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Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells
DISSERTATION for the degree of DOCTOR OF SCIENCES of the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH
presented by ERWIN POVODEN-KARADENIZ Mag. rer. nat. born on March 18, 1973 Citizen of Austria
accepted on the recommendation of Prof. Dr. Ludwig J. Gauckler, examiner Prof. John T.S. Irvine, co-examiner Dr. Ming Chen, co-examiner
Dedicated to my parents
Whatever creates or increases happiness or some part of happiness, we ought to do; whatever destroys or hampers happiness, or gives rise to its opposite, we ought not to do.
I am deeply grateful to my supervisor Professor Gauckler. He gave me a great chance by taking me into the boat: a boat that is not only sailed to scientific success. It took me away from an insecure float wobbling in the surf and approaches a promising future. Endless gratitude belongs to my wife who stays by my side throughout highs, downs, and distances, preventing me from losing the way; she is my firm anchor. I am greatly indebted to Nicholas Grundy for open doors, his patience of a saint, great teaching, and picky reviewing. He catalyzed my way into the field of thermodynamic modeling, airing the “modeling is fun” approach at any time. I would further like to thank Ming Chen for continuing scientific support and advising; he was often motivating me to spin the wheel of accurate and fast modeling and publishing. I owe thanks to Franc and Flavia Dugal-Borsari who saved me from an unintentional outdoor adventure in Zurich during a time when it was extremely difficult to find a new accommodation. It was a very pleasant time in Zollikon. I thank Brandon Bürgler and Jennifer Rupp for their pleasing office companionship at the beginning of my work: they facilitated my jump into the ETH waters. I would also like to thank Toni Ivas for abiding collegiality, cooperation, and friendship. I thank the rest of the office crew, Thomas Ryll and Rene Tölke, for always enjoyable working hours.
Zurich, December 2008
3.3 1.3.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.1 3.1.2 22.214.171.124 1.4.3 Stoichiometric solid oxides Solid solution phases – the Compound Energy Formalism (CEF) Vacancies and the concept of reciprocal reactions 4 .3.1 Introduction 1.4.4 1.2.2 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes New ways – alternative materials 2 3 Aim of study Method 3.3 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 1.6 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” 1.2 1.2 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC Thermodynamic modeling 3.3.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 1.2 3.1 3.5 1.2 1.1 1.1 126.96.36.199.
2.2 4.1 Introduction 4.1 Technology 4.1.1 Introduction 188.8.131.52 184.108.40.206.2 220.127.116.11 Conclusions 5 Thermodynamic calculations of impacts of chromium on Sr-doped 5 .3 Experimental Thermodynamic modeling Optimization of parameters Results Discussion 18.104.22.168.1 Introduction 4.1 Calculation of defect chemistry using the Calphad approach 51 52 53 53 53 54 58 59 66 67 73 77 77 78 86 89 93 96 97 101 102 103 103 109 117 128 134 134 135 137 140 143 Optimization of model parameters Thermodynamic reassessment of the Cr-O system in the framework of SOFC research 4.6 Experimental data Previous assessments of the Cr-O System Thermodynamic modeling Optimization of parameters Results and discussion Thermodynamic assessments 4.5 4.3 4 4.6 22.214.171.124 4.2.2 4.7 Conclusions 4.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials 4.1.4 4.5 126.96.36.199 Assessment of data from the literature Modeling and optimization Results and discussion 4.3 4.3 4.4 Literature review of the La-Cr system Literature review of the La-Cr-O system Thermodynamic modeling and optimization Results and discussion 4.4 4.3.3 4.4.6 Conclusions Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications 4.5 188.8.131.52.3.3.2 4.Table of Contents 3.7 Applications on SOFC Thermodynamic assessment of the La-Cr-O system 4.3 4.2.
3.Table of Contents manganite (LSM) cathodes for SOFC 5.4 5.1MnO3-δ contaminated by chromium Thermodynamic calculations of (La0.2)0.3.2 5.3 5.3.8Sr0.9Sr0.1 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 .5 Thermodynamic calculations of La0.3.3 Introduction Method Results 5.1 5.4 5.2 5.
In the third chapter the reader learns. 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. and some are kinetically controlled. 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. 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. The associated chemical changes of the LSM phase. 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. Some of these processes are governed by thermodynamics. as well as the formation of a new spinel phase occur under thermodynamic control: decreasing concentrations of vacancies in LSM that contains chromium are calculated at decreased oxygen partial pressure reflecting SOFC operation at high current load. Chapter 4 deals with the construction of the La-SrMn-Cr-O oxide database based on the assessments of subsystems. some of them probably occurring simultaneously.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. Furthermore spinel blocks pores and thus impedes the oxygen 7 . In chapter 1 the basics of planar SOFC are briefly explained. The chromium is known to deteriorate the electrical performance of the cathodes. and previous findings of chromium “poisoning” of SOFC are critically reviewed. even if the system is in a thermodynamic non-equilibrium state. how thermodynamic calculations can lead to a better understanding of a system. This has calamitous consequences for the electrochemical properties of the cathode. and the modeling approach used in this study is presented. It is shown that chromium “poisoning” of SOFC cathodes is a rather complex process consisting of several steps.
With this contribution the prevailing question is resolved. Appropriate measures can be foreseen preventing the long-term degradation of SOFC cathodes in combination with high-chromium containing interconnects. which of the phenomena in a chromium-“poisoned” LSM cathode are governed by thermodynamics.Summary reduction required for the function of the cell. 8 . Cr2O3(s) (s = solid) that hampers the diffusion of oxygen into the electrolyte is a metastable phase in LSM contaminated by chromium.
