.A. V. Bailey. G. W. Soc. pp.I. Electrochem.. R. P. 476-87.M. Minerals and Equilibria. Wolf. W. Notes. T. Tables for elements 35 through 53 in the standard order of arrangement. Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3. Schumm. pp. 1985. 30. 76(3).. 29. Heidelberg. 14(Suppl. Boericke. molybdenum. K. Davies. Schmitt.K. Chromium. and tungsten: thermodynamic properties. E. 36.B. Fromm. A. Burr. Halow. Degterov. Syverud.. 103(2). 1969.W. Thermodynamic consideration on the system Cr-Cr2O3. J. Thermochemistry of chromium compounds. Ac. NBS Tech. Janaf thermochemical tables . 1975.H. 39. and CrO-Cr2O3-CaO systems. D. Phys.M. S. L. Soc. Contributions to the data on theoretical metallurgy.. 39. 34. A. E. Coughlin. S. N. J. New York.A. Shirokov. Selected values of chemical thermodynamic properties. 1956. F. Springer Verlag. Thermodynamic properties of carbides of chromium. 819-32. Bur.M.. W.. 32. 31. M. Navrotsky. Ramsey. Flurip. Hall.L. 35. 1996. A.J. Ettmayer. especially oxides at high temperature. Dellien. 38. 1944. Elektrochem. 1954. J. 1976. 1954. Bangert.G. 662. Z. Chem.. R. pp.P. CrO-Cr2O3-Al2O3. Mah. Lux. Hepler. Garrels and C. A. McDonald.. Heats of formation of chromium oxide and cadmium oxide from combustion calorimetry.. J.A. Thermodynamics of the oxidation of chromium. Roth. 33. Geochim. 75 . Mines Bull. 46. 1973.3rd ed. 80 pp. pp. Akad. Parker. 1): pp. Phase Equilib. N. 521-34 (in German). pp. p. Rev. Am. Huffman. 644-45. D. Wagman. Dokl. Christ: Solutions. 283-310. Jr. 27.R. 43 pp. chemical equilibria. 37.
50.A. pp. pp. Calphad. P. 1987. Sr-Cu-O. 78-82.. pp. Povoden. 599-605. 2257-60. M. 48. Metallkd.J. Chipman. Jansson. 47. A. Kowalski. A. J. pp. 227-38.J. Calculation of defect chemistry using the Calphad approach.T. A model of alloying effects in ferromagnetic metals. Atomic interactions in molten alloy steels. pp. 2003. J.. L. 2(3).W. 109-19. Jarl. 16A. 136. Fraser. A.. 15. J. Iron Steel Inst. Sundman. 46. 33-41. E. pp. p. pp. M. Hallstedt. Phase Equilib. 52. 1957. M. 196. Ågren. Mater. The oxygen partial-pressure dependence of the defect structure of chromium(III)oxide. 43. K. AgO. Young. pp. Calphad. ASM. 177-91. Ohio. 81(5). B. M. Determination of chemical and magnetic interchange energies in bcc alloys. 19(3). pp. 483-99. Calphad. Sundman. Gauckler. Ag-Cu-O. 1994.. 134(9). Calphad. Sundman. 45. T. Ca-Cu-O and Sr-Ca-Cu-O systems. 53. L. I. pp. SGTE data for pure elements.A. Z. Burr: in Ductile Chromium. Calphad.W. 1985. Hillert. Hillert. M. 27(2). Electrochem. Bi-Sr-O. Gauckler. Dinsdale. 49. Gerretson. 66(10). D. G. 1985.T. 2005. 44. 54. Ivas. J. Cleveland.. Spencer. 76 . B. pp. Hallstedt. B. 1991. Thermodynamic assessment of the copper-oxygen system. Risold. 97-106. Trans.H.R. B. 1994. pp. Inden. 354-66. Metall. Calphad. 42. 1978. 25(4). Nucl. 261-66. Cr-O and Cr-Ni-O systems using the ionic liquid and compound energy models. L. 41. Z. Grundy. A thermodynamic assessment of the Ni-O. 15(4). 1990.J. B. J. B. J. Hillert. Predicting miscibility gaps in reciprocal liquids. bcc and fcc phases. Matsui. J. 1955. Metallkd. Modification of the two-sublattice model for liquids. 15(5). J. Revision of the thermodynamic descriptions of the Cu-O. T. 1995.H. Dinsdale. 180. 1975. 2001. Soc.N. Existence of hypostoichiometric chromium sesquioxide at low oxygen partial pressures. J.J. Bi-Cu-O. Taylor. Thermodynamic reevaluation of the Cr-O. A. A. Fe-O and Ni-O systems: 229-43. de Witt. 51.. D. 1991. 577-82. pp. General treatment. E. 317-425. Gauckler. Remodelling of the liquid. Caplan. A two-sublattice model of molten solutions with different tendency of ionization.Thermodynamic assessments 40.J. Calphad. Naito. pp. 30. M.
Mater. 97. a consistent set of thermodynamic model parameters is optimized for the Cr-Mn-O system based on experimental data. We are contributing to the understanding of the underlying thermodynamics of these processes by assessing the MnCr-O system using the CALPHAD approach. The Thermo-Calc databank system.% Cr. B. mobilization predominantly via the gas phase of Cr originating from the alloy interconnect leads to the formation of Cr2+xO3 (eskolaite) and chromium manganese spinel MnyCr3-yO4 which block catalytically active sites as well as pores. Mn2-yCryO3. and 0. 9(2).2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials E. and Mn-Cr binaries from Grundy et al. B.1 Introduction For the planar design of SOFC the use of heat-resistant high chromium alloys has been promoted as a suitable alternative to earth alkaline doped LaCrO3 ceramic interconnect materials[1.. thus substantially diminishing the triple phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface.O. and L.. A. The thermodynamic data of the pure elements are taken from Dinsdale. By application of the CALPHAD method. Gauckler Int. 153-90. pp. 2006. 569-78.2]. Sundman. 1985. Jansson.8 wt.J.. Chromium manganese spinel MnyCr3-yO4 and its tetragonally distorted polymorph are described using the compound energy model. Andersson.2. J. J. Povoden et al.Thermodynamic assessments 55. and (Mn1-yCry)1-xO are considered. Povoden. Res. Grundy. Cr-O.45 wt. Also solid solutions of the phases (Cr1-yMny)2+xO3. The processes by which these protective oxide scales reduce the chromium poisoning and their effect on cell degradation during long-term SOFC operation are not well known yet. and Lee  77 . 22.N. pp.% Mn resulted in an improvement of short-term SOFC operation.6 wt. 4. Calphad. Simner et al. and the liquid is described using the two-sublattice model for ionic liquids. and the data for the Mn-O. Relevance for solid oxide fuel cells is discussed. However. 4. observed that the formation of chromium manganese spinel layers on top of a Cr2O3 oxide scale on the surface of a Mn-containing ferritic stainless steel (Crofer22 APU) interconnect with 76.% Fe.
4 (p.2. 78 . 80) shows the calculated phase diagram at pO2 = 1×10-4 Pa . bcc for chromium manganese alloy with bcc A2 structure.2 (p. β-hsm (βhausmannite) for the cubic and α-hsm (α-hausmannite) for the tetragonally distorted Mn3O4 endmember of the spinel solid solution. 4. bxb for Mn2O3 (bixbyite) with dissolved Cr.2. 4. and 4. and liq for the liquid phase.3 (p.2. 80). 4. MnO2. however all the binary oxides except pyrolusite (prl). α-spl for tetragonally distorted polymorph spinel solid solution. whereas spinel of the formula [B3+](A2+B3+)O4 with half of B on the tetrahedral sites – marked with angular brackets in the above formulas – is called inverse spinel.Thermodynamic assessments respectively. 79). show varying degrees of mutual solid solubility. Normal spinel is given by the formula [A2+](B3+)2O4. In the case of cubic MnyCr3-yO4 both the trivalent cations of manganese and chromium show a remarkable preference to fill the octahedral sites marked with round brackets in above formulas. The most prominent oxide phase in the Mn-Cr-O system is cubic chromium manganese spinel with the formula MnyCr3-yO4. esk for Cr2+xO3 (eskolaite) with dissolved Mn.2.1. Fig.2 Experimental Phase diagram data: Our calculated phase diagram of the MnOx-Cr2O3 system in air is shown in Figs. mgs for Mn1-xO (manganosite) with dissolved Cr. No new ternary phases are found in the Mn-Cr-O system.2. 4. Spinel containing a large amount of Mn3+ becomes tetragonally distorted on lowering the temperature as a consequence of the macroscopic Jahn-Teller effect that is caused by the distortion of the octahedral sites occupied by Mn3+. In this work we use the following abbreviations: β-spl for cubic chromium manganese spinel solid solution.
4. with experimental data.2. 4. 79 .1 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. Fig.2. The gas phase was not included in the calculation. The gas phase was not included in the calculation.2 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air.Thermodynamic assessments Fig.
showing the expanded stability field of β-spl + mgs.4 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 under strongly reducing conditions ( PO2 = 1×10-4 Pa ). 4. with experimental data.2. Fig.2.3 Mn rich part of the calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. 80 .Thermodynamic assessments Fig. 4.
 studied the MnOx-Cr2O3 system using quenching techniques and high temperature X-ray diffractometry in air in the temperature range from T = 973 K to 1673 K. Pollert et al. They find β-spl + α-spl + bxb coexisting in equilibrium at T = 1183 ± 5 K.2.2. and Pollert et al. 4. They consider the solubility limit of Mn in (Cr1-yMny)2+xO3 to be negligible.. investigated the compositions of coexisting β-spl + mgs and β-spl + esk from pO = 2×10-6 to 2×102 Pa at T = 1873 K thus determining the range of solid solubility of 2 β-spl by quenching techniques under controlled CO-CO2 atmosphere (Fig.Thermodynamic assessments Speidel and Muan present a phase diagram of the MnOx-Cr2O3 system in air in the temperature range 873 K to 2253 K resulting from the determination of phase equilibria using quenching techniques and X-ray and microscopic examination (Fig. 79). Their data are shown in Figs. They report a minimum temperature of β-spl stability of T = 973 K and lower solubility of Cr in tetragonally distorted MnyCr3-yO4 and of Cr in Mn2-yCryO3. The solubility limit of Cr in Mn2-yCryO3 is measured by these authors to be y = 0. p. but it is lower than the findings from Speidel and Muan. Pollert et al.42 at oxygen partial pressure >> 20000 Pa. 79 and 4. This value is in agreement with the result from Geller and Espinosa. Tanahashi et al.[14. next page). 81 .15] studied phase stabilities in the MnOx-Cr2O3 system in the temperature range from T = 1100 K to 1620 K in air by means of X-ray measurement of annealed samples.2. and β-spl + esk + liq in equilibrium at T = 2243 ± 20 K. p.5. 80. report a solubility limit of y = 1. They estimate a minimum temperature of T = 773 K for the stability of β-spl.14 at T = 1105 K in air.2.3. 4.2. Their resulting phase diagram is in considerable disagreement with the findings of Speidel and Muan.2. p. The Mn solubility in (Cr2-yMny)1+xO3 reported from Speidel and Muan is significantly higher than it is found by Golikov et al. 4. Golikov et al. From the absence of changes of the lattice parameters of esk in equilibrium with β-spl annealed at T = 1105 K and 1620 K in air compared to pure Cr2O3 they conclude that the solubility of Mn in (Cr2-yMny)1+xO3 is low and does not depend significantly on temperature.
1473 K. β-spl in equilibrium with esk. and 1873 K. They found almost unchanging solubility of Cr in (Mn1-yCry)1-xO from pO = 2×10-6 to 2 ×102 Pa at T = 1873 K.2. and mgs in equilibrium with β-spl in the pseudo-binary MnOx-Cr2O3 system as a function of oxygen partial pressures at T = 1073 K. In order to identify the equilibrium compositions. Phase relations were verified using X-ray diffraction. As the compositions of mgs 2 solid solution are located on the line connecting Mn1-xO with CrO in the ternary phase 82 . 4. They report small solubility of Mn in (Cr1-yMny)2+xO3 at pO2 = 2×10-6 . The compositions of β-spl are located on a line connecting MnCr2O4 with β-hsm in the ternary plot. esk in equilibrium with β-spl.5).Thermodynamic assessments Fig. From this result Tanahashi et al. 4. conclude that Mn is dissolved in cubic MnyCr3-yO4 in the form of Mn3O4. which increases slightly with increasing oxygen partial pressure. each phase in the quenched specimens was subjected to electron probe microanalysis (EPMA). Experimental data are included. and significantly increasing Cr solubility in cubic MnyCr3-yO4 with decreasing oxygen partial pressure (Fig. They found increasing Mn solubility in cubic MnyCr3-yO4 at oxygen partial pressure higher than 2 ×10-2 Pa .5 Cr contents of β-spl in equilibrium with mgs.2.
Also the experimental result on the three phase equilibrium MnO + MnCr2O4 + bcc from Ranganathan is plotted.Thermodynamic assessments diagram. Dotted lines are tie lines. two-phase fields and three-phase fields.1 to 10-13 Pa (Fig. Fig. There are no data on oxygen nonstoichiometry of MnyCr3-yO4. 82). 1173 K. 4. 4. single solid solution phase equilibria (heavy lines).2. these authors conclude that chromium oxide dissolves in (Mn1-yCry)1-xO in the form of CrO.5.2 cat.% at T = 1323 K performing an isopiestic experiment (Fig. For the invariant three phase equilibrium mgs + β-spl + bcc Ranganathan and Hajra measured the Mn content in bcc to be 25. Three-phase field boundaries are denoted with thin solid lines. Bobov et al.6 Ternary phase diagram of the system Cr-Mn-O with stoichiometric single phase equilibria (points).2. 4. investigated the composition changes of the two phase equilibrium β-spl + mgs at T = 1073 K.2.6). p. 83 . and 1273 ± 5 K in the oxygen partial pressure range from 0.
We recalculate this value using the most recently assessed Δf °GMnO  and Δ f °GCr2O3  β-spl values at T = 1873 K giving Δ f °GMnCr2O4 = –66 ± 8 kJ mol-1.2.MnyAl3-yO4 solid solutions formed from Cr2O3-Al2O3 mixtures at T = 1873 K.1) β-spl Using compiled Δf °GMnO and Δf °GCr2O3  they calculate Δ f °GMnCr2O4 from its oxides to be –59 ± 8 kJ mol-1. This means that the Gibbs energy of formation of β-spl of the composition MnCr2O4 from its 84 . Tsai and Muan experimentally determined compositions of coexisting MnyCr3-yO4 .2.5AlO2 = AlO1. 79). With decreasing Mn-content the temperature for the transition decreases (Fig. From these data and the activities of CrO1. enthalpies and entropies of MnyCr3-yO4 samples annealed at T = 1723 K using X-ray analysis and DTA measurement.4 for the formation of α-spl.2.2.5 + Mn0. Thermodynamic data: Cubic spinel (β-spl): Only values for the standard Gibbs energy of formation of β-spl of the composition MnCr2O4 β-spl are published.5 in Mn0.Thermodynamic assessments Holba et al.Cr3+)2O4 this corresponds to a minimum concentration of [Mn3+] = 0. p.5CrO2 (4.2) (4. solid Cr and oxygen at T = 1873 K in the pO range from 2×10-6 to 1. which is equivalent to Δf G of 1 2(Δ f GMnCr2O4 − Δ f GMnAl2O4 ) .5CrO2 obtained from a previous study they derive ΔG of the reaction CrO1.5×10-4 Pa from the 2 standard Gibbs free energy changes of the reactions Mn (in molten Fe) + 2 Cr (in molten Fe) +2 O2(g) = MnCr2O4 and Mn (in molten Cu) + 2 Cr (s) + 2O2(g) = MnCr2O4 (4.3) β-spl to be –10 kJ mol-1 at T = 1873 K. derive Δ f °GMnCr2O4 = –958 ± 8 kJ mol-1 from liquid Mn.5AlO2 and AlO1.8 do not show Jahn–Teller distortion at room temperatures. investigated the martensitic α-spl → β-spl transition temperatures. Giving α-spl the formula [Mn2+](Mn3+. Samples with y < 1. 4.5 in Mn0. and remain β-spl. Tanahashi et al.2.5 + Mn0.
1 kJ mol-1.0 kJ mol-1 at T=1523 K. and –36. 4. 4.6 kJ mol-1 β-spl giving Δ f °GMnCr2O4 = –52.6 kJ mol-1 at T = 1873 K. present thermodynamic data on the transition of α-spl to β-spl.2.4 ± 10 kJ mol-1.Thermodynamic assessments oxides using this calculation technique depends on the value of Δf °GMnAl2O4 . 85 . Biggers by using the same technique as Tsai and Muan β-spl MnO-Cr2O3 system found Δ f °GMnCr2O4 = –59. Filled symbols correspond to originally reported literature data. According to these authors the transition of pure α-hsm to β-hsm takes place at T=1445 K. –46.7. Using other values for Δ f °GMnAl2O4 reported β-spl in the literature[25-27] leads to deviating Δ f °GMnCr2O4 of –34. with experimental data and error bars. and ΔS α β = 13 J K-1 mol-1. ΔΗ α β = 18810 J mol-1. Fig.  in the CoO- β-spl The spread of Δ f °GMnCr2O4 values resulting from different studies and our recalculations is shown in Fig. Δ f °GMnAl2O4 = –32. Tetragonally distorted spinel (α-spl): Pollert et al.2. unfilled symbols correspond to recalculated values.1 kJ mol-1.7 Calculated Gibbs energy of formation of β-spl of the composition MnCr2O4 as a function of temperature. Tsai and Muan chose the value determined by Lenev and Novokhatskiy.
30].4) This endmember is considerably more stable than the endmember of the formula [Cr2+](Mn3+)2O4.Cr2+](Cr3+. In our CALPHAD assessment the °G values of all compounds are given relative to the enthalpy of selected reference states for the elements at T = 298.Mn2+.Thermodynamic assessments 4. Thus the endmember ° β-spl β-spl G[Cr 2+ ](Mn3+ ) O becomes less stable the more stable °G[Mn 2+ ](Cr3+ ) O becomes.2. The Gibbs energies of the endmembers [Mn2+](Mn3+)2O4 that corresponds to β-hsm. As the degree of inversity of β-spl is very low.2. Lu et al. However there is no experimental data quantifying the amount of Mn4+ in β-spl. so we stick to the less complex description without Mn2+ and Mn4+ on the octahedral sites. and [Cr2+](Cr3+)2O4 that corresponds to Cr3O4 are taken from the assessed binaries[7. β-spl can therefore be described by the simple formula [Mn2+. We define this last endmember using a reciprocal relation ° Cr O β-spl β-hsm β-spl G[Cr2+ ](Mn3+ ) O = °G[Cr32+ 4](Cr3+ ) O + 1 3 °G[Mn 2+ ](Mn3+ ) O − °G[Mn2+ ](Cr3+ ) O 2 4 2 4 2 4 2 4 (4.Mn4+)2O4. The Gibbs energy of the endmember of the formula [Mn2+](Cr3+)2O4 is given by the expression ° Cr O β-spl β-hsm G[Mn 2+ ](Cr3+ ) O = 2 3 °G[Cr32+ 4](Cr3+ ) O + 1 3 °G[Mn 2+ ](Mn3+ ) O + Aβ-spl + Bβ-splT 2 4 2 4 2 4 (4. measured the electrical conductivity of β-spl.Mn3+.2.Cr2+](Cr3+. To maintain electroneutrality Mn2+ is formed on the octahedral sites resulting in a charge disproportionation reaction. 2 4 2 4 86 . In our description we further go along with the presumption that the amount of oxygen vacancies may be neglected. This state is denoted SER (Stable Element Reference).3 Thermodynamic modeling Cubic spinel (β-spl): There is experimental evidence on the presence of Cr2+ in β-spl as the Cr endmember of β-spl was found to be a stable phase in a small temperature range[29.Mn3+)2O4 using the compound energy model[31–33]. Considering these findings an alternative description of β-spl would read [Mn2+. They propose small polaron hopping between Mn3+ and Mn4+ on the octahedral sites as mechanism for the electrical conductivity.15 K and p = 105 Pa.5) The Gibbs energy of the reciprocal reaction is taken to be zero. All endmembers of our model β-spl are neutral.8].
the two endmembers of α-spl read [Mn2+](Mn3+)2O4 and [Mn2+](Cr3+)2O4.34] show that α-spl is stabilized at high Mn contents.) 3 + Abxb (4. The Gibbs energy of [Mn2+](Cr3+)2O4 is given by ° Cr O α-spl α-hsm G[Cr2+ ](Mn3+ ) O = 2 3 °G[Cr32+ 4](Cr3+ ) O + 1 3 °G[Mn 2+ ](Mn3+ ) O + Aα-spl + B α-splT 2 4 2 4 2 4 (4. The Gibbs energy of [Mn2+](Mn3+)2O4 is equal to α-hsm.7) The experimental data could be reproduced without the optimization of a temperature dependent parameter. as the degree of inversity is increasing with higher temperature. The Gibbs energy of the endmember (Mn3+)2(O2-)3 is taken from Grundy et al. and the Gibbs energy of (Cr3+)2(O2-)3 is given by ° bxb esk G(Cr3+ ) O = °G(Cr3+ ) 2 3 2 (Va)1 (O 2.6) Bixbyite (bxb): Geller and Espinosa postulate the incorporation of Cr into Mn2-yCryO3 by a simple substitution mechanism between Cr3+ and Mn3+.15.Mn3+)2O4 to describe α-spl.Mn3+. Hence. Manganosite (mgs): Based on the proposed incorporation of Cr into (Mn1-yCry)1-xO in the form of CrO we tested a description of mgs given by (Mn2+. Using this description the solubility of Cr in function of oxygen partial pressure experimentally determined by Tanahashi could not be reproduced correctly.2. Experiments[11. (Mn2+.Va)(O2-). Thus we may describe bxb as (Mn3+.Cr2+.Cr3+)2(O2-)3.15]..2. whereas for ordering due to Jahn–Teller distortion the opposite holds. It is very unlikely that trivalent cations are incorporated into the tetrahedral sites of α-spl. The incorporation of chromium of valencies other than three is mentioned nowhere in literature. This is a reasonable assumption as the radii of these ions are very similar.Mn3+. and the Cr solubility in tetragonally distorted MnyCr3-yO4 does not extend beyond MnCr2O4. Due to these considerations we may write [Mn2+](Cr3+.Cr3+.Thermodynamic assessments Tetragonally distorted spinel (α-spl): The transformation of β-spl to α-spl is due to the Jahn-Teller distortion of the octahedral sites occupied by trivalent Mn ions leading to the tetragonal structure of α-spl[11.Va)(O2-) leads to far more satisfactory 87 .14.
The model description of mgs is shown in Fig. 4. The Gibbs energy of the neutral endpoint ( Cr 3+ 2/3 Va1/3 ) O is given by 2 3 °G mgs + 1 3 °G mgs + RT (1 3ln1 3 + 2 3ln 2 3) and based on the Gibbs energy of 1 mole of (Va )O1 3 (Cr3+ )O1 mgs Gas esk. Using °G(Va)O1 = 1 °GO2 the following expression for the parameter °G mgs is obtained 3+ 2 (Cr )O1 ° G mgs = 1 2 °G esk 3+ 3+ (Cr )O1 (Cr )2 (Va)1 (O2.. The Gibbs energy of (Mn3+)2(Cr3+)1(O2-)3 is given by 88 .8) The Gibbs energies of the three other endmembers are taken from Grundy et al.2. Fig.8 Geometrical representation of the mgs phase described using the compound energy model.Thermodynamic assessments reproduction of these data. With this description we are in agreement with O’Keefe and Valigi who observe a decrease in the lattice parameter of mgs compared to undoped Mn1-xO providing strong support for the assumption that it is Cr3+ that is substituting the much larger Mn2+ ion and which is forcing the lattice to contract.Mn3+)2(Cr3+. Agreeing with these authors we model the solubility of Mn by (Cr3+. These experiments also provide evidence against Cr being incorporated interstitially.Cr2+.)3 Gas − 1 3 °GO − 3 2 RT (1 3ln1 3 + 2 3ln 2 3) + Amgs 2 (4.2.8. 4.2. Eskolaite (esk): Pollert et al. postulate the incorporation of trivalent Mn ions into (Cr1-yMny)2+xO3.Va)1(O2-)3.
39] .Thermodynamic assessments ° G esk3+ (Mn )2 (Cr3+ )1O3 = °G bxb3+ (Mn )2 (O2.Cr2+.)3 + °GCr SER + Aesk (4. Experimental data on the oxygen solubility in pure bcc A2 chromium metal were used for the description of (Cr)1(O.2.10) We take the Gibbs energies of the other endmembers from Povoden et al.Va)3.9) and the Gibbs energy of (Mn3+)2(Va)1(O2-)3 by ° G esk3+ (Mn )2 (Va)1O3 = °G bxb3+ (Mn )2 (O2. No data are reported for the oxygen solubility in pure bcc A2 manganese metal. 89 ..2. 90-92). and Lee.Va)3.Vaq-)q using the two-sublattice model for ionic liquids parameter 0 Lliq3+ Cr . Liquid: We model the liquid phase as (Cr3+.1 (pp.)3 + Aesk (4.The binary interaction parameters are taken from Grundy et al. Cr-Mn alloys: We describe the oxygen solubility in bcc by an interstitial solution model of the form (Cr..Mn3+ :O2- [38. Povoden et al. Mn3+.2. The liquidus temperature is optimized using the interaction . Assuming low oxygen solubility in bcc bcc manganese metal we give a large value to the endmember °GMn:O .2. 4.Mn)1(O.4 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Mn-Cr-O system is given in Table 4. The descriptions of further alloy phases are taken from.Mn2+)p(O2-..
− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+ :O2.1 Thermodynamic description of the Cr-Mn-O system a) Element Element Reference Mass H298 .Va q.H0 S298 Cr Mn O Liquid (liq) BCC_A2 CBCC_A12 ½ mol O2 51.9479T = −188487.Va q- L 0 liq Mn 2+ .543 32.Thermodynamic assessments Table 4.− 2 H Cr − 3H O = GCR2O3_L liq SER SER GCr 2+ :O2.− 2 H Mn − 2H O = 2GMN1O1_L 0 liq Cr 2+ :O2.0 4341.Va q- L L 0 liq Cr 2+ ..6587T = 504 + 0.O)3 90 .− 2 H Cr − 2H O = 2GCR1O1_L liq SER GMn 2+ :Va q.− 2 H Mn − 3H O = GMN2O3_L liq SER SER GMn 2+ :O2.Mn 3+ ) p (O 2.Mn 3+ :O 2- L Bcc A2 alloy (bcc) (Mn.+ qyVa ..6 0 liq Mn 2+ :O 2.Va q- L L = 121000 = 129519 = −45459 = −33859  = −15009 + 13..2.)q p = 2 yO2.− H Cr = GCR_L liq SER GCr3+ :Va q..Cr 3+ .Cr)1 (Va.008 102.Mn 2+ :Va q- L 0 liq Cr 3+ .Mn 2+ :Va q1 liq Cr 2+ .0 4996.Mn 2+ .− H Mn = 2GMN_L + GMN2O3_L − 3GMN1O1_L liq SER SER GMn3+ :O2.996 54.938 15..Va q1 liq Mn 2+ :O 2.999 4050.0 23. q = 2 yCr 2+ + 2 yMn 2+ + 3 yCr3+ + 3 yMn3+ ° ° ° ° ° ° ° ° liq SER GCr 2+ :Va q.52 (Cr 2+ .Mn 3+ :O 2.− H Mn = GMN_L liq SER GMn3+ :Va q.
Mn 3+ :O 2- L Bixbyite (bxb) (Mn 3+ .Mn:Va L = −20328 + 18.− 2 H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.− 2 H Mn − H Cr − 3H O = GMN2O3 + GHSERCR  + 39503 esk SER SER GMn 3+ :Va:O 2.48643 − 0.Va)1 (O 2.)1 ° ° ° mgs SER SER GMn 2+ :O 2.5GCR2O3 + 71549.− 2 H Cr − 3H O = GCR2O3 esk SER SER GCr 3+ :Cr3+ :O 2.5213 − 22.− 2 H Cr − 3H O = GCR2O3 + 3459 ° Eskolaite (esk) (Cr 2+ .Va L = −709542 p = 0.)3 ° bxb SER SER GMn 3+ :O2.28 esk Tcesk = 308.72035( yCr − yMn ) 2 − 1.− H Mn − H O = GMN1O1 − 21883.− 2 H Mn − 3H O = GMN2O3 bxb SER SER GCr 3+ :O 2.Mn 3+ .2923T 3 esk SER SER GCr 2+ :Va:O 2.27 yMn + yCr yMn [0.Mn 3+ :O 2- L = −42104.Mn:Va L 0 bcc Cr:O.8766 = 46513.− H Cr − H O = 0.Cr 3+ ) 2 (O 2.2923T 3 esk SER SER SER GMn 3+ :Cr3+ :O2.Va)1 (O 2.)3 ° ° ° esk SER SER GCr 3+ :Va:O 2.4183T  1 bcc Cr. Cr 3+ .93265( yCr − yMn ) 4 ] Manganosite (mgs) (Mn 2+ .6 yCr3+ :Cr3+ :O2esk β esk = 3 yCr :Cr 3+ 3+ 3+ :O 22- T esk c = 308.7339T  = −9162 + 4.− H Mn − H O = GMN1O1 mgs SER SER GCr 3+ :O 2.6 yCr 2+ :Va:O2- :O 22- esk β esk = 3 yCr :Va:O Cubic spinel (β-spl) 91 .6 y esk Cr 3+ :Va:O 2- esk β esk = 3 yCr :Va:O esk β esk = 3 yCr :Cr 2+ 2+ 3+ esk Tcesk = 308.1533 1 mgs Mn 2+ .3 − 7.6 yCr 2+ :Cr3+ :O2esk Tcesk = 308.1853365T 0 mgs Mn 2+ .− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.− 2 H Mn − 3H O = GMN2O3 + 39503 ° ° ° Magnetic contribution p = 0.008 yCr − 0.117( yCr − yMn )8 ] β bcc = −0.Thermodynamic assessments ° ° ° ° bcc SER GCr:Va − H Cr = GHSERCR  bcc SER GMn:Va − H Mn = GHSERMN bcc SER SER GCr:O − H Cr − 3H O = GHSERCR  + 3GHSEROO + 243T bcc SER SER GMn:O − H Mn − 3H O = GHSERMN + 3GHSEROO 0 bcc Cr.5 yCr − 580 yMn + yCr yMn [−1325 − 1133( yCr − yMn ) 2 − 10294( yCr − yMn ) 4 + 26706( yCr − yMn ) 6 − 28.4 Tcbcc = −311. Cr 3+ .Mn 3+ ) 2 (Cr 3+ .93845T mgs SER SER GMn 3+ :O2.− 3H Cr − 3H O = GCR2O3 + GHSERCR  esk SER SER GCr 2+ :Cr3+ :O 2.
