Diss. ETH No.

18139

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

Zurich, 2008

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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.

Aristoteles

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Acknowledgements
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

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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 1.6 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 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 1.2 1.3 1.4 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 1.2 1.2 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes New ways – alternative materials 2 3 Aim of study Method 3.2 3.4.3.1 1.1 1.3.1 3.3 Stoichiometric solid oxides Solid solution phases – the Compound Energy Formalism (CEF) Vacancies and the concept of reciprocal reactions 4 .2.3.5 1.2.3.3.1.2.1.3.4.1 3.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.1 Introduction 1.

5 4.1.3 4.1.4.2.3 Experimental Thermodynamic modeling Optimization of parameters Results Discussion 4.1.5 4.6 Experimental data Previous assessments of the Cr-O System Thermodynamic modeling Optimization of parameters Results and discussion Thermodynamic assessments 4.6 Conclusions Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications 4.2 4.2.2.4 Assessment of data from the literature Modeling and optimization Results and discussion 4.4.4.1.5 Conclusions 5 Thermodynamic calculations of impacts of chromium on Sr-doped 5 .5 4.4 Literature review of the La-Cr system Literature review of the La-Cr-O system Thermodynamic modeling and optimization Results and discussion 4.1.2.2.1 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 4.3.2 4.6 4.2.3.4.7 Conclusions 4.4 4.3 4.3.2.4 4.1 Technology 4.1 Introduction 4.1.2 4.Table of Contents 3.1 Introduction 4.7 Applications on SOFC Thermodynamic assessment of the La-Cr-O system 4.4 3.3 4.4.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials 4.3 4 4.2.3.3.2 4.1 Introduction 4.3.3 4.1.4 4.

3.3.2)0.5 Thermodynamic calculations of La0.Table of Contents manganite (LSM) cathodes for SOFC 5.1MnO3-δ contaminated by chromium Thermodynamic calculations of (La0.8Sr0.2 5.4 5.2 5.9MnO3-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 .4 5.3 Introduction Method Results 5.1 5.3 5.3.9Sr0.1 5.3.

how thermodynamic calculations can lead to a better understanding of a system. and some are kinetically controlled. even if the system is in a thermodynamic non-equilibrium state. and previous findings of chromium “poisoning” of SOFC are critically reviewed. some of them probably occurring simultaneously. In chapter 1 the basics of planar SOFC are briefly explained.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. 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. The chromium is known to deteriorate the electrical performance of the cathodes. 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. Some of these processes are governed by thermodynamics. and the modeling approach used in this study is presented. 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. It is shown that chromium “poisoning” of SOFC cathodes is a rather complex process consisting of several steps. This has calamitous consequences for the electrochemical properties of the cathode. In the third chapter the reader learns. 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. Furthermore spinel blocks pores and thus impedes the oxygen 7 . Chapter 4 deals with the construction of the La-SrMn-Cr-O oxide database based on the assessments of subsystems. 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. and the aim of this study (chapter 2) is to gather a deeper understanding of these unsolved problems by using thermodynamics. The associated chemical changes of the LSM phase.

Appropriate measures can be foreseen preventing the long-term degradation of SOFC cathodes in combination with high-chromium containing interconnects. 8 . With this contribution the prevailing question is resolved. which of the phenomena in a chromium-“poisoned” LSM cathode are governed by thermodynamics. Cr2O3(s) (s = solid) that hampers the diffusion of oxygen into the electrolyte is a metastable phase in LSM contaminated by chromium.Summary reduction required for the function of the cell.

Zusammenfassung

Zusammenfassung
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

Zusammenfassung

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.

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Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects

1

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

Introduction

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).

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cathode and electrolyte consist of refractory solid oxide ceramics. The electrodes are required to have high reactivity and the electrolyte must allow high oxygen ion diffusion. The electrons flow from the anode through the external electric circuit to the cathode.2 (next page) for the widely used planar-design SOFC. a = anode. These ions migrate through the electrolyte to the anode. as shown in Fig. At the anode the oxygen ions react with hydrogen of the fuel to form water and release electrons. The oxygen. The direct-current electricity is produced by the electron flow through the external electric circuit.1.1 Scheme of the electrochemical processes in a fuel cell with O2 oxidant and H2 fuel. All the components of the cell need to be matched in their thermal expansion in order to minimize mechanical stresses.5 to 1 W cm-2.7 to 1 V and power around 0. and ceramicmetal composites are used for the anode. 1. Normally many cells are electrically connected in series by an interconnect. A single cell produces a voltage of 0. forming a cell stack to obtain higher voltage and power. supplied at the cathode reacts with electrons from the external electric circuit to form oxygen ions. e = electrolyte.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. 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. White circles symbolize pores. c = cathode. 12 . 1. In an SOFC.1.

difficulties in sintering and manufacturing and low mechanical strength[2] required the development of alternative interconnect materials. as the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. Nowadays the state-of-the-art interconnect is commonly a chromiumcontaining metal plate[3-5]. stability in both oxidizing and reducing atmospheres at the high cell operating temperature (from about T = 973 K to 1273 K). and their thermal and redox-stability is satisfying[1]. a thermal expansion coefficient close to that of the cathode and the anode. 1. low permeability for oxygen and hydrogen to minimize direct combination of oxidant and fuel during cell operation.2 Planar design of SOFC The interconnect separates the fuels and oxidants in adjacent cells. the electronic conductivity of several LaCrO3-based ceramics under SOFC operating conditions is high. 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. and chemical compatibility (no reactions) with other cell materials. a low ionic conductivity. However high costs of these materials.2 The problem of chromium “poisoning” In the 1990is LaCrO3-based ceramics were intensively investigated for interconnect applications in SOFC.1.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. 1. It is the most demanding component in a planar SOFC as it should have a high electronic conductivity.1. as chromium alloys come close to all desired properties. 13 .

1. But when it was learned that Cr2O3(s).6 mg at T = 1473 K at a gas flow rate of 200 ml min-1 after 20 h.3 mg at T = 1273 K after 72 h. and -diffusion processes. the weight loss being 0. Furthermore.6 mg at T = 1373 K and 2. 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.3-2. Since weight loss takes place under oxidizing conditions. In stagnant air the volatilization was 0. or at discontinuities such as fractures in the film and would then evaporate. 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. the volatile species must be a higher oxide of chromium. Appreciable volatilization occurred in dry oxygen. neither the vapour pressure of Cr2O3(s) nor its dissociation pressure is high enough to account for the quantities of deposits observed[10]. and it was suggested that high-valent gaseous Cr-oxide and Cr-oxyhydroxides detrimentally affect the O2 -adsorbtion. and at T = 1373 and 1473 K in flowing dry and wet oxygen as well as in dry and wet argon. The volatilization in wet oxygen was significantly higher after 20 h at the same gas flow rate: 2.1) 14 .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. Caplan and Cohen[10] investigated the evaporation of Cr2O3(s) by measuring the weight loss when Cr2O3(s) pellets with 1. lost weight when heated in oxygen. -reduction. in the absence of metal.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. it became evident that a volatile Cr-oxide was being formed[10].2 cm in diameter and height were heated at T = 1273 K in stagnant air.6 mg at T = 1473 K. 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.1 mg at T = 1373 K and 5. This was a surprising result. A known volatile oxide of Cr is CrO3.2. 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.

1.3) Δ°G of reaction 1. However.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects is thermodynamically unfavourable at high temperatures[10].2) Cr2 O3(s) + 1 2O2(g) + H 2 O(g) → 2CrO2 (OH)(g) (1. Δ°G of Eq. in a recent combined experimental and modeling study[18] these earlier findings are rejected for high temperatures: in wet atmosphere CrO2(OH)2(g) is predominant in the gas from T ≤ 1173 K.18] cited above. and Δ°G of reaction 1. The existence of gaseous Cr-oxyhydroxides as oxidation products (Eqs. data for O2(g) from Dinsdale[12].1 is calculated to be +321 kJ at T = 1273 K using assessed thermodynamic data for Cr2O3(s) from Povoden et al. and this was affirmed by thermodynamic modeling[19].2.2. the formation of CrO3(g) occurs under kinetic control[10].2.2 is calculated to be −158 kJ at T = 1273 K using combined data from Opila et al. This tendency is shown in Fig. Their formation by oxidation of Cr2O3 in wet air reads: Cr2 O3(s) + 1 2O2(g) + 2H 2 O(g) → 2CrO2 (OH)2(g) (1.2. 15 .2 and 1.[11]. whereas at higher temperatures the gas phase mainly contains CrO3(g) and CrO2OH(g). As gaseous CrO3(g) was detected experimentally by mass spectrometry when Cr2O3(s) was heated under oxidizing conditions. 1. and for CrO3(g) from Ebbinghaus[13]. Ebbinghaus[13] 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.3) in wet atmosphere was experimentally proven in several studies[14-17].[18] and Ebbinghaus[13]. 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. 1. These findings are supported by the higher volatilization of Cr2O3(s) in wet air.3 is calculated to be +134 kJ at T = 1273 K using combined data from Kim and Belton[14] and Ebbinghaus[13].

2. 1. reaching pCr = 4. 3.12x10-5 Pa at T = 673 K and increases as a function of increasing temperature.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig.[20] to measure the vaporization rate of Cr from Cr5Fe1Y2O3 (Ducrolloy) and Crofer22APU (high-Cr ferritic steel). and the 16 .6 μg h-1 for 3 mol% H2O in air at T = 973 K. at T = 1073 K for a time period of about 500 h. 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. Mass loss of Cr2O3(s) at T = 973 K and 1073 K was measured in air with different amounts of water. two high-chromium alloy interconnects widely used in SOFC.[21] used a transpiration method proposed by Gindorf et al. the mass loss being higher at higher water content and higher temperature: the constant rate of mass loss was 0.1 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. Cr-vaporization in SOFC: Konysheva et al.2 μg h-1 for 3 mol% H2O in air at T = 1073 K.57x10-3 Pa at T = 1223 K[20]. and 18.3 μg h-1 for 25 mol% H2O in air at T = 1073 K.

Badwal et al. However. Experimental results[21-29. With increasing humidity the difference in the vaporization rates between the two alloys increases. and the chromium problem is restricted to the interconnect-cathodeelectrolyte region of SOFC.1 Degradation of SOFC caused by chromium from the interconnect Considering the experimental data from Caplan and Cohen[10]. The amount of Cr in these degraded cells was 140 μg cm-2 with Cr5Fe1Y2O3.[22] mentioned significant amounts of deposited Cr2O3(s) in the air exhaust of the cell.35] of the degradation of SOFC with LSM cathodes caused by chromium are listed in Table 1. 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.5 higher than with Crofer22APU.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects vaporization rate increases with increasing temperatures for both alloys. thus quantitative chromium “poisoning” rates affecting the cathode are difficult to determine. for an SOFC setup with a Cr5Fe1Y2O3 interconnect plate. this value being by about a factor of 2. 17 . an LSM cathode. 1.3. This is in line with the experimental observation[21] 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.31. an yttriumstabilized zirconia (YSZ) electrolyte and a Ni-zirconia cermet (ceramic-metallic composite) anode operated at T = 1173 K and 1273 K.34. pp. 18-21.32.1.3 Literature survey 1.3.

Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Table 1.1 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 19 .

Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 20 .

and intensity measurements using electron probe microanalysis showed that Cr was concentrated at the cathode-electrolyte interface.7 V to about 0.1MnO3-δ. In a test of the same setup under open circuit conditions for 21 .9Sr0. 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.1 V. The cell voltage decreased over this time from initially about 0.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. 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. The cell was electrochemically tested at T = 1273 K under a current load of 300 mA cm-2 for 400 h.[23].

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. Simner et al. 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. 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[28] led to the following results: the overpotentials without interconnects or with LaCrO3-base interconnects consistently became less negative with time. whereas ohmic losses (resistance to 22 . its power density decreasing from a maximum of 0.[22] reported that the degradation rate of SOFC with a Cr5Fe1Y2O3 interconnect plate. an LSM cathode. a YSZ electrolyte and a Ni-zirconia cermet anode at T = 1273 K and a current density of 250 mA cm-2. a Sm2O3-CeO2 interlayer between cathode and electrolyte.[23] thus linked the cell degradation to the time that the discharge current was applied. whereas the opposite was observed for SOFC with Cr-alloy interconnect. holding the cells at 0.48 W cm-2. 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. and Cr was randomly distributed across the cathode.1 V during an operation time of 2500 h.[22] ascribed the voltage decrease to increasing losses of cathodic overpotential. the cell started to degrade severely after 20 h of testing.[29] presented cell performance data of an SOFC with LSM cathode.7 V: without the interconnect steel. Later these results were confirmed by Badwal et al. But using a Cr-Fe-alloy interconnect. the cell performance was stable for 110 h. the power density being 0.2 The role of current load on electrical losses of degraded SOFC Badwal et al. On the other hand the voltage of the cell with Cr-Fe-alloy interconnect decreased rapidly as a function of operation time.3.2 W cm-2 to 0.[22]: these authors tested the cell performance of an SOFC with a Cr5Fe1Y2O3 interconnect plate. the voltage drop being 0. The cell performance without interconnect plate deteriorated only little by less than 0. an LSM cathode. and to chromium deposited at the LSM-YSZ interface filling pores. All these experimental studies[22-29] unambiguously proved that chromium stemming from the alloy interconnect causes the degradation of SOFC. Taniguchi et al.05 W cm-2 after 110 h.4 V after only 16 h.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. 1.

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.[30] tested the reversibility of degradation in a half-cell setup with CrFe-alloy interconnect.32. a La0. Paulson and Birss[34] reported rapid deterioration of the performance of a half-cell setup with a stainless steel disk containing 15. Zhen et al. At the beginning of the cell tests. Matsuzaki and Yasuda[28] measured an overpotential loss from initially −500 mV to −2000 mV after 14 h in a half-cell setup with an Inconel 600 interconnect. The total polarization resistance (Rpol) of a half-cell setup using a Cr-Fe-alloy interconnect.07 V.33]. whereas at 280 mA cm-1 the voltage dropped by 0.[27] 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.6Sr0.4MnO3-δ cathode and a YSZ electrolyte at 300 mA cm-2 current density. Konysheva et al.2)0.5 V potential. in agreement with earlier findings[22.25] at 1173 K and a current density of 200 mA cm-2. 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.28. losses increased sharply and reached their maximum values after only 15 h of cell operation.[24.65Sr0. La0. 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. LSM cathode and a YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2.98MnO3-δ cathode and a YSZ electrolyte over 5 to 10 h at T = 1073 K applying a −0.[21].5 Ohm cm2 for a thickness of 23 . Rpol being 0.3MnO3-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. In earlier studies using the same setup a rapid decrease from −360 to −560 mV after 10 minutes[25. Konysheva et al.23.31].6 V.25. However the cell degraded rapidly again when the current was switched on again. 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[27] or −420 to −170 mV [24. using a half-cell with a Cr5Fe1Y2O3 interconnect.8Sr0. 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[27]. in general agreement with Jiang et al. The overpotential losses were higher and the cell deterioration was faster at higher current density.21 % Cr on top of a (La0.26] was observed. A plateau of degradation was reached after about 400 h of testing.

and 2 Ohm cm2 for 7 μm[30].[24. LSM cathode and YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2. 1. 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.[32] observed less overpotential losses at lower temperatures in a half-cell with CrFe-alloy interconnect.6Sr0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 50 μm.[22] observed an increased size of the high frequency arc during the current passage in half-cell tests using a Cr5Fe1Y2O3 interconnect plate.[23] were the first who reported the occurrence of Cr-Mn-spinel in Cr“poisoned” SOFC with an LSM cathode by using XRD analysis.7 V. from −900 to −1200 mV at T = 1073 K. Jiang et al. reflecting increasing cathode resistance.[27] reported the existence of a high frequency and a low frequency arc in impedance spectra of a half-cell with Cr-Fe-alloy interconnect.4 Microstructures in degraded SOFC Cathodic polarization: Taniguchi et al.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.3. 0.3. Mazusaki and Yasuda[28] concluded from the interpretation of impedance spectra of a half-cell with an Inconel 600 interconnect. an LSM cathode and a YSZ electrolyte as a function of operation time. a La0.26. The total polarization resistance was also higher at higher current load. 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. Zhen et al. but not due to the increase in ohmic resistance. 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[35]. This finding was confirmed 24 . 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. The degradation was higher at higher temperatures at 0. and from −800 to −1120 mV at T = 973 K after 10 minutes.75 Ohm cm2 for 13 μm.33] and Jiang et al. 1.3 Impedance spectroscopy measurements and implications on the degradation process Badwal et al.32].

an LSM cathode. Using a half-cell setup with Inconel 600. in some of the experiments forming a dense layer of several microns at the cathode-electrolyte interface.36] documented spinel formation at the LSM-YSZ interface already after 4 h. a YSZ electrolyte and a Nizirconia cermet anode at T = 1173 and 1273 K under current load. no Cr-deposits formed after 50 h of testing under open circuit conditions[25. but under anodic polarization very fine grains of Cr2O3 were forming exclusively at the LSM-YSZ interface. Using the same setup as above. Jiang et al. Zhen et al. LSM cathode and YSZ electrolyte Matsuzaki and Yasuda[31] 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.05 μm) of Cr2O3 towards the cathode-electrolyte interface. and the cell-degradation was weak[21]. In some cases these authors also observed Cr2O3(s) at the cathode-electrolyte interface.36]. In the same setup without LSM-YSZ functional layer no chromium-deposits were detected without current at T = 1073 K over 393 h. Badwal et al. The grain size of spinel was about 0. Very small grains of Cr-deposits formed at T = 1373 K under open circuit conditions. an LSM/LSM-YSZ cathode double layer and a YSZ electrolyte chromium-deposits were only found in the LSM layer under open circuit conditions.7 μm after 50 h. unfortunately the specific conditions for its formation were not given in more detail. On the other hand Cr-Mn spinel formed already at 25 . and the cell degradation was strong[21]. Using the same setup. The amount of spinel at the cathode-electrolyte interface was much larger than within the LSM cathode particularly after a period of current load. In a half-cell setup with a Cr-Fe-alloy interconnect. but further details on their spatial distribution and composition were not given. 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.[25.[27] 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-2.17 μm after 4 h of cell testing and increased to about 0.[22] further observed spinel in the contact region between interconnect and cathode. Under the same testing conditions as above. The deposition zone broadened as the polarization time increased from about 60 μm after 50 h to 89 μm after 129 h.[22] who detected small amounts of Cr-Mn spinel after 100 h of operation of SOFC with a Cr5Fe1Y2O3 interconnect plate. For the same setup large quantities of spinel had formed after 2000 to 2500 h of cell operation. The zone of these large faceted crystals was followed by a zone of very fine grains (about 0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects by Badwal et al.

and spinel crystals were found on the surface of a thin Cr2O3-layer adjacent to the electrolyte. after the half-cell was tested by a sequence of 8 chronoamperometry experiments at −0. No spinel formation was observed in these experiments. After 5 minutes of testing at T = 1173 K very fine Cr-deposits (< 100 nm) already formed on the YSZ-surface. and the density and size of deposits increased by time. After 160 h of testing at 100 mA cm-2 current load. a La0. A reference test without polarization did not lead to these features.[32]. large gaps between YSZ grains formed. These authors observed the formation of a 500 μm broad zone of 8 individual.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. up to 10 μm away from the LSM-YSZ interface after 160 h of testing.5 V and T = 1073 K.2)0. Paulson and Birss[34] investigated the microstructures in a half-cell setup with a stainless steel disk containing 15.72Sr0.21 % Cr attached on top of a 4 mm2 square (La0.98MnO3-δ cathode that rested on a 144 mm2 square YSZ electrolyte. Cr2O3 completely filled gaps between YSZ grains. Jiang et al. exclusively covering the YSZ surface. 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. In direct contact with YSZ about 500 nm large Cr2O3-grains were detected. After 20 h spinel formation was observed forming a 40 to 50 μm wide band at the LSM-YSZ interface. Cr-deposits consisting of Cr2O3 and Cr-Mn-spinel were concentrated in an about 2 μm broad region at the LSM-YSZ interface. Transmission electron microscopy analyses revealed the layered structure of the composites: a 0.[36] reported the formation of very fine particles of Cr2O3.8Sr0. and the deposition was less pronounced at T = 1073 K and 973 K. Influence of temperature: Microstructural changes during half-cell tests of a setup consisting of a Cr-Fe-alloy interconnect. almost completely 26 .5 μm thick layer directly adjacent to the YSZ containing mainly Cr2O3 is covered by a spinel layer. The morphology of the particles was different than the morphology of the deposits under cathodic polarization.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. dense Cr2O3-layers at the edge of LSM on the YSZ surface. Cr2O3 was also found inside YSZ. and 30 μm from the LSM-YSZ contact after 940 h.

a Sm2O3-CeO2 interlayer between cathode and electrolyte and a YSZ electrolyte with a Crofer22APU interconnect operated at T = 1073 K.[35] measured about 2.3MnO3-δ/LSM+YSZ double layer cathode and a YSZ electrolyte after tests without current showing very small degradation.% of Cr at 10 μm distance from the cathode-electrolyte interface. associated with large grains (about 1 μm) of spinel.% Cr in the Sm2O3-CeO2 interlayer.65Sr0.3. In SOFC with LSM cathodes and a Cr-Fe-steel interconnect that were tested at T=1073 K for 300 h at 0. holding the cell at 0. but no Cr in LSM using energy dispersive scanning electron microscopy. The Cr-content dropped to about 0. 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. Krumpelt et al. It further decreased slightly towards the interconnectcathode interface. This may lead to a dramatic drop of the oxygen diffusion coefficient in LSM by about 60%[36] and pers.5 wt. 27 . Simner et al.[21] compared the total amounts of chromium in half-cells with Cr-Fe-alloy interconnects.vacancy within about 10 Å around Cr3+. 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. comm. By using molecular dynamics simulation techniques it was stated recently that only 890 ppm Cr3+ in LSM significantly increase the formation energy of O2.7 V.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects covering the YSZ surface. this is only 15 to 20 % higher than in the cell operated without current.7 V for 120 h. The decreasing degradation at lower temperatures was ascribed to slower diffusion and lower partial pressure of gaseous Cr-species.[29] measured 5 at. a La0. 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.8 wt.% at 14 μm distance from the contact to the electrolyte.5 Amounts of chromium in SOFC tested with and without current load Konysheva et al. although the degradation of the polarized cell was remarkably higher. 1. and under 200 mA cm-2 current density showing strong degradation as a function of testing time at T = 1073 K. In a half-cell with LSM cathode.

33. 1) Several authors[21-23. 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. electron-donating LSM and oxygen-accepting YSZ are available[38]. 1.3.30-31.32. including changes of the chemical composition of the LSM surface.3. Badwal et al. 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. 1.33].1 when solid solubility of Cr in LSM[39] is considered and spinel contains the molar fraction of Cr. 1.3.3.3.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. 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”.37]. and gas.2.6 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.[22] 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.1) Eq.230. YSZ. and 2) Chemical dissociation of Crspecies on the LSM surface[24-26.2 is a possible reaction for the formation of spinel with a higher amount of Mn.33] ascribe the mechanism of chromium “poisoning” to the reduction of gaseous CrO3(g) and Cr-oxyhydroxides at the cathode-electrolyte interface. 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. and blocking of pores by Cr-Mn spinel and Cr2O3(s).2) 28 . Badwal et al.[22] emphasized that chromium “poisoning” would consist of several processes. In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary (TPB) between LSM.31. 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.1. Both reduction and chemical dissociation processes reflect non-equilibrium conditions. reduction of CrO3(g) at the cathode-electrode interface competing with the normal oxygen reduction reaction. described by inverse Eq. where the reaction partners for the reduction.

5) considering the main chromium molecules that interact with LSM for spinel with X(Cr) = 2X(Mn). 1. 1. thus assuming a lower activation energy for the LSM-Cr-gas reaction. sp-form = spinel formation. 1. depends on the activation energy. However the formation of spinel can also be interpreted as a direct solid-gas reaction. more oxygen is produced.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects For equal y in Eqs.3. Which of the possible reaction paths is realized.3. The true shape of the curves depends on the activation energy Ea and is thus not known.1 and 1. The shape of the curves in Fig.1 is a simplified illustration of possible reaction paths that lead to the end product Cr-Mn spinel. Such gas-solid reaction can be split into two reaction steps: formation of 29 . Oxygen production stems from the reduction of Mn3+ in perovskite to Mn2+ in spinel.3. and the LSM-Cr-gas reaction occurs as a parallel process leading to the formation of spinel.2 less Cr2O3 is needed for the formation of Mn2CrO4.3. 1. As it is not assured if spinel in fact forms in a solid-solid reaction.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). reactions of direct formation of spinel by the interaction between Cr-gas and LSM can be formulated (Eqs. These assumptions would mean that fast reduction of Cr-gas to Cr2O3(s) occurs as one process.3.3.1 Possible reaction paths for the spinel formation as a function of Gibbs energy. Fig. 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. 1. Ea of the concerning reaction. and this is not known.3 to 1. Fig.3. red = reduction. and the mobility of the gas phase is high. and LSM gets more deficient in Mn.

However they did not discuss the dependence of oxygen diffusion upon pO2 .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) (1.32.[43] 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.1 to 1. 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) (1.32.4) 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. This in turn will also lead to less Mn2+ in LSM[40] and consequently lower oxygen diffusion in LSM.33.3.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.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[24-27.37] oxygen diffusion is inhibited by the nuclei-formation.3.33.3. opposite to the trend that would be expected under the control of the vacancy diffusion mechanism. 1. 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[44]. Yasuda et al.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[41] concluded from the low oxygen self-diffusion coefficients of the order of 4×10-14 cm2 s-1 at T = 1173 K[42] that long range bulk migration of oxygen ions cannot play a significant role for the cathode performance. and consequently to Cr-Mn spinel and Cr2O3(s). The ionic conductivity was lower at lower oxygen partial pressures.5 that oxygen is produced during the formation of spinel. Huang et al. As Mn2+ is associated to vacancy formation in LSM that is necessary for the oxygen diffusion.3.[24-27.[44] concluded that 30 . It can be seen from Eqs.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.

94x10-9 in air[23].2.32. We believe that the oxygen vacancy diffusion mechanism contributes to the oxygen diffusion under high current loads. It was also mentioned in the early paper of Caplan and Cohen[10] that substantial precipitation of Cr2O3(s) from CrO3(g) occurred in the cooler part of the experimental setup.9Sr0. η = −0.4x10-6.1 has a large negative value. This phenomenon was well explained by continuous feeding of an initial 31 . 1.1CoO3-δ in which oxygen ions are transported by the vacancy mechanism.33. 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. Paulson and Birss[34]. 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 . Contradictory interpretations[43] 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.8Sr0.185 V. as it was directly proven by isotopic and tracer diffusion[44] experiments. This is close to 270 kJ mol-1 for La0. This confirms the suggestion that the formation of oxygen vacancies in LSM contributes to the oxygen diffusion at high current loads[22]. This indicates that a vacancy diffusion mechanism also applies to LSM[45]. and η = −0.2MnO3-δ at 973 K and pO2 = 10-4 Pa is δ = 2.336 V corresponding to pO2 = 10-4 Pa[46]. 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. Reduction of CrO3(g) to Cr2O3(s) was such predominant as to make sampling of gaseous CrO3(g) difficult. when the oxygen partial pressure at the cathode-electrolyte interface is decreased significantly. The calculated amount of oxygen vacancies (δ) in La0. The activation energy for the diffusion of oxygen for LSM is in the range of 250 to 300 kJ mol-1. compared to δ = 3. In an investigation of active sites for the oxygen reduction at the O2/LSM/YSZ interface[46] for three different overvoltages of cathode polarization (η = −0. as oxygen vacancies are simply not available under these conditions.336 V.37].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. as Δ°G of the reduction being the inversion of reaction Eq.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. The electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach[24-27.[21] observed the extension of dense Cr2O3layers into YSZ.

The region of spinel formation extends several microns from the TPB into the cathode.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Cr2O3-layer with CrO3(g).30. But how can one explain the strictly localized deposition of Cr2O3 that also occurs under anodic polarization[37]? Under oxidizing conditions little Mn2+ is expected to be present in LSM[40]. Cr2O3(s) deposition should also occur under open-circuit conditions.34]. and the degradation can be associated to the dissociation process[24-27. If CrO3(g) is electrochemically reduced to Cr2O3(s) in a cell. Some indications for two independent chromium poisoning mechanisms can be found in the work from Jiang et al.33. which does not seem to be the case for the spinel phase.[24. from impedance spectra analyses it was in fact possible to distinguish two distinctive depositions of Cr-species. In this case the contribution of reduction to the Cr-“poisoning” has to be rejected. and the normal charge transfer can take place by switching it on again. the latter becoming reduced at the new TPB consisting of YSZ and electron-donating Cr2O3(s)[21.37] and subsequent formation of spinel. which is increasing as a function of increasing polarization. and the second with a higher rate on the YSZ electrolyte surface. This explanation is in line with the microstructural features of tested cells both under open circuit voltage and under current load. In this case no chromium will be deposited at the cathode-electrolyte interface under open-circuit conditions.23.26.37]: the two phases formed in the scope of a polarized LSM cathode exhibit distinctive microstructures: spinel forms large grains. Thus it is obvious that the explanation of the “poisoning” process by the chemical dissociation approach alone is not without doubt. and it is also in line with the observed temporary reversibility of the cell deterioration[22. partly layered structures. whereas an explanation by the chemical dissociation approach is not satisfying. whereas in a polarized cathode the reduction of CrO3(g) takes place and competes with the oxygen reduction leading to Cr2O3(s) deposition. This is in contrast with the complicated mechanism for the formation of Cr2O3(s) under anodic 32 . which both seemed to be inhibited by chromium poisoning. Also two different diffusion processes were distinguished.32. one with a lower rate on the LSM surface. whereas the phase that was most likely identified as Cr2O3 occurs in fine-grained. Furthermore. whereas Cr2O3 is always located directly at the cathode-electrolyte interface. 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.28.31]: by switching off the polarization the competing reduction of CrO3(g) no longer occurs. From the occurrence of finegrained Cr2O3 the existence of a large number of nuclei for its formation is concluded. which was definitively not observed. thus the formation of nuclei by the proposed LSM-Cr interaction won’t occur.

[37] that includes diffusion of Mn3+/Mn2+ driven by the oxygen evolution reaction at the cathode/electrolyte interface. 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. the number of the latter being less than under cathodic polarization. but several processes may lead to the deterioration of cell 33 . and thus lack of spinel formation. contrary to the situation of a strong pO2 gradient under cathodic polarization. this apparent antagonism is abolished. and thus under these conditions LSM has no tendency at all to accept oxygen. again with Mn2+ acting as agent for the formation of Cr-Mn-O nuclei. 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. This different behavior of Pt and LSM electrodes under Cr-poisoning was used as an evidence for the exclusive validity of the dissociation approach. if both the chemical dissociation as well as the reduction of gaseous Cr-species is occurring with different proportions. Oxygen deficiency is negligible in LSM under high pO2 [40]. based on an early finding that LSM behaves like a metallic electrode at low polarization potentials[47] that was not quantified. and in LSM a pO2 gradient is expected under polarization. contrary to an LSM electrode. LSM cathode and a YSZ electrolyte at T = 1173 K and a current density of 200 mA cm-2 from Zhen et al. opposite to the situation with a platinum cathode. which is indeed not the case in a platinum cathode. vacancies are expected to form in LSM under increasing polarization.[27] are particularly interesting: the slope of the cathode polarization curve (Fig.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects polarization established by Jiang et al. This is indeed true for the case of CrO3(g) and Cr-oxyhydroxide reduction being the only Cr-poisoning mechanism. However. In cell tests of a polarized platinum electrode using a Cr-containing interconnect no Cr was observed. 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. However this conclusion was not tested in the light of the oxygen partial pressure gradient towards the electrode-electrolyte interface: contrary to platinum. In this context experimental results of a half-cell test with Cr-Fe-alloy (RA446) interconnect. where the reaction partners for the reduction. This is an indication against one unique “poisoning” mechanism. Alternatively. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available[38]. 4 b[27]) as a function of time reveals an inflection point after about 6 1/2 h.

thereby still more decreasing the oxygen partial pressure at a newly formed Cr2O3(s)/electrolyte interface[30]: the TPB between LSM and YSZ diminishes more and more by the blocking of Cr2O3(s).8 S m-1 at T = 1282 K[48] and pO2 = 1 Pa. as electronic conductivity of Cr2O3 is significantly higher at higher pO2 (1. The deposition of chromium followed by its reduction near this interface blocks direct oxygen access to the electrochemically active sites. This results in a lower oxygen partial pressure at the interface as compared to that in air. thus the remaining TPB/YSZ active sites are almost unaffected under open current circuit. 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. the LSMCr interaction is again favored in the region close to YSZ as pO2 decreases at the TPB. and oxygen cannot access the TPB. the oxygen ions from this new. 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. Applying a current load. The higher the current density under SOFC operation.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects performance. weak catalytic reaction diffuse into YSZ. Oxygen is mainly reduced at the new TPB between Cr2O3(s) and YSZ.[30] give the following explanation. 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. even though the decrease is expected to be less due to less LSM/YSZ active sites caused by the first degradation. and their respective influence on the cell deterioration may vary as a function of time. under open circuit the LSM-Cr interactions occur randomly throughout the cathode.[23]. Under polarization. the lower is the oxygen partial pressure at the contact between LSM and YSZ. Reduction already takes place at higher pO2 at the beginning of the current load operation. 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 in air[48]). 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. 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. Konysheva et al. As Cr2O3(s) has a small electronic conductivity of 0. 34 .

Number 2 denotes the region of interactions between LSM and chromium leading to spinel formation by solid-solid reaction. 1. followed by diffusion of the gaseous products into the cathode. 1. 1.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Oxygen ions diffuse into YSZ.3.1 to 1.3.2 Model of chromium poisoning of an SOFC with Cr-interconnect and LSM cathode based on the findings in the literature. and the degradation increases as a function of time. Numbers refer to locations of processes that are decisive for the degradation Number 1 in Fig. current load.1 leading to the redeposition of Cr2O3(s) at the cathode-electrolyte interface. 1.3.2.2 denotes the interconnect-cathode interface region where oxidation of Cr2O3(s) to gaseous Cr-oxides and Cr-oxyhydroxides by Eqs.2. and chromium content is schematized in the picture.2 is a visualisation of the microstructural consequences of chromium in an LSM cathode.3.5.2.1 to 1.2. The reported dependence of structural features of the degraded cell on the operation temperature. 1. Eqs. Fig.3 to 1. Fig. 1. 35 .3 occurs. but new oxygen is not supplied to the new TPB. or gas-solid reaction.3. 1. and number 3 denotes the reduction of gaseous Cr-species by the reverse of Eq. Active LSM/YSZ sites further diminish by ongoing formation of spinel and Cr2O3 deposits.3. Eqs.3.

sputtered Co.15MnO3-δ[50].[22] 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.2FeO3-δ[67]. 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.50].4.Co)3O4[68].5O3[65].Al)N[69]. If the buffer layer contains an ionic conductor. (La.8Fe0.33MnO3[64].2O3[58]. La0.1 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes More than ten years ago Badwal et al. but a combination of the quoted strategies is advisable to further improve the long-time stability of SOFC performance. 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[30]: increasing the ionic conductivity of the LSM cathode that is predominantly electronically conducting down to pO2 = 10-7 Pa[70] by admixture of YSZ results in an 36 .6Sr0. La0. However.2Mn0.5O3-δ[66].6O4[53.4Mn1.8Sr0. thereby improving the electrical conductivity of the interconnect-cathode interface[49-69].85Sr0. 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. MnCo2O4[54-61]. La0.8Sr0. However. more active sites for the oxygen reduction will result in a higher Cr-tolerance.05Mn1.5Co0.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.65]. 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. Furthermore such a buffer layer may act as a sink for CrO3(g) thus diminishing nuclei formation on LSM. La0. Ce0.8Sr0. two-segment Cr-Al-Y-O nanocomposite and (Mn. Co3O4[53].Sr)CoO3[63].3MnO3[58.475O4[62]. so far volatilization could not be suppressed completely. Ni. as well as (Ti.475Co1. Cu1.2Mn0. Mn.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. coating alone does not solve the problems associated to chromium poisoning completely.4Co0. La0. La0. or Cu-Mn[51].5Co0. Co-Mn. or Mn2CrO4[52]. La.67Sr0.65Sr0. or Cu[52].54]. La0. as Cr in the ppm range significantly influences the oxygen diffusion in the LSM cathode[36].

73]. La0. The highest tolerance against the effects of chromium under SOFC operating conditions combined with high electrical conductivity has been reported recently for (La.71. The ionic conductivity can be increased by doping the B-site of ABO3 perovskite with reducible cations.4.Ba)(Co. 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.Fe)O3-δ (LBCF) are more tolerant against chromium “poisoning”. Besides. and (La. Based on these findings they predicted that highly Cr-tolerant cathodes can be developed. the reduction of gaseous chromium will not be restricted to the small area at the TPB due to a smaller oxygen partial pressure gradient.Fe)O3-δ (LNF). particularly LSCF and LNF show rather high ionic contributions to the total electrical conductivity.4Co0. whereas no proper nuclei were reported for LBCF.Ba)(Co.Fe)O3-δ (LBCF)[71. Matsuzaki and Yasuda[31] concluded from insignificant Crdeposits in tested SOFC with Cr-Fe-alloy interconnect. In recent time it was found that new cathode materials such as La1-xSrxCo1-yFeyO3-δ (LSCF).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. Effects of Cr upon the degradation of La1-xSrxCo1-yFeyO3-δ (LSCF)[26.2O1. La(Ni. which makes this material a promising candidate for a steady long-term SOFC performance.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.8O3-δ (LSCF) cathode and Ce0.2Fe0.74]. 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. La(Ni. The amount of Cr- 37 .2 New ways – alternative materials Badwal et al. LNF and LBCF revealed extraordinary high tolerance against chromium poisoning. and the cell is more tolerant against chromium[30].[22] already considered alternative cathode materials to reduce or stop the formation of the spinel phase.6Sr0. All these perovskites are mixed electronic-ionic conductors.Fe)O3-δ (LNF)[71. In all these cathodes Cr-deposition was observed throughout the cathode both under polarization and without polarization.72]. contrary to LSM.Ni)FeO3-δ [71. Thus the number of active sites is increased. 1.75] cathodes were investigated using impedance spectroscopy. and (La. 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.8Sm0.

284-93. 127. which was explained by a removing effect of nuclei for the chromium deposition under polarization conditions. 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. 3. aging mechanisms and lifetime in solid-oxide fuel cells. J. 1-15. 2005. 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. Materials Science and Engineering A. but their influence on the Cr deposition compared to the reduction of CrO3(g) cannot be decided yet. Power Sources. pp. Even if the reduction reaction is considered to be the dominant mechanism of chromium poisoning. The higher the contribution of the ionic conduction the less complete reduction is expected due to prolonged lack of an electron donator. 2004. Metallic interconnects for solid oxide fuel cells. J. that is towards lower oxygen partial pressures. 2004. and a typical mixed ionic-electronic conductor such as LSCF can take over both functions. However under strong polarization one can expect that LSCF gets more and more ionic conducting towards the electrode-electrolyte interface. References 1. However. Stimming. Tu. pp. Fergus. Solid State Ionics. nuclei might form in addition. As an alternative to the complicated nuclei mechanism. The amount of deposited Cr in LSCF was even larger without polarization than under polarization. 38 . 2.W. 271-83. 397.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects poisoning of LSCF was considerable. 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”. Fergus. 171. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. Improved inhibition of the reduction of CrO3(g) is predicted for LNF. H. J.W. Advances. as this phase has a particularly high ionic conductivity. U. Thus reduction of CrO3(g) takes place inside the whole cathode even without being promoted electrochemically by polarization of the cell. pp. most likely resulting in retarding or inhibiting of the reduction reaction. 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.