Die thermodynamische La-Sr-Mn-Cr-O Oxid-datenbank wird basierend auf dem Assessment oxidischer Subsysteme mit dem CALPHAD-ansatz (Berechnung von Phasendiagrammen) aufgebaut. Die neue Datenbank wird auf das Problem der „Chromvergiftung“ von Srdotierten Lanthan-Manganit-kathoden ((La1−xSrx)1−yMnO3-δ oder LSM) für FestoxidBrennstoffzellen (SOFC) angewandt, welches von gasförmigen Cr spezies der hochgradig Crführenden Interkonnektor-Legierung herrührt. Es ist bekannt, dass das Crom die elektrische Leistung der Kathoden verschlechtert. In Kapitel 1 werden die Grundlagen von planaren SOFC kurz erklärt, und es wird ein kritischer Überblick über bisherige Erkenntnisse der „Chromvergiftung“ von SOFC gegeben. Basierend auf den Erkenntnissen aus der Literatur wird klar, dass einige Fragen, welche die Schlüsselmechanismen der „Chromvergiftung“ betreffen, noch nicht beantwortet wurden. Das Ziel dieser Studie (Kapitel 2) ist es, unter Verwendung der Thermodynamik ein tieferes Verständnis dieser ungelösten Probleme zu erlangen. Im dritten Kapitel lernt der Leser, wie thermodynamische Berechnungen zu einem besseren Verständnis eines Systems führen können, selbst wenn dieses System sich in einem thermodynamischen Ungleichgewichtszustand befindet, und der in dieser Studie verwendete Modellansatz wird vorgestellt. Kapitel 4 beschäftigt sich mit der Konstruktion der La-Sr-Mn-Cr-O OxidDatenbank, basierend auf den Assessments der Subsysteme. In Kapitel 5 wird die neue Datenbank auf das Problem der „Chromvergiftung“ von SOFC mit Cr-interkonnektoren und LSM-kathoden angewandt: Eine konsistente phenomenologische Beschreibung des Prozesses der „Chromvergiftung“ von SOFC-kathoden wird gegeben, welche sowohl im Einklang mit experimentellen Erkenntnissen in der Literatur als auch mit thermodynamischen Berechnungen unter Verwendung der präsentierten Datenbank steht. Es wird gezeigt, dass „Chromvergiftung“ von SOFC-kathoden ein ziemlich komplexer Vorgang mit mehreren, teilweise gleichzeitig in der Zelle ablaufenden Schritten ist. Manche dieser Prozesse sind thermodynamisch kontrolliert, und manche laufen unter kinetischer Kontrolle ab. Eine Schlüsselrolle spielt die Adsorbtion von gasförmigem CrO3(g) (g = gasförmig) und Chromium-oxyhydroxiden, welche vom Interkonnektor stammen, an LSM und die Reaktion von Chrom mit LSM. Die damit verbundenen chemischen Änderungen der LSM-phase und die Bildung einer neuen Spinellphase finden unter thermodynamischer Kontrolle statt. Die 9
Berechnungen ergeben abnehmende Konzentrationen der Leerstellen in Cr-hältigem LSM unter erniedrigtem Sauerstoffpartialdruck, und somit bei Betrieb von SOFC unter hohem Laststrom . Das hat katastrophale Konsequenzen für die elektrochemischen Eigenschaften der Kathode. Weiters blockiert Spinell Poren und behindert so die für die Funktion der Zelle notwendige Sauerstoffreduktion. Cr2O3(s) (s = fest), welches die Diffusion von Sauerstoff in den Elektrolyt erschwert, ist eine metastabile Phase in Cr-kontaminiertem LSM. Mit diesem Beitrag werden einige der vorherrschenden Fragen über „Chromvergiftung“ von SOFC geklärt, und geeignete Maßnahmen zur Verhinderung der Langzeitdegradation von SOFC-kathoden in Kombination mit hochgradig Chrom-führenden Interkonnektoren können vorhergesagt werden.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects
E. Povoden and L.J. Gauckler, to be submitted to Int. J. Mater. Rev. For the use of LSM cathodes in planar SOFC a comprehensive understanding of the mechanisms of the cell degradation caused by chromium diffusing from the interconnects into the cell is needed. This “poisoning” has been intensively investigated over the last decade. In this paper the affects of Cr on the degradation of SOFC with LSM cathodes and Cr-alloy interconnects are reviewed: the suggested models of chromium “poisoning” of planar SOFC with chromium-alloy interconnects and (La1-xSrx)1-yMnO3-δ (LSM) cathodes from the literature are critically assessed. Taking into account all available experimental findings on the affects of chromium on Sr-doped lanthanum manganite cathodes in planar solid oxide fuel cells, it can be concluded that several “poisoning” processes contribute to the deterioration of the cell performance. The review of all available experimental findings on the degradation of SOFC caused by chromium allows predictions, as to how the extent of degradation caused by chromium depends on the current load, operation temperature, operation time, as well as the amount of chromium diffusing from the interconnect.
1.1.1 Principles of SOFC A fuel cell directly converts chemical energy into electrical energy. A solid oxide fuel cell consists of two porous electrodes that are separated by a dense, oxygen ion-conducting electrolyte. A simple schematic of the electrochemical process is shown in Fig. 1.1.1 (next page).
In an SOFC. A single cell produces a voltage of 0. c = cathode. forming a cell stack to obtain higher voltage and power. The direct-current electricity is produced by the electron flow through the external electric circuit. The electrons flow from the anode through the external electric circuit to the cathode. a = anode.1. The electrodes are required to have high reactivity and the electrolyte must allow high oxygen ion diffusion. and ceramicmetal composites are used for the anode.1 Scheme of the electrochemical processes in a fuel cell with O2 oxidant and H2 fuel.2 (next page) for the widely used planar-design SOFC. White circles symbolize pores. At the anode the oxygen ions react with hydrogen of the fuel to form water and release electrons. supplied at the cathode reacts with electrons from the external electric circuit to form oxygen ions. cathode and electrolyte consist of refractory solid oxide ceramics.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. The oxygen. e = electrolyte. 12 . as shown in Fig. All the components of the cell need to be matched in their thermal expansion in order to minimize mechanical stresses. These ions migrate through the electrolyte to the anode. 1. The materials for the cell components need to have a sufficient chemical and structural stability at rather high temperatures up to 1273 K that occur during cell production as well as during cell operation. Normally many cells are electrically connected in series by an interconnect.7 to 1 V and power around 0.1.5 to 1 W cm-2. 1.
It is the most demanding component in a planar SOFC as it should have a high electronic conductivity. and their thermal and redox-stability is satisfying. 13 . as chromium alloys come close to all desired properties. as the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. 1. a thermal expansion coefficient close to that of the cathode and the anode. difficulties in sintering and manufacturing and low mechanical strength required the development of alternative interconnect materials. 1.2 The problem of chromium “poisoning” In the 1990is LaCrO3-based ceramics were intensively investigated for interconnect applications in SOFC.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. 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.2 Planar design of SOFC The interconnect separates the fuels and oxidants in adjacent cells. Nowadays the state-of-the-art interconnect is commonly a chromiumcontaining metal plate[3-5]. a low ionic conductivity. However high costs of these materials. stability in both oxidizing and reducing atmospheres at the high cell operating temperature (from about T = 973 K to 1273 K).1. the electronic conductivity of several LaCrO3-based ceramics under SOFC operating conditions is high. low permeability for oxygen and hydrogen to minimize direct combination of oxidant and fuel during cell operation.1. and chemical compatibility (no reactions) with other cell materials.
Appreciable volatilization occurred in dry oxygen.3 mg at T = 1273 K after 72 h. 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.1 mg at T = 1373 K and 5. This was a surprising result. But when it was learned that Cr2O3(s). but its formation by the reaction Cr2 O3(s) + 3 2O2(g) → 2CrO3(g) (1.2. In stagnant air the volatilization was 0. and -diffusion processes.6 mg at T = 1373 K and 2. and at T = 1373 and 1473 K in flowing dry and wet oxygen as well as in dry and wet argon. Volatilization of Cr2O3(s) was neither observed in dry nor in wet argon. in the absence of metal.1) 14 . The volatilization in wet oxygen was significantly higher after 20 h at the same gas flow rate: 2. the volatile species must be a higher oxide of chromium.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.6 mg at T = 1473 K.2 cm in diameter and height were heated at T = 1273 K in stagnant air. Since weight loss takes place under oxidizing conditions. lost weight when heated in oxygen. it became evident that a volatile Cr-oxide was being formed. Furthermore. the weight loss being 0. neither the vapour pressure of Cr2O3(s) nor its dissociation pressure is high enough to account for the quantities of deposits observed. -reduction. 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. and it was suggested that high-valent gaseous Cr-oxide and Cr-oxyhydroxides detrimentally affect the O2 -adsorbtion.6 mg at T = 1473 K at a gas flow rate of 200 ml min-1 after 20 h.3-2. Caplan and Cohen investigated the evaporation of Cr2O3(s) by measuring the weight loss when Cr2O3(s) pellets with 1. A known volatile oxide of Cr is CrO3. or at discontinuities such as fractures in the film and would then evaporate. 1.2 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. 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.