4 and 0 Lliq3+ . PARROT takes into account all sorts of thermodynamic and phase diagram data simultaneously.31451 J mol-1 K-1.4 and 0 liq L Cr3+ . The optimization of the thermodynamic parameters is performed using the PARROT module of the Thermo Calc database system.Mn3+ :O2- .2.− 3H Cr − 4H O = GCR3O4 β-spl SER SER GMn 2+ :Mn 3+ :O 2.− H Cr − 2 H Mn − 4H O = GCR3O4+GMN3O4B -GSPINEL Tetragonally distorted spinel (α-spl) (Mn 2+ )1 (Cr 3+ . β-spl To optimize the parameters Aβ-spl and Bβ-spl in Eq. 4. 4.Mn 3+ ) 2 (O 2.7 cat.4 and Aα-spl and Bα-spl in Eq. 4.2.%) and α-spl is used to optimize Aβ-spl and Bβ-spl in Eq. The program minimizes the sum of squared errors between the experimentally determined phase diagram and thermodynamic data and the corresponding calculated data.Cr 2+ )1 (Cr 3+ . K. 4.Thermodynamic assessments (Mn 2+ .4 we use the Δ f °GMnCr2O4 value derived from Tsai and Muan using Δ f °GMnAl2O4 from Kim and McLean and the composition of bcc in equilibrium with β-spl and mgs reported by Ranganathan and Hajra. The temperature found from Speidel and Muan for Cr the two phase equilibrium of Mn rich β-spl (Mn = 94.4. mol.Mn 3+ ) 2 (O 2. 4.1T a) Note: All parameters are in SI units: J.2.Mn3+ :O2.− 3H Mn − 4H O = GMN3O4 ° Functions GSPINEL = 2 GCR3O4+ 1 GMN3O4B 3 3 −210795.− H Mn − 2 H Cr − 4H O = GTSPINEL α-spl SER SER GMn 2+ :Mn 3+ :O 2..2.2. All these data are given a high weight.) 4 ° α-spl SER SER SER GMn 2+ :Cr 3+ :O 2.− H Mn − 2 H Cr − 4H O = GSPINEL β-spl SER SER GCr 2+ :Cr 3+ :O 2. we selectively adjust the relative weight of each experimental data point and exclude data that are inconsistent with the majority of the data points during the optimization procedure. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.69T GTSPINEL = 2 GCR3O4+ 1 GMN3O4 3 3 −200941.105 from Speidel and Muan to optimize Aβ-spl and Bβ-spl in Eq. Pa: R = 8.9+75. Further the melting temperature of β-spl in air found by Speidel and Muan is used to optimize Aβ-spl and Bβ-spl in Eq. and we use data on the solubility of Cr in MnyCr3-yO4 at T=1873 K under varying 92 .) 4 ° ° ° ° β-spl SER SER SER GMn 2+ :Cr 3+ :O2.5+61.− 3H Mn − 4H O = GMN3O4B β-spl SER SER SER GCr 2+ :Mn 3+ :O 2. Further we use – with lower weights – the temperature of the two phase equilibrium β-spl + liq at X(Cr) = 0.
prl + bxb is stable in a small area from T = 668 K to 694 K and X(Cr) = 0 to 0.65 prl and β-spl coexist in air. The maximum Cr solubility in Mn2-yCryO3 is 23 cat. 4. 4. Temperature data from Speidel and Muan and Pollert et al. 4. 80 the Mn rich part of the diagram is shown in detail. 82). β-spl and esk coexist from X(Cr) = 0. p. 4. p.2. and data from Pollert et al. 79. 4.7 is optimized using data on the solubility of Cr in Mn2-yCryO3 from Pollert.2. 4.2. and for Aesk in Eq.5. 22.214.171.124. p.9 and 4. 4. 4. From T = 513 K to 668 K and maximum X(Cr) = 0. and Aα-spl and Bα-spl in Eq.2.2.2 cat.2. 126.96.36.199 data on the solubility of Mn in (Cr1-yMny)2+xO3 from Pollert et al. p. 82 are used. mgs is not stable in air. p. The two-phase field bxb + α-spl is only found in a very small area at about 1150 K.2.66 to 0.8 data on the solubility of Cr in (Mn1-yCry)1-xO from Tanahashi et al.2. 4.% at T = 668 K in air.175 at T = 1156 K.1 and 4. on the phase equilibria α-spl + β-spl and α-spl + β-spl + bxb are used to optimize Aβ-spl and Bβ-spl in Eq.2. 79 to optimize Aβ-spl and Bβ-spl in Eq.5.992 at 1203 K in air.2. are used (Fig. p.6. At pO2 = 400 Pa it starts to form in equilibrium with β-spl in a small area at the Mn-rich side of the MnOx-Cr2O3 system around T = 1840 K. on the two phase equilibrium β-spl + bxb in air (Fig. 82. αspl coexists with β-spl from X(Cr) = 0 at T = 1441 K to X(Cr) = 0.2. 79 shows the temperature dependence of the diffusionless transformation of α-spl to β-spl.5.% at 2243 K in air. 4.2. on the temperature dependence of the diffusionless transformation of α-spl to β-spl shown in Fig. The maximum Mn solubility in (Cr1-yMny)2+xO3 is 0.Thermodynamic assessments oxygen partial pressures from Tanahashi et al. 4.67 in air.2. 4.3. p. bxb is stable from T = 694 K to 1154 K in air. p. 4. 79 and Fig.2.054 in air. β-spl is stable in a large temperature range from T = 513 K to 2243 K and from X(Cr) = 0 to X(Cr) = 0. The dotted line in Fig. Single phase α-spl is stable in a small T–X(Cr) range from T = 1153 K to 1441 K and X(Cr) = 0 to 0. In Fig. 4. 80) to optimize Aβ-spl and Bβ-spl in Eq.23 in air. p. This two-phase field expands under more reducing conditions which can be seen in the calculated phase diagram of 93 . for Amgs in Eq.2. Abxb in Eq.5 Results Phase diagram data: The calculated phase diagram of the pseudo-binary system MnOx-Cr2O3 in air is shown in Figs.2. and Aα-spl and Bα-spl in Eq. 188.8.131.52.2. We use data from Holba et al. prl coexists with esk at T < 513 K in air. shown in Fig. 184.108.40.206.2. shown in Fig.
1173 K.5. and from Bobov et al. p. In the isothermal phase diagram of the Mn-Cr-O system at T = 1323 K of Fig. p. 4. and 1273 K in function of log(pO2 ) are compared to the calculated results from this work.Thermodynamic assessments the pseudo-binary MnOx-Cr2O3 system at an oxygen partial pressure of 1×10-4 Pa in Fig.2.9 (next page). on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl and esk + β-spl at 1873 K. 80.2. Experimental data from Tanahashi et al.6.2. 83 the stable alloy phases of the system are plotted in addition to the oxides based on the assessment of the binary Cr-Mn system from Lee. Isothermal sections of the Cr2O3-MnO-MnO2 system at different temperatures are plotted in Fig. 4. 82 experimental and calculated solubility data of Cr in mgs + β-spl. 4. 4.4. and Mn in esk + β-spl are presented. on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl at T = 1073 K. The data from Bobov et al. were not used for the optimization. In Fig. p. 94 .2.
Dotted lines are tielines. 4. Stoichiometric single phase equilibria are points. Three-phase field boundaries are denoted with thin lines.Thermodynamic assessments Fig.2. and single solid solution phase equilibria are heavy lines.9 Isothermal sections of the ternary system Cr2O3-MnO-MnO2 showing oxide and liquid evolution as a function of temperature and composition. 95 .
9 a to c). The calculated temperature dependence of the -1 Gibbs energy of formation of of β-spl of the composition MnCr2O4 from the oxides MnO and β-spl Cr2O3 is shown in Fig.2. 4. Fig. 4.2.3 (p. In the β-spl temperature range from 1050 to 1800 K Δ f °GMnCr2O4 from the oxides is given by the term –89167 + 29. For both cases Speidel and Muan mention the speculative character of their phase diagram due to the lack of experimental data. 4. The oxygen nonstoichiometry of mgs is yet insignificant (Fig. 80). 4. 4.2. 4.2 (p.9 b).2.2. 4. Our calculated T0 line for the diffusionless transformation of α-spl → β-spl is in perfect agreement with experiments by Holba et al. Large deviations of our calculated phase diagram from the phase diagram presented by these authors concern the stability of the liquid and phase stabilities at low temperatures. on the other hand cannot be reproduced.9 a) disappear. (Fig. 79).2. 4.7.6 (p.338 T with an error of ± 0.2.[14. and the two-phase fields prl + bxb. p.15 K.15 K. p.2. and β-spl Δ f °GMnCr2O4 = –1634017 J mol at T = 298. °SMnCr2O4 = 116 J mol-1 K-1.. At T=1700 K α-spl is no longer stable and the three-phase regions mgs + α-spl + β-spl and bxb + α-spl + β-spl (Fig.2.2. entropy and Gibbs energy of formation of β-spl of the composition β-spl β-spl MnCr2O4 from the elements is Δf °H MnCr2O4 = –1599421 J mol-1. Our assessed phase diagram is in excellent agreement with the findings of Pollert et al. 4. 79).5.2. ° α-spl S = 98 J mol-1K-1. β-spl + bxb.Thermodynamic assessments Thermodynamic data: The calculated enthalpy. and Fig. 82 agrees well with the results from Tanahashi et al. For α-spl of the composition MnCr2O4 we calculate Δ f °H α-spl = –1596517 J mol-1. 4. The three-phase regions prl + esk + bxb and bxb + esk + β-spl. 83). 85. At T = 1873 K we get Δ f °GMnCr2O4 = –34388 J mol-1. 95) represents the phase relations of the oxides and the evolution of liquid formation. as shown in Figs. 4.9 (p. and Δf °G α-spl = –1625681 J mol-1 at T = 298. and mgs + β-spl dominate the system in a wide temperature range from T=1200 K to 1900 K (Figs.2.21 %.6 Discussion Phase diagram data: Our assessed phase diagram is in rough agreement with the findings from Speidel and Muan.15] and Ranganathan et al. but it increases at elevated 96 . The calculated dependence of β-spl solid solubility on oxygen partial pressures shown in Fig. At this temperature small oxygen nonstoichiometry of esk is apparent. p. The results from Bobov et al.
4. Even more three phase regions due to increasing liquid formation start to exist at T = 2000 K (Fig.2. 220.127.116.11. Thermodynamic data: β-spl β-spl Our calculated Δ f °GMnCr2O4 value at T = 1873 K is in agreement with the Δ f °GMnCr2O4 value spl derived from Tsai and Muan using Δ f °GMnAl2O4 from Kim and McLean.9 d)..2. At T = 1900 K liquid is formed at the Mn-rich side of the system.Thermodynamic assessments temperatures becoming apparent at T = 2000 K (Fig. 83. 4.9 c). 83 associated with decreasing 97 . 4. The occurrence of other Cr-Mn phases in the protective scales formed during thermal exposure of Crofer 22 APU interconnects is not expected thermodynamically. 4.7 Applications on SOFC Due to the large stability range of β-spl and esk in air it is not realistic to prevent the formation of these unwanted phases under oxidizing conditions at the cathode side of SOFC operated with high Cr alloy interconnects and LSM cathode. p. 4. p. found that the electrical conductivity of chromium manganese spinel increases with increasing Mn-content.2. The problem of the application of synthesized Mn-rich α-spl on the interconnect for the purpose of combining a decrease of Cr evaporation with enhanced electrical conductivity is that α-spl will with time tend towards its stable composition of MnCr2O4.9 c). p. 4. and the-three phase fields bxb + β-spl + liq and mgs + β-spl + liq emerge (Fig.6. and ΔSα β values for the transformation of α-spl to β-spl are very small. This is obvious from Fig. At T = 2400 K the only remaining stable solid phases are esk and prl (Fig. 4. which is at point A in Fig. Recently Qu et al. The calculated ΔHα needed for the transformation to take place.2.2. At T = 1900 K phase relations become more complex due to incipient melting (Fig. indicating that only very little energy is 4. 84) on Crofer22 APU alloy is expected under SOFC operating conditions.9 d).2. Hence. Our assessed ΔHα β and ΔSα β values for the transition of α-hsm to β-hsm compare β favorably with the values reported by Holba et al. the formation of a protective Cr2O3 single phase layer followed by a chromium manganese spinel on Mn bearing interconnects as it is observed by Simner et al.9 f). In a thermodynamic view the formation of β-sp with the composition MnCr2O4 (Point A in Fig. The composition of Crofer22 APU alloy is close to the Cr-corner of the Mn-Cr-O phase diagram. must be kinetically controlled.6.2.
H. Hilpert. R. Badwal.A. Vol. 1994. Y.).J. Kinzel. There is a surprising lack of thermodynamic data on β-spl. D.8 Conclusions Due to the lack of inversity and oxygen nonstoichiometry of spinel we chose a model description of β-spl and α-spl without the introduction of vacancies into the spinel structure. Solid State Ionics. 1037. compositions and transformations of unwanted MnxCr3-xO4 spinel solid solution and eskolaite phases in solid oxide fuel cells under any desired temperature and oxygen partial pressure conditions. °S. and the only available -1 β-spl Δ f °GMnCr2O4 values are spread over a range of 31 kJ mol .Thermodynamic assessments electrical conductivity. K.P. A. M. J. Nickel. 2. Foger. Quadakkers. and we present well-founded Δf°H. 1-15. 98 . Hilpert. 3. H. Vielstich. 2. Ramprakash. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. 99. 703. pp.). K.2. W. First European Solid Oxide Fuel Cell Forum Proceedings. References 1.S. K. Zhang. John Wiley & Sons. Technology and Applications. Chichester. S. Göttingen. Gasteiger (Eds. Recalculating old experiments using new thermodynamic data together with phase diagram data we achieved a description. Bossel (Ed.W. Our Thermo Calc dataset resulting from the presented CALPHAD modeling of the Mn-CrO system allows the calculation of phase stabilities. p. 297-310. p. in: W. Das. Miller. All features of the system are well described with the optimization of only 8 additional optimization parameters. Singheiser. in: U. 2004. J.P. and Δf°G data for β-spl and α-spl. 4. Handbook of Fuel Cells – Fundamentals. Druckerei J. Solid State Ionics. which is very close to the experimental findings of several authors. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. 2003. L. Also α-spl will then transform to β-spl and on thermal cycling of the SOFC back to α-spl leading to mechanical stresses that might result in the appearance of cracks. Lamm. Deller. 4. 1997. 171. pp. Fergus.
Miscibility gap of MnxCr3-xO4 spinels. 2001.J. 9. Yang. pp.N. Zh. 8. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 10. Gauckler.G. V. M. Xia. Fiz. Soc. 1975. 149-58.. 21-39.. Sci. J. Phys. Simner. 853-60. Res. 1963.. 17. 3763-69. A. pp. 152.-G. pp. B 1. 1919-1933. 7.P. J. Y. Tanahashi. Novak. Diff. Zalazinsky. J. Mater..W. Phase equilibrium diagram of the system Mn-Cr-O. 1991. T. 750-751 (in Russian). Phase equilibria of the MnO-SiO2CrOx system at 1873 K under controlled oxygen partial pressure. A. 27. pp. E. 99 . Assessment of the Mn-O system. 14. 46.V. Phase diagram of the Mn2O3-Cr2O3 system in air. Cr3+. 9. Fujisawa. Balakirev. J. 556-65. The system manganese oxide-Cr2O3 in air. G. 1145-47. 6.. C. J. Soc. 1309-1315. L. 10. A. Golikov.D. S. pp. 12. Magnetic structure of manganese chromite. J. A. Holba.. Peculiarities of phase-diagram in the reduction of Me0. Phys. Dinsdale. E. 126. 38.Thermodynamic assessments 5.R. Golikov. Nevriva. SOFC performance with Fe-Cr-Mn alloy interconnect. 11. 562-65. 18.. Grundy. Pollert.M. Bull. M. Solid State Chem. T. Speidel. Hajra. 1977. 58. 2005. pp.P. 577-78. V. Pollert. Trans. B. Novak. A. Bobov. Pollert. Res. E. 1984. 2006...P.N. Corliss. A thermodynamic evaluation of the Cr-Mn and Fe-Cr-Mn systems. G. pp. Stevenson. 15. L. Gauckler. Alloy oxide equilibria in the Cr-Mn-O system. Rev. pp. Phys. 1962.. 353-62. Yamauchi. A. 1993. 1980.M. Metall. 41. Hallstedt. Phase Equilib. Mater. Muan. 71. ISIJ Int. and Ga3+ substituted Mn2O3. Tetragonal distortion of spinel solid-solutions MnCr2O4Mn3O4.F. J. B-J. Ranganathan. pp. pp. 13. A740-45. 1970. pp. Furuta. 1453-56. Pederson. Y. Geller. Anderson. G. Grundy. N. Balakirev. A 24.F. SGTE Data for Pure Elements. M. Khim.. Phase Equilib. J. Calphad. pp. L. E.. Chufarov. 1987.I. 15(4). 317-425. M. pp. L. M. Solids. 19. Bull. Espinosa. Ceram. D. J. J. Mater.H. Hastings. Electrochem. 2003. pp. Magnetic and crystallographic transitions in Sc3+. 16. pp.P. 1987. S.. Nevriva. Lee. S. Bull. 15. Chem. Am. 24.J.V. Rev. Z.25Mn2. J. P.75O4 solid-solutions. Povoden. Nevřiva.
A.. A. 2000.. Hillert. Shannon. Phase diagram of system MnO-Al2O3 and thermodynamic properties of MnAl2O4. A. Q. Met. Parts I and II. Pennsylvania State University. 33. 75. 225-232. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. Ceram. 3. Metall. Hillert. Toker. Application of the Compound-Energy Model to Oxide Systems.. 161-76. Guillermet. I. Metall.. Izv. Muan. pp.F. Alloy. Paranthaman. pp. 1988. 1966. Biggers: Ph. 26.A. University Park. 24. J.. 87-92. Am. pp. Thesis. Weinheim. 1050-53. Kim. 73. A 32. McLean. Lenev. Muan. Dimitrov. Lu. Trans. Lam: United States Patent 6039788. Activity composition relations in FeCr2O4-FeAl2O4 and MnCr2O4MnAl2O4 solid-solutions at 1500°C and 1600 °C. pp. T. Trans. 35. 66.Y. B. M. R. A. Equilibrium phase-relations and thermodynamics of the Cr-O system in the temperature-range of 1500°C to 1825°C. L. I.T. Furuta.. Zhu. J. Electrical conductivity of the manganese chromite spinel solid solution. 88. B. N. B. Tsai. Thermodynamics of iron-manganese aluminate spinel inclusions in steel. 43. J. 10B. Can.(in Russian). 79(2). A. Akad. B.K.. 29. pp. 1407-11. N. pp.Cr2O3 solid solution at 1873 K. 34. Payzant. pp. 2005. 1966.V.D. The Compound Energy Formalism. 25. pp. 1979. 89-92. Ceram. 1976. Taniguchi. T. Ceram. 2003. 34. Barin: Thermochemical Data of Pure Substances. 2nd Ed. Soc. Jacob. Fujisawa. Cmpd. Acta Metall. J. VCH Verlagsgesellschaft mbH. 28.T. 22.Thermodynamic assessments 20. E. C. Janke. Z. 1995. Jansson. K. Muan.K. 75. 100 . 1993.A.M. Steel Res. 22. Darken. Acta Crystallogr. 32. 1991. Tanahashi. 1981. J. Metall. Jansson. Soc. pp. Novokhatskiy. Nauk SSSR. Am. Weyl. Revision of thermodynamic data on MnO-Al2O3 melts. Z. H.. D. R. Sundman. Standard Gibbs free energy of formation of MnO-saturated MnO. 30. 23. ISIJ Int. pp. S. L. 21. 81-87. Activity composition relations in refractory oxide solid-solutions at high-temperatures – the system Cr2O3-Al2O3.-O. Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides. J. Control of the manganese-oxygen reaction in pure iron melts. H. 751-67. Sundman. M. M. 437-445.F. Yamauchi. C. Hillert.. 575-84.S.P. M. 20. Soc. pp. A. 320. 31. 1412-15. 2001. B.. 7-13. Andersson. M.T. J. 1986.D. pp. Tsai. PA.. 1992. 1992.. pp. Am. 27. B. Metallkd.
Gauckler J.3 Thermodynamic assessment of the La-Cr-O system E. Power sources. M. 153-90. Phys. 16A. W. 31. 114-24. 42. Sundman. Ivas. Grundy. Povoden.M. Jian. D. Fraser. Phase Equilib. Chen . 39. Modification of the Two-sublattice Model for Liquids. In the La-Cr system reported solubility of lanthanum in bcc chromium is considered in the modeling. Jansson.J. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. 1957. 42. A. J. Phys.N. Diff. Valigi. p. V. 41. Jansson. Eremenko. Ivey. Cleveland. L. pp. Burr. Russ. (accepted) The La-Cr and the La-Cr-O systems are assessed using the Calphad approach. Emphasis is placed on a detailed description of the perovskite phase: the orthorhombic to rhombohedral transformation and the contribution to the Gibbs energy due to a magnetic order-disorder transition are considered in the model. and oxygen solubilities in bcc and fcc metals are modeled. Chem. J. 1968. 1985. Lukashenko. 15. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. Andersson. 1970. Trans.5 phase diagrams in pure oxygen. 37. 153. Ågren. M.5-CrO1. pp. The calculated La-Cr phase diagram as well as LaO1. Metall. Caplan. in: Ductile Chromium.G.A. Thermodynamic properties of alloys of manganese with transition elements of fourth period (Cr Fe Co Ni) and with copper. M. J. Calphad. 947-962. Ohio. and L. Hillert. Qu. Solids.J. Phase equilibria of the La-Cr-O system are calculated at T = 1273 K as a function of oxygen partial pressure. Hill. J. The following standard data of 101 . 196. 343-. 38. A. In the La-Cr-O system the Gibbs energy functions of La2CrO6. 9(2). pp. O’Keefe. pp. and perovskitestructured LaCrO3 are presented. ASM. 1985. Sundman. air. B. M. 1991. The electrical properties and defect structure of pure and chromium-doped MnO. B. Sidorko. D. 40. B. Chem.Thermodynamic assessments 36.. The Thermo-Calc Databank System.-O. M. Calphad. pp. A. 109-19. 2006. Sundman. pp.M. B. V. 4.R. B. G. T. La2(CrO4)3.M. and under reducing conditions are presented. J. 261-66. J.
aiming on minimizing the squared errors between 102 .97 Pa.Mn)2O4 spinel and Cr2O3 along with a severe cell voltage decrease[1-4].1 Introduction In SOFC. As the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar.oxides° H 298 K (LaCrO3 ) = −73.0034 T (kJ mol-1) (T = 1273 K to 2673 K) is calculated.Thermodynamic assessments stoichiometric perovskite are The calculated: Δf.7 kJ mol-1 .3. recently Sr-. The assessment of the La-Cr-O system using the Calphad approach is based on the recently reassessed La-O and Cr-O subsystems. It is also a starting point for extensions to thermodynamic databases with additional components serving as dopants in LaCrO3 for SOFC interconnect and cathode applications. The liquid phase is modeled using the two-sublattice model for ionic liquids. V-doped and Zn-doped La1-xCaxCrO3-δ have been considered as promising alternative interconnect materials for SOFC.2 J mol-1 K -1 . All available experimental phase diagram. Diffusion of chromium from the metallic interconnect with high chromium content into the cathode leads to the formation of Mn(Cr. pO2 (decomp) = 10-20. oxides. Cation nonstoichiometry of La1-xCrO3 perovskite is described using the compound energy formalism (CEF). The decomposition of the perovskite phase by the reaction 1 3 LaCrO3 → La 2 O3 + Cr + O2 (g) ↑ is calculated as a function of temperature and oxygen partial 2 4 pressure: at 1273 K the oxygen partial pressure of the decomposition. 4.403–0. The presented thermodynamic assessment of the La-Cr-O system is laying the grounding for extensions to the thermodynamic La-Sr-Mn-Cr-O oxide database that is required to understand the thermodynamics of SOFC degradation by chromium. Gibbs energy of formation from the and ° S 298 K (LaCrO3 ) = 109.oxides G(LaCrO3 ) = –72. and structurechemical data are critically assessed. The lattice stabilities of elements are adopted from Dinsdale. Sr-doped lanthanum manganites (LSM) with the perovskite structure are used as cathode materials in SOFC. thermodynamic. and the model is submitted to a defect chemistry analysis. and Crdiffusion into the cathode from LaCrO3-based interconnects is significantly lower than from Cr-containing metallic interconnects. Furthermore earth alkaline-containing LaCrO3 has been proposed as a cathode material in a recent study by Jiang et al. Δf. the thermodynamic stability of the cathode is particularly important for efficient long-term operation.
 reported a La solubility of 0. Tm(air) = 2773 K was determined by Foëx and by Coutures using a thermal analysis technique described in more detail in earlier publications.% Cr2O3 (T = 2323±20 K). and Epstein et al. This is not surprising as experiments are complicated due to the high investigation temperatures and evaporation of predominantly Cr[25.13].14.4 at. Small solubility of La in αCrss was reported [12. as well as a large liquidliquid miscibility gap[12.% Cr2O3 (T = 2243 K) or 12 at.3 Literature review of the La-Cr-O system In the LaO1.[22-24] The melting temperature was measured with optical pyrometers.3. and at 84 at.13].% Cr2O3 (T = 2248 K) or 80 at. Furthermore deviations between the data from Tresvjatskiy et al. The solubility of La in αCrss decreases towards lower temperatures. The melting temperature of lanthanum chromite in air.% at 1983 K. and the exact value of the oxygen partial pressure was not specified. Tm(argon) = 2703 K was reported by Tresvjatskiy et al. from T = 1073 K up to the melting of Cr using metallographic and microhardness techniques to be 2. Svechnikov et al.5 at. modeling of the La-solubility in bcc-structured Cr. but in the graphic presentation of the phase diagram in the same paper Tm(argon) ≈ 2600 K.. denoted as αCrss .Thermodynamic assessments experiments and calculation during the optimization of model parameters using the PARROT module of the Thermocalc software. Experimentally determined special points in the LaO1.% in αCrss at T = 1533 K. 4.5 quasibinary system reveal a considerable spread. As small additions of rare-earth metals essentially increase the high-temperature corrosion resistance of chromium.% Cr.3.68 at. determined the partial enthalpy of mixing in La-Cr liquid with infinite dilution of Cr. found La < 0. No intermetallic phases were found in the La-Cr system[12.1 at. Berezutskii et al. 4. The solubility of La in αCrss was determined in investigations by Savitskii et al.5.26].5 system two eutectics were found at 19 at.% Cr and a monotectic at T = 1983 K or T = 2103 K and 96 at.% Cr2O3 (T = 2473±20 K) in argon atmosphere on either side of the congruently melting perovskitestructured lanthanum chromite[18-20] (in this study oxides containing Cr(III) and Cr with higher valencies than three are denoted as chromite and chromate respectively). and Berjoan 103 .2 Literature review of the La-Cr system The La-Cr system has a eutectic at T = 1138 K[12. whereas Cr is almost insoluble in La.5-CrO1.% at T = 2103 K.% or 99.CrO1.13] and 3. is of technological interest.04 at. ΔH Cr at T = 1700 K using high-temperature calorimetry.17] .
3. phase stability. Using differential scanning calorimetry (DSC) he determined the enthalpy change of the reaction 3 2La 2 O3 + Cr2 O3 + O2(g) → 2La 2 CrO6 2 (4.25O2(g) ↑ → (4.31]. which in both studies was not exactly specified.1 (next page). thermodynamics[30.33-35. solubilities in αCrss are missing.Thermodynamic assessments may partly originate from differences of the oxygen partial pressure.5Cr2 O3 + 2.1) at T=1055 K and pO2 =83000 Pa to be −151±8 kJ mol-1.  . The enthalpy of formation of La2(CrO4)3 from the elements at T = 298 K was proposed by Tsyrenova et al. to be −3961±11. The peritectic phase diagram proposed by Cassedanne is in gross conflict with the phase diagram data from the other groups. The perovskite phase: Existing experimental data of lanthanum chromite perovskite structure[33-45].3.3. However these were in significant disagreement with later results obtained by the same author.. and nonstoichiometry[55-56] along with the investigation techniques used are listed in Table 4.2) An enthalpy change of 231 kJ mol-1 was determined for this reaction at the average temperature of T = 960 K.7 kJ mol-1. Stoichiometries and thermal stability ranges of lanthanum chromates with complex formulae were reported by Berjoan et al.46-53]. and Grundy et al. LaCrO4 has been interpreted as a mixed-valent intermediate decomposition product of La2(CrO4)3[30. whereas experiments on oxygen Lanthanum chromates: The following lanthanum chromates were documented: Berjoan reported that orthorhombic La2CrO6 forms at T > 923 K. Experimental oxygen solubilities in pure Cr and La were considered in thermodynamic assessments by Povoden et al. La2(CrO4)3 decomposes by 890 −1030 K La 2 (CrO4 )3 ⎯⎯⎯⎯⎯ 2LaCrO3 + 0. 104 .43.
002115T ± 0.35 kJmol-1 this work. calculated Gibbs energy of formation by 1 3 La 2 O3 + Cr2 O3 → LaCrO3 2 4 T = 1273 K Δ °G = −76.29 ± 0.5Cr2 O3 + 2.7 kJmol−1 .4 HT (high temperature) .2 Jmol-1K -1 this work.38 kJmol −1 CaF2 .calorimetry T = 1350 K 133. calculated 94. calculated = −73.75 kJmol−1 this work.based emf Δ °G = −79.Thermodynamic assessments Table 4. calculated Δ °G = −44. calculated Δ °G = −78. calculated = −3961 ± 11.1 ± 1.758 + 0.11 × 10−4 this work.1× 10−5 Knudsen mass spectrometry La CrO6 = −73.2 kJmol-1 this work. calculated 2 Δ f. calculated = −62.oxides ° H 1078K ° LaCrO3 Standard entropy S 298K LaCrO3 = 109.2 HT .calorimetry Activity of Cr2 O3 in LaCrO3 T = 2100 K T = 2100 K La 2 CrO6 Enthalpy of the formation reaction La 2 O3 + 0. 1273 . calculated ° 2 S 298K La CrO6 = 330 Jmol-1K -1 this work.oxides ° H 298K aCr2O3 = 1.5O 2(g) → La 2 CrO6 2 Δ f.elements ° H 298K = −3845 kJmol−1 this work.3.elements ° H 298K ° 2 S 298K La (CrO4 )3 = 516 Jmol−1K −1 this work.7 kJmol-1 this work.79 kJmol-1 Drop solution calorimetry in 2PbO × B2 O3 LaCrO3 LaCrO3 Δ f. 855 -1073 K CaF2 .885 K CaF2 .oxides ° H 298K La (CrO4 )3 = −372 kJmol−1 this work.45 + 0.5 kJmol −1 solid oxide electrolyte .based emf Δ °G = −94. fitted 105 .0 kJmol−1 this work.1 Calculated and experimental thermodynamic data of La-Cr oxides Rhombohedral LaCrO3 Standard enthalpy Δ f.0034T (kJmol−1 ). 700 . calculated aCr2O3 = 1.1 kJmol −1 Knudsen mass spectrometry Δ G = −72.5Cr2 O3 +1. calculated La (CrO4 )3 La (CrO4 )3 La 2 (CrO 4 )3 2 Δ f. calculated Enthalpy of the formation reaction La 2 O3 +1.1 × 10−4 ± 1.05 this work.4(kJmol −1 ). (kJmol−1 ) T = 1090 K 98.based emf Enthalpy increments H − H 298 K .08530T (kJmol−1 ).5Cr2 O3 + 2.9 ± 1. calculated Enthalpy of the dissociation reaction La 2 (CrO 4 )3 → 2LaCrO3 + 0.06 ± 2. calculated = −73. calculated 139.emf Δ °G = −42.25O 2(g) 2 ΔH 298K La (CrO4 )3 = 231 kJmol−1 and this work.2673 K this work.25O 2(g) → La 2 (CrO 4 )3 2 Δ f.oxides ° H 975K LaCrO3 = −1368.oxides ° H 298K Δ f.403 − 0.52 kJmol −1 this work.elements ° H 298K Δ f. this work. calculated T = 1273 K T = 1273 K T = 2100 K T = 2100 K ° Δ °G = −30.19.
XRD 533 estimated from neutron powder diffraction 509 DSC. simultaneous DSC .XRD 523 a) starting transition.XRD (air and vacuum) 563 ± 5 DTA.33-42]. DSC 535 cooling. DSC.84 at 503 − 583 K  calculated from adiabatic calorimetry 277 at 544 ± 1 K a) DSC 403.XRD 540 ± 2 a) HT . this work. calculated 502.08 J mol-1 and 0.Thermodynamic assessments Crystal and magnetic structure: LaCrO3 is orthorhombic (o-prv) at room temperature and transforms to rhombohedral structure (r-prv) at higher temperatures[20.75 a) calculated from adiabatic shield calorimetry a) used for optimization The reported transformation temperatures lie between T = 503 K and 583 K. DSC 533 ± 5 a) HT . HT .XRD 528 − 533 a) HT . DSC 550 HT .2 along with the investigation techniques used. this work. Table 4. XRD Enthalpy change of transition (Jmol−1 ) 340.microscopy.5 a) calculated from DSC 0. calculated 503 − 583 adiabatic calorimetry 544 ± 1 a) DTA.3.XRD 541 a) completed transition. The determined enthalpy and entropy changes vary from 277 J mol-1 to 502.08 ± 41. HT . HT . simultaneous DSC . dilatometry. The temperatures.63. dilatometry 545 heating. calculated 0.x .XRD 533 ± 3 a) DTA 543 XRD 533 HT .XRD.2 Calculated and experimental data of the orthorhombic to rhombohedral transition of LaCrO3 Transition temperature (K) 540.ray photography 550 HT .25 at 536 K a) calculated from adiabatic shield calorimetry 340 ± (10 .3.40) at 533 ± 5 a) DSC 380 at 550 K DSC 310 at 509 K DSC Entropy change of transition (Jmol-1K −1 ) 0. this work.5 J mol-1 to 106 . enthalpy and entropy changes of this first-order transition taken from the literature are listed in Table 4. dilatometry 536  a) adiabatic shield calorimetry.XRD.XRD. thermogravimetry.96 at 503 − 583K calculated from adiabatic calorimetry 0. HT .