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. 176.-H. I. D. 695-703. Power Sources.Y. J. A127-A134. 2006. and V doped-LaCrO3 interconnect materials prepared by Pechini. A. 2007. 2006. Lee. Marozau. Shul. J. Jiang. D. 78. Irvine. pp. S. Arai. 189-96.C. Shin. Soc. pp.P. Chiba. Solid State Ionics. M.-H.Fe)O3 cathodes of solid oxide fuel cells. Lim. G. Electroceram. 2008. T. Mixed conductivity and electrochemical behavior of (La0. Characterization and performance of (La.T.Y. 70. J. Pu.-Y. C. S.Sr)(Co. Peck. pp. pp. Development of Cr-tolerant cathodes for solid oxide fuel cells.Fe)O3 as a cathode material with high tolerance to chromium poisoning for solid oxide fuel cells. Y. 177. Boey.V.D. Jiang. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. Y. Hydrogen Energ. J. 2006. 11. Tsipis.-R.P. Diwu. Song. Cr Poisoning suppression in solid oxide fuel cells using LaNi(Fe)O3 electrodes. X.5Mn0. J. K. Jiang. pp.Y. Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells. Zhen. Liu. 2008.S. J. Wu. 2008.I.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. L.P. Zhang. 44 .5O3-δ. 73. S. Dong.-H. X. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. Wang. J. Tok. J. Cross. Electrochem. 2007. Solid St. SolidState Lett.C.I. Boey.R. pp. H. Developing TiAlN coatings for intermediate temperature solid oxide fuel cell interconnect applications. R.-H. Zhen. 2008. B42-6. 178. pp. R. Meng. Sato..P. 71. Zhen. Nozawa. V. L.. J. Tok. 77. 2008. A9-12. C. Xu. Komatsu.Ba)(Co.P. F.-G. 61-6. Ong. Ni. 75. Y.V. Johnson. S. 82-89.25)0. 17.. S. Jiang. 72.. E. 33. J. P. Viskup. F. 76. pp.Y. M. Kim. Zhao. J. Zhen. Power Sources. Int. La(Ni. Power Sources.75Sr0. Frade. Properties of Cu.D. Y. Electrochem. J. 9. K. Jiang. S. S. pp. Liu. Deposition of Cr species at (La.P. Liu. J. Li.P. 153. 74.P. A. J. T. 723-27. Li. Kharton. G. pp. 170. 180. A. and D. K.D. Y. 451-56.95Cr0. Power Sources. Liu. Arakawa. C. Electrochem. 101-13.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 69.

which further retards the diffusion process of oxygen into the electrolyte. This means that the kinetic control on the mechanisms of chromium 45 . it seems that strategies against the cell degradation have been mostly established in a rather random way so far. but the effects of chromium would be observed only after thermodynamic equilibrium is obtained. 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. For a more systematic and thus more efficient combination of strategies a strong knowledge about the mechanisms of chromium poisoning of SOFC is required. If the process of chromium “poisoning” were completely governed by thermodynamics. However. which of these processes play a dominant role for the degradation and which don’t. and some strategies against cell degradation caused by chromium have already been successfully applied. 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. 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. Reduction of CrO3(g) at the TPB leads to the formation of electrically low conducting Cr2O3.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. The causes and consequences of chromium poisoning are clear. 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. this behaviour would not be expected. So far it was not possible to define unambiguously.

Aim of study is high. and what are the conditions that favour their formation? This work aims to answer these questions by the application of thermodynamic calculations. 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 a degrading cell is in a non-equilibrium state particularly at the early stages of the degradation. in this study the author focuses on the effects of Cr on the degradation of SOFC with LSM cathodes. In recent times many materials have been tested for SOFC cathodes.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. the obvious question why the results of thermodynamic calculations should be feasible for a deeper understanding of the mechanisms 46 . and as LSM cathodes are still considered to serve as promising cathodes due to their high electrical conductivity and stability at SOFC operating conditions. and can this change be explained by thermodynamics? -) Which of the phases observed in LSM contaminated by chromium form under thermodynamic control. 3 Method 3. Thus. As a degrading cell is in a non-equilibrium state. 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. Therefore the thermodynamic La-Sr-Mn-Cr-O oxide database needs to be established based on the assessments of low-order subsystems.

1. for instance under reducing oxygen partial pressures reflecting the situation at the TPB under current load. taking into account experimental data on the chromium “poisoning” of SOFC and using a thermodynamic La-Sr-Mn-Cr-O oxide database.equilibrium (A) ⎯⎯ equilibrium (B) → (3. a with the positive electrical charge r and b with the positive electrical charge q. temperatures.1 reflects the path the system takes towards its equilibrium state. For instance. one can draw conclusions on the evolution of the phase chemistry of degraded LSM cathodes. C in Eq. 3. Hence.Method of chromium “poisoning” needs some explanation: from the conditions of the non-equilibrium state at the beginning of the degradation process.2.2 Thermodynamic modeling 3. by choosing the starting conditions composition of LSM and defined amount of Cr at a specific temperature. The presented thermodynamic database of the La-Sr-Mn-Cr-O oxide system is constructed using the CALPHAD approach[1]. 47 . using the thermodynamic database one can calculate the expected thermodynamic equilibrium.1) By calculating thermodynamic equilibria for a LSM cathode that is affected by chromium (A) in the relation above. containing m and n moles of two different sorts of cations. the theoretical final state of chromium poisoning after a very long time is found by thermodynamic equilibrium calculations (B). composition of LSM.1. can be calculated using the thermodynamic La-Sr-Mn-Cr-O oxide database: C non . and for solid solution phases as a function of temperature and composition. 3. including the operating temperature. The optimization of model parameters is based on the accurate assessment of experimental thermodynamic and phase diagram data of oxide subsystems. and oxygen partial pressures. 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. C can be predicted for changing cathode compositions. From A and B. and the rate of chromium diffusion the equilibrium state of chromium “poisoning”. It contains the optimized Gibbs energy functions of solid oxide phases: for stoichiometric phases as a function of temperature.1 Stoichiometric solid oxides The stoichiometric ternary phase α.

2. b q )t (O2. mr + nq + 2 p = 0 (3.2.1 is true.) w ( t .2. D.1) α The molar Gibbs energy of α.2. the sublattice formula of the resulting solid solution phase β(ss) reads (a r . 3. Eq. A and B are optimized by thermodynamic and phase diagram data.)u n ° (b G + Gm t m v r ° α Gm = °Gm ( a r )m (bq )n (O2. another sort of cation with the positive charge q. E and F are optimized to heat capacity data only.Method respectively. E.2. Eq. c with the negative electrical charge s. the three types of ions sitting in three distinctive crystallographic sublattices. 3. and p moles of one sort of anions. 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. w ∈ N ). v.2. u. As Cp(α) is defined by C p = −C − 2 DT − 6 ET 2 − 2 FT −2 (3.5 is the criterion for charge neutrality: 48 .)u and Ox2: (b q )v (O2.4: m ° ( a )t (O2. To account for the charge neutrality criterion.)w + ptv − muv − nwt ° O (g) Gm + A + BT 2tv 2 (3. °Gm can be based on the molar Gibbs energies of existing binary oxides Ox1: (a r )t (O2. and F are model parameters to be optimized by thermodynamic and phase diagram data. bq can sit in the same sublattice as a.) p = q )v (O2.4) ° α Gm is the Gibbs energy of formation of the phase α relative to the oxide components.)u containing cation a with the positive charge r. 3.3) α C.2.)u .2. For oxides c = O and charge s = −2.2 Solid solution phases – the Compound Energy Formalism (CEF) If in the binary oxide Ox1: (a r )t (O2. C. °Gm at constant pressure is given by ° α Gm = A + BT + CT ln T + DT 2 + ET 3 + FT ( −1) (3. B. D. 3. can be described by the sublattice formula (a r )m (b q )n (c s ) p .2) A.

The second-last term accounts for the configurational entropy of mixing of t moles of a and b.2..°Gma 2+ )2 (O2. In the sublattice form the phase can be written as (a3+ . The molar Gibbs energy of the phase at constant pressure reads 3+ ° A ( Gm 2 O3−δ = °Gma 2+ . A standing for the cation sublattice.)3 ( + ya2+ yO2.6) where yar is the site fraction of cation a on the cation sublattice. (a 3+ )2 (Va)3 .. 3.31451 J mol-1 K-1.)u . and ybq is the site fraction cation b on the cation sublattice. If the cation is reduced. The Gibbs energy of β(ss) at constant pressure reads ° β Gmss = yar °G ( a r) t (O2.)u and (bq )t (O2.Method u= t ( ya q + yb q ) 2 (3. with only one cation a accepting the charge 3+ or 2+ in the cation sublattice.Va )3 (3. For β(ss) the two compounds read (a r )t (O2.ln yO2.)3 .2.°Gma 3+ )2 (O2.+ yVa ln yVa + EGma ( ) ( ) . the molar Gibbs energy of the solid solution phase contains the Gibbs energies of the compounds. a 2+ )2 (O2. (a 2 + )2 (O 2.3 Vacancies and the concept of reciprocal reactions Let us consider the case of a binary oxide phase (A)2(B)3.. and (a 2 + )2 (Va)3 of the phase are required for the molar Gibbs energy 49 .)3 . Va)3 .5) Using the Compound Energy Formalism (CEF)[2-4]. 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.)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. The oxygen nonstoichiometry is denoted “O3-δ”.)u β + tRT yar ln yar + ybq ln yar + EGmss ( ) (3.2.7) Once again the molar Gibbs energies of all the 4 endmember compounds (a3+ )2 (O2.)u + ybq °G (b q )t (O2. R=8. a 2+ )2 (O2.2. and B denoting the anion sublattice.Va )3 ( = ya3+ yO2. the charge neutrality criterion is no longer obeyed by an anionic sublattice that is completely filled with oxygen. 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.

Va)3 approximating its overall Gibbs energy for Δ°Grec > 0 and Δ°Grec = 0. Va)3 is a reciprocal phase[4].2. the reference should favorably be a highly charged compound. for instance oxygen nonstoichiometry data. included.Method of the phase. is theoretically obtained by mixing equal amounts of either (a3+ )2 (O 2. a 2+ )2 (O2. 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.)3 .1. 3.2.)3 .Va)3 . thus far off neutral compositions that can really exist. a 2+ )2 (O2. and its Gibbs energy can be optimized with experiments that are related to the reduction of the phase.. 50 .2.)3 with the reduced compound (a 2+ )2 (2 3O2. The 2+ charged center composition of the square.1 that is redrawn from Hillert[4]. Va)3 the 6+ charged compound (a3+ )2 (Va)3 is chosen as reference..1 The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . As the chosen molar Gibbs energy of the reference is unlikely the true value. but a line of neutral compositions connects (a3+ )2 (O2. Fig. It thus can exist. 3. denoted with R. and (a3+ . The composition square of the phase can be seen in Fig. However.. The three other endmembers are charged and cannot exist. denoted with A in Fig. (a3+ a 2+ )2 (3 2O2. 3. For the example of the reciprocal solid solution phase (a3+ .3 2 Va)3 . A system that obeys this relation is called a reciprocal system. plotted above the composition square. a 2+ )2 (O2. with the neutral line and the reduced compound. the only neutral endmember is (a3+ )2 (O2.)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 and the reference (a 3+ )2 (Va)3 are fixed. the Gibbs energies of the remaining endmembers are significantly different for Δ°Grec > 0 and Δ°Grec = 0. Va)3 at very low temperatures (to make the configurational entropic contribution negligible). Va)(c 2 + . and oxygen partial pressure. c3+ . In Fig. and without excess terms for the Gibbs energy is visualized in Fig. as long as these endmembers are charged and away from the existing composition range of the phase. c 4 + . the Gibbs energy surface is flat and no tendency of demixing of A exists. b 2 + . On the other hand.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[5] such as (A)(B)O3-δ perovskite with a complex sublattice formula. for instance (a 3+ . 3. a 2+ )2 (O2. Anyway. This is not a problem for the description of a reciprocal oxide phase. Va)(O 2.1 (page 50) only the edge of this plane is seen as bold line. 51 . 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.) 3 − °G ( a 2+ ) 2 (Va)3 (3. and the theoretic compound A will tend to demix to (a3+ )2 (O2.Method The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . 3. Δ°Grec is positive. when the Gibbs energies of the endmember (a 3+ )2 (O 2. Note that in order to obtain the same Gibbs energy of the reduced compound R for Δ°Grec > 0 and Δ°Grec = 0. it is legitimate to define Δ°Grec = 0.2.)3 and (a 2+ )2 (Va)3 by only slightly oxidizing or reducing it. and no experiments define a proper value of the reciprocal reaction parameter.1 (page 50) and approximates the whole Gibbs energy of the phase. the Gibbs energy surface is curved. d 3+ . 3. Va)3 for a Cr-doped LSM perovskite as a function of composition.) 3 − °G ( a 3+ ) 2 (O 2.)3 − (a3+ )2 (O 2. the true surface shape of a reciprocal oxide phase with charged endmembers is not known.2.. For this purpose model parameters of the reduced and oxidized compounds are optimized with experimental information on charge carriers.2. site fractions and oxygen content. temperature.. if Δ°Grec is zero.8) If Δ°G of the reciprocal reaction. d 4+ .)3 − (a 2 + )2 (Va)3 : Δ °G rec = °G ( a 3+ ) 2 (Va)3 + °G ( a 2+ ) 2 (O 2. As no tendency of demixing was reported for the nonstoichiometric oxide solid solutions that are treated in this study.

Saunders. Calphad.O.Method 3. T. 81-87. A. Hillert. 9(2).P. 5. J. 30. 52 . Acta Metall. 6. Jansson. 437-445. B. 161-76. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.J. pp. N. Cmpd. 2. Jansson. Elsevier Science Ltd. 479 p. Calphad Calculation of Phase Diagrams. 4. Gauckler. Alloy. B. L. Hillert.3 Optimization of model parameters The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc[6] database system. Hillert. Z. B. pp. 2001. Ivas. 1988. A. Sundman. M. 1.-O. The Thermo-Calc databank system. 2006. 33-41. 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. Metallkd. Vol. B. Grundy. 153-90.. References 1. Jansson. Andersson. J.. B. pp. This weighting process is based on the accurate assessment of experimental thermodynamic and phase diagram data. 3. 34.F. pp. Miodownik.. Povoden. 79(2).N. Application of the Compound-Energy Model to Oxide Systems. The Compound Energy Formalism. Pergamon Materials Series.. J. Andersson. Calphad. Sundman. 1985. pp. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously. E. Calculation of Defect Chemistry Using the CALPHAD Approach. M. 320. M. 1998. B. 1986. The program minimizes the sum of squared errors between calculated and experimentally determined phase diagram and thermodynamic data. A. Sundman. Guillermet. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers.

and power-generation capability. 353-62. However.. Nonstoichiometry of eskolaite (Cr2+xO3) is described using the compound energy model.Thermodynamic assessments 4 Thermodynamic assessments 4. due to the high operating temperature (>1173 K). and the liquid is described using the two-sublattice model for ionic liquids. which block active sites as well as pores.1 Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research E.J.% 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.1.% Fe and 1 wt.% Cr. For the planar design SOFC. Phase Equilib. A comprehensive compilation and evaluation of experimental and thermodynamic data for the Cr-O system is presented and. Microstructural analyses of the cathode of SOFC show the formation of Cr2O3 and (CrMn)3O4. A.1 Technology SOFC offers high fuel conversion efficiencies and. 2006. Diff. Gauckler J. 4. Loss of performance caused by the migration of Cr originating from the alloy interconnect is well documented by several investigators. ceramic and metal interconnect materials have been tested and evaluated over the years. Namely a Cr5Fe1Y2O3 oxide dispersion strengthened alloy with the composition 94 wt. 5 wt. pp. 27. Cr3O4 is described as a stoichiometric compound. low manufacturing costs and high thermal conductivity[1]. Povoden. and L. Also the magnetic transition in Cr2O3 and the oxygen solubility in Cr are modeled. 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. Meanwhile the use of Cr-based alloy interconnect materials has gained popularity due to their relative ease of fabrication. a consistent set of thermodynamic model parameters is optimized based on new experiments. thus substantially reducing the triple- 53 . by application of the CALPHAD method.N. combined heat. Grundy.

1.1.1 Special points in the Cr-O system Eutectic Melting of Cr2O3 in Eutectic composition. 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. Eskolaite (Cr2O3) is the dominating stable oxide phase over a wide temperature range.Thermodynamic assessments phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. Table 4.1.[6] experimental Bunting[7] experimental air. 4. tectic T (K) ----T (K) ----Reference Kanolt[4] experimental Wilde and Rees[5] experimental McNally et al.1. X(O) ----Cr3O4 detected ----Stability range Mono- of Cr3O4. Results of special points in the Cr-O phase diagram from several studies are summarized in Table 4. These authors document the existence of a large miscibility gap between the metallic and the oxide melt. T (K) T (K) 2257 2317 2603 ---- 2543 ± 25 -- 54 .2 Experimental data Phase diagram data: Experimental investigations of phase diagrams in the Cr-O system were made by Ol’shanskii and Shlepov[2] and Toker[3].

499 0. who measured T = 2543 ± 25 K also in air.[13] 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.513 0. Grube and Knabe[8] found that 1 wt. Lam[9] reported the existence of molten chromium with oxygen impurities of 1400 ppm at T = 2133 K. Mc Nally[6] measured a melting temperature of 2603 K in air using an induction furnace. calculated Note: Itallicized data were used for optimization The melting temperatures of eskolaite in air reported from Kanolt[4] and Wilde and Rees[5] can be discarded as being too low. experimental Johnson and Muan[12] experimental Degterov and Pelton[39] calculated Kowalski and Spencer[40] calculated Taylor and Dinsdale[41] calculated Toker et al. The question of the existence of a crystalline Cr3O4 phase was discussed controversially by several authors. This value significantly deviates from the result of Bunting[7]. Microstructures of a quenched 55 . The monotectic reaction of Cr (bcc) metal and liquid was found at T = 2083 K by Grube and Knabe[8] and by Ol’shanskii and Shlepov[2].% Cr2O3 lowers the melting point of metallic Cr from T = 2163 K to between T = 2043 K and 2063 K.496 0. whereas Toker et al. Concerning the pure Cr-O system.[13] experimental This work.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[2].523 0. Ol’shanskii and Shlepov[2] and Johnson and Muan[12] did not find Cr3O4 up to the eutectic temperature of chromium oxide. Investigations made by Hilty et al.Thermodynamic assessments --2571 ---2539 1933 1918 1941 1929 1937 1938 ± 2 1938 0.[10] and Hook and Adair[11] led them to postulate the existence of a crystalline Cr3O4 phase in the Cr-Fe-O system.497 0.52 0.

[17].Thermodynamic assessments chromium melt with maximum oxygen impurities of about 2930 ppm lately investigated by Lam[9] document an inner Cr3O4 phase and an outer Cr2O3 phase in dispersed oxides in large chromium grains and grain boundaries. The independent results of corrected cell potentials of the two measurement series are excellent. Pehlke et al. 1273 K. Davies and Smeltzer[16] determined log( pO2 ) values of Cr2O3 at T=1173 K. Novokhatskii and Lenev[15] studied the equilibrium of the reduction of Cr2O3 to Cr with hydrogen from T=1493 K to 1893 K. Thermodynamic data: Oxygen Potentials: Grube and Flad[14] 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.[13] 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. 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.[18]. causing transfer of oxygen through the cell. Applying the same technique as Pehlke et al. Appreciable sublimation of metallic chromium was not observed. At T ≥ 1573 K they were confronted with the loss of a quarter of Cr in the case of oxidation. and 1373 K. These authors used a flow method where thermal diffusion problems were suppressed by inserting corundum bushes into the reaction tube. Toker et al. as well as transport of oxygen ions from the cathode to the Cr/Cr2O3 anode. days for T < 1100 K. Disagreement between the emf results from Pehlke et al. The data are in close agreement with the gas-solid equilibrium measurements by Jeannin et al. Pugliese and Fitterer[19]. Holzheid and O’Neill[21] 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. as well as the importance of sufficient time to attain equilibrium. thus at these temperatures log( pO2 ) values were determined solely from the reduction of Cr2O3. that is. This indicates that the first phase to crystallize on solidification is Cr3O4 giving strong evidence for the stability of this phase. using an electrochemical cell with a calcia-zirconia electrolyte and a Fe/FeO reference electrode.[17] used two separate series of emf measurements employing the solid oxide electrolyte galvanic cell technique from T = 1148 K to 1548 K. Thus in this study the authors accept the findings of Toker et al.[13] and Lam[9].[17]. and Tretjakow and Schmalzried[20] were assigned to possible electronic conduction in the zirconia electrolyte used by the latter authors. The obtained 56 .

heat Contents. Heat Capacities.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[22] and a very high temperature gas-mixing study of Toker et al. The latter authors measured a consistent data set of heat capacities of synthetic eskolaite from T = 1.20 ×10−3 T − 3.17 ± 0. Resulting Cp data correspond nicely to the most recent calorimetric results from Klemme et al.37 J mol-1 K-1 at T = 298.43 K.53 + 2.15 K Chase et al. Bruce and Cannell[24] applied a two-dimensional temperature wave method using a single crystal of Cr2O3 to calculate specific heat in the temperature range 290.4 % for Cp (20 K < T < 200 K) and 0.3) For ° S298K (Cr2O3) Chase et al.1. 4. and entropies: Anderson’s[23] calorimetric data set of Cp-values lacks detailed documentation of the experimental procedure.1.53T + 1. Uncertainties of 0.2 results in C p = 28.[25].2) Temperature derivation of Eq. data presentation. and fitted the data to the heat of diffusion equation that considers some material properties employing a least-mean-squares fit.56 K. Documentation of the experiments.736 ×105 T −1 − 9759 (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 . and fitting procedure are worked out very carefully.1. The accuracy of this study is evident from excellent data reproduction by performing two runs in the entire temperature range. who calculated ° S298K (Cr2O3) = 81.1.68 ≤ T ≤ 323.1) yielding ° H T − ° H 298K = 28. For Cp(Cr2O3) = 120.[27].[13].[26] relied on the calculated results from heat content measurements performed by Kelley et al.736 ×105 T −2 (4.5 K to 340 K with mean increments of 0. 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 ° (4.10 ×10−3 T 2 + 3.[26] relied on the results from Anderson[23].7 % for Cp (T < 20 K) were estimated.

Shirokov[30] estimated Δ f. Mah[32].3 J K-1 mol-1 from their measurements.[26] evaluated Δ f.el° H 298K (CrO) = –305. Shirokov[30] estimated ° S298K of a metastable CrO phase to be 46.72 kJ mol-1 from Wagman et al.74 ± 1.el° H 298K (Cr2O3) = –1128. The latter authors proposed a 58 . 4. For the calculation of Δ f.[28] adopted their ° S298K (Cr2O3) value from Wagman et al.5 kJ mol-1 (el=elements) by applying a calorimetric technique. Ramsey et al.el° H 298K (Cr2O3) = –1128. This procedure was critically documented by other authors. Some difficulty caused by moisture adsorption was encountered in weighing the combustion products.86 J K-1 mol-1. Degterov and Pelton[39] reassessed the CrO-Cr2O3 subsystem for the molten slag database using a modified quasi-chemical model for the liquid phase. Kowalski and Spencer[40] used the associated solution model for the liquid phase based on the experimental data used by Taylor and Dinsdale[41]. who calculated ° S298K (Cr2O3) = 85.[37] 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[2].4 kJ mol-1 by evaluating emf data from Holzheid and O’Neill[21]. Klemme et al.1 J K-1mol-1 by reevaluating emf data from Holzheid and O’Neill[21]. Klemme et al. and thermodynamic estimates for CrO from Shirokov[30].el° H 298K (Cr2O3) the heat content data given by Kelley et al. Dellien et al. calculated Δ f.98 ± 1.Thermodynamic assessments functions.42 kJ mol-1. while Dellien et al.[25].1.[33] used heat capacity and entropy data from tabulations of Coughlin[34] to obtain Δ f.[28] adopted Δ f.8 ± 2.4 kJ mol-1 from several earlier studies.7 ± 8. thermodynamic data for Cr-Cr2O3 from Fromm and Gebhardt[38].el° H 298K (Cr2O3) =–1140.[25] recommended Δ f.[27] were used.[29].el° H 298K (Cr2O3) = –1139. Enthalpies of Formation: Roth and Wolf[31] found Δ f.[25] recommend ° S298K (Cr2O3) = 83. which is in good agreement with an early finding by Bunting[7] who measured T = 2543 ± 25 K.7 kJ mol-1. Chase et al.[29]. Klemme et al.4 kJ mol-1 for metastable CrO.2 ± 0. Their calculated liquidus temperature of Cr2O3 in air is T = 2571. for example.el° H 298K (Cr2O3) = –1122.el° H 298K (Cr2O3) = –1134.16 K.el° H 298K (Cr2O3) = –1125. This was circumvented by heating the combustion products to T = 1323 K.3 Previous assessments of the Cr-O system Banik et al. using a bomb calorimetric combustion technique at 1323 K and 30 atm oxygen pressure. Navrotsky[35] cited Garrels and Christ[36] for Δ f.06 kJ mol-1.

There is a large uncertainty concerning the exact melting point of Cr2O3. Eskolaite shows an antiferromagnetic to paramagnetic transition at T = 305. which are the two-sublattice ionic model for the liquid and the compound energy model for the Cr2+xO3 phase. especially as their miscibility gap does not close on increasing temperature. and only few thermodynamic data of the Cr3O4 phase and the liquid phase exist. and the temperature of the monotectic reaction of Cr(bcc) and liquid between the assessments of the Cr-O system.4) 59 .1. 4. Their calculated values for the enthalpy of formation and the entropy of Cr3O4 are in agreement with an estimate done by Chipman[42].[27]. The use of six parameters for the description of the Cr3O4 phase is somewhat incommensurate with the scanty experimental information of this phase. This is reflected by significant variations of the position of the eutectics. Taylor and Dinsdale[41] fitted Cp data from Anderson[23] close to the antiferromagnetic to paramagnetic transition and data from Chase et al. the stability field of Cr3O4.Thermodynamic assessments phase diagram in good agreement with the experimental data obtained by Toker[3].1. Kelley et al. Experimental information on phase relations for their assessment was taken from Ol’shanskii and Shlepov[2]. 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. and Grube and Knabe[8]. Toker[3]. 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. space group R3c . The magnetic properties of eskolaite can be described using a magnetic ordering model proposed by Inden[43]. The heat capacity of Cr3O4 was taken as 7/5 times the nonmagnetic value for Cr2O3 according to Neumann and Kopp’s rule.[26] at elevated temperatures as a sum of magnetic and nonmagnetic contributions.5 K. using the same thermodynamic models as the authors use in this work. and simplified by Hillert and Jarl[44]. In this model.4 Thermodynamic modeling Solid phases: The crystal structure of eskolaite is α-Al2O3 type.

1. This means that reduction is accomplished by the formation of interstitial Cr3+ and not by the formation of oxygen vacancies.7) 60 .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 = (4.5 and 4.[46]. 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. 4. however. the latter because of the large size of Cr2+.28.1.6). Inserting this ' into Eq.Cr3+)2 (Cr3+.1. which is in agreement with Young et al.Va)1 (O2-)3 can be modeled using experimental data from Matsui and Naito[45]. and τ = T/Tc. To explain their experimental results Matsui and Naito[45] proposed a defect reaction that leads to the same proportionality. it is important to submit the experimental data to a defect-chemistry analysis. 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. Tc and β are both dependent on the composition. Both are unlikely: the former because it is unlikely to get Cr4+ on reduction.Thermodynamic assessments where β is a parameter related to the total magnetic entropy.1. their equation violates the fundamentals of defect chemistry and must be rejected in favor of the defect reaction given above (Eqs.6) ' Assuming small defect concentrations all concentrations except [CrCr ] and [Cri••• ] are ~ 1 and ' can be ignored. The magnetic parameter p equals 0. Tc is the critical temperature for magnetic ordering. Due to charge neutrality the relation [Cri••• ] = 3[CrCr ] must hold.1. When modeling nonstoichiometry in an oxide phase. and Cri•••• giving a slope of pO −3 20 2 . The defect chemistry of Cr2+xO3 with the sublattice occupation (Cr2+. 4.6 gives the proportionalities [Cri••• ] ∝ pO2 −3 16 and [CrCr ] ∝ pO2 −3 16 . The following other interstitial defects could be assumed: Cri•• giving a slope of pO2 −1 4 .1.

the present authors believe that the different slopes are caused by a competing defect reaction. Cr3+ → Cr2+ + Cr4+. Fig. for example charge disproportionation.1. The three other corner compositions present charged compounds. 4.1 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 corner Cr3+:Va:O2corresponds to stoichiometric Cr2O3.Thermodynamic assessments ' leads to a proportionality of [Va •• ] ∝ PO2 −1 6 and [CrCr ] ∝ PO2 −1 6 . as it would make the description quite complex. As the most reasonable way to model reduction is to use the reduced neutral endpoint 61 . The present authors didn’t consider this by their defect chemistry model.1 is a graphic representation of the model the authors use to describe the oxygen nonstoichiometry of eskolaite.[46]. 4. In contrast to Matsui and Naito[45] who explain this assuming that neutral Cr forms interstitially. The low nonstoichiometry data from Matsui and Naito[45] show a different slope than their higher nonstoichiometry data. similar to the case of LaMnO3 perovskites[47]. where each corner of the composition square represents a °G parameter. Only compounds along the neutral line can exist on their own. Also the defects cannot explain the electrical properties measured by Young et al.1. This slope does not correspond O to the experimental findings of Matsui and Naito[45]. Fig.

°G of the 3+ charged endmember (Cr3+)2 (Cr3+)1 (O2-)3 is chosen as reference and given the value °GCr3+ :Cr3+ .10 are listed in Table 4.1. This is done by using the two equations for the stoichiometric and the reduced endpoints.63-64.Thermodynamic assessments (Cr2+)2 (Cr3+2/3Va1/3)1 (O2-)3. by choosing an arbitrary reference.1.2.1. one has to find functions of °G of three charged corners expressed solely in terms of the neutral compositions.1. 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. Then the reciprocal relation reads ° G Cr3+ :Cr3+ + °G Cr 2+ :Va = °G Cr3+ :Va + °G Cr 2+ :Cr3+ = ΔGr (4. and by defining a reciprocal reaction giving four equations with which all °Gs at the corners can be expressed. 62 .1.8 to 4.8) 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.1. 4.10) This means that without introducing interaction parameters one gets an ideal description between Cr2O3 and Cr2+xO3. pp. which leads to ° G Cr3+ :Cr3+ + °G Cr 2+ :Va − °G Cr3+ :Va − °G Cr 2+ :Cr3+ =0 (4.1. 4. labeled A in Fig. The expressions for all °Gs at the corners resulting from Eq.1.

= 121000 Solid Cr (bcc_A2) (Cr)1 (O. Cr 3+ ) 2 (Cr 3+ .2923T 3 Cr O3 SER SER GCr 22+ :Va:O 2.Va q.5 p = 0.Va)1 (O 2.+ qyVa .= 0 LCr3+ :O2.H0 4050.Va q.− 3H Cr − 3H O = GCRO0 + 1 GHSERCR [49] − 5.Thermodynamic assessments Table 4.0 S298 23.− 2 H Cr -3H O = GCR2O3 3+ Cr 3 SER SER GCr 2O:Cr3+ :O 2.− H Cr = 2GCR_L[49] + GCR2O3_L − 3GCR1O1_L L SER SER GCr3+ :O2.008 CrO ° Cr1O SER SER GCr:O1 − H Cr − H O = GCR1O1 Cr2O3 (Cr 2+ .− 3H Cr − 3H O = GCRO0 − 2 GHSERCR [49] − 5.0 Cr3O4 ° Cr3O SER SER GCr:O 4 − 3H Cr − 4 H O = GCR3O4 Functions 63 .. q = 2 yCr 2+ + 3 yCr3+ ° ° ° ° L SER GCr 2+ :Va q...2923T 3 p = 0.Va)3 ° ° bcc SER GCr:Va − H Cr = GHSERCR [49] bcc SER SER GCr:O − H Cr − 3H O = GHSERCR + 3GHSEROO[49] + 243T 0 bcc Cr:O.− 2 H Cr − 3H O = GCR2O3_L L SER SER GCr 2+ :O2.− 2 H Cr − 2H O = 2GCR1O1_L Reference Cr (bcc_A2) 1 2 Mass 51.52 mol O2 0 LCr 2+ :O2.Cr 3+ ) p (O 2.4 β = −0.Va q.543 102.6 β = 3.− H Cr = GCR_L[49] L SER GCr3+ :Va q.Va L = −709542 Tc = −311.996 15.2 Thermodynamic description of the Cr-O System Element Element Cr O Liquid (Cr 2+ .)3 ° ° ° ° Cr 3 SER SER GCr 2O:Va:O 2.999 H298 .)q p = 2 yO2.28 Tc = 308.1.− 3H Cr − 3H O = GCR2O3 + GHSERCR [49] 3+ Cr O3 SER SER GCr 22+ :Cr3+ :O 2.0 4341.

and one can reduce the number of parameters to only two.Vaq-)q is chosen. The descriptions for solid and liquid chromium metal and gaseous O2 are from Dinsdale[49]. Its heat capacity is given by Neumann and Kopp’s rule.5GHSEROO[49] + 255269 − 53.31451 J mol-1 K-1. 4. As the experimental data on the liquid phase are scarce. The oxygen solubility in solid Cr(bcc) can be described by an interstitial solution model of the form (Cr)1(O.2 (next page) is a graphic expression of the model. K. The Cr3O4 phase is based on the eskolaite phase. The sublattice occupation (Cr3+.4T Note: All parameters are in SI units: J. Ionic liquid: The two-sublattice ionic liquid model[50.8T ln T −4. Metastable CrO is described in the same way. the latter constraint is not needed in the model. 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. 64 .5GHSEROO[49] + 339673 − 121.56T − 119.5GCR2O3 − 0. and gaseous O are from Dinsdale[49] In contrast to Taylor and Dinsdale[41]. the number of parameters is kept as low as possible.76T GCRO0 = 108305 + GCR2O3 + 2 GHSERCR [49] 3 GCR2O3_L = GCR2O3 + 439078 − 169T GCR1O1_L = 0. Pa: R = 8.Va that must of course be negative.97 × 10-3T 2 + 1050000T -1 GCR1O1 = 0.51] is selected to describe the ionic liquid.1.Thermodynamic assessments GCR2O3 = −1164542 + 728. 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.5GHSEROO[49] + 280045 − 93.. liquid Cr. Fig. 0 LCr2+ :O2. For the optimization of model parameters. 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.5GCR2O3 − 0.Cr2+)p(O2-.5GCR2O3 − 0.Va)3. Parameters for solid Cr. With this expression one is able to obtain reasonable results for the liquid phase using the positive interaction parameters. where each corner of the composition square represents a °G parameter of the liquid phase. literature data from Caplan and Fraser[48] are used.. mol.Va and 0 LCr3+ :O2.82T GCR3O4 = 1.Va that are required to give the miscibility gap.

1. 4. In this model description of the liquid phase metallic Cr-liquid can be described by both the corners Cr2+:Va and Cr3+:Va. 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[53]. Hallstedt and Gauckler[54] recently reoptimized the Cu-O liquid. for example +600000 as given to °GCu2+ :Va by Hallstedt et al. 4. The eutectic temperature is mainly determined by the value of the corner Cr2+:O2-.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.[52] in his original assessment of the Cu-O system.1. obtaining the parameter °GCu2+ :Va from the reciprocal relation and giving it a reciprocal energy of 0.Thermodynamic assessments Fig. The liquid composition changes along the hyperbolic curves in Fig. This considerably improved the description of the Cu-O liquid and removed the inverted 65 . Cr3+:Va must be metastable compared to Cr2+:Va. A special feature of the Cr-O system is the occurrence of a eutectic very close to the composition of CrO.2. One way of doing this would be to simply say that Cr3+:Va equals Cr2+:Va plus a large positive term. The °GL of liquid Cr is taken from Dinsdale[49]. One derives the °GL functions of the oxide compositions (Cr3+:O2-) and (Cr2+:O2-) from the eskolaite phase.

[25] close to the antiferromagnetic to paramagnetic transition temperature. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.16 data from Holzheid and O’Neill[21] were used. Thus metallic liquid is given by the corner L parameter °GCr3+ :Va is obtained by the reciprocal reaction given as ° G LCr2+ :Va .Thermodynamic assessments miscibility gap found at high temperatures in the original assessment[52]. The melting temperature of eskolaite in air was taken from Bunting[7].The ° G L 3+ Cr :Va = 2 °G L 2+ Cr :Va + °G L 3+ Cr :O2- − 3 °G L 2+ Cr :O2- + ΔGr .1.[13].1. The data used were heat content data from Kelley et al. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously.[13]. 63-64). In the next step the authors optimized the nonstoichiometry of Cr2+xO3 using data from Matsui and Naito[45]. experimental data on the liquidus at the oxygen poor side from Toker et al. with low relative weight.5 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Cr-O system is given in Table 4. Finally the solubility of O in solid Cr was optimized using data 66 . These parameters were then kept fixed during the rest of the optimization.el° H 298.2 (pp.[18] and Toker et al. The program minimizes the sum of squared errors between the calculated and experimentally determined phase diagram and thermodynamic data. ΔGr = 0 (4. and. using experimental phase equilibria data from Toker et al. The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc[55] database system. They assessed Cr3O4 and the liquid simultaneously. To determine the parameters describing the enthalpy and entropy of Cr2O3 log( pO2 ) data from Jeannin et al.[27] and Cp data from Klemme et al.[25] at T = 290 K and from T = 335 K to 338 K with a low relative weight. high temperature emf data from Holzheid and O’Neill [21] .[13]. and experimental data on the liquidus at the oxygen rich side of the miscibility gap from Ol’shanskii and Shlepov[2].1.11) 4.16 and ° S298. In principle. 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. An identical strategy is employed here. The authors optimized Tc and β using Cp data from Klemme et al. Δ f. The first parameters to be optimized were the Cp-parameters of Cr2O3.

4. 4. 4.6 Results and discussion Phase diagram: The calculated phase diagram with oxygen isobars is shown in Fig.1. 54-55) values that were used for our optimization are written in italic letters.4 (next page).1. 67 .1. logarithmic) given.Thermodynamic assessments from Caplan and Fraser[48].1. 4.3 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. Fig.1.3. In Table 4.1 (p.