15 .2. μ(O) being −300 J mol-1 referred to pure oxygen gas result from combined thermodynamic data[11-14.3) Δ°G of reaction 1. 1.2 is calculated to be −158 kJ at T = 1273 K using combined data from Opila et al. The existence of gaseous Cr-oxyhydroxides as oxidation products (Eqs. and Ebbinghaus.2) Cr2 O3(s) + 1 2O2(g) + H 2 O(g) → 2CrO2 (OH)(g) (1.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects is thermodynamically unfavourable at high temperatures. and for CrO3(g) from Ebbinghaus. Δ°G of Eq.3) in wet atmosphere was experimentally proven in several studies[14-17].2 and 1.18] cited above. However. in a recent combined experimental and modeling study these earlier findings are rejected for high temperatures: in wet atmosphere CrO2(OH)2(g) is predominant in the gas from T ≤ 1173 K. 1.2. and this was affirmed by thermodynamic modeling. This tendency is shown in Fig.1 is calculated to be +321 kJ at T = 1273 K using assessed thermodynamic data for Cr2O3(s) from Povoden et al. and Δ°G of reaction 1.2. 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. These findings are supported by the higher volatilization of Cr2O3(s) in wet air. data for O2(g) from Dinsdale. whereas at higher temperatures the gas phase mainly contains CrO3(g) and CrO2OH(g). 1. As gaseous CrO3(g) was detected experimentally by mass spectrometry when Cr2O3(s) was heated under oxidizing conditions. Ebbinghaus estimated a significantly higher partial pressure of CrO2(OH)2(g) compared to CrO3(g) in wet atmosphere up to T = 1600 K based on available thermodynamic data of gaseous Cr-species..2.2.3 is calculated to be +134 kJ at T = 1273 K using combined data from Kim and Belton and Ebbinghaus. the formation of CrO3(g) occurs under kinetic control.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 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. at T = 1073 K for a time period of about 500 h. and the 16 .2.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. reaching pCr = 4. Cr-vaporization in SOFC: Konysheva et al.57x10-3 Pa at T = 1223 K. 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. to measure the vaporization rate of Cr from Cr5Fe1Y2O3 (Ducrolloy) and Crofer22APU (high-Cr ferritic steel).2 μg h-1 for 3 mol% H2O in air at T = 1073 K. used a transpiration method proposed by Gindorf et al. 1. two high-chromium alloy interconnects widely used in SOFC.12x10-5 Pa at T = 673 K and increases as a function of increasing temperature. the mass loss being higher at higher water content and higher temperature: the constant rate of mass loss was 0. and 18. Mass loss of Cr2O3(s) at T = 973 K and 1073 K was measured in air with different amounts of water.6 μg h-1 for 3 mol% H2O in air at T = 973 K.3 μg h-1 for 25 mol% H2O in air at T = 1073 K. 3.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects vaporization rate increases with increasing temperatures for both alloys. this value being by about a factor of 2. Experimental results[21-29. Badwal et al. However.3. for an SOFC setup with a Cr5Fe1Y2O3 interconnect plate. and the chromium problem is restricted to the interconnect-cathodeelectrolyte region of SOFC. an yttriumstabilized zirconia (YSZ) electrolyte and a Ni-zirconia cermet (ceramic-metallic composite) anode operated at T = 1173 K and 1273 K. 1.35] 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. pp. With increasing humidity the difference in the vaporization rates between the two alloys increases. 18-184.108.40.206.1 Degradation of SOFC caused by chromium from the interconnect Considering the experimental data from Caplan and Cohen. The amount of Cr in these degraded cells was 140 μg cm-2 with Cr5Fe1Y2O3. thus quantitative chromium “poisoning” rates affecting the cathode are difficult to determine.5 higher than with Crofer22APU. This is in line with the experimental observation that only a fraction of the chromium deposited at the cathode side contributes to the strong degradation of SOFC with LSM cathodes and Cr-alloy interconnects that were tested under a current load of 200 mA cm-2 for 393 h.3 Literature survey 1. mentioned significant amounts of deposited Cr2O3(s) in the air exhaust of the cell.34.31. 17 . an LSM cathode.
3.1 Results of chromium poisoning of SOFC with and without Cr-containing interconnects with LSM cathodes collected from the literature 18 .Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Table 1.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 19 .
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 20 .
.1MnO3-δ. The cell voltage decreased over this time from initially about 0. 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.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. In a test of the same setup under open circuit conditions for 21 . and intensity measurements using electron probe microanalysis showed that Cr was concentrated at the cathode-electrolyte interface.1 V.9Sr0. The cell was electrochemically tested at T = 1273 K under a current load of 300 mA cm-2 for 400 h.7 V to about 0. 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.
 thus linked the cell degradation to the time that the discharge current was applied.3. Taniguchi et al. reported that the degradation rate of SOFC with a Cr5Fe1Y2O3 interconnect plate. the cell performance was stable for 110 h. the cell started to degrade severely after 20 h of testing.7 V: without the interconnect steel.: these authors tested the cell performance of an SOFC with a Cr5Fe1Y2O3 interconnect plate. hindering the supply of oxygen gas and decreasing the number of reaction sites for the oxygen reduction. the power density being 0. an LSM cathode.4 V after only 16 h. and to chromium deposited at the LSM-YSZ interface filling pores.05 W cm-2 after 110 h.2 The role of current load on electrical losses of degraded SOFC Badwal et al. a Sm2O3-CeO2 interlayer between cathode and electrolyte. holding the cells at 0.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.2 W cm-2 to 0. Later these results were confirmed by Badwal et al. The cell performance without interconnect plate deteriorated only little by less than 0. a YSZ electrolyte and a Pt counter electrode (in the following SOFC with Pt counter electrode are denoted as half-cell) with and without Crofer22APU interconnect at T = 1073 K. whereas ohmic losses (resistance to 22 . 1. and Cr was randomly distributed across the cathode.1 V during an operation time of 2500 h. A comparison of measurements of the overpotentials of SOFC with LSM cathode and high-Cr alloy interconnect with measurements without interconnect[24-27] or LaCrO3-based interconnect led to the following results: the overpotentials without interconnects or with LaCrO3-base interconnects consistently became less negative with time. its power density decreasing from a maximum of 0. But using a Cr-Fe-alloy interconnect. 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. presented cell performance data of an SOFC with LSM cathode. a YSZ electrolyte and a Ni-zirconia cermet anode at T = 1273 K and a current density of 250 mA cm-2. 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. On the other hand the voltage of the cell with Cr-Fe-alloy interconnect decreased rapidly as a function of operation time. Simner et al.48 W cm-2. an LSM cathode. ascribed the voltage decrease to increasing losses of cathodic overpotential. the voltage drop being 0. whereas the opposite was observed for SOFC with Cr-alloy interconnect. All these experimental studies[22-29] unambiguously proved that chromium stemming from the alloy interconnect causes the degradation of SOFC.