% to 1. Heat capacity and enthalpy increment data: the heat capacities of LaCrO3 were measured by Korobeinikova and Reznitskii from T = 340 K to 900 K using adiabatic calorimetry. and Dudek et al. (150 to 450 K) using DSC. and T = 1273 K respectively. T = 700 to 885 K. in agreement with Berjoan (T = 1923 ± 20 K) using dilatometry. Chemical stability: Nakamura et al.28 cat. La2O3.76 cat. Chen et al. Höfer and Kock (480 to 610 K) and Satoh et al. reported no weight loss of lanthanum chromite at T=1273 K from pure oxygen to pO2 =10-16. Berjoan further reported prevailing of the cubic structure at T = 2173 K. and Sakai and Stølen (T = 272 K to 1000 K) using adiabatic shield calorimetry. LaCrO3/MgO-stabilized ZrO2/Cr2O3.. On the other hand Geller and Raccah as well as Höfer and Kock did not observe the rhombohedral to cubic transition up to T = 1873 K and T = 1823 K respectively using differential thermal analysis (DTA). or 295 K. Enthalpy increments of LaCrO3 at T = 1090 K and 1350 K were measured by Suponitskii using a high-temperature heat-conducting calorimeter. Cation nonstoichiometry and defect chemistry: Maximum excess Cr in single-phase La1-xCrO3 of 0. (T=100 K to 1000 K) using laser-flash calorimetry. Sakai et al. derived the Gibbs energy of formation of LaCrO3 from the determination of the thermodynamic activity of Cr2O3 in LaCrO3 for the Cr2O3-poor phase boundary of LaCrO3 in the temperature range from T = 1887 K to 2333 K using Knudsen effusion mass spectrometry.% excess 107 .38 cat. Single phase lanthanum chromite with 0. and Momin et al. (T = 77 K to 280 K) using alternating current calorimetry. LaF3/CaF2/LaF3. LaCrO3. A magnetic order-disorder transition was documented to occur at T ≈ 287 K. 289 K. reported T = 1923 K using high-temperature x-ray diffraction (HT-XRD). Cr2O3/O2. Azad et al.Thermodynamic assessments 0.% in furnace-cooled LaCrO3 annealed at T = 1773 K in air was reported from Khattak and Cox.. O2/La2O3. and its oxgen nonstoichiometry is negligible. Peck et al. Cr/Pt at 1273 K. Chen et al.. This means that the perovskite phase does not decompose within this oxygen partial pressure range. measured electromotive force (emf) of the solid oxide galvanic cell Pt/Cr. Gibbs energy of formation: in order to obtain the Gibbs energy of formation of LaCrO3. Enthalpy of formation: Cheng and Navrotsky determined the enthalpy of formation of LaCrO3 by oxide melt solution calorimetry at T = 1078 K. A transformation from rhombohedral to cubic structure at a temperature close to T = 1300 K was reported by Ruiz et al. measured emf of Pt. Pt in pure oxygen from T = 855 K to 1073 K. whereas Coutures et al. Satoh et al.1 Pa using thermogravimetry combined with X-ray diffraction (XRD).96 J mol-1 K-1.
This feature was assigned to a reduced number of Cr4+ due to partial removal of oxygen during the annealing of the originally lanthanum-deficient perovskite phase. On the other hand a slope of pO2 1 4 from T=700 K to 1300 K and purely intrinsic conductivity > 1600 K stated by Shvaiko-Shvaikovskii et al. resistivity and thermo-emf at pO2 = 1Pa and pO = 102 Pa . in line with the results from thermogravimetry.1% in weight. affirming the lack of oxygen vacancies in the structure. deduced n-type conductivity from measurements of transport number.% excess Cr2O3 from T = 1573 K to 1673 K from pO2 = 1.0 ×104 Pa . Interpretations of the defect chemistry of the perovskite phase were made from electrical conductivity measurements: the electrical conduction in lanthanum chromite is almost purely electronic[37.05 % up to T = 1250 K. reported that concentrations of lanthanum vacancies and holes slightly increase from T = 1550 K to 1700 K. Akashi et al. The transition from reduced to stoichiometric chromite was accompanied by a decrease of about 0.57].59] agree that the electrical neutrality is maintained by holes and lanthanum vacancies.0 ×103 Pa to pO2 = 2. In contrast to the other authors Shvaiko-Shvaikovskii et al. the same as reported in an earlier study.58-60]. Ruiz et al. However n-type conductivity was not approved by any further study. Several groups[58. is inconsistent with the findings from Akashi et al. and Meadowcroft proposed the occurrence of chromium vacancies instead of lanthanum vacancies. Akashi et al. The conductivity was proportional to pO2 3 16 .Thermodynamic assessments Cr was prepared at T = 1773 K in a pure oxygen atmosphere. measured the isothermal electrical conductivity of an equilibrated La1-xCrO3-Cr2O3 mixture with 5 vol. 108 . They observed an extraordinarily slow equilibration of the samples: More than four months were required to measure the electrical conductivity at equilibrium state. and that the carrier is the hole in lanthanum chromite[25. observed an intensity decrease of the high frequency band in a Raman spectrum of lanthanum chromite measured after annealing the phase in vacuum at T = 1273 K. ShvaikoShvaikovskii et al. reported that the ionic transport number in lanthanum chromite is less than 0. the electrical conductivity being 2 proportional to pO2 −3 8 . thus the presence of interstitial Cr in reduced chromite was proposed. Iliev et al.
These chromates can be interpreted as intermediate products in the 109 .La:Va was given a positive value. We chose the solubility values from Svechnikov et al.15 K and 10 Pa.Thermodynamic assessments 4. The Gibbs energy of the end-member (Cr)(O)1. Solid oxides: Lanthanum chromates: The Gibbs energy function of La2CrO6 was based on the sum of the Gibbs energy functions of La2O3.5 is defined as 3 2 3 ° gas G + A + BT 4 O2 ° SER SER G(Cr)(O)1. compositionindependent interaction parameter 0 Lbcc Cr. For the reasons discussed recently. it was thus necessary to consider these mixed-valent chromates in a provisional version of the thermodynamic La-Cr-O database in spite of their arguable stoichiometries. for its optimization. The formation of chromates that contain mixed Cr valences may be explained by gradual reduction of Cr6+ in La2CrO6 as the temperature increases.Va)1. and O2 in proper stoichiometries and A + BT parameters that were fitted to the enthalpy of formation from the oxides. 5  A and B are adjustable parameters. Due to the lack of experimental data the oxygen solubility in αCrss was modeled as an ideal extension of the oxygen solubilities in pure La and Cr. we reassess the oxygen-solubility in Cr(bcc) using the model (Cr)(O. Povoden et al. In order to refine the model parameters of La2CrO6.3.5. The thermal stability of La2CrO6 is slightly influenced by the thermodynamics of the intermediate. Cr2O3. and αCrss is then given by the two-sublattice description (La. using the PARROT module of the Thermocalc software A was given the fix value 0 for the reasons discussed in an earlier paper.O)1.Cr)(Va.5.O)3.Va were optimized with the same experimental data.1 as well as thermal stability data. 4.32]. mixedvalent chromates mentioned above. and to optimize their model parameters with phase diagram data[19.5 − H Cr − H O = °GCr(bcc) + (4.3. as these data are more comparable to solubilities in other rare earths-transition elements systems.3) SER H x is the standard enthalpy of the stable state of element x at 298. Eq. described the solubility of oxygen in Cr(bcc) using the model Cr(Va. and B and a regular interaction parameter 0 LCr:O.4 Thermodynamic modeling and optimization Metal phases: In order to account for the solubility of La in αCrss .3. the zeroth-order.
These lanthanum chromates with conflicting stoichiometries[19. activity-data of Cr2O3 in LaCrO3 from Peck et al. Stoichiometric perovskite: The Gibbs energy function of stoichiometric rhombohedral r-prv LaCrO3 with the sublattice formula (La3+)(Cr3+)(O2-). heat capacity-data obtained by adiabatic calorimetry from Sakai and Stølen.3.32] and is completed at T = 1473 K or 1523 K. 4.5 .2 and do not include this phase in the modeling.Thermodynamic assessments scope of a sluggish decomposition of La2CrO6. The Gibbs energy function of La2(CrO4)3 was formulated using the same strategy as for La2CrO6. The perovskite phase: The following denotations are used in this section: the superscript prv is written if the regarding Gibbs energy expression is the same for both orthorhombic and rhombohedral perovskite. B. GVCR4O and GLCR4O are set equal for orthorhombic and rhombohedral perovskite. and consequently ambiguous stoichiometries of mixed-valent intermediate chromates.. and C are optimized using the enthalpy of formation from Cheng and Navrotsky.5 x) La 2 O3 + La1.4) Slight differences of the oxygen partial pressure during experiments may be reflected by a variable extent of Cr-reduction.5) The parameters A. and enthalpy increment-data 110 .32] (4. GRPRV denotes the Gibbs energy function for stoichiometric rhombohedral perovskite. The model parameters were fitted to the experimental enthalpy and temperature of decomposition. The superscripts o-prv and r-prv stand for Gibbs energy expressions that have different values for orthorhombic and rhombohedral perovskite. which starts at T = 1153 K[19. GVCR4O and GLCR4O stand for the Gibbs energy functions of the completely oxidized neutral endmember.3.32] are not included in the presented thermodynamic database.3. °GLaCrO3 is given by ° r-prv SER SER SER GLaCrO3 − HLa − H Cr − 3H O = °GLa3+ :Cr3+ :O2− = GRPRV = 1° 1 GCr2O3  + °GLa2O3  + Gmag + A + BT + CT ln T 2 2 (4.x CrO3 + O2 (g) ↑ 2 2 mixed-valent chromates → La 2 CrO6 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ [19.(1. We go along with the interpretation of LaCrO4 being an intermediate reaction product during the decomposition of La2(CrO4)3 by Eq. The enthalpy of formation from the elements was not used as it is a calculated value. The simplified decomposition reaction reads 1+ x 1.
40] and entropies[34.5-CrO1. is unlikely due to the densely-packed perovskite structure. and the perovskite formula essentially remains La1-xCrO3. and oxygen nonstoichiometry can be excluded from thermogravimetry and electrical conductivity[37. The optimization of selective model parameters listed in Table 4. irreconcilable trouble is encountered at the extension to the LaO1.64].Va)(Cr3+. 111 . While this model results in a satisfying reproduction of experimental data.35] of transition having been obtained by combined investigation techniques and being internally most consistent.Cr4+. B-site vacancies are energetically less favored than A-site vacancies in the perovskite structure[63.40. Thus the defects in n-type conducting lanthanum chromite are ambiguous and were not considered in the model. A phase diagram with congruent melting of lanthanum chromite and two eutectics[18. This means that the simplest sublattice model to describe cation nonstoichiometric La1-xCrO3 reads (La3+. 112-114) resulted in negligible concentrations of Va on the B-site and the anion sublattice.3 (pp.35. Cation-nonstoichiometric perovskite: To choose a proper model for nonstoichiometric perovskite the following considerations are made: the formation of interstitial Cr in lanthanum chromite proposed by Shvaiko-Shvaikovskii et al.19] cannot be reproduced by using the emf-experiments[49-52]. enthalpies[34. Thus these data were excluded from the optimization.Cr4+)(O2-)3.Va)3. as there is no existing thermodynamic data for this transition.Va)(Cr3+.3.42]. These are solved by allowing Va on the B-site and the anion sublattice of lanthanum chromite just like in lanthanum manganite leading to the appropriate sublattice formula (La3+. A+BT parameters of the low-temperature orthorhombic perovskite phase were optimized with those temperatures[34.58] measurements.5 system required for SOFC applications due to diversities between the model descriptions of lanthanum chromite and lanthanum manganite.5-MnO1.Thermodynamic assessments measured at high temperatures.38. The rhombohedral to cubic transformation at high temperatures is not considered in the model.35.Va)(O2-.
La3+:O2.− H Cr = GCRLIQ liq SER GCr3+:Vaq..La3+ :Vaq.3.Vaq.La3+ :O2. O)1. Cr 2+ .= Lliq 3+ :O2.008 yCr  112 .− 2 H Cr − 3H O = 5GCROLIQ − 179638 + 79.O = −355151.= 61397 − 5.− HLa = GLALIQ liq SER SER GLa3+:O2.− 2 HLa − 3H O = GLA2O3LIQ liq SER GCr 2+ :Vaq. q = 3 yLa3+ + 2 yCr 2+ + 3 yCr3+ ° ° ° ° ° ° liq SER GLa3+:Vaq. Va q.17755T 2 4 3 SER 3° SER ° bcc GLa:O − HLa − H O = GLABCC + G (O 2(g) ) − 855000 + 142.− H Cr = 2GCRLIQ − GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+:O2.+ qyVa .= −101850 − 39016( yCr 2+ − yLa3+ ) Cr Lliq 3+..5 yCr  β bcc = −0.)q p = 2 yO2. Cr)(Va.− 2 H Cr − 2H O = 2GCR1O1_L Interaction terms Lliq 2+ :O2.La:Va = 83500 p = 0.422 ° Lbcc Cr.923T  liq SER SER GCr 2+ :O2.Thermodynamic assessments Table 4.5T  2 4 Lbcc Cr:Va.Vaq.3 Model descriptions and Gibbs energy functionsa) Liquid (liq) (La 3+ .5 ° ° bcc SER GCr:Va − HFe = GHSERCR  bcc SER GLa:Va − HLa = GLABCC 3 SER 3° bcc SER GCr:O − H Cr − H O = GHSERCR  + G (O 2(g) ) + 113..4 Tcbcc = −311.= −101850 − 39016( yCr3+ − yLa3+ ) Cr Bcc A2 phase (La.23T + (65393 − 23T )( yCr 2+ − yLa3+ ) Cr Lliq 2+ . Cr 3+ ) p (O 2.= 121000 Cr Cr Lliq 2+ .
− 2HLa − 3HCr − 12HO = GLA2CR3O12 La (CrO ) 113 ..− HLa − HCr − 3HO = 5 6 GS4O +GOPRV − GS3V + 1 6GS4V + Gmag ° r-prv SER SER SER GLa3+ :Cr4+:O2.− HLa − HCr − 3HO = 5 6GS4O +GRPRV − GS3V + 1 6GS4V + Gmag ° ° ° o-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GOPRV − 1.5 °G(O2(g) ) + Gmag r-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GRPRV − 1.Cr3+ k = O-2.41263T + Gmag ° r-prv SER GVa:Cr3+:Va − HCr = GRPRV + 1.Chromates La 2CrO6 (La 3+ )2 (Cr 6+ )(O2.35 yi:j:k i = La 3+ .5 °G(O2(g) ) + Gmag ° o-prv SER SER GVa:Cr3+:O2.894 yi:j:k SER SER SER 2 GLa3+ :Cr6 :O2.Va:O2. Va La .Va)(Cr 4+ .= Lprv3+:Cr4+.− HLa − HCr − 3HO = GRPRV + Gmag o-prv SER SER SER GLa3+ :Cr4+:O2.75 °G(O2(g) ) − 1.− HLa − HCr − 3HO = GOPRV + Gmag r-prv SER SER SER GLa3+ :Cr3+:O2.5GVCR4O +0.Cr3+ .35056T + Gmag Interaction term Lprv3+:Cr3+.5GVVV − 2GLCR4O + 0.− HCr − 3HO = GRPRV + 1.75 °G(O2(g) ) − 1.= 250000 La La Magnetic contribution Tco-prv = Tcr-prv = 291.)12 ° SER SER SER 4 3 2 GLa3+ :Cr6+:O2.Va j = Cr 4+ .41263T + Gmag ° o-prv SER SER r-prv SER SER GVa:Cr4+:O2.5GVCR4O +0.5GVVV − 2GLCR4O + 0.)6 ° prv β o-prv = β r-prv = 0.75 °G(O2(g) ) − 1.Va:O2.5GVVV − 2GLCR4O − 0.41263T + Gmag ° o-prv SER GVa:Cr3+:Va − HCr = GOPRV + 1.5GVCR4O +0.Thermodynamic assessments La1-xCrO3 perovskite (La 3+ . Va)3 ° ° ° o-prv SER SER SER GLa3+ :Cr3+:O2.75 °G(O2(g) ) − 1.41263T + Gmag ° r-prv SER SER GVa:Cr3+:O2.5GVCR4O +0.5 °G(O2(g) ) + 4.35056T + Gmag ° o-prv SER r-prv SER GVa:Cr4+:Va − HCr = °GVa:Cr4+:Va − HCr = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O − °G(O2(g) ) + 4.5 °G(O2(g) ) + Gmag o-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GOPRV − 1.− HCr − 3HO = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O + 0.5 °G(O2(g) ) + Gmag ° r-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GRPRV − 1. Va)(O2.− HCr − 3HO = GOPRV + 1.− 2HLa − HCr − 6HO = GLA2CRO6 6+ La CrO La 2 (CrO4 )3 (La 3+ )2 (Cr 6+ )3 (O2.− HCr − 3HO = °GVa:Cr4+:O2.5GVVV − 2GLCR4O − 0.
R = 8.5GCR2O3 − 73591 + 2.00307T 2 + 190000T −1 +0.01T − 0.25 °G(O2(g) ) GS3O = −472704 + 191.75 °G(O2(g) ) − 72615 − 4.7186T − 47. The third-last term accounts for the configurational entropy of mixing. and yk is the site fraction of O2.38T − 47.00307T 2 + 190000T −1 +0. yj is the site fraction of Cr3+. The second-last term describes the excess Gibbs energy of mixing due to interactions of ions in the mixture.68T ln T Neutral nonstoichiometric perovskite endmembers GS4O = −597648 + 213. These are accounted for by the 114 .31451 Jmol K −1 −1 Using the compound energy formalism (CEF)[66-68] the molar Gibbs energy of La1-xCrO3 reads ⎛ ⎜ ⎝ ⎞ ⎟ ⎠ ° prv prv Gm = ∑∑∑ yi y j yk °Gi: j:k + RT ⎜ ∑ yi ln yi + ∑ y j ln y j + ∑ yk ln yk ⎟ + EGm + Gmag (4.56T ln(T ) − 0.5GCR2O3 − 73931 + 3.Thermodynamic assessments Functions Perovskite Stoichiometric orthorhombic perovskite GOPRV = 0.56T ln(T ) − 0.9T − 47.68T ln T Stoichiometric rhombohedral perovskite GRPRV = 0.5GCR2O3 + 0.3. Cr4+ and Va on the B-sublattice.25 °G(O2(g) ) − 291802 − 250T GLCR4O =1 3GLA2O3A + 0. mol.6) i j k i j k where yi is the site fraction of Va and La3+ on the A-sublattice.56T ln(T ) − 0.5GCR2O3 + 2. K.5GCR2O3 + 0.31451 J mol-1 K-1.and Va on the anion sublattice of the perovskite A1-xBO3.5GCR2O3 GVCR4O = 0.25 °G(O2(g) ) La 2CrO6 GLA2CRO6 = GLA2O3A + 0.25 °G(O2(g) ) − 200000 Perovskite reference GS4V = −607870 + 268.5T La 2 (CrO4 )3 GLA2CR3O12 = GLA2O3A + 1.5GCR2O3 + 0. R = 8.25 °G(O2(g) ) − 371557 + 205T a) All parameters are in SI units : J.5GLA2O3A + 0.38T − 0.00307T 2 + 190000T −1 +0.5GCR2O3 − 1.5GLA2O3A + 0.5GCR2O3 + 0.
 The magnetic parameters Tc and β were fitted to the C p data around the magnetic transition temperature from Sakai and Stølen. Thus the authors prv prv adopted °G(La3+ )(Cr 4+ )(O2.3. The parameters of the compound energy formalism are the Gibbs energies of the not necessarily neutral 12 end-member compounds °Gi: j:k . 4.Thermodynamic assessments optimization of interaction parameters. 115 .5 3 system  .3.3 (pp.. Fig. 4. For the magnetic part of the Gibbs energy a magnetic ordering-model proposed by Inden and simplified by Hillert and Jarl was used.1 Representation of the Cr-containing part of the model for nonstoichiometric lanthanum chromite. ° prv prv G(La3+ )(Cr 4+ )(O2. The neutral compounds used for the optimization are marked by the black spots.1 is a visualization of the Cr-containing part of the model the authors use to describe the cation nonstoichiometry of lanthanum chromite.5-SrO-CrO1. The thin lines margin the neutral plane.) and °G(La3+ )(Cr 4+ )(Va) from Povoden et al. The last term designates the magnetic contribution to the Gibbs energy. A short summary of this model can be found in Chen et al.3. Fig. These endmembers of 3 3 nonstoichiometric perovskite have been fixed firmly by a sufficient number of consistent experiments in 3 the LaO1. 112-114). with the 8 Cr-containing compounds being the corners of the cube. Only compounds inside the neutral plane can exist on their own.) and °G(La3+ )(Cr 4+ )(Va) are given in Table 4.
the Croverstoichiometry in a furnace-cooled specimen reported by Khattak and Cox does most likely not represent the overstoichiometry at an intermediate temperature and was not used for the optimization.3.r-prv SER SER o-prv.7 and A of Eq. The 116 .8 it describes random mixing of La3+ and Va on the A-site.3.7 describes random mixing of O2. °G(Va)(Cr3+ )(Va) .3.8 are optimized using experimental data of excess Cr in perovskite. the 12 endmembers of the compound energy formalism of the perovskite phase are defined. °G(Va)(Va)(O2.5 to 4.3. were used to obtain ° prv prv prv prv G(Va)(Cr3+ )(O2. The parameters A and B of Eq. 4.r-prv GLaCrVa3 − HLa − H Cr = °GLa3+ :Cr3+ :Va = GLaCrO3 − (4.) .  : 3° G (O2(g) ) 2 ° o-prv.8) 1 1 1 gas = GLCR4O = °GCr2O3  + °GLa2O3  + °GO2  + Gmag + A 2 3 4 prv GLa2 3CrO3 − ° and reciprocal relations which were set zero in analogy to Grundy et al.8 and adopting the Gibbs energies of the remaining endmembers ° prv prv prv prv G(La3+ )(Va)(O2. In Eq. 4. 4.9) Using Eqs. 4. and °G(Va)(Va)(Va)3 from Grundy et al. °G(La3+ )(Va)(Va) . Furthermore the temperature dependence of lanthanum vancancy and hole concentrations from Akashi et al.) .3. 3 3 3  .3. ° prv G(La3+ )(Cr3+ )(Va) results from a reciprocal relation which was set zero in analogy to Grundy et 3 al. The configurational entropy3 3 3 3 term in Eq.3. As cation diffusion in La1-xCrO3 is extremely slow even at high temperatures.3.3.) . 4.) .with Va on the anion sublattice. °G(Va)(Cr 4+ )(O2. was considered in the optimization.Thermodynamic assessments The neutral Cr4+ -containing endmembers 2° 1 ⎛ 2 2 1 1⎞ GVa:Cr 4+ :O2− + °GVa:Cr 4+ :Va + 3RT ⎜ ln + ln ⎟ 3 3 ⎝ 3 3 3 3⎠ 1 1 gas = GVCR4O = °GCr2O3  + °GO2  + Gmag + A + BT 2 4 prv SER SER GVaCrO2 − H Cr − 2 H O = ° (4.7) and 2 SER 2 1 ⎛ 2 2 1 1⎞ SER SER H = °GLa3+ :Cr 4+ :O2− + °GVa:Cr 4+ :O2− + RT ⎜ ln + ln ⎟ − H Cr − 3H O 3 La 3 3 ⎝ 3 3 3 3 ⎠ (4. and °G(Va)(Cr 4+ )(Va) .
14. 117 .74] was used for the description of the liquid phase of the La-Cr-O system. the temperature of the eutectic at the Cr-rich side from Berjoan. and Foëx. The liquid is thus given by the model description (La3+.and the two subregular 1Lliq 3+ . we defined pO2 = 1 Pa.Va:Cr4+ :O2.Va:Cr3+ :O2. Furthermore the two regular interaction parameters 0 Lliq 3+ .La3+ :Va and subregular 1Lliq 2+ .5 Results and Discussion The La-Cr system: The calculated phase diagram of the La-Cr system is presented in Fig. 4.3.3.= 0 Lliq 2+ .Thermodynamic assessments introduction of positive interaction parameters 0Lprv3+ .Vaq-)q.that were given La La the same values circumvents too high Cr4+ contents at low temperatures that would be in conflict with the experiments.13. together with experimental phase diagram data[12.5 system from Tresvjatskiy et al.La3+ :O2- L were optimized.. The chromium species considered in the liquid are Cr2+ and Cr3+. It was based on the liquid descriptions of the binary subsystems.Cr3+)p(O2-. Using the following data for their optimization led to the lowest error between experiments and calculation: the composition and temperature of the eutectic at the La-rich side and the composition of the eutectic at the Cr-rich side in the oxide LaO1. as were the two sub-regular interaction parameters. 4.2 (next page).La3+ :O2. Higher oxidation states are unlikely to exist in the liquid at normal oxygen partial pressures.CrO1. and the congruent melting temperature of the perovskite phase from Coutures et al. Berjoan and Tresvjatskiy et al. The liquid phase: The two-sublattice model for ionic liquids[73.La3+ :Va Cr Cr interaction parameters to account for interactions between La and Cr. As a value of the oxygen partial pressure is required for the optimization.La3+ :O2.14] at the eutectic and monotectic in the metallic La-Cr system and the partial enthalpy of mixing of Cr. It was assumed that the interactions between Cr2+-La3+ and Cr3+-La3+ are of the same order of magnitude in the oxide melt.17].La3+ :O2.Cr2+.5. The experimentally determined temperatures and liquid compositions[13. did not specify the value of the prevailing oxygen partial pressure during their phase diagram experiments conducted in an argon atmosphere.and 0Lprv3+ .= Cr Cr Cr 1 liq Cr 2+ . ΔH Cr  in La-Cr liquid were used to optimize the temperature-dependent regular 0 Lliq 2+ . thus the two regular interaction parameters were set equal to each other.
The model description of the bcc phase results in a tiny solubility of Cr in La(bcc). denoted as γ La ss .3. The calculated enthalpies of mixing are shown in Fig.17] . which further decreases as a function of increasing temperature. 118 .Thermodynamic assessments Fig. the lowest temperature of stable γ La ss .2 Calculated phase diagram of the La-Cr system with data from the literature included (symbols).3. 4.3 (next page) together with the experimentally determined value that is well reproduced by the calculation.La:Va used to model the bcc phase results in a large miscibility gap between the La-rich and Cr-rich metals.% at 1134 K. which is tantamount to a small solubility of La in αCrss in agreement with the experiments [14. 4. The positive value of 0Lbcc Cr. of 2 ×10-3 at.
This is unfortunately associated with Cr an inverse liquid-liquid miscibility gap with a minimum at X(Cr) = 0. Considerable deviations of the calculated liquidus from experiments at the Cr-rich side of the system can be ascribed to the problem of two different melting temperatures for Cr cited in the literature.3. and integral enthalpies of mixing as a function of composition.CrO1.La3+ :Va L and 1Lliq 2+ . and Svechnikov et al. in air at 119 . A satisfying reproduction of the experimental data was obtained by considering a moderate temperature dependence of 0 liq Cr 2+ ..25 and T ≈ 5000 K that is of course unphysical.Thermodynamic assessments Fig.5 phase diagrams in pure oxygen at pO2 =105 Pa.La3+ :Va . at T = 1700 K included (symbol with error-bar).3 Calculated partial enthalpies of mixing of La and Cr in La-Cr liquid.5. which are T = 2180 K and 2130 K. 4. The higher value was favored by Dinsdale and is adopted in this study. whereas the lower melting temperature was chosen by Savitskii et al. The La-Cr-O system: Phase equilibria: Calculated LaO1. with the experiment from Berezutskii et al.
19] and the conflicting data on the melting temperature of lanthanum chromite in argon atmosphere the presented liquid description is rather tentative.4 together with experimental data[18-21].3.3. 4. Due to the ambiguous oxygen partial pressure of phase diagram experiments[18. and under reducing conditions representing argon atmosphere at pO2 = 1 Pa with experimental data included (symbols). reflected by the disappearance of Cr overstoichiometry. A decrease of Cr4+ during annealing of an originally lanthanum-deficient perovskite phase under reducing conditions is predicted by the model. Excess Cr in lanthanum chromite is favored at high oxygen partial pressures. Fig.4 Calculated phase diagrams of the LaO1. Under oxidizing conditions Cr3+ is favored over Cr2+ in the liquid. Analogous to Fe in the La-Fe-O system this oxidation of Cr2+ to Cr3+ governs shifts of eutectic compositions and temperatures and the increase of the melting temperature of the perovskite phase on increasing the oxygen partial pressure. and orthorhombic perovskite is stable only at pO2 ≤102 Pa. and the liquid stability increases considerably at the Cr-rich part of the system 120 .5 system in pure oxygen.5-CrO1. La2CrO6 is stable within a wide temperature-range in pure oxygen. 4. air atmosphere. On the other hand a significant amount of Cr3+ in the ionic liquid is reduced to Cr2+ under reducing conditions.Thermodynamic assessments pO2 = 21278 Pa. This is in line with the interpretations of Raman spectra from Iliev et al. whereas it does not form in air and argon atmosphere. and under reducing conditions at pO2 = 1 Pa representing the typical oxygen partial pressure in argon atmosphere are shown in Fig. Be it that the reported thermodynamic data of La2CrO6 and La2(CrO4)3 are correct. lanthanum chromite is expected to be metastable at room temperature.
4.2 (p. At pO2 = 10-34.1 (p.5. It is obvious that no mutual solubilities of La and Cr in bcc metal in equilibrium with oxides are expected. Despite this discrepancy we did not go for an alternative liquid model for the sake of consistency with our previously assessed systems. The liquid description using the twosublattice model for ionic liquids also resulted in a significantly larger decrease of the melting temperature of lanthanum chromite at pO2 ≈ 1 Pa than the given values in argon atmosphere. Fig.5 calculated phase equilibria of the La-Cr-O system at T = 1273 K are shown as a function of oxygen partial pressure. 105-107) is a compilation of the Gibbs energy functions and model descriptions of the phases in the La-Cr-O system obtained in this study.3 (pp. was obtained using the new model description (Cr)(O. 105).04 Pa metallic liquid forms at the lanthanum-rich side of the phase diagram.5 Calculated phase equilibria of the La-Cr-O system at T = 1273 K as a function of oxygen partial pressure. 121 .3. In Fig. Calculated and experimental data on the orthorhombic to rhombohedral transition of LaCrO3 are listed in Table 4. 4. 106). Table 4.Va)1. The same oxygen solubility in Cr as in the assessment by Povoden et al.3. Thermodynamic data: Calculated thermodynamic data of solid oxides are listed together with experimental data from the literature in Table 4.3.3.Thermodynamic assessments leading to a considerably lowered eutectic temperature.3.
6 Calculated heat capacities of LaCrO3 (solid curve) as a function of T with experimental data included (symbols). The dashed line marks the temperature of the o-prv ↔ r-prv transition.3.Thermodynamic assessments Lanthanum chromates: Testing an optimization of model parameters of La2(CrO4)3 by using all available thermodynamic data[29. whereas the calculated standard enthalpy of formation from the elements was rejected. and/or by significant deviations between the thermodynamic standard data used for the calculation of the enthalpy of formation from the elements and assessed values[8-10]. 4. Anyway the model parameters were fitted to the experimental data.3. The calculated C p -curve extrapolates well to high temperatures.6. The considerable error might be explained by experimental difficulties to reach equilibrium at the low investigation temperatures. The perovskite phase: the calculated heat capacities of LaCrO3 are compared with experiments from the literature in Fig. The use of C p -data from Sakai and Stølen along with enthalpy increment-data from Suponitskii to optimize the 122 . Fig. bearing in mind the high degree of uncertainty of the resulting description.31] resulted in gross disagreement between optimized and reported values. 4.
The experimentally determined C p -peak around 545 K caused by the first-order transition o-prv ↔ r-prv is in fact a discontinuity which cannot be implemented in the model. Experimental enthalpy increments are well reproduced by the calculation (see Table 4. As CTlnT was set equal for o-prv and r-prv.6.28 or p = 0. stated that the Gibbs energy of formation of LaCrO3 cannot be studied properly using the solid oxide electrolyte method due to experimental difficulties in measuring the low oxygen potentials encountered in a mixture of coexisting LaCrO3-La2O3-Cr. whereby the proper p-value for structures other than bcc. Only the use of the latter data for the optimization resulted in the proper phase diagram with congruent melting of the perovskite phase and two eutectics. The calculated transition temperature of T = 540 K is shown by the broken line in Fig.or oxygen-containing atmosphere. 105.Thermodynamic assessments parameter CTlnT of the Gibbs energy of stoichiometric perovskite resulted in the lowest error between experiments and calculation. p=0. fcc.3. Due to the consistency between both groups of calorimetric experiments[30. Yet it is obvious that the CaF2based emf-technique is neither suitable for the determination of thermodynamic data of lanthanum chromite. the transition temperature being in agreement with the experiments.28.70] using p = 0.3.1. p. In this case the emf depends on the activity 123 . as it unavoidably leads to emf that are too low. It needs to be clarified why all of the emf-measurements are problematic: Azad et al. For the sake of compatibility with the recent assessment of the La-Fe-O system we chose p = 0.4. The calculated Gibbs energies of the formation of LaCrO3 from the oxides 1 La O + 1 Cr O → LaCrO 3 2 2 3 2 2 3 (4. p.1. The resulting Gibbs energies of formation from emf-measurements are remarkably less negative than the Gibbs energies of formation derived from Knudsen mass spectrometry. Two values for the magnetic parameter p are possible depending on the crystal structure.35] the term CTlnT is fixed firmly. The C p -anomaly is equally well reproduced by the model[69.3. A small peak which was found around 855 K can be explained most likely by the decomposition of an undetected impurity phase. their C p is the same. and hcp is not available in the literature.28 and p=0. The calculated C p -peak at T = 290 K reflects the temperature of the magnetic order-disorder transition. 4. A possible explanation is found in a study by Akila and Jacob: Fine precipitates of CaO can form on the surface of CaF2 in water.10) are listed as a function of temperature together with data from the literature [49-53] in Table 4.3.4. 105).