2 68 . 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.497 it decomposes in a peritectic reaction at T = 1973 K forming Cr2O3 and liquid.4 Enlargement of the calculated Cr-O phase diagram close to the CrO composition.1.[13] and an earlier experiment from Ol’shanskii and Shlepov[2] is slightly deviating from former optimizations.497. 4. For the monotectic temperature of the reaction of Cr (bcc) and liquid the present authors calculate T = 2117 K. and for the eutectic one gets T=1938 K at a mole fraction of oxygen of 0. Fig. The calculated liquidus temperature of eskolaite in air is T = 2539 K. Cr3O4 is formed at T = 1918 K by the eutectoid reaction Cr2 O3 + Cr + 1 2O2 → Cr3O4 . At a mole fraction of oxygen > 0. 4.5 (next page) shows the calculated oxygen potential phase diagram of the Cr-O system with experimental log( pO ) data included. with experimental data and oxygen isobars (Pa.1. in good agreement with the measurement from Bunting[7].Thermodynamic assessments Fig.

1. Fig. 4.1. The shape and size of the miscibility gap is speculative due to the lack of experimental data.6 Stability of Cr3O4 in the log( pO2 ) versus temperature diagram 69 .5 Calculated oxygen potential phase diagram of the Cr-O system. with experimental log( pO2 ) data as a function of temperature from different studies The experimentally determined phase stabilities from Toker et al.Thermodynamic assessments Fig. The stability of Cr3O4 is shown in the log( pO2 ) versus temperature diagram in Fig.[13] are particularly well reproduced by the authors’ optimization.1. 4. 4.6.

1.8 (next page). If the commonly used – however grubby – notation “Cr2O3-δ” is applied.% at T=1938 K.Thermodynamic assessments The solubility of oxygen in Cr(bcc) is shown in Fig.1.4. Fig. 4.08 at.7 Calculated oxygen solubility in Cr(bcc) with experimental data and oxygen isobars (Pa. 4. but it results simply from the extrapolation of experimental data from Matsui and Naito[45] 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 4.7.098 at T = 1918 K. 70 .1.1. The comparison of the calculated nonstoichiometry in Cr2+xO3 with the experimental data by Matsui and Naito[45] is given in Fig. logarithmic) included For the maximum solubility of oxygen in Cr(bcc) one calculates 0. The cation overstoichiometry resulting from the presented optimization might seem somewhat high. 4. the total charge of Cr is given by 6+2δ. The maximum calculated δ = 0.

Thermodynamic assessments Fig. 71 .1.8) and leads to the reduced neutral endpoint being too stable at low temperatures. Therefore. 4. 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. 4.1. The data at low oxygen nonstoichiometries were not used.8 Optimized nonstoichiometry of Cr2+xO3 with the only available experimental data from Matsui and Naito[45] included. Optimization of a temperature dependence is represented by dotted lines. Solid lines result from our accepted optimization without considering temperature dependence. as the introduction of an additional defect species would be required to reproduce these. The low nonstoichiometry data show a different slope than the higher nonstoichiometry data. 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 . The solid lines correspond to the optimization that is accepted in this work. Obviously the calculated results show a temperature dependence that is significantly stronger compared to the experiments.

1. Cp. For Δ f.9) are well represented by our assessment.9 Comparison of calculated heat capacities of Cr2O3 with experimental data For the magnetic parameter β we calculate 3. Fig. and ° S298K = −79 J K -1 mol-1 based on the estimates of Shirokov[30].el° H 298K (Cr2O3) we calculate –1123 kJ mol-1.685 kJ mol-1.1. 4. 72 .555 J K-1 mol-1.el° H 298K (Cr3O4) we calculate –1402 kJ mol-1.0. These values for Cr3O4 deviate significantly from the results of Taylor and Dinsdale[41] who calculated Δ f ° H 298K (Cr3O4) = –1447. and ° S298K (Cr3O4) = 150.Thermodynamic assessments Thermodynamic Data: The heat capacities. and for Tc we get 308.el° H 298K = −306 kJ mol-1 . which is in particularly good agreement with the data from Ramsey et al. For Δ f. 4. For a metastable CrO phase we calculate Δ f.6. which is very close to the results from Holzheid and O’Neill[21]. and for ° S298K (Cr2O3) we get 85 J K-1mol-1.[33]. and for ° S298K (Cr3O4) we get 175 J K-1mol-1. of the solid Cr2O3 phase (Fig.

The system palladium–chromium. 1978. Laboratory furnace for studies in controlled atmospheres. Ceram. pp.S. 91(3).L. 42(7). it must be kept in mind that experimental data on the liquid miscibility gap are largely missing. Grube.1. Pennsylvania State University. J. Brit. 793-804 (in German). 2000. pp.D. Ribbe. Melting and casting of high purity chromium with controlled oxygen content. Res. V. J. pp. 491-93. pp. P. 123-55. 4. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.T.C.K. Thesis. J. I. Trans. Y.I. Wilde..N. Dokl. 203(2).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. 947-49.W. 6(6). Bur. T.P. W. 99. S.H. Nauk. and that a large variation of the measured melting points of eskolaite exists. United States Patent 6039788. Lam. 7. 73 . Sci. Ramprakash. R. Min. pp. K. Soc. J. 3. N. The ternary system MgO-Al2O3-Cr2O3. D. E. Akad. W. pp. References 1.I. 1931.P.N. Equilibrium phase relations and thermodynamics for the systems Cr-O and Fe-Cr-O in the temperature range 1500 to 1825 °C. 9. 8. Eng. Solid State Ionics. R.K. F. 1953. Forgeng. However. R. Ol’shanskii.. pp. Stand.Y. Sistema Cr-Cr2O3. Folkman. 42(11).Thermodynamic assessments 4.F. 1936. Kanolt. Zhang. 253-68. 10. 1913. Peters. Nat. Wash. 1943. Acad. 315-18. McNally.. C. pp. 1955. Shlepov. Metall. Badwal. 1961. 561-64. Ceram. Phase equilibria in the system Cr2O3-Al2O3. 1997. 2. Knabe. R. Bunting. SSSR. G. 5. R. Toker..J. Am. J. 44(10). Elektrochem.. Hilty. 3. W. melting points of MgO in a N2 atmosphere and of Cr2O3 in N2 and in air atmospheres.. 297-310. Y. Deller. Rees. Foger. Melting points of some refractory oxides. 6. Oxygen solubility and oxide phases in the FeCr-O system. Z.

H. Pugliese. Metall. pp. T. Am. Pehlke. Z. Hook. A. 23. A.R. The heat capacities of chromium. Richardson. Elektrochem. Soc. Geochim. 15(9). Smeltzer. 396-402 (in German). 1974. 1968. 1827-31. Metall. 22.. Schnelle. 19. J. O’Neill. Ceram. Adair.S. 1278-83. Jacob. Novokhatskii. Jeannin. L. and Cr2O3 at low temperatures and derived thermodynamic properties. J. Phase diagrams for the systems Si-O and Cr-O. Soc. 230(6). Berich.. 377-89 (in German)... Specific heat of Cr2O3 near the Neel temperature. Schmalzried. pp. 59. Radzilowski. Aime.M.W. Thermodynamic properties of Cr2O3 and FeCr2O4 at high temperatures. R. Mineral. pp. F. B. E. The thermodynamics of spinel phases (chromite. F. Ac. Johnson.T. 21. 15. 1991. N.D. 17.. 14. ferrite. pp. Activities in iron–chromium alloys. Ac. Gmelin. Geochim. A. 2000. 74 . 430-33. 24.. 227(2).M. S. Soc.. Solid oxide electrolyte emf cell determination of the standard free energy of Cr2O3 and applications to chromium–bearing mineral systems. pp. Russ. Oxygen and metal activities of the chromium–nickel–oxygen system between 900° and 1100°C. 300-5. K. pp.H. 4451-59. Inorg. Metall. H. D.S. Equilibrium phase relations and thermodynamics of the Cr-O system in the temperature range of 1500 °C to 1825 °C. 48(7).E. aluminate). Bruce. Rev. Muan. 1997-2002. pp. chromous chloride and chromic chloride at low temperatures.. J.D. Ceram. Cannell. pp. pp. 1970. Darken. The formation and dissolution of chromium oxides in chromium. Activities and phase boundaries in the Cr–Ni system using a solid electrolyte technique. 488-91. 51(8). R. 69(5). Bunsen Gesell. Y. H. pp. Anderson. L. 1965. Tretjakow.S. C. 11(9).T. 20. 225-32. O’Neill. Cosmochim. Flad.. 1977. T. Am.N. pp.S. 121(4). Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites. 1963. Klemme. H. Soc. 124. G. FeCr2O4. J. Soc.E. C. A. M. 12. H. R. Toker. W.. R. Electrochem. Lenev. 833-45. 25. pp. J.Thermodynamic assessments 11. Chem. 1975. 18. 1964. pp. Cosmochim. 1966. 1977. pp. 39. G. Soc. Davies. chromic oxide. 59(3).D. Affinity and enthalpy of the solid solution in the system Cr-Ni. Holzheid. B.. The heat capacity of MgCr2O4. W. Trans. Trans. Mannerskantz. 1(7). Phys. Am. Fitterer. 1937. pp. The Cr-Cr2O3 oxygen buffer and the free energy of formation of Cr2O3 from high-temperature electrochemical measurements. R. A. 1078-80. 1995. Muan. 543-49. Mazandarany.Y. 16. L. 85. 1942. Metall. 1686-93. 22(2).A. 475-79. Electrochem. Aime. 13. Grube. J.

R. 103(2). 940-42.R. Soc. 32. 35. Z. Boericke. D. E. McDonald. 1973.. Gebhardt: Gases and Carbon in Metals.H. Nauk. Schmitt. W. Ac. Thermodynamics of the oxidation of chromium. Dellien. Navrotsky. P. J.A.B. W. 476-87. 17(6). I. 39. 410. 75 . 2. SSSR.P. Electrochem. Hall. 1996. 521-34 (in German). Shirokov. 270(4).M. Bangert. 1969. Thermodynamic properties of carbides of chromium.M. Chem.. 38. 34.. 31. A. Metal. S. 76(13).. A. Jr. 102. Wagman. J. 39. Berlin. Tables for elements 35 through 53 in the standard order of arrangement. Ettmayer. Rev.M. Kelley. molybdenum. Evans. and tungsten: thermodynamic properties. Downey.. Chase. Flurip. W. and CrO-Cr2O3-CaO systems. 819-32. Elektrochem. R. Chem. pp. Cosmochim. and standard potentials.. 14(Suppl. Heidelberg.3rd ed. CrO-Cr2O3-Al2O3. Springer Verlag.Thermodynamic assessments 26. pp.A.J. Coughlin. Christ: Solutions.. Heats of formation of chromium oxide and cadmium oxide from combustion calorimetry. Chromium. 1985.A. M. especially oxides at high temperature. 1976. 33. J. 37. Schumm. Bur. pp. 1940. 45-46 (in German). E. 644-45. Thermodynamic properties of chromous oxide.. 283-310.S. Data. 1976. Soc. Paper. pp. Phase Equilib.D. N. Selected values of chemical thermodynamic properties. 43 pp. Phys. 1954. Mines Tech.I. 36. Minerals and Equilibria. Halow. Mines Bull. L. D. J. Banik.G. Wolf. chemical equilibria. J. V.D.L. 1): pp. Janaf thermochemical tables . p.K. Pelton. T. 1944. Fromm. 71(10): pp. 46. 80 pp. Notes. Z. Mah. pp. E. Harper & Row. 30.M. 1956. Contributions to the data on theoretical metallurgy. R. S. B. pp..W. Ramsey.H. J. G. Metallkd. 1975. 1980. F. Hepler.N. Thermochemistry of chromium compounds. p.H. The heat of formation of chromium oxide. Lux. 29. A. 135-38. K. J. Garrels and C. Huffman. 27. New York. Thermodynamic consideration on the system Cr-Cr2O3. Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3. Roth. D. Davies. 3363-65. 662. U. I. D. Dokl. 28. NBS Tech. F. pp. C. Geochim.A. 542. A.. 76(3). Chem. Ref. Caplan. 1965. Degterov. Bailey. Syverud. 1954. Bur. Burr. N. Am. Akad. Parker.

19(3).A.W. Soc. Remodelling of the liquid.. 47. Existence of hypostoichiometric chromium sesquioxide at low oxygen partial pressures. B. pp. 180. 317-425. 1987. Gauckler. Calphad. Gauckler. Taylor. Burr: in Ductile Chromium. Cr-O and Cr-Ni-O systems using the ionic liquid and compound energy models. J. Calphad. Metall. Povoden. Gauckler. M. 46. Hallstedt. B. L.T.J.T. Thermodynamic reevaluation of the Cr-O. Risold. Dinsdale. pp. 1991. Sundman. Calphad. 483-99. Hallstedt. 354-66. 1957. Predicting miscibility gaps in reciprocal liquids. pp. Caplan. 41. 1955. Chipman. Iron Steel Inst. Jansson. pp. E. pp.W. Naito. Gerretson. pp. M. A. pp. Determination of chemical and magnetic interchange energies in bcc alloys. 33-41. 1978.J. D. B. J. Hillert. L. M. Modification of the two-sublattice model for liquids. 15(4). 49. Metallkd. Ag-Cu-O. 177-91. J. 54. Ågren. L. 227-38. M. 577-82.A. pp. Thermodynamic assessment of the copper-oxygen system. p. J. 1975. 599-605.Thermodynamic assessments 40.. pp. A thermodynamic assessment of the Ni-O. M. E. 50. Calphad. Matsui. Jarl. 136. 15. Young. D. Hillert. Dinsdale. Kowalski. 27(2). 109-19. Z. 48. AgO. Sundman. Grundy. Spencer. pp..N. 261-66. 2003. Fe-O and Ni-O systems: 229-43. T. ASM. Revision of the thermodynamic descriptions of the Cu-O. Nucl. Cleveland. J. Calphad. 51. Z. 1994. Ohio. 196. A. SGTE data for pure elements. 2(3). 1991. T. 2005. A. Calphad. J. M.J. 1995. B. J. 1985. 1994. Calculation of defect chemistry using the Calphad approach.R. 25(4). Bi-Sr-O. 78-82. A. 42. Atomic interactions in molten alloy steels. 76 . Trans. 16A. A. Inden. 134(9). 15(5). pp. 1985. A model of alloying effects in ferromagnetic metals. 2001. Ca-Cu-O and Sr-Ca-Cu-O systems. pp. Ivas.J.. 53.J. Phase Equilib. Bi-Cu-O. de Witt. The oxygen partial-pressure dependence of the defect structure of chromium(III)oxide. Sr-Cu-O. 52. Fraser.H. bcc and fcc phases.H. 44. J. 45. 43. 97-106. General treatment. 30.. P. 1990. 2257-60. K. Metallkd. Calphad. Electrochem.. B. 81(5). Sundman. I. pp. 66(10). B. Hillert. G. J. pp. A two-sublattice model of molten solutions with different tendency of ionization. Mater.

J. and Mn-Cr binaries from Grundy et al. B. 4. J.8 wt.N. The thermodynamic data of the pure elements are taken from Dinsdale[6]. Sundman. 9(2). The Thermo-Calc databank system. thus substantially diminishing the triple phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface[4]. Jansson. We are contributing to the understanding of the underlying thermodynamics of these processes by assessing the MnCr-O system using the CALPHAD approach. and the data for the Mn-O. and L. pp. a consistent set of thermodynamic model parameters is optimized for the Cr-Mn-O system based on experimental data. By application of the CALPHAD method.% Cr. 22. B. 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.Thermodynamic assessments 55.J.O.45 wt. and Lee [9] 77 .[5] 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. Povoden et al. pp. Also solid solutions of the phases (Cr1-yMny)2+xO3. Res.% Mn resulted in an improvement of short-term SOFC operation.[7]. 2006. 569-78.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials E. A. and 0.2.% Fe. 4. Povoden. Simner et al. Gauckler Int. and the liquid is described using the two-sublattice model for ionic liquids.[8].. 153-90. mobilization predominantly via the gas phase[3] 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. Cr-O. Andersson.2]. and (Mn1-yCry)1-xO are considered. However. Calphad. Mn2-yCryO3. 97.6 wt. Chromium manganese spinel MnyCr3-yO4 and its tetragonally distorted polymorph are described using the compound energy model.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. 1985. Mater. Relevance for solid oxide fuel cells is discussed. Grundy.

2. 4.4 (p. 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. show varying degrees of mutual solid solubility. β-hsm (βhausmannite) for the cubic and α-hsm (α-hausmannite) for the tetragonally distorted Mn3O4 endmember of the spinel solid solution.1. 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+[11]. The most prominent oxide phase in the Mn-Cr-O system is cubic chromium manganese spinel with the formula MnyCr3-yO4.2 (p. however all the binary oxides except pyrolusite (prl).3 (p. mgs for Mn1-xO (manganosite) with dissolved Cr.2. and 4. 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[10]. 80). esk for Cr2+xO3 (eskolaite) with dissolved Mn.2 Experimental Phase diagram data: Our calculated phase diagram of the MnOx-Cr2O3 system in air is shown in Figs. No new ternary phases are found in the Mn-Cr-O system. 80) shows the calculated phase diagram at pO2 = 1×10-4 Pa . Fig. and liq for the liquid phase. 4. 4. MnO2. Normal spinel is given by the formula [A2+](B3+)2O4.Thermodynamic assessments respectively.2. α-spl for tetragonally distorted polymorph spinel solid solution. 4.2. In this work we use the following abbreviations: β-spl for cubic chromium manganese spinel solid solution. bxb for Mn2O3 (bixbyite) with dissolved Cr.2. 79). bcc for chromium manganese alloy with bcc A2 structure. 78 .

2.2. 4.2 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. The gas phase was not included in the calculation. 4.1 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. The gas phase was not included in the calculation. 79 . Fig. with experimental data.Thermodynamic assessments Fig.

4. 80 .3 Mn rich part of the calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. 4. Fig.2.4 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 under strongly reducing conditions ( PO2 = 1×10-4 Pa ). with experimental data.Thermodynamic assessments Fig. showing the expanded stability field of β-spl + mgs.2.

3.42 at oxygen partial pressure >> 20000 Pa. next page). Their resulting phase diagram is in considerable disagreement with the findings of Speidel and Muan[12]. This value is in agreement with the result from Geller and Espinosa[16]. 80. 81 .2. 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. 4.15] 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. Their data are shown in Figs. The solubility limit of Cr in Mn2-yCryO3 is measured by these authors to be y = 0.2.[14. The Mn solubility in (Cr2-yMny)1+xO3 reported from Speidel and Muan[12] is significantly higher than it is found by Golikov et al. 4.[13] and Pollert et al. 79). Pollert et al. 4. They consider the solubility limit of Mn in (Cr1-yMny)2+xO3 to be negligible.[14]. p.14 at T = 1105 K in air.[17] 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. They find β-spl + α-spl + bxb coexisting in equilibrium at T = 1183 ± 5 K. p. and β-spl + esk + liq in equilibrium at T = 2243 ± 20 K.Thermodynamic assessments Speidel and Muan[12] 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. Pollert et al.[14] report a solubility limit of y = 1.2. 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. but it is lower than the findings from Speidel and Muan[12].2.2.[13] 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. p. They estimate a minimum temperature of T = 773 K for the stability of β-spl. 79 and 4. Golikov et al. Tanahashi et al.5.2.

β-spl in equilibrium with esk.2. each phase in the quenched specimens was subjected to electron probe microanalysis (EPMA). esk in equilibrium with β-spl.5). They report small solubility of Mn in (Cr1-yMny)2+xO3 at pO2 = 2×10-6 .[17] conclude that Mn is dissolved in cubic MnyCr3-yO4 in the form of Mn3O4. They found increasing Mn solubility in cubic MnyCr3-yO4 at oxygen partial pressure higher than 2 ×10-2 Pa . 4. and significantly increasing Cr solubility in cubic MnyCr3-yO4 with decreasing oxygen partial pressure (Fig. Phase relations were verified using X-ray diffraction. which increases slightly with increasing oxygen partial pressure. and 1873 K. From this result Tanahashi et al. In order to identify the equilibrium compositions.2. The compositions of β-spl are located on a line connecting MnCr2O4 with β-hsm in the ternary plot. As the compositions of mgs 2 solid solution are located on the line connecting Mn1-xO with CrO in the ternary phase 82 .5 Cr contents of β-spl in equilibrium with mgs. Experimental data are included.Thermodynamic assessments Fig. 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. 4. 1473 K. 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.

4. p.Thermodynamic assessments diagram. Fig. For the invariant three phase equilibrium mgs + β-spl + bcc Ranganathan and Hajra[19] measured the Mn content in bcc to be 25.2. 1173 K. 82).1 to 10-13 Pa (Fig.6). 83 . There are no data on oxygen nonstoichiometry of MnyCr3-yO4. Bobov et al. Also the experimental result on the three phase equilibrium MnO + MnCr2O4 + bcc from Ranganathan[19] is plotted.2.6 Ternary phase diagram of the system Cr-Mn-O with stoichiometric single phase equilibria (points). two-phase fields and three-phase fields. Dotted lines are tie lines. single solid solution phase equilibria (heavy lines).2. 4. and 1273 ± 5 K in the oxygen partial pressure range from 0.[18] investigated the composition changes of the two phase equilibrium β-spl + mgs at T = 1073 K. these authors conclude that chromium oxide dissolves in (Mn1-yCry)1-xO in the form of CrO.5. Three-phase field boundaries are denoted with thin solid lines. 4.2 cat.% at T = 1323 K performing an isopiestic experiment (Fig.

Tanahashi et al. Giving α-spl the formula [Mn2+](Mn3+. 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.4 for the formation of α-spl.Cr3+)2O4 this corresponds to a minimum concentration of [Mn3+] = 0.2.[11] investigated the martensitic α-spl → β-spl transition temperatures.2.2) (4. We recalculate this value using the most recently assessed Δf °GMnO [7] and Δ f °GCr2O3 [8] β-spl values at T = 1873 K giving Δ f °GMnCr2O4 = –66 ± 8 kJ mol-1. Tsai and Muan[22] experimentally determined compositions of coexisting MnyCr3-yO4 . From these data and the activities of CrO1. Samples with y < 1.2.MnyAl3-yO4 solid solutions formed from Cr2O3-Al2O3 mixtures at T = 1873 K. p.5AlO2 = AlO1.5CrO2 (4. 79). solid Cr and oxygen at T = 1873 K in the pO range from 2×10-6 to 1. This means that the Gibbs energy of formation of β-spl of the composition MnCr2O4 from its 84 .5 + Mn0.Thermodynamic assessments Holba et al. 4.5AlO2 and AlO1. which is equivalent to Δf G of 1 2(Δ f GMnCr2O4 − Δ f GMnAl2O4 ) . enthalpies and entropies of MnyCr3-yO4 samples annealed at T = 1723 K using X-ray analysis and DTA measurement.3) β-spl to be –10 kJ mol-1 at T = 1873 K. With decreasing Mn-content the temperature for the transition decreases (Fig.5 in Mn0.[20] derive Δ f °GMnCr2O4 = –958 ± 8 kJ mol-1 from liquid Mn.2.2.8 do not show Jahn–Teller distortion at room temperatures. and remain β-spl.5 + Mn0.5 in Mn0.5CrO2 obtained from a previous study[23] 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 (4.1) β-spl Using compiled Δf °GMnO and Δf °GCr2O3 [21] they calculate Δ f °GMnCr2O4 from its oxides to be –59 ± 8 kJ mol-1.

Tetragonally distorted spinel (α-spl): Pollert et al. Fig.7 Calculated Gibbs energy of formation of β-spl of the composition MnCr2O4 as a function of temperature. with experimental data and error bars.4 ± 10 kJ mol-1. unfilled symbols correspond to recalculated values. ΔΗ α β = 18810 J mol-1. 85 . Filled symbols correspond to originally reported literature data. Using other values for Δ f °GMnAl2O4 reported β-spl in the literature[25-27] leads to deviating Δ f °GMnCr2O4 of –34. 4.Thermodynamic assessments oxides using this calculation technique depends on the value of Δf °GMnAl2O4 .6 kJ mol-1 at T = 1873 K.1 kJ mol-1. [22] in the CoO- β-spl The spread of Δ f °GMnCr2O4 values resulting from different studies and our recalculations is shown in Fig.[15] present thermodynamic data on the transition of α-spl to β-spl. Tsai and Muan[22] chose the value determined by Lenev and Novokhatskiy[24].2.6 kJ mol-1 β-spl giving Δ f °GMnCr2O4 = –52. and ΔS α β = 13 J K-1 mol-1. Biggers[28] by using the same technique as Tsai and Muan β-spl MnO-Cr2O3 system found Δ f °GMnCr2O4 = –59. Δ f °GMnAl2O4 = –32. –46. 4. and –36. According to these authors the transition of pure α-hsm to β-hsm takes place at T=1445 K.2.7.1 kJ mol-1.0 kJ mol-1 at T=1523 K.

Considering these findings an alternative description of β-spl would read [Mn2+. The Gibbs energies of the endmembers [Mn2+](Mn3+)2O4 that corresponds to β-hsm.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. They propose small polaron hopping between Mn3+ and Mn4+ on the octahedral sites as mechanism for the electrical conductivity.Mn3+.15 K and p = 105 Pa[6].5) The Gibbs energy of the reciprocal reaction is taken to be zero. In our description we further go along with the presumption that the amount of oxygen vacancies may be neglected. β-spl can therefore be described by the simple formula [Mn2+.2. and [Cr2+](Cr3+)2O4 that corresponds to Cr3O4 are taken from the assessed binaries[7. so we stick to the less complex description without Mn2+ and Mn4+ on the octahedral sites.Cr2+](Cr3+. 2 4 2 4 86 .Mn4+)2O4.2.8].Cr2+](Cr3+.Mn2+. This state is denoted SER (Stable Element Reference). To maintain electroneutrality Mn2+ is formed on the octahedral sites resulting in a charge disproportionation reaction. Thus the endmember ° β-spl β-spl G[Cr 2+ ](Mn3+ ) O becomes less stable the more stable °G[Mn 2+ ](Cr3+ ) O becomes. As the degree of inversity of β-spl is very low[10].[34] measured the electrical conductivity of β-spl. 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. 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. However there is no experimental data quantifying the amount of Mn4+ in β-spl.Mn3+)2O4 using the compound energy model[31–33]. Lu et al. 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 (4.4) This endmember is considerably more stable than the endmember of the formula [Cr2+](Mn3+)2O4.30].2. All endmembers of our model β-spl are neutral.Thermodynamic assessments 4.

Cr3+)2(O2-)3. Manganosite (mgs): Based on the proposed incorporation of Cr into (Mn1-yCry)1-xO in the form of CrO[15] we tested a description of mgs given by (Mn2+.7) The experimental data could be reproduced without the optimization of a temperature dependent parameter.Mn3+. 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.Cr2+.15.34] show that α-spl is stabilized at high Mn contents.Va)(O2-).15]. as the degree of inversity is increasing with higher temperature. Due to these considerations we may write [Mn2+](Cr3+. the two endmembers of α-spl read [Mn2+](Mn3+)2O4 and [Mn2+](Cr3+)2O4. Hence. The incorporation of chromium of valencies other than three is mentioned nowhere in literature. It is very unlikely that trivalent cations are incorporated into the tetrahedral sites of α-spl.2. This is a reasonable assumption as the radii of these ions are very similar[35].Va)(O2-) leads to far more satisfactory 87 . The Gibbs energy of [Mn2+](Mn3+)2O4 is equal to α-hsm.Mn3+.Mn3+)2O4 to describe α-spl. Thus we may describe bxb as (Mn3+.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. Experiments[11.6) Bixbyite (bxb): Geller and Espinosa[16] postulate the incorporation of Cr into Mn2-yCryO3 by a simple substitution mechanism between Cr3+ and Mn3+.[7].) 3 + Abxb (4.Cr3+. and the Cr solubility in tetragonally distorted MnyCr3-yO4 does not extend beyond MnCr2O4. Using this description the solubility of Cr in function of oxygen partial pressure experimentally determined by Tanahashi[17] could not be reproduced correctly. The Gibbs energy of the endmember (Mn3+)2(O2-)3 is taken from Grundy et al. (Mn2+.14. whereas for ordering due to Jahn–Teller distortion the opposite holds.2. 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.

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. The Gibbs energy of (Mn3+)2(Cr3+)1(O2-)3 is given by 88 .8 Geometrical representation of the mgs phase described using the compound energy model.8) The Gibbs energies of the three other endmembers are taken from Grundy et al.8.Va)1(O2-)3.Thermodynamic assessments reproduction of these data.2.[14] postulate the incorporation of trivalent Mn ions into (Cr1-yMny)2+xO3.2. 4.)3 Gas − 1 3 °GO − 3 2 RT (1 3ln1 3 + 2 3ln 2 3) + Amgs 2 (4.2.Mn3+)2(Cr3+. These experiments also provide evidence against Cr being incorporated interstitially. 4. The model description of mgs is shown in Fig. Fig. Eskolaite (esk): Pollert et al.[7].Cr2+. With this description we are in agreement with O’Keefe and Valigi[36] 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. 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. Agreeing with these authors we model the solubility of Mn by (Cr3+.

The binary interaction parameters are taken from Grundy et al. 90-92).[7].Mn2+)p(O2-. Liquid: We model the liquid phase as (Cr3+.Va)3[8].9) and the Gibbs energy of (Mn3+)2(Va)1(O2-)3 by ° G esk3+ (Mn )2 (Va)1O3 = °G bxb3+ (Mn )2 (O2. Povoden et al.)3 + Aesk (4.4 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Mn-Cr-O system is given in Table 4. Mn3+.10) We take the Gibbs energies of the other endmembers from Povoden et al.)3 + °GCr SER + Aesk (4. The descriptions of further alloy phases are taken from[9].Cr2+.Va)3.Thermodynamic assessments ° G esk3+ (Mn )2 (Cr3+ )1O3 = °G bxb3+ (Mn )2 (O2.39] .Vaq-)q using the two-sublattice model for ionic liquids parameter 0 Lliq3+ Cr .2.Mn)1(O. 89 . and Lee[9].2. No data are reported for the oxygen solubility in pure bcc A2 manganese metal. The liquidus temperature is optimized using the interaction .[8]. Experimental data on the oxygen solubility in pure bcc A2 chromium metal[37] were used for the description of (Cr)1(O.Mn3+ :O2- [38.1 (pp. 4.[8]. Assuming low oxygen solubility in bcc bcc manganese metal we give a large value to the endmember °GMn:O . Cr-Mn alloys: We describe the oxygen solubility in bcc by an interstitial solution model of the form (Cr.2.2.

Va q1 liq Mn 2+ :O 2.Va q- L 0 liq Mn 2+ .− H Mn = GMN_L[7] liq SER GMn3+ :Va q.− H Cr = GCR_L[9] liq SER GCr3+ :Va q.6587T = 504 + 0..H0 S298 Cr Mn O Liquid (liq) BCC_A2 CBCC_A12 ½ mol O2 51.543 32.Mn 2+ :Va q1 liq Cr 2+ ..− 2 H Mn − 2H O = 2GMN1O1_L[8] 0 liq Cr 2+ :O2..008 102..2.Cr)1 (Va.Thermodynamic assessments Table 4.Mn 3+ ) p (O 2.6 0 liq Mn 2+ :O 2.− 2 H Cr − 2H O = 2GCR1O1_L[9] liq SER GMn 2+ :Va q.Mn 2+ .Mn 3+ :O 2.Cr 3+ .996 54.0 4996.938 15.999 4050.− 2 H Cr − 3H O = GCR2O3_L[9] liq SER SER GCr 2+ :O2.52 (Cr 2+ .)q p = 2 yO2.Mn 2+ :Va q- L 0 liq Cr 3+ .− H Cr = 2GCR_L + GCR2O3_L[9] − 3GCR1O1_L[9] liq SER SER GCr3+ :O2.Va q- L L = 121000[9] = 129519[8] = −45459[8] = −33859 [8] = −15009 + 13..− 2 H Mn − 3H O = GMN2O3_L[8] liq SER SER GMn 2+ :O2.− H Mn = 2GMN_L[7] + GMN2O3_L[8] − 3GMN1O1_L[8] liq SER SER GMn3+ :O2.0 23.Mn 3+ :O 2- L Bcc A2 alloy (bcc) (Mn.9479T = −188487.+ qyVa .1 Thermodynamic description of the Cr-Mn-O system a) Element Element Reference Mass H298 . q = 2 yCr 2+ + 2 yMn 2+ + 3 yCr3+ + 3 yMn3+ ° ° ° ° ° ° ° ° liq SER GCr 2+ :Va q.Va q.O)3 90 .0 4341.Va q- L L 0 liq Cr 2+ .

)3 ° ° ° esk SER SER GCr 3+ :Va:O 2.3 − 7.5GCR2O3[9] + 71549.Va)1 (O 2.Mn:Va L 0 bcc Cr:O.)3 ° bxb SER SER GMn 3+ :O2. Cr 3+ .− H Cr − H O = 0.4183T [10] 1 bcc Cr.− 3H Cr − 3H O = GCRO0[9] + 1 GHSERCR [7] − 5.6 yCr 2+ :Va:O2- :O 22- esk β esk = 3 yCr :Va:O Cubic spinel (β-spl) 91 .− 2 H Cr − 3H O = GCR2O3[9] esk SER SER GCr 3+ :Cr3+ :O 2.− H Mn − H O = GMN1O1[8] − 21883.008 yCr − 0.27 yMn + yCr yMn [0.93845T mgs SER SER GMn 3+ :O2.− 2 H Mn − 3H O = GMN2O3[8] + 39503 ° ° ° Magnetic contribution[9] p = 0.Va)1 (O 2.Mn 3+ :O 2- L Bixbyite (bxb) (Mn 3+ .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.− 2 H Mn − H Cr − 3H O = GMN2O3[8] + GHSERCR [7] + 39503 esk SER SER GMn 3+ :Va:O 2.4 Tcbcc = −311.Mn 3+ :O 2- L = −42104.)1 ° ° ° mgs SER SER GMn 2+ :O 2.48643 − 0.Va L = −709542[9] p = 0.7339T [10] = −9162 + 4.1533[8] 1 mgs Mn 2+ .− 3H Cr − 3H O = GCR2O3[9] + GHSERCR [7] esk SER SER GCr 2+ :Cr3+ :O 2.5 yCr − 580 yMn + yCr yMn [−1325 − 1133( yCr − yMn ) 2 − 10294( yCr − yMn ) 4 + 26706( yCr − yMn ) 6 − 28.72035( yCr − yMn ) 2 − 1.2923T 3 esk SER SER SER GMn 3+ :Cr3+ :O2.6 yCr3+ :Cr3+ :O2esk β esk = 3 yCr :Cr 3+ 3+ 3+ :O 22- T esk c = 308.6 yCr 2+ :Cr3+ :O2esk Tcesk = 308.Mn 3+ ) 2 (Cr 3+ .Mn 3+ .− 2 H Mn − 3H O = GMN2O3[8] bxb SER SER GCr 3+ :O 2. Cr 3+ .Mn:Va L = −20328 + 18.− H Mn − H O = GMN1O1[8] mgs SER SER GCr 3+ :O 2.− 2 H Cr − 3H O = GCRO0[9] − 2 GHSERCR [7] − 5.93265( yCr − yMn ) 4 ][10] Manganosite (mgs) (Mn 2+ .2923T 3 esk SER SER GCr 2+ :Va:O 2.1853365T 0 mgs Mn 2+ .Cr 3+ ) 2 (O 2.28 esk Tcesk = 308.8766[8] = 46513.5213 − 22.− 2 H Cr − 3H O = GCR2O3[9] + 3459 ° Eskolaite (esk) (Cr 2+ .117( yCr − yMn )8 ][10] β bcc = −0.Thermodynamic assessments ° ° ° ° bcc SER GCr:Va − H Cr = GHSERCR [7] bcc SER GMn:Va − H Mn = GHSERMN[7] bcc SER SER GCr:O − H Cr − 3H O = GHSERCR [7] + 3GHSEROO[7] + 243T bcc SER SER GMn:O − H Mn − 3H O = GHSERMN[7] + 3GHSEROO[7] 0 bcc Cr.

Cr 2+ )1 (Cr 3+ .2. Further the melting temperature of β-spl in air found by Speidel and Muan[12] is used to optimize Aβ-spl and Bβ-spl in Eq. 4. 4. All these data are given a high weight.− 3H Cr − 4H O = GCR3O4[9] β-spl SER SER GMn 2+ :Mn 3+ :O 2.69T GTSPINEL = 2 GCR3O4+ 1 GMN3O4[8] 3 3 −200941.− 3H Mn − 4H O = GMN3O4[8] ° Functions GSPINEL = 2 GCR3O4+ 1 GMN3O4B[8] 3 3 −210795. 4. mol.− H Cr − 2 H Mn − 4H O = GCR3O4+GMN3O4B[8] -GSPINEL Tetragonally distorted spinel (α-spl) (Mn 2+ )1 (Cr 3+ .4 and 0 Lliq3+ .5+61. and we use data on the solubility of Cr in MnyCr3-yO4 at T=1873 K under varying 92 .9+75. Pa: R = 8. The program minimizes the sum of squared errors between the experimentally determined phase diagram and thermodynamic data and the corresponding calculated data.105 from Speidel and Muan[12] to optimize Aβ-spl and Bβ-spl in Eq.− H Mn − 2 H Cr − 4H O = GTSPINEL α-spl SER SER GMn 2+ :Mn 3+ :O 2. The optimization of the thermodynamic parameters is performed using the PARROT module of the Thermo Calc[40] database system. 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.− H Mn − 2 H Cr − 4H O = GSPINEL β-spl SER SER GCr 2+ :Cr 3+ :O 2.2.Mn 3+ ) 2 (O 2.Mn 3+ ) 2 (O 2.4 and Aα-spl and Bα-spl in Eq. 4.) 4 ° α-spl SER SER SER GMn 2+ :Cr 3+ :O 2.4 we use the Δ f °GMnCr2O4 value derived from Tsai and Muan[23] using Δ f °GMnAl2O4 from Kim and McLean[25] and the composition of bcc in equilibrium with β-spl and mgs reported by Ranganathan and Hajra[19]..Mn3+ :O2.4.− 3H Mn − 4H O = GMN3O4B[8] β-spl SER SER SER GCr 2+ :Mn 3+ :O 2.2. K. PARROT takes into account all sorts of thermodynamic and phase diagram data simultaneously.2.) 4 ° ° ° ° β-spl SER SER SER GMn 2+ :Cr 3+ :O2.31451 J mol-1 K-1.2.1T a) Note: All parameters are in SI units: J. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. β-spl To optimize the parameters Aβ-spl and Bβ-spl in Eq.%) and α-spl is used to optimize Aβ-spl and Bβ-spl in Eq.4 and 0 liq L Cr3+ .7 cat.Mn3+ :O2- .Thermodynamic assessments (Mn 2+ . Further we use – with lower weights – the temperature of the two phase equilibrium β-spl + liq at X(Cr) = 0. The temperature found from Speidel and Muan[12] for Cr the two phase equilibrium of Mn rich β-spl (Mn = 94. 4.