Konysheva et al.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. 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.8Sr0.23. losses increased sharply and reached their maximum values after only 15 h of cell operation. Zhen et al. A plateau of degradation was reached after about 400 h of testing. with a tendency of stabilization of the cell performance after this testing period at much lower magnitude of output current. Rpol being 0.98MnO3-δ cathode and a YSZ electrolyte over 5 to 10 h at T = 1073 K applying a −0. in general agreement with Jiang et al. whereas at 280 mA cm-1 the voltage dropped by 0.6 V. La0.26] was observed. 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.21 % Cr on top of a (La0. Paulson and Birss reported rapid deterioration of the performance of a half-cell setup with a stainless steel disk containing 15. tested the reversibility of degradation in a half-cell setup with CrFe-alloy interconnect. in agreement with earlier findings[22.31].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 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.5 Ohm cm2 for a thickness of 23 . using a half-cell with a Cr5Fe1Y2O3 interconnect. In earlier studies using the same setup a rapid decrease from −360 to −560 mV after 10 minutes[25.[24.25. Matsuzaki and Yasuda measured an overpotential loss from initially −500 mV to −2000 mV after 14 h in a half-cell setup with an Inconel 600 interconnect. LSM cathode and a YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2. In reference tests without Cr-Fe-alloy interconnect the results were opposite to the tests with Cr-Fe-alloy interconnects: the polarization increased from −550 to −300 mV or −420 to −170 mV [24. However the cell degraded rapidly again when the current was switched on again. 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.25] at 1173 K and a current density of 200 mA cm-2.2)0.33]. a La0..4MnO3-δ cathode and a YSZ electrolyte at 300 mA cm-2 current density. At the beginning of the cell tests.32. The total polarization resistance (Rpol) of a half-cell setup using a Cr-Fe-alloy interconnect. Konysheva et al.6Sr0.28.5 V potential. The overpotential losses were higher and the cell deterioration was faster at higher current density.07 V.65Sr0.
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. 1. a La0.26.4MnO3-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. 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.3.[24.3. 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. observed an increased size of the high frequency arc during the current passage in half-cell tests using a Cr5Fe1Y2O3 interconnect plate.75 Ohm cm2 for 13 μm.3 Impedance spectroscopy measurements and implications on the degradation process Badwal et al. reported the existence of a high frequency and a low frequency arc in impedance spectra of a half-cell with Cr-Fe-alloy interconnect. 0. This finding was confirmed 24 . 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.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 50 μm. LSM cathode and YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2. and from −800 to −1120 mV at T = 973 K after 10 minutes. were the first who reported the occurrence of Cr-Mn-spinel in Cr“poisoned” SOFC with an LSM cathode by using XRD analysis.6Sr0. The total polarization resistance was also higher at higher current load.4 Microstructures in degraded SOFC Cathodic polarization: Taniguchi et al. an LSM cathode and a YSZ electrolyte as a function of operation time. and 2 Ohm cm2 for 7 μm. Jiang et al.32].33] and Jiang et al. reflecting increasing cathode resistance. The degradation was higher at higher temperatures at 0. 1. Zhen et al. Mazusaki and Yasuda concluded from the interpretation of impedance spectra of a half-cell with an Inconel 600 interconnect. observed less overpotential losses at lower temperatures in a half-cell with CrFe-alloy interconnect. but not due to the increase in ohmic resistance. from −900 to −1200 mV at T = 1073 K.7 V.
On the other hand Cr-Mn spinel formed already at 25 . Jiang et al.05 μm) of Cr2O3 towards the cathode-electrolyte interface. The zone of these large faceted crystals was followed by a zone of very fine grains (about 0. Using the same setup. an LSM/LSM-YSZ cathode double layer and a YSZ electrolyte chromium-deposits were only found in the LSM layer under open circuit conditions. In some 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. but further details on their spatial distribution and composition were not given. no Cr-deposits formed after 50 h of testing under open circuit conditions[25. For the same setup large quantities of spinel had formed after 2000 to 2500 h of cell operation.36] documented spinel formation at the LSM-YSZ interface already after 4 h. who detected small amounts of Cr-Mn spinel after 100 h of operation of SOFC with a Cr5Fe1Y2O3 interconnect plate. Very small grains of Cr-deposits formed at T = 1373 K under open circuit conditions. 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-2.7 μm after 50 h. In a half-cell setup with a Cr-Fe-alloy interconnect. but under anodic polarization very fine grains of Cr2O3 were forming exclusively at the LSM-YSZ interface.17 μm after 4 h of cell testing and increased to about 0. and the cell-degradation was weak. Badwal et al. a YSZ electrolyte and a Nizirconia cermet anode at T = 1173 and 1273 K under current load. Using the same setup as above.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects by Badwal et al. Under the same testing conditions as above. The amount of spinel at the cathode-electrolyte interface was much larger than within the LSM cathode particularly after a period of current load. 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. in some of the experiments forming a dense layer of several microns at the cathode-electrolyte interface. and the cell degradation was strong. Using a half-cell setup with Inconel 600. LSM cathode and YSZ electrolyte Matsuzaki and Yasuda reported the formation of a dense layer of Cr-deposit at the LSM-YSZ interface after a cell test at T = 1073 K and a current density of 300 mA cm-2 over 100 h of polarization. unfortunately the specific conditions for its formation were not given in more detail. an LSM cathode.[25. The deposition zone broadened as the polarization time increased from about 60 μm after 50 h to 89 μm after 129 h. The grain size of spinel was about 0. Zhen et al. further observed spinel in the contact region between interconnect and cathode.
Cr-deposits consisting of Cr2O3 and Cr-Mn-spinel were concentrated in an about 2 μm broad region at the LSM-YSZ interface. up to 10 μm away from the LSM-YSZ interface after 160 h of testing. exclusively covering the YSZ surface. No spinel formation was observed in these experiments.72Sr0. and the deposition was less pronounced at T = 1073 K and 973 K. and 30 μm from the LSM-YSZ contact after 940 h. After 20 h spinel formation was observed forming a 40 to 50 μm wide band at the LSM-YSZ interface.2)0. These authors observed the formation of a 500 μm broad zone of 8 individual.5 μm thick layer directly adjacent to the YSZ containing mainly Cr2O3 is covered by a spinel layer. after the half-cell was tested by a sequence of 8 chronoamperometry experiments at −0. Cr2O3 completely filled gaps between YSZ grains.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.98MnO3-δ cathode that rested on a 144 mm2 square YSZ electrolyte. almost completely 26 . Transmission electron microscopy analyses revealed the layered structure of the composites: a 0. Paulson and Birss investigated the microstructures in a half-cell setup with a stainless steel disk containing 15. 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. Cr2O3 was also found inside YSZ.. Influence of temperature: Microstructural changes during half-cell tests of a setup consisting of a Cr-Fe-alloy interconnect. Anodic polarization: After a half-cell test of an SOFC with Cr-Fe-alloy interconnect operated for 6 h at T = 1173 K and a current density of 200 mA cm-2.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. Jiang et al. and spinel crystals were found on the surface of a thin Cr2O3-layer adjacent to the electrolyte. In direct contact with YSZ about 500 nm large Cr2O3-grains were detected.8Sr0. After 160 h of testing at 100 mA cm-2 current load. a La0. The morphology of the particles was different than the morphology of the deposits under cathodic polarization. large gaps between YSZ grains formed.21 % Cr attached on top of a 4 mm2 square (La0. reported the formation of very fine particles of Cr2O3.5 V and T = 1073 K. A reference test without polarization did not lead to these features.