The calculated decomposition of the perovskite phase by Eq.97 at 1273 K.3.11 is plotted as a function of temperature and oxygen partial pressure in Fig. 4. Defect chemistry of the perovskite phase: 124 .11) is pO2 = 10-20. 4. and changing activity of CaO at the electrode/electrolyte interface can alter the chemical potential of fluorine at this electrode and thus the emf across the electrolyte.3. Chemical stability of the perovskite phase: The calculated oxygen partial pressure for the decomposition of lanthanum chromite by the reaction 1 3 LaCrO3 → La 2 O3 + αCr + O2 (g) ↑ 2 4 (18.104.22.168 Calculated decomposition of lanthanum chromite as a function of temperature and oxygen partial pressure.7.Thermodynamic assessments of CaO at the electrode/electrolyte interface. 4. Fig.
3. and charge neutrality is maintained by 1 • [Va ′′′ ]= [CrCr ] La 3 (4. A La 125 . and [OO ] can be considered to be ~ 1. CrCr .3. La x x • ′′′ The concentrations of the defects LaLa . yprv 3+ . yprv . 4.8 (next page) for lanthanum chromite in equilibrium with Cr2O3.)3 2 4 (4.3. yprv 3+ .13) and the equilibrium constant of the oxidation reaction is x • x [Va ′′′ ]1 3[La La ]2 3[CrCr ][OO ]3 La x x x 3 14 [La La ][CrCr ][OO ] pO2 K ox = (4. Va La . The line for yprv 3+ at 1073 K cannot be seen as it is very close to 1.15) • Substituting this into Eq. if [Va ′′′ ] and [Va •• ] are O Cr assumed to be negligible according to Akashi et al.14 gives the proportionalities [Va ′′′ ]. and CrCr in La1-xCrO3 correspond to the site 3 fractions yprv 3+ . A La A Va B Cr B Cr A La A Va B Cr y prv 4+ and the tiny fractions y prv and y prv are plotted logarithmically as a function of B Cr B Va O Va log pO2 at T = 1073 K and 1673 K in Fig. [CrCr ] .14) x x x For small oxidation extent [La La ] . [CrCr ] ∝ PO2 16 . 4.Thermodynamic assessments Applying a defect chemistry analysis of La1-xCrO3 in equilibrium with Cr2O3 the following defect reaction for its oxidation can be written in the sublattice form. and yprv 4+ in the compound energy formalism.3.: 1 (La 3+ )(Cr 3+ )(O2.)3 + O2(g) → (La 3+3 Va1 3 )(Cr 4+ )(O2. yprv 3+ .12) Using Kröger-Vink notation this defect reaction reads 1 2 x 1 x x x • x La La +CrCr +3OO + O2(g) → La La + Va ′′′ + CrCr +3OO 4 3 3 La (4. yprv .3.3.
 may be explained by problems of reaching equilibrium due to extraordinarily slow cation diffusion in • ′′′ lanthanum chromite.0 ×103 Pa and pO2 = 2. pO 2 . 4. is calculated from very high to very low oxygen partial pressures. hence oxidation of LaCrO3 to La1-xCrO3 governs the electrical conductivity of perovskite with fixed activity of Cr2O3 at unity between pO2 = 105 Pa and 10-8 Pa at this • temperature.8 Calculated site fractions of species in La1-xCrO3 in thermodynamic equilibrium with Cr2O3 logarithmically plotted at T = 1073 K and 1673 K as a function of of 3/16 of the calculated defect concentrations is indicated in the triangle. In Fig.12.3.Thermodynamic assessments Fig. This slope is • fixed by the defect reaction Eq. 4. The slope • At T=1073 K a constant slope of 3/16 of the defect concentrations [Va ′′′ ] and [CrCr ] shown in La the triangle.9 (next page) the calculated slopes of VaLa and CrCr are 126 . 4. The calculated slopes of [Va ′′′ ] and [CrCr ] are equal to the slope of the electrical La conductivity from 1573 to 1673 K between pO2 = 1..3.0 ×104 Pa determined by Akashi et al. At T = 1673 K the slope of 3/16 of [Va ′′′ ] and [CrCr ] is La reproduced by the calculated slope using the compound energy formalism at 105 Pa > pO > 2 10-8 Pa. The conflicting data from Shvaiko-Shvaikovskii et al.3.
The calculated amount of [Va ′′′ ] relative to [CrCr ] is fixed by the criterion for La charge neutrality. derived from electrical conductivity measurements (symbols with error-bars.. 4. The calculated concentrations agree well with the data derived from electrical conductivity • measurements. 4. Eq. as calculated [Va ′′′ ] and [Va •• ] are very small. 127 .15. broken lines).3. Fig. The presented defect chemistry calculations are still rather tentative.3.Thermodynamic assessments • compared with slopes of [Va ′′′ ] and [CrCr ] determined by Akashi et al. as the temperature and oxygen partial pressure dependence of excess Cr in La1-xCrO3 has not been investigated systematically so far.9 Calculated defect concentrations in La1-xCrO3 in thermodynamic equilibrium with Cr2O3 (solid lines) logarithmically plotted as a function of reciprocal temperature along with the data from Akashi et al. The calculated O Cr relative defect concentrations are in line with those proposed by Akashi et al. as a function of La reciprocal temperatures.
Mechanism and kinetics. Foger. Bossel (Ed. P. The thermodynamic descriptions of lanthanum chromates and the liquid phase are rather tentative due to humble or sketchy experimental information. Vol. Using the new database the stability limits of lanthanum chromite in function of temperature and oxygen partial pressure can be quantified. 99. A. Solid State Ionics. R. Proceedings of the 26th Risoe International Syposium on 128 .6 Conclusions Model parameters of the presented thermodynamic La-Cr-O database were optimized with assessed thermodynamic and phase diagram data. Ramprakash and J.Thermodynamic assessments 4. and the calculated slopes of defect concentrations in function of oxygen partial pressure and temperature are in line with the slopes derived from electrical conductivity measurements.-M. 3. 1997. Kjaer and J. D. Hilpert. The proposed existence of lanthanum vacancies and holes to maintain charge neutrality in lanthanum chromite with excess Cr is reproduced by the model. 297-310. Deller. H. Zhang. and Cheng and Navrotsky. Badwal. and K. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.H. M. Zhang. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells. 2. However the amounts of excess Cr in La1-xCrO3 used for the optimization of the cation nonstoichiometry are preliminary. pp. pp. References 1. Miller. 4013-22. S. I.P. Larsen. 147(11). A. Druckerei J. 1994.P. J. Y. Carlsson. 2. Cr-Mn deposition at the three-phase boundary observed by TEM.).. S. K. First European Solid Oxide Fuel Cell Forum Proceedings. K. p. 4. Nickel. P. Electrochem. 703. The orthorhombic to rhombohedral transition in lanthanum chromite and the magnetic order-disorder transformation are well reproduced by the model. Foger. Göttingen. U. Jiang. The thermodynamic modeling of lanthanum chromite was based on experimental thermodynamic data reported by Peck et al.3. Soc. 2000. as the use of these data for the optimization of model parameters resulted in a proper reproduction of the phase equilibria derived from experiments. Kinzel. S. and further work on the temperature dependence of excess Cr as a function of temperature and oxygen partial pressure would allow a more accurate quantification of the defect chemistry of lanthanum chromite. J.G. Das.
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J. Some Observations on the Formation and Structure of Lanthanum Chromite. T. pp. Soc. 33. pp. 493-506. 1-14 (in German). Acad. W. K. 40. Ni)O3 Perovskite System. Mater. Korobeinikova. Nauk SSSR. Hashimoto. 1985. 183-90. Pavlikov. Chim. Yu. 2000. 10. A. B. I lanthanum chromate(V).. H. and Entropy of Lanthanum Chromite between 298 and 900 °K. H. Izv. T. Enthalpy. Sc..A. Terao. Phase Transformations of Certain Chromites of the Rare Earth Elements. Tolochko. 1520-24 (in Russian). Lett. Specific Heat. 1963. 34.-M. Geller. 5-8 (in French). 140(10). T. A. Tsuda. Tresvyatskii. K.B. S.Thermodynamic assessments 31. N. Tagawa. 154. Y. Höfer. Coutures.. Schwarz. 524-29. LaCrO3 at Room Temperature. Kock. 39. 276. Neorg. 679-82 (in Russian). Solid State Chem. 1271-74 (in French). pp. 805-06. Chem. K. Rev. Phase Transitions in Solid Solutions Based on Lanthanum Chromite. 38. Nauk SSSR. Traverse. L. 32. Z. Neorg. pp. Stølen. E. H. C. Y. pp. Akad. Paris B.P. Anorg. Structural Phase Transition of Orthorhombic LaCrO3 Studied by Neutron Powder Diffraction. at Temperatures from 298. S. 132.F. pp. On the chromates(V) of the rare earths. Sakai. Kamiyama. Analysis of Crystal Structure and Phase Transition of LaCrO3 by Various Diffraction Measurements.E. Solid State Ionics. 1967. 309-16 (in French). Thermodyn. 1973. R. T. High Temp.15 K. P. M. Hashimoto. Sc. Foëx. 322(1-2). Momin. Allg. K. 131 . Reznitskii. Heat Capacity and Thermodynamic Properties of Lanthanum(III) Chromate(III): LaCrO3... C. Morii. N.G.G. Crystal Chemistry and Thermal Behavior in the La(Cr. V. Kamiyama. M. S. A. N. 41. Oikawa. Yoshida. 2(4).V.F.. 10. Takagi. Structural study and thermal decomposition of lanthanum based chromate. Chem. 1991. Oikawa. Phys. 27(5). J. Zonov. 1976.S. 1995. D.M. A. 264. A.P. Anthony. pp. S. Sakai K. Kishi. Paris C. Mater.. 14(4). 42. Phase Transitions in Perovskitelike Compounds of the Rare Earths. 1966. Kononyuk. Mater. 1973.N. J. High-Temperature X-ray Diffractometric Studies of LaCrO3. 1993.. LaCrO4. On the Semiconducting Properties of Lanthanum Chromite. Electrochem. Shimojyo. Raccah.M. Acad. Lopato. Tanaka.R.P. Miner. pp. Sci. Rev. J. 36. M. 1167-72.C. 43. pp. 23(9). 1970. J. 2000. pp. V. I. Evaluation of the Thermal Conductivity. pp. Berjoan. 37. J. 2(4). J. Mirza. pp.. Lyutsko. Dokiya. N. Mathews.R. Tsuzuki. Akad. 1246-48. Ruiz. 2889-94. Izv. 35. pp.
Alloys Compt. Heat Capacity Measurement of Lanthanum Chromite by Laser Flash Method. 2007. Kamegashira. 53. Pressure-Induced Structural Phase Transition of LaCrO3. Mn. 176-82. Abstracts of the 27th Symposium on Thermal Analysis and Calorimetry. Dokiya. Hao. Cr. Chen. Cmaidalka. Method. 14. Xing. pp. pp. Solid State Commun.Sr)CrO3 System. Miller. Kobertz. 5(3). Polish J. Mat. J. 1990. H. 79(12). N. pp. Yuan. O. Abrashev. Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties. V.P.. 7677 (in Japanese). Hashimoto. Thermodynamic Stability of LaCrO3 by a CaF2Based E. Experimental Results.M. K. N. Enthalpies of Formation of LaMO3 Perovskites (M=Cr.-L. pp. Li.. Tagawa. Phys.-Q. 57-62. Kawada. Dokiya. P. Nature. 214301-1214301-7. Z. M. 46. Japan. Dudek. Koseki. Fe. 74. Mater. Y.V. Nakamura. Y. Petzow. Kikegawa. pp.P.G. X. Wang. Satoh. A.. Z. Kojima. Chen. 1977. 20(1). 166(1).. J. Khattack and D. Thermodynamic Stability of LaCrO3 and CaZrO3 Using a Solid-State Galvanic Cell Method. Kozlowska-Róg. R. pp. 48. 108(9). 50. Bull. L. Sudha. A. Yoshida. N. Stability of the Perovskite Phase LaBO3 (B=V. Structural Studies of the (La. Iliev. J. M. pp. Am. M. 55. 52. 45. M. Li. 19-24 (in Chinese). Determination of the Standard Free Energy of Formation of LaCrO3 at 1273 K.Y. pp. Kolev. 191-200. T. 25(5). W. 1996. A. Thermodynamic Properties of LaCrO3. 2006. K. W. Electron Paramagnetic Resonance and Antiferromagnetism in LaCrO3. X. Heat Capacities of LnCrO3 (Ln=Rare Earth). 54. J. Hilpert. H. T.. Chem. 445-46. H. Hadjiev. Ceram. Mater. J. M. 192(4). Sun. 1987. pp. Res. Yokokawa. 3266-72. pp. 81. Rev. 691-94. Huang.. Murakami. C. Nickel. pp.. Chung. Navrotsky. Cheng.-H. A.F. Cox. Meng. 1997. November 1991. 2005. and Ni). 463-72. 12.E. 23-29. Zhou. pp. 1979. Ni) in Reducing Atmosphere I.-Y. Weinberg. D. pp. Róg. 1998. 51. H. D. Azad.Thermodynamic assessments 44. N. I. Peck. 49. Kyoto. Res. Zhongguo Xitu Xuebao. Soc. S. H. Less-Common Met. G. Gauckler. S. R. Co. 649-59. Y.N. 47. G. N. 2006. M. F. Rare Metals. Fe.. Res. 56. Sreedharan. 132 . M. G. J. Litvinchuk. Co. Matsushita. 259.M. Sakai. T. Raman Spectroscopy of Low-Temperature (Pnma) and High-Temperature (R 3 c) Phases of LaCrO3. Y. M. Larssen. Takahashi. 1961. 562-66. T.J. Bull. B. Takagi.
M.B.-O. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. Chem. Mater. pp. Akashi. Povoden-Karadeniz. L.F. 65.S. 1971. Akad.. Gopalakrishnan. J. B. J. Shvaiko-Shvaikovskii. 15(8). Lal. Electrical Transport in Light Rare-Earth Orthochromites. L. pp. Grundy. Hillert. Determination of Chemical and Magnetic Interchange Energies in BCC Alloys. T. Ivas.Thermodynamic assessments 57. E.. Jansson.V. pp. Chem. Gauckler. 2003.J. M. M. 24(3).. 68. Saunders. V.. Indian J. 36. Phase Equilib. Andersson. Vol.R. T. 71. Fierro. T. M. 1978. J.. E. Advances in Catalysis.. 58. 66(10).G. Calphad. Hillert. 1984. 1. Povoden. 32. Hallstedt. Transport of Lanthanum Ion and Hole in LaCrO3 Determined by Electrical Conductivity Measurements.E. pp. pp. Goto. M.K. Neorg. 61. Tejuca. 1441-45 (in Russian). 79(2). 62. Metallkd. 2006. Calculation of Defect Chemistry Using the CALPHAD Approach. H. 69. 70.. 2003. J. C. Solid State Ionics. Hillert.N. Thermodynamic Assessment of the Co-O System. 345-58. 33-41.G. 34. G.. Pergamon Materials Series. B. 212-27. 30. 577-82. Z. A. Nauk SSSR.J. Solids. J. Metallkd. pp. 243-. pp. pp. 177-83. 164. p 227-38. Hillert. Jansson. Diff.G. A Model of Alloying Effects in Ferromagnetic Metals. Gauckler. B. Ordered Defects & Nonstoichiometry in Metal Oxides of Perovskite & Related Structures. accepted 63.P. Rao. Cmpd. 1979. J. pp. Tripathi. pp. 23A. K. Mater.N. B. 1975. 133 . A. I. 1982. Sundman. Thermodynamic Assessment of the La-Fe-O System. Alloy. Elsevier Science Ltd. Vidyasagar. Jarl. -Manganites and -Ferrites. 94-96. 59. 60. A. Wanklyn. Phase Equilib. C.L. Sci.. B. L. 320. pp. B. Z. Calphad. Ivas.P.N. 66. Popov.J. V. V.. Structure and Reactivity of Perovskite-Type Oxides. G. 17. Maruyama. T. pp. Superstructures. 1998. Phys. J. 437-45. T. General Treatment. 1989. p 161-76. Chen. 2(3). Calphad Calculation of Phase Diagrams. 1986. Application of the Compound-Energy Model to Oxide Systems. Izv. Rao. 64. N. Guillermet. A. 81-87. 67. 265-84. J. Gauckler. M. 1988. M. Sundman. Acta Metall. 2001.N. Gordon. M. The Compound Energy Formalism. A. Influence of the Synthesis Conditions on the Electrical Properties of LaCrO3. Electrical Transport in Rare Earth OrthoChromites. Inden. Miodownik. Chen. Rao. L.R. 1595-1609. Grundy.
B. 73. Chen.J. The Mobility of Oxygen Ions in CaF2. 15. L. Chen. Povoden.Thermodynamic assessments 72.1 Introduction Sr-doped lanthanum manganite (LSM) with the perovskite structure ABO3-δ is used as cathode materials in SOFC. pp. These requirements are conformed by using the CALPHAD approach. 4. thermodynamic driving forces and activities. Jacob. 261-66. Metall. 4. 74. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. K. A. Gauckler to be submitted The thermodynamic La-Sr-Mn-Cr-O oxide database is obtained as an extension of thermodynamic assessments of oxide subsystems using the Calphad approach. Appl. 75. R. Hillert. Gibbs energy functions of SrCrO4. A. Trans.T. J. 1985.N. pp.4 Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications E. Gauckler. Povoden. Sundman.. M. 1991. B. 16A. The database should meet the demand to calculate stable and metastable phase equilibria. 1990. M. Grundy. Modification of the Two-sublattice Model for Liquids. B. 294-300. Grundy. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization.N. and SrCr2O4 are presented. 20. and L. Ågren.4. Experimental solid solubilities and nonstoichiometries in La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ are reproduced by the model. A thermodynamic La-Sr-Mn-Cr-O oxide database is highly desirable for the development of endurable SOFC: thermodynamic calculations set an important base for the optimization of cathodes aiming to avoid long-term degradation due to chromium poisoning. J. A.J. Jansson. Akila. E.2]. Sr2. pp. submitted to Scripta Mater. M. Calphad. 109-19. Electrochem. as well as defect concentrations of the cathode contaminated by Cr at different temperatures and oxygen partial pressures.67Cr2O8. However diffusion of chromium from the metallic interconnects into the cathode leads to a severe cell voltage decrease that was linked to the formation of Crcontaining phases[1. Sr2CrO4. Sundman. For the construction of the 134 .
0. with a slight modification: Grundy et al. Sr-Cr-O oxide: Thermodynamic functions for Sr-Cr-oxides in the SSUB database are based on estimates. The stoichiometry of a phase defined as Sr3Cr2O8 was later corrected to be essentially Sr2. Differences concern the reported stabilities of further compounds[11. 4.4. Cr-O. and the LaSr-Mn-O oxide database is taken from Grundy et al. Sr3Cr2O7 was approved as high pressure phase only. Due to large differences between the ionic radii of La3+ and Mn3+ and possible coordination numbers (1. The 135 . Limited solution of Sr in La1-xSrxCrO3-δ perovskite was confirmed by a later investigation.67Cr2O8 by using microprobe analysis.785 Å for at maximum 6-fold coordinated Mn3+) we omit Mn3+ on the A-site. No quaternary phases or solid solutions were found in the Sr-Mn-Cr-O oxide system.5 Å for 12-fold coordinated La3+. Sr-Mn-Cr-O oxide is treated as ideal extension from the subsystems. whereas emf measurements using CaF2-based emftechnique led to conflicting results likely caused by competing reactions. La-Sr-Cr-O oxide: In the La-Sr-Cr-O oxide and La-Mn-Cr-O oxide systems no quaternary stoichiometric compounds were reported.Thermodynamic assessments La-Sr-Mn-Cr-O oxide database La-Mn-Cr-O oxide and La-Sr-Cr-O oxide systems are assessed. allowed Mn3+ on the A-site of LSM to reproduce experimental oxygen nonstoichiometries under low oxygen partial pressures.15-19]: for the stabilities of SrCr2O4 and Sr2CrO4 we trust the accurate study of Jacob. which is in agreement with Negas and Roth. in agreement with Hartl and Braungart.12. We propose optimized thermodynamic functions for oxide phases of the Sr-Cr-O oxide system resulting from the assessment of all available experimental data: agreement exists between Gibbs energies of formation of SrCrO4 determined by emf technique using a Y2O3 stabilized ZrO2 electrolyte[11. Calculation of the oxygen nonstoichiometry of perovskite + MnO instead of metastable single phase perovskite leads to a good agreement between experimental and calculated nonstoichiometries. Phase equilibria in the La-Sr-Cr-O oxide system in air at 1223 K and under vacuum at 1873 K were determined by using solid state technique. and La-Cr-O databases are adopted[3-5].2 Assessment of data from the literature Previous assessments of the La-O.12]. On the other hand the conflicting phase equilibria presented by Kisil lack experimental details.
Sr)CrO4 were stable in air.3 at T = 1173 K that Cr4+ were absent in the latter. 136 .2.Thermodynamic assessments existence of several Ruddlesden-Popper phases is restricted to reducing conditions. and 0.5O3-δ with x = 0. 0. solely Sr(La. 0.11 using drop calorimetry at T = 1080 K. and −0. Perovskite+MnCr2O4 spinel equilibrium of a powdered mixture of La0.Sr)CrO4 showed reproducible stoichiometry.Sr)CrO4 is ambiguous.5Cr0.3 using Knudsen mass spectrometry.1. concluded from the similarity between X-ray absorbtion spectra of Cr K of LaCrO3 and La1-xSrxMn0.25.04. and 0. 0.9Cr0.1. 0. and La0. Plint et al.24]. Thus its extension to the quinary database would not be reliable.09.1O3-δ was measured using thermogravimetry. Myoshi et al.1. Complete solid solution between the LaMnO3 and the LaCrO3 perovskites was affirmed. investigated the single phase region of La1-xSrxCrO3 with x = 0. La-Sr-Mn-Cr-O oxide: In the La-Sr-Mn-Cr-O oxide system complete solid solubility of Mn and Cr is reported for La1-xSrxMn1-yCryO3-δ perovskite.3 at T = 1273K. Nonstoichiometry data for La1-xSrxCrO3-δ with x=0.2CrO3-δ at 1273 K were measured as a function of oxygen partial pressure using thermogravimetry. thermodynamic data are missing. whereas negative δ essentially stands for cation nonstoichiometriy.1. In contrast to Peck et al. Cr4+ and oxygen vacancies are regarded as the major defects[23. Positive δ in the perovskite formula reflects oxygen deficiency.8Sr0. La-Mn-Cr-O oxide: In the La-Mn-Cr-O oxide system no quaternary stoichiometric compounds were reported. and 0.3 as a function of temperature and oxygen partial pressure using XRD analysis. The exact temperature and oxygen partial pressure range of Sr(La. and the solubility of Cr is unknown.8Sr0. Cheng and Navrotsky measured enthalpies of formation of La1-xSrxCrO3-δ with x = 0. and 1573 K.Sr)CrO4 is omitted in the modeling. −0.2MnO3 and Cr2O3 at 1073 K was reported after 1000 h of heat treatment in air. 1473K.2.2.2. and 0. As Ruddlesden-Popper phases have not been reported to form during SOFC operation with LSM cathodes. Peck et al. δ of LaMn0. 1373 K. −0.2. An isothermal section of the La-Mn-Cr-O oxide system at 1073 K in air and pure oxygen has been published without further commenting of experimental evidences. 0. Sr(La. and 0.3. and δ = 0. it was proposed earlier that Sr(La. determined the Gibbs energy of formation of La1-xSrxCrO3 with x = 0.
4. Transitions of LaMn1-xCrxO3-δ are complex as they depend on temperature. Gibbs energy functions of Sr-Croxides were formulated as 1 2 ° SER SER SER gas G(Sr)x(Cr)y(O)z − xH Sr − yH Cr − zH O = x °GSrO + y °GCr2O3 + v °GO2  + A + BT (4.36−40].25 for SrCrO4. most likely due to interactions that cannot be reproduced by the model. in terms of the applicability of the new database for SOFC the authors omit structural transitions in the modeling. SrCr2O4. and La1-xSrxMn1-yCryO3-δ [8. Consistency among transition data for La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ prevails. All 137 . whereas diversities exist regarding the transitions in La1-xSrxMn1-yCryO3-δ . Sr2.67Cr2O8 following the proposed formula and for the Ruddlesden-Popper phase Sr2CrO4. their modeling was omitted without consequences for the applicability of the database for SOFC.3 Modeling and optimization Sr-Cr-O oxide: The sublattice models (Sr2+)(Cr6+)(O2-)4 and (Sr2+)(Cr3+)2(O2-)4 are employed for the descriptions of SrCrO4 and SrCr2O4.41] were reported. However we did not obtain satisfying results in higher-order perovskites.67Cr2O8+SrCrO4+Cr2O3 as a function of temperature and oxygen partial pressure[11. 0.67Cr2O8. Magnetic transitions have been well reproduced by an ordering-model[42. and the equilibrium Sr2. (Sr2+)8/3(Va)1/3(Cr6+)2/3(O2-)8/3(Cr5+)4/3(O2-)16/3 and (Sr2+)(O2-)1(Sr2+)(Cr4+)(O2-)3 were chosen for Sr2.43] for LaCrO3.12]. H a is the standard enthalpy of the stable state of element a at 298. LaMn1-xCrxO3-δ [26. and Sr2CrO4 respectively.and perovskite layers of the latter.12] and phase stabilities of SrCr2O4 and Sr2CrO4 investigated by equilibration experiments of different mixed oxide compositions under controlled atmospheres. their optimization with the following experimental phase diagram and thermodynamic data using the PARROT module of the Thermocalc software resulted in the lowest error between model and experiments: Gibbs energies of formation of SrCrO4[11.15 K and 105 Pa.Thermodynamic assessments The perovskite phase: Magnetic and structural transitions of La1-xSrxCrO3-δ [29−35].4. Thus.75. As the magnetic transitions are low temperature features. 4. accounting for the structural feature of alternating rocksalt. A and B are adjustable parameters.1) SER v = 0. 7/6. and 0. composition and oxygen partial pressure.
15832T kJmol-1 this work. T = 298 K. Δ ° H = −59. calc.= GS3V + 1 6GS4O − 1 6GS4V GSr 2+ :Cr 3+ :Va = GS3V − 5 6GS4O + 5 6GS4V Table 4.4 kJmol-1 this work. δ = 0. δ = 0. calc. δ = 0.7 kJmol-1 x = 0.4.166T kJmol-1 .3.11.1. δ = 0. Δ ° H = −20. Δ °G = −93. calc. BSr2CrO4 = 50 J ASrCr2O4 = 98000 J.0 kJmol-1 this work. ° Δ ° H = −67.2. δ = 0.2.67 Cr2 O8 + SrCrO 4 + Cr2 O3 Δμ O 2 = −265. calc. Δμ O 2 = −262.67Cr2O8 = 219 J La1 − xSrxCrO3 − δ ° gas GLa3+ :Cr 4+ :Va = 5 6GS4O − GS3V + 1 6GS4V + GRPRV − 1.859 + 0.5 kJmol-1 x = 0.106904T kJmol-1 . δ = 0. Δ °G = −213.15553T kJmol-1 .67Cr2O8 = −508507 J.1073 − 1473 K Δμ O 2 = −276. Δ ° H = −56.13157T kJmol-1 .1 Optimized model parameters Sr . Δ H = −65. T = 298 K.88 kJmol-1 x = 0. calc. BSrCrO4 = 131.340 + 0.4.5 °GO2  ° ° ° GLa3+ :Cr 4+ :O2.Cr oxides ASrCrO4 = −273771 J.Thermodynamic assessments reported phase equilibria are correctly reproduced by the model. Δ °G = −88. Table 4. Δ °G = −85. T = 298 K.767 + 0. calc.6 J ASr2CrO4 = −145000 J.6 kJmol-1 this work. T = 298 K. Optimized parameters and calculated and experimental thermodynamic data are listed in Table 4. T = 2000 K. calc. Δ °G = −102.7 kJmol-1 x = 0.09. Δ H = −48. calc. δ = 0.2 kJmol-1 this work.3 kJmol-1 this work.2.1 kJmol-1 this work.48 kJmol -1 138 . Δ ° H = −34.5 J ASr2. δ = 0.76 kJmol -1 x = 0. calc.1 and 4.04. calc. Δ °G = −93.3.1080 − 1380 K (1 − x) 2 La 2 O3 + xSrO + 1 2 Cr2 O3 + x 4 O 2 − δ 2 O2 = La1− xSrx CrO3−δ x = 0. Δ ° H = −50. Δ ° H = −20.72 kJmol-1 x = 0.54 kJmol-1 x = 0. Δ °G = −109.13152T kJmol-1 this work.3 kJmol-1 this work.3.2 Calculated and experimental thermodynamic data SrO +1 2 Cr2 O3 + 3 4 O 2 = SrCrO 4 Δ °G = −273. BSr2.= 5 6GS4O − GS3V + 1 6GS4V + GRPRV GSr 2+ :Cr 3+ :O2. δ = 0.4.1. T = 298 K. T = 2000 K.050 + 0. Δ ° H = −55. ° Δ ° H = −36. T = 2000 K.950 − 1280 K Sr2. T = 298 K. Δ ° H = −34. calc.774 + 0.2 + 0.4 kJmol-1 this work.4.2. BSrCr2O4 = −95.8 kJmol-1 this work.1.15 kJmol-1 x = 0.851 − 1116 K Δ °G = −273.825 ± 0.
The molar Gibbs energy of the perovskite phase then reads ⎛ ⎜ ⎝ ⎞ ⎟ ⎠ ° prv prv Gm = ∑∑∑ yi y j yk °Gi: j:k + RT ⎜ ∑ yi ln yi + ∑ y j ln y j + 3∑ yk ln yk ⎟ + EGm i j k i j k (4. R = 8.8Sr0. yj is the site fraction of each cation and Va on the B-sublattice. °G(Sr2+)(Cr4+)(Va)3 1° 5 gas GCr2O3  − °GO2  2 4 ° SER SER GSrCrVa3 − H Sr − H Cr = °GSr2+ :Cr 4+ :Va = GS4V = °GSrO + (4. The molar Gibbs energy °G of La1-xSrxCrO3-δ is uniquely defined as follows: °Gs of the endmembers (La3+)(Cr3+)(O2-)3.3) is chosen as reference.Va)3 with A. this is achieved by using the same model.Va)3. The parameters of the compound energy formalism are the Gibbs energies of the end-member compounds °Gi: j:k . Typical compositions of Sr-doped lanthanum manganites used for SOFC cathodes. It can be accounted for by introducing interaction parameters. (Va)(Va)(O2-)3. (La3+)(Cr3+)(Va)3. (La3+)(Va)(Va)3.48]. B = cations and Va = vacancies using the compound energy formalism. Thus it is reliable to take the Gibbs energies of the compounds of rhombohedral perovskite from  for the model. e.4. and small amounts of Cr brought into the cathode unlikely lead to a change of the structure.4.Sr2+. and (Va)(Va)(Va)3 and ternary interaction parameters are adopted[5.Va)(O-2.Thermodynamic assessments The perovskite phase: It is essential for a consistent description of the perovskite phase that defects that occur in the structure in low-order systems remain on the same sites at the extension to higher order. The last term describes the excess Gibbs energy of mixing.and Va on the anion sublattice. We adopt the description (A. Using the above model and the proposed defect chemistry[22-24] the sublattice formula for La1-xSrxCrO3-δ reads (La3+.Cr4+. (La3+)(Va)(O2-)3. The second-last term accounts for the configurational entropy of mixing.g.Va)(B. and yk is the site fraction of O2. and A and B parameters of °G of two neutral compounds 139 .2MnO3-δ are rhombohedral at SOFC operating temperatures (T=1073 K to 1273 K). (Sr2+)(Va)(Va)3.31451 J mol-1 K-1. La0.6.Va)(O2-.2) where yi is the site fraction of each cation and Va on the A-sublattice. (Sr2+)(Va)(O2-)3.Va)(Cr3+.
solid solubilities[18.Va)3. and in Figs. Thus for LaMn1-xCrxO3-δ we propose the sublattice formula (La3+.5.4.4) ° SER SER SER GSrCrO2.Cr4+.Mn3+:O2-) = +9421 J.5 − H Sr − H Cr − 2. 4.Va)(O . 4. All endmember compounds have been defined in the assessed subsystems.5Va0.Sr .Cr . and (Sr2+)(Cr3+)(Va)3 are obtained by conversions of reciprocal equations that are set zero and are listed in Table 4.1 (p.4.4. 4.4. °Gs of the remaining endmembers (La )(Cr )(Va)3.Mn .5H O = GS3V = 5° 1 1 ⎛5 5 1 1⎞ GSr2+ :Cr3+ :O2− + °GSr2+ :Cr3+ :Va + RT ⎜ ln + ln ⎟ = °GSrO + °GCr2O3  + A + BT 6 6 2 ⎝6 6 6 6⎠ (4. The 3+ 2+ sublattice 2+ 3+ formula 4+ 3+ of 4+ the 2- quinary perovskite reads (La .4.4 denotes °G (Sr2+)(Cr4+)(O2-)3.1 and 4.Va)(Mn .Cr3+.Va)3. (Sr2+)(Cr3+)(O2-)3.Cr . with A = 27027 and B = −69.6.4 Results and discussion The reproduction of experimentally determined Gibbs energies and enthalpies of formation.24] of La1-xSrxCrO3-δ.20]. 3+ 4+ (La3+)(Cr4+)(O2-)3. The regular interaction parameter 0L(La3+:Cr3+.Thermodynamic assessments ° SER SER SER GSrCrO3 − H Sr − H Cr − 3H O = °GSr2+ :Cr 4+ :O2− = GS4O = °GSrO + 1° 1 gas  G + °GO2  + A + BT 2 Cr2O3 4 (4.Mn3+:O2-) accounting for interactions between Cr and Mn cations is fitted to experimental nonstoichiometries.4.Va)(Mn2+.5 in Eq.Mn4+.5Va0.4.2 for ° GSrCrO2. it is reliable to allow Cr4+ on the B-site: as Cr4+ exists in nonstoichiometric lanthanum chromite perovskite.2 (next page). and nonstoichiometries[23. 0L(La3+:Cr3+.Va)(O2-. 138).2 (p. 140 . All endmembers have been defined in the assessed subsystems. and phase equilibria in the La-Sr-Cr-O oxide system by the modeling is satisfying as shown in Table 4.4.Mn3+. A = 136453 and B = −91. 138). it is expected that it is not removed from the structure if the phase is doped. 4. Eq.4.5) are optimized with all available experimental data of the perovskite phase. Though structure-chemical information of site occupancies in LaMn1-xCrxO3-δ perovskite is missing.Mn .