αspl coexists with β-spl from X(Cr) = 0 at T = 1441 K to X(Cr) = 0. Abxb in Eq. 4. This two-phase field expands under more reducing conditions which can be seen in the calculated phase diagram of 93 .2.10 data on the solubility of Mn in (Cr1-yMny)2+xO3 from Pollert et al.2 cat. 4. 4. 80) to optimize Aβ-spl and Bβ-spl in Eq.67 in air.65 prl and β-spl coexist in air.2. 4. β-spl and esk coexist from X(Cr) = 0. 4.2.4.3.[17] are used (Fig. 4. p.2. and data from Pollert et al.[17] shown in Fig. 4.2. 4. and Aα-spl and Bα-spl in Eq.2. The two-phase field bxb + α-spl is only found in a very small area at about 1150 K.9 and 4.2. From T = 513 K to 668 K and maximum X(Cr) = 0.2. p.Thermodynamic assessments oxygen partial pressures from Tanahashi et al. p.2. prl coexists with esk at T < 513 K in air.7 is optimized using data on the solubility of Cr in Mn2-yCryO3 from Pollert[14]. The dotted line in Fig.[14] shown in Fig.6.5. 79. 4.3.% at T = 668 K in air. 82.66 to 0.[14] on the two phase equilibrium β-spl + bxb in air (Fig.992 at 1203 K in air. 4.2.[14] 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. 4.5 Results Phase diagram data: The calculated phase diagram of the pseudo-binary system MnOx-Cr2O3 in air is shown in Figs. 79 shows the temperature dependence of the diffusionless transformation of α-spl to β-spl.2. mgs is not stable in air. p.8 data on the solubility of Cr in (Mn1-yCry)1-xO from Tanahashi et al. 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. p.23 in air.2. 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. Temperature data from Speidel and Muan[12] and Pollert et al. 4.2.2. 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. In Fig.2.1 and 4. 79 and Fig. p. and for Aesk in Eq. p. 82).2. for Amgs in Eq.[11] on the temperature dependence of the diffusionless transformation of α-spl to β-spl shown in Fig. 80 the Mn rich part of the diagram is shown in detail. The maximum Mn solubility in (Cr1-yMny)2+xO3 is 0. 82 are used. 4. 4. The maximum Cr solubility in Mn2-yCryO3 is 23 cat. bxb is stable from T = 694 K to 1154 K in air.6. 4.175 at T = 1156 K. p.2.2.2.4.2.2.054 in air.4. and Aα-spl and Bα-spl in Eq. 4.5. prl + bxb is stable in a small area from T = 668 K to 694 K and X(Cr) = 0 to 0. 4.5. We use data from Holba et al. 4. 79 to optimize Aβ-spl and Bβ-spl in Eq. p.% at 2243 K in air.2.2.

82 experimental and calculated solubility data of Cr in mgs + β-spl.2. 4. and from Bobov et al.6.2. In Fig. 94 . p. p.5. and Mn in esk + β-spl are presented. 4. In the isothermal phase diagram of the Mn-Cr-O system at T = 1323 K of Fig. 4. 4. 80.2.9 (next page).[17] on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl and esk + β-spl at 1873 K.4.[18] on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl at T = 1073 K. 1173 K. p.[18] were not used for the optimization.Thermodynamic assessments the pseudo-binary MnOx-Cr2O3 system at an oxygen partial pressure of 1×10-4 Pa in Fig. Isothermal sections of the Cr2O3-MnO-MnO2 system at different temperatures are plotted in Fig. and 1273 K in function of log(pO2 ) are compared to the calculated results from this work.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[9]. The data from Bobov et al. Experimental data from Tanahashi et al.

2. and single solid solution phase equilibria are heavy lines. Dotted lines are tielines.Thermodynamic assessments Fig. Three-phase field boundaries are denoted with thin lines. 4.9 Isothermal sections of the ternary system Cr2O3-MnO-MnO2 showing oxide and liquid evolution as a function of temperature and composition. 95 . Stoichiometric single phase equilibria are points.

4. and β-spl Δ f °GMnCr2O4 = –1634017 J mol at T = 298. Our calculated T0 line for the diffusionless transformation of α-spl → β-spl is in perfect agreement with experiments by Holba et al. 4. Fig. 4. Our assessed phase diagram is in excellent agreement with the findings of Pollert et al. 4.2. p.15 K.9 a to c). 82 agrees well with the results from Tanahashi et al.3 (p.15 K.2.15] and Ranganathan et al.2.6 (p.2. At T = 1873 K we get Δ f °GMnCr2O4 = –34388 J mol-1. The calculated dependence of β-spl solid solubility on oxygen partial pressures shown in Fig.Thermodynamic assessments Thermodynamic data: The calculated enthalpy. 4.2. and Δf °G α-spl = –1625681 J mol-1 at T = 298.9 b). and Fig. 80).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. The oxygen nonstoichiometry of mgs is yet insignificant (Fig. and mgs + β-spl dominate the system in a wide temperature range from T=1200 K to 1900 K (Figs. At this temperature small oxygen nonstoichiometry of esk is apparent. 79).2.[19] as shown in Figs.21 %.[17].7. 79).[11] (Fig. In the β-spl temperature range from 1050 to 1800 K Δ f °GMnCr2O4 from the oxides is given by the term –89167 + 29.338 T with an error of ± 0. 4. 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. β-spl + bxb. ° α-spl S = 98 J mol-1K-1. °SMnCr2O4 = 116 J mol-1 K-1. For both cases Speidel and Muan[12] mention the speculative character of their phase diagram due to the lack of experimental data. The results from Bobov et al. 95) represents the phase relations of the oxides and the evolution of liquid formation. 83). 4.9 (p. 4.2.2 (p.[18] on the other hand cannot be reproduced. 4. 4.5.2.6 Discussion Phase diagram data: Our assessed phase diagram is in rough agreement with the findings from Speidel and Muan[12].2. but it increases at elevated 96 .9 a) disappear. For α-spl of the composition MnCr2O4 we calculate Δ f °H α-spl = –1596517 J mol-1. p. 4. The three-phase regions prl + esk + bxb and bxb + esk + β-spl.2.2. and the two-phase fields prl + bxb.[14. 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. 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. 85. p.

6.2.2.2.9 d).2.2.2. At T = 2400 K the only remaining stable solid phases are esk and prl (Fig. 4. Hence.6. 4.[5] must be kinetically controlled. The composition of Crofer22 APU alloy is close to the Cr-corner of the Mn-Cr-O phase diagram. p. 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.[12]. which is at point A in Fig. 4. 4. p. 4. Recently Qu et al. indicating that only very little energy is 4.9 c). This is obvious from Fig. p. 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. and the-three phase fields bxb + β-spl + liq and mgs + β-spl + liq emerge (Fig. 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[22] using Δ f °GMnAl2O4 from Kim and McLean[25].[42] found that the electrical conductivity of chromium manganese spinel increases with increasing Mn-content.2.9 c). 84) on Crofer22 APU alloy is expected under SOFC operating conditions. 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. and ΔSα β values for the transformation of α-spl to β-spl are very small.Thermodynamic assessments temperatures becoming apparent at T = 2000 K (Fig.9 f). 4. 83.6.7 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.2. 83 associated with decreasing 97 . Even more three phase regions due to increasing liquid formation start to exist at T = 2000 K (Fig. In a thermodynamic view the formation of β-sp with the composition MnCr2O4 (Point A in Fig. The calculated ΔHα needed for the transformation to take place. At T = 1900 K phase relations become more complex due to incipient melting (Fig. 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 d).2. At T = 1900 K liquid is formed at the Mn-rich side of the system. 4.

3.). 297-310. Druckerei J. M. 2. Deller. D. 4. and the only available -1 β-spl Δ f °GMnCr2O4 values are spread over a range of 31 kJ mol . Zhang. L. Badwal.P. pp. 2. Das. John Wiley & Sons. First European Solid Oxide Fuel Cell Forum Proceedings. Bossel (Ed. Solid State Ionics. 1037. Ramprakash. 1994. 2004.). W. Chichester. Recalculating old experiments using new thermodynamic data together with phase diagram data we achieved a description. p. 1-15. Vielstich. °S. p. J. Our Thermo Calc[40] dataset resulting from the presented CALPHAD modeling of the Mn-CrO system allows the calculation of phase stabilities. 2003. in: W. H. Vol. Miller.2. 703. Göttingen. Gasteiger (Eds.Thermodynamic assessments electrical conductivity. There is a surprising lack of thermodynamic data on β-spl. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. K. R. 99. 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.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. 4. and we present well-founded Δf°H.A. Handbook of Fuel Cells – Fundamentals. pp. Y. Quadakkers. in: U. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. K. Lamm. 1997.W. Hilpert. 171. S. J. A. Nickel. H.P. 98 . References 1. and Δf°G data for β-spl and α-spl. Technology and Applications. which is very close to the experimental findings of several authors. Fergus. 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.J. All features of the system are well described with the optimization of only 8 additional optimization parameters.S. K. Singheiser. Solid State Ionics. Kinzel. Foger. Hilpert.

V.P. 46. Espinosa.V. 6. 16. Phase equilibrium diagram of the system Mn-Cr-O. Muan. 2005.M. 2001.Thermodynamic assessments 5. E. SGTE Data for Pure Elements. J. B 1. Ceram. 15(4). 8. pp.G.. Assessment of the Mn-O system. Hajra. 15. S. B. pp.R. J. Balakirev. Hallstedt. 10. Cr3+. Solids.. Bull. T. A740-45. 58.F. Magnetic and crystallographic transitions in Sc3+. Novak.F. J. N. 71. pp. M. pp. G.P. 353-62. A. Phys.. Solid State Chem..D. E. Metall. 750-751 (in Russian). Fiz. A. pp. J. Peculiarities of phase-diagram in the reduction of Me0. The system manganese oxide-Cr2O3 in air.M. Phase Equilib. 1991. Dinsdale. Bobov.W. Furuta. 3763-69. J.. 853-60. 152. 10. A. Anderson. 1984. T. A. Gauckler.75O4 solid-solutions. 15. pp. 577-78. Alloy oxide equilibria in the Cr-Mn-O system. pp.P. J. J. Fujisawa.J. 38. L. 1962.V. 14. J. 27. 11. L. C. Tanahashi. 12. Hastings.. L. Magnetic structure of manganese chromite. pp. Grundy. 9. S. Phys. Golikov. A. Pederson. 562-65. Pollert.25Mn2. M. Bull. 1987. Khim. Am. Zh. Nevřiva. Balakirev. Grundy. G. Phase diagram of the Mn2O3-Cr2O3 system in air.. G. Mater. 2006. pp. A. Yamauchi. Rev.J. 1977. 1309-1315. pp. S. J. 1145-47. Rev. 19. pp. 2003. 21-39. Soc. ISIJ Int. 126. M. P. 1453-56.I. Soc.. Nevriva.. Ranganathan. Mater. Povoden. 556-65. Stevenson. V. Pollert. SOFC performance with Fe-Cr-Mn alloy interconnect. pp. Phase equilibria of the MnO-SiO2CrOx system at 1873 K under controlled oxygen partial pressure. Golikov. Corliss. Z. L. 17. 18. Lee. 9. and Ga3+ substituted Mn2O3.. 7. Yang. Chufarov. J. Nevriva.N. 317-425. Calphad. 99 . 1919-1933. Geller. Res. Diff.H. Y. 149-58. Speidel. Bull. Novak. M.-G. Pollert. 1993.. B-J. Mater. Zalazinsky. Holba. 1987. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Phys. Chem. M. pp. Trans. pp. 1975. E. Xia.P. pp. Y. Simner. Tetragonal distortion of spinel solid-solutions MnCr2O4Mn3O4. 24. Electrochem. 41. E. Sci. Miscibility gap of MnxCr3-xO4 spinels.N. 1980.. A thermodynamic evaluation of the Cr-Mn and Fe-Cr-Mn systems. Phase Equilib. 13. A 24.. Res. D. 1970. J. Gauckler. 1963.

751-67. pp. Am. 10B. Toker. Furuta. Electrical conductivity of the manganese chromite spinel solid solution. Shannon. 22. pp. Application of the Compound-Energy Model to Oxide Systems. McLean. 81-87. 66. 88. 225-232.. 32. 21. ISIJ Int. D. 1993. Lam: United States Patent 6039788. Barin: Thermochemical Data of Pure Substances.(in Russian).. Novokhatskiy. I. Muan.Thermodynamic assessments 20.D. 2001. 3. B. L. Jacob. J. 87-92. 1966. 23. 1407-11. 575-84. L. 25. A 32.. 2000. A. Jansson.Y. T. Darken. B. Hillert. Ceram. J. Muan. 1412-15. 24. 20. 2005. pp. Kim. 26. Z. Lu. B. Hillert. 75. A. Steel Res. R. Am. N. H. Paranthaman.S. pp. Metall. 7-13. Nauk SSSR. Pennsylvania State University. B.. Ceram. 89-92. pp. Weyl. Activity composition relations in refractory oxide solid-solutions at high-temperatures – the system Cr2O3-Al2O3. Hillert. Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides. Guillermet. Revision of thermodynamic data on MnO-Al2O3 melts. Taniguchi. 73. A. Alloy. Acta Metall. Phase diagram of system MnO-Al2O3 and thermodynamic properties of MnAl2O4. 1992. 79(2). M. 1981. J.. Andersson.T. R. 33. Sundman. Akad. Q. Izv. Standard Gibbs free energy of formation of MnO-saturated MnO. Control of the manganese-oxygen reaction in pure iron melts. 437-445. Z. J. Can.A. 28. Janke. 27. J. 2nd Ed. Zhu. 1966. 34. H. 1976. Jansson. Biggers: Ph.A. Am.D.. 34. Tsai. pp.T. Lenev. pp. 35. pp. 1995. University Park. 43.. Dimitrov. 2003. pp. 1992. K. 1991. Soc. Soc. A. B.K. Equilibrium phase-relations and thermodynamics of the Cr-O system in the temperature-range of 1500°C to 1825°C. T.Cr2O3 solid solution at 1873 K. Weinheim. 29. Trans.. Payzant.-O. A..P. pp. Cmpd.M. 75. The Compound Energy Formalism.F. pp. 161-76. VCH Verlagsgesellschaft mbH.. Muan. Tsai. Thesis. J.. Activity composition relations in FeCr2O4-FeAl2O4 and MnCr2O4MnAl2O4 solid-solutions at 1500°C and 1600 °C. Sundman. C. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. pp. E. Metall. Parts I and II. N. Met. PA. pp. Fujisawa. S. Metall. 31. 1979. Acta Crystallogr. Metallkd. Ceram. 30. Yamauchi. M. Tanahashi. A.T.F. I. M. J. 1050-53. C.K. 320.V. M. M. Soc. Thermodynamics of iron-manganese aluminate spinel inclusions in steel. 22. 1986. 100 . Trans. B. 1988..

B. 1985. Cleveland. Metall. 261-66. Calphad.N. and L. Chen . 343-. 1985. Eremenko. Russ. 42. pp. Ivas. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects.M. D. T. air. Chem. Phase equilibria of the La-Cr-O system are calculated at T = 1273 K as a function of oxygen partial pressure. G. B. The following standard data of 101 . Sidorko. 16A. 1968. 9(2). 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. 153-90. J.R. V. Chem. Modification of the Two-sublattice Model for Liquids. (accepted) The La-Cr and the La-Cr-O systems are assessed using the Calphad approach. 41.. B. and oxygen solubilities in bcc and fcc metals are modeled. Fraser. pp. Phys. Povoden. 114-24. Hill.J. Diff. 31. A. Gauckler J. The Thermo-Calc Databank System. 37. B. In the La-Cr system reported solubility of lanthanum in bcc chromium is considered in the modeling. Qu. 1991.M. Solids. Jansson.5-CrO1. 947-962. Valigi. 39. J.5 phase diagrams in pure oxygen. 38. pp. J. M. Ivey. Sundman. pp. Burr. M. B. L. 1970. La2(CrO4)3.M.A. Lukashenko. W. M. A. pp. 40. p. 2006. In the La-Cr-O system the Gibbs energy functions of La2CrO6. Caplan. Thermodynamic properties of alloys of manganese with transition elements of fourth period (Cr Fe Co Ni) and with copper. Hillert. pp. D. and under reducing conditions are presented. and perovskitestructured LaCrO3 are presented. 15. J. 1957. Power sources. J. in: Ductile Chromium. Jian. The calculated La-Cr phase diagram as well as LaO1. 4. Ohio. 196.J.G. A. Phys. Grundy. ASM. J. 42. Phase Equilib.Thermodynamic assessments 36. Sundman. The electrical properties and defect structure of pure and chromium-doped MnO. 153. 109-19. Jansson. O’Keefe. Ågren. Andersson.3 Thermodynamic assessment of the La-Cr-O system E.-O. V. M. Sundman. Calphad. Trans. M. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization.

aiming on minimizing the squared errors between 102 . The assessment of the La-Cr-O system using the Calphad approach is based on the recently reassessed La-O[8] and Cr-O subsystems[9]. thermodynamic.oxides° H 298 K (LaCrO3 ) = −73. Diffusion of chromium from the metallic interconnect with high chromium content into the cathode leads to the formation of Mn(Cr.Mn)2O4 spinel and Cr2O3 along with a severe cell voltage decrease[1-4]. Sr-doped lanthanum manganites (LSM) with the perovskite structure are used as cathode materials in SOFC. Furthermore earth alkaline-containing LaCrO3 has been proposed as a cathode material in a recent study by Jiang et al[7].97 Pa.oxides G(LaCrO3 ) = –72. and Crdiffusion into the cathode from LaCrO3-based interconnects is significantly lower than from Cr-containing metallic interconnects. The liquid phase is modeled using the two-sublattice model for ionic liquids.0034 T (kJ mol-1) (T = 1273 K to 2673 K) is calculated. V-doped[5] and Zn-doped[6] La1-xCaxCrO3-δ have been considered as promising alternative interconnect materials for SOFC. and the model is submitted to a defect chemistry analysis. 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.2 J mol-1 K -1 .7 kJ mol-1 . Cation nonstoichiometry of La1-xCrO3 perovskite is described using the compound energy formalism (CEF). 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.403–0. the thermodynamic stability of the cathode is particularly important for efficient long-term operation. oxides. recently Sr-. 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. pO2 (decomp) = 10-20. 4. Δf.1 Introduction In SOFC. The lattice stabilities of elements are adopted from Dinsdale[10].3. As the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. and structurechemical data are critically assessed. All available experimental phase diagram.Thermodynamic assessments stoichiometric perovskite are The calculated: Δf. Gibbs energy of formation from the and ° S 298 K (LaCrO3 ) = 109.

3.5 quasibinary system reveal a considerable spread. Tm(argon) = 2703 K was reported by Tresvjatskiy et al.13]. but in the graphic presentation of the phase diagram in the same paper Tm(argon) ≈ 2600 K. and Epstein et al.[14] reported a La solubility of 0. Svechnikov et al.[18].4 at. whereas Cr is almost insoluble in La[13]. Tm(air) = 2773 K was determined by Foëx[21] and by Coutures[20] using a thermal analysis technique described in more detail in earlier publications.%[12] or 99.[22-24] The melting temperature was measured with optical pyrometers. As small additions of rare-earth metals essentially increase the high-temperature corrosion resistance of chromium[16]. as well as a large liquidliquid miscibility gap[12.% Cr[13] and a monotectic at T = 1983 K[12] or T = 2103 K[14] and 96 at.% Cr2O3 (T = 2248 K)[18] or 80 at. 4.% at 1983 K.3.[12] from T = 1073 K up to the melting of Cr using metallographic and microhardness techniques to be 2. The solubility of La in αCrss was determined in investigations by Savitskii et al.14.5.% Cr2O3 (T = 2323±20 K)[19]. is of technological interest.5 at. Furthermore deviations between the data from Tresvjatskiy et al.13] and 3. denoted as αCrss . Berezutskii et al. The melting temperature of lanthanum chromite in air.26]. Experimentally determined special points in the LaO1.[15] determined the partial enthalpy of mixing in La-Cr liquid with infinite dilution of Cr.% at T = 2103 K. modeling of the La-solubility in bcc-structured Cr.17] . This is not surprising as experiments are complicated due to the high investigation temperatures and evaporation of predominantly Cr[25.3 Literature review of the La-Cr-O system In the LaO1.% in αCrss at T = 1533 K.5-CrO1.Thermodynamic assessments experiments and calculation during the optimization of model parameters using the PARROT module of the Thermocalc[11] software.2 Literature review of the La-Cr system The La-Cr system has a eutectic at T = 1138 K[12.[17] found La < 0. Small solubility of La in αCrss was reported [12.1 at.CrO1. No intermetallic phases were found in the La-Cr system[12.68 at. The solubility of La in αCrss decreases towards lower temperatures. and the exact value of the oxygen partial pressure was not specified. ΔH Cr at T = 1700 K using high-temperature calorimetry.5 system two eutectics were found at 19 at. 4.04 at.%[14] Cr.% Cr2O3 (T = 2243 K)[18] or 12 at.[18] and Berjoan[19] 103 .% Cr2O3 (T = 2473±20 K)[19] 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).13]. and at 84 at.

[29] to be −3961±11. and nonstoichiometry[55-56] along with the investigation techniques used are listed in Table 4.1 (next page). However these were in significant disagreement with later results obtained by the same author[19]. Stoichiometries and thermal stability ranges of lanthanum chromates with complex formulae were reported by Berjoan et al. whereas experiments on oxygen Lanthanum chromates: The following lanthanum chromates were documented: Berjoan[19] reported that orthorhombic La2CrO6 forms at T > 923 K.25O2(g) ↑ → (4. The peritectic phase diagram proposed by Cassedanne[27] is in gross conflict with the phase diagram data from the other groups.5Cr2 O3 + 2.33-35. 104 . 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. The enthalpy of formation of La2(CrO4)3 from the elements at T = 298 K was proposed by Tsyrenova et al. which in both studies was not exactly specified.46-53].31].Thermodynamic assessments may partly originate from differences of the oxygen partial pressure.3. solubilities in αCrss are missing. [28] .[30] LaCrO4 has been interpreted as a mixed-valent intermediate decomposition product of La2(CrO4)3[30.7 kJ mol-1.[9] and Grundy et al.[32]. phase stability[54].3.2) An enthalpy change of 231 kJ mol-1 was determined for this reaction at the average temperature of T = 960 K. The perovskite phase: Existing experimental data of lanthanum chromite perovskite structure[33-45].43. thermodynamics[30. 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 + 0.3.1) at T=1055 K and pO2 =83000 Pa to be −151±8 kJ mol-1.

38 kJmol −1[52] CaF2 .1 kJmol −1[53] Knudsen mass spectrometry Δ G = −72. calculated La (CrO4 )3 La (CrO4 )3 La 2 (CrO 4 )3 2 Δ f.1 ± 1.Thermodynamic assessments Table 4.based emf Δ °G = −94.2 kJmol-1 this work.0034T (kJmol−1 ).oxides ° H 298K aCr2O3 = 1. calculated aCr2O3 = 1.75 kJmol−1 this work.3.19. calculated 139.2673 K this work. 700 .29 ± 0. calculated[29] 2 Δ f. calculated Δ °G = −44.7 kJmol-1 this work.08530T (kJmol−1 ).5Cr2 O3 +1.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.elements ° H 298K ° 2 S 298K La (CrO4 )3 = 516 Jmol−1K −1 this work.11 × 10−4 this work.9 ± 1. calculated ° 2 S 298K La CrO6 = 330 Jmol-1K -1 this work.4(kJmol −1 ).79 kJmol-1 Drop solution calorimetry in 2PbO × B2 O3[46] LaCrO3 LaCrO3 Δ f.7 kJmol−1 .403 − 0.1 × 10−4 ± 1. calculated Gibbs energy of formation by 1 3 La 2 O3 + Cr2 O3 → LaCrO3 2 4 T = 1273 K Δ °G = −76.885 K[51] CaF2 .35 kJmol-1 this work. calculated = −73.emf Δ °G = −42.based emf Enthalpy increments H − H 298 K .758 + 0.45 + 0.1 Calculated and experimental thermodynamic data of La-Cr oxides Rhombohedral LaCrO3 Standard enthalpy Δ f. calculated Δ °G = −78.5Cr2 O3 + 2. calculated Enthalpy of the dissociation reaction La 2 (CrO 4 )3 → 2LaCrO3 + 0.05 this work. (kJmol−1 ) T = 1090 K 98.4[30] HT (high temperature) . calculated Enthalpy of the formation reaction La 2 O3 +1. calculated T = 1273 K T = 1273 K T = 2100 K T = 2100 K ° Δ °G = −30.0 kJmol−1 this work. calculated = −3961 ± 11.oxides ° H 975K LaCrO3 = −1368.5 kJmol −1[49] solid oxide electrolyte .002115T ± 0. fitted 105 .elements ° H 298K = −3845 kJmol−1 this work.2[30] HT . calculated = −73.oxides ° H 298K Δ f.oxides ° H 1078K ° LaCrO3 Standard entropy S 298K LaCrO3 = 109.25O 2(g) 2 ΔH 298K La (CrO4 )3 = 231 kJmol−1[30] and this work. calculated 94.elements ° H 298K Δ f.52 kJmol −1 this work.5O 2(g) → La 2 CrO6 2 Δ f. 1273 .based emf Δ °G = −79.25O 2(g) → La 2 (CrO 4 )3 2 Δ f.oxides ° H 298K La (CrO4 )3 = −372 kJmol−1 this work.2 Jmol-1K -1 this work. this work.calorimetry T = 1350 K 133.5Cr2 O3 + 2. 855 -1073 K[50] CaF2 . calculated = −62.1× 10−5[53] Knudsen mass spectrometry La CrO6 = −73.06 ± 2.

HT . dilatometry 545[41] heating. DSC.5[34] a) calculated from DSC 0. XRD Enthalpy change of transition (Jmol−1 ) 340.25 at 536 K[35] a) calculated from adiabatic shield calorimetry 340 ± (10 .XRD 540 ± 2[40] a) HT . this work.2 Calculated and experimental data of the orthorhombic to rhombohedral transition of LaCrO3 Transition temperature (K) 540. dilatometry.XRD. calculated 503 − 583[33] adiabatic calorimetry 544 ± 1[34] a) DTA.08 J mol-1 and 0. calculated 0.XRD 528 − 533[38] a) HT . enthalpy and entropy changes of this first-order[44] transition taken from the literature are listed in Table 4. thermogravimetry.XRD.63.84 at 503 − 583 K [33] calculated from adiabatic calorimetry 277 at 544 ± 1 K[34] a) DSC 403.XRD (air and vacuum) 563 ± 5[36] DTA.XRD. DSC 550[41] HT .XRD 533 ± 3[38] a) DTA 543[39] XRD 533[20] HT . HT . this work. DSC 533 ± 5[40] a) HT .33-42].ray photography 550[37] HT . DSC 535[41] cooling. Table 4. simultaneous DSC .3.5 J mol-1 to 106 . The temperatures. simultaneous DSC .75[35] a) calculated from adiabatic shield calorimetry a) used for optimization The reported transformation temperatures lie between T = 503 K and 583 K.3. calculated 502. HT .x .08 ± 41.XRD 541[42] a) completed transition.40) at 533 ± 5[40] a) DSC 380 at 550 K[41] DSC 310 at 509 K[44] DSC Entropy change of transition (Jmol-1K −1 ) 0.XRD 523[42] a) starting transition. this work.2 along with the investigation techniques used. HT .microscopy. The determined enthalpy and entropy changes vary from 277 J mol-1 to 502.Thermodynamic assessments Crystal and magnetic structure: LaCrO3 is orthorhombic (o-prv) at room temperature and transforms to rhombohedral structure (r-prv) at higher temperatures[20.96 at 503 − 583K[33] calculated from adiabatic calorimetry 0. dilatometry 536 [35] a) adiabatic shield calorimetry.XRD 533[43] estimated from neutron powder diffraction 509[44] DSC.

[45] (150 to 450 K) using DSC.% excess 107 . whereas Coutures et al. Chen et al.Thermodynamic assessments 0. Cation nonstoichiometry and defect chemistry: Maximum excess Cr in single-phase La1-xCrO3 of 0. A transformation from rhombohedral to cubic structure at a temperature close to T = 1300 K was reported by Ruiz et al. and Dudek et al. A magnetic order-disorder transition was documented to occur at T ≈ 287 K[35].[49] measured electromotive force (emf) of the solid oxide galvanic cell Pt/Cr.[54] reported no weight loss of lanthanum chromite at T=1273 K from pure oxygen to pO2 =10-16.1 Pa using thermogravimetry combined with X-ray diffraction (XRD).% in furnace-cooled LaCrO3 annealed at T = 1773 K in air was reported from Khattak and Cox[55].[50]. On the other hand Geller and Raccah[38] as well as Höfer and Kock[34] did not observe the rhombohedral to cubic transition up to T = 1873 K and T = 1823 K respectively using differential thermal analysis (DTA).[20] reported T = 1923 K using high-temperature x-ray diffraction (HT-XRD).96 J mol-1 K-1. Chen et al. Gibbs energy of formation: in order to obtain the Gibbs energy of formation of LaCrO3. Single phase lanthanum chromite with 0.[52] measured emf of Pt.28 cat.38 cat. Chemical stability: Nakamura et al. or 295 K[46]. and its oxgen nonstoichiometry is negligible. Höfer and Kock[34] (480 to 610 K) and Satoh et al. Azad et al.[45] (T = 77 K to 280 K) using alternating current calorimetry.[35] (T=100 K to 1000 K) using laser-flash calorimetry. Heat capacity and enthalpy increment data: the heat capacities of LaCrO3 were measured by Korobeinikova and Reznitskii[33] from T = 340 K to 900 K using adiabatic calorimetry.[53] 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. O2/La2O3. LaCrO3/MgO-stabilized ZrO2/Cr2O3. La2O3.[37] and Momin et al. Cr/Pt at 1273 K.[51]. Sakai et al. LaF3/CaF2/LaF3. Pt in pure oxygen from T = 855 K to 1073 K. This means that the perovskite phase does not decompose within this oxygen partial pressure range. in agreement with Berjoan[19] (T = 1923 ± 20 K) using dilatometry. and T = 1273 K respectively. Enthalpy increments of LaCrO3 at T = 1090 K and 1350 K were measured by Suponitskii[30] using a high-temperature heat-conducting calorimeter. Cr2O3/O2. LaCrO3. Peck et al.% to 1. T = 700 to 885 K. Satoh et al. Enthalpy of formation: Cheng and Navrotsky[47] determined the enthalpy of formation of LaCrO3 by oxide melt solution calorimetry at T = 1078 K. Berjoan[19] further reported prevailing of the cubic structure at T = 2173 K. and Sakai and Stølen[43] (T = 272 K to 1000 K) using adiabatic shield calorimetry.76 cat. 289 K[45].[41].

thus the presence of interstitial Cr in reduced chromite was proposed.[58] measured the isothermal electrical conductivity of an equilibrated La1-xCrO3-Cr2O3 mixture with 5 vol.57]. 108 .[56] 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.[58] reported that concentrations of lanthanum vacancies and holes slightly increase from T = 1550 K to 1700 K.[57] and Meadowcroft[25] proposed the occurrence of chromium vacancies instead of lanthanum vacancies.59] agree that the electrical neutrality is maintained by holes and lanthanum vacancies.05 % up to T = 1250 K.[37] reported that the ionic transport number in lanthanum chromite is less than 0. The transition from reduced to stoichiometric chromite was accompanied by a decrease of about 0. the electrical conductivity being 2 proportional to pO2 −3 8 . They observed an extraordinarily slow equilibration of the samples: More than four months were required to measure the electrical conductivity at equilibrium state. Akashi et al. Iliev et al.[58] ShvaikoShvaikovskii et al. In contrast to the other authors Shvaiko-Shvaikovskii et al. Akashi et al.0 ×104 Pa . Several groups[58. The conductivity was proportional to pO2 3 16 . and that the carrier is the hole in lanthanum chromite[25.0 ×103 Pa to pO2 = 2.[57] deduced n-type conductivity from measurements of transport number.% excess Cr2O3 from T = 1573 K to 1673 K from pO2 = 1.[57] is inconsistent with the findings from Akashi et al.1% in weight.Thermodynamic assessments Cr was prepared at T = 1773 K in a pure oxygen atmosphere[56]. Ruiz et al. in line with the results from thermogravimetry[54]. resistivity and thermo-emf at pO2 = 1Pa and pO = 102 Pa .58-60]. the same as reported in an earlier study[25]. 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. However n-type conductivity was not approved by any further study. 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. affirming the lack of oxygen vacancies in the structure.

as these data are more comparable to solubilities in other rare earths-transition elements systems.O)3. and αCrss is then given by the two-sublattice description (La.3) SER H x is the standard enthalpy of the stable state of element x at 298.[9] described the solubility of oxygen in Cr(bcc) using the model Cr(Va.Va)1. The thermal stability of La2CrO6 is slightly influenced by the thermodynamics of the intermediate. and B and a regular interaction parameter 0 LCr:O.3. and to optimize their model parameters with phase diagram data[19. 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.5. 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.O)1.La:Va was given a positive value. mixedvalent chromates mentioned above. The Gibbs energy of the end-member (Cr)(O)1.4 Thermodynamic modeling and optimization Metal phases: In order to account for the solubility of La in αCrss . Cr2O3. For the reasons discussed recently[62]. compositionindependent interaction parameter[61] 0 Lbcc Cr.3.5.3. These chromates can be interpreted as intermediate products in the 109 . The formation of chromates that contain mixed Cr valences may be explained by gradual reduction of Cr6+ in La2CrO6 as the temperature increases.32]. In order to refine the model parameters of La2CrO6.1 as well as thermal stability data.Cr)(Va.5 is defined as 3 2 3 ° gas[10] G + A + BT 4 O2 ° SER SER G(Cr)(O)1. 5 [10] A and B are adjustable parameters.Va were optimized with the same experimental data[9]. Solid oxides: Lanthanum chromates: The Gibbs energy function of La2CrO6 was based on the sum of the Gibbs energy functions of La2O3.15 K and 10 Pa.[14] for its optimization.5 − H Cr − H O = °GCr(bcc)[10] + (4. we reassess the oxygen-solubility in Cr(bcc) using the model (Cr)(O. Povoden et al. We chose the solubility values from Svechnikov et al.Thermodynamic assessments 4. 4. the zeroth-order. and O2 in proper stoichiometries and A + BT parameters that were fitted to the enthalpy of formation from the oxides. using the PARROT module of the Thermocalc software[11] A was given the fix value 0 for the reasons discussed in an earlier paper[9]. Eq.

and consequently ambiguous stoichiometries of mixed-valent intermediate chromates.(1. The model parameters were fitted to the experimental enthalpy and temperature of decomposition[30]. heat capacity-data obtained by adiabatic calorimetry from Sakai and Stølen.5 . GVCR4O and GLCR4O stand for the Gibbs energy functions of the completely oxidized neutral endmember.32] (4. The simplified decomposition reaction reads 1+ x 1. GRPRV denotes the Gibbs energy function for stoichiometric rhombohedral perovskite. These lanthanum chromates with conflicting stoichiometries[19. The enthalpy of formation from the elements[29] was not used as it is a calculated value.3.4) Slight differences of the oxygen partial pressure during experiments may be reflected by a variable extent of Cr-reduction.2 and do not include this phase in the modeling.3. The superscripts o-prv and r-prv stand for Gibbs energy expressions that have different values for orthorhombic and rhombohedral perovskite. and C are optimized using the enthalpy of formation from Cheng and Navrotsky[47]. GVCR4O and GLCR4O are set equal for orthorhombic and rhombohedral perovskite.Thermodynamic assessments scope of a sluggish decomposition of La2CrO6. activity-data of Cr2O3 in LaCrO3 from Peck et al.[35] and enthalpy increment-data 110 . °GLaCrO3 is given by ° r-prv SER SER SER GLaCrO3 − HLa − H Cr − 3H O = °GLa3+ :Cr3+ :O2− = GRPRV = 1° 1 GCr2O3 [9] + °GLa2O3 [8] + Gmag + A + BT + CT ln T 2 2 (4.x CrO3 + O2 (g) ↑ 2 2 mixed-valent chromates → La 2 CrO6 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ [19.5 x) La 2 O3 + La1. Stoichiometric perovskite: The Gibbs energy function of stoichiometric rhombohedral r-prv LaCrO3 with the sublattice formula (La3+)(Cr3+)(O2-).[53].32] and is completed at T = 1473 K[32] or 1523 K[19]. which starts at T = 1153 K[19. 4. 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.3.32] are not included in the presented thermodynamic database. We go along with the interpretation of LaCrO4 being an intermediate reaction product during the decomposition of La2(CrO4)3 by Eq.5) The parameters A. B.

While this model results in a satisfying reproduction of experimental data.Thermodynamic assessments measured at high temperatures[30].40] and entropies[34. and the perovskite formula essentially remains La1-xCrO3. A+BT parameters of the low-temperature orthorhombic perovskite phase were optimized with those temperatures[34.58] measurements. Thus the defects in n-type conducting[57] lanthanum chromite are ambiguous and were not considered in the model.Va)(O2-.42]. 112-114) resulted in negligible concentrations of Va on the B-site and the anion sublattice.Cr4+. as there is no existing thermodynamic data for this transition. The optimization of selective model parameters listed in Table 4.5-CrO1.35.Va)(Cr3+.19] cannot be reproduced by using the emf-experiments[49-52]. This means that the simplest sublattice model to describe cation nonstoichiometric La1-xCrO3 reads (La3+.5-MnO1. and oxygen nonstoichiometry can be excluded from thermogravimetry[54] and electrical conductivity[37. The rhombohedral to cubic transformation at high temperatures is not considered in the model.35. irreconcilable trouble is encountered at the extension to the LaO1.3. B-site vacancies are energetically less favored than A-site vacancies in the perovskite structure[63.38.Va)3.40.Cr4+)(O2-)3.5 system required for SOFC applications due to diversities between the model descriptions of lanthanum chromite and lanthanum manganite[65].35] of transition having been obtained by combined investigation techniques and being internally most consistent.Va)(Cr3+.[57] is unlikely due to the densely-packed perovskite structure. 111 . 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.3 (pp.64]. Thus these data were excluded from the optimization. enthalpies[34. These are solved by allowing Va on the B-site and the anion sublattice of lanthanum chromite just like in lanthanum manganite[65] leading to the appropriate sublattice formula (La3+. A phase diagram with congruent melting of lanthanum chromite and two eutectics[18.