In SOFC with LSM cathodes and a Cr-Fe-steel interconnect that were tested at T=1073 K for 300 h at 0. In a half-cell with LSM cathode.% Cr in the Sm2O3-CeO2 interlayer.3. This may lead to a dramatic drop of the oxygen diffusion coefficient in LSM by about 60% and pers. 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. 1.3MnO3-δ/LSM+YSZ double layer cathode and a YSZ electrolyte after tests without current showing very small degradation. 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. a La0. It further decreased slightly towards the interconnectcathode interface. Krumpelt et al.7 V for 120 h. but no Cr in LSM using energy dispersive scanning electron microscopy. comm. this is only 15 to 20 % higher than in the cell operated without current. The decreasing degradation at lower temperatures was ascribed to slower diffusion and lower partial pressure of gaseous Cr-species.8 wt. compared the total amounts of chromium in half-cells with Cr-Fe-alloy interconnects. The Cr-content dropped to about 0. Simner et al.vacancy within about 10 Å around Cr3+.5 wt.5 Amounts of chromium in SOFC tested with and without current load Konysheva et al. 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.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects covering the YSZ surface. measured 5 at. measured about 2. holding the cell at 0.7 V. By using molecular dynamics simulation techniques it was stated recently that only 890 ppm Cr3+ in LSM significantly increase the formation energy of O2. a Sm2O3-CeO2 interlayer between cathode and electrolyte and a YSZ electrolyte with a Crofer22APU interconnect operated at T = 1073 K. and under 200 mA cm-2 current density showing strong degradation as a function of testing time at T = 1073 K.% at 14 μm distance from the contact to the electrolyte. associated with large grains (about 1 μm) of spinel.65Sr0. although the degradation of the polarized cell was remarkably higher.% of Cr at 10 μm distance from the cathode-electrolyte interface. 27 .
230. YSZ.2.1) Eq. 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”.3. including changes of the chemical composition of the LSM surface.31. described by inverse Eq. 1) Several authors[21-23.2) 28 .37].33].30-31.2 is a possible reaction for the formation of spinel with a higher amount of Mn. reduction of CrO3(g) at the cathode-electrode interface competing with the normal oxygen reduction reaction. This reduction reaction would compete with the oxygen reduction and would lead to blocking of the active sites at the TPB and subsequent formation of Cr-Mn spinel by the reaction of Cr2O3(s) with LSM.3. emphasized that chromium “poisoning” would consist of several processes. 1. and blocking of pores by Cr-Mn spinel and Cr2O3(s). 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. Both reduction and chemical dissociation processes reflect non-equilibrium conditions. 1. and gas. and 2) Chemical dissociation of Crspecies on the LSM surface[24-26. electron-donating LSM and oxygen-accepting YSZ are available. Badwal et al. 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) (1.3.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. Badwal et al.32.33] ascribe the mechanism of chromium “poisoning” to the reduction of gaseous CrO3(g) and Cr-oxyhydroxides at the cathode-electrolyte interface. 1. 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. where the reaction partners for the reduction. 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.1.3.6 Critical assessment of proposed mechanisms of chromium “poisoning” For the mechanisms of chromium “poisoning” two models have been proposed: 1) Reduction of gaseous Cr-species under polarization[21-23.3.1 when solid solubility of Cr in LSM is considered and spinel contains the molar fraction of Cr. In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary (TPB) between LSM.33.
5) considering the main chromium molecules that interact with LSM for spinel with X(Cr) = 2X(Mn).2 less Cr2O3 is needed for the formation of Mn2CrO4. 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. and the LSM-Cr-gas reaction occurs as a parallel process leading to the formation of spinel.3. and the mobility of the gas phase is high.3. red = reduction.1 and 1.3.1 is a simplified illustration of possible reaction paths that lead to the end product Cr-Mn spinel. Fig. 1.3.3. Ea of the concerning reaction.3 to 1. The shape of the curves in Fig. more oxygen is produced. 1. and LSM gets more deficient in Mn. sp-form = spinel formation. 1. Which of the possible reaction paths is realized. 1.1 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). These assumptions would mean that fast reduction of Cr-gas to Cr2O3(s) occurs as one process. Fig. depends on the activation energy. However the formation of spinel can also be interpreted as a direct solid-gas reaction. 1. Such gas-solid reaction can be split into two reaction steps: formation of 29 . thus assuming a lower activation energy for the LSM-Cr-gas reaction.3. Oxygen production stems from the reduction of Mn3+ in perovskite to Mn2+ in spinel.3.1 Possible reaction paths for the spinel formation as a function of Gibbs energy. reactions of direct formation of spinel by the interaction between Cr-gas and LSM can be formulated (Eqs.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects For equal y in Eqs. and this is not known. The true shape of the curves depends on the activation energy Ea and is thus not known. As it is not assured if spinel in fact forms in a solid-solid reaction.
 confirmed these early suggestions by evaluating the ionic conductivity of LSM from pure oxygen to pO2 = 300 Pa at temperatures from 953 K to 1153 K using YSZ as blocking electrode.3) La1− xSrx MnO3−δ + 3 yCrO2 (OH)2(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2O4 + 3 yH 2O(g) + 5 2 y O2(g) (1.3.5 that oxygen is produced during the formation of spinel.3. and consequently to Cr-Mn spinel and Cr2O3(s).33.3. 1.33. The role of the oxygen vacancy diffusion mechanism in an LSM cathode has been considered controversially: Mogensen and Skaarup concluded from the low oxygen self-diffusion coefficients of the order of 4×10-14 cm2 s-1 at T = 1173 K that long range bulk migration of oxygen ions cannot play a significant role for the cathode performance.3. Yasuda et al. This in turn will also lead to less Mn2+ in LSM and consequently lower oxygen diffusion in LSM.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.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.3. As Mn2+ is associated to vacancy formation in LSM that is necessary for the oxygen diffusion. It can be seen from Eqs.32. However they did not discuss the dependence of oxygen diffusion upon pO2 .37] oxygen diffusion is inhibited by the nuclei-formation. 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. Thus the pO2 at the locations of the spinel formation is expected to increase. opposite to the trend that would be expected under the control of the vacancy diffusion mechanism.[24-27.4) La1− xSrx MnO3−δ + 3 yCrO2 (OH)(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2 O4 + 3 2 y H 2 O(g) + 3 4 y O2(g) (1. Huang et al. concluded that 30 . The differences of oxygen contributions to respective reactions stem from the reaction step of Cr2O3(s) formation: La1− xSrx MnO3−δ + 3 yCrO3(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2 O4 + 5 2 y O2(g) (1. The ionic conductivity was lower at lower oxygen partial pressures.32.5) 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[24-27.1 to 1.