Calculated phase equilibria are the same as in. Filled circles. blank circles. two phase. 141 . 4.Thermodynamic assessments Fig.4. prv = La1-xSrxCrO3-δ.5 system calculated at T = 1223 K in air atmosphere (solid lines) with experimental data included (symbols).5-SrO-CrO1.1 LaO1. and circles with crosses denote single phase. and three phase equilibria.
The calculated nonstoichiometries of La1-xSrxCrO3-δ are in good agreement with the experimental values at higher temperatures. The calculated isothermal section of the La-Mn-Cr-O oxide system at T = 1273 K in air is presented in Fig.23] nonstoichiometries of La1-xSrxCrO3-δ at different temperatures for x = 0. α-spl = tetragonally distorted Cr-Mn-spinel.4. 142 .2.4. 4.5 system calculated at T = 1273 K in air atmosphere.4.3. prv = LaMn1-xCrxO3-δ. as shown in Fig. p. and 0. However it was not possible to reproduce the nonstoichiometries at T = 1073 K and 973 K.1.3 LaO1. 4. 0. possibly caused by equilibration difficulties due to slow diffusion.Thermodynamic assessments Fig. Deducing from the change of δ from T = 1273 K to 1173 K the measured increase of δ from T = 1173 K to 1073 K might be too small.3 as a function of oxygen partial pressure. 4.5-MnOx-CrO1.4 (next page). β-spl = cubic Cr-Mn-spinel. 0. 4.25. 141 Calculated (lines) and experimental (symbols)[22.2. Fig.4.
Va)3 for the quinary perovskite phase.9Cr0.4.Va)(O2-. Thus we stick to a model without interaction parameters.1O3-δ at different temperatures as a function of oxygen partial pressure.Sr2+. The new database is adapted for quantitative calculations of 143 . We propose the model (La3+. Optimized by experiments in pseudoternary and pseudoquaternary oxide subsystems. and the conclusion of missing Cr4+ is not based on a direct chemical analysis of Cr valencies.Mn4+.Cr4+. We believe that complete removal of Cr4+ from the perovskite structure is unlikely.4.Va)(Mn2+. this model allows the quantitative calculation of defects as a function of composition. Experimentally determined nonstoichiometry of LaCrO3 indicates the existence of some Cr4+. 4.5 Conclusions The thermodynamic La-Sr-Mn-Cr-O oxide database has been obtained by combining thermodynamic assessments of oxide subsystems. To approximate the absence of Cr4+ in quinary perovskite. temperature.4 Calculated (lines) and experimental (symbols) nonstoichiometries of LaMn0.Thermodynamic assessments Fig. 4. Experimental findings[8. and oxygen partial pressure.Mn3+:O2-). it would be necessary to give large positive values to the regular interaction parameters 0 0 L(Sr2+:Cr3+.Cr3+.Mn3+:O2-) and L(Sr2+:Cr4+.Mn3+.28] are in line with our calculations.
pp. 1991. Aldinger. Yang. Kawada. pp. and L. 2007. Grundy. 5. Soc. The SGTE casebook: thermodynamics at work. Phase relations in the system Sr-Cr-O and thermodynamic properties of SrCrO4 and Sr3Cr2O8. R.P. J. S. K. 353-62. Badwal. A. 1969. 138. 1018-27. 46-53.). Diff. M. Hack (ed. 2006. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. B25. 1901-07.D. pp. E. T.N. E. Shannon. Chem. M.N. 2000.-K. Russ. J. Chem. Phase Equilib. Institute of Materials. Mechanism and kinetics. A. Petrov. S. Acta Crystall. 2006. Zhang. A. K.. 21. London. pp. 771-774. R... Electrochem Soc.K. 2004. Zinkevich. Durygin. Demina.J. Zhang. P. K. N. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research.J. M. 1721. Gauckler. Jacob. Sakai. L. References 1. Solids. Dokiya. Inorg. B- Stru. Solid State Ionics.J. Povoden. Phys.N. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. Geupel. 297-310.. Foger. Yokokawa. Thermodynamic assessment of the La-Cr-O system. J. 2000. 7. Z. 11. Diff. H.N. F. C. 3. Chemical thermodynamic considerations in sintering of LaCrO3-based perovskites. Chen. S. pp. J. Liu. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells I. Ivas. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.P. Gauckler. 2. Saxena.. Gauckler.A. A. K. 4. E.T. La1-xMn1-yO3-z perovskites modelled with and without antisite defects using the Calphad approach. pp. 147. 67. Y. Grundy. Hallstedt. Phase Equilib. S. Foger. 9. Electrochem. 27(4). T. K. J. Jiang. A. 1996. pp. Ramprakash and J. 10. 52. Filonova. B. 8..N. 99. Deller. Solid State Ionics. accepted 6. J. Grundy. 4013-4022. A.Thermodynamic assessments phase equilibria and defect chemistry in a Sr-doped lanthanum manganite SOFC cathode poisoned by chromium. 1997. pp.T. P. L. 925-.. 173. J. J. Povoden.P. S. pp. 144 . Phase Equilib. M. Prewitt. Effective ionic radii in oxides and fluorides. Abraham.
Hilpert. 23. pp.M. Solid State Ionics. 1998. a hightemperature compound with defect-bariumphosphate-structure. B. J. K.K. 20. Soc. Navrotsky. Peck. Mater. Ch. E.. Sr2. 25.-H. Hilpert. 143. 145 . R. Akila and K. pp. 178. pp. Roth. Standard Gibbs energies of formation of SrCrO4 and Sr3Cr2O8. 177. 1992. L. Mater. 12. O. Sreedharan.33(CrO4)1. 564-73. 4112-. Res. Maruyama. Yamauchi. 1158-61. D. T. Z. Kaimai. A. T. K. Braungart. R. J. 16. Thermochim. Boroomand. 22. Phase diagram studies in the SrO-Cr2O3-La2O3 system in air and under low oxygen pressure. J. 73A. Sr or Ba) from emf-measurements. pp. H. 119-24. 294-300. Revisiting the Sr-Cr(IV)-O system at high pressure and temperature with special reference to Sr3Cr2O7. J. Slobodin. A. F. 952-953 (in German).G. Europ. Solid State Ionics. O. 9. 24. 2005. pp.. R. 2007. Yokokawa. Phase formation in the system SrO-CrO3-Cr2O3. R. 2001. Defect formation and mechanical stability of perovskites based on LaCrO3 for solid oxide fuel cells (SOFC).M. 39. Castillo-Martínez. E. 18. Nonstoichiometry of the perovskitetype oxide La1-xSrxCrO3-δ. K. 13. N.W. Zuev. Kisil. A. Cheng. Negas. Azad. Naturforsch. 300920. Hilpert. 129-36.T. System SrO-chromium oxide in air and oxygen. 194. Wessel. Steinbrech.V. K. 20. Mizusaki. Strontiumchromate(V. VI). pp. 1490-91.. Electrochem. F. S.. K. 19. Ceram. pp. Jacob. 234-44. J. T. Myoshi. S. pp. Energetics of La1-xAxCrO3-δ perovskites (A = Ca or Sr). 1989. Solid State Chem.. A. S. The mobility of oxygen ions in CaF2. M. 2003. Akashi.67Va0. The standard Gibbs energies of formation of ACrO4 (A=Ca. 1978. T. Vaporization and thermodynamics of La1-xSrxCrO3-δ investigated by Knudsen effusion mass spectrometry.Thermodynamic assessments 12. Sudha. 1990. 401-12. T. 59-65. 17. Inorg..H. 33. 1999. Sharova. 23. Solid State Chem. Solid State Ionics. 1984. H. pp.. pp. pp. 14. Matsumoto. 1969. Inoue. Nickel.S. Miller. Appl. D. Solid State Sci. Hartl. J. Singheiser. Ishikawa. Pt. Jim. Mizusaki. 21.33(CrO4)0. Fueki.67. Peck. Teller. pp.A. Onuma. NBS A Phys. M. K. 431-42. A. J. pp. Acta.. Y. H. Kawada. Miller. Yashiro. J. Alario-Franco. 2004. M. R. T. 123. 15. B. Meschke.
Pomjakushin. Komatsu. Sakai. 177.9Cr0.P. Evolution of crystal structure with the oxygen content in the LaMn0. pp. Caneiro. Solid State Chem. Plint. 2005-08. Matter. Hashimoto.85Sr0. 0.-P. P. Irvine. 170.75Sr0.M. Thermodynamic considerations on Cr poisoning in SOFC cathodes. Structural studies of (La. Electronic transport in the novel SOFC anode material La1-xSrxCr0.15). J. 12. Cox. Horita.12) compound. T.00 ≤ 3+δ ≤ 3. 11.A. 474. S. Ohba.R. Xiong.K. Takahashi. H. H. Inami. 57-. 2005. Magnetic and neutron diffraction study on perovskites La1-xSrxCrO3. F. Y. Tezuka.25CrO3 at high temperatures. T.05CrO3 and La0. T. 404-10. Matsunaga.5Mn0.: Condens. 30. Greaves. Takahashi. Arai. H. C. C. C. Matsunaga. Phys.E. T. Morales. 404-10. H. Solid State Ionics.15CrO3 by means of powder neutron diffraction. N. Long. M.G.. 18. 463-71. Matsunaga. Atake. Y. K. 26. Y. Y.1O3+δ (3. S. K. K. pp. Acta. Solid State Comm.A. Y. J. 141. Morii. O.: Condens. 35. Francesconi. Yamaji.M.5O3±δ. pp. Phys. Shimojo. Morii. Y. D. 502-06. 32. 34. 2008. L. Khattak. Y.E. Y. 3193-98. 1998. Matter. R..S.. Y. 2003. H. Thermochim. xSrxCrO3 Analysis of magnetic and structural phase transition behaviors of La1- for preparation of phase diagram. pp. 2569-78. 29. K. H. 177. Chakraborty. Matsubara. Hinatsu. 2008. 1999.95Sr0. Tyagi. Hashimoto. Takahashi. 2006. K. 28. A. 132-.M. 2008. Phys. Solid State Ionics. Cabeza. Thermochim. J. 176. Arai. Yokokawa. H. Matter. Y. M. pp. T. S. 145.: Condens. pp. J. Studies on magnetic properties of La0. Power Sources.Thermodynamic assessments 25.Sr)CrO3 system. Bull. 222-29. Structural study of La0. Magnetization and resistivity in chromium doped manganites. 36. N. A.13. 435. 33. F. 31. P. 27. Tezuka. Brito. Muirhead. Sato. Kawaji. H. 2000. 8661-72. J. Res. Ramanadham. A. pp. Connor. K. Shimojo. Oikawa. J.. 2006. 12. Kishimoto.S.R. T. J. pp.T. Solid State Chem. 2006. Acta. T. V. Hinatsu. Hashimoto. Bari. Chiba. K. Analysis of relationship between magnetic property and crystal structure of La1-xSrxCrO3 (x=0. M. M. 1977. 4151-60. Krishna. Tao. M. Nakamura. Nakamura. Nakamura. Mat. 146 . Yusuf.
47. Yau. 46. pp. 437-43. 2008. M. B. pp. 532-40. 2(3). 2001. Calphad. and 0. 9. 353-61. Hillert and M. 2000. S. Mater. J. B. (a). M.. Hrovat. E. Kallel. S. Soc. L.-O. SGTE data for pure elements. Am. 153-90.. Sol. 0. J.3). Calphad. Z.. Nordblad. M. Assessment of the La-Mn-O system. M.5. M. J. Bernik. Metni. Kolar. Alloy Compd. pp. 457. Hallstedt. Risold.1. Andrè. H. M. Phys. Chem. Howard. M. J. The thermo-calc databank system. 320.T.Thermodynamic assessments 37. 66(10). S. H. nuclear structure. Folgado. El-Fadli. Determination of chemical and magnetic interchange energies in bcc alloys. 0.25) using the Rietveld method of analysis. 1996. Structural effects of Co and Cr substitution in LaMnO3+δ. 2005. I.2. Inden. Vincent. Sci. 577-82. A. 40.. 1685-87. 1978.U. B. G. 44. Mater. 39. Anderson. J. pp. Diff. 1975. L. B. The strontium-oxygen system. General treatment. A. Zemni. J.A. R. Dhahri. Martinez. J. Sapiña. Lett. 227-38. 131-51 147 . 43. 1992. A. F. 1997. Z. D. and magnetic properties of LaCr1-yMnyO3 (y=0. 41. J. 38. Preliminary data on solid solubility between LaCrO3 and LaFeO3 or LaMnO3. Beltrán. 42..R. Gauckler. Beltrán. J. Synthesis. Dhahri. pp. Metallkd. pp. 161-76. H. Jarl. E. Gauckler. D. Holc.N. 184. M. Oumezzine. Calphad. 2001. Sundman. The compound energy formalism. Tellgren. 20. D.7Sr0. pp.. Effect of Cr doping in La0.3Mn1-xCrxO3 with 0 ≤ x ≤ 0. F. 75. Hillert. X-ray-powder diffraction structural phasetransition study of La(Cr1-xMnx)O3 (x=0 to 0. Kuscer. pp. 45. Phase Equilib. 319-25. Grundy. Alloy. D. pp. Ghedira. 48. Ceram. Dinsdale. 317-425. Stat. Tseggai.J. A model of alloying effects in ferromagnetic metals.V. 1991. Cmpd. N. Chen. Calphad. G. 16..-K. Rundlöf. 15(4). Hallstedt.J. J. P. 10. 1985. 26. 143-46. Andersson. Jansson. J. Bourèe.
T.Thermodynamic calculations of impacts of chromium on LSM cathodes 5 Thermodynamic calculations of impacts of chromium on Srdoped lanthanum manganite (LSM) cathodes for solid oxide fuel cells (SOFC) E. Chen. Gauckler. Even though the chromium problem cannot be solved satisfactorily by varying the cathode composition or the SOFC operating conditions. 148 . In particular the concentrations of cation and oxygen vacancies are smaller than in an LSM without chromium under decreased oxygen partial pressure at 1273 K. The spinel formation goes along with increasing Mn2+ in LSM under decreasing oxygen partial pressures. Ivas. and L. Povoden. whereas Cr2O3 is metastable. and partly they occur under kinetic control: at the cathode/electrolyte interface of a Cr-“poisoned” cell Cr-Mn spinel exists in thermodynamic equilibrium with LSM. Proper strategies to prevent the problem of chromium “poisoning” are proposed. From the results of these calculations it is concluded that the processes of chromium poisoning of solid oxide fuel cells (SOFC) are partly explicable by thermodynamics. to be submitted A new thermodynamic database is used for thermodynamic equilibrium calculations in a Srdoped lanthanum manganite cathode (LSM) affected by chromium at typical operation temperatures of 1073 K and 1273 K as a function of oxygen partial pressure.J. and the contribution of a vacancy mechanism for the oxygen diffusion in LSM is thermodynamically hampered in the presence of chromium at high temperature and high current loads. M. the deterioration of the cell performance is expected to be less pronounced when the cell is operated at lower temperatures and current loads. This has consequences for the electrochemical properties of the cell: the electronic conductivity of the cathode will decrease. From the thermodynamic calculations structural chemical changes in the cathode perovskite caused by the interaction with chromium can be predicted: it is shown that the interaction of chromium with the LSM cathode leads to a change of the defect chemistry of the perovskite phase.
This reduction reaction would compete with the oxygen reduction and lead to blocking of the active sites at the triple phase boundary (TPB). good electronic and negligible ionic conductivity. The chemical dissociation approach is coherently based on the interpretation of a large number of impedance spectra. Consequences of Cr poisoning have been investigated specifically in (La1-xSrx)MnO3-δ (LSM) perovskite-structured cathodes. Ad 2) In contrast to 1) it was proposed that gaseous Cr-species would be chemically dissociated to LSM under the polarization of the cell. where the reaction partners for the reduction. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. thermal stability. mechanical strength.Thermodynamic calculations of impacts of Cr on LSM cathodes 5. On the other hand the electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach. Both groups of researchers agree that without polarization Cr is randomly deposited inside the cathode. Consequently Cr-Mn spinel and Cr2O3(s) would form. Ad 1) In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary. associated to these nuclei. and -diffusion process.1 Introduction Chromium-containing metallic interconnects are commonly used in planar-design solid oxide fuel cells (SOFC) due to their high oxidation resistance. In the last decade a lot of efforts were made to elucidate the degradation mechanisms. where they cause the degradation of the cell by detrimentally affecting the O2adsorbtion. and no Cr2O3(s) is formed. though partly with conflicting results. -reduction. Mn2+ would serve as agent for the formation of Cr-Mn-O nuclei that would be able to migrate to the triple phase boundary and further into the electrolyte. However high-valent gaseous Cr-oxide and chromium-oxyhydroxides can diffuse under fuelcell operation conditions from the interconnect into the cathode up to the cathode-electrolyte interface. 149 . as well as low fabrication costs. This affinity would be linked to the creation of free Mn2+ on the surface of LSM due to the oxygen partial pressure gradient caused by the polarization. For the mechanism of chromium poisoning two models have been proposed: 1) reduction of gaseous CrO3(g) in dry atmosphere or chromium oxyhydroxide(g) in wet atmosphere under polarization[2-6] and 2) chemical dissociation of Crspecies on the LSM surface[7-14].
Thermodynamic calculations of impacts of Cr on LSM cathodes
In the critical assessment in chapter 1.3.6 it was concluded that doubtless reasons to reject the reduction approach do not exist. One critical point concerns the extension of dense Cr2O3layers into the YSZ electrolyte: this phenomenon can be explained best by continuous feeding of an initial Cr2O3-layer with CrO3(g), the latter becoming reduced at a new TPB consisting of YSZ and electron-donating Cr2O3(s). On the other hand this process cannot be explained satisfactorily by using the chemical dissociation approach. Even though particularly the early stages of chromium “poisoning” occur in thermodynamic non-equilibrium, the system SOFC develops towards thermodynamic equilibrium by time. This is reflected by a flattening of the curves that reflect the performance deterioration as a function of time, such as the curves of voltage drop and overpotential loss. Thus thermodynamic calculations allow interpretations of the phase equilibria that result from the interactions between LSM and chromium, as well as changes of the phase chemistry that are associated with the chromium contamination of LSM cathodes.
The La-Sr-Mn-Cr-O oxide database is used for the following thermodynamic calculations: phase equilibria in Cr-contaminated LSM (in the following denoted as LSM(Cr)), phase compositions of LSM(Cr) and Cr-Mn spinel, defect concentrations of LSM(Cr), as well as driving forces for the formation of Cr2O3 were calculated with the poly-module of the ThermoCalc software. The following model descriptions were used: for the Cr-contaminated cathode perovskite with the
2+ 4+ 3+
sublattice for cubic
(La ,Sr ,Va)(Mn ,Mn ,Mn ,Cr ,Cr ,Va)(O ,Va)3, for tetragonally distorted spinel (Mn2+)(Mn3+,Cr3+)2(O2-)4 was chosen, (Mn2+,Cr2+)(Mn3+,Cr3+)2(O2-)4 was used, and for Cr2O3 (Cr2+,Cr3+)2(Cr3+,Va)(O2-)3 was taken. Uptake of Cr in LSM is expected, as a complete solid solubility of Cr in LSM has been shown experimentally. For proper thermodynamic calculations of phase equilibria thermodynamic conditions need to be set that reflect the conditions of the chromium contamination of SOFC: the bulk pressure (room pressure, 101325 Pa), the operation temperature (typically from T = 1073 K to 1273 K), the oxygen partial pressure, the cathode composition, and the amount of chromium.
Thermodynamic calculations of impacts of Cr on LSM cathodes
The oxygen partial pressure at the interconnect-cathode interface is air. Under current load it is expected that the oxygen partial pressure will strongly decrease close to the cathodeelectrolyte interface in the triple phase boundary (TPB) region where the oxygen reduction in LSM takes place: the oxygen partial pressure at the cathode-electrolyte interface, pO2(i) can be approximated from the measured cell voltage of a Pt/LSM/YSZ/Ni-Cermet/Pt solid oxide cell and the fuel composition by using the equation for the overall electromotive force E of the cell:
pO RT 2(i) ln 4 F pO
R = 8.31451 J mol-1 K-1, F = 96485.309 C mol-1 and pO2(an) is given by the ratio of H2-H2O in
the fuel. From a measured cell voltage of 0.7 V at T = 1173 K (fuel: 97 vol.% H2, 3 vol.% H2O) and a high current load of 300 mA cm-2 a strong decrease of the oxygen partial pressure at the oxygen reduction sites is expected, pO2(i) ≈ 0.01 Pa. As we are interested in the influences of chromium throughout a cathode under realistic operation conditions of SOFC, results of the thermodynamic calculations are presented for pO ≤ 21278 Pa ≥ 0.01 Pa.
Several LSM cathode compositions can be found in the literature. Part of them is cation stoichiometric, and part of them has excess Mn that is known to prevent unwanted formation of electrochemically isolating zirconate at the cathode/electrolyte interface. In this study two cathode compositions are used for the thermodynamic calculations: La0.9Sr0.1MnO3-δ and (La0.8Sr0.2)0.9MnO3-δ. The sublattice model for this perovskite phase allows the formation of vacancies on each site and changing valencies of Mn as a function of temperature and oxygen partial pressure. The amount of chromium in the system is defined by the partial pressure of the Cr-gas phase:
⎛ μ Cr ⎞ ⎟ ⎝ RT ⎠
pCr = exp ⎜
This means that by knowing the partial pressure of the Cr-gas phase in the TPB region, it is possible to calculate the thermodynamics of the chromium contamination. The problem is that the definite amount of gas that contributes to the degradation phenomena is not known
Thermodynamic calculations of impacts of Cr on LSM cathodes
exactly, as only a fraction of the Cr-gas that evaporates from the Cr2O3 scale on the Cr-alloy interconnect interacts with LSM or is reduced. Fortunately the amount of deposited Cr in a degraded LSM cathode has been analyzed as a function of distance from the cathode/YSZ electrolyte interface, and the combined data of X(Cr) and the oxygen partial pressure at the TPB fix the chemical potential of Cr. The amount of deposited Cr close to the LSM(Cr)/YSZ interface was about 3 wt.% after a long cell test of 300 h at T = 1073 K. If one assumes that the pO2 under the test conditions was 1 Pa at the the LSM(Cr)/YSZ interface (normal cell performance), the chemical potential of the Cr-gas phase can be calculated. Even though it is clear that the chemical potential of Cr will change if the amount of evaporated Cr from different interconnect materials is different, the Cr-gas reservoir is assumed to be in a saturated state due to “unlimited” supply from the interconnect during the cell performance, and thus its chemical potential is fixed in the thermodynamic calculations. This simplification is reasonable, as in all investigated cell tests with LSM and Cr-alloy interconnects the degradation was similar, so that changing chromium amounts due to different interconnect alloys are obviously not detrimental for the cell degradation. H2O (operation of SOFC in humid air) is not considered in the calculations, as neither hydroxides nor solubilities of hydrogen or OH− were included in the La-Sr-Mn-Cr-O oxide database.
Thermodynamic calulcations of La0.9Sr0.1MnO3 contaminated by chromium
Fig. 5.3.1 (next page) shows phase fractions in Cr-“poisoned” La0.9Sr0.1MnO3-δ at constant chemical potential of CrO3, μ(CrO3) = −300000 J mol-1 referred to 100000 Pa of CrO3(g) as a function of oxygen partial pressure at T = 1273 K and 1073 K, and in Figs. 5.3.2 (next page) and 5.3.3 (p. 153) phase equilibria are indicated: the cathode remains single phase at pO2 > 102.75 Pa. By decreasing the oxygen partial pressure, tetragonally distorted Mn3O4 spinel (t-sp), the manganese endmember of the Cr-Mn spinel solid solution phase forms.
5.9Sr0.1(Mn.3.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.1MnO3-δ as a function of oxygen partial pressure at T=1273 K and 1073 K at μ(CrO3) = −300000 J mol-1 Fig. with A and B standing for the cation sublattices and C standing for the oxygen sublattice. Vertical lines indicate boundaries between different phase equilibria 153 .9Sr0.3.2 Phase equilibria in Cr-“poisoned” La0. A.9Sr0. and C denote sublattices of the perovskite phase.1 phase fractions in Cr-“poisoned” La0.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1. 5.1MnO3-δ and defect concentrations of La0. B.
Thermodynamic calculations of impacts of Cr on LSM cathodes
Fig. 5.3.3 Phase equilibria in Cr-“poisoned” La0.9Sr0.1MnO3-δ and defect concentrations of
La0.9Sr0.1(Mn,Cr)O3-δ as a function of oxygen partial pressure at T = 1073 K and
μ(CrO3)= −300000 J mol-1. The vertical line indicates the boundary between phase equilibria
At T = 1273 K (Figs. 5.3.1, p. 153 and 5.3.2, p. 153), tetragonally distorted spinel remains stable to pO2 = 10-0.4 Pa. At lower pO2 cubic Mn-Cr spinel forms. At 1073 K (Figs. 5.3.1, p. 152 and 5.3.3), tetragonally distorted spinel remains stable to pO2 = 100.75 Pa, followed by the formation of cubic spinel at lower pO2 . This means that by decreasing the oxygen partial pressure from pO2 = 104.3, the pressure of air, to 10-1.5 Pa, the amount of spinel in the contaminated cell increases. At 1073 K Cr-Mn spinel formation is less pronounced, and CrMn spinel formation starts at lower pO2 than at 1273 K. To find out about the structural chemical changes in the cathode perovskite caused by reaction with chromium, the fractions of species in a specific sublattice (site fractions) are calculated at
T=1273 K and 1073 K (plots in Figs. 5.3.2, p. 152 and 5.3.3) as a function of pO2 The results .
are compared with the calculated site fractions in a cathode with a very small chemical
Thermodynamic calculations of impacts of Cr on LSM cathodes
potential of Cr, μ(CrO3) = −106 J mol-1 that means with practically no Cr (Figs. 5.3.4 to 5.3.5).
Fig. 5.3.4 Defect concentrations in La0.9Sr0.1MnO3-δ
as a function of oxygen partial pressure at T=1273 K.
Fig. 5.3.5 Defect concentrations in La0.9Sr0.1MnO3-δ
as a function of oxygen partial pressure at T = 1073 K. 155
Thermodynamic calculations of impacts of Cr on LSM cathodes
In general defect concentrations of the Cr-contaminated LSM differ from the defect concentrations in LSM without Cr at a high temperature of 1273 K: with Cr the concentrations of vacancies on the A- and B-sublattices decrease stronger by decreasing the oxygen partial pressure. The increase of oxygen vacancies by decreasing the oxygen partial pressure on the other hand is weaker when chromium is present. At T = 1273 K and pO2 = 1 Pa, which is the expected pO2 at the LSM/YSZ interface at 250 mA cm-2 current load, the site fractions of cation vacancies on the A- and B-sublattices for LSM(Cr) are y(Va)A = 1.98x10-6, y(Va)B=4.3x10-6, whereas in LSM y(Va)A = 3.086x10-6 and y(Va)B = 7.096x10-6 are calculated. The concentration of oxygen vacancies at 1 Pa and T = 1273 K in LSM(Cr) is slightly higher than in LSM, y(Va)C = 3.01x10-5 in LSM(Cr),compared to y(Va)C = 2.57x10-5 in LSM. A pronounced drop of cation and oxygen vacancies is calculated at 1273 K and pO2 = 10-1 Pa, the expected oxygen partial pressure at the TPB under a high current load of 300 mA cm-2: the concentration of oxygen vacancies in LSM(Cr) is y(Va)C = 3.39x10-5, compared to
y(Va)C = 9.48x10-5 in LSM. This means that if the oxygen partial pressure at the LSM/YSZ
interface strongly decreases the vacancy concentrations will drop significantly. The concentrations of Cr3+ and Cr4+ in LSM(Cr) increase when the temperature increases and the oxygen partial pressure decreases. The calculated compositions of tetragonally distorted spinel (Fig. 5.3.6 a, next page) and cubic spinel (Fig. 5.3.6 b) formed during chromium “poisoning” show a strong dependence upon the oxygen partial pressure: only under low oxygen partial pressures a significant amount of chromium is found in the spinel phase, whereas at higher oxygen partial pressures the spinel phase has a composition close to Mn3O4. At T = 1073 K the spinel phase contains less chromium than at T = 1273 K.
3.2)0.9MnO3-δ as a function of oxygen partial pressure at T = 1273 K and 1073 K and μ(CrO3) = −300000 J mol-1 157 .7 phase fractions in Cr-“poisoned” (La0.3. 5.2)0. Fig.3.8Sr0.3.6 Calculated site fractions of ions in cubic spinel (6 a) and tetragonally distorted spinel (6 b) formed during chromium “poisoning” at T = 1273 K and 1073 K 5. tetragonally distorted Mn3O4 (t-sp) is expected to form.8Sr0. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.7 it is obvious that in this widely used LSM composition Cr-“poisoning” leads to the formation of additional phases already at high oxygen partial pressures: A small amount of about 5 mol% of the pure spinel endmember.9MnO3-δ contaminated by chromium From Fig. At T = 1073 K Mn2O3 is stable in a Cr-contaminated LSM cathode with excess Mn in air.2 Thermodynamic calculations of (La0. 5.
158 .3.2)0. 5. the compositions of the spinel phases formed during chromium “poisoning” become richer in Cr under more reducing conditions. 5.3.9 (next page).8 the compositional changes of cubic spinel are plotted as a function of oxygen partial pressure at T = 1273 K.8 Calculated site fractions of ions in cubic spinel formed during chromium “poisoning” at T = 1273 K It is interesting whether the consequences of chromium for the concentrations of defects in LSM(Cr) with excess Mn are more or less pronounced than in cation-stoichiometric LSM(Cr): Phase equilibria and defect concentrations in a (La0. In general.8Sr0. Fig.9MnO3-δ cathode are shown in Fig.3.Thermodynamic calculations of impacts of Cr on LSM cathodes In Fig. 5. as in the case of cation-stoichiometric LSM.
2)0.8Sr0. 5. 5.8Sr0.8Sr0. In LSM(Cr) the concentrations of these cation vacancies drop strongly at low pO2 .Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.10 (next page) is a comparison of defect concentrations of (La0.10) at 1273 K.9 Phase equilibria in Cr-“poisoned” (La0.3.10) and without Cr (solid lines in Fig. The vacancy concentrations on the A-sites and B-sites of the Cr-contaminated perovskite phase are basically in the middle between these vacancy concentrations in LSM. 159 .Cr)O3-δ as a function of oxygen partial pressure at T = 1273 and μ(CrO3) = −300000 J mol-1.2)0.3.9(Mn.9(Mn.2)0. The vertical line indicates the boundary between different phase equilibria Fig. Mn2+ is higher in LSM(Cr) than in LSM at higher pO2 .Cr)O3-δ and defect concentrations in (La0. 5.9MnO3-δ with Cr (broken lines in Fig.3. 5. and the concentration of oxygen vacancies is lower in LSM(Cr) than in LSM at relatively high and low pO2 .3.
Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. Calculated concentrations of all species in LSM(Cr) and tetragonally distorted spinel in equilibrium are listed in Table 22.214.171.124.2)0.1 Pa. Table 5.Cr)O3-δ (dashed lines) and (La0.10 Defect concentrations in (La0. next page.2)0.3. 5.947O3-δ spinel formation becomes important only at pO2 < 0. as it is illustrated in Fig. 160 .148Mn0.8Sr0.3 Thermodynamic testing of LSM with Mn-deficiency Only in a cathode with Mn-deficiency it is possible to push the formation of additional phases towards a lower oxygen partial pressure: for the case of La0.9(Mn.3.1 Compositions of LSM(Cr) and spinel in equilibrium at different T at pO2=1 Pa with and without Cr. 5. 5.9MnO3-δ (solid lines) as a function of oxygen partial pressure at T = 1273.8Sr0.3.3.871Sr0.
Cr)0. 161 . and the concentration of oxygen vacancies is almost an order of magnitude lower then in (La0.12.8Sr0. 5.871Sr0.947O3-δ is half of an order of magnitude higher than in (La0.2)0. next page: The concentration of oxygen vacancies in La0. However.9MnO3-δ at pO2 = 10-1 Pa.2)0. after reaching a plateau at pO2 = 103 Pa.3.Cr)0.871Sr0.148(Mn. y(Va)C even decrease slightly towards lower pO2 .11 Phase fractions in a Cr-“poisoned” Mn-deficient LSM as a function of oxygen partial pressure at T = 1273 and 1073 K and μ(CrO3) = −300000 J mol-1. The influence of chromium on defect concentrations in La0.8Sr0.148(Mn.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.3.947O3-δ is illustrated in Fig. 5.9MnO3-δ at high oxygen partial pressures.
5. and thus its formation is kinetically controlled. This is the amount of energy that is needed to bring the phase to its stable state. 162 .3. In Fig.8Sr0.947O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1 (solid lines).4 Formation of Cr2O3 This phase was not found in the thermodynamic calculations. the more energy is needed to stabilize the phase. and the driving force for the formation of the phase is low.9MnO3 without chromium.3.148(Mn. the phase is thermodynamically stable. The more negative the driving force.871Sr0. Vertical lines indicate boundaries between different phase equilibria 5.Cr)0. If the driving force is 0.2)0.13 (next page) the driving force of Cr2O3 is plotted as a function of temperature at two different pO2 in a LSM cathode with excess Mn under Cr-“poisoning”. One can get an idea about the degree of metastability of a phase by calculating its thermodynamic driving force. Dashed lines indicate the defect concentrations in (La0.3.12 Phase equilibria in Cr-“poisoned” Mn-deficient LSM and defect concentrations in La0. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.
Thermodynamic calculations of impacts of Cr on LSM cathodes
Fig. 5.3.13 Driving force of Cr2O3 as a function of temperature
at different pO2 at μ(CrO3) = −300000 J mol-1. The driving force for the formation of Cr2O3 is less negative at higher oxygen partial pressures.
In the following the results of the thermodynamic calculations are compared to experimental findings on chromium poisoning from the literature. Interpretations are given, which of the chromium poisoning mechanisms occur under thermodynamic control. By carrying out equilibrium calculations of state-of-the-art LSM cathodes with the compositions La0.9Sr0.1MnO3-δ and (La0.8Sr0.2)0.9MnO3-δ at constant chromium in the gas phase it was tested if spinel formation would be favored thermodynamically under low oxygen partial pressure, i.e. close to the electrode-electrolyte interface under polarization conditions. The calculations showed that this is indeed the case. As the A-sublattice of the spinel is completely filled by Mn2+ under the cell operation conditions, and the only source for this species is LSM, it is obvious that spinel formation will be associated with increasing Mn2+ in LSM. Thus, as Mn2+ in LSM increases as a function of decreasing pO2 , also the amount of
Thermodynamic calculations of impacts of Cr on LSM cathodes
spinel formed is higher at low oxygen partial pressure. Cr-gas reveals increasing affinity to LSM towards the electrode-electrolyte interface: both Cr solid solution in LSM and spinel formation increase under decreasing the oxygen partial pressure. From the calculation it is interpreted that the spinel phase that forms under Cr-“poisoning” of the cathode will contain a high amount of Mn, if the oxygen partial pressure at the cathode/electrolyte interface is about 1 Pa. Only at lower pO2 significant Cr is incorporated in the spinel phase, with the stoichiometric MnCr2O4 phase forming at about pO2 = 10-1 Pa. Though spinel formation is thermodynamically driven in Cr-contaminated SOFC, it seems that spinel formation per se is not one of the keys of severe cell degradation due to chromium, but the affinity of Cr-gas to the LSM surface, as even very small Cr contamination in the ppm range apparently leads to a dramatic decrease of the oxygen diffusion in LSM. From impedance spectroscopy analyses it was consistently concluded that the oxygen diffusion is severely influenced by chromium. The thermodynamic calculations showed that Cr interacting with LSM leads to a change of the defect chemistry of the perovskite phase, and particularly to a decreasing amount of oxygen vacancies at high temperatures and low oxygen partial pressures. As the formation of oxygen vacancies in LSM is inhibited, oxygen diffusion to the triple phase boundary is retarded. The results of the thermodynamic defect chemistry calculations of LSM(Cr) thus indicate that the deterioration of the oxygen diffusion is higher under at decreased oxygen partial pressures reflecting high current loads. Cr2O3 is found in degraded SOFC, particularly under high current load. However this phase was not found in the thermodynamic calculations, and its driving force remains negative under SOFC operating conditions. This means that its formation is kinetically controlled. Even though Cr2O3 is not a thermodynamically stable phase in Cr-contaminated SOFC, a strong tendency exists for CrO3(g) to be reduced to Cr2O3(s) at the TPB, as the reduction reaction has a large negative ΔG. It was also mentioned earlier that a high tendency for the precipitation of Cr2O3(s) from CrO3(g) exists. In addition to the adsorption process it is expected that a great many of Cr-gas molecules are driven further to the energy valley for their reduction, namely the TPB. Thus it is non-contradictory that coupling of Cr-gas to LSM and subsequent spinel formation at the LSM surface, and the reduction of CrO3 (g) at the TPB leading to the metastable reduction product Cr2O3(s) occur simultaneously. An alternative way to form Cr2O3 was discussed by Konysheva et al.: The kinetic decomposition of the spinel phase may occur in an oxgen partial pressure gradient due to different mobilities of Mn2+ and Cr3+.
Thermodynamic calculations of impacts of Cr on LSM cathodes
In addition to the inhibiting of oxygen diffusion to the TPB and blocking of active triple phase boundary sites by the thermodynamically controlled formation of spinel and the kinetically driven formation of Cr2O3(s) and thus retarded diffusion of oxygen ions into the electrolyte, further unwanted consequences of chromium poisoning can be ascribed to the low electrical conductivity of Cr2O3. Also Cr-Mn-spinel and Cr-doped LSM are significantly less conductive than pure LSM[26-29]. The electrical conductivity of Cr-Mn spinel decreases as its Cr-content increases. From the thermodynamic calculations it can be predicted that increasing the current load will lead to the formation of a spinel phase with a low electrical conductivity. The ohmic resistance of spinel will also increase due to more Cr dissolved in spinel as the amount of deposits of chromium in the cathode increases as a function of time. Furthermore it is expected that the electrical conductivity of LSM is influenced by chromium particularly under high current loads, as chromium leads to decreased concentrations of cation and oxygen vacancies in LSM(Cr) relative to LSM under such operating conditions of SOFC.
Thermodynamic calculations of LSM contaminated by chromium showed that the formation of spinel is thermodynamically driven, whereas Cr2O3 is a metastable phase that forms under kinetic control in degraded SOFC. The formation of spinel is favored under low oxygen partial pressures, thus in an SOFC under current load this phase is found predominantly at the LSM/YSZ interface. The interaction between chromium and LSM leads to changes of the defect chemistry of the LSM perovskite phase. Particularly diminished concentration of oxygen vacancies relative to LSM without chromium may be a reason for the inhibited oxygen diffusion in degraded SOFC at high temperatures and high current loads . This is also true for Mn-deficient LSM compositions, though the formation of spinel can be restricted to lower oxygen partial pressures. Its defect chemistry is particularly problematic at low oxygen partial pressures, the concentration of oxygen vacancies being strongly diminished relative to LSM with excess Mn. Anyway the use of a Mn-deficient LSM cathode for SOFC is not recommended due to the formation of electrically isolating zirconate.
Soc. Solid State Ionics.. Matsuzaki. 2001. 127.Thermodynamic calculations of impacts of Cr on LSM cathodes By lowering the operation temperature of SOFC additional phases are expected to form at lower oxygen partial pressures. 4. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator. 2004. Taniguchi.P. J. Paulson. Power Sources. Y. 73-9. Power Sources. Yasuda. Saitoh. 2004.P. Badwal. 166 . Foger. Electrochem. Tu. pp.C. J. Kawamura. Electrochem. K. J. Y. H. Matsuzaki. Jiang. J. interaction between Mn from LSM with Cr may be cumbered by proper doping of the perovskite with further B-site cations. Akiyama. pp. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells I. 7. Y. I.I. U. A126-31. pp. Advances. Birss. 2000. pp. Thus it is expected that in this case the consequences of Crpoisoning will persist particularly at high current loads. pp. Solid State Ionics. Yasuda. S. Ramprakash. Soc. R. pp. Kadowaki. aging mechanisms and lifetime in solid-oxide fuel cells. Soc.S. 1997. chromium “poisoning” of SOFC with an LSM cathode and Cr-alloy interconnect can only be prevented by applying effective coatings that act as diffusion barrier in combination with additional functional layers. 3. 3195-3205. 271-278. 297-310. Electrochem. 1995. I. 148. M. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes. 151(11). 6. Zhang. Apateanu. H. 284-93.P.P. Zhang. S. S. S. pp. Even though the deterioration of the cell performance due to chromium is expected to be less pronounced when the operation temperature and current load is decreased. T. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. Foger. J. 132. L. J. Yasuo.. 2000. References 1. 55. Deller. From the thermodynamic point of view it can be summarized that there are neither optimized SOFC operating conditions nor optimized LSM compositions that eliminate the chromium problem in SOFC with LSM cathode and Cr-alloy interconnect. 5. T. Stimming. Miyake. Mechanisms and kinetics. A1961-68.. Furthermore. Y. 147(9). 2. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Chromium poisoning of LSM-YSZ SOFC cathodes. 99. Y. J. V. K.
P. pp. Gauckler. Res. Inorg. Jansson. J. S. 16. K. J. Hallstedt. Li. 167 . 695-703. 22. 2006. J. pp. Demina.A. 2008. 153-190. 3664-71.Sr)MnO3 and (La. 27. Y. A. Calphad. 9.. J. 11. Ceam.P. 4013-22. Jiang. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. pp. 9. Hydrogen Energy.Ba)(Co. The Thermo-Calc databank system. S. pp. pp. 31.P. Soc. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. A. 162.P.. A comparison of O2 reduction reactions on porous (La. A. B. Electrochem. Int. Mater. 13. 21. 4th international symposium on solid oxide fuel cells and pers. Jiang. Chem.N. Gauckler. J. Grundy. Power Sources.. Povoden. J.N. 191-201. J. Jiang. Diff. Electrochem. 97. 32. B (119) (2005) 80-86. 2006. J. Filonova. 20. E. Zhang. 180. E. Povoden. 52. Jiang. Power Sources. 438-442. pp. 10.P. 12. B.N. pp. Assessment of the La-Sr-Mn-O system. pp.J.P. J.D.G.. Petrov. S. Grundy. J. 1043-1052. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells. 146. 2007. 1-22. S. Jiang.N. Zhen. Europ.-O. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. J. Zhang. 23.Thermodynamic calculations of impacts of Cr on LSM cathodes 8. A. 2001. J. Wu. 361-73. 2002. Caplan and M. Jiang.N.J. X. Zhang. I. Zhen. Mater. J. 28. Zhen. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. Eng. S. Fergus. 771-774. 18. pp.W. pp. Krumpelt et al. J. S. 1985. S. 14. L. 17. 2006. L. Zheng. A. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Cohen. Use of gaseous Cr species to diagnose surface and bulk process for O2reduction in solid oxide fuel cells. Gauckler. 22. Y. 2000. Soc. 2007. Characterization and performance of (La. Apateanu. J. 353-62. D. J. M. Solid State Ionics. 2004. Applied Electrochem.J. 1961.. Andersson. Calphad. Mechanisms and kinetics. Sundman.P. 2004. S. Russ. Zheng and P. comm.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. Y.P. B. 56978. pp.. Soc.Sr)(Co.. 181-192. Sci. 2002. 108. Phase Equilib. pp. pp. 39-43. pp. The volatilization of chromium oxide. Grundy. L.D. E. Foger. FY Annual report. L..P.Fe)O3 electrodes. Jiang. 15. 19. 147. Int.
pp.M. Tagawa. NJ (1995). Hilpert. Caneiro. 2006. Jian. in SOFC-IV. H. R. A. Hill. 1212-16. Electrochem.G. Solid State Ionics. Horita. A. Koc. M. Penkalla.U. Hammou. 153. Effect of cathode thickness and current density. N. Singhal. 25.B. Howard. NJ (1989). Electrochem. H. S. Eds. T. H.A. Singheiser. 114-24. Siebert. N.C. Yokokawa. S. J. 26. 28. L. PV 89-11. M. M. W.. 29.P. J.. The Electrochemical Society Proceedings Series. pp. Hammouche. Phillips.M. O. 1991. Pennington.. 176. 2007. Maruyama. Sammes.. Yamaji. 220. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. in SOFC-1. Sakai. B1252-B64. Structure and transport property of manganese-chromium-iron oxide as main compound in oxide scales of alloy interconnects for SOFCs. pp. 27. Konysheva. Power sources. A. J. K. H.Thermodynamic calculations of impacts of Cr on LSM cathodes 24. 168 . S. Ivey. Pennington. Kishimoto. Ed. K. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. 2005. Soc. Qu. 472. M. D. Soc. pp. Kleitz. Yamamoto. 681-686. Chromium poisoning of the porous composite cathode. Brito. L. Xiong. The Electrochemical Society Proceedings Series. E. Y. Dokiya. 138. 154 (12).C. PV 95-01. p. p. Mertens. J. J. Singhal. Anderson.E. T. H. E.
836315*T-34.004045175*T**2 -5.008371705*T**2 +6.00189435*T**2 -1..894+218.284604*T-26.06113*T-17.072353*T-21. Dinsdale 1991 @@ La.6651E+03 4.15 169 . Dinsdale 1991 @@ La.34397*T-163.5388*T*LN(T).18*T-50.35429E+01.413+59. 2000 Y -8205. @@ ---------------------------------------------------------@@ Functions @@ ---------------------------------------------------------@@ Standard data for elements.94+157.3088*T*LN(T). bcc ENTER-SYMBO FUNCTION GLABCC 298.390071*T-34.882+181. 4000 N @@ Cr.25865E-07*T**3.6902E+01.001295165*T**2.492988*T-39..15 -8856.9547989E-05*T**3-36581228*T**(-1).0*T*LN(T)-2. 1193 Y -136609.88526E+32*T**(-9).1996E+01 2.403+120. double hcp ENTER-SYMBO FUNCTION GHSERLA 298. 6000 N @@------------------------------------------------------------------@@ Solid metals.3088*T*LN(T).15 -3952. Povoden-Karadeniz 2008 @@ GO G ENTER-ELEMENT LA CR VA @@ELEMENT NAME REF.056395E-06*T**3+21167204*T**(-1).3891E+02 5. 4000 N @@ La.0500E+03 0 S0 0.91+1123. AMEND-ELEMENT CR BCC_A2 5.1659411*T*LN(T)-. AMEND-ELEMENT VA VACUUM 0 H0 6. fcc ENTER-SYMBO FUNCTION GLAFCC 298. 1134 Y -16377.34*T*LN(T)-.7919*T*LN(T)-0.387295093*T**2 +4. 550 Y -3381. 800 Y +321682.440708*T*LN(T)-0.08252*T+513.673-3565.908*t*LN(T)+0. 2000 Y -15608.47721E-06*T**3+139250*T**(-1).15 -7968.48*T-26. STATE ATOMIC MASS AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1.053968535*T**2 -4.988+174.Appendix Appendix La-Cr databasea) @@ Database La-Cr.413074*T*LN(T)+0.8932E-07*T**3-399448*T**(-1)..161+88. bcc ENTER-SYMBO FUNCTION GHSERCR 298. 2180 Y -34869.344+344.
386+178.0037094435*T**2 -2.015+146.984+335.61216717E-06*T**3+154422.338363*T-111.85*T**(-1).042032405*T**2 -3. 600 Y +426628.011938995*T**2 +1.30043383E-07*T**3-34158815*T**(-1). 3200 Y +497751.207991*T-19.3088*T*LN(T).71447833E-07*T**3+102710.976+955.928-44.15*T**(-1).0188*T*LN(T)+0.004045175*T**2 -5.588679E-07*T**3+10285.001513089*T**2 -4.33826017E-06*T**3-312130.020171603*T**2 +2. 10000 N @@ Cr gas.7919*T*LN(T)-0.878375*T-139.0037862445*T**2 -2. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.82257667E-08*T**3+5.69883E-07*T**3-1738066.54399*T-34. 800 Y +613345.004961847*T**2 -1.747-246.00406*T*LN(T)+0. 1400 Y +642608.28626*T+17.232-104.Appendix -6109.653+18. 2000 Y -12599.15 +390765. 1300 Y +404460. 1134 Y -124598.47721E-06*T**3+139250*T**(-1)+2.905-85.908*T*LN(T)+. 2180 Y -16459. from SGTE ENTER-SYMBO FUNCTION F7491T 298.843-369. from SGTE ENTER-SYMBOL FUNCTION F7763T 298.15 +5332.878761*T-21.005444405*T**2 +4. 1100 Y +393886.3088*T*LN(T).5192158*T-21.016725*T-42.418475E+08*T**(-1).02767321*T**2 170 .0441+773.346741*T*LN(T)+0.56798*T*LN(T)+.7643*T*LN(T)-.791973*T*LN(T)-0.066199E-06*T**3+20994153*T**(-1).37615E-21*T**7.36083*T*LN(T)+7.83676*T*LN(T)-0.085237*T+2.93775E-06*T**3-133541*T**(-1).616317*T-50*T*LN(T).70261E-07*T**3+2891891*T**(-1).955-30.2*T**(-1).06299*T*LN(T)-0. 6000 N @@ Cr2 gas.797+89.004+171. 8200 Y -92343. 6000 N @@-----------------------------------------------------------@@ Gas functions @@ La gas.17+114. from SGTE @@ La(g) ENTER-SYMBO FUNCTION F12026T 298.403+41.96003*T*LN(T)+.018431*T-34.15 +15483. 4000 N @@ ---------------------------------------------------------------------@@ Liquid metal functions.006002155*T**2 +1. 1134 Y -3942.253215E-04*T**2 -1.23648333E-07*T**3-722515*T**(-1).331-31.1074654*T-19.007085085*T**2 -4.00189435*T**2 -1.64743*T*LN(T)-.3347881*T-22. 4000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.1*T**(-1).15 +422273.0188191*T*LN(T)-0.15 +598511.059775*T-26.4786162*T-13.25865E-07*T**3.5*T**(-1).23012*T-11.5353212*T-40.
.0428*T*LN(T)+3...7145*T*LN(T)+.028597625*T**2 -4..CR:VA.CR:VA.. ENTER-PAR G(GAS.CR:VA.15 60713-5.188555*T-52.5.LA:VA....15 +GLAFCC.1) 298. 5800 Y -484185.. 3900 Y +347492.CR..CR:VA.0) 298. ENTER-PAR G(LIQ. set-interactive a) databases scripts can be used in Thermocalc with the extension . dhcp ENTER-PHASE LADHCP.LA.0) 298. @@ La..0) 298.. @@ Interaction parameters from binaries ENTER-PAR L(LIQ....0) 298.008.15 64573-23*t.15 +GLALIQ.15 +F12026T+RTLNP..0) 298......0) 298. VA.15 +GCR_L. ENTER-PAR G(LAFCC. N. 2300 Y +553119.0) 298.0) 298...15 +F7491T+RTLNP. 6000 N @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Metals @@ La.. ENTER-PAR G(GAS.137623*T-105.LA:VA.15 +GLABCC.15 -0.9699545E-04*T**2 +1.. @@ ----------------------------------------------------------------@@ Alloys @@ BCC_A2 ALLOY ENTER-PHASE BCC. ENTER-PAR G(GAS..4843765E+08*T**(-1)..0) 298.CR2..895+159....25559*T-334....Appendix +1.. AMEND-PHASE-DESC BCC MAGN -1 0. ideal extension from lower-order systems ENTER-PHASE LIQ.4 ENTER-PAR TC(BCC..LA.15 +GHSERCR.0) 298... ENTER-PAR G(BCC..LA. @@-----------------------------------------------------------@@ Gas ENTER-PHASE GAS G 1 LA CR CR2.004229401*T**2 +1.... ENTER-PAR G(LIQ...15 +GHSERLA..605906E-06*T**3-5831655*T**(-1). 2 1 1 LA CR... @@ ------------------------------------------------------------------------@@ Liquid. 2 1 0.34+623....5939925E-07*T**3+14793625*T**(-1).LA.LA:VA. @@ GO PAR SET-OUT-LEVEL..15 -311. VA...97520167E-07*T**3+7.49*t..0) 298. ENTER-PAR G(LADHCP.51783483E-07*T**3+1....0) 298. AMEND-PHASE LIQ COMP 2.. ENTER-PAR G(BCC.055+2598. ENTER-PAR L(LIQ.07969*T*LN(T)-. VA.CR:VA..15 +F7763T+RTLNP...CR:VA..0) 298. 2 1 3 LA CR..15 83500...... ENTER-PAR L(BCC.. VA.CR:VA... 2 1 1 LA.tcm 171 ...135805E+08*T**(-1).5 LA .. fcc ENTER-PHASE LAFCC.LA:VA. ENTER-PAR BMAGN(BCC.
3891E+02 6. first version: Feb2006 by Povoden. AMEND-ELEMENT CR BCC_A2 5.7620E+01 6..4938E+01 4.65340E+02.0500E+03 2. @@ @@ -------------------------------------------------------------------@@ Species @@ -------------------------------------------------------------------ENTER-SPECIES LA+2 LA/+2 ENTER-SPECIES LA+3 LA/+3 ENTER-SPECIES SR+2 SR/+2 ENTER-SPECIES MN+2 MN/+2 ENTER-SPECIES MN+3 MN/+3 ENTER-SPECIES MN+4 MN/+4 ENTER-SPECIES O2 O2 ENTER-SPECIES O3 O3 ENTER-SPECIES O-2 O/-2 ENTER-SPECIES SRO SRO ENTER-SPECIES SRO2 SRO2 ENTER-SPECIES CR+2 CR/+2 ENTER-SPECIES CR+3 CR/+3 ENTER-SPECIES CR+4 CR/+4 ENTER-SPECIES CR+6 CR/+6 ENTER-SPECIES CR1O1 CR1O1 ENTER-SPECIES CR1O2 CR1O2 ENTER-SPECIES CR1O3 CR1O3 172 . Solubility of Cr in SrMnO3 not known @@ --> Subsystem Sr-Mn-Cr-O is a purely ideal extention @@ @@ no oxygen solubility in La-oxide description (taken from Zinkevich et @@ al.1008E+01 0 0.35429E+01.6902E+01. STATE ATOMIC MASS H0 S0 AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1. AMEND-ELEMENT SR SR_FCC_A1 8.Appendix La-Sr-Mn-Cr-O-(H) oxide database @@ LA-SR-Mn-CR-O-(H) oxide.9960E+03 3.. as only few phase @@ diagram data exist! @@ -------------------------------------------------------------------GO G ENTER-ELEMENT LA SR MN CR O VA H @@ELEMENT NAME REF. AMEND-ELEMENT VA VACUUM 0 0 0..1996E+01 4.. @@ Actual version: Dec2008 by Povoden-Karadeniz @@ @@ COMMENTS @@ @@ Sr-Cr-O liquid: simple description..5680E+03 5.0252E+02.) considered @@ @@ Quinary Ruddlesden popper phase is very tentative.. AMEND-ELEMENT H 1/2_MOLE_H2(G) 0.2008E+01.5999E+01 4.5694E+01..6651E+03 5. Povoden-Karadeniz @@ @@ Database La-Sr-Mn-Cr-O-(H). AMEND-ELEMENT O 1/2_MOLE_O2(G) 1. associate at composition SrCrO4 can @@ help for better fit to experiments – future work @@ @@ No data exist for Sr-Mn-Cr-O. AMEND-ELEMENT MN CBCC_A12 5.3410E+03 1.
48*T-26.1659411*T*LN(T)-.94+157.284604*T-26.27966+130.196104*T-30.367+107. 4000 N @@ Sr.001295165*T**2.059572*T-23.06113*T-17. 1519 Y -28733.8742*T**(-1).656847E30*T**(-9).8932E-07*T**3-399448*T**(-1).908*t*LN(T)+0.34*T*LN(T)-.88526E+32*T**(-9).47721E-06*T**3+139250*T**(-1).390071*T-34. 6000 N @@ O1.4582*T*LN(T)-0.005098873*T**2 +6. fcc ENTER-SYMBO FUNCTION GHSERSR 298.15 -3480.403+120. bcc ENTER-SYMBO FUNCTION GHSERCR 298.67477E-07*T**3-2055*T**(-1).84189E-07*T**3+850134*T**(-1).2648*T-48*T*LN(T)+1. 2000 N @@ Cr.61225E-3*T**2 -1. 1000 Y 173 . 2000 Y -15608.344+344.882+181.183879*T-23.15 -8115.872255-25.251266E-3*T**2 +1. 550 Y -3381.1355068*T*LN(T)-0.00734768*T**2 +69827.00189435*T**2 -1.18*T-50.Appendix ENTER-SPECIES CR2O3 CR2O3 ENTER-SPECIES CR3O4 CR3O4 ENTER-SPECIES CRH1 CRH1 ENTER-SPECIES CRH1O1 CRH1O1 ENTER-SPECIES CRH1O2 CRH1O2 ENTER-SPECIES CRH1O3 CRH1O3 ENTER-SPECIES CRH2O2 CRH2O2 ENTER-SPECIES CRH2O3 CRH2O3 ENTER-SPECIES CRH2O4 CRH2O4 ENTER-SPECIES CRH3O3 CRH3O3 ENTER-SPECIES CRH3O4 CRH3O4 ENTER-SPECIES CRH4O4 CRH4O4 ENTER-SPECIES CRH4O5 CRH4O5 ENTER-SPECIES CRH5O5 CRH5O5 ENTER-SPECIES CRH6O6 CRH6O6 ENTER-SPECIES H2 H2 ENTER-SPECIES H2O1 H2O1 ENTER-SPECIES H1O1 H1O1 ENTER-SPECIES H1O2 H1O2 ENTER-SPECIES H2O2 H2O2 @@ @@ ---------------------------------------------------------@@ Functions @@ ---------------------------------------------------------@@ SER Lattice stabilities.0*T*LN(T)-2.5028601*T-11. 820 Y -13380.413+59. double hcp ENTER-SYMBO FUNCTION GHSERLA 298.15 -7968.102+153. 2180 Y -34869.1*T**(-1).41+312.3088*T*LN(T). 3000 N @@ Mn.0905432*T*LN(T)-3.15 -7532. cbcca12 ENTER-SYMBO FUNCTION GHSERMN 298. Dinsdale 1991 @@ La.6184604E-07*T**3-38364. (1/2 O2) ENTER-SYMBO FUNCTION GHSEROO 298.15 -8856.008371705*T**2 +6.905*T*LN(T)-4.
76*T. @@ CR-SPINEL CR3O4 ENTER-SYMBO FUNCTION GCR3O4 298. MNO ENTER-SYMBO FUNCTION GMN1O1 298.006854*T**2 +808000*T**(-1)-1E7*T**(-2).6846E+02*T-9. ENTER-SYMBO FUNCTION GLA2O3H 298.45091278E+05+3.15 +1..85001409E-03*T**2+2..986*T+GLA2O3D.74079033E-02*T**2+9.5*GHSEROO+255269-53. Grundy 2003 @@ MANGANOSITE.. Grundy 2006 ENTER-SYMBO FUNCTION GMN2O3 298.15 43192-18..15 +GSROSOL+GHSEROO-43740+70*T...056E-02*T**2 +6.89567858E+02*T-1.43703676E+06+8.56*T*LN(T)-0..164542E+06+7.15 +108305+GCR2O3+0.555*T+GLA2O3D.....15 -4..05E+06*T**(-1). ENTER-SYMBO FUNCTION GLA2O3X 298.86138663E+05*T**(-1). @@ BETA-HAUSMANNITE. @@ ESKOLAITE. Risold 1996 @@ SrO ENTER-SYMBO FUNCTION GSROSOL 298.54747566E+02*T*LN(T) -1.95379396E+02*T-6. Povoden 2005 @@ METASTABLE CRO ENTER-SYMBO FUNCTION GCR1O1 298..15 -607870+268. @@ -------------------------------------------------------------- 174 . @@ PYROLYSITE..728+31.82*T.59355626E+02*T-4.15 -1.0822E+05*T**(-1)..5*GCR2O3-0..629*T*LN(T)-0. @@ Mn-oxides..25243E-04*T**2 +1.52766201E+01*T*LN(T) -7. @@ Cr-O oxides..64955386E+05*T**(-1).80284521E-03*T**2+6.12922234E+05*T**(-1). @@ ALPHA-HAUSMANNITE. 3300 Y -13986...9579637E-04*T**2 +6..9664*T-120..74079033E-02*T**2+9..68352649E+01*T*LN(T) -3...15 -1.8138015*T*LN(T)-5. Cr2O3 ENTER-SYMBO FUNCTION GCR2O3 298.. 6000 N @@-----------------------------------------------------------@@ Binary oxides.66666666667*GHSERCR.9*T-47.15 -1..0721E-08*T**3+4383200*T**(-1)..96393E+05+5.15 -5.5*GHSEROO+280045-93.97E-03*T**2 +1..15 +0. @@ reduced neutral endmember of CR2O3 ENTER-SYMBO FUNCTION GCRO0 298. MN1O2 ENTER-SYMBO FUNCTION GMN1O2 298.911E+01*T*LN(T)-2..9536*T*LN(T)-4. @@ SrO2 ENTER-SYMBO FUNCTION GSRO2SOL 298..2856E+02*T-119.66000166*T-16... @@ @@ MN2O3-FUNCTION.8*T*LN(T)-4..54747566E+02*T*LN(T) -1. BETA-MN3O4 (CUBIC) ENTER-SYMBO FUNCTION GCMN3O4 298..15 -1833257+692.... Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3D 298.Appendix -6568. ALPHA-MN3O4 (DISTORTED) ENTER-SYMBO FUNCTION GTMN3O4 298..86138663E+05*T**(-1). optimized @@ La-oxides.15 -9.259625*T-18..778*T**(-1). MODIFIED.78055555E-09*T**3+262904.02477557E+05+2..15 32350-13.76015+12. @@ Sr-oxides.5*GCR2O3-0.00307*T**2 +190000*T**(-1)..41618912E+06+8.75120338E+02*T-1.