La:Va = 83500 p = 0.23T + (65393 − 23T )( yCr 2+ − yLa3+ ) Cr Lliq 2+ .3 Model descriptions and Gibbs energy functionsa) Liquid (liq) (La 3+ .= 61397 − 5.5T [28] 2 4 Lbcc Cr:Va. Cr 2+ .La3+:O2.008 yCr [9] 112 .Vaq.)q p = 2 yO2. q = 3 yLa3+ + 2 yCr 2+ + 3 yCr3+ ° ° ° ° ° ° liq SER GLa3+:Vaq. Va q.− 2 HLa − 3H O = GLA2O3LIQ[8] liq SER GCr 2+ :Vaq.− 2 H Cr − 2H O = 2GCR1O1_L[9] Interaction terms Lliq 2+ :O2. O)1.Thermodynamic assessments Table 4.+ qyVa . Cr)(Va.17755T 2 4 3 SER 3° SER ° bcc GLa:O − HLa − H O = GLABCC[10] + G (O 2(g) )[10] − 855000 + 142.3.− HLa = GLALIQ[8] liq SER SER GLa3+:O2.923T [9] liq SER SER GCr 2+ :O2.= −101850 − 39016( yCr 2+ − yLa3+ ) Cr Lliq 3+.= −101850 − 39016( yCr3+ − yLa3+ ) Cr Bcc A2 phase (La.5 yCr [9] β bcc = −0...= Lliq 3+ :O2..422 ° Lbcc Cr.5 ° ° bcc SER GCr:Va − HFe = GHSERCR [10] bcc SER GLa:Va − HLa = GLABCC[10] 3 SER 3° bcc SER GCr:O − H Cr − H O = GHSERCR [10] + G (O 2(g) )[10] + 113.= 121000[9] Cr Cr Lliq 2+ .− H Cr = GCRLIQ[10] liq SER GCr3+:Vaq. Cr 3+ ) p (O 2.− H Cr = 2GCRLIQ[10] − GCR2O3_L[9] − 3GCR1O1_L[9] liq SER SER GCr3+:O2.La3+ :Vaq.La3+ :O2.O = −355151.4[9] Tcbcc = −311.Vaq.− 2 H Cr − 3H O = 5GCROLIQ − 179638 + 79.

5GVVV[65] − 2GLCR4O + 0.41263T + Gmag ° o-prv SER SER r-prv SER SER GVa:Cr4+:O2.5 °G(O2(g) )[10] + 4.5GVVV[65] − 2GLCR4O + 0.Cr3+ .35056T + Gmag Interaction term Lprv3+:Cr3+.− HCr − 3HO = GRPRV + 1.− 2HLa − 3HCr − 12HO = GLA2CR3O12 La (CrO ) 113 .− HLa − HCr − 3HO = GRPRV + Gmag o-prv SER SER SER GLa3+ :Cr4+:O2.5GVCR4O +0.5 °G(O2(g) )[10] + Gmag r-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GRPRV − 1.− HCr − 3HO = GOPRV + 1.)6 ° prv β o-prv = β r-prv = 0.5GVVV[65] − 2GLCR4O − 0.Va)(Cr 4+ .41263T + Gmag ° o-prv SER GVa:Cr3+:Va − HCr = GOPRV + 1.5GVCR4O +0.75 °G(O2(g) )[10] − 1.− HLa − HCr − 3HO = 5 6GS4O[72] +GRPRV − GS3V[72] + 1 6GS4V[72] + Gmag ° ° ° o-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GOPRV − 1.35056T + Gmag ° o-prv SER r-prv SER GVa:Cr4+:Va − HCr = °GVa:Cr4+:Va − HCr = = 2GVCR4O + 1 3GVVV[65] − 4 3GLCR4O − °G(O2(g) )[10] + 4. Va)(O2.− 2HLa − HCr − 6HO = GLA2CRO6 6+ La CrO La 2 (CrO4 )3 (La 3+ )2 (Cr 6+ )3 (O2.Thermodynamic assessments La1-xCrO3 perovskite (La 3+ .Va:O2.− HLa − HCr − 3HO = 5 6 GS4O[72] +GOPRV − GS3V[72] + 1 6GS4V[72] + Gmag ° r-prv SER SER SER GLa3+ :Cr4+:O2.)12 ° SER SER SER 4 3 2 GLa3+ :Cr6+:O2.41263T + Gmag ° r-prv SER GVa:Cr3+:Va − HCr = GRPRV + 1.5 °G(O2(g) )[10] + Gmag o-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O[72] − GS3V[72] +1 6GS4V[72] +GOPRV − 1.− HCr − 3HO = = 2GVCR4O + 1 3GVVV[65] − 4 3GLCR4O + 0.75 °G(O2(g) )[10] − 1.5GVCR4O +0.= 250000 La La Magnetic contribution Tco-prv = Tcr-prv = 291.75 °G(O2(g) )[10] − 1.75 °G(O2(g) )[10] − 1.5GVCR4O +0.Chromates La 2CrO6 (La 3+ )2 (Cr 6+ )(O2.5 °G(O2(g) )[10] + Gmag ° r-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O[72] − GS3V[72] +1 6GS4V[72] +GRPRV − 1.5GVVV[65] − 2GLCR4O − 0.− HLa − HCr − 3HO = GOPRV + Gmag r-prv SER SER SER GLa3+ :Cr3+:O2.Cr3+ k = O-2. Va La .− HCr − 3HO = °GVa:Cr4+:O2.41263T + Gmag ° r-prv SER SER GVa:Cr3+:O2.894 yi:j:k SER SER SER 2 GLa3+ :Cr6 :O2.5 °G(O2(g) )[10] + Gmag ° o-prv SER SER GVa:Cr3+:O2.Va:O2.= Lprv3+:Cr4+.35 yi:j:k i = La 3+ . Va)3 ° ° ° o-prv SER SER SER GLa3+ :Cr3+:O2.Va j = Cr 4+ ..

00307T 2 + 190000T −1 +0.56T ln(T ) − 0.5GLA2O3A[8] + 0.25 °G(O2(g) )[10] − 200000 Perovskite reference[72] GS4V[72] = −607870 + 268.75 °G(O2(g) )[10] − 72615 − 4.56T ln(T ) − 0.3. Cr4+ and Va on the B-sublattice.25 °G(O2(g) )[10] − 291802 − 250T GLCR4O =1 3GLA2O3A[8] + 0.5T La 2 (CrO4 )3 GLA2CR3O12 = GLA2O3A[8] + 1.01T − 0.25 °G(O2(g) )[10] − 371557 + 205T a) All parameters are in SI units : J.5GLA2O3A[8] + 0. The third-last term accounts for the configurational entropy of mixing.5GCR2O3[9] + 0. R = 8.31451 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.and Va on the anion sublattice of the perovskite A1-xBO3. mol.5GCR2O3[9] GVCR4O = 0.00307T 2 + 190000T −1 +0.7186T − 47.38T − 0.25 °G(O2(g) )[10] GS3O[72] = −472704 + 191.5GCR2O3 − 1. R = 8.68T ln T Stoichiometric rhombohedral perovskite GRPRV = 0. These are accounted for by the 114 .5GCR2O3[9] + 0.56T ln(T ) − 0.5GCR2O3[9] + 0.00307T 2 + 190000T −1 +0.5GCR2O3[9] − 73591 + 2.Thermodynamic assessments Functions Perovskite Stoichiometric orthorhombic perovskite GOPRV = 0.6) i j k i j k where yi is the site fraction of Va and La3+ on the A-sublattice. The second-last term describes the excess Gibbs energy of mixing due to interactions of ions in the mixture.9T − 47. and yk is the site fraction of O2.5GCR2O3[9] + 0. yj is the site fraction of Cr3+.5GCR2O3[9] + 2.38T − 47.68T ln T Neutral nonstoichiometric perovskite endmembers GS4O[72] = −597648 + 213.31451 J mol-1 K-1.25 °G(O2(g) )[10] La 2CrO6 GLA2CRO6 = GLA2O3A[8] + 0.5GCR2O3[9] − 73931 + 3. K.

115 . The thin lines margin the neutral plane. with the 8 Cr-containing compounds being the corners of the cube.1 Representation of the Cr-containing part of the model for nonstoichiometric lanthanum chromite. 4.3. The last term designates the magnetic contribution to the Gibbs energy.[72].) and °G(La3+ )(Cr 4+ )(Va) are given in Table 4. The neutral compounds used for the optimization are marked by the black spots.[71] The magnetic parameters Tc and β were fitted to the C p data around the magnetic transition temperature from Sakai and Stølen[35]. ° prv prv G(La3+ )(Cr 4+ )(O2. Fig.3.) and °G(La3+ )(Cr 4+ )(Va) from Povoden et al. For the magnetic part of the Gibbs energy a magnetic ordering-model proposed by Inden[69] and simplified by Hillert and Jarl[70] was used.1 is a visualization of the Cr-containing part of the model the authors use to describe the cation nonstoichiometry of lanthanum chromite. Thus the authors prv prv adopted °G(La3+ )(Cr 4+ )(O2. 4. Only compounds inside the neutral plane can exist on their own.3. Fig. The parameters of the compound energy formalism are the Gibbs energies of the not necessarily neutral 12 end-member compounds °Gi: j:k . These endmembers of 3 3 nonstoichiometric perovskite have been fixed firmly by a sufficient number of consistent experiments in 3 the LaO1. 112-114). A short summary of this model can be found in Chen et al.3 (pp.5-SrO-CrO1.Thermodynamic assessments optimization of interaction parameters.5 3 system [72] .

[58] was considered in the optimization. 4.3.) . The parameters A and B of Eq.7 and A of Eq. °G(La3+ )(Va)(Va) .3. 4.3. the 12 endmembers of the compound energy formalism of the perovskite phase are defined.5 to 4.3. °G(Va)(Cr 4+ )(O2. the Croverstoichiometry in a furnace-cooled specimen reported by Khattak and Cox[55] does most likely not represent the overstoichiometry at an intermediate temperature and was not used for the optimization. 3 3 3 [65] .) .3.) .8) 1 1 1 gas = GLCR4O = °GCr2O3 [9] + °GLa2O3 [8] + °GO2 [10] + Gmag + A 2 3 4 prv GLa2 3CrO3 − ° and reciprocal relations which were set zero in analogy to Grundy et al. As cation diffusion in La1-xCrO3 is extremely slow even at high temperatures. 4. 4.7 describes random mixing of O2.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 [9] + °GO2 [10] + Gmag + A + BT 2 4 prv SER SER GVaCrO2 − H Cr − 2 H O = ° (4. The configurational entropy3 3 3 3 term in Eq.8 it describes random mixing of La3+ and Va on the A-site. The 116 .3.8 and adopting the Gibbs energies of the remaining endmembers ° prv prv prv prv G(La3+ )(Va)(O2.7) 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 ⎠ (4.3. and °G(Va)(Va)(Va)3 from Grundy et al. [65] : 3° G (O2(g) )[10] 2 ° o-prv.3.8 are optimized using experimental data of excess Cr in perovskite[56].) .with Va on the anion sublattice. °G(Va)(Va)(O2.r-prv GLaCrVa3 − HLa − H Cr = °GLa3+ :Cr3+ :Va = GLaCrO3 − (4. ° prv G(La3+ )(Cr3+ )(Va) results from a reciprocal relation which was set zero in analogy to Grundy et 3 al. 4. Furthermore the temperature dependence of lanthanum vancancy and hole concentrations from Akashi et al.[65] were used to obtain ° prv prv prv prv G(Va)(Cr3+ )(O2. In Eq. °G(Va)(Cr3+ )(Va) .9) Using Eqs.r-prv SER SER o-prv. and °G(Va)(Cr 4+ )(Va) .3.

14] at the eutectic and monotectic in the metallic La-Cr system and the partial enthalpy of mixing of Cr. Higher oxidation states are unlikely to exist in the liquid at normal oxygen partial pressures.= 0 Lliq 2+ . Furthermore the two regular interaction parameters 0 Lliq 3+ . the temperature of the eutectic at the Cr-rich side from Berjoan[19].= Cr Cr Cr 1 liq Cr 2+ .that were given La La the same values circumvents too high Cr4+ contents at low temperatures that would be in conflict with the experiments.17]. The liquid phase: The two-sublattice model for ionic liquids[73. ΔH Cr [15] in La-Cr liquid were used to optimize the temperature-dependent regular 0 Lliq 2+ .Thermodynamic assessments introduction of positive interaction parameters 0Lprv3+ . 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 LaO1.74] was used for the description of the liquid phase of the La-Cr-O system.13. The liquid is thus given by the model description (La3+. 4.[20] and Foëx[21]. Berjoan[32] and Tresvjatskiy et al. It was based on the liquid descriptions of the binary subsystems.Vaq-)q. The chromium species considered in the liquid are Cr2+ and Cr3+.5 system from Tresvjatskiy et al. 4.3.La3+ :O2- L were optimized.and 0Lprv3+ .La3+ :Va and subregular 1Lliq 2+ . It was assumed that the interactions between Cr2+-La3+ and Cr3+-La3+ are of the same order of magnitude in the oxide melt.La3+ :Va Cr Cr interaction parameters to account for interactions between La and Cr. together with experimental phase diagram data[12.Cr3+)p(O2-.Cr2+.[18].14. The experimentally determined temperatures and liquid compositions[13.La3+ :O2.3.CrO1.[18] did not specify the value of the prevailing oxygen partial pressure during their phase diagram experiments conducted in an argon atmosphere.2 (next page). as were the two sub-regular interaction parameters.5 Results and Discussion The La-Cr system: The calculated phase diagram of the La-Cr system is presented in Fig.and the two subregular 1Lliq 3+ .Va:Cr3+ :O2. thus the two regular interaction parameters were set equal to each other. we defined pO2 = 1 Pa.Va:Cr4+ :O2.La3+ :O2. As a value of the oxygen partial pressure is required for the optimization. 117 .5.La3+ :O2. and the congruent melting temperature of the perovskite phase from Coutures et al.

The positive value of 0Lbcc Cr. The calculated enthalpies of mixing are shown in Fig. denoted as γ La ss .3.3.La:Va used to model the bcc phase results in a large miscibility gap between the La-rich and Cr-rich metals. 4. which further decreases as a function of increasing temperature. which is tantamount to a small solubility of La in αCrss in agreement with the experiments [14. 118 . 4.2 Calculated phase diagram of the La-Cr system with data from the literature included (symbols).Thermodynamic assessments Fig. The model description of the bcc phase results in a tiny solubility of Cr in La(bcc).3 (next page) together with the experimentally determined value[15] that is well reproduced by the calculation. the lowest temperature of stable γ La ss .17] .% at 1134 K. of 2 ×10-3 at.

whereas the lower melting temperature was chosen by Savitskii et al. 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.[12] and Svechnikov et al. The higher value was favored by Dinsdale[10] and is adopted in this study. with the experiment from Berezutskii et al.25 and T ≈ 5000 K that is of course unphysical.La3+ :Va L and 1Lliq 2+ .Thermodynamic assessments Fig. This is unfortunately associated with Cr an inverse liquid-liquid miscibility gap with a minimum at X(Cr) = 0.La3+ :Va .[15] at T = 1700 K included (symbol with error-bar). in air at 119 .5. which are T = 2180 K and 2130 K.[14].CrO1.3 Calculated partial enthalpies of mixing of La and Cr in La-Cr liquid.3. and integral enthalpies of mixing as a function of composition. A satisfying reproduction of the experimental data was obtained by considering a moderate temperature dependence of 0 liq Cr 2+ .5 phase diagrams in pure oxygen at pO2 =105 Pa. The La-Cr-O system: Phase equilibria: Calculated LaO1. 4.

Due to the ambiguous oxygen partial pressure of phase diagram experiments[18. On the other hand a significant amount of Cr3+ in the ionic liquid is reduced to Cr2+ under reducing conditions. Analogous to Fe in the La-Fe-O system[62] 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.Thermodynamic assessments pO2 = 21278 Pa.4 Calculated phase diagrams of the LaO1. and under reducing conditions at pO2 = 1 Pa representing the typical oxygen partial pressure in argon atmosphere are shown in Fig.3. Fig. A decrease of Cr4+ during annealing of an originally lanthanum-deficient perovskite phase under reducing conditions is predicted by the model. 4. Under oxidizing conditions Cr3+ is favored over Cr2+ in the liquid.4 together with experimental data[18-21]. air atmosphere. and orthorhombic perovskite is stable only at pO2 ≤102 Pa.5 system in pure oxygen. Excess Cr in lanthanum chromite is favored at high oxygen partial pressures.3.19] and the conflicting data on the melting temperature of lanthanum chromite in argon atmosphere[18] the presented liquid description is rather tentative. La2CrO6 is stable within a wide temperature-range in pure oxygen. and under reducing conditions representing argon atmosphere at pO2 = 1 Pa with experimental data included (symbols). 4. This is in line with the interpretations of Raman spectra from Iliev et al. and the liquid stability increases considerably at the Cr-rich part of the system 120 . whereas it does not form in air and argon atmosphere. lanthanum chromite is expected to be metastable at room temperature.5-CrO1. reflected by the disappearance of Cr overstoichiometry.[56] Be it that the reported thermodynamic data of La2CrO6[19] and La2(CrO4)3[30] are correct.

2 (p.04 Pa metallic liquid forms at the lanthanum-rich side of the phase diagram.1 (p. In Fig. Fig. 106).3. It is obvious that no mutual solubilities of La and Cr in bcc metal in equilibrium with oxides are expected.[9] was obtained using the new model description (Cr)(O. Calculated and experimental data on the orthorhombic to rhombohedral transition of LaCrO3 are listed in Table 4.3.Va)1.3 (pp. The same oxygen solubility in Cr as in the assessment by Povoden et al. 105). 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[18]. At pO2 = 10-34. 4.3.3. 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. Despite this discrepancy we did not go for an alternative liquid model for the sake of consistency with our previously assessed systems. Thermodynamic data: Calculated thermodynamic data of solid oxides are listed together with experimental data from the literature in Table 4.Thermodynamic assessments leading to a considerably lowered eutectic temperature. 4.5 Calculated phase equilibria of the La-Cr-O system at T = 1273 K as a function of oxygen partial pressure.5 calculated phase equilibria of the La-Cr-O system at T = 1273 K are shown as a function of oxygen partial pressure.3. 121 . Table 4.5.

31] resulted in gross disagreement between optimized and reported values.Thermodynamic assessments Lanthanum chromates: Testing an optimization of model parameters of La2(CrO4)3 by using all available thermodynamic data[29.3. whereas the calculated standard enthalpy of formation from the elements[29] was rejected.6. The considerable error might be explained by experimental difficulties to reach equilibrium at the low investigation temperatures.6 Calculated heat capacities of LaCrO3 (solid curve) as a function of T with experimental data included (symbols). Fig. The perovskite phase: the calculated heat capacities of LaCrO3 are compared with experiments from the literature in Fig. 4. The use of C p -data from Sakai and Stølen[35] along with enthalpy increment-data from Suponitskii[30] to optimize the 122 . Anyway the model parameters were fitted to the experimental data[30]. The dashed line marks the temperature of the o-prv ↔ r-prv transition. 4. bearing in mind the high degree of uncertainty of the resulting description. The calculated C p -curve extrapolates well to high temperatures.3. and/or by significant deviations between the thermodynamic standard data used for the calculation of the enthalpy of formation from the elements[29] and assessed values[8-10].

105).[50] 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.28 and p=0. Due to the consistency between both groups of calorimetric experiments[30. In this case the emf depends on the activity 123 . Yet it is obvious that the CaF2based emf-technique is neither suitable for the determination of thermodynamic data of lanthanum chromite. The calculated C p -peak at T = 290 K reflects the temperature of the magnetic order-disorder transition. The C p -anomaly is equally well reproduced by the model[69. 4. A small peak which was found around 855 K can be explained most likely by the decomposition of an undetected impurity phase[35].Thermodynamic assessments parameter CTlnT of the Gibbs energy of stoichiometric perovskite resulted in the lowest error between experiments and calculation. The calculated transition temperature of T = 540 K is shown by the broken line in Fig. 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.35] the term CTlnT is fixed firmly.28.1. For the sake of compatibility with the recent assessment of the La-Fe-O system[62] we chose p = 0.70] using p = 0.4.28 or p = 0. 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. It needs to be clarified why all of the emf-measurements are problematic: Azad et al. p. as it unavoidably leads to emf that are too low. whereby the proper p-value for structures other than bcc. and hcp is not available in the literature.6. p=0.4. fcc.10) are listed as a function of temperature together with data from the literature [49-53] in Table 4.3.3. Experimental enthalpy increments[30] are well reproduced by the calculation (see Table 4.or oxygen-containing atmosphere. their C p is the same.1.3.3. As CTlnT was set equal for o-prv and r-prv. 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. A possible explanation is found in a study by Akila and Jacob[75]: Fine precipitates of CaO can form on the surface of CaF2 in water. Two values for the magnetic parameter p are possible depending on the crystal structure. The resulting Gibbs energies of formation from emf-measurements are remarkably less negative than the Gibbs energies of formation derived from Knudsen mass spectrometry[53]. the transition temperature being in agreement with the experiments. 105.

The calculated decomposition of the perovskite phase by Eq. 4.11) is pO2 = 10-20.3. 4.3.3. Fig. Defect chemistry of the perovskite phase: 124 .7 Calculated decomposition of lanthanum chromite as a function of temperature and oxygen partial pressure.Thermodynamic assessments of CaO at the electrode/electrolyte interface.7. 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 (4. 4.3.97 at 1273 K. 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.11 is plotted as a function of temperature and oxygen partial pressure in Fig.

3. and yprv 4+ in the compound energy formalism.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 (4.3. La x x • ′′′ The concentrations of the defects LaLa . and [OO ] can be considered to be ~ 1.)3 + O2(g) → (La 3+3 Va1 3 )(Cr 4+ )(O2. 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.8 (next page) for lanthanum chromite in equilibrium with Cr2O3. [CrCr ] . yprv 3+ . Va La .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. yprv 3+ . The line for yprv 3+ at 1073 K cannot be seen as it is very close to 1. 4.14) x x x For small oxidation extent [La La ] . and charge neutrality is maintained by 1 • [Va ′′′ ]= [CrCr ] La 3 (4. CrCr .)3 2 4 (4. yprv 3+ .14 gives the proportionalities [Va ′′′ ].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.3. yprv .[58]: 1 (La 3+ )(Cr 3+ )(O2. if [Va ′′′ ] and [Va •• ] are O Cr assumed to be negligible according to Akashi et al.15) • Substituting this into Eq. yprv . A La 125 . [CrCr ] ∝ PO2 16 .3.3. 4.3. and CrCr in La1-xCrO3 correspond to the site 3 fractions yprv 3+ .

0 ×103 Pa and pO2 = 2.12. The slope • At T=1073 K a constant slope of 3/16 of the defect concentrations [Va ′′′ ] and [CrCr ] shown in La the triangle. This slope is • fixed by the defect reaction Eq. In Fig. 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. 4. 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. is calculated from very high to very low oxygen partial pressures. pO 2 .Thermodynamic assessments Fig.0 ×104 Pa determined by Akashi et al.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.3.3.[57] may be explained by problems of reaching equilibrium due to extraordinarily slow cation diffusion in • ′′′ lanthanum chromite. 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.[58].9 (next page) the calculated slopes of VaLa and CrCr are 126 .3. 4.

broken lines). as calculated [Va ′′′ ] and [Va •• ] are very small.[58] as a function of La reciprocal temperatures.[58] derived from electrical conductivity measurements (symbols with error-bars. The calculated O Cr relative defect concentrations are in line with those proposed by Akashi et al. 4. 4.3.3.15.Thermodynamic assessments • compared with slopes of [Va ′′′ ] and [CrCr ] determined by Akashi et al. The presented defect chemistry calculations are still rather tentative. The calculated concentrations agree well with the data derived from electrical conductivity • measurements[58].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 amount of [Va ′′′ ] relative to [CrCr ] is fixed by the criterion for La charge neutrality. 127 . as the temperature and oxygen partial pressure dependence of excess Cr in La1-xCrO3 has not been investigated systematically so far. Eq. Fig.[58].

Foger. However the amounts of excess Cr in La1-xCrO3 used for the optimization of the cation nonstoichiometry are preliminary. Using the new database the stability limits of lanthanum chromite in function of temperature and oxygen partial pressure can be quantified. K. P. Druckerei J. and K. Jiang. M. R.P. Badwal..[53] and Cheng and Navrotsky[46]. Zhang. Solid State Ionics. Soc. Kinzel. A. D. The orthorhombic to rhombohedral transition in lanthanum chromite and the magnetic order-disorder transformation are well reproduced by the model. Göttingen. Mechanism and kinetics.-M. as the use of these data for the optimization of model parameters resulted in a proper reproduction of the phase equilibria derived from experiments. P. 2. 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. S. J.6 Conclusions Model parameters of the presented thermodynamic La-Cr-O database were optimized with assessed thermodynamic and phase diagram data. J. Deller.). Vol. First European Solid Oxide Fuel Cell Forum Proceedings. S. The thermodynamic modeling of lanthanum chromite was based on experimental thermodynamic data reported by Peck et al. Bossel (Ed.Thermodynamic assessments 4. 4013-22.3. S. 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. Miller. H. 1997. A. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Carlsson. The thermodynamic descriptions of lanthanum chromates and the liquid phase are rather tentative due to humble or sketchy experimental information. Foger.H. 147(11). Hilpert. Larsen. Y. 99. Zhang. Electrochem.G. 4. Ramprakash and J. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells.P. References 1. pp. The proposed existence of lanthanum vacancies and holes to maintain charge neutrality in lanthanum chromite with excess Cr is reproduced by the model. 1994. Proceedings of the 26th Risoe International Syposium on 128 . U. 297-310. 703. Nickel. Cr-Mn deposition at the three-phase boundary observed by TEM. I. 2. 2000. K. p. 3. Kjaer and J. Das. pp.

12. 353-362. Properties of Cu. Zinkevich. Dinsdale. V. N. Aldinger. 129 . 8. pp. Crystal structures of metals and alloys. 155-62.I. Solids. Pu.T. Nauk. Geupel. G.P. Phys. 2005.F. 177. Jiang. B. S. 723-27. J. (Eds. E. 9.I. pp.N.I.N. M. Diff. M. S. Kim. N.Thermodynamic assessments Materials Science: Solid State Electrochemistry. pp. pp. Andersson. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. K. Russian J. pp. J. S. V.-H. J. 15(4). 82-89. High-temperature corrosion of dilute chromium-lanthanum alloys.G. Ivanov. Keshelava. Kholopov. 1986. Grundy.. Phase diagram for alloys in the chromium-lanthanum system. Ceram. Y. B. J. Meng. L. Lim. pp. Chem. 17. Sundman.K. J. pp. Calphad. 7. 6. 264 (in Russian). Diwu. 11. 1985. and V doped-LaCrO3 interconnect materials prepared by Pechini.M. 167-71 (in Ukrainian). Linderoth. B.-R. J. Dong. 153-90. Z. X. O. Kobzenko.-Y. 1960.V. 1991. Naukova Dumka. Powder Metall Met. Liu. R. Dopov.P. Berezutskii. Yttrium and lanthanum solubility in chromium. 1901-07. Tavadze. 451-56. Thermochemistry of binary alloys of lanthanum with 3d-transition metals. 10. Lee. Li. Kobal. Power Sources. 362-63.V. Risø National Laboratory. F.M. 1973. Shin. Peck..P. G. 2006. Smith et al. The Thermo-Calc databank system. 13.-O. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 5. Kireev.N. V.-H.F. G. Calphad. A. 9(2). S. J.-G. D. 2006. M. T. Wang. Roskilde. pp. Kiev. Bulia. 2008. A. 317-425.-H. 5(3). pp. 335-350. 67. 2006. 1986. L. Liu. A. Jansson. O. Ivancenko. p. Met. A. Chem. 27(4). Terekhova. Denmark. Durygin. Yang. 15..). Liu.V.M. Oxid. Saxena.-H. Song. 266271. Inorg. 2008. Savitskii. Shul.. A. SGTE data for pure elements. 25(5-6). Power Sources. S. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. pp. Barabash and Y. P. 14. 2. D. pp. E. J.P. Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells. Wu. 176. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. Mikadze. Povoden. A.. Gauckler. Svechnikov. J.-K. L. Liu. Phase Equilib. Akad. pp. F. Zhao. Usenko. Ong. M. V. Ni. 2006.J. 45(5-6). and D. M. 16. J. Electroceram.

1965. M.Thermodynamic assessments 17. S. 2. Berjoan. S. B. 2005.A. pp. 6389-92 (in French)... 1968.. Dickerson. Foёx. Temp. B. 13. Rev. Grundy.A. 1963.J. Hautes. 1976. Cassedanne.N. L. 309-26 (in French). 45-50. R. O.R. Foёx. Chemical equilibria involving lanthanum chromite.M. A. Phase correlation in the systems formed by oxides of rare earths and by oxide of chromium. 9(1). Khim. R. 28. Tresvjatskiy. Gauckler. Tsyrenova. 2(2).N.-P. Hautes. J. A. Temp. Phase Equilib. 1980. Badie. pp. 20. An. Anorg. Measurement of the freezing points of refractory oxides. Berjoan.. Solubility limits of yttrium and the lanthanide rare-earth elements in chromium and chromium-iron alloys.. R. 24.. Fiz.K. Cienc. Stability and thermodynamic properties of rare earth perovskites. L. Comments on the allotropic transformations of the rare earth sesquioxides. Chem. 30. 25. Thermodynamic assessment of the lanthanumoxygen system. M. BMI-1376. Comparison of thermal properties of oxygen-containing compounds of rare-earth elements. 3. 18.V. A... pp. V. J. 57-60 (in French). Z. Foёx.G. Acad. Bauer. 48(11). pp. Ceram. Yu. Coutures. 94-99. 33136. 45(2). Meadowcroft. Energy Comm. Rouanet. Int. Energy. 119-35 (in French). S. Y. Contribution to the study of interactions between oxygen and mixed lanthanum oxide and chromium oxide(III). Int. 2004. 22(2). 130 . A. 1965. 22. High Temp. Some properties of strontium-doped lanthanum chromite. Shevchenco. Sol. Hautes. Measurement of the solidification points of several refractory oxides.P. or lanthanum chromite.F. Rev. Paris. 19. U. Thermal properties and thermochemistry of lanthanide chromates. 313-24 (in German). 40(1).M. pp. 5. 1974. Gr. Suponitskii.L. Examination of the equilibrium diagram La2O3-Cr2O3. Zh. 21. Appl. J. Chem.S. 29.. Refract. 105-13. pp. M. pp. Russ.L. J.. 1966. 1959. Flamand. J. Lopato. R. pp. Pavlivov. 1225-33. Suvorov. Ed. J.. 1968. 2705-07. 8. Epstein. At. Bras. 1969. Int. pp. pp. Int. Brit. scandium and yttrium. Sc. 260. 337.B. Examination of freezing points of rare earth oxides and chromites. 2001. pp. Foёx. 54(2). Acad. S. 23. Hallstedt. Temp. Karapetyants. pp. Ind.. Coutures.B. Sci. 61-67. 26. 294-99. 27. C. Phys. Suponitskii. M. M. Rev. D. pp. Thermochemical properties of lanthanum chromates(VI).. Shevchik. 13. Allg. A.G.

39. Akad.F.M. Raccah. 27(5).M.-M. J. Pavlikov. Tagawa. Lopato. A.P. Allg. Hashimoto. Coutures. 524-29. Kamiyama. Hashimoto. Traverse. Izv. M. Sc. A. 23(9). Thermodyn. Structural study and thermal decomposition of lanthanum based chromate. Mater. 14(4). pp. N. Analysis of Crystal Structure and Phase Transition of LaCrO3 by Various Diffraction Measurements. J. Rev. Sci. Nauk SSSR. S. R. Stølen. Paris B. Foëx. T.G. 154.C. Miner.R. 32. Mater. 1520-24 (in Russian). 1991. Neorg. Anthony.B. Some Observations on the Formation and Structure of Lanthanum Chromite. Rev. 42. Acad. 40. Kamiyama. Terao. 41. 276. Schwarz. 1973. H. Takagi. Phase Transitions in Perovskitelike Compounds of the Rare Earths. J. pp. Mirza. M. LaCrO4.S. Chim. at Temperatures from 298. High Temp. Korobeinikova. 5-8 (in French). E. 679-82 (in Russian).. Heat Capacity and Thermodynamic Properties of Lanthanum(III) Chromate(III): LaCrO3. W.P. Sakai K.G. Structural Phase Transition of Orthorhombic LaCrO3 Studied by Neutron Powder Diffraction. Yu. T. Ni)O3 Perovskite System. 43. 35. H. Izv. N. Kishi.. 805-06.A. On the Semiconducting Properties of Lanthanum Chromite. pp. T. 2(4). 2889-94. 1976. pp. S. 183-90. Lyutsko. 36. K. Höfer. Mater. T. S. Phys. 10. Specific Heat. 37. D. B. Neorg. K. Acad. Electrochem. J. 1993. Sc.F. pp. 1-14 (in German). 1985. Enthalpy. A. 1271-74 (in French). Chem. Crystal Chemistry and Thermal Behavior in the La(Cr. 1963. Y. Dokiya.N. 33. 2(4). Tolochko. 1967. V..Thermodynamic assessments 31. Momin.. Ruiz.. 1995. Akad. 2000. J. pp. Lett. C. N. Kock. Tsuda. C. M. LaCrO3 at Room Temperature.R. Berjoan. I lanthanum chromate(V). pp. Sakai. Morii. and Entropy of Lanthanum Chromite between 298 and 900 °K. H.. Anorg. P. 2000. pp. 10. Phase Transitions in Solid Solutions Based on Lanthanum Chromite.E. Chem. 1167-72. 322(1-2). Soc. J. Tresvyatskii. Yoshida. 309-16 (in French). J. 1973. Solid State Chem. 1966. S.. Oikawa..P. pp. Z. 34. Tanaka. I. V. Evaluation of the Thermal Conductivity. 1246-48. 493-506. 131 .V. Geller. N. A. Nauk SSSR. A.15 K. 132. Tsuzuki. Y. pp. pp. High-Temperature X-ray Diffractometric Studies of LaCrO3. pp. L. 140(10). 264. 38. K. Mathews. Solid State Ionics. Zonov. pp. Oikawa. K. Reznitskii. 1970. Paris C. Kononyuk. Shimojyo. Phase Transformations of Certain Chromites of the Rare Earth Elements. On the chromates(V) of the rare earths..

Cr. P. pp. 49. A.Thermodynamic assessments 44. Y. Kikegawa. Hashimoto. 1987. Kyoto. 691-94. Determination of the Standard Free Energy of Formation of LaCrO3 at 1273 K. Li.-Y. pp. Y..E. M. Dokiya. 2007. 47. Wang. J. H. X. Heat Capacity Measurement of Lanthanum Chromite by Laser Flash Method. L. Kolev. Cmaidalka. Chung. 55. Ni) in Reducing Atmosphere I. J. 7677 (in Japanese). Electron Paramagnetic Resonance and Antiferromagnetism in LaCrO3. Rev. N. Thermodynamic Properties of LaCrO3.F. pp. 81. Huang. G. Structural Studies of the (La. K. 1998.P. Res. N. Mater. 1997.-L. Navrotsky. Z. J. pp. Zhongguo Xitu Xuebao. T. 57-62.M. Bull. Mn. 74. Method. Khattack and D. Kojima. C.M. pp. Japan. N.N. Mat. M.Sr)CrO3 System. S. Yokokawa. D. Nature. Raman Spectroscopy of Low-Temperature (Pnma) and High-Temperature (R 3 c) Phases of LaCrO3. Solid State Commun. Weinberg. Kobertz. 2005. Less-Common Met. Li. 14. X. Chem. J.. I. Abstracts of the 27th Symposium on Thermal Analysis and Calorimetry. 3266-72. Yoshida. Res. M. T. Hao. 166(1). M. Larssen. M. H. 25(5). Takahashi. pp. N. A. pp. B. 20(1). Ceram. Mater. Petzow. November 1991. Hadjiev. Bull. Kawada. F. 54. 2006. Co. Litvinchuk. Sreedharan. 50. 192(4). pp. Azad. T. Alloys Compt. 1990. Thermodynamic Stability of LaCrO3 and CaZrO3 Using a Solid-State Galvanic Cell Method. 19-24 (in Chinese). Iliev. 23-29. Z. Sudha. Phys. Dudek. Abrashev. Heat Capacities of LnCrO3 (Ln=Rare Earth). 1961. Sun. Thermodynamic Stability of LaCrO3 by a CaF2Based E. G. Nickel. N. Res. Soc. 1979. A..J. 445-46.. 46. Rare Metals. W. Enthalpies of Formation of LaMO3 Perovskites (M=Cr. 56. Tagawa.P. Kozlowska-Róg. Chen. M. Polish J. Zhou. and Ni). Takagi. A. Co. 5(3).. pp. Róg. 52. 176-82. Pressure-Induced Structural Phase Transition of LaCrO3. Murakami. Stability of the Perovskite Phase LaBO3 (B=V.. Miller. Cox. Koseki. Dokiya. 132 . pp. H. 1996. M. Meng. 562-66.V. 45. V. Xing. W. J. Sakai.. Matsushita. 463-72. Y. 2006. Cheng. D. 48.Y. M. Satoh. T.-H. 649-59. H. 214301-1214301-7. S. 79(12). 51. 259. 191-200. Fe. J. Chen. Experimental Results. Hilpert. Y. O.. pp.G. Kamegashira. pp. Nakamura. R. pp. Yuan. G. Am.-Q. Fe. 12. Gauckler. R. Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties. 53. K. H. 108(9). 1977. Peck.

S. Tripathi..P. Popov. Sundman. C. T.E. 1975. Metallkd. 66. p 227-38. V. 1988. 24(3). Gauckler. accepted 63.G. pp. 32.N.N. H. 68. J. 2006. 1441-45 (in Russian). 1979.G. Chen.N.M. M. Lal. 2001. Hillert. 60. Gauckler. Jansson. Z. Ordered Defects & Nonstoichiometry in Metal Oxides of Perovskite & Related Structures. Gordon. Hillert. Z. 1998. M. pp. M. 2003. 577-82. 65. Miodownik. Phys. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. J. Calphad Calculation of Phase Diagrams. General Treatment. 66(10). Sci..K. Metallkd. Alloy.R. Rao. pp. A. Electrical Transport in Rare Earth OrthoChromites. Solid State Ionics. pp. p 161-76. Andersson. 30. L. 1989. B. M. pp. Fierro. Thermodynamic Assessment of the La-Fe-O System. Structure and Reactivity of Perovskite-Type Oxides. Izv. A. pp. 61. L.V. 59. Influence of the Synthesis Conditions on the Electrical Properties of LaCrO3. 71. Jarl..-O. Akashi. T. Calculation of Defect Chemistry Using the CALPHAD Approach. E. T. 1984. Sundman. A. J. Hallstedt. 1978. Calphad. 265-84.N. 1971. Determination of Chemical and Magnetic Interchange Energies in BCC Alloys. B. Rao. Phase Equilib. The Compound Energy Formalism.. Akad. Grundy. B. 243-.J. 437-45.B. Calphad. 1595-1609.. T. 1982. Vol. K. Wanklyn. pp. Advances in Catalysis. T. L. Mater. Maruyama. A Model of Alloying Effects in Ferromagnetic Metals. 62. 15(8). Transport of Lanthanum Ion and Hole in LaCrO3 Determined by Electrical Conductivity Measurements. L. Phase Equilib. E. Chen. V. M. J. 320. 58. Gauckler. pp. B. A.R. 17. 70. V. Diff. 67. I. 164. 133 . Guillermet. N. A. Grundy. 33-41. Hillert.. pp. Povoden-Karadeniz.J. B. 23A. Neorg.F. Rao. Hillert.Thermodynamic assessments 57. Chem. 34.L. Chem.. -Manganites and -Ferrites. Saunders. Cmpd.. Ivas. 2003. Solids. Elsevier Science Ltd. Acta Metall. 1986. Electrical Transport in Light Rare-Earth Orthochromites. pp. 79(2). Superstructures. Pergamon Materials Series. 2(3). G.. 177-83. pp. Indian J. J. M. Gopalakrishnan. 81-87.P. M. J. Jansson. 36. Vidyasagar. B. 69. C. Shvaiko-Shvaikovskii. 64.. 345-58. Tejuca. Nauk SSSR. Mater.G. 1. Thermodynamic Assessment of the Co-O System. 94-96. G. Inden. Goto.J. Ivas. Povoden. 212-27. Application of the Compound-Energy Model to Oxide Systems. pp. J. J.