as well as Konysheva et al.4x10-6. Reduction of CrO3(g) to Cr2O3(s) was such predominant as to make sampling of gaseous CrO3(g) difficult. This is close to 270 kJ mol-1 for La0.2. Paulson and Birss. This confirms the suggestion that the formation of oxygen vacancies in LSM contributes to the oxygen diffusion at high current loads. 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. In an investigation of active sites for the oxygen reduction at the O2/LSM/YSZ interface for three different overvoltages of cathode polarization (η = −0.37]. compared to δ = 3. 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.32.9Sr0.33. It was also mentioned in the early paper of Caplan and Cohen that substantial precipitation of Cr2O3(s) from CrO3(g) occurred in the cooler part of the experimental setup. The calculated amount of oxygen vacancies (δ) in La0. This phenomenon was well explained by continuous feeding of an initial 31 .185 V.336 V corresponding to pO2 = 10-4 Pa.1 has a large negative value. This indicates that a vacancy diffusion mechanism also applies to LSM. as Δ°G of the reduction being the inversion of reaction Eq.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. η = −0. as oxygen vacancies are simply not available under these conditions.8Sr0. and η = −0. The activation energy for the diffusion of oxygen for LSM is in the range of 250 to 300 kJ mol-1. when the oxygen partial pressure at the cathode-electrolyte interface is decreased significantly. The electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach[24-27. We believe that the oxygen vacancy diffusion mechanism contributes to the oxygen diffusion under high current loads.1CoO3-δ in which oxygen ions are transported by the vacancy mechanism.94x10-9 in air.336 V. as it was directly proven by isotopic and tracer diffusion experiments.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. observed the extension of dense Cr2O3layers into YSZ. 1. Contradictory interpretations from the dependence of the ionic conductivity on pO2 need to be judged with care due to the difficulty of controlling the numerous factors that can influence the results of the blocking electrode method used.2MnO3-δ at 973 K and pO2 = 10-4 Pa is δ = 2. Based on the findings from the literature it can be summarized that in LSM oxygen diffuses through grain boundaries at high pO2 .
which both seemed to be inhibited by chromium poisoning. But how can one explain the strictly localized deposition of Cr2O3 that also occurs under anodic polarization? Under oxidizing conditions little Mn2+ is expected to be present in LSM. whereas in a polarized cathode the reduction of CrO3(g) takes place and competes with the oxygen reduction leading to Cr2O3(s) deposition.37] and subsequent formation of spinel. partly layered structures. Cr2O3(s) deposition should also occur under open-circuit conditions.33.31]: by switching off the polarization the competing reduction of CrO3(g) no longer occurs.28.37]: the two phases formed in the scope of a polarized LSM cathode exhibit distinctive microstructures: spinel forms large grains.34].23.30. and the degradation can be associated to the dissociation process[24-27. and the second with a higher rate on the YSZ electrolyte surface.32. Thus it is obvious that the explanation of the “poisoning” process by the chemical dissociation approach alone is not without doubt. 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. and it is also in line with the observed temporary reversibility of the cell deterioration[22. one with a lower rate on the LSM surface. thus the formation of nuclei by the proposed LSM-Cr interaction won’t occur. The region of spinel formation extends several microns from the TPB into the cathode. and the normal charge transfer can take place by switching it on again. In this case the contribution of reduction to the Cr-“poisoning” has to be rejected. In this case no chromium will be deposited at the cathode-electrolyte interface under open-circuit conditions. the latter becoming reduced at the new TPB consisting of YSZ and electron-donating Cr2O3(s)[21. whereas an explanation by the chemical dissociation approach is not satisfying. This explanation is in line with the microstructural features of tested cells both under open circuit voltage and under current load. This is in contrast with the complicated mechanism for the formation of Cr2O3(s) under anodic 32 . which was definitively not observed.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Cr2O3-layer with CrO3(g). Furthermore. whereas the phase that was most likely identified as Cr2O3 occurs in fine-grained.26. Also two different diffusion processes were distinguished. Some indications for two independent chromium poisoning mechanisms can be found in the work from Jiang et al. From the occurrence of finegrained Cr2O3 the existence of a large number of nuclei for its formation is concluded.[24. from impedance spectra analyses it was in fact possible to distinguish two distinctive depositions of Cr-species. which is increasing as a function of increasing polarization. which does not seem to be the case for the spinel phase. If CrO3(g) is electrochemically reduced to Cr2O3(s) in a cell.
LSM cathode and a YSZ electrolyte at T = 1173 K and a current density of 200 mA cm-2 from Zhen et al. the number of the latter being less than under cathodic polarization. Alternatively. 4 b) as a function of time reveals an inflection point after about 6 1/2 h. opposite to the situation with a platinum cathode. This is an indication against one unique “poisoning” mechanism. and in LSM a pO2 gradient is expected under polarization. However this conclusion was not tested in the light of the oxygen partial pressure gradient towards the electrode-electrolyte interface: contrary to platinum. based on an early finding that LSM behaves like a metallic electrode at low polarization potentials that was not quantified.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects polarization established by Jiang et al. if both the chemical dissociation as well as the reduction of gaseous Cr-species is occurring with different proportions. this apparent antagonism is abolished. In cell tests of a polarized platinum electrode using a Cr-containing interconnect no Cr was observed. However. 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. Oxygen deficiency is negligible in LSM under high pO2 . but several processes may lead to the deterioration of cell 33 . again with Mn2+ acting as agent for the formation of Cr-Mn-O nuclei. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. This different behavior of Pt and LSM electrodes under Cr-poisoning was used as an evidence for the exclusive validity of the dissociation approach. 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. This is indeed true for the case of CrO3(g) and Cr-oxyhydroxide reduction being the only Cr-poisoning mechanism. vacancies are expected to form in LSM under increasing polarization. where the reaction partners for the reduction. 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. It was further mentioned that the existence of Cr-containing products away from the TPB would be in disagreement with the reduction approach. are particularly interesting: the slope of the cathode polarization curve (Fig. contrary to an LSM electrode. In this context experimental results of a half-cell test with Cr-Fe-alloy (RA446) interconnect. and thus lack of spinel formation. which is indeed not the case in a platinum cathode. that includes diffusion of Mn3+/Mn2+ driven by the oxygen evolution reaction at the cathode/electrolyte interface. contrary to the situation of a strong pO2 gradient under cathodic polarization. and thus under these conditions LSM has no tendency at all to accept oxygen.
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. the oxygen ions from this new. Applying a current load. 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. under open circuit the LSM-Cr interactions occur randomly throughout the cathode. and oxygen cannot access the TPB. Reduction already takes place at higher pO2 at the beginning of the current load operation. the lower is the oxygen partial pressure at the contact between LSM and YSZ. 34 . The deposition of chromium followed by its reduction near this interface blocks direct oxygen access to the electrochemically active sites.8 S m-1 at T = 1282 K and pO2 = 1 Pa. 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. Oxygen is mainly reduced at the new TPB between Cr2O3(s) and YSZ. This results in a lower oxygen partial pressure at the interface as compared to that in air. The temporary reversibility of the deterioration by switching the cell off and on again can also be explained: in contrast to current load operation. As Cr2O3(s) has a small electronic conductivity of 0. weak catalytic reaction diffuse into YSZ.. as electronic conductivity of Cr2O3 is significantly higher at higher pO2 (1. thus the remaining TPB/YSZ active sites are almost unaffected under open current circuit. 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. and their respective influence on the cell deterioration may vary as a function of time. Konysheva et al. the LSMCr interaction is again favored in the region close to YSZ as pO2 decreases at the TPB. Under polarization. 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. thereby still more decreasing the oxygen partial pressure at a newly formed Cr2O3(s)/electrolyte interface: the TPB between LSM and YSZ diminishes more and more by the blocking of Cr2O3(s).8 S m-1 in air). give the following explanation. even though the decrease is expected to be less due to less LSM/YSZ active sites caused by the first degradation.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects performance. the oxygen ions formed at this interface are transported from the cathodeelectrolyte interface through the electrolyte. The higher the current density under SOFC operation.