.5*GHSEROO-154101-2.. @@ SrMn3Oz as SrMnO3_Mn2O3 ENTER-SYMBO FUNCTION GSM4OZ 298.70000000E+01*T. ENTER-SYMBO FUNCTION RE_BETA 298.....15 GLA2O3D+1.5*GCR2O3+9...5*GMN2O3-68300. Povoden 2008 @@ LA2CRO6 ENTER-SYMBO FUNCTION GLA2CRO6 298.. 2005 ENTER-SYMBO FUNCTION GL2MNO4 298.15 +2*GSROSOL+2.15 +GSROSOL+GMN1O2-1. optimized (except perovskite functions) @@ @@ Functions of the La-Sr-O system. ENTER-SYMBO FUNCTION GSM3OZ 298. ENTER-SYMBO FUNCTION GL3O_RP2 298..15 @@ 8*GLA2O3D+3. @@ RP3 ENTER-SYMBO FUNCTION GSM4_RP3 298.71704891E+01*T. ENTER-SYMBO FUNCTION LA_BETA 298.. @@ RP2 ENTER-SYMBO FUNCTION GS4O_RP2 298...19200000E+04......5E+04. ENTER-SYMBO FUNCTION GSM3_HEX 298. @@ Sr7Mn4O1 175 .. @@ @@ Functions of the Sr-Mn-O system.799*T..5E+04.15 +4*GSROSOL+3*GMN1O2-3....15 +GSROSOL+GLA2O3D+GMN2O3-137400.15 0..5*GLA2O3D+0.15 +2*GSROSOL+2..158E+04.32830000E+05.... @@ @@ Functions of the La-Cr-O system.99100000E+04-90*T. Grundy 2004 ENTER-SYMBO FUNCTION SR_ALPHA 298..14*T.. ENTER-SYMBO FUNCTION SRX_ALPH 298..11300000E+05.15 +2*GSROSOL+2.......5*GHSEROO-540404-9.79100000E+03. ENTER-SYMBO FUNCTION RE_ALPHA 298. @@ RP1 ENTER-SYMBO FUNCTION GS4O_RP1 298.Appendix @@ Ternary oxides. ENTER-SYMBO FUNCTION SRH_ALPH 298..15 +GMN2O3+GSM3_HEX-2.73000000E+03 -1..26029731E+04-3.5E+04. ENTER-SYMBO FUNCTION GL3O_RP1 298.15 0..... @@ intermediate La-chromates @@ LA16 @@ ENTER-SYMBO FUNCTION GLA16 298.15 +GLA2O3D+GMN1O1+6.15 +3*GSROSOL+2*GMN1O2-8.......5*GCR2O3+4..15 GLA2O3D+0.5*GHSEROO-73045-4.5*GCR2O3+1.5*GLA2O3D+GCR2O3+2.5*GHSEROO-371557+205*T..78500000E+05.15 +GSROSOL+0. Grundy 2004 @@ HEX Phase ENTER-SYMBO FUNCTION GSM4_HEX 298.5*GMN2O3-7.15 @@ 3. @@ @@ Functions of the La-Mn-O system.. @@ LA7 @@ ENTER-SYMBO FUNCTION GLA7 298.55*T.15 +GLA2O3D+2.... @@ LA2CR3O12 ENTER-SYMBO FUNCTION GLA2CR3 298.. Grundy et al.15 +GSROSOL+0..15 +2*GSROSOL+GMN1O2-1...15 +GMN2O3+GSM4_HEX-8..
@@ ENTER-SYMBO FUNCTION GL3OR 298..15 +GSROSOL+0. Povoden 2005 @@ CUBIC SPINEL ENTER-SYMBO FUNCTION GSPINEL 298.19*T*LN(T) +232934*T**(-1)-3429+4... ENTER-SYMBO FUNCTION GLCR3O_RP1 298.4*t....19*T*LN(T) +232934*T**(-1).. ENTER-SYMBO FUNCTION GVVV 298.15 +0.Appendix ENTER-SYMBO FUNCTION GS7M4 298...33333333334*GTMN3O4-200942+75..666666667*GCR3O4+..5*GCR2O3+0.5*GHSEROO.72*t..5*GLA2O3D+0.15 +0.5*GMN2O3-63367+51. @@ SRCR2O7 ENTER-SYMBO FUNCTION GSC2O7 298... ENTER-SYMBO FUNCTION GL4O 298..77*T-7. @@ ENTER-SYMBO FUNCTION GL3OL 298...... Povoden 2008 @@ Ruddlesden Popper phase ENTER-SYMBO FUNCTION GREFRP 298.31*T..66666667*GSROSOL+GCR2O3+2..15 0.5*T....666666667*GCR3O4+.69*T. @@ SR2CRO4 ENTER-SYMBO FUNCTION GS2CO4 298.77*T-7..6*T..5*GHSEROO-273771 +131. @@ SR3CR2O8 ENTER-SYMBO FUNCTION GS3C2O8 298.44550000E+04 176 .15 +2.73000000E+03-1.5*GLA2O3D+0.15 +0.. @@ @@ Functions of the Mn-Cr-O system.15 +0..5*GMN2O3-63367+51.5*GCR2O3+1.. ENTER-SYMBO FUNCTION GV4O 298..15 +GSROSOL+0.15 +GLACRO3+GSROSOL+7000-25*t.15 +2*GSROSOL+0..19*T*LN(T) +232934*T**(-1)+400-0.75*GMN1O2-91857+20.15 +GSROSOL+GCR2O3+98000-95.5*GLA2O3D+0. @@ SRCRO4 ENTER-SYMBO FUNCTION GSCO4 298.77*T-7.5*GLA2O3D+0.15 0.15 +0.15 +0. @@ @@ Functions of the La-Sr-Cr-O oxide system.. @@ TETRAGONALLY DISTORTED SPINEL ENTER-SYMBO FUNCTION GTSPINEL 298...5*GHSEROO-145000+50*T..1*T.15 +7*GSROSOL+4*GMN1O2-6.5*GCR2O3+0..15 2*GSROSOL+0.. Povoden 2008 @@ SRCR2O4 ENTER-SYMBO FUNCTION GSC2O4 298.....333333*GLA2O3D+GMN1O2-53760. @@ ---------------------------------------------------------------@@ Perovskite functions @@ Grundy 2005 @@ Charge compensated by Mn+4 (correct) ENTER-SYMBO FUNCTION GL3O 298.333333333333*GHSEROO -508507+219*T..5*GLA2O3D+GMN1O1+27672.3+61. @@ @@ Functions of the Sr-Cr-O system...12450000E+05+50*T.33333333334*GCMN3O4-210795.15 +GSROSOL+GCR2O3+3*GHSEROO-325047+196*T.15 +6*GL2O+4*GL4O+3*GV4O-12*GL3O-254212..5*GMN2O3-7..... ENTER-SYMBO FUNCTION GMS3O 298..5*GMN2O3-63367+51. ENTER-SYMBO FUNCTION GL2O 298.
ENTER-SYMBO FUNCTION ANTI 298.15 0.5*GCR2O3-2.018431*T-34.15 +15483. ENTER-SYMBO FUNCTION GLACR4O 298..68*T* LN(T). ENTER-SYMBO FUNCTION GALACRO3 298.15 +GSROSOL+0.15 GSROSOL+0.11300000E+05+2. @@ Reciprocals: all 0!!!!! @@ @@ Povoden 2008 @@ LaCrO3-PEROVSKITE ENTER-SYMBO FUNCTION GLACRO3 298..69000000E+00*T.15 +GHSERMN+17859.981237E-06*T**3-265559*T**(-1). 6000 N @@ --------------------------------------------------------------------- 177 . 4000 N @@ Sr ENTER-SYMBO FUNCTION GSRLIQ 298.997-10.1840595E-2*T**2 +4.....15 0..38*T-0...118994*T-5.020171603*T**2 +2. 3000 N @@ Mn ENTER-SYMBO FUNCTION GMN_L 298.23012*T-11... ENTER-SYMBO FUNCTION GMS4O 298.5*GCR2O3-73591+2..15 +GSROSOL+GMN1O2-1.5*GHSEROO+10222-55..0668978*T*LN(T)-3.616317*T-50*T*LN(T)..37615E-21*T**7.91-12...15 +2194.908*T*LN(T)+.42*t..93775E-06*T**3-133541*T**(-1).5*GCR2O3+0. 1519 Y +GHSERMN+18739.15 +GLACRO3-340+0.29+213.5*GHSEROO-200000. @@ Functions for defect chemistry ENTER-SYMBO FUNCTION GVCR4O 298.5*GCR2O3+0..41929E-21*T**7.656847E30*T**(-9). 1134 Y -3942.463*T*LN(T). 2180 Y -16459.Appendix -1.004+171.406219*T-39.5*GHSEROO-291802-250*t.015+146.2386*T+135166-88. @@ Function for neutral endmember SR(CR+3.5*GCR2O3+11.70000000E+01*T. 3000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298....26500000E+04 -7.. @@ Function for neutral endmember SrCrO3 ENTER-SYMBO FUNCTION GS4O 298.15 0. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298....5*GCR2O3+0. 1050 Y -10855.5*GLA2O3D+0.51-13..33333*GLA2O3D+.2288*T-1.059775*T-26..5*GHSEROO..47721E-06*T**3+139250*T**(-1)+2.3088*T*LN(T).VA)O3 ENTER-SYMBO FUNCTION GN 298.63*t.52*t.00189435*T**2 -1.6208*T-4.15 +5332.984+335.15 GSROSOL+0... @@ (LaSr)CrO3+/-delta-Perovskite @@ Reference SrCrVa3 ENTER-SYMBO FUNCTION GS4V 298. @@ ---------------------------------------------------------------------@@ LIQUID FUNCTIONS @@ ---------------------------------------------------------------------@@ Liquid metal functions.15 +547422.0188191*T*LN(T)-0.653+18.
331-31.48744*T*LN(T)-.178604*T-117. 500 Y -62418.9513659*T-30. Risold ENTER-SYMBO FUNCTION GSROLIQ 298.629*T*LN(T)-0. ENTER-SYMBO FUNCTION GMN2O3_L 298.35563E+08*T**(-1).224944*T-121.006854*T**2 +808000*T**(-1)-1E7*T**(-2)+141329-56.008463125*T**2 +1.36083*T* LN(T) +7.3+37..15 +173449.06284295E+01*T.C. optimized @@ liquid La2O3.15 GMN1O1+4.708+805.R. 4000 Y +307209.5*GCR2O3-0.62+32.869-31.928-44.15 -332319.00607059*T**2 +9..237405*T+14.0063*T**2 +31300*T**(-1)+9.671+1078.36845867E-08*T**3+6.003139382*T**2 -1. @@ liquid Mn oxides.083*T-30.S). 8400 Y -403765. REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCR1O1_G 298.253215E-04*T**2-1.S.097*T*LN(T)-0. source: Thermocenter of russian academy @@ of science (T..722975E-07*T**3-64209900*T**(-1). 601 N @@ -----------------------------------------------------------------------@@ GAS FUNCTIONS @@ --------------------CHROMIUM GAS---------------------------------------@@ CR Gas: SGTE v 3.135*T**(-1).2320948*T**2-9. Class: 4 ENTER-SYMBO FUNCTION GH2O_L 298.. Class: 4 @@ SGTE=scientific group thermodata Europe @@ ENTER-SYMBO FUNCTION F7491T 298.49525609E+04+4.15 GCR2O3+439078-169*T.14296167E-05*T**3+978019*T**(-1). 1100 Y +393886..588679E-07*T**3+10285.5192158*T-21.15 +176483..555*T*LN(T)+0.1304*T*LN(T) -..00631160667*T**3+5.5329*T*LN(T)+.0 (1998).A.282+741.8669*T*LN(T) +.1*T*LN(T).31437957E+01*T.45*T-22596.4*T.15*T**(-1).00119977*T**2 -1. 6000 N @@ CR1O1 Gas (SGTE 1998. 1000 Y +167489....19*T*LN(T) +27.A. ENTER-SYMBO FUNCTION GCR2O3_L 298.. @@ liquid SrO.18729*T+495..15 -1833257+692.1684007*T-39.15 +2*GMN1O1+GHSEROO-6.C. 900 Y +170853.23648333E-07*T**3-722515*T**(-1).39465890E+04-2. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3LIQ 298.41*T*LN(T).Appendix @@ Liquid oxide functions.74749*T*LN(T)+.9664*T-120.S Class: 5) ENTER-SYMBO FUNCTION F7705T 298.8788-3288..15 0.15 -566346+449*T-73.C. 600 Y -331037. @@------------------------------------------------------------------@@ LIQUID WATER.2897*T*LN(T)-.69E-7*T**3.5567E-7*T**3. 178 .229905E-07*T**3+35263..917665E-05*T**3-18523425*T**(-1).1074654*T-19. 540 Y -8528143.59563*T-186.001513089*T**2 -4.5*GHSEROO+339673-121. @@ liquid Cr oxides.15 +390765.. Grundy ENTER-SYMBO FUNCTION GMN1O1_L 298.R.4-33.R....31*T-40.502-414. Povoden ENTER-SYMBO FUNCTION GCR1O1_L 298. from T.A. 10000 N @@ CR1O1 Gas. from T.6220*T.00148*T**2 +873600*T**(-1)+1.52515733E-07*T**3+682877*T**(-1).9+142414.48508*T**2-.504926*T**2+4.63356E+08*T**(-1).96003*T*LN(T)+.
45470312*T-28.696*T*LN(T)-0.78611*T*LN(T).039707355*T**2 -4. 1300 Y +49468.494-20.S Class: 4) ENTER-SYMBO FUNCTION F10963T 298.4437*T*LN(T)-.A.00206456*T**2 -5.09+299.89*T-82.10457667E-06*T**3+12362250*T**(-1).09482*T-134. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION F13349T 298.00012*T**2 +932050*T**(-1)-8. 2800 Y 179 .59*T-39.15 -109942. 6000 N @@ O3 Gas (SGTE 1998.33E-9*T**3.108664-15.05082*T*LN(T)-0.00623741*T**2-6.0155*T**2 +245800*T**(-1)+2.1284109*T**2 +5.01283575*T**2 -3.15 +243206.6+6101.35707*T*LN(T)+0.10286*T*LN(T)+.Appendix 3000 N @@ CR1O2 Gas.02763076*T**2 +4.383-1950. 6000 N @@ H Gas (JANAF 1982.45*T**(-1).3956+710.423-52.23131283E-08*T**3-42897.569*T*LN(T)-0. reassessment Chen 2006.4989821*T-20.01667E-8*T**3.60539333E-06*T**3+99530. 2950 Y +252301.075-3566.84857*T*LN(T)-0. 1000 Y -118120+123.58118*T*LN(T)-.44768833E-06*T**3-2. 2800 Y +409416.80563*T+421.09852775*T**2 -2.5*T**(-1).9096643*T-27.2001*T*LN(T)-.81*T-56.621+24.043+890.306855E-06*T**3-21589870*T**(-1).6128262*T-17. 1000 Y +180.413565E-04*T**2 +7.5273873*T-31. 2100 Y -18840. 4900 Y +97590.0922361*T**2 +4.40916*T*LN(T) -.623+176. 2100 Y +866367. 3000 N @@ CR1O3 Gas.43044*T*LN(T) -.3696*T*LN(T)+.00016*T**2 +1814700*T**(-1)+7.97393+78.01555*T*LN(T)+1.1304835E+08*T**(-1).798361*T-149.0027589925*T**2 -7.610855E+08*T**(-1).2*T*LN(T)-.0847281*T-17.9608*T*LN(T)+.64520667E-09*T**3-3973170.1663+92.3*T**(-1).78+10. from T.S Class: 4) ENTER-SYMBO FUNCTION F14021T 298.13383*T-764.00584168*T**2 +3. 3000 N @@-------------------OXYGEN GAS------------------------------------@@ O Gas (JANAF 1982.5*T**(-1).401E-6*T**3.15 +211801.0010728235*T**2 +1.3120249*T-32.15 +130696.526*T*LN(T)-0.14281783E-08*T**3+3561002.8612582*T-21.1699975E+08*T**(-1).007055445*T**2+3.879+30.1894682*T-31. 700 Y +114760. 3500 Y -1866338.555105E-07*T**3-2. reassessed by Ming Chen 2006.C.15 -341231. 1100 Y -256145.626737*T-60. 6000 N @@ H2O1 Gas (SGTE 1998.43E-6*T**3.70834*T+223.99+130.46390667E-07*T**3+56582.09*T**(-1). 1000 Y -354716.R.17486667E-07*T**3+1572175*T**(-1). from T.01526167E-08*T**3-64163. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O3_G 298.45*T**(-1).R.15 -250423.59784667E-06*T**3+9.21188*T*LN(T)-5.05535833E-07*T**3+1246309.5*T**(-1).434+4.15 -9522.C. 6000 N @@ -------------O-H GAS----------------------------------@@ H2 Gas (JANAF THERMOCHEMICAL TABLES SGTE) ENTER-SYMBO FUNCTION H2GAS 298.944-37. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION HGAS 298.A.61*T-57.0216*T**2 +428900*T**(-1)+3. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O2_G 298.2687055E-04*T**2 -1.8435*T*LN(T)+.14618667E-07*T**3-1280036*T**(-1).
3000 N @@ CR(OH)2 Gas.326117*T-69.053*T*LN(T) -0.259882*T-92.S Class: 1) ENTER-SYMBO FUNCTION F10666T 298.277-65.0016703495*T**2-1.0018*T**2+2218000*T**(-1)-2.75E-7*T**3. assessment Chen 2006.2016233*T-40. 20000 N @@ H1O1 Gas (SGTE 1998.34404917E-07*T**3+116618. 20000 N @@ H1O2 Gas (SGTE 1998.91863E-08*T**3-6415210*T**(-1).94271*T*LN(T) -.0019361405*T**2-1. 800 Y -7932.77*T-83. 1000 Y 56684+136.42189E-05*T**2-1.724*T*LN(T) -0.971-37.4391015E+08*T**(-1).99164+54.24542*T*LN(T) +.2E-7*T**3.002*T**2+185600*T**(-1)-1. from T.001713168*T**2-6.Appendix -268423.39E-6*T**3.175*T*LN(T) +0.94216*T*LN(T) -.9096451*T-29.A.927*T*LN(T) -0. 3000 Y +31735.771+239.775*T*LN(T) -.953+370.0023107985*T**2+5.573855E-09*T**3+26048030*T**(-1).257*T*LN(T) -0.0031*T**2+266750*T**(-1)-9.1173*T*LN(T) +6.51E-7*T**3. 3600 Y -67875.15 -351288.007931945*T**2+4.45435*T*LN(T) -.1497212*T-26.65*T**(-1).82*T**(-1). 6000 N @@ H2O2 Gas (JANAF SECOND EDIT SGTE) ENTER-SYMBO FUNCTION F10983T 298.86*T-75.418+116.30298483E-10*T**3-8.05*T**(-1).15E-8*T**3.5127-12. 700 Y -156470.7*T-72.406716*T-68.018507875*T**2+2. 1500 N @@-------------------CR-O-H GAS---------------------------------------@@ CR(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O1_G 298.S Class: 4) ENTER-SYMBO FUNCTION F10729T 298.122915E-07*T**3+925845*T**(-1).2921095E-09*T**3-4.4+195. 8600 Y +41016.A.10636*T*LN(T) -.659505E-06*T**3+65357.C.2768*T*LN(T) +6.213599E-04*T**2-1. from T.6898+15.97699*T*LN(T) +.52*T-74. 8400 Y -489068.29733833E-07*T**3+684985.8961+275.292415E+08*T**(-1).4077*T*LN(T) +.0783-20. combined assessment Chen 2006 @@ based on Ebbinghaus 1995 @@ and from Povoden based on Kim and Belton 1974 @@ (data suggested by Opila 2007) ENTER-SYMBO FUNCTION GCRH1O3_G 298.882+553.15 -497678+273. 18000 Y -165728.7343256*T-24.52+180.551*T*LN(T) +0.32333233E-08*T**3+1.0146*T**2+715900*T**(-1)+2.12331E-04*T**2-6.135E-7*T**3.C.0018*T**2+1338300*T**(-1)+9.9*T*LN(T) -.645643*T-59. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O2_G 298. +326722. 1000 Y -492562+351.36297E-06*T**3-29469. 18000 Y -154907.15 +68260+52.15 -147258.15 +30698.242048*T-24.003149545*T**2+1.47539017E-08*T**3+1.0792741*T-24.5*T**(-1).1931655E+08*T**(-1).R.77872*T*LN(T) +2.96842*T*LN(T) -.15 -274384.47*T-96. 3000 N @@ CRO2(OH) Gas. 1000 Y -276268.686636*T-25.5*T**(-1).R. 3000 N @@ CRO(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O2_G 298.799205E-07*T**3-25503.42186*T*LN(T) -.65*T**(-1).505+120.53*T-57.690197*T-42.0007*T**2+243850*T**(-1)-9. 1000 Y 180 .765625E+08*T**(-1).334E-8*T**3.003069987*T**2+6.32+190.87*T-46.00501027*T**2+2.97594167E-08*T**3+2458230.191295*T-50.15 +1075.64106-55.0015*T**2+938850*T**(-1)+5.036948065*T**2+6.
3000 N @@ CRO(OH)3 Gas. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O4_G 298.74*T-146.026-56.8967E-07*T**3+1688150*T**(-1). assessment Chen 2006.349852E-04*T**2-1.76+600.86+694.13133917E-07*T**3+1368173*T**(-1).15 +432449. assessment Chen 2006 based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O3_G 298.6*T-109.01*T**2+4151100*T**(-1)+5.0054*T**2+1023500*T**(-1)-1.89*T-216. 1000 Y -991549. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O3_G 298.2*T-109. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH5O5_G 298.0099*T**2+770750*T**(-1)+5. combined assessment Chen 2006 @@ based on Ebbinghaus 1995 @@ and from Povoden-Karadeniz based on Opila 2007 ENTER-SYMBO FUNCTION GCRH2O4_G 298.15 -578683+391.18913267E-06*T**3-77266.15 -1029121.Appendix -359644+228.77E-6*T**3.15 -978211.004*T**2+1.524*T*LN(T) -0.35E-07*T**3+665100*T**(-1).8867E-7*T**3.97*T-180.C.35E-7*T**3.0065*T**2+2669300*T**(-1)+3.0086*T**2+3058600*T**(-1)+4.355E-6*T**3.1+867.41*T*LN(T) -0.9865812*T-37.46-2142.99681*T*LN(T) +3.5*T-163*T*LN(T) +0.7+464. 1000 Y -861477.05+820.45*T-229.945E-07*T**3+4671850*T**(-1).019*T**2+513600*T**(-1)+1. assessment Chen 2006.15 -902751.3*T-121.0096*T**2+4.874*T*LN(T) -0.A. assessment Chen 2006.15 -851590.014*T**2+1. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH4O4_G 298.25*T*LN(T) -0.004*T**2+2094950*T**(-1)+1.5*T*LN(T) +0.6*T-162. 1000 Y +421602.00056*T**2+663150*T**(-1)-5.15 -976204+672.3*T-137.0049*T**2+3311450*T**(-1)+2.65*T*LN(T) -0.457*T*LN(T) -0. 3000 N @@ CRO(OH)4 Gas.7467E-7*T**3. 5500 Y +1270342. 1000 Y -656538+448.93E-7*T**3.6*T-195.34E-7*T**3.002*T*LN(T) -0.4+51. 3000 N @@ CRO(OH)2 Gas. 3000 N @@ CR(OH)6 Gas. 3000 N @@ CR(OH)5 Gas. 1000 Y -806262+567*T-131.8+813.97*T-79.67833E-07*T**3.00994042*T**2+1. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH6O6_G 298.713-424.11767E-6*T**3.819*T*LN(T) -0.014*T**2+6008850*T**(-1)+7.60191*T+219.008*T**2+840600*T**(-1)-1.12+967. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION G_CRH4O5 298.098*T*LN(T) -0.6+712.545E-7*T**3.91E-7*T**3.006*T**2+498450*T**(-1)-2.973194012145*T-158.2*T*LN(T) -0.16*T*LN(T) -0. 3500 Y +587860.9958E-06*T**3.3E-7*T**3.525*T*LN(T) -0. assessment Chen 2006. 1000 Y -997791.R. 3000 N @@ CR(OH)3 Gas. 1000 Y -909897.37019*T*LN(T) -. assessment Chen 2006.004*T**2+785800*T**(-1)-2.378E-6*T**3.15 -787712+400*T-107.83+534.386334*T-22.455*T*LN(T) -0.S Class: 4) ENTER-SYMBO FUNCTION F7586T 298.006*T**2+2525450*T**(-1)+2.9391*T*LN(T) 181 .9*T-190. 1000 Y -1053466+1080. assessment Chen 2006.86*T*LN(T) -0.15 -650064.007723995*T**2+7. 3000 N @@ CR(OH)4 Gas. 1000 Y -582354+394.049*T*LN(T) -0. 3000 N @@ CRO2(OH)2 Gas.36214*T+18.6022*T*LN(T) -.37*T-125. from T.05*T**(-1). 3000 N @@ CRH1 Gas (SGTE 1998.99444833E-08*T**3-86705500*T**(-1).
ENTER-PAR G(LA2O3SS..SR+2:VA..LA+3:O-2.87691*T.15 +2........Appendix -.. ENTER-PAR L(LA2O3SS.SR+2:O-2....15 -20000.0) 298.0)..... ENTER-PAR G(LA2O3_HEXSS.0).. ENTER-PAR G(BETA...15 +168700-78. 2 2 3 LA+3 SR+2... @@ ---------------------------------------------------------------------@@ Ternary oxides @@ @@ LA-SR-O. 2 2 3 LA+3 SR+2..LA+3:O-2..LA+3:VA. ENTER-PAR G(MN1O2.15 +193600-78...0).149E+05-7. ENTER-PAR G(LA2O3SS.SR+2:O-2..15 +193600-78.20451E+08*T**(-1)..LA+3. ENTER-PAR G(LA2O3SS....0). ENTER-PAR G(LA2O3SS.0). +GLA2O3X....LA+3.. +SRH_ALPH-2*GHSEROO +15.0) 298.33333333*RE_BETA +15.SR+2:VA..15 -20000.1) 298.87691*T.LA+3..SR+2:O-2. O.15 +GMN1O2. ENTER-PAR L(LA2O3_CUBSS. @@ ENTER-PHASE LA2O3_HEXSS.. ENTER-PAR G(LA2O3_HEXSS.LA+2:O-2.15 +GLA2O3D..0) 298.SR+2:O-2...0). +GLA2O3X-3*GHSEROO.SR+2:O-2. ENTER-PAR G(SRO2.SR+2:O-2. O-2 VA......1) 298.SR+2:VA...1*T.LA+3... Chen @@ ENTER-PHASE LA2O3SS..LA+3:VA.87691*T..SR+2:VA....LA+3:VA. 6000 N @@ @@ @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Binary oxides @@ @@ Sr oxides. Risold @@ ENTER-PHASE SRO2..034109635*T**2+7. ENTER-PAR G(LA2O3_HEXSS.SRO2..87691*T...0) 298.0) 298..0).15 +GSRO2SOL......0)... +LA_BETA. ENTER-PAR L(LA2O3_CUBSS.LA+3..SR+2:O-2. @@ ENTER-PHASE LA2O3_CUBSS... ENTER-PAR G(LA2O3_HEXSS.0). Grundy.. +SR_ALPHA+GHSEROO +15.MN:O. ENTER-PAR G(LA2O3_CUBSS. ENTER-PAR L(LA2O3_CUBSS. O-2 VA....277845E-07*T**3-5.1*T. +SRX_ALPH2*GHSEROO+15.1*T. ENTER-PAR L(LA2O3_HEXSS..0). ENTER-PAR L(LA2O3_CUBSS.....81E+01*T.. 182 .SR+2:VA... ENTER-PAR G(LA2O3SS.LA+3:O-2.. MN1O2 ENTER-PHASE MN1O2. @@ La4SrO7 as BETA phase ENTER-PHASE BETA.0). ENTER-PAR G(LA2O3SS.. ENTER-PAR G(BETA..87691*T....0). +SRX_ALPH+GHSEROO+15.SR+2:O-2. 2 1 2 MN. +SR_ALPHA+416100+GHSEROO -0.0) 298.15 +168700-78.. Grundy @@ @@ STOICHIOMETRIC PYROLYSITE. 1 SRO2.. +GLA2O3D-3*GHSEROO. @@ @@ Mn oxides..LA+3:O-2.0).SR+2:VA. O-2 VA. O-2 VA.. +GLA2O3H.1*T...LA+3...0).LA+2:VA.0) 298...15 +2.0) 298... 2 2 3 LA+3 SR+2. 2 2 3 LA+2 LA+3 SR+2.LA+3:VA. +SRH_ALPH+GHSEROO+15..... +GLA2O3H-3*GHSEROO. ENTER-PAR L(LA2O3SS. ENTER-PAR G(BETA....149E+05-7.LA+3. +SR_ALPHA-2*GHSEROO +15.87691*T.0).0) 298.. ENTER-PAR G(LA2O3_CUBSS...87691*T. +LA_BETA-3*GHSEROO....SR+2:VA.. ENTER-PAR L(LA2O3_HEXSS. ENTER-PAR G(LA2O3_CUBSS. ENTER-PAR G(LA2O3_CUBSS.15 +GLAO... +GLAO-GHSEROO.....LA+3.0) 298.81E+01*T.
0)..87691*T. +0.0)..0) 298... Grundy @@ ENTER-PHASE L2MNO4.... +GSM3_HEX-2.. 3 1 1 3 SR+2..0) 298.0). O-2.. @@ ENTER-PHASE SRMNO3_HEX. 3 2 1 4 LA+3. ENTER-PAR G(SRO. 183 . ENTER-PAR G(LA4SR3O9..5*GHSEROO +11.Appendix ENTER-PAR G(BETA. MN+4. +2*GLA2O3D+3*GSROSOL+229800 -136.SR+2:VA....0) 298. O-2 VA.SR+2:MN+3:O-2.0).....15 +GLA7.66666667*RE_BETA+15..8*T. @@ ENTER-PAR G(LA16. MN+4.. MN+3. +GSM4OZ-3*GHSEROO.. ENTER-PAR G(SRMN3O6.. Povoden @@ @@ STOICHIOMETRIC LA2CRO6 ENTER-PHASE LA2CRO6.... 3 4 3 9 LA+3.. +GSM4_RP3. @@ @@ SR-MN-O. ENTER-PAR G(SRMN3O6.0) 298.SR+2:VA.15 -121000-237. @@ STOICHIOMETRIC LA7 @@ ENTER-PHASE LA7.. ENTER-PAR L(BETA. ENTER-PAR G(SRMN3O6.15 +GLA16.0) 298..LA+3:MN+2:O-2.. @@ @@ LA-MN-O.. CR+6....SR+2:MN+3:O-2:MN+4:VA.. 3 4 3 10 SR+2.. 4 1 1 1 5 LA+3.. ENTER-PAR G(LA2CRO6... O-2.. @@ @@ LA-CR-O... 0..... +GSM4OZ....23859*T..VA:O-2...LA:CR:O.23859*T.SR+2:MN+3:O-2:MN+3:VA..5*GHSEROO +11..5*GHSEROO +11.. +GSM3OZ+0..LA+3:SR+2:O-2. O-2. CR. ENTER-PAR L(BETA.15 +GLA2CRO6. @@ ENTER-PHASE SR4MN3O10. 3 2 1 6 LA+3. O-2.15 +GLMN2O5..8*T.0) 298.SR+2:MN+4:O-2........0).SR+2:MN+3:O-2:MN+3:O-2..0) 298. @@ ENTER-PAR G(LA7.0). MN+3 MN+4.. +SR_ALPHA+416100-2*GHSEROO +0...... 3 7 2 16 LA. ENTER-PAR G(L2MNO4. @@ La4Sr3O9... Grundy @@ ENTER-PHASE SR7MN4O15.. 2 1 1 LA+3 SR+2 VA. MN+3 MN+4.... @@ SrO Solid Solution ENTER-PHASE SRO.LA+3...0). MN+2..LA+3:MN+3:MN+4:O-2..LA+3:CR+6:O-2.SR+2:MN+3:VA..5*GHSEROO +11.. 3 16 7 44 LA. ENTER-PAR G(SRO.23859*T..0)..0). ENTER-PAR G(SRMNO3_HEX...0).. O-2.. ENTER-PAR G(SRMNO3_HEX..SR+2:O-2.LA+3:O-2. CR.15 +GL2MNO4. O-2 VA... O.. MN+3.0). 3 7 4 15 SR+2.0) 298..SR+2:O-2...SR+2:MN+3:O-2:MN+4:O-2..... O-2.LA:CR:O.LA+3..0). O-2. MN+4.... +GSM3_HEX+0.23859*T. 3 2 3 12 LA+3. +GSROSOL.SR+2:MN+4:O-2.. CR+6. SR+2.15 -121000-237.5*GLA2O3D+113700.. O-2. Stoichiometric ENTER-PHASE LA4SR3O9. +GS7M4. 5 1 2 3 1 3 SR+2.. +GSM3OZ-2. ENTER-PAR G(LA2CR3.. O-2.... @@ intermediate La-chromates @@ STOICHIOMETRIC LA16 @@ ENTER-PHASE LA16. ENTER-PAR G(SR4MN3O10... ENTER-PAR G(LMN2O5. ENTER-PAR G(SR7MN4O15.. @@ ENTER-PHASE LMN2O5..0).15 +GLA2CR3.... ENTER-PAR G(SRO..... @@ @@ STOICHIOMETRIC LA2CR3O12 ENTER-PHASE LA2CR3. O...LA+3:CR+6:O-2. @@ ENTER-PHASE SRMN3O6. ENTER-PAR G(SRMN3O6.75*T..