M. Appl. pp. 4. A. E. Grundy..4.N. Grundy. A. Chen. Sundman.67Cr2O8. The Mobility of Oxygen Ions in CaF2. B.J. Hillert. Chen. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. R. Povoden. Experimental solid solubilities and nonstoichiometries in La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ are reproduced by the model. B. 75.2]. K. Jansson. 1990. and SrCr2O4 are presented.Thermodynamic assessments 72.J.1 Introduction Sr-doped lanthanum manganite (LSM) with the perovskite structure ABO3-δ is used as cathode materials in SOFC. 294-300. 16A. 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. 15. Electrochem. 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. Sundman. B. pp. 1991. 1985. Ågren. as well as defect concentrations of the cathode contaminated by Cr at different temperatures and oxygen partial pressures. Gauckler. 261-66. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. A. These requirements are conformed by using the CALPHAD approach. J. Povoden. 109-19. Sr2. Trans. 4. 73. 20.4 Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications E. Akila. J. The database should meet the demand to calculate stable and metastable phase equilibria. L. thermodynamic driving forces and activities. Metall. Modification of the Two-sublattice Model for Liquids. M. and L. Jacob. pp. Calphad. 74.N. submitted to Scripta Mater. M. For the construction of the 134 . Gibbs energy functions of SrCrO4. 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.T. Sr2CrO4.

Sr3Cr2O7[12] was approved as high pressure phase only[17].5 Å for 12-fold coordinated La3+.785 Å for at maximum 6-fold coordinated Mn3+)[7] we omit Mn3+ on the A-site. 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[11.12. The stoichiometry of a phase defined as Sr3Cr2O8[15] was later corrected to be essentially Sr2.2 Assessment of data from the literature Previous assessments of the La-O. Calculation of the oxygen nonstoichiometry of perovskite + MnO instead of metastable single phase perovskite[6] leads to a good agreement between experimental and calculated nonstoichiometries. Limited solution of Sr in La1-xSrxCrO3-δ perovskite[18] was confirmed by a later investigation[20].4.Thermodynamic assessments La-Sr-Mn-Cr-O oxide database La-Mn-Cr-O oxide and La-Sr-Cr-O oxide systems are assessed. in agreement with Hartl and Braungart[19].[6] with a slight modification: Grundy et al. Due to large differences between the ionic radii of La3+ and Mn3+ and possible coordination numbers (1. 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.12]. The 135 . 0. and La-Cr-O databases are adopted[3-5]. which is in agreement with Negas and Roth[15]. 4. Differences concern the reported stabilities of further compounds[11.67Cr2O8 by using microprobe analysis[18]. On the other hand the conflicting phase equilibria presented by Kisil[16] lack experimental details. 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[18]. Sr-Cr-O oxide: Thermodynamic functions for Sr-Cr-oxides in the SSUB database[9] are based on estimates[10]. whereas emf measurements using CaF2-based emftechnique[13] led to conflicting results likely caused by competing reactions[14]. Cr-O.[6] allowed Mn3+ on the A-site of LSM to reproduce experimental oxygen nonstoichiometries under low oxygen partial pressures. No quaternary phases or solid solutions were found in the Sr-Mn-Cr-O oxide system[8].15-19]: for the stabilities of SrCr2O4 and Sr2CrO4 we trust the accurate study of Jacob[11]. and the LaSr-Mn-O oxide database is taken from Grundy et al. Sr-Mn-Cr-O oxide is treated as ideal extension from the subsystems.

04. 136 . Myoshi et al. and 0. 0. 0.1.1O3-δ was measured using thermogravimetry[26]. La-Mn-Cr-O oxide: In the La-Mn-Cr-O oxide system no quaternary stoichiometric compounds were reported. Thus its extension to the quinary database would not be reliable. and 0. thermodynamic data are missing. The exact temperature and oxygen partial pressure range of Sr(La. δ of LaMn0.2.8Sr0.3 at T = 1173 K that Cr4+ were absent in the latter. 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[25].[18] it was proposed earlier that Sr(La.3 as a function of temperature and oxygen partial pressure using XRD analysis.09.8Sr0.2MnO3 and Cr2O3 at 1073 K was reported after 1000 h of heat treatment in air[28].[21] determined the Gibbs energy of formation of La1-xSrxCrO3 with x = 0.2. and 1573 K[23]. Positive δ in the perovskite formula reflects oxygen deficiency. and the solubility of Cr is unknown.Sr)CrO4 were stable in air[10].11 using drop calorimetry at T = 1080 K.5O3-δ with x = 0.25.2.Sr)CrO4 is omitted in the modeling. 0. Perovskite+MnCr2O4 spinel equilibrium of a powdered mixture of La0. and δ = 0. Plint et al. 0. Sr(La. −0. whereas negative δ essentially stands for cation nonstoichiometriy.Thermodynamic assessments existence of several Ruddlesden-Popper phases is restricted to reducing conditions. solely Sr(La. Complete solid solution between the LaMnO3 and the LaCrO3 perovskites was affirmed[8].9Cr0.3.[27] concluded from the similarity between X-ray absorbtion spectra of Cr K of LaCrO3 and La1-xSrxMn0. 1473K.2. In contrast to Peck et al.1. 1373 K.Sr)CrO4 is ambiguous. and La0. and 0.Sr)CrO4 showed reproducible stoichiometry[18].3 using Knudsen mass spectrometry. Cheng and Navrotsky[22] measured enthalpies of formation of La1-xSrxCrO3-δ with x = 0.2CrO3-δ at 1273 K[24] were measured as a function of oxygen partial pressure using thermogravimetry.24]. and 0.2.3 at T = 1273K. and −0.[20] investigated the single phase region of La1-xSrxCrO3 with x = 0.1. 0. Cr4+ and oxygen vacancies are regarded as the major defects[23.5Cr0. 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[8]. As Ruddlesden-Popper phases have not been reported to form during SOFC operation with LSM cathodes.1. and 0. Peck et al. Nonstoichiometry data for La1-xSrxCrO3-δ with x=0. −0.

However we did not obtain satisfying results in higher-order perovskites.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.and perovskite layers of the latter. As the magnetic transitions are low temperature features. and the equilibrium Sr2.67Cr2O8. 0. their modeling was omitted without consequences for the applicability of the database for SOFC.15 K and 105 Pa[45]. most likely due to interactions that cannot be reproduced by the model. (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. and Sr2CrO4 respectively.36−40]. accounting for the structural feature of alternating rocksalt. A and B are adjustable parameters.41] were reported. 4. in terms of the applicability of the new database for SOFC the authors omit structural transitions in the modeling. Consistency among transition data for La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ prevails. and 0. 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[44] + y °GCr2O3[4] + v °GO2 [45] + A + BT (4.4. LaMn1-xCrxO3-δ [26.1) SER v = 0.12] and phase stabilities of SrCr2O4 and Sr2CrO4 investigated by equilibration experiments of different mixed oxide compositions under controlled atmospheres[11]. composition and oxygen partial pressure.4. All 137 . Thus.75.Thermodynamic assessments The perovskite phase: Magnetic and structural transitions of La1-xSrxCrO3-δ [29−35].67Cr2O8 following the proposed formula[19] and for the Ruddlesden-Popper phase Sr2CrO4. Magnetic transitions have been well reproduced by an ordering-model[42.67Cr2O8+SrCrO4+Cr2O3 as a function of temperature and oxygen partial pressure[11. 7/6. SrCr2O4. and La1-xSrxMn1-yCryO3-δ [8.43] for LaCrO3[5].12]. their optimization with the following experimental phase diagram and thermodynamic data using the PARROT module of the Thermocalc software[46] resulted in the lowest error between model and experiments: Gibbs energies of formation of SrCrO4[11. Sr2.25 for SrCrO4. whereas diversities exist regarding the transitions in La1-xSrxMn1-yCryO3-δ . Transitions of LaMn1-xCrxO3-δ are complex as they depend on temperature. H a is the standard enthalpy of the stable state of element a at 298.

106904T kJmol-1 . T = 298 K.5 °GO2 [45] ° ° ° GLa3+ :Cr 4+ :O2. δ = 0.1.15 kJmol-1[21] x = 0. calc. Optimized parameters and calculated and experimental thermodynamic data are listed in Table 4. T = 2000 K.0 kJmol-1 this work.88 kJmol-1[21] x = 0. calc. Δ ° H = −55. δ = 0.1 Optimized model parameters Sr . T = 2000 K.1 kJmol-1 this work. Δμ O 2 = −262.2 kJmol-1 this work. ° Δ ° H = −36. Δ °G = −88.7 kJmol-1[20] x = 0.4.= 5 6GS4O − GS3V + 1 6GS4V + GRPRV[5] GSr 2+ :Cr 3+ :O2. calc. calc.Thermodynamic assessments reported phase equilibria[11] are correctly reproduced by the model.1080 − 1380 K[10] (1 − x) 2 La 2 O3 + xSrO + 1 2 Cr2 O3 + x 4 O 2 − δ 2 O2 = La1− xSrx CrO3−δ x = 0.76 kJmol -1[21] x = 0.2 + 0.4. T = 298 K.67Cr2O8 = 219 J La1 − xSrxCrO3 − δ ° gas GLa3+ :Cr 4+ :Va = 5 6GS4O − GS3V + 1 6GS4V + GRPRV[5] − 1.4 kJmol-1 this work.67 Cr2 O8 + SrCrO 4 + Cr2 O3 Δμ O 2 = −265.5 J ASr2.15832T kJmol-1 this work. ° Δ ° H = −67.1 and 4.340 + 0. calc.3 kJmol-1 this work.859 + 0. calc.15553T kJmol-1 . δ = 0. BSr2CrO4 = 50 J ASrCr2O4 = 98000 J. Δ H = −65.2 Calculated and experimental thermodynamic data SrO +1 2 Cr2 O3 + 3 4 O 2 = SrCrO 4 Δ °G = −273. T = 2000 K. Δ ° H = −20.4 kJmol-1 this work. BSr2.1073 − 1473 K[11] Δμ O 2 = −276.09. δ = 0.3 kJmol-1 this work.54 kJmol-1[21] x = 0. calc. δ = 0. T = 298 K. Δ ° H = −50.67Cr2O8 = −508507 J.950 − 1280 K[10] Sr2. Δ ° H = −34.4.3.5 kJmol-1[20] x = 0.2. Δ ° H = −20.825 ± 0. δ = 0.2. Δ °G = −93.3. δ = 0. δ = 0.= GS3V + 1 6GS4O − 1 6GS4V GSr 2+ :Cr 3+ :Va = GS3V − 5 6GS4O + 5 6GS4V Table 4. T = 298 K.2.8 kJmol-1 this work.7 kJmol-1[20] x = 0.3.72 kJmol-1[21] x = 0. Δ °G = −93.767 + 0.6 kJmol-1 this work. Table 4.2.4. calc.13152T kJmol-1 this work. Δ H = −48. T = 298 K.1. Δ °G = −85. Δ °G = −102. Δ ° H = −56.13157T kJmol-1 . calc. calc.851 − 1116 K[12] Δ °G = −273.1. Δ ° H = −59.6 J ASr2CrO4 = −145000 J.48 kJmol -1[21] 138 .774 + 0. calc.04. Δ °G = −109.11.166T kJmol-1 .050 + 0. T = 298 K.Cr oxides ASrCrO4 = −273771 J. Δ ° H = −34. BSrCrO4 = 131. δ = 0. Δ °G = −213. BSrCr2O4 = −95.

3) is chosen as reference. It can be accounted for by introducing interaction parameters. and small amounts of Cr brought into the cathode unlikely lead to a change of the structure. The last term describes the excess Gibbs energy of mixing. We adopt the description (A. B = cations and Va = vacancies[6] using the compound energy formalism[47]. The second-last term accounts for the configurational entropy of mixing.31451 J mol-1 K-1. °G(Sr2+)(Cr4+)(Va)3 1° 5 gas GCr2O3 [4] − °GO2 [45] 2 4 ° SER SER GSrCrVa3 − H Sr − H Cr = °GSr2+ :Cr 4+ :Va = GS4V = °GSrO[44] + (4.4.Va)(O-2. La0. Using the above model and the proposed defect chemistry[22-24] the sublattice formula for La1-xSrxCrO3-δ reads (La3+.Cr4+.Va)(Cr3+.6.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.Va)(O2-. (La3+)(Cr3+)(Va)3.Va)3 with A.4. (Sr2+)(Va)(Va)3. Thus it is reliable to take the Gibbs energies of the compounds of rhombohedral perovskite from [5] for the model.8Sr0. and A and B parameters of °G of two neutral compounds 139 .2) where yi is the site fraction of each cation and Va on the A-sublattice.Va)(B.Sr2+. R = 8. The molar Gibbs energy °G of La1-xSrxCrO3-δ is uniquely defined as follows: °Gs of the endmembers (La3+)(Cr3+)(O2-)3.Va)3.and Va on the anion sublattice. yj is the site fraction of each cation and Va on the B-sublattice. The parameters of the compound energy formalism are the Gibbs energies of the end-member compounds °Gi: j:k .2MnO3-δ are rhombohedral at SOFC operating temperatures (T=1073 K to 1273 K). e. (La3+)(Va)(Va)3. (Sr2+)(Va)(O2-)3. 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. (La3+)(Va)(O2-)3. Typical compositions of Sr-doped lanthanum manganites used for SOFC cathodes. and yk is the site fraction of O2.g. (Va)(Va)(O2-)3. and (Va)(Va)(Va)3 and ternary interaction parameters are adopted[5.48]. this is achieved by using the same model.

All endmember compounds have been defined in the assessed subsystems.Va)3.Sr .5. (Sr2+)(Cr3+)(O2-)3.5 in Eq.Mn . Thus for LaMn1-xCrxO3-δ we propose the sublattice formula (La3+. °Gs of the remaining endmembers (La )(Cr )(Va)3.4.Mn3+:O2-) = +9421 J.Va)(Mn2+.4. 4.4.Mn3+:O2-) accounting for interactions between Cr and Mn cations is fitted to experimental nonstoichiometries[26].1 and 4.Mn3+.Cr .4. A = 136453 and B = −91.5) are optimized with all available experimental data of the perovskite phase. and in Figs.24] of La1-xSrxCrO3-δ. with A = 27027 and B = −69.4. 3+ 4+ (La3+)(Cr4+)(O2-)3.Cr3+. 0L(La3+:Cr3+.6. 138). 4. Eq.4.20]. The 3+ 2+ sublattice 2+ 3+ formula 4+ 3+ of 4+ the 2- quinary perovskite reads (La . 4.2 (p. and (Sr2+)(Cr3+)(Va)3 are obtained by conversions of reciprocal equations that are set zero[48] and are listed in Table 4. The regular interaction parameter 0L(La3+:Cr3+.Cr . solid solubilities[18.Mn . All endmembers have been defined in the assessed subsystems. it is expected that it is not removed from the structure if the phase is doped.1 (p.2 for ° GSrCrO2.Va)3.5Va0.5Va0.5H O = GS3V = 5° 1 1 ⎛5 5 1 1⎞ GSr2+ :Cr3+ :O2− + °GSr2+ :Cr3+ :Va + RT ⎜ ln + ln ⎟ = °GSrO[44] + °GCr2O3 [4] + A + BT 6 6 2 ⎝6 6 6 6⎠ (4. and nonstoichiometries[23.4) ° SER SER SER GSrCrO2.Va)(Mn .4.4 Results and discussion The reproduction of experimentally determined Gibbs energies[21] and enthalpies of formation[22]. 140 .Thermodynamic assessments ° SER SER SER GSrCrO3 − H Sr − H Cr − 3H O = °GSr2+ :Cr 4+ :O2− = GS4O = °GSrO[44] + 1° 1 gas [4] G + °GO2 [45] + A + BT 2 Cr2O3 4 (4.4.Mn4+.5 − H Sr − H Cr − 2.4 denotes °G (Sr2+)(Cr4+)(O2-)3.4.Va)(O . 4.Va)(O2-. Though structure-chemical information of site occupancies in LaMn1-xCrxO3-δ perovskite is missing. 138). it is reliable to allow Cr4+ on the B-site: as Cr4+ exists in nonstoichiometric lanthanum chromite perovskite[5].Cr4+. and phase equilibria in the La-Sr-Cr-O oxide system by the modeling is satisfying as shown in Table 4.2 (next page).

141 . Calculated phase equilibria are the same as in[17]. and three phase equilibria.4. and circles with crosses denote single phase. blank circles. two phase. Filled circles. prv = La1-xSrxCrO3-δ.1 LaO1.Thermodynamic assessments Fig. 4.5 system calculated at T = 1223 K in air atmosphere (solid lines) with experimental data[17] included (symbols).5-SrO-CrO1.

0. 4. Fig.5-MnOx-CrO1. prv = LaMn1-xCrxO3-δ. However it was not possible to reproduce the nonstoichiometries at T = 1073 K and 973 K. 142 . possibly caused by equilibration difficulties due to slow diffusion.4.23] nonstoichiometries of La1-xSrxCrO3-δ at different temperatures for x = 0. α-spl = tetragonally distorted Cr-Mn-spinel.4.25.Thermodynamic assessments Fig. The calculated nonstoichiometries of La1-xSrxCrO3-δ are in good agreement with the experimental values at higher temperatures. 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. p.3 LaO1. The calculated isothermal section of the La-Mn-Cr-O oxide system at T = 1273 K in air is presented in Fig.3.2. 141 Calculated (lines) and experimental (symbols)[22.4. 4.1. 4.4. 4. β-spl = cubic Cr-Mn-spinel.5 system calculated at T = 1273 K in air atmosphere. and 0.2. as shown in Fig. 0.4 (next page).3 as a function of oxygen partial pressure.

Va)(O2-.Mn4+. Optimized by experiments in pseudoternary and pseudoquaternary oxide subsystems. The new database is adapted for quantitative calculations of 143 .28] are in line with our calculations.4. We propose the model (La3+. 4. Experimentally determined nonstoichiometry of LaCrO3 indicates the existence of some Cr4+. and the conclusion of missing Cr4+[27] is not based on a direct chemical analysis of Cr valencies.Cr3+. temperature.Va)(Mn2+. and oxygen partial pressure.Thermodynamic assessments Fig.1O3-δ at different temperatures as a function of oxygen partial pressure.Cr4+. Thus we stick to a model without interaction parameters. Experimental findings[8. 4.4 Calculated (lines) and experimental (symbols)[27] nonstoichiometries of LaMn0. We believe that complete removal of Cr4+ from the perovskite structure is unlikely.Mn3+:O2-) and L(Sr2+:Cr4+.5 Conclusions The thermodynamic La-Sr-Mn-Cr-O oxide database has been obtained by combining thermodynamic assessments of oxide subsystems. this model allows the quantitative calculation of defects as a function of composition. it would be necessary to give large positive values to the regular interaction parameters 0 0 L(Sr2+:Cr3+.4.Va)3 for the quinary perovskite phase. To approximate the absence of Cr4+[27] in quinary perovskite.Sr2+.9Cr0.Mn3+.Mn3+:O2-).

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2003. H. 31. 2008.. Sakai. Phys.S. 18. Yokokawa. C. Xiong. Yamaji. 474. Arai. Magnetic and neutron diffraction study on perovskites La1-xSrxCrO3. T. 404-10. pp. J. Solid State Comm.5Mn0. Solid State Ionics.Sr)CrO3 system. Y. Inami. Takahashi. pp. pp. T. Matsunaga.. Ohba.00 ≤ 3+δ ≤ 3. Greaves. Khattak. 435. T.95Sr0. Studies on magnetic properties of La0. Yusuf. Y. 141. Hashimoto. Irvine. S. Acta. K. 27. Y. 2006. xSrxCrO3 Analysis of magnetic and structural phase transition behaviors of La1- for preparation of phase diagram. F. T. H. 2006. Kishimoto. M. Thermodynamic considerations on Cr poisoning in SOFC cathodes. Hinatsu. Francesconi.R. 35. Morii. J. Y. F.15). Matsubara. pp. Kawaji. J. M. Tao. 1998. H.: Condens. Chakraborty. C. Evolution of crystal structure with the oxygen content in the LaMn0.E.9Cr0. K. A. Matsunaga. 2006.P. C. R.-P. S. Power Sources.75Sr0. Structural studies of (La. 57-. V. H. 170. Nakamura. O. J. Solid State Ionics. 463-71. N. 145. N. K. T. Y. Hinatsu. Cabeza. H. Morales. H. Takahashi. Long. M. H. pp. M. Caneiro. Cox.Thermodynamic assessments 25. 2005-08. 8661-72. T. 2569-78. 11. Nakamura. 222-29. 404-10. Takahashi.E.5O3±δ. Brito. Morii. S. 2008.15CrO3 by means of powder neutron diffraction. Y.K. Nakamura. 29. Bari. Tyagi. D. 176. A. P. 1999. 26. Connor. 177.. J.M. Oikawa. Y. pp. Matter. 1977. Electronic transport in the novel SOFC anode material La1-xSrxCr0. K. Pomjakushin.R. Acta. Arai. Y.A. 36. 4151-60. 502-06. 2005. Phys. Mat. Muirhead. Shimojo. Sato. 30.T.85Sr0.13.: Condens. H. Thermochim. pp. L. M.M. Chiba. Krishna. pp. Analysis of relationship between magnetic property and crystal structure of La1-xSrxCrO3 (x=0. K. Hashimoto. Komatsu. 177. J.1O3+δ (3. Shimojo. Phys. Bull.S.G. Plint. 28. Solid State Chem. Hashimoto.M.05CrO3 and La0. Tezuka. K. 146 .: Condens. 34. 12. 2000. Tezuka. P. K. Res. 33. Matter. 132-. Atake. 0.. Matsunaga. Y. Structural study of La0. Magnetization and resistivity in chromium doped manganites.25CrO3 at high temperatures. A. Y. Solid State Chem. Thermochim.A. 12. 3193-98. Matter. J. 32. 2008.12) compound. T. Ramanadham. Horita.

Hillert. 1975. Howard. Calphad. D. 1992. Jarl. 2(3). pp. Andersson.. pp. Bernik. Folgado.A. H. Chem..1. 184. H. Lett. Alloy Compd. 319-25. Hillert and M.3). Tellgren. 2005. and 0. pp. G. Gauckler. B. 1985. 43. Sci. J. M.-K.Thermodynamic assessments 37. 66(10). Dinsdale.. Assessment of the La-Mn-O system. pp.T. Oumezzine. 0. Hallstedt. 2000. G. 46. Dhahri. Stat. Anderson. Alloy. M. J. General treatment. J. The thermo-calc databank system. Kallel.N. I. Calphad. 532-40. 577-82. 143-46. El-Fadli.7Sr0. Zemni. X-ray-powder diffraction structural phasetransition study of La(Cr1-xMnx)O3 (x=0 to 0.J. B. The compound energy formalism.. Structural effects of Co and Cr substitution in LaMnO3+δ. Effect of Cr doping in La0.2. 457. Martinez. J. 26. 44. pp. Preliminary data on solid solubility between LaCrO3 and LaFeO3 or LaMnO3.5. 227-38. Cmpd. M. Diff. A. Z. Chen. S. Nordblad. F. Rundlöf. P. 10. Phase Equilib. Soc. J. M.R. Bourèe. 317-425. Kolar. J.-O. A. Vincent. pp. H. D.V. 75. Synthesis. 42. M.3Mn1-xCrxO3 with 0 ≤ x ≤ 0. Z. 353-61. B. A. J. Ceram. S. L. 15(4). pp. Holc.25) using the Rietveld method of analysis. Determination of chemical and magnetic interchange energies in bcc alloys. Tseggai. Beltrán. The strontium-oxygen system. F. 1991. Sapiña. M. N. E.. A model of alloying effects in ferromagnetic metals. (a). Mater. and magnetic properties of LaCr1-yMnyO3 (y=0. 153-90. 161-76. J. Ghedira. M. 1978. 437-43. 2008. 45. Metallkd.. Andrè. 48. M. Dhahri. Gauckler.U. 1997. Beltrán. 41. Phys. 2001. Am. 40. Mater.J. nuclear structure. 320. 9. L. Calphad. R. SGTE data for pure elements. 131-51 147 . D. Metni. Calphad. B. D. 20. Sol. Hrovat. E. Grundy. 16.. pp. Jansson. S. Hallstedt. 1685-87. J. J. Sundman. pp. 2001. 1996. 38. Inden. J. Risold. 47. Kuscer. Yau. 39. 0.

This has consequences for the electrochemical properties of the cell: the electronic conductivity of the cathode will decrease. M. whereas Cr2O3 is metastable. 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. Povoden. 148 . 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. Ivas. 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. the deterioration of the cell performance is expected to be less pronounced when the cell is operated at lower temperatures and current loads. Chen. Even though the chromium problem cannot be solved satisfactorily by varying the cathode composition or the SOFC operating conditions. 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.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. T. Gauckler. 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. and L. The spinel formation goes along with increasing Mn2+ in LSM under decreasing oxygen partial pressures. 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.J. Proper strategies to prevent the problem of chromium “poisoning” are proposed.

Thermodynamic calculations of impacts of Cr on LSM cathodes 5. 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. This reduction reaction would compete with the oxygen reduction and lead to blocking of the active sites at the triple phase boundary (TPB). Ad 1) In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary. where they cause the degradation of the cell by detrimentally affecting the O2adsorbtion. 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]. 149 . Consequently Cr-Mn spinel and Cr2O3(s) would form. Consequences of Cr poisoning have been investigated specifically in (La1-xSrx)MnO3-δ (LSM) perovskite-structured cathodes. mechanical strength. thermal stability. though partly with conflicting results. and no Cr2O3(s) is formed. -reduction. On the other hand the electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available[15]. In the last decade a lot of efforts were made to elucidate the degradation mechanisms. Both groups of researchers agree that without polarization Cr is randomly deposited inside the cathode. associated to these nuclei. 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. as well as low fabrication costs. and -diffusion process[1]. 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. The chemical dissociation approach is coherently based on the interpretation of a large number of impedance spectra. 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.1 Introduction Chromium-containing metallic interconnects are commonly used in planar-design solid oxide fuel cells (SOFC) due to their high oxidation resistance. good electronic and negligible ionic conductivity.

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[6]: 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.

5.2

Method

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[16]. The following model descriptions were used: for the Cr-contaminated cathode perovskite with the
3+

general
2+

formula
4+ 3+

ABO3
2+ 4+ 3+

a

proper
2-

sublattice for cubic

description spinel,

reads AB2O4,

(La ,Sr ,Va)(Mn ,Mn ,Mn ,Cr ,Cr ,Va)(O ,Va)3, for tetragonally distorted spinel (Mn2+)(Mn3+,Cr3+)2(O2-)4 was chosen[17], (Mn2+,Cr2+)(Mn3+,Cr3+)2(O2-)4 was used[18], and for Cr2O3 (Cr2+,Cr3+)2(Cr3+,Va)(O2-)3 was taken[18]. Uptake of Cr in LSM is expected, as a complete solid solubility of Cr in LSM has been shown experimentally[19]. 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.

150

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

E=

(5.2.1)

2(an)

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[2] 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.
2

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[20] 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 ⎜

(5.2.2)

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

151

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[21], 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.

5.3
5.3.1

Results
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.

152

with A and B standing for the cation sublattices and C standing for the oxygen sublattice.1MnO3-δ as a function of oxygen partial pressure at T=1273 K and 1073 K at μ(CrO3) = −300000 J mol-1 Fig.9Sr0.9Sr0. 5.3.9Sr0. Vertical lines indicate boundaries between different phase equilibria 153 . 5.3. and C denote sublattices of the perovskite phase.2 Phase equilibria in Cr-“poisoned” La0.1MnO3-δ and defect concentrations of La0. A. B.1 phase fractions in Cr-“poisoned” La0.1(Mn.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.

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

154

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.

156

3.2 Thermodynamic calculations of (La0.6 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. 5. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.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 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.3.7 phase fractions in Cr-“poisoned” (La0.3. Fig. At T = 1073 K Mn2O3 is stable in a Cr-contaminated LSM cathode with excess Mn in air.2)0.3.9MnO3-δ contaminated by chromium From Fig. tetragonally distorted Mn3O4 (t-sp) is expected to form.8Sr0.2)0.8Sr0. 5.

Fig. as in the case of cation-stoichiometric LSM.9MnO3-δ cathode are shown in Fig. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes In Fig. In general. 158 .2)0.8 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 (La0.8 the compositional changes of cubic spinel are plotted as a function of oxygen partial pressure at T = 1273 K.3. the compositions of the spinel phases formed during chromium “poisoning” become richer in Cr under more reducing conditions. 5.3.3.9 (next page).8Sr0. 5.

9 Phase equilibria in Cr-“poisoned” (La0. Mn2+ is higher in LSM(Cr) than in LSM at higher pO2 .10) and without Cr (solid lines in Fig. 5.9MnO3-δ with Cr (broken lines in Fig.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 and μ(CrO3) = −300000 J mol-1.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.9(Mn. In LSM(Cr) the concentrations of these cation vacancies drop strongly at low pO2 . 5.8Sr0. and the concentration of oxygen vacancies is lower in LSM(Cr) than in LSM at relatively high and low pO2 .10 (next page) is a comparison of defect concentrations of (La0. 5. The vertical line indicates the boundary between different phase equilibria Fig.3.3.3. 159 . 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.8Sr0.3. 5.9(Mn.10) at 1273 K.Cr)O3-δ and defect concentrations in (La0.2)0.8Sr0.2)0.2)0.

Table 5. next page. 5. 5. Calculated concentrations of all species in LSM(Cr) and tetragonally distorted spinel in equilibrium are listed in Table 5.9MnO3-δ (solid lines) as a function of oxygen partial pressure at T = 1273.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.Cr)O3-δ (dashed lines) and (La0.3.10 Defect concentrations in (La0.3.1.1 Compositions of LSM(Cr) and spinel in equilibrium at different T at pO2=1 Pa with and without Cr.871Sr0.3 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. 160 .9(Mn.3.8Sr0.2)0.1 Pa.3.947O3-δ spinel formation becomes important only at pO2 < 0.2)0.148Mn0.8Sr0.11.3. 5. as it is illustrated in Fig.

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-1.8Sr0.871Sr0.12. after reaching a plateau at pO2 = 103 Pa.148(Mn.Cr)0.3.947O3-δ is half of an order of magnitude higher than in (La0. next page: The concentration of oxygen vacancies in La0.9MnO3-δ at pO2 = 10-1 Pa.Cr)0. 5.148(Mn.8Sr0.2)0.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.9MnO3-δ at high oxygen partial pressures. y(Va)C even decrease slightly towards lower pO2 . 5.2)0.947O3-δ is illustrated in Fig. However. The influence of chromium on defect concentrations in La0. 161 .871Sr0. and the concentration of oxygen vacancies is almost an order of magnitude lower then in (La0.3.

One can get an idea about the degree of metastability of a phase by calculating its thermodynamic driving force.148(Mn.3.13 (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”.3. The more negative the driving force. If the driving force is 0.8Sr0.9MnO3 without chromium. Dashed lines indicate the defect concentrations in (La0.3.4 Formation of Cr2O3 This phase was not found in the thermodynamic calculations.2)0. In Fig. 5.12 Phase equilibria in Cr-“poisoned” Mn-deficient LSM and defect concentrations in La0. Vertical lines indicate boundaries between different phase equilibria 5. and the driving force for the formation of the phase is low. This is the amount of energy that is needed to bring the phase to its stable state.Cr)0. the more energy is needed to stabilize the phase.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. 5. 162 . the phase is thermodynamically stable. and thus its formation is kinetically controlled.871Sr0.947O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1 (solid lines).

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.

5.4

Discussion

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

163

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[22]. 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[23]. 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.[24]: The kinetic decomposition of the spinel phase may occur in an oxgen partial pressure gradient due to different mobilities of Mn2+ and Cr3+.

164

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[25]. 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.

5.5

Conclusions

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.

165

2000. 4. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. 127. Matsuzaki. 5. Jiang. 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. 1995. Solid State Ionics. S. 166 . J.C. Kawamura. Electrochem. pp. Yasuo. Stimming. Miyake. A1961-68. Taniguchi. K. L. Zhang. 3. Electrochem. Akiyama. Power Sources. M. aging mechanisms and lifetime in solid-oxide fuel cells. Deller. 7. T. pp.. Solid State Ionics. Tu. 2004. 3195-3205. 99. 284-93.P. Y. Advances. Birss. interaction between Mn from LSM with Cr may be cumbered by proper doping of the perovskite with further B-site cations. Yasuda. Ramprakash..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. R. pp. 297-310. Foger.S. Chromium poisoning of LSM-YSZ SOFC cathodes. Soc. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. Power Sources. Soc. U. Paulson. 2. Y.P. 6. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator. H. S. J. Furthermore.I. J.P. pp. 148. Mechanisms and kinetics.. pp. Zhang. J.P. J. T. I. Y. Electrochem. 147(9). pp. Y. S. 2004. 132. 1997. Badwal. I. Saitoh. Soc. V. Foger. 2000. J. References 1. A126-31. Thus it is expected that in this case the consequences of Crpoisoning will persist particularly at high current loads. 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. 151(11). Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells I. pp. Matsuzaki. Apateanu. Y. K. 55. J. 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. 271-278. 73-9. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes. 2001. Yasuda. S. Kadowaki. H.

B.P. J. 22.P. Applied Electrochem. Zhen. 39-43. Assessment of the La-Sr-Mn-O system. pp.Sr)MnO3 and (La. Sci. 2004. J. Inorg. 4th international symposium on solid oxide fuel cells and pers. 12. S. Povoden. Soc. 2006. 2001. 31. pp. J. Grundy. 11. Fergus. J. 16. Jansson. Hallstedt. The Thermo-Calc databank system. Jiang. S.J. Andersson. Calphad. Krumpelt et al. K. 191-201. E. J. pp. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Apateanu. Jiang. 162. 180. 1961. Jiang. 3664-71. 146. 771-774. 438-442. 1985. A. B.. Filonova.N.J. E. Zhen. Calphad.. Grundy. Gauckler. J. Phase Equilib.P. pp. 56978. Povoden. Mater. Electrochem. pp. 167 . Ceam.P. pp. Zhen.Thermodynamic calculations of impacts of Cr on LSM cathodes 8. Caplan and M. Zheng and P. Grundy.N. Zheng. Y. pp.N. 22. J. S. pp. Jiang. Zhang. Y. Europ. B (119) (2005) 80-86. comm.N. 23. 18. B. J. Mechanisms and kinetics.A. 2004. A.Ba)(Co. 353-62. J. Demina. J. M.N. 4013-22. Jiang. 52. 15. 17. Zhang. Mater. J. FY Annual report.. 153-190. 2008. pp.Sr)(Co. 9. D. 2000.P. Soc. 97. 13. Electrochem. Int.P.. S.. Petrov. S.J. 10. L. 181-192.-O. 21. pp. A. Characterization and performance of (La. Cohen. pp. 27.W. J. Power Sources.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. S.P. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. Y. Power Sources. Wu. Use of gaseous Cr species to diagnose surface and bulk process for O2reduction in solid oxide fuel cells. Jiang. I. 695-703. Eng. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells. Foger. pp. 19. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. Zhang. Gauckler. A. The volatilization of chromium oxide. S. J. 2007. J. Solid State Ionics. X.P.. S. Chem. L. 2007. Hydrogen Energy. A. 2002. 108. Li. 361-73. 1043-1052. E. 14.D. 1-22. 9. 2006. J. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. Int. Soc. Jiang.P. L. Res. 147. Diff.. 28.G.Fe)O3 electrodes. Sundman. A comparison of O2 reduction reactions on porous (La. J.. pp.D. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Russ. L. Gauckler. 2002. pp. 2006. 20. 32.

H. O. 472. in SOFC-1. Howard. 153. Singheiser.. M.P. p. Solid State Ionics.E. N. B1252-B64. Penkalla. L. p. K. 1991. 27. 154 (12). J.M. Dokiya. 2005. J. Pennington. Tagawa. Sammes. R. J. Qu. Soc. Hill. Kleitz.Thermodynamic calculations of impacts of Cr on LSM cathodes 24. Hammou. W. Effect of cathode thickness and current density. Maruyama. 2007. Hammouche. Structure and transport property of manganese-chromium-iron oxide as main compound in oxide scales of alloy interconnects for SOFCs.. J. 168 . PV 89-11. pp. L.. N. Yokokawa. 176. pp. PV 95-01. pp. K. Eds.C. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. T. Yamamoto. A. E. Sakai. J. Electrochem. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. Koc. D. Singhal.M. Chromium poisoning of the porous composite cathode. Caneiro. Hilpert.G.C. NJ (1995). E.. Singhal. T. Pennington. M. NJ (1989). M. Power sources. 114-24. Anderson. A. A. Soc. Brito. H. 29. Ed. 2006. 220. 138. H. M.B. The Electrochemical Society Proceedings Series. S. S. 28. H.A. in SOFC-IV.U. Xiong. Ivey. Y. Mertens. Yamaji. S. Horita. 25. pp. Electrochem. Phillips. Siebert. Konysheva. 1212-16. 26. Kishimoto. The Electrochemical Society Proceedings Series. 681-686. H. Jian.