1.5. and the degradation increases as a function of time. Number 2 denotes the region of interactions between LSM and chromium leading to spinel formation by solid-solid reaction. 35 .2. 1.3. Fig.2 denotes the interconnect-cathode interface region where oxidation of Cr2O3(s) to gaseous Cr-oxides and Cr-oxyhydroxides by Eqs.3. Eqs.3. followed by diffusion of the gaseous products into the cathode.3.1 to 1.1 leading to the redeposition of Cr2O3(s) at the cathode-electrolyte interface. 1.3. Numbers refer to locations of processes that are decisive for the degradation Number 1 in Fig.3.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Oxygen ions diffuse into YSZ. 1.1 to 1.2. and chromium content is schematized in the picture.3 to 1. Fig.3 occurs. Eqs. or gas-solid reaction.3. 1. 1. but new oxygen is not supplied to the new TPB.2. and number 3 denotes the reduction of gaseous Cr-species by the reverse of Eq.2 Model of chromium poisoning of an SOFC with Cr-interconnect and LSM cathode based on the findings in the literature. Active LSM/YSZ sites further diminish by ongoing formation of spinel and Cr2O3 deposits.2 is a visualisation of the microstructural consequences of chromium in an LSM cathode.2. current load. 1. The reported dependence of structural features of the degraded cell on the operation temperature.
but a combination of the quoted strategies is advisable to further improve the long-time stability of SOFC performance.Sr)CoO3. more active sites for the oxygen reduction will result in a higher Cr-tolerance.33MnO3. Co3O4. Furthermore such a buffer layer may act as a sink for CrO3(g) thus diminishing nuclei formation on LSM.4Mn1. or Cu.65].54]. MnCo2O4[54-61].67Sr0. La0.5Co0. as Cr in the ppm range significantly influences the oxygen diffusion in the LSM cathode. Cu1.6O4[53.1 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes More than ten years ago Badwal et al. If the buffer layer contains an ionic conductor. or Cu-Mn. La0. Ce0. 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[49.2FeO3-δ.65Sr0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1.4Co0.8Sr0.5O3-δ. La.2Mn0.15MnO3-δ.85Sr0.475Co1. thereby improving the electrical conductivity of the interconnect-cathode interface[49-69]. La0.8Sr0. La0.50].Al)N.05Mn1. La0.4.3MnO3[58. sputtered Co.6Sr0. so far volatilization could not be suppressed completely.5O3. Ni. 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.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.8Sr0.Co)3O4. This was recently shown for a cell with a YSZ-LSM functional layer: a functional LSM-YSZ layer adjacent to the YSZ electrolyte led to a lower cell degradation: increasing the ionic conductivity of the LSM cathode that is predominantly electronically conducting down to pO2 = 10-7 Pa by admixture of YSZ results in an 36 .475O4. or Mn2CrO4. 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. La0. Mn.8Fe0. (La. 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. as well as (Ti. La0.5Co0. coating alone does not solve the problems associated to chromium poisoning completely. Co-Mn. However.2O3. two-segment Cr-Al-Y-O nanocomposite and (Mn. However.2Mn0.
Fe)O3-δ (LBCF)[71.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.2O1. and (La.4Co0. The amount of Cr- 37 . La(Ni. Effects of Cr upon the degradation of La1-xSrxCo1-yFeyO3-δ (LSCF)[26.8O3-δ (LSCF) cathode and Ce0. particularly LSCF and LNF show rather high ionic contributions to the total electrical conductivity. Matsuzaki and Yasuda concluded from insignificant Crdeposits in tested SOFC with Cr-Fe-alloy interconnect. contrary to LSM.Fe)O3-δ (LNF)[71.Fe)O3-δ (LNF). LNF and LBCF revealed extraordinary high tolerance against chromium poisoning. The ionic conductivity can be increased by doping the B-site of ABO3 perovskite with reducible cations.Ba)(Co.2 New ways – alternative materials Badwal et al.4.74]. the reduction of gaseous chromium will not be restricted to the small area at the TPB due to a smaller oxygen partial pressure gradient. Besides. All these perovskites are mixed electronic-ionic conductors.Ni)FeO3-δ [71. La0. Thus the number of active sites is increased.75] cathodes were investigated using impedance spectroscopy. which makes this material a promising candidate for a steady long-term SOFC performance. The highest tolerance against the effects of chromium under SOFC operating conditions combined with high electrical conductivity has been reported recently for (La.73].71. and (La.2Fe0.Fe)O3-δ (LBCF) are more tolerant against chromium “poisoning”. 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. In recent time it was found that new cathode materials such as La1-xSrxCo1-yFeyO3-δ (LSCF).Ba)(Co. 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. 1. already considered alternative cathode materials to reduce or stop the formation of the spinel phase. Based on these findings they predicted that highly Cr-tolerant cathodes can be developed. La(Ni.6Sr0. 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. In all these cathodes Cr-deposition was observed throughout the cathode both under polarization and without polarization. whereas no proper nuclei were reported for LBCF.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.8Sm0. and the cell is more tolerant against chromium.72].
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”. nuclei might form in addition. The amount of deposited Cr in LSCF was even larger without polarization than under polarization. Improved inhibition of the reduction of CrO3(g) is predicted for LNF. Even if the reduction reaction is considered to be the dominant mechanism of chromium poisoning. However. References 1.W. 271-83. 2004. H. 2004. 2. 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.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects poisoning of LSCF was considerable. 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. Thus reduction of CrO3(g) takes place inside the whole cathode even without being promoted electrochemically by polarization of the cell. J. U. which was explained by a removing effect of nuclei for the chromium deposition under polarization conditions. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. J. but their influence on the Cr deposition compared to the reduction of CrO3(g) cannot be decided yet. As an alternative to the complicated nuclei mechanism.W. and a typical mixed ionic-electronic conductor such as LSCF can take over both functions. 127. pp. J. Power Sources. 38 . Fergus. 397. most likely resulting in retarding or inhibiting of the reduction reaction. 3. Advances. Materials Science and Engineering A. as this phase has a particularly high ionic conductivity. Fergus. 1-15. 171. Solid State Ionics. pp. However under strong polarization one can expect that LSCF gets more and more ionic conducting towards the electrode-electrolyte interface. Stimming. The higher the contribution of the ionic conduction the less complete reduction is expected due to prolonged lack of an electron donator. that is towards lower oxygen partial pressures. Tu. 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. 2005. 284-93. pp. aging mechanisms and lifetime in solid-oxide fuel cells. Metallic interconnects for solid oxide fuel cells.