15 +4.87691*T. ENTER-PAR G(RP2... Povoden-Karadeniz) ENTER-PHASE MN2O3...CR+3:O-2:VA... ENTER-PAR TC(MN2O3.... doubtful phase @@ ENTER-PHASE SC2O7. O-2 VA. Povoden-Karadeniz 184 .0). ENTER-PAR G(MNO_HALIT... ENTER-PAR G(MN2O3.. @@ @@ SR2. ENTER-PAR G(MNO_HALIT.0) 298.15 +GMN1O1-21883.0) 298..0) 298.1853365*T. ENTER-PAR G(MN2O3..67CR2O8 ENTER-PHASE S3C2N. ENTER-PAR G(S2CO4.15 +GCR2O3+3459....MN+3:O-2:VA.15 +GMN2O3-3*GHSEROO...15 +3.. @@ @@ ESKOLAITE. @@ @@ CR-MN-O.15 +GS3C2O8. ENTER-PAR G(MN2O3..CR+3:O-2:VA... 3 1 2 4 SR+2.0) 298.0) 298..MN+3:O-2:O-2.SR+2:CR+6:O-2.15 +GSC2O4.....CR+3:O-2:O-2.MN+3:O-2:VA...15 +GCR2O3-2*GHSEROO +100000+15..MN+3:O-2. ENTER-PAR L(MNO_HALIT....0) 298.SR+2:SR+2:MN+4:O-2.28 ENTER-PAR TC(MN2O3. O-2.SR+2:CR+3:O-2...15 +GMN1O1..6.15 +GS4O_RP2. 3 2 3 1 MN+3 CR+3.15 +GSC2O7.0) 298..CR+3:VA:VA..... @@ ENTER-PAR G(SC2O7.15 -4.666667 2 8 SR...0) 298..0) 298.. ENTER-PAR G(RP2.15 +GSCO4. @@ @@ Mn2O3 (Compatible with C-Y2O3.87691*T.MN+3:O-2... ENTER-PAR BMAGN(MN2O3.0) 298. CR+4.. 4 1 2 2 7 SR+2.. O-2..MN+2..15 +309..CR+3:VA:O-2.87691*T..0) 298.MN+3:O-2. Povoden-K...0) 298....0).59.0) 298. .. O-2 VA... @@ @@ RP2..0) 298. @@ SRCRO4.15 +GMN2O3.. +GSM4_HEX.MN+3:O-2:VA.0) 298... ENTER-PAR G(MN2O3...SR+2:SR+2:MN+3:O-2. Povoden @@ @@ NONSTOICHIOMETRIC MANGANOSITE (MNO) SOLID SOLUTION. 3 1 1 4 SR+2..MN+2:O-2.21048766E+04. CR+6. Chen... ENTER-PAR G(MN2O3.. ENTER-PAR BMAGN(MN2O3. @@ SR2CRO4 ENTER-PHASE S2CO4. Povoden-Karadeniz ENTER-PHASE SCO4.93845*T +71549... NONSTOICHIOMETRIC CR2O3 SOLID SOLUTION.... AMEND-PHASE MN2O3 MAGN. O. ENTER-PAR G(SCO4. MN+3 MN+4.15 +GCR2O3+GHSEROO +100000+15.5213 -22..0) 298..1) 298..15 +GMN2O3+GHSEROO +100000+15.15 +GS2CO4.. ENTER-PAR G(MNO_HALIT.15 +3*GSROSOL+GMN2O3+GHSEROO. ENTER-PAR G(MN2O3..SR+2:CR+6:O-2. 3 1 2 7 SR+2.VA:O-2.....SR+2:CR+4:O-2....CR+3:O-2:VA..15 0..0) 298.15 +GMN2O3-2*GHSEROO +100000+15.. O-2.MN+2..0) 298.15 +0..MN+3:VA:O-2. ENTER-PAR L(MNO_HALIT.SR+2:MN+4:VA.15 +308.. 2 1 1 MN+2 MN+3 CR+3 VA. Grundy. ENTER-PAR G(SRMNO3_HEX.5*GCR2O3-7. CR+6.0) 298..SR:CR:O. Grundy.65131533E+04... O-2. CR+3.... ENTER-PHASE MNO_HALIT..SR+2:MN+4:O-2.. 3 2 1 4 SR+2. ENTER-PAR G(SC2O4.. ENTER-PAR G(MNO_HALIT.3.. ENTER-PAR G(MN2O3. Povoden @@ @@ SRCR2O4 ENTER-PHASE SC2O4.87691*T..0) 298. @@ @@ SR-CR-O.. ENTER-PAR G(MN2O3. +GSM4_HEX-3*GHSEROO. O-2.. ENTER-PAR G(S3C2N. SR+2.15 +0.0) 298..Appendix ENTER-PAR G(SRMNO3_HEX.. Grundy modified it in LSM modeling ENTER-PHASE RP2. O-2.0) 298.0) 298.....15 +GCR2O3-3*GHSEROO.0) 298. @@ SRCR2O7. 3 2.MN+3:VA:VA... CR.CR+3:O-2.
15 +309.0) 298.MN+2:CR+3:O-2.. ENTER-PAR BMAGN(CR2O3. ENTER-PAR G(TMNCR2O4.6.15 +GCRO0 -0.......33333333334*GHSERCR -5...... ENTER-PAR G(CR2O3. Povoden-Karadeniz ENTER-PHASE TMNCR2O4.MN+2:MN+3:O-2. ENTER-PAR G(LS3MN2O7. ENTER-PAR G(RPEROV.15 +GL3O_RP2+GS4O_RP2 -3*GSROSOL -GMN2O3-GHSEROO-R_RP2.15 +GSPINEL.15 +GCRO0 +. O-2 VA..15 +GMN2O3+GSERCR+39503.0) 298.6...15 +309. MN+3 CR+3.0) 298.. Grundy.... ENTER-PAR G(CR2O3. ENTER-PAR BMAGN(CR2O3..0) 298.. ENTER-PAR G(CR2O3.15 +GCMN3O4.6. .0) 298.SR+2:LA+3:MN+3:O-2.15 +0.. ENTER-PAR G(CMNCR2O4.15 +3.0) 298.. ENTER-PAR G(CMNCR2O4.CR+2:CR+3:O-2.. ENTER-PAR G(CR2O3.28 ENTER-PAR TC(CR2O3. ENTER-PAR G(CR2O3.. ENTER-PAR TC(CR2O3.15 +0...15 +GMN2O3+39503.. O-2... ENTER-PAR G(CR2O3..0) 298.2923*T..CR+2:VA:O-2.15 +3.SR+2:MN+2:VA...SR+2:MN+2:O-2.47717*T.SR+2:LA+3:MN+4:O-2....15 +308..23859*T. Grundy.CR+2:MN+3:O-2.SR+2:MN+3:O-2.0) 298..15 +308.0) 298..15 +GS4O_RP2..47717*T...0) 298..15 +GCR2O3+GHSERCR.. @@ -----------------------------------------------------------------------@@ Quinary phases. ENTER-PAR TC(CR2O3..CR+2:CR+3:O-2.... +GMS4O. @@ @@ CUBIC SPINEL..CR+3:CR+3:O-2.SR+2:SR+2:MN+3:O-2..0). MN+2 MN+3 MN+4 CR+3 CR+4 VA. ENTER-PAR G(CMNCR2O4.0) 298. @@ ENTER-PAR G(RPEROV...15 +GTSPINEL.15 +3.. Grundy @@ ENTER-PHASE LS3MN2O7... ENTER-PAR G(CMNCR2O4.CR+2:CR+3:O-2.15 +GL3O_RP2.CR+2:CR+3:O-2..CR+3:CR+3:O-2. ENTER-PAR G(TMNCR2O4. ENTER-PAR G(RPEROV. +GMS3O+GL2O-GL3OR2*GHSEROO+22...... @@ DISTORTED_SPINEL. O-2.. 3 1 2 4 MN+2.0)....0) 298.0) 298..0) 298.. ENTER-PAR G(LS3MN2O7... Povoden-Karadeniz ENTER-PHASE CMNCR2O4....5*GHSEROO+11. MN+3 MN+4. O-2.15 +3..0) 298.. Povoden-Karadeniz ENTER-PHASE RPEROV.SR+2:SR+2:MN+4:O-2.CR+3:VA:O-2..CR+3:VA:O-2. +GMS3O+0.. LA+3 SR+2.... ENTER-PAR G(RPEROV.MN+3:CR+3:O-2.0) 298. Grundy. ENTER-PAR TC(CR2O3.0) 298....59. @@ -----------------------------------------------------------------------@@ Quaternary oxides @@ @@ La-Sr-Mn-O.2923*T.MN+2:MN+3:O-2..CR+3:VA:O-2...MN+3:VA:O-2.0) 298.0) 298.15 +GCR2O3. ENTER-PAR G(LS3MN2O7.15 +308.CR+3:CR+3:O-2.0) 298..15 +308. ENTER-PAR BMAGN(CR2O3..0) 298... +GMS3O+GL2O-GL3OR+GHSEROO +22. ENTER-PAR BMAGN(CR2O3... ideal extensions from lower-order systems @@ @@ high temperature rhombohedral perovskite.... 3 1 2 4 MN+2 CR+2..0) 298.0) 298.0) 298.. 185 . ENTER-PAR G(LS3MN2O7.. O-2.MN+3:VA:O-2.SR+2:MN+4:O-2.. 3 2 1 3 MN+3 CR+2 CR+3...CR+2:VA:O-2.MN+2:CR+3:O-2.MN+3:VA:O-2.0) 298..15 +GCR3O4+GCMN3O4-GSPINEL.59...... ENTER-PAR TC(CR2O3. 3 1 1 3 LA+3 SR+2 VA..0)... 4 1 2 2 7 SR+2.666666666667*GHSERCR -5.CR+2:VA:O-2.6.0) 298.0) 298..0) 298.15 +3*GSROSOL+GMN2O3 +GHSEROO.MN+3:CR+3:O-2..0).15 +GTMN3O4.... ENTER-PAR BMAGN(CR2O3. MN+3 CR+3..Appendix ENTER-PHASE CR2O3. AMEND-PHASE CR2O3 MAGN..15 +GCR3O4. ENTER-PAR BMAGN(CR2O3. ENTER-PAR TC(CR2O3....MN+3:CR+3:O-2.. CR+3 VA.
0)..76318*T....VA:MN+3:O-2..1666667*GS4O +0.VA:CR+4:O-2..VA:CR+4:VA. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.LA+3:MN+4:VA.0)..35057*T. ENTER-PAR G(RPEROV. ENTER-PAR G(RPEROV. G(RPEROV.0).35056*T. +GS4V.0). G(RPEROV..5*GV4O -1..62121*T..SR+2:VA:VA...5*GV4O +0..5*GHSEROO+11. +GL2O-2.5*GHSEROO+11..35056*T.0).66667*GL4O+0.. +GL3OR+1. +GL3OR+1....0). +2*GV4O+0.41263*T... ENTER-PAR G(RPEROV.62121*T.LA+3:MN+2:O-2.5*GVVV +1. ENTER-PAR G(RPEROV. G(RPEROV..5*GV4O -0.LA+3:MN+4:O-2. +GL2O+1. ENTER-PAR G(RPEROV..5*GV4O+0.33333*GLACR4O +GHSEROO+4.23859*T.. GS4O+GLACRO3-GN-0. +GMS3O-GL3OR+2*GL4O -1.333*GL4O -2*GHSEROO+4.VA:MN+2:VA.. +GN+0....SR+2:VA:O-2..166667*GVVV -3.8333333*GS4V.5*GV4O+0. +GLACRO3+1. +GS4O..0).SR+2:MN+4:VA..2386*T. ENTER-PAR G(RPEROV..0)....5*GHSEROO+11. +2*GL4O-1. +GL3OR.3333*GVVV -1.. ENTER-PAR G(RPEROV...0).5*GHSEROO-1...Appendix ENTER-PAR G(RPEROV.5*GVVV +2*GHSEROO+12.0).33333*GVVV -1. ENTER-PAR G(RPEROV...82596*T.5*GVCR4O+0.5*GVVV -2*GLACR4O-1.SR+2:CR+4:O-2. ENTER-PAR G(RPEROV..33333*GL4O +GHSEROO+4.. +GL3OR-3*GHSEROO.LA+3:VA:O-2...3333*GVVV-1....0).41263*T.5*GHSEROO -1.5*GV4O+0..0). +GLACRO3-3*GHSEROO.VA:MN+4:O-2. ENTER-PAR G(RPEROV.5*GVVV-2*GL4O -GHSEROO+9.. +2*GVCR4O+0.35057*T.5*GHSEROO+1.5*GVVV -2*GLACR4O+1. +GMS4O-3*GHSEROO.LA+3:MN+2:VA..5*GVCR4O+0...5*GV4O+0..333*GLACR4O -2*GHSEROO+4... ENTER-PAR G(RPEROV.1666667*GS4O +0.0).. +0. +2*GL4O+0. ENTER-PAR G(RPEROV..41263*T. ENTER-PAR G(RPEROV.........0).33333*GVVV-1.5*GVVV-2*GL4O +1.VA:VA:VA..8333333*GS4O +0.. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.16666667*GS4V.41263*T.0)..SR+2:CR+3:VA...5*GVVV-2*GL4O -1. ENTER-PAR G(RPEROV.0). G(RPEROV. +0.16666667*GS4V.5*GHSEROO -1. +GMS3O-2... ENTER-PAR G(RPEROV.LA+3:MN+3:VA.166667*GVVV -0.0).. @@ Optimized interactions 186 .0).. +GVVV.. ENTER-PAR G(RPEROV.0).16666667*GS4V+GLACRO3 -3*GHSEROO.0)...... ENTER-PAR G(RPEROV.LA+3:VA:VA.. +GL2O+0.SR+2:CR+3:O-2...5*GVVV-1.5*GHSEROO+5.SR+2:CR+4:VA.VA:MN+3:VA...0).5*GHSEROO +1. +GN-0.VA:VA:O-2. G(RPEROV.LA+3:CR+4:VA.5*GVVV-GL3OR -GHSEROO+12. ENTER-PAR G(RPEROV......1666667*GS4O -0.66667*GL4O+0. GS4O-GN-0..LA+3:CR+3:O-2.SR+2:MN+3:VA...5*GV4O -0..0).5*GHSEROO-1.5*GV4O+0... +2*GV4O+0. +GLACRO3.VA:CR+3:VA... G(RPEROV..41263*T.VA:MN+4:VA.0).LA+3:CR+4:O-2. ENTER-PAR G(RPEROV. +GMS3O+2*GL4O-1... ENTER-PAR G(RPEROV.. +2*GVCR4O+0.LA+3:MN+3:O-2...0)..0).2386*T... +GLACRO3+1.41263*T.76318*T..0). +GVVV+3*GHSEROO...0).0)..VA:CR+3:O-2.0).. G(RPEROV.5*GHSEROO+5.0)........ G(RPEROV..LA+3:CR+3:VA.0)....
ENTER-PAR G(ION.... @@ ENTER-PAR G(RP.. scarce experimental data @@ ENTER-PHASE RP..MN+2:O-2.MN+2:VA..VA:O-2.LA+3....LA+3. 20.Appendix ENTER-PAR L(RPEROV..0) 298...LA+3:MN+4. @@ ENTER-PAR G(RP.15 +GCR_L.. ENTER-PAR L(RPEROV. AMEND-PHASE IONIC_LIQUID COMP 2.MN+2:O-2. ENTER-PAR L(RPEROV.SR+2:MN+4:O-2.MN+2:O-2.MN+3:O-2.1).0) 298..0)..SR+2:VA.1).0) 298..SR+2:CR+4.0) 298.. 9248....29519000E+05..VA.5*t.VA.....SR+2:CR+4.LA+3:O-2..MN+2:O-2.... -117000.LA+3..CR+2:O-2.... ENTER-PAR L(RPEROV.. ENTER-PAR L(ION..VA..0) 298.. @@ ENTER-PAR G(RP.0) 298.... @@ Interaction parameters from binaries ENTER-PAR L(ION.. @@ @@ Ruddlesden-Popper phase... ENTER-PAR L(ION...SR+2:MN+3:O-2..0) 298... ENTER-PAR G(ION. @@ ENTER-PAR G(RP.LA+3.LA+3.VA:O-2....LA+3:CR+3..MN+3:O-2.. ENTER-PAR L(RPEROV.LA+3. @@ ENTER-PAR G(RP. preliminary.0).MN+3:O-2. ENTER-PAR G(ION. -2. @@ ENTER-PAR L(RP..15 GS2CO4+GLCR3O_RP1 @@ -GREFRP.. 5 1 1 1 3 1 SR+2...LA+3:CR+3...LA+3:CR+4. @@ ENTER-PAR G(RP.LA+3:MN+4.LA+3:CR+4:O-2:O-2.1) 298..15 -1.. 250000.. ideal extension from lower-order systems.SR+2:SR+2..15 GREFRP..MN+3:O-2.0) 298..15 +GL3O_RP1+GS4O_RP1 @@ -2*GSROSOL-0. ENTER-PAR L(RPEROV..15 +GLCR3O_RP1.VA:O-2. ENTER-PAR G(ION.0) 298.15 +GSRLIQ.MN+3:O-2.LA+3:VA...15 -119062. ENTER-PAR L(RPEROV..SR+2:LA+3:MN+3:O-2:O-2.CR+3:O-2.CR+2:O-2.. ENTER-PAR G(ION..VA:MN+4:O-2.15 -3..15 +GS4O_RP1.15 -11316..0) 298.0) 298. ENTER-PAR L(RPEROV.0) 298.. O-2 VA.4.SR+2:SR+2. ENTER-PAR L(ION.....6.SR+2:MN+2:VA. ENTER-PAR L(RPEROV.15 2*GCR1O1_L....5*GMN2O3 @@ +0..CR+2:VA. ENTER-PAR L(ION.. @@ ENTER-PAR G(RP.SR+2:SR+2:CR+3:O-2:O-2..15 +11368. @@ Interaction parameters from ternaries ENTER-PAR L(ION... -136600.LA+3.CR+3:VA.. ENTER-PAR L(ION..0) 298. ENTER-PAR L(RPEROV.MN+2:VA...15 0.1) 298.SR+2:LA+3:CR+3:O-2:O-2. ENTER-PAR G(ION..LA+3:CR+3:O-2:O-2....LA+3.MN+4:O-2...0) 298.15 +GL3O_RP1..5*GHSEROO...15 0. ENTER-PAR L(RPEROV.15 -1297. ENTER-PAR G(ION...SR+2:SR+2:CR+4:O-2:O-2..0) 298.15 +121000.15 1....0).....MN+2:VA..15 +2*GSROLIQ.0) 298.15 +GCR2O3_L.1) 298..0) 298..0) 298.1).0) 298...SR+2:O-2.0).. @@ O-2.15 185.0) 298.CR+3:O-2. O-2.SR+2:LA+3:MN+4:O-2:O-2.......0) 298..0) 298.MN+3:VA.0) 298.15 100000.5*GHSEROO..LA+3.15 GS2CO4.15 +GLALIQ.LA+3:CR+3.MN+2.SR+2:MN+4:VA.VA. MN+3 MN+4 CR+3 CR+4. ENTER-PAR G(ION.SR+2:SR+2:MN+3:O-2:O-2.. -117000.15 +2*GCR_L+GCR2O3_L-3*GCR1O1_L.0) 298....15 -4.15 +2*GMN1O1_L.MN+3:O-2..SR+2:SR+2:MN+4:O-2:O-2.0) 298.0) 298.0) 298..5*GMN2O3 @@ -0. ENTER-PAR L(RPEROV.15 +121000. Povoden-Karadeniz ENTER-PHASE IONIC_LIQUID Y LA+3 SR+2 MN+2 MN+3 CR+2 CR+3.15 +GMN2O3_L......... LA+3 SR+2.. @@ -----------------------------------------------------------------------@@ Liquid.0) 298..1) 298. ENTER-PAR G(ION.0) 298...15 +GLA2O3LIQ.0) 298..SR+2:MN+2:O-2.. -136600. ENTER-PAR G(ION.LA+3:CR+3.0) 298....0) 298.54590000E+04...15 +2*GSROSOL+0. @@ ENTER-PAR L(RP..15 +GMN_L.15 +2*GMN_L+GMN2O3_L-3*GMN1O1_L.. 187 .0).15 3766. ENTER-PAR G(ION.. 250000... ENTER-PAR G(ION. @@ ENTER-PAR G(RP. @@ next two interaction parameters can be used to fit @@ Cr4+ amount in perovskite ENTER-PAR L(RPEROV. ENTER-PAR L(RPEROV.15 100000.SR+2:LA+3:CR+4:O-2:O-2..38590000E+04..1).. ENTER-PAR L(ION.MN+3:O-2. ENTER-PAR L(RPEROV...
.CRH4O4...15 +F13349T+RTLNP.0) 298.CR1O1.15 -176300.0) 298. ENTER-PAR L(ION..15 -101850..0) 298..1) 298.15 +GCRH6O6_G+RTLNP. ENTER-PAR G(GAS.....15 +GCRH4O5_G+RTLNP.15 +GCR1O2_G+RTLNP.15 -101850.0) 298.15 200000.1) 298. ENTER-PAR L(IONIC. ENTER-PAR G(GAS..15 +GCR1O3_G+RTLNP. ENTER-PAR L(ION.0) 298.15 -39016...LA+3..CR+2:VA.MN+2:O-2.LA+3.0) 298.0) 298...CR+3:O-2...15 +F10963T+RTLNP.0) 298. ENTER-PAR L(IONIC. ENTER-PAR G(GAS.15 -15009+13.SR+2.CRH2O2..CRH1O3... ENTER-PAR L(IONIC.SR+2.. ENTER-PAR G(GAS..H2O2.15 +GCRH3O3_G+RTLNP..0) 298..MN+3..O2. 20000 N @@ @@ O2 reference gas ENTER-PHASE O2GAS...6587*T.15 +F10963T+RTLNP.1) 298.CRH1.CRH3O3..0) 298.CR+3:O-2.15 +HGAS+RTLNP.0) 298.CR1O2.....15 -179575.. 1500 N ENTER-PAR G(GAS.0) 298.15 +GCRH2O2_G+RTLNP..0) 298..15 +GCRH1O1_G+RTLNP.. @@-----------------------------------------------------------@@ Cr-GAS... ENTER-PAR G(GAS.LA+3..1) 298.CR+2:O-2...CRH5O5. ENTER-PAR L(ION.15 +504+0...H1O1.0) 298.0) 298.0) 298.15 -119062. 6000 N ENTER-PAR G(GAS.SR+2.15 +GCRH3O4_G+RTLNP..0) 298.0) 298..MN+2.0) 298..CRH4O5..15 +60713-5..15 +F13704T+RTLNP.MN+2:VA..Appendix ENTER-PAR L(ION.. ENTER-PAR G(GAS. 6000 N ENTER-PAR G(GAS.CRH1O2..15 +GCRH4O4_G+RTLNP.. ENTER-PAR G(GAS. ENTER-PAR G(STEAM.SR+2..1) 298.15 -188487.CRH3O4.CR+2:O-2... ENTER-PAR G(GAS. ENTER-PAR L(ION.. ENTER-PAR L(ION.0) 298.LA+3..15 -39016.15 -176300.CR+2:VA. 20000 N ENTER-PAR G(GAS.. ENTER-PAR G(GAS.SR+2.. ENTER-PAR L(ION.CRH6O6..15 +GCRH1O3_G+RTLNP.15 +46000.15 +GCRH2O4_G+RTLNP. ENTER-PAR L(IONIC. ENTER-PAR L(ION.. ENTER-PAR G(GAS.SR+2..15 +GCR1O3_G+RTLNP.O. 1 CR1O3. 188 .CRH2O4. @@ @@ H2O reference gas ENTER-PHASE STEAM.MN+2....15 +GCRH5O5_G+RTLNP.CRH2O3.4) 298.15 -619869..1) 298.LA+3..CR+2:VA. ENTER-PAR L(ION.15 +64573-23*T...15 -179575.49*T... ENTER-PAR G(CRGAS..LA+3.15 +F10666T+RTLNP.. ENTER-PAR L(ION.H2...CR+3:O-2...15 +F10983T+RTLNP.0) 298.CRH1O1.0) 298.0) 298.. ENTER-PAR G(GAS.. SGTE and reassessments by Chen. 6000 N ENTER-PAR G(GAS.. ENTER-PAR L(IONIC..CR1O3..CR+2:VA.15 +GCRH2O3_G+RTLNP..CR+2:VA.MN+3:O-2...0) 298.SR+2...CR+3:O-2. ENTER-PAR G(GAS...15 -9111... 20000 N ENTER-PAR G(GAS.0) 298.CR+3:O-2..CR1O3.15 +GCRH1O2_G+RTLNP.CR+2:O-2...0) 298.0) 298..0) 298.9479*T.0) 298. ENTER-PAR G(GAS.H.0) 298...15 -619869.0) 298. ENTER-PAR L(ION.0) 298.H1O2..H2O1..15 +GCR1O1_G+RTLNP. 6000 N ENTER-PAR G(GAS.. ENTER-PAR L(ION.0) 298..MN+2:VA... ENTER-PAR G(GAS.0) 298.0) 298.. 1 H2O1. ENTER-PAR G(GAS..0) 298.15 +F14021T+RTLNP....15 +H2GAS+RTLNP..15 +F10729T+RTLNP.0) 298.15 +F7586T+RTLNP.H2O1.CR+2:O-2.7....0) 298. ENTER-PAR L(IONIC... Povoden-Karadeniz ENTER-PHASE GAS G 1 CR CR1O1 CR1O2 CR1O3 O O2 O3 H2 H H2O1 H1O1 H1O2 H2O2 CRH1 CRH1O1 CRH1O2 CRH1O3 CRH2O2 CRH2O3 CRH2O4 CRH3O3 CRH3O4 CRH4O4 CRH4O5 CRH5O5 CRH6O6.O3. 6000 N ENTER-PAR G(GAS.SR+2.. 20000 N ENTER-PAR G(GAS.LA+3. ENTER-PAR L(ION... 1 O2.MN+3:O-2. 6000 N ENTER-PAR G(GAS.0) 298. @@ @@ CRO3 reference gas ENTER-PHASE CRGAS..LA+3..
O2. N.....0) 298.15 @@ GO PAR @@ SET-OUT-LEVEL...Appendix ENTER-PAR G(O2GAS... set-interactive +2*GHSEROO+RTLNP. 189 .
Graz Publications R. 192-208. Dr. N. Badertscher. M. Erwin Date and place of birth: March 18. ETH Zurich. Burkhard.. D. Pestalozzistrasse 5. Ludwig J. and E. 2002. Contr.Curriculum vitae Curriculum Vitae Personal data Povoden-Karadeniz. Prof. Povoden. carbon and strontium isotope systematics in two profiles across the Glarus thrust: implications for fluid flow. Berliner Ring. Prof. Austria Education 01/2005 – 12/2008 Ph. Dr. 190 . Dr. Department of Materials. 143. Gauckler. Georg Hoinkes and Prof. pp. Miner. 1992-1999 Geoscience Studies. Nonmetallic Inorganic Materials. Oxygen. Switzerland. 1973. Abart. thesis: „ Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells“. Petrol. Karl-Franzens University Graz Master thesis: „Kontaktmetamorphose und Fluid-Gestein-Interaktion in der östlichen Monzoni Kontaktaureole“. Rainer Abart 1983-1991 Realistisches Gymnasium. Graz 1979-1983 Elementary School. Graz.
Ivas. M. Chen. pp. Thermodynamic assessment of the La-Fe-O system. Diff. E. 1. 97. Horacek.N. Grundy. T. M.N. 2006. Gauckler.N. J. to be submitted. Petrol. A. and L. Grundy.J. pp. Povoden. Gauckler. Povoden. Chen. 353-62. A. Gauckler. Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole. to be submitted. M. Miner. T.. Ivas. 2002. E. E.Diff. and L. and L. A.N. and L.J. Presentations Assessment of the Cr-O system in the frame of SOFC research E. Gauckler 191 . Gauckler.N.J. A. E. J. Povoden. 569-78.J.J. to be submitted. Gauckler. pp. M. Diff. Grundy. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. Ivas. 99-120. E. Povoden. Povoden. Phase Equilib. T. Phase Equilib. Mater. Gauckler. Povoden. M. Calphad. Calculation of defect chemistry using the CALPHAD approach. 33-41. Gauckler. 76. Grundy. E.N.J.. J. Phase Equilib. Chen. J. T. A. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 30.J. and R. and L. and L. Grundy. Grundy. A. Chen. Abart. Thermodynamic assessment of the La-Cr-O system. Povoden. pp.Curriculum vitae E. and L. Gauckler. pp. 27. Int. 12-27. 2009. Thermodynamic calculations of impacts of chromium on Sr-doped Lanthanum manganite (LSM) cathodes for solid oxide fuel cells (SOFC). 2006. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. 2006.N. Res. Ivas. (accepted) E. and L. A.J. Povoden-Karadeniz. Grundy. and L... Povoden. E. Povoden.J. Degradation of planar solid oxide fuel cells with (La1-xSrx)1-yMnO3 cathodes and Cr-alloy interconnects.
Switzerland.J. Gauckler Oral Presentation Thermo 2006. and L.N. A. August 4th.J. Grundy. Gauckler Oral Presentation 3rd Fuel Cell Research Symposium. May 6th – 11th. and L.J.N. Povoden.Curriculum vitae Poster Presentation CALPHAD XXXIV. Boulder. 2007 Thermodynamic assessment of the La-Cr-O and LaO3/2-MnOx-CrO3/2 Systems 192 . Switzerland. USA. Gauckler Poster Presentation CALPHAD XXXVI.J. Pennsylvania. Povoden. March 16th. Netherlands. Grundy. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fuel cell (SOFC) materials using the CALPHAD approach E. Austria. A. Colorado. 2005 Thermodynamic assessment of the Cr-Mn-O system for solid oxide fuel cell (SOFC) materials E. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fel cell (SOFC) materials E. and L. Povoden. Z. October 20th. Vienna. Gauckler Oral Presentation HTMC XII. A. September 18th – 22nd. Povoden Oral Presentation 1st EMPA symposium for Ph.D. EMPA Dübendorf. 2005 Thermodynamic Assessment of the Cr-Mn-O System for Solid Oxide Fuel Cell (SOFC) Materials E. Peng. Pennsylvania State University. and L. Grundy.N. students. EMPA Dübendorf. Maastricht. May 06th -11th. 2006 The BiO3/2-SbO3/2-ZnO Phase Diagram at 1115°C in air E. USA. Povoden.
Chen. Pennsylvania State University.The La-Sr-Mn-Cr-O system E.5-SrO-FeO1.J. June 16th – 21st. USA. and L.N. 2007 The thermodynamic LaO1. Povoden.5-CrO1.5-CrO1.5-SrO-MnO1. June 27th. Lehrstuhl für physikalische Chemie. and L. Povoden. Grundy. A. May 6th – 11th.5-SrO-FeO1.5-CrO1. March 28th. ETH Zurich. Gauckler Oral Presentation CALPHAD XXXVI. Saariselkä. 2007 Thermodynamic modeling for solid oxide fuel cell research .N. M. A. Pennsylvania.Curriculum vitae E. Povoden Oral Presentation Guest Talk.5 databases for SOFC applications using the CALPHAD approach E.5-CrO1. Povoden Oral Presentation 2nd MRC Graduate Symposium . Monatnuniversität Leoben. 2008 193 .5 databases for solid oxide fuel cells (SOFC) applications E.5 and LaO1. Finland. Grundy. Gauckler Oral Presentation CALPHAD XXXVII.J.5-SrO-MnO1.5 and LaO1. 2008 Thermodynamic LaO1.
. For these reasons. Povoden-Karadeniz et al. 109. (Me)1(Va.Va)1. p 2837 the correct model is (La. Calphad. A further reason why we use this description is that for SOFC applications we are primarily interested in the oxide portion of the phase diagram and we have found that the endmember Me(O)3 used to describe oxygen solubility in the metallic phase can inadvertently appear in the oxide portion of the phase diagram.5 based on the argument. The following argumentation for modeling of the oxygen solubility in bcc using (physically wrong!) Me(O..Va)1. and in order to keep this assessment compatible with our previous assessments we reassess the oxygen solubility in bcc Fe using the model (Fe)(O. 2007.5: “…in case there is information of the ordering of element X between different vacant positions in bcc described by (Me)1(Va)1(Va)1(Va)1 this is taken into account.O)3 is undoubtedly a reasonable model description for the oxygen solubility in bcc. p.O)1.Va)3 and not (La.Cr)(O. In previous papers the authors have proposed the model Me(Va.” . 112 According to the latest discussion by B.Va)1.3. accepted.X)3 is to be used…” Thus the model was also corrected in the thermodynamic assessment of the La-Fe-O system. J. Phase Equilib.5 was given in a preliminary manuscript of the La-FeO system and is repeated here for the sake of clarification: “…as there are three octahedral interstitial sites per metal atom in the bcc unit cell located on the cube faces and cube edges Me(Va.. lines 7-14 and Table 4. 31(1).5…. that it is energetically very unfavorable to simultaneously occupy both the octahedral interstitial sites on the cube faces and cube edges as these lie very close to each other.Erratum.Cr)(O.3. Hallstedt et al. p. otherwise the disordered model for interstitials in bcc. Diff.
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