STATE ATOMIC MASS AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1.48*T-26. 2000 Y -15608.440708*T*LN(T)-0.008371705*T**2 +6.34*T*LN(T)-.3088*T*LN(T).1659411*T*LN(T)-.3891E+02 5.88526E+32*T**(-9).91+1123.390071*T-34.161+88.9547989E-05*T**3-36581228*T**(-1).387295093*T**2 +4.988+174. 4000 N @@ Cr. @@ ---------------------------------------------------------@@ Functions @@ ---------------------------------------------------------@@ Standard data for elements.15 -3952.344+344.Appendix Appendix La-Cr databasea) @@ Database La-Cr.1996E+01 2.6902E+01.673-3565.908*t*LN(T)+0.00189435*T**2 -1. bcc ENTER-SYMBO FUNCTION GLABCC 298.004045175*T**2 -5.492988*T-39..08252*T+513.47721E-06*T**3+139250*T**(-1).072353*T-21. double hcp ENTER-SYMBO FUNCTION GHSERLA 298.15 -7968.7919*T*LN(T)-0.056395E-06*T**3+21167204*T**(-1).0*T*LN(T)-2.413+59. Povoden-Karadeniz 2008 @@ GO G ENTER-ELEMENT LA CR VA @@ELEMENT NAME REF.0500E+03 0 S0 0. 800 Y +321682. fcc ENTER-SYMBO FUNCTION GLAFCC 298. Dinsdale 1991 @@ La. 550 Y -3381.15 169 ..3088*T*LN(T).94+157.403+120.34397*T-163.882+181. 2000 Y -8205..413074*T*LN(T)+0.15 -8856. AMEND-ELEMENT VA VACUUM 0 H0 6. 2180 Y -34869.894+218.18*T-50. 1193 Y -136609. AMEND-ELEMENT CR BCC_A2 5. 6000 N @@------------------------------------------------------------------@@ Solid metals. Dinsdale 1991 @@ La.836315*T-34.001295165*T**2.284604*T-26.5388*T*LN(T).25865E-07*T**3.6651E+03 4.06113*T-17.8932E-07*T**3-399448*T**(-1). 4000 N @@ La. 1134 Y -16377.35429E+01.053968535*T**2 -4. bcc ENTER-SYMBO FUNCTION GHSERCR 298.

from SGTE @@ La(g) ENTER-SYMBO FUNCTION F12026T 298.878375*T-139.403+41.004045175*T**2 -5.653+18.7919*T*LN(T)-0.17+114.2*T**(-1). 1400 Y +642608.23648333E-07*T**3-722515*T**(-1).005444405*T**2 +4.011938995*T**2 +1.0037862445*T**2 -2.02767321*T**2 170 .15 +422273.338363*T-111.61216717E-06*T**3+154422. 800 Y +613345. from SGTE ENTER-SYMBO FUNCTION F7491T 298.83676*T*LN(T)-0.616317*T-50*T*LN(T). 1100 Y +393886.253215E-04*T**2 -1.016725*T-42.042032405*T**2 -3. 1134 Y -124598.93775E-06*T**3-133541*T**(-1).346741*T*LN(T)+0.3347881*T-22. 4000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.23012*T-11.085237*T+2.96003*T*LN(T)+.15 +15483. 4000 N @@ ---------------------------------------------------------------------@@ Liquid metal functions.004+171.588679E-07*T**3+10285.30043383E-07*T**3-34158815*T**(-1).878761*T-21.15 +390765.25865E-07*T**3.56798*T*LN(T)+. 3200 Y +497751.15*T**(-1).37615E-21*T**7.5192158*T-21. 10000 N @@ Cr gas.007085085*T**2 -4.54399*T-34.984+335.Appendix -6109.015+146.207991*T-19. 6000 N @@-----------------------------------------------------------@@ Gas functions @@ La gas.36083*T*LN(T)+7.747-246.905-85.82257667E-08*T**3+5.001513089*T**2 -4.418475E+08*T**(-1).928-44.5*T**(-1).0188191*T*LN(T)-0.018431*T-34.020171603*T**2 +2. from SGTE ENTER-SYMBOL FUNCTION F7763T 298.066199E-06*T**3+20994153*T**(-1). 8200 Y -92343.00189435*T**2 -1.71447833E-07*T**3+102710.69883E-07*T**3-1738066.00406*T*LN(T)+0. 1300 Y +404460.006002155*T**2 +1.0441+773.1*T**(-1). 2000 Y -12599.1074654*T-19.15 +598511.004961847*T**2 -1.232-104.059775*T-26.64743*T*LN(T)-.843-369.791973*T*LN(T)-0.331-31.976+955. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.7643*T*LN(T)-.70261E-07*T**3+2891891*T**(-1). 600 Y +426628.47721E-06*T**3+139250*T**(-1)+2. 6000 N @@ Cr2 gas.3088*T*LN(T).15 +5332.85*T**(-1).33826017E-06*T**3-312130.0188*T*LN(T)+0.908*T*LN(T)+.5353212*T-40. 1134 Y -3942.955-30. 2180 Y -16459.06299*T*LN(T)-0.3088*T*LN(T).0037094435*T**2 -2.4786162*T-13.797+89.28626*T+17.386+178.

ENTER-PAR G(LIQ... 2 1 0. @@ ------------------------------------------------------------------------@@ Liquid. @@-----------------------------------------------------------@@ Gas ENTER-PHASE GAS G 1 LA CR CR2.. 5800 Y -484185.0428*T*LN(T)+3.7145*T*LN(T)+...CR:VA...CR:VA....CR2.15 +F7491T+RTLNP. @@ GO PAR SET-OUT-LEVEL.15 +GHSERCR. ENTER-PAR G(LAFCC..15 +GHSERLA. set-interactive a) databases scripts can be used in Thermocalc with the extension .CR:VA.. ENTER-PAR BMAGN(BCC..34+623..0) 298.LA.tcm 171 ..CR:VA..51783483E-07*T**3+1.. AMEND-PHASE LIQ COMP 2.LA.4 ENTER-PAR TC(BCC..LA:VA..LA:VA..15 83500.0) 298. ENTER-PAR L(BCC.07969*T*LN(T)-..5 LA ..CR:VA. @@ ----------------------------------------------------------------@@ Alloys @@ BCC_A2 ALLOY ENTER-PHASE BCC.188555*T-52.9699545E-04*T**2 +1.0) 298.0) 298. fcc ENTER-PHASE LAFCC..137623*T-105.0) 298...605906E-06*T**3-5831655*T**(-1).49*t..135805E+08*T**(-1).. ENTER-PAR G(GAS.15 +GLALIQ.15 +GCR_L....0) 298.0) 298..15 64573-23*t.LA..0) 298.Appendix +1...LA:VA.15 +F12026T+RTLNP. AMEND-PHASE-DESC BCC MAGN -1 0....4843765E+08*T**(-1)....97520167E-07*T**3+7.5939925E-07*T**3+14793625*T**(-1).... N.. ENTER-PAR G(LIQ.055+2598.CR.. 3900 Y +347492...15 +GLABCC..CR:VA..004229401*T**2 +1..CR:VA..895+159.1) 298.... VA..LA. @@ La.15 +GLAFCC. ENTER-PAR L(LIQ. ENTER-PAR G(BCC. VA.15 -311.15 +F7763T+RTLNP. 2 1 1 LA CR.. @@ Interaction parameters from binaries ENTER-PAR L(LIQ...5.028597625*T**2 -4.15 60713-5. ENTER-PAR G(GAS.0) 298.. ideal extension from lower-order systems ENTER-PHASE LIQ...LA:VA..... 2 1 3 LA CR. VA.. 2300 Y +553119.. ENTER-PAR G(LADHCP.. VA... 2 1 1 LA.0) 298.25559*T-334.0) 298. ENTER-PAR G(BCC.15 -0...0) 298..0) 298. dhcp ENTER-PHASE LADHCP. 6000 N @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Metals @@ La. ENTER-PAR G(GAS..008.

0252E+02. @@ @@ -------------------------------------------------------------------@@ 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 ... AMEND-ELEMENT H 1/2_MOLE_H2(G) 0. AMEND-ELEMENT CR BCC_A2 5.2008E+01.3410E+03 1.7620E+01 6...0500E+03 2. AMEND-ELEMENT O 1/2_MOLE_O2(G) 1.) considered @@ @@ Quinary Ruddlesden popper phase is very tentative. Povoden-Karadeniz @@ @@ Database La-Sr-Mn-Cr-O-(H). @@ Actual version: Dec2008 by Povoden-Karadeniz @@ @@ COMMENTS @@ @@ Sr-Cr-O liquid: simple description.65340E+02.5999E+01 4. first version: Feb2006 by Povoden. AMEND-ELEMENT VA VACUUM 0 0 0.. associate at composition SrCrO4 can @@ help for better fit to experiments – future work @@ @@ No data exist for Sr-Mn-Cr-O.3891E+02 6.Appendix La-Sr-Mn-Cr-O-(H) oxide database @@ LA-SR-Mn-CR-O-(H) oxide. 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..6902E+01.1008E+01 0 0.5694E+01.4938E+01 4.35429E+01.1996E+01 4.5680E+03 5. AMEND-ELEMENT SR SR_FCC_A1 8.9960E+03 3. as only few phase @@ diagram data exist! @@ -------------------------------------------------------------------GO G ENTER-ELEMENT LA SR MN CR O VA H @@ELEMENT NAME REF. STATE ATOMIC MASS H0 S0 AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1.. AMEND-ELEMENT MN CBCC_A12 5.6651E+03 5.

390071*T-34.905*T*LN(T)-4.3088*T*LN(T).284604*T-26.1659411*T*LN(T)-.48*T-26.908*t*LN(T)+0.196104*T-30. bcc ENTER-SYMBO FUNCTION GHSERCR 298.008371705*T**2 +6.47721E-06*T**3+139250*T**(-1).27966+130. 550 Y -3381. 6000 N @@ O1.88526E+32*T**(-9).61225E-3*T**2 -1.15 -8115. Dinsdale 1991 @@ La.00734768*T**2 +69827.06113*T-17.15 -8856.2648*T-48*T*LN(T)+1.251266E-3*T**2 +1.6184604E-07*T**3-38364.8742*T**(-1). double hcp ENTER-SYMBO FUNCTION GHSERLA 298. (1/2 O2) ENTER-SYMBO FUNCTION GHSEROO 298.344+344.00189435*T**2 -1. cbcca12 ENTER-SYMBO FUNCTION GHSERMN 298. 4000 N @@ Sr.0*T*LN(T)-2.34*T*LN(T)-. 3000 N @@ Mn.059572*T-23.403+120.15 -7968.15 -3480.84189E-07*T**3+850134*T**(-1).656847E30*T**(-9).367+107.1*T**(-1). 1000 Y 173 .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.0905432*T*LN(T)-3. 820 Y -13380.1355068*T*LN(T)-0.41+312. 2000 Y -15608.005098873*T**2 +6.18*T-50.5028601*T-11.94+157. fcc ENTER-SYMBO FUNCTION GHSERSR 298.8932E-07*T**3-399448*T**(-1). 1519 Y -28733.15 -7532.882+181.4582*T*LN(T)-0.872255-25.67477E-07*T**3-2055*T**(-1).102+153.001295165*T**2. 2180 Y -34869. 2000 N @@ Cr.183879*T-23.413+59.

02477557E+05+2.15 -1. Povoden 2005 @@ METASTABLE CRO ENTER-SYMBO FUNCTION GCR1O1 298..15 -4.12922234E+05*T**(-1)..74079033E-02*T**2+9.629*T*LN(T)-0. @@ Sr-oxides.15 -607870+268.15 -1833257+692.2856E+02*T-119..728+31...8138015*T*LN(T)-5.555*T+GLA2O3D. MNO ENTER-SYMBO FUNCTION GMN1O1 298. Cr2O3 ENTER-SYMBO FUNCTION GCR2O3 298.259625*T-18...911E+01*T*LN(T)-2.5*GHSEROO+255269-53.986*T+GLA2O3D.41618912E+06+8.15 -1..15 +108305+GCR2O3+0.66000166*T-16.9579637E-04*T**2 +6..15 +1.86138663E+05*T**(-1).. Grundy 2006 ENTER-SYMBO FUNCTION GMN2O3 298.5*GCR2O3-0..15 43192-18..95379396E+02*T-6.. Grundy 2003 @@ MANGANOSITE..78055555E-09*T**3+262904..97E-03*T**2 +1.66666666667*GHSERCR.6846E+02*T-9.778*T**(-1).76015+12.43703676E+06+8.52766201E+01*T*LN(T) -7...15 -5.5*GCR2O3-0.15 -1. @@ ALPHA-HAUSMANNITE.15 +GSROSOL+GHSEROO-43740+70*T.15 +0..68352649E+01*T*LN(T) -3.86138663E+05*T**(-1)..85001409E-03*T**2+2... ENTER-SYMBO FUNCTION GLA2O3X 298..64955386E+05*T**(-1)... optimized @@ La-oxides. 3300 Y -13986. @@ @@ MN2O3-FUNCTION. @@ -------------------------------------------------------------- 174 .54747566E+02*T*LN(T) -1.15 -9..54747566E+02*T*LN(T) -1..05E+06*T**(-1).56*T*LN(T)-0.0822E+05*T**(-1). Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3D 298..75120338E+02*T-1.5*GHSEROO+280045-93.. ALPHA-MN3O4 (DISTORTED) ENTER-SYMBO FUNCTION GTMN3O4 298...80284521E-03*T**2+6...9*T-47. @@ Mn-oxides.82*T. MN1O2 ENTER-SYMBO FUNCTION GMN1O2 298.45091278E+05+3. @@ reduced neutral endmember of CR2O3 ENTER-SYMBO FUNCTION GCRO0 298.96393E+05+5. @@ BETA-HAUSMANNITE. MODIFIED.15 32350-13..25243E-04*T**2 +1.9664*T-120.9536*T*LN(T)-4. @@ SrO2 ENTER-SYMBO FUNCTION GSRO2SOL 298.89567858E+02*T-1.. 6000 N @@-----------------------------------------------------------@@ Binary oxides..8*T*LN(T)-4... @@ PYROLYSITE.164542E+06+7. Risold 1996 @@ SrO ENTER-SYMBO FUNCTION GSROSOL 298.76*T.. @@ Cr-O oxides. @@ ESKOLAITE..74079033E-02*T**2+9. @@ CR-SPINEL CR3O4 ENTER-SYMBO FUNCTION GCR3O4 298...59355626E+02*T-4.00307*T**2 +190000*T**(-1). ENTER-SYMBO FUNCTION GLA2O3H 298. BETA-MN3O4 (CUBIC) ENTER-SYMBO FUNCTION GCMN3O4 298.0721E-08*T**3+4383200*T**(-1).056E-02*T**2 +6.006854*T**2 +808000*T**(-1)-1E7*T**(-2).Appendix -6568..

...71704891E+01*T.15 +GMN2O3+GSM3_HEX-2.19200000E+04...15 +GLA2O3D+GMN1O1+6. ENTER-SYMBO FUNCTION SRX_ALPH 298..15 0.. @@ @@ Functions of the La-Cr-O system.99100000E+04-90*T.26029731E+04-3.78500000E+05.158E+04..15 +GSROSOL+0. @@ @@ Functions of the La-Mn-O system.. optimized (except perovskite functions) @@ @@ Functions of the La-Sr-O system..15 +GMN2O3+GSM4_HEX-8. ENTER-SYMBO FUNCTION GSM3OZ 298. @@ @@ Functions of the Sr-Mn-O system. @@ RP1 ENTER-SYMBO FUNCTION GS4O_RP1 298.. @@ Sr7Mn4O1 175 .5E+04. ENTER-SYMBO FUNCTION GSM3_HEX 298.799*T.15 GLA2O3D+0.14*T...15 +2*GSROSOL+2. ENTER-SYMBO FUNCTION RE_BETA 298..15 +2*GSROSOL+2.5*GCR2O3+9... Grundy et al..15 0.55*T..15 +2*GSROSOL+GMN1O2-1..73000000E+03 -1..5*GCR2O3+1.15 @@ 3.15 +4*GSROSOL+3*GMN1O2-3..15 +GLA2O3D+2..11300000E+05...5*GHSEROO-371557+205*T. 2005 ENTER-SYMBO FUNCTION GL2MNO4 298..5*GCR2O3+4.5*GMN2O3-68300.. ENTER-SYMBO FUNCTION LA_BETA 298. Grundy 2004 @@ HEX Phase ENTER-SYMBO FUNCTION GSM4_HEX 298....5*GHSEROO-73045-4. @@ LA7 @@ ENTER-SYMBO FUNCTION GLA7 298. ENTER-SYMBO FUNCTION RE_ALPHA 298.. ENTER-SYMBO FUNCTION SRH_ALPH 298.5*GHSEROO-154101-2..5E+04..15 +GSROSOL+GMN1O2-1..5*GLA2O3D+GCR2O3+2. Grundy 2004 ENTER-SYMBO FUNCTION SR_ALPHA 298.15 @@ 8*GLA2O3D+3.70000000E+01*T.. ENTER-SYMBO FUNCTION GL3O_RP2 298. ENTER-SYMBO FUNCTION GL3O_RP1 298. @@ intermediate La-chromates @@ LA16 @@ ENTER-SYMBO FUNCTION GLA16 298..5E+04....15 +GSROSOL+GLA2O3D+GMN2O3-137400.. @@ RP2 ENTER-SYMBO FUNCTION GS4O_RP2 298..15 +3*GSROSOL+2*GMN1O2-8. @@ SrMn3Oz as SrMnO3_Mn2O3 ENTER-SYMBO FUNCTION GSM4OZ 298. Povoden 2008 @@ LA2CRO6 ENTER-SYMBO FUNCTION GLA2CRO6 298.15 GLA2O3D+1.... @@ LA2CR3O12 ENTER-SYMBO FUNCTION GLA2CR3 298.....5*GLA2O3D+0..32830000E+05...15 +GSROSOL+0....5*GHSEROO-540404-9.. @@ RP3 ENTER-SYMBO FUNCTION GSM4_RP3 298.79100000E+03..15 +2*GSROSOL+2.Appendix @@ Ternary oxides......5*GMN2O3-7.

15 +0. @@ SR2CRO4 ENTER-SYMBO FUNCTION GS2CO4 298..19*T*LN(T) +232934*T**(-1). @@ ENTER-SYMBO FUNCTION GL3OL 298.5*T.77*T-7. @@ @@ Functions of the La-Sr-Cr-O oxide system..15 2*GSROSOL+0.. @@ TETRAGONALLY DISTORTED SPINEL ENTER-SYMBO FUNCTION GTSPINEL 298.6*T.. @@ SRCRO4 ENTER-SYMBO FUNCTION GSCO4 298..19*T*LN(T) +232934*T**(-1)-3429+4..Appendix ENTER-SYMBO FUNCTION GS7M4 298.15 0....5*GLA2O3D+0.5*GMN2O3-63367+51.5*GCR2O3+0.77*T-7. ENTER-SYMBO FUNCTION GLCR3O_RP1 298.15 +2..19*T*LN(T) +232934*T**(-1)+400-0.15 +6*GL2O+4*GL4O+3*GV4O-12*GL3O-254212.333333333333*GHSEROO -508507+219*T....15 +2*GSROSOL+0.75*GMN1O2-91857+20.72*t.5*GCR2O3+0...5*GLA2O3D+0.33333333334*GTMN3O4-200942+75. @@ SR3CR2O8 ENTER-SYMBO FUNCTION GS3C2O8 298.31*T....15 +0.. ENTER-SYMBO FUNCTION GMS3O 298.666666667*GCR3O4+.4*t..77*T-7.66666667*GSROSOL+GCR2O3+2..5*GLA2O3D+0.15 0.5*GMN2O3-63367+51.. @@ @@ Functions of the Mn-Cr-O system.333333*GLA2O3D+GMN1O2-53760.69*T.. ENTER-SYMBO FUNCTION GVVV 298....15 +GSROSOL+GCR2O3+3*GHSEROO-325047+196*T.15 +0. ENTER-SYMBO FUNCTION GV4O 298..5*GHSEROO-273771 +131... @@ ---------------------------------------------------------------@@ Perovskite functions @@ Grundy 2005 @@ Charge compensated by Mn+4 (correct) ENTER-SYMBO FUNCTION GL3O 298...15 +0. @@ SRCR2O7 ENTER-SYMBO FUNCTION GSC2O7 298...5*GHSEROO. Povoden 2008 @@ SRCR2O4 ENTER-SYMBO FUNCTION GSC2O4 298.33333333334*GCMN3O4-210795..15 +GLACRO3+GSROSOL+7000-25*t...73000000E+03-1.3+61.. Povoden 2005 @@ CUBIC SPINEL ENTER-SYMBO FUNCTION GSPINEL 298.15 +GSROSOL+GCR2O3+98000-95.12450000E+05+50*T..15 +GSROSOL+0. Povoden 2008 @@ Ruddlesden Popper phase ENTER-SYMBO FUNCTION GREFRP 298....1*T.5*GMN2O3-63367+51. ENTER-SYMBO FUNCTION GL4O 298. @@ @@ Functions of the Sr-Cr-O system.15 +0....15 +GSROSOL+0.5*GHSEROO-145000+50*T.. @@ ENTER-SYMBO FUNCTION GL3OR 298.15 +0.5*GCR2O3+1.5*GMN2O3-7..15 +7*GSROSOL+4*GMN1O2-6....5*GLA2O3D+GMN1O1+27672.. ENTER-SYMBO FUNCTION GL2O 298.44550000E+04 176 .5*GLA2O3D+0.666666667*GCR3O4+..

15 +GSROSOL+0.118994*T-5.0188191*T*LN(T)-0.1840595E-2*T**2 +4..00189435*T**2 -1. 1519 Y +GHSERMN+18739..38*T-0.6208*T-4..5*GCR2O3+0.5*GCR2O3+0. 1050 Y -10855.5*GCR2O3-2..984+335.52*t. 4000 N @@ Sr ENTER-SYMBO FUNCTION GSRLIQ 298.15 GSROSOL+0.15 +GHSERMN+17859..020171603*T**2 +2.15 GSROSOL+0. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.Appendix -1. 2180 Y -16459.653+18. @@ Function for neutral endmember SR(CR+3..41929E-21*T**7. @@ Reciprocals: all 0!!!!! @@ @@ Povoden 2008 @@ LaCrO3-PEROVSKITE ENTER-SYMBO FUNCTION GLACRO3 298.5*GHSEROO-291802-250*t.93775E-06*T**3-133541*T**(-1). 6000 N @@ --------------------------------------------------------------------- 177 .5*GCR2O3-73591+2.0668978*T*LN(T)-3...5*GCR2O3+0.. ENTER-SYMBO FUNCTION GLACR4O 298.91-12.406219*T-39..908*T*LN(T)+.15 +2194.....015+146. @@ (LaSr)CrO3+/-delta-Perovskite @@ Reference SrCrVa3 ENTER-SYMBO FUNCTION GS4V 298..981237E-06*T**3-265559*T**(-1).15 +GLACRO3-340+0. @@ ---------------------------------------------------------------------@@ LIQUID FUNCTIONS @@ ---------------------------------------------------------------------@@ Liquid metal functions.059775*T-26. @@ Function for neutral endmember SrCrO3 ENTER-SYMBO FUNCTION GS4O 298.47721E-06*T**3+139250*T**(-1)+2.004+171.... 1134 Y -3942...463*T*LN(T).3088*T*LN(T).15 0.11300000E+05+2..15 0.51-13. @@ Functions for defect chemistry ENTER-SYMBO FUNCTION GVCR4O 298.15 +5332. 3000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.5*GHSEROO-200000.VA)O3 ENTER-SYMBO FUNCTION GN 298.15 +547422..5*GCR2O3+11.15 0..29+213..018431*T-34.70000000E+01*T.616317*T-50*T*LN(T)..23012*T-11.42*t..2288*T-1.997-10..37615E-21*T**7. ENTER-SYMBO FUNCTION GALACRO3 298.63*t.33333*GLA2O3D+.26500000E+04 -7.68*T* LN(T)... ENTER-SYMBO FUNCTION GMS4O 298.2386*T+135166-88.5*GLA2O3D+0.656847E30*T**(-9).15 +GSROSOL+GMN1O2-1.5*GHSEROO+10222-55. 3000 N @@ Mn ENTER-SYMBO FUNCTION GMN_L 298.69000000E+00*T..15 +15483.5*GHSEROO. ENTER-SYMBO FUNCTION ANTI 298.

48508*T**2-. source: Thermocenter of russian academy @@ of science (T.00631160667*T**3+5.629*T*LN(T)-0.Appendix @@ Liquid oxide functions. optimized @@ liquid La2O3.31*T-40.19*T*LN(T) +27.49525609E+04+4.15 +173449.C.8669*T*LN(T) +.R..135*T**(-1).1684007*T-39.C. 6000 N @@ CR1O1 Gas (SGTE 1998. 900 Y +170853.4-33.237405*T+14..178604*T-117.917665E-05*T**3-18523425*T**(-1).2897*T*LN(T)-.5192158*T-21..001513089*T**2 -4. @@ liquid Mn oxides.0 (1998)..06284295E+01*T.1074654*T-19.229905E-07*T**3+35263.. 601 N @@ -----------------------------------------------------------------------@@ GAS FUNCTIONS @@ --------------------CHROMIUM GAS---------------------------------------@@ CR Gas: SGTE v 3.928-44.36083*T* LN(T) +7.15 +390765.0063*T**2 +31300*T**(-1)+9.62+32.00148*T**2 +873600*T**(-1)+1.5329*T*LN(T)+.083*T-30.2320948*T**2-9.15 0.. Povoden ENTER-SYMBO FUNCTION GCR1O1_L 298.15*T**(-1).9513659*T-30.63356E+08*T**(-1).14296167E-05*T**3+978019*T**(-1). 10000 N @@ CR1O1 Gas. Grundy ENTER-SYMBO FUNCTION GMN1O1_L 298.708+805.1*T*LN(T). Risold ENTER-SYMBO FUNCTION GSROLIQ 298.39465890E+04-2.588679E-07*T**3+10285.23648333E-07*T**3-722515*T**(-1). @@------------------------------------------------------------------@@ LIQUID WATER.A..C. 540 Y -8528143.15 -566346+449*T-73.41*T*LN(T).555*T*LN(T)+0.59563*T-186.. @@ liquid SrO.253215E-04*T**2-1.671+1078.. 8400 Y -403765.R..S)...5567E-7*T**3.504926*T**2+4. ENTER-SYMBO FUNCTION GCR2O3_L 298.A.008463125*T**2 +1.1304*T*LN(T) -.003139382*T**2 -1..00607059*T**2 +9..15 -1833257+692.A.224944*T-121.52515733E-07*T**3+682877*T**(-1).4*T. 1000 Y +167489. ENTER-SYMBO FUNCTION GMN2O3_L 298. 600 Y -331037.45*T-22596. from T.006854*T**2 +808000*T**(-1)-1E7*T**(-2)+141329-56. 4000 Y +307209. 178 .R. 1100 Y +393886.5*GCR2O3-0.36845867E-08*T**3+6.15 +2*GMN1O1+GHSEROO-6.9664*T-120.8788-3288. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3LIQ 298. REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCR1O1_G 298.722975E-07*T**3-64209900*T**(-1). from T.869-31.15 GCR2O3+439078-169*T. Class: 4 @@ SGTE=scientific group thermodata Europe @@ ENTER-SYMBO FUNCTION F7491T 298.15 +176483.5*GHSEROO+339673-121.31437957E+01*T..S.15 -332319.282+741. 500 Y -62418.502-414.00119977*T**2 -1.6220*T..331-31..74749*T*LN(T)+.097*T*LN(T)-0.15 GMN1O1+4. Class: 4 ENTER-SYMBO FUNCTION GH2O_L 298.48744*T*LN(T)-.35563E+08*T**(-1).96003*T*LN(T)+.. @@ liquid Cr oxides.69E-7*T**3.18729*T+495.S Class: 5) ENTER-SYMBO FUNCTION F7705T 298.3+37.9+142414.

4989821*T-20.59784667E-06*T**3+9. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O3_G 298. 1000 Y -118120+123.6128262*T-17. 2800 Y 179 .15 -9522.R.14281783E-08*T**3+3561002.00012*T**2 +932050*T**(-1)-8.78+10.35707*T*LN(T)+0.60539333E-06*T**3+99530. 2100 Y -18840.1284109*T**2 +5.944-37.01555*T*LN(T)+1.01667E-8*T**3.64520667E-09*T**3-3973170. 2800 Y +409416.00584168*T**2 +3. 2100 Y +866367.44768833E-06*T**3-2. 6000 N @@ O3 Gas (SGTE 1998.14618667E-07*T**3-1280036*T**(-1).45470312*T-28.6+6101.621+24.0922361*T**2 +4.Appendix 3000 N @@ CR1O2 Gas. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION HGAS 298.05082*T*LN(T)-0.1699975E+08*T**(-1).S Class: 4) ENTER-SYMBO FUNCTION F10963T 298.00623741*T**2-6.09852775*T**2 -2.8435*T*LN(T)+.798361*T-149.3120249*T-32. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O2_G 298.1304835E+08*T**(-1).58118*T*LN(T)-.526*T*LN(T)-0. reassessment Chen 2006.61*T-57.383-1950.15 -250423.2*T*LN(T)-.10286*T*LN(T)+.8612582*T-21.01283575*T**2 -3.555105E-07*T**3-2.45*T**(-1).3956+710.02763076*T**2 +4.43E-6*T**3.0010728235*T**2 +1.10457667E-06*T**3+12362250*T**(-1).0216*T**2 +428900*T**(-1)+3.9608*T*LN(T)+.89*T-82. 700 Y +114760. 1300 Y +49468.09482*T-134. 6000 N @@ H2O1 Gas (SGTE 1998.00206456*T**2 -5.1663+92.075-3566.610855E+08*T**(-1).45*T**(-1). 1000 Y -354716.4437*T*LN(T)-.043+890. 6000 N @@ -------------O-H GAS----------------------------------@@ H2 Gas (JANAF THERMOCHEMICAL TABLES SGTE) ENTER-SYMBO FUNCTION H2GAS 298.09*T**(-1).43044*T*LN(T) -.5*T**(-1).15 +130696.401E-6*T**3. reassessed by Ming Chen 2006.494-20.70834*T+223.696*T*LN(T)-0.2001*T*LN(T)-.0155*T**2 +245800*T**(-1)+2.33E-9*T**3.81*T-56. 6000 N @@ H Gas (JANAF 1982.C. 3000 N @@-------------------OXYGEN GAS------------------------------------@@ O Gas (JANAF 1982.3696*T*LN(T)+.879+30.569*T*LN(T)-0.15 -341231.15 +211801.413565E-04*T**2 +7.46390667E-07*T**3+56582.A. 4900 Y +97590.9096643*T-27. 1100 Y -256145.97393+78. 3500 Y -1866338.13383*T-764. from T.3*T**(-1).17486667E-07*T**3+1572175*T**(-1).0847281*T-17.623+176.0027589925*T**2 -7.80563*T+421.S Class: 4) ENTER-SYMBO FUNCTION F14021T 298.40916*T*LN(T) -.23131283E-08*T**3-42897.15 -109942.01526167E-08*T**3-64163.A. 1000 Y +180.05535833E-07*T**3+1246309.15 +243206.007055445*T**2+3.5*T**(-1).306855E-06*T**3-21589870*T**(-1).09+299.21188*T*LN(T)-5.1894682*T-31.R.C.00016*T**2 +1814700*T**(-1)+7.434+4.84857*T*LN(T)-0.59*T-39.78611*T*LN(T).626737*T-60. 3000 N @@ CR1O3 Gas.5*T**(-1). 2950 Y +252301.5273873*T-31.423-52. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION F13349T 298.039707355*T**2 -4. from T.99+130.2687055E-04*T**2 -1.108664-15.

3000 N @@ CR(OH)2 Gas. 700 Y -156470.334E-8*T**3.4077*T*LN(T) +.659505E-06*T**3+65357.2E-7*T**3.053*T*LN(T) -0.10636*T*LN(T) -. 1000 Y -492562+351.0018*T**2+2218000*T**(-1)-2. assessment Chen 2006.213599E-04*T**2-1.36297E-06*T**3-29469.99164+54.0016703495*T**2-1.77872*T*LN(T) +2.0031*T**2+266750*T**(-1)-9.39E-6*T**3.003069987*T**2+6. 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. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O2_G 298.65*T**(-1).2768*T*LN(T) +6.882+553.47*T-96. 18000 Y -154907. 3600 Y -67875.018507875*T**2+2.R.418+116.9*T*LN(T) -.771+239.551*T*LN(T) +0.953+370.0146*T**2+715900*T**(-1)+2.191295*T-50.42186*T*LN(T) -.690197*T-42.A.686636*T-25.86*T-75. 3000 N @@ CRO2(OH) Gas. 3000 Y +31735.175*T*LN(T) +0.406716*T-68.82*T**(-1).2016233*T-40.007931945*T**2+4.C.645643*T-59. 20000 N @@ H1O2 Gas (SGTE 1998.32333233E-08*T**3+1.C.0007*T**2+243850*T**(-1)-9.122915E-07*T**3+925845*T**(-1).47539017E-08*T**3+1.0018*T**2+1338300*T**(-1)+9. from T.724*T*LN(T) -0.0783-20.15E-8*T**3.6898+15.971-37. 20000 N @@ H1O1 Gas (SGTE 1998.94216*T*LN(T) -.52*T-74.64106-55.9096451*T-29.15 -274384.24542*T*LN(T) +.7343256*T-24.15 +1075.0023107985*T**2+5.765625E+08*T**(-1).96842*T*LN(T) -.4391015E+08*T**(-1).259882*T-92. 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: 1) ENTER-SYMBO FUNCTION F10666T 298.S Class: 4) ENTER-SYMBO FUNCTION F10729T 298.05*T**(-1). 1000 Y 56684+136.573855E-09*T**3+26048030*T**(-1).1497212*T-26.1931655E+08*T**(-1).277-65.326117*T-69.001713168*T**2-6.15 +68260+52.97594167E-08*T**3+2458230.8961+275.45435*T*LN(T) -.75E-7*T**3. 1000 Y 180 .77*T-83. 1000 Y -276268.R.15 -147258.2921095E-09*T**3-4. 8400 Y -489068.0019361405*T**2-1.29733833E-07*T**3+684985.91863E-08*T**3-6415210*T**(-1).505+120.15 -351288.53*T-57.292415E+08*T**(-1).12331E-04*T**2-6.4+195. 3000 N @@ CRO(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O2_G 298.A.42189E-05*T**2-1.52+180.799205E-07*T**3-25503.003149545*T**2+1.94271*T*LN(T) -.15 -497678+273.87*T-46.5*T**(-1). from T.7*T-72. 800 Y -7932.002*T**2+185600*T**(-1)-1. 8600 Y +41016.0015*T**2+938850*T**(-1)+5.Appendix -268423.15 +30698.34404917E-07*T**3+116618.97699*T*LN(T) +.135E-7*T**3.5*T**(-1). +326722.51E-7*T**3.0792741*T-24.30298483E-10*T**3-8.65*T**(-1). 6000 N @@ H2O2 Gas (JANAF SECOND EDIT SGTE) ENTER-SYMBO FUNCTION F10983T 298.32+190.927*T*LN(T) -0.036948065*T**2+6.5127-12.242048*T-24. 18000 Y -165728.257*T*LN(T) -0.1173*T*LN(T) +6.00501027*T**2+2.775*T*LN(T) -.

019*T**2+513600*T**(-1)+1.05+820. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION G_CRH4O5 298.004*T**2+1.R. 3000 N @@ CRO(OH)2 Gas.002*T*LN(T) -0.89*T-216. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH5O5_G 298.15 -976204+672.6*T-162.0096*T**2+4. assessment Chen 2006.525*T*LN(T) -0. 3000 N @@ CR(OH)4 Gas.46-2142.9*T-190.008*T**2+840600*T**(-1)-1.4+51.67833E-07*T**3.098*T*LN(T) -0. 5500 Y +1270342.1+867.15 -851590.6*T-195.049*T*LN(T) -0.0065*T**2+2669300*T**(-1)+3.01*T**2+4151100*T**(-1)+5.006*T**2+2525450*T**(-1)+2. assessment Chen 2006. assessment Chen 2006. 3000 N @@ CRH1 Gas (SGTE 1998. 1000 Y -997791. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH4O4_G 298.41*T*LN(T) -0. combined assessment Chen 2006 @@ based on Ebbinghaus 1995 @@ and from Povoden-Karadeniz based on Opila 2007 ENTER-SYMBO FUNCTION GCRH2O4_G 298.86+694.457*T*LN(T) -0.16*T*LN(T) -0.5*T-163*T*LN(T) +0.0054*T**2+1023500*T**(-1)-1.004*T**2+785800*T**(-1)-2.60191*T+219.65*T*LN(T) -0.6022*T*LN(T) -.15 -650064. 1000 Y -806262+567*T-131. 1000 Y -991549.13133917E-07*T**3+1368173*T**(-1). based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH6O6_G 298. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O3_G 298.026-56.45*T-229.25*T*LN(T) -0. 3000 N @@ CR(OH)5 Gas.97*T-79.74*T-146.77E-6*T**3.C.18913267E-06*T**3-77266.15 -578683+391.6+712.15 -1029121.Appendix -359644+228.15 -787712+400*T-107. 3000 N @@ CRO(OH)3 Gas. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O4_G 298.006*T**2+498450*T**(-1)-2. 1000 Y -1053466+1080.349852E-04*T**2-1.37019*T*LN(T) -.007723995*T**2+7. 1000 Y -861477.386334*T-22.99681*T*LN(T) +3. 1000 Y +421602.3*T-121.9958E-06*T**3.15 -978211.5*T*LN(T) +0.A.004*T**2+2094950*T**(-1)+1.455*T*LN(T) -0. 3000 N @@ CRO2(OH)2 Gas.945E-07*T**3+4671850*T**(-1).819*T*LN(T) -0.0086*T**2+3058600*T**(-1)+4.15 +432449. assessment Chen 2006 based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O3_G 298.91E-7*T**3.15 -902751. 1000 Y -909897. 1000 Y -656538+448. 3000 N @@ CR(OH)3 Gas.6*T-109.3E-7*T**3.7467E-7*T**3.8867E-7*T**3.11767E-6*T**3.35E-7*T**3.86*T*LN(T) -0.12+967.0049*T**2+3311450*T**(-1)+2. assessment Chen 2006.35E-07*T**3+665100*T**(-1).7+464.00994042*T**2+1.99444833E-08*T**3-86705500*T**(-1). assessment Chen 2006.545E-7*T**3.S Class: 4) ENTER-SYMBO FUNCTION F7586T 298.524*T*LN(T) -0.05*T**(-1).00056*T**2+663150*T**(-1)-5.014*T**2+1.9865812*T-37.9391*T*LN(T) 181 .97*T-180.378E-6*T**3.8+813.2*T*LN(T) -0.355E-6*T**3.34E-7*T**3.874*T*LN(T) -0.37*T-125. 3500 Y +587860.713-424.8967E-07*T**3+1688150*T**(-1).93E-7*T**3. 3000 N @@ CRO(OH)4 Gas.0099*T**2+770750*T**(-1)+5.014*T**2+6008850*T**(-1)+7.973194012145*T-158.36214*T+18.2*T-109. 3000 N @@ CR(OH)6 Gas.83+534. 1000 Y -582354+394.76+600. assessment Chen 2006.3*T-137. from T.

+SRX_ALPH2*GHSEROO+15..277845E-07*T**3-5.SR+2:O-2..15 +GLAO.. @@ ---------------------------------------------------------------------@@ Ternary oxides @@ @@ LA-SR-O.LA+3. +SR_ALPHA+416100+GHSEROO -0.15 +2..1*T...33333333*RE_BETA +15. ENTER-PAR G(LA2O3_HEXSS. 2 1 2 MN..15 +168700-78. +LA_BETA-3*GHSEROO....SR+2:O-2.LA+3...SR+2:O-2. O.LA+3:O-2.LA+3:VA....15 +GLA2O3D.0) 298. 2 2 3 LA+3 SR+2. 1 SRO2... +GLA2O3X-3*GHSEROO.SRO2. +SRH_ALPH-2*GHSEROO +15.LA+3.SR+2:VA. ENTER-PAR L(LA2O3_CUBSS.SR+2:O-2.. O-2 VA.LA+2:VA..0).87691*T. ENTER-PAR L(LA2O3_HEXSS.....15 +GMN1O2.15 +GSRO2SOL.LA+3... +GLA2O3D-3*GHSEROO..15 +193600-78.... +SRH_ALPH+GHSEROO+15..0)..15 -20000..SR+2:O-2.SR+2:VA.LA+3:O-2. O-2 VA.0)... ENTER-PAR G(LA2O3SS.. +SRX_ALPH+GHSEROO+15. @@ ENTER-PHASE LA2O3_HEXSS. +GLA2O3X..0).LA+3:VA. 2 2 3 LA+3 SR+2..0) 298. ENTER-PAR G(LA2O3SS..... +LA_BETA..SR+2:VA. ENTER-PAR L(LA2O3_CUBSS...... ENTER-PAR G(LA2O3_HEXSS..SR+2:O-2.Appendix -....0) 298.87691*T.1*T. 2 2 3 LA+3 SR+2..87691*T.15 +193600-78...... 2 2 3 LA+2 LA+3 SR+2.15 +168700-78. ENTER-PAR G(LA2O3_CUBSS.. Grundy @@ @@ STOICHIOMETRIC PYROLYSITE.SR+2:O-2..0) 298. ENTER-PAR G(LA2O3SS. ENTER-PAR L(LA2O3SS...SR+2:VA...149E+05-7..0) 298.0).0). ENTER-PAR G(BETA.87691*T. Chen @@ ENTER-PHASE LA2O3SS. ENTER-PAR G(LA2O3_HEXSS.81E+01*T.. ENTER-PAR L(LA2O3_CUBSS....20451E+08*T**(-1).SR+2:VA..1) 298. @@ La4SrO7 as BETA phase ENTER-PHASE BETA.0)...81E+01*T. ENTER-PAR G(LA2O3_CUBSS.034109635*T**2+7. O-2 VA.. Risold @@ ENTER-PHASE SRO2.. ENTER-PAR G(BETA. +SR_ALPHA-2*GHSEROO +15.. MN1O2 ENTER-PHASE MN1O2.LA+3.87691*T.15 -20000..0) 298... ENTER-PAR G(LA2O3SS.1*T.. +GLA2O3H...0) 298... ENTER-PAR L(LA2O3_CUBSS....0).LA+3:O-2.. ENTER-PAR G(MN1O2.LA+2:O-2. ENTER-PAR G(LA2O3_HEXSS.0) 298... @@ ENTER-PHASE LA2O3_CUBSS. O-2 VA. 6000 N @@ @@ @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Binary oxides @@ @@ Sr oxides.LA+3.........87691*T..0). ENTER-PAR G(LA2O3SS..SR+2:O-2.SR+2:VA..0).0)..87691*T.. Grundy. ENTER-PAR G(LA2O3_CUBSS. ENTER-PAR L(LA2O3SS.LA+3:VA. ENTER-PAR G(LA2O3_CUBSS. +GLAO-GHSEROO.LA+3:O-2.0). +SR_ALPHA+GHSEROO +15...SR+2:VA. 182 ..1) 298..1*T.0)........ ENTER-PAR G(SRO2..15 +2.LA+3:VA... ENTER-PAR L(LA2O3_HEXSS. @@ @@ Mn oxides.. ENTER-PAR G(LA2O3SS. +GLA2O3H-3*GHSEROO.0) 298...MN:O.LA+3... ENTER-PAR G(BETA.0) 298.0).0).149E+05-7.LA+3.

. 3 2 1 4 LA+3..8*T. @@ ENTER-PAR G(LA16. ENTER-PAR G(SRMNO3_HEX. MN+3. @@ ENTER-PHASE SRMN3O6. O.. MN+4. O-2.... Grundy @@ ENTER-PHASE L2MNO4..SR+2:MN+3:O-2:MN+3:O-2. 3 16 7 44 LA.. ENTER-PAR G(SRMN3O6..... O.LA+3:SR+2:O-2..LA:CR:O. MN+3 MN+4. +GSM4OZ-3*GHSEROO..23859*T. Povoden @@ @@ STOICHIOMETRIC LA2CRO6 ENTER-PHASE LA2CRO6.5*GHSEROO +11.LA+3.15 +GLA7. 3 2 3 12 LA+3...15 +GL2MNO4. @@ ENTER-PAR G(LA7.Appendix ENTER-PAR G(BETA. ENTER-PAR G(SR7MN4O15.. ENTER-PAR G(LA4SR3O9.. 3 4 3 10 SR+2. Stoichiometric ENTER-PHASE LA4SR3O9... 4 1 1 1 5 LA+3..SR+2:MN+3:O-2:MN+4:VA.. MN+2..0) 298.SR+2:MN+3:O-2:MN+4:O-2. ENTER-PAR G(SRMN3O6.0)... +GSM4OZ.. O-2. ENTER-PAR G(SRO. +GSM3_HEX+0.....15 +GLA16. @@ @@ LA-MN-O. ENTER-PAR G(LA2CR3..15 -121000-237.........8*T..LA+3:CR+6:O-2. @@ STOICHIOMETRIC LA7 @@ ENTER-PHASE LA7.87691*T.15 -121000-237. O-2 VA..SR+2:MN+4:O-2.0) 298...... ENTER-PAR G(SR4MN3O10.. +GSM3OZ-2. ENTER-PAR G(SRMN3O6.. 3 2 1 6 LA+3.... ENTER-PAR G(LMN2O5..0).0) 298.. 3 4 3 9 LA+3... O-2..75*T.. CR+6. O-2. @@ @@ SR-MN-O. O-2 VA.. 3 7 2 16 LA.5*GHSEROO +11..LA+3:MN+2:O-2. MN+4. ENTER-PAR G(LA2CRO6.VA:O-2. O-2.23859*T. +GSM4_RP3. O-2.. ENTER-PAR G(SRO.0).SR+2:MN+4:O-2.. CR+6. +GS7M4..0)... +GSROSOL.LA+3:MN+3:MN+4:O-2....LA:CR:O... O-2. @@ La4Sr3O9. @@ @@ STOICHIOMETRIC LA2CR3O12 ENTER-PHASE LA2CR3.5*GLA2O3D+113700. CR.15 +GLMN2O5. ENTER-PAR G(SRMNO3_HEX...23859*T. 3 7 4 15 SR+2.... @@ ENTER-PHASE SRMNO3_HEX.. 0.SR+2:MN+3:O-2......LA+3:O-2.0)..SR+2:O-2. @@ ENTER-PHASE LMN2O5...66666667*RE_BETA+15..0)..SR+2:O-2.........0).SR+2:VA. MN+3.0).....0).. @@ ENTER-PHASE SR4MN3O10. +GSM3_HEX-2.15 +GLA2CR3.0)..5*GHSEROO +11... +GSM3OZ+0.15 +GLA2CRO6..0) 298. SR+2.... +0.. 2 1 1 LA+3 SR+2 VA. @@ @@ LA-CR-O. +SR_ALPHA+416100-2*GHSEROO +0..SR+2:VA. +2*GLA2O3D+3*GSROSOL+229800 -136. CR.0) 298. 183 ..LA+3:CR+6:O-2.. Grundy @@ ENTER-PHASE SR7MN4O15. O-2. @@ intermediate La-chromates @@ STOICHIOMETRIC LA16 @@ ENTER-PHASE LA16. MN+3 MN+4. ENTER-PAR G(L2MNO4. @@ SrO Solid Solution ENTER-PHASE SRO. ENTER-PAR L(BETA.0) 298. ENTER-PAR L(BETA...5*GHSEROO +11.0) 298.0) 298....23859*T.SR+2:MN+3:VA. MN+4. ENTER-PAR G(SRMN3O6. ENTER-PAR G(SRO. 3 1 1 3 SR+2..SR+2:MN+3:O-2:MN+3:VA...0).......0).0)..LA+3. 5 1 2 3 1 3 SR+2. O-2.

SR:CR:O.CR+3:O-2:O-2. ENTER-PAR G(MNO_HALIT. Grundy.15 +3.. ENTER-PAR G(MNO_HALIT. O...0) 298.SR+2:MN+4:VA. ENTER-PAR G(MN2O3.SR+2:CR+6:O-2.. ENTER-PAR G(MN2O3.0) 298.15 0.15 +GMN2O3...MN+3:O-2.15 +4.15 +GSC2O7.. 3 1 2 4 SR+2...87691*T.. AMEND-PHASE MN2O3 MAGN.. O-2.MN+3:O-2. ENTER-PAR G(MN2O3... ENTER-PAR TC(MN2O3.67CR2O8 ENTER-PHASE S3C2N. O-2... CR.MN+3:O-2..CR+3:VA:VA. 3 2 3 1 MN+3 CR+3.. Grundy modified it in LSM modeling ENTER-PHASE RP2.... 3 1 2 7 SR+2..MN+3:O-2:VA. Povoden-K.Appendix ENTER-PAR G(SRMNO3_HEX.... ENTER-PAR L(MNO_HALIT.87691*T.1853365*T.0) 298.21048766E+04.5213 -22.15 -4.. @@ @@ SR2.....0) 298.SR+2:CR+6:O-2.SR+2:CR+4:O-2. @@ @@ SR-CR-O...15 +GS3C2O8.. Povoden @@ @@ SRCR2O4 ENTER-PHASE SC2O4.. O-2..93845*T +71549.0) 298.. Povoden-Karadeniz 184 . O-2.0) 298. @@ @@ RP2. ENTER-PAR G(MNO_HALIT..CR+3:O-2:VA.15 +GCR2O3+3459.0) 298..0) 298... 3 1 1 4 SR+2.. Povoden @@ @@ NONSTOICHIOMETRIC MANGANOSITE (MNO) SOLID SOLUTION. ENTER-PAR G(MN2O3. ENTER-PAR BMAGN(MN2O3.15 +0..87691*T..0) 298... ENTER-PAR L(MNO_HALIT.0) 298.15 +GMN2O3-2*GHSEROO +100000+15.... MN+3 MN+4... NONSTOICHIOMETRIC CR2O3 SOLID SOLUTION.MN+2.. ENTER-PAR BMAGN(MN2O3.... ENTER-PAR G(MN2O3..0) 298.CR+3:O-2:VA.15 +GS4O_RP2.0) 298..666667 2 8 SR... ENTER-PAR G(S2CO4. ENTER-PHASE MNO_HALIT....15 +GSC2O4.. Povoden-Karadeniz ENTER-PHASE SCO4.87691*T..MN+3:O-2:VA.15 +GCR2O3+GHSEROO +100000+15.1) 298.. Grundy..15 +GCR2O3-2*GHSEROO +100000+15. Chen. ENTER-PAR G(S3C2N.15 +GMN1O1..0) 298.. doubtful phase @@ ENTER-PHASE SC2O7... ENTER-PAR G(SCO4..MN+2:O-2..MN+3:VA:O-2.....28 ENTER-PAR TC(MN2O3...VA:O-2. @@ SRCRO4.. O-2 VA..0) 298... 3 2 1 4 SR+2.. .. +GSM4_HEX-3*GHSEROO.0) 298. ENTER-PAR G(SRMNO3_HEX..65131533E+04.0).59.15 +3*GSROSOL+GMN2O3+GHSEROO.... CR+3...MN+3:O-2:VA. Povoden-Karadeniz) ENTER-PHASE MN2O3. ENTER-PAR G(MN2O3.CR+3:O-2:VA. CR+6..0) 298.15 +GSCO4.15 +GMN2O3+GHSEROO +100000+15.15 +308..0) 298.SR+2:CR+3:O-2..3.0) 298.6..MN+3:VA:VA. ENTER-PAR G(MN2O3.. O-2. ENTER-PAR G(SC2O4. @@ @@ CR-MN-O. 4 1 2 2 7 SR+2.CR+3:O-2.15 +GMN2O3-3*GHSEROO.. @@ SRCR2O7. O-2 VA..CR+3:VA:O-2.0) 298.SR+2:MN+4:O-2..5*GCR2O3-7...0) 298.MN+2. CR+6.MN+3:O-2:O-2.SR+2:SR+2:MN+4:O-2..15 +GS2CO4.0) 298....15 +309... @@ @@ Mn2O3 (Compatible with C-Y2O3..15 +GMN1O1-21883...15 +GCR2O3-3*GHSEROO... ENTER-PAR G(RP2. CR+4.0). @@ ENTER-PAR G(SC2O7. O-2. @@ SR2CRO4 ENTER-PHASE S2CO4.. +GSM4_HEX.0) 298.. 2 1 1 MN+2 MN+3 CR+3 VA..0) 298. SR+2.. @@ @@ ESKOLAITE.. ENTER-PAR G(RP2.15 +0. ENTER-PAR G(MN2O3. 3 2.0) 298.SR+2:SR+2:MN+3:O-2. ENTER-PAR G(MNO_HALIT...

Povoden-Karadeniz ENTER-PHASE TMNCR2O4..MN+3:CR+3:O-2.0) 298...0) 298.5*GHSEROO+11. ENTER-PAR G(RPEROV.. MN+3 MN+4.15 +GSPINEL.MN+3:VA:O-2.6. ENTER-PAR BMAGN(CR2O3.SR+2:MN+3:O-2. O-2 VA.... MN+2 MN+3 MN+4 CR+3 CR+4 VA.SR+2:MN+2:O-2.0) 298. ENTER-PAR G(CR2O3... ENTER-PAR G(CR2O3.. ENTER-PAR G(CR2O3.. 3 2 1 3 MN+3 CR+2 CR+3.. O-2.. ENTER-PAR G(TMNCR2O4..0) 298.... @@ @@ CUBIC SPINEL.0) 298.MN+3:VA:O-2...2923*T.SR+2:LA+3:MN+4:O-2.59.15 +GTMN3O4.CR+3:VA:O-2. ENTER-PAR BMAGN(CR2O3... O-2. 3 1 2 4 MN+2 CR+2... ENTER-PAR BMAGN(CR2O3..0) 298.666666666667*GHSERCR -5. ENTER-PAR G(LS3MN2O7.......0) 298.15 +3..0) 298.SR+2:MN+2:VA. Grundy.SR+2:SR+2:MN+4:O-2. Povoden-Karadeniz ENTER-PHASE CMNCR2O4..CR+3:CR+3:O-2. .15 +308.15 +GMN2O3+39503.0).6. @@ DISTORTED_SPINEL....15 +0....15 +309...0) 298.. Grundy.6..0) 298.0) 298.0) 298..0) 298.. +GMS3O+0....0) 298.. MN+3 CR+3...CR+2:CR+3:O-2.0) 298.0) 298..CR+2:VA:O-2.CR+3:VA:O-2..MN+3:VA:O-2.. +GMS4O. @@ -----------------------------------------------------------------------@@ Quaternary oxides @@ @@ La-Sr-Mn-O......0) 298.15 +GCR3O4. ENTER-PAR BMAGN(CR2O3.. O-2. LA+3 SR+2. MN+3 CR+3. @@ -----------------------------------------------------------------------@@ Quinary phases..15 +3.CR+2:VA:O-2. ENTER-PAR G(CMNCR2O4.. @@ ENTER-PAR G(RPEROV. Grundy. ENTER-PAR TC(CR2O3.33333333334*GHSERCR -5.CR+3:CR+3:O-2..SR+2:SR+2:MN+3:O-2.47717*T. ENTER-PAR BMAGN(CR2O3..6..0) 298.CR+3:CR+3:O-2.CR+3:VA:O-2...2923*T..0).15 +GCR3O4+GCMN3O4-GSPINEL...15 +308.CR+2:VA:O-2..28 ENTER-PAR TC(CR2O3...15 +3. ENTER-PAR G(CR2O3. +GMS3O+GL2O-GL3OR2*GHSEROO+22..SR+2:MN+4:O-2.SR+2:LA+3:MN+3:O-2.0) 298. ENTER-PAR TC(CR2O3.CR+2:MN+3:O-2....CR+2:CR+3:O-2. +GMS3O+GL2O-GL3OR+GHSEROO +22.MN+3:CR+3:O-2. ENTER-PAR G(LS3MN2O7..MN+3:CR+3:O-2..0) 298...15 +GL3O_RP2....15 +GCR2O3.0) 298. ENTER-PAR G(CMNCR2O4.0) 298... ENTER-PAR G(TMNCR2O4. ENTER-PAR G(CR2O3. O-2.CR+2:CR+3:O-2.15 +308.CR+2:CR+3:O-2.15 +GTSPINEL.47717*T.. ENTER-PAR TC(CR2O3. ENTER-PAR G(RPEROV. ENTER-PAR G(LS3MN2O7..15 +GCRO0 -0. 3 1 2 4 MN+2.15 +0.. ENTER-PAR G(CMNCR2O4.. 185 .59.. Grundy @@ ENTER-PHASE LS3MN2O7..15 +GL3O_RP2+GS4O_RP2 -3*GSROSOL -GMN2O3-GHSEROO-R_RP2.0).15 +3..15 +3*GSROSOL+GMN2O3 +GHSEROO. ENTER-PAR G(RPEROV...0) 298... ENTER-PAR G(CMNCR2O4.MN+2:CR+3:O-2..MN+2:CR+3:O-2... ENTER-PAR G(LS3MN2O7....Appendix ENTER-PHASE CR2O3. ENTER-PAR TC(CR2O3.15 +308. ENTER-PAR G(CR2O3..0). ideal extensions from lower-order systems @@ @@ high temperature rhombohedral perovskite.0) 298. Povoden-Karadeniz ENTER-PHASE RPEROV.MN+2:MN+3:O-2...23859*T... 3 1 1 3 LA+3 SR+2 VA..0) 298. ENTER-PAR TC(CR2O3.15 +309.0) 298..15 +GCMN3O4...15 +GCR2O3+GHSERCR... AMEND-PHASE CR2O3 MAGN. ENTER-PAR BMAGN(CR2O3. CR+3 VA.MN+2:MN+3:O-2.0) 298.15 +GMN2O3+GSERCR+39503.....15 +GCRO0 +.0) 298. 4 1 2 2 7 SR+2.15 +GS4O_RP2.....

33333*GVVV-1... +GL2O+1..66667*GL4O+0.VA:MN+3:O-2.. +2*GVCR4O+0.0).5*GHSEROO+1.35057*T..0). ENTER-PAR G(RPEROV..Appendix ENTER-PAR G(RPEROV.. G(RPEROV. +GL3OR+1.3333*GVVV-1..LA+3:CR+3:O-2..62121*T.. +GMS3O+2*GL4O-1.5*GHSEROO -1.SR+2:MN+4:VA..0).0)..LA+3:MN+4:VA...0)...VA:VA:O-2..5*GV4O -0.LA+3:CR+4:O-2..23859*T. G(RPEROV. ENTER-PAR G(RPEROV. +2*GV4O+0..5*GVVV-1. ENTER-PAR G(RPEROV....76318*T. ENTER-PAR G(RPEROV.5*GV4O+0. ENTER-PAR G(RPEROV..SR+2:VA:VA....SR+2:VA:O-2. +GMS3O-2.1666667*GS4O +0..82596*T...41263*T.LA+3:VA:O-2.2386*T. ENTER-PAR G(RPEROV.. ENTER-PAR G(RPEROV.0). ENTER-PAR G(RPEROV...VA:VA:VA...66667*GL4O+0.. +GLACRO3+1....41263*T....35057*T.5*GHSEROO+11... G(RPEROV..5*GHSEROO+5.5*GVVV-2*GL4O +1.5*GVVV -2*GLACR4O-1.VA:CR+4:VA.VA:MN+4:O-2.. +GL3OR.VA:MN+4:VA... +GL3OR+1.333*GL4O -2*GHSEROO+4.VA:CR+3:VA.41263*T..5*GV4O+0.0)..5*GVCR4O+0.16666667*GS4V....0).5*GHSEROO+5.41263*T.LA+3:MN+2:VA.3333*GVVV -1..5*GHSEROO+11. G(RPEROV...5*GV4O+0..33333*GL4O +GHSEROO+4....0)...0)...... +GLACRO3. GS4O-GN-0..5*GHSEROO-1... ENTER-PAR G(RPEROV..0).. ENTER-PAR G(RPEROV.LA+3:MN+4:O-2....8333333*GS4V.1666667*GS4O +0.0).5*GHSEROO +1.0).0).16666667*GS4V. G(RPEROV. +GMS4O-3*GHSEROO.166667*GVVV -0. ENTER-PAR G(RPEROV.1666667*GS4O -0.5*GHSEROO-1.. @@ Optimized interactions 186 .5*GVVV-2*GL4O -1.0)..LA+3:MN+2:O-2.. +2*GV4O+0. +GS4V. +GN+0.0)..33333*GVVV -1.LA+3:VA:VA.. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV..LA+3:CR+4:VA. ENTER-PAR G(RPEROV.41263*T..41263*T.0).0).. ENTER-PAR G(RPEROV....76318*T..2386*T. G(RPEROV..LA+3:MN+3:O-2. ENTER-PAR G(RPEROV. +GN-0..0).35056*T. GS4O+GLACRO3-GN-0... ENTER-PAR G(RPEROV. +GL2O+0..5*GHSEROO+11.LA+3:CR+3:VA... +2*GL4O+0. +GVVV.VA:CR+3:O-2..0). +GLACRO3-3*GHSEROO.. +GL3OR-3*GHSEROO.0).0).SR+2:CR+4:O-2...0).VA:CR+4:O-2.5*GV4O -0....VA:MN+2:VA..16666667*GS4V+GLACRO3 -3*GHSEROO. +GLACRO3+1....166667*GVVV -3. +2*GL4O-1..5*GV4O+0.....5*GVCR4O+0..35056*T.SR+2:CR+4:VA.5*GVVV -2*GLACR4O+1. G(RPEROV.5*GVVV +1. ENTER-PAR G(RPEROV.0).SR+2:CR+3:VA. G(RPEROV. +0.... +GVVV+3*GHSEROO.333*GLACR4O -2*GHSEROO+4.5*GVVV-2*GL4O -GHSEROO+9.5*GVVV-GL3OR -GHSEROO+12...LA+3:MN+3:VA.0). +GS4O. ENTER-PAR G(RPEROV.5*GV4O +0.0).8333333*GS4O +0..5*GV4O -1. +GMS3O-GL3OR+2*GL4O -1.62121*T. +2*GVCR4O+0...SR+2:MN+3:VA.0).VA:MN+3:VA. +GL2O-2.0).5*GVVV +2*GHSEROO+12.0)... ENTER-PAR G(RPEROV.. +0. ENTER-PAR G(RPEROV.33333*GLACR4O +GHSEROO+4.5*GV4O+0.0).. ENTER-PAR G(RPEROV.5*GHSEROO -1.0). ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.SR+2:CR+3:O-2...

LA+3..5*GHSEROO.SR+2:LA+3:CR+3:O-2:O-2. @@ ENTER-PAR G(RP.15 GS2CO4..Appendix ENTER-PAR L(RPEROV.15 -3. @@ ENTER-PAR G(RP.. ENTER-PAR G(ION.0) 298.15 +11368. @@ ENTER-PAR G(RP...SR+2:SR+2:MN+3:O-2:O-2.. ENTER-PAR G(ION. ENTER-PAR L(RPEROV.. ENTER-PAR L(RPEROV.15 +GCR_L.. preliminary.. ENTER-PAR L(RPEROV.0) 298.15 185.LA+3:CR+4:O-2:O-2..SR+2:MN+2:O-2.0).0) 298...1) 298..15 GREFRP..MN+3:O-2..0) 298..... ENTER-PAR L(ION..SR+2:MN+2:VA...LA+3:CR+4.15 +121000.0). @@ ENTER-PAR G(RP..0) 298...... @@ @@ Ruddlesden-Popper phase.15 3766..0)...15 +GLALIQ..0) 298...LA+3:CR+3.LA+3:CR+3:O-2:O-2.0) 298. ENTER-PAR L(ION...SR+2:VA..1) 298.. 5 1 1 1 3 1 SR+2. @@ Interaction parameters from ternaries ENTER-PAR L(ION.0) 298..VA:O-2..SR+2:MN+4:VA.0) 298..0) 298. O-2 VA.0) 298............ AMEND-PHASE IONIC_LIQUID COMP 2. ENTER-PAR L(RPEROV..LA+3:CR+3.LA+3. @@ Interaction parameters from binaries ENTER-PAR L(ION..0) 298.LA+3:MN+4.15 +GLCR3O_RP1.VA.CR+3:O-2. 20. ENTER-PAR G(ION...... ideal extension from lower-order systems.. ENTER-PAR L(RPEROV.1).LA+3:CR+3..VA.. ENTER-PAR L(RPEROV... ENTER-PAR G(ION..5*GMN2O3 @@ -0.0) 298. @@ ENTER-PAR L(RP..15 +GSRLIQ.1) 298..15 GS2CO4+GLCR3O_RP1 @@ -GREFRP.15 100000..MN+2:VA...LA+3.15 -119062.. ENTER-PAR G(ION.0) 298. Povoden-Karadeniz ENTER-PHASE IONIC_LIQUID Y LA+3 SR+2 MN+2 MN+3 CR+2 CR+3...5*GMN2O3 @@ +0..VA.15 +121000..MN+2:O-2.CR+2:VA.0) 298..SR+2:CR+4. O-2.0) 298. ENTER-PAR L(RPEROV..SR+2:SR+2:CR+4:O-2:O-2..0) 298.. 9248..SR+2:LA+3:CR+4:O-2:O-2. ENTER-PAR G(ION.SR+2:CR+4.0) 298. scarce experimental data @@ ENTER-PHASE RP. @@ ENTER-PAR L(RP.15 +GL3O_RP1. @@ ENTER-PAR G(RP. ENTER-PAR G(ION.54590000E+04..0) 298.15 +2*GSROLIQ..MN+4:O-2...0) 298..15 2*GCR1O1_L.0) 298. ENTER-PAR G(ION.MN+3:O-2.SR+2:LA+3:MN+3:O-2:O-2.VA.0) 298. ENTER-PAR G(ION. @@ ENTER-PAR G(RP.. ENTER-PAR L(RPEROV.15 +GL3O_RP1+GS4O_RP1 @@ -2*GSROSOL-0..LA+3..0) 298.15 +GMN2O3_L.15 -1. @@ ENTER-PAR G(RP. ENTER-PAR G(ION.15 0. ENTER-PAR G(ION.LA+3.0) 298.VA:O-2..MN+3:O-2..SR+2:MN+3:O-2..15 +GCR2O3_L...4....15 -11316...SR+2:SR+2.MN+2:O-2. 187 .. ENTER-PAR L(ION. @@ O-2. ENTER-PAR L(RPEROV.0) 298. ENTER-PAR L(RPEROV.MN+2:VA.CR+3:O-2..15 +2*GMN_L+GMN2O3_L-3*GMN1O1_L.38590000E+04..15 1..0) 298. -136600.VA:O-2....LA+3:VA..15 -4...SR+2:MN+4:O-2....1) 298..MN+2:O-2. 250000. @@ next two interaction parameters can be used to fit @@ Cr4+ amount in perovskite ENTER-PAR L(RPEROV.LA+3:O-2.0) 298.. -117000..0) 298.LA+3:MN+4.CR+2:O-2.....0)... MN+3 MN+4 CR+3 CR+4. ENTER-PAR L(RPEROV..15 100000..0) 298. ENTER-PAR L(ION.....6.29519000E+05.0) 298... ENTER-PAR L(ION...SR+2:SR+2.MN+3:O-2. ENTER-PAR G(ION..LA+3.. ENTER-PAR L(RPEROV.5*GHSEROO... LA+3 SR+2. -117000.MN+2:O-2...VA:MN+4:O-2..15 +GS4O_RP1. 250000.. @@ ENTER-PAR G(RP.1)..15 -1297.SR+2:SR+2:CR+3:O-2:O-2. -136600.LA+3.15 +2*GCR_L+GCR2O3_L-3*GCR1O1_L.0) 298..MN+2....MN+3:O-2. ENTER-PAR L(ION.SR+2:SR+2:MN+4:O-2:O-2.CR+3:VA... @@ -----------------------------------------------------------------------@@ Liquid.5*t.1)..LA+3:CR+3..SR+2:LA+3:MN+4:O-2:O-2.15 +GLA2O3LIQ.0).MN+3:O-2..MN+2:VA..MN+3:VA.15 +GMN_L.15 +2*GSROSOL+0..1).SR+2:O-2......MN+3:O-2.15 +2*GMN1O1_L.0) 298.LA+3.. ENTER-PAR L(RPEROV..CR+2:O-2. -2..15 0.LA+3.

20000 N ENTER-PAR G(GAS...15 +46000...0) 298.MN+2:VA..15 +GCRH6O6_G+RTLNP.15 +F10963T+RTLNP....O3.SR+2...15 +GCRH5O5_G+RTLNP..7.0) 298.15 +GCRH1O1_G+RTLNP.MN+2.. 6000 N ENTER-PAR G(GAS. ENTER-PAR G(GAS.. 1 H2O1..0) 298. ENTER-PAR G(STEAM..15 -101850..15 +F7586T+RTLNP..0) 298. ENTER-PAR L(ION...CRH3O4.. ENTER-PAR L(ION...CR1O3..15 -39016..1) 298.15 +GCRH1O2_G+RTLNP.15 -15009+13.0) 298.. ENTER-PAR G(GAS. ENTER-PAR L(IONIC.H1O2.15 +F10983T+RTLNP.. ENTER-PAR L(ION. 6000 N ENTER-PAR G(GAS. ENTER-PAR L(IONIC. 20000 N ENTER-PAR G(GAS.SR+2..15 +60713-5..... ENTER-PAR L(ION.H2.15 +F10666T+RTLNP. ENTER-PAR G(GAS.SR+2.15 200000. ENTER-PAR G(GAS..CRH1O1.0) 298.CRH2O3.MN+3:O-2...LA+3.0) 298.0) 298..CR+2:VA.CRH2O4..15 +F13704T+RTLNP. @@ @@ H2O reference gas ENTER-PHASE STEAM.CRH2O2. ENTER-PAR L(ION.15 -619869.CR+2:O-2..O.0) 298.. ENTER-PAR L(ION.15 +F10963T+RTLNP. ENTER-PAR L(ION...CR+2:VA.0) 298.1) 298.CR+3:O-2.0) 298.LA+3. 20000 N ENTER-PAR G(GAS....MN+2.0) 298. ENTER-PAR G(GAS.15 +F14021T+RTLNP. 6000 N ENTER-PAR G(GAS.15 +GCRH3O4_G+RTLNP..0) 298.CR+3:O-2.LA+3..4) 298..H2O1.H2O1.15 +F13349T+RTLNP.. 6000 N ENTER-PAR G(GAS.0) 298.15 +64573-23*T.0) 298.0) 298...15 +GCR1O3_G+RTLNP.. @@ @@ CRO3 reference gas ENTER-PHASE CRGAS..15 +H2GAS+RTLNP... ENTER-PAR G(GAS.... ENTER-PAR L(ION.LA+3..0) 298..0) 298..0) 298.H1O1.15 -119062.CR+2:O-2....CR+2:VA.0) 298.15 +GCRH2O4_G+RTLNP.CRH1O2. ENTER-PAR L(IONIC.LA+3.0) 298.1) 298.0) 298. ENTER-PAR G(GAS.CRH1..15 +F10729T+RTLNP. 188 . ENTER-PAR G(GAS....0) 298.CR1O1. ENTER-PAR G(GAS.0) 298.CRH3O3.CRH1O3.0) 298.CR+2:O-2...0) 298.15 +HGAS+RTLNP.0) 298.CR+2:VA.MN+2:O-2. 1 CR1O3.15 -176300.0) 298.15 -101850. 20000 N @@ @@ O2 reference gas ENTER-PHASE O2GAS..15 +GCR1O2_G+RTLNP.15 +GCR1O3_G+RTLNP....CR+2:O-2.MN+2:VA.. ENTER-PAR G(CRGAS.15 +GCR1O1_G+RTLNP.SR+2.SR+2...0) 298.. 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..15 +GCRH4O5_G+RTLNP.CR+3:O-2..15 +GCRH2O3_G+RTLNP.15 +GCRH1O3_G+RTLNP...MN+3..15 +504+0.MN+3:O-2.CRH5O5.0) 298..SR+2..CR1O3.15 -9111..15 -188487.O2.1) 298..CR+3:O-2. 1500 N ENTER-PAR G(GAS.. ENTER-PAR L(ION..H2O2.SR+2.. 6000 N ENTER-PAR G(GAS.0) 298..15 +GCRH3O3_G+RTLNP. ENTER-PAR G(GAS..0) 298. ENTER-PAR L(IONIC.0) 298.0) 298.0) 298.CR1O2... ENTER-PAR G(GAS... 6000 N ENTER-PAR G(GAS.1) 298. ENTER-PAR G(GAS..LA+3.....CRH4O4.15 -176300...15 -179575.. ENTER-PAR G(GAS..CR+3:O-2...CRH4O5..CR+2:VA.. 1 O2.15 -179575..0) 298. ENTER-PAR L(IONIC.H..9479*T. ENTER-PAR L(ION.15 -619869.0) 298..49*T..6587*T.. ENTER-PAR G(GAS.. @@-----------------------------------------------------------@@ Cr-GAS. ENTER-PAR L(ION.15 +GCRH2O2_G+RTLNP.1) 298.SR+2.. ENTER-PAR L(ION.15 +GCRH4O4_G+RTLNP.15 -39016. SGTE and reassessments by Chen.0) 298.LA+3.Appendix ENTER-PAR L(ION..CRH6O6.... ENTER-PAR G(GAS. ENTER-PAR L(IONIC.0) 298..LA+3..

set-interactive +2*GHSEROO+RTLNP.O2..15 @@ GO PAR @@ SET-OUT-LEVEL.Appendix ENTER-PAR G(O2GAS.. N..0) 298...... 189 .

Contr. Abart. Erwin Date and place of birth: March 18. 143. 1973. Dr. Dr. Austria Education 01/2005 – 12/2008 Ph. ETH Zurich. 192-208. Graz 1979-1983 Elementary School. 2002. and E. 190 . Georg Hoinkes and Prof. Switzerland. Karl-Franzens University Graz Master thesis: „Kontaktmetamorphose und Fluid-Gestein-Interaktion in der östlichen Monzoni Kontaktaureole“. carbon and strontium isotope systematics in two profiles across the Glarus thrust: implications for fluid flow. Dr. Prof. Petrol. Rainer Abart 1983-1991 Realistisches Gymnasium. Berliner Ring. M. Ludwig J. Graz Publications R. thesis: „ Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells“. Oxygen. N.. Department of Materials. 1992-1999 Geoscience Studies. Gauckler. Povoden. D. Burkhard. Prof. pp. Graz. Pestalozzistrasse 5.Curriculum vitae Curriculum Vitae Personal data Povoden-Karadeniz. Badertscher. Nonmetallic Inorganic Materials. Miner.

Povoden.J. (accepted) E. Ivas. Gauckler.J. 2006. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. to be submitted. E. T. Chen. Abart.. 2006. T. A. Ivas. 353-62.J. Chen. pp.N.N. Int. T. Phase Equilib. 2002. Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole. A. Thermodynamic assessment of the La-Cr-O system. pp. 1. E. Thermodynamic calculations of impacts of chromium on Sr-doped Lanthanum manganite (LSM) cathodes for solid oxide fuel cells (SOFC). Povoden. Mater. and L. M. M. pp. Phase Equilib. J. Miner. pp. A.Curriculum vitae E. E. M. to be submitted. 33-41. Gauckler. T. M. 99-120. Grundy. and L. Chen. 76.J. and R. Ivas. Grundy.J. and L.N. Povoden-Karadeniz. E. Povoden. Gauckler. Diff. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. Povoden. 97. Gauckler.N. Degradation of planar solid oxide fuel cells with (La1-xSrx)1-yMnO3 cathodes and Cr-alloy interconnects. M. and L.. Grundy. and L. Res.J. Phase Equilib. Gauckler. 569-78. A. 2009. Presentations Assessment of the Cr-O system in the frame of SOFC research E. and L.N. 2006. 30. E. E. Chen. A. A.J. Povoden. E.N. Ivas. Grundy. Povoden. J. Calculation of defect chemistry using the CALPHAD approach. Diff. Gauckler. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Petrol.. Gauckler. Grundy. Povoden. Grundy. A. J. pp.N. Povoden. Grundy. Thermodynamic assessment of the La-Fe-O system. Calphad. 12-27. to be submitted. Gauckler.J. Horacek.J.Diff. and L. J. and L. and L. 27. Povoden. Gauckler 191 ..

and L. and L. Vienna. Z. students.Curriculum vitae Poster Presentation CALPHAD XXXIV. Colorado. 2005 Thermodynamic Assessment of the Cr-Mn-O System for Solid Oxide Fuel Cell (SOFC) Materials E.N. USA. Povoden. Povoden. Gauckler Oral Presentation 3rd Fuel Cell Research Symposium. May 6th – 11th. EMPA Dübendorf.J. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fuel cell (SOFC) materials using the CALPHAD approach E. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fel cell (SOFC) materials E. A. Switzerland.D. Maastricht. Pennsylvania State University.N. Povoden Oral Presentation 1st EMPA symposium for Ph. Switzerland. Povoden. and L.J. Austria. 2007 Thermodynamic assessment of the La-Cr-O and LaO3/2-MnOx-CrO3/2 Systems 192 . Gauckler Poster Presentation CALPHAD XXXVI. Gauckler Oral Presentation Thermo 2006. Grundy. EMPA Dübendorf. Gauckler Oral Presentation HTMC XII. Grundy. Netherlands. USA. September 18th – 22nd. October 20th.N. 2005 Thermodynamic assessment of the Cr-Mn-O system for solid oxide fuel cell (SOFC) materials E. Grundy.J. Povoden. 2006 The BiO3/2-SbO3/2-ZnO Phase Diagram at 1115°C in air E.J. A. Pennsylvania. March 16th. A. Boulder. May 06th -11th. and L. August 4th. Peng.

The La-Sr-Mn-Cr-O system E.5-SrO-FeO1. Gauckler Oral Presentation CALPHAD XXXVI.5-SrO-FeO1.N. A. 2007 Thermodynamic modeling for solid oxide fuel cell research .J. Povoden Oral Presentation Guest Talk.J. Monatnuniversität Leoben. M. Povoden. A. Chen. Lehrstuhl für physikalische Chemie.N. Pennsylvania State University. and L.5-SrO-MnO1.5 databases for SOFC applications using the CALPHAD approach E. Povoden Oral Presentation 2nd MRC Graduate Symposium . ETH Zurich. Grundy.5-CrO1. Finland. Gauckler Oral Presentation CALPHAD XXXVII. May 6th – 11th. March 28th. and L. June 16th – 21st.5 databases for solid oxide fuel cells (SOFC) applications E.5 and LaO1.5 and LaO1. Pennsylvania. 2008 Thermodynamic LaO1. Povoden. USA.5-CrO1.Curriculum vitae E. Saariselkä. Grundy.5-CrO1.5-CrO1. 2008 193 . June 27th. 2007 The thermodynamic LaO1.5-SrO-MnO1.

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.5….. 112 According to the latest discussion by B.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.Erratum.” . Povoden-Karadeniz et al.Va)3 and not (La.Cr)(O.3... J. otherwise the disordered model for interstitials in bcc. (Me)1(Va.5 based on the argument. p 2837 the correct model is (La. For these reasons.O)1.Va)1. Phase Equilib.X)3 is to be used…” Thus the model was also corrected in the thermodynamic assessment of the La-Fe-O system. lines 7-14 and Table 4.3. 31(1). Hallstedt et al. p.Cr)(O.O)3 is undoubtedly a reasonable model description for the oxygen solubility in bcc. 109. Diff.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. Calphad. The following argumentation for modeling of the oxygen solubility in bcc using (physically wrong!) Me(O. 2007. 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. In previous papers the authors have proposed the model Me(Va. accepted. p. 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.Va)1.Va)1.

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