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The causes and consequences of chromium poisoning are clear. So far it was not possible to define unambiguously. and some strategies against cell degradation caused by chromium have already been successfully applied. which of these processes play a dominant role for the degradation and which don’t. For a more systematic and thus more efficient combination of strategies a strong knowledge about the mechanisms of chromium poisoning of SOFC is required. this behaviour would not be expected. If the process of chromium “poisoning” were completely governed by thermodynamics. However. 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. 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. it seems that strategies against the cell degradation have been mostly established in a rather random way so far. Reduction of CrO3(g) at the TPB leads to the formation of electrically low conducting Cr2O3. Mn2+ in LSM plays an important role for the adsorption of gaseous CrO3(g) and Croxyhydroxide on LSM resulting in blocked oxygen transport from the cathode to the electrolyte.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. but the effects of chromium would be observed only after thermodynamic equilibrium is obtained. which further retards the diffusion process of oxygen into the electrolyte. This means that the kinetic control on the mechanisms of chromium 45 . 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.
and a degrading cell is in a non-equilibrium state particularly at the early stages of the degradation. and as LSM cathodes are still considered to serve as promising cathodes due to their high electrical conductivity and stability at SOFC operating conditions. the obvious question why the results of thermodynamic calculations should be feasible for a deeper understanding of the mechanisms 46 . 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.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. Therefore the thermodynamic La-Sr-Mn-Cr-O oxide database needs to be established based on the assessments of low-order subsystems. and can this change be explained by thermodynamics? -) Which of the phases observed in LSM contaminated by chromium form under thermodynamic control. and what are the conditions that favour their formation? This work aims to answer these questions by the application of thermodynamic calculations. In particular LSM cathodes have been intensively investigated over the last decade. As a degrading cell is in a non-equilibrium state. 3 Method 3. and several studies can be found regarding the degradation of LSM cathodes caused by chromium. In recent times many materials have been tested for SOFC cathodes.Aim of study is high. in this study the author focuses on the effects of Cr on the degradation of SOFC with LSM cathodes. Thus.
equilibrium (A) ⎯⎯ equilibrium (B) → (3. for instance under reducing oxygen partial pressures reflecting the situation at the TPB under current load. 3. the theoretical final state of chromium poisoning after a very long time is found by thermodynamic equilibrium calculations (B). temperatures. taking into account experimental data on the chromium “poisoning” of SOFC and using a thermodynamic La-Sr-Mn-Cr-O oxide database. can be calculated using the thermodynamic La-Sr-Mn-Cr-O oxide database: C non . The presented thermodynamic database of the La-Sr-Mn-Cr-O oxide system is constructed using the CALPHAD approach. and for solid solution phases as a function of temperature and composition. 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.Method of chromium “poisoning” needs some explanation: from the conditions of the non-equilibrium state at the beginning of the degradation process. It contains the optimized Gibbs energy functions of solid oxide phases: for stoichiometric phases as a function of temperature.1 reflects the path the system takes towards its equilibrium state. The optimization of model parameters is based on the accurate assessment of experimental thermodynamic and phase diagram data of oxide subsystems.1.2 Thermodynamic modeling 3. 47 . composition of LSM. C in Eq. and oxygen partial pressures.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. and the rate of chromium diffusion the equilibrium state of chromium “poisoning”. C can be predicted for changing cathode compositions. including the operating temperature. Hence.1 Stoichiometric solid oxides The stoichiometric ternary phase α. From A and B.2. For instance. 3. by choosing the starting conditions composition of LSM and defined amount of Cr at a specific temperature. one can draw conclusions on the evolution of the phase chemistry of degraded LSM cathodes. using the thermodynamic database one can calculate the expected thermodynamic equilibrium. a with the positive electrical charge r and b with the positive electrical charge q.1.
the three types of ions sitting in three distinctive crystallographic sublattices.1 is true.)w + ptv − muv − nwt ° O (g) Gm + A + BT 2tv 2 (3. c with the negative electrical charge s. 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. 3. B. D.2. To account for the charge neutrality criterion. 3.2) A.4) ° α Gm is the Gibbs energy of formation of the phase α relative to the oxide components. mr + nq + 2 p = 0 (3. w ∈ N ). °Gm at constant pressure is given by ° α Gm = A + BT + CT ln T + DT 2 + ET 3 + FT ( −1) (3. u. A and B are optimized by thermodynamic and phase diagram data. the sublattice formula of the resulting solid solution phase β(ss) reads (a r . 3. For oxides c = O and charge s = −2.) w ( t . can be described by the sublattice formula (a r )m (b q )n (c s ) p . °Gm can be based on the molar Gibbs energies of existing binary oxides Ox1: (a r )t (O2.2.4: m ° ( a )t (O2. C.2.)u and Ox2: (b q )v (O2. Eq. E and F are optimized to heat capacity data only.)u . and F are model parameters to be optimized by thermodynamic and phase diagram data. Eq.3) α C. another sort of cation with the positive charge q.2.)u containing cation a with the positive charge r.2. bq can sit in the same sublattice as a. 3. v.2. As Cp(α) is defined by C p = −C − 2 DT − 6 ET 2 − 2 FT −2 (3.2.5 is the criterion for charge neutrality: 48 .Method respectively. and p moles of one sort of anions.2 Solid solution phases – the Compound Energy Formalism (CEF) If in the binary oxide Ox1: (a r )t (O2. D.1) α The molar Gibbs energy of α. E.)u n ° (b G + Gm t m v r ° α Gm = °Gm ( a r )m (bq )n (O2. b q )t (O2.) p = q )v (O2.2.
°Gma 3+ )2 (O2. and ybq is the site fraction cation b on the cation sublattice.7) Once again the molar Gibbs energies of all the 4 endmember compounds (a3+ )2 (O2.Va )3 (3. the charge neutrality criterion is no longer obeyed by an anionic sublattice that is completely filled with oxygen. 3. The oxygen nonstoichiometry is denoted “O3-δ”.2.)3 ( + ya3+ yVa °Gma 3+ )2 (Va )3 3+ ( + ya2+ yVa °Gma )2 (Va )3 ( + 2 RT ya3+ ln ya3+ + ya2+ ln ya2+ + 3RT yO2.5) Using the Compound Energy Formalism (CEF)[2-4].ln yO2. a 2+ )2 (O2.)3 .Va )3 ( = ya3+ yO2.)3 .)u + ybq °G (b q )t (O2.)u . For β(ss) the two compounds read (a r )t (O2. (a 3+ )2 (Va)3 .. a 2+ )2 (O2. (a 2 + )2 (O 2.)u β + tRT yar ln yar + ybq ln yar + EGmss ( ) (3. If the cation is reduced. a 2+ )2 (O2. The molar Gibbs energy of the phase at constant pressure reads 3+ ° A ( Gm 2 O3−δ = °Gma 2+ . Va)3 .2.31451 J mol-1 K-1.Method u= t ( ya q + yb q ) 2 (3. The second-last term accounts for the configurational entropy of mixing of t moles of a and b.)u and (bq )t (O2. R=8.3 Vacancies and the concept of reciprocal reactions Let us consider the case of a binary oxide phase (A)2(B)3. the molar Gibbs energy of the solid solution phase contains the Gibbs energies of the compounds. and B denoting the anion sublattice..2.°Gma 2+ )2 (O2.)3 ( + ya2+ yO2. 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. A standing for the cation sublattice. and (a 2 + )2 (Va)3 of the phase are required for the molar Gibbs energy 49 . In the sublattice form the phase can be written as (a3+ . 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..2. with only one cation a accepting the charge 3+ or 2+ in the cation sublattice.6) where yar is the site fraction of cation a on the cation sublattice. The Gibbs energy of β(ss) at constant pressure reads ° β Gmss = yar °G ( a r) t (O2.+ yVa ln yVa + EGma ( ) ( ) .
Va)3 the 6+ charged compound (a3+ )2 (Va)3 is chosen as reference. 3. However.. a 2+ )2 (O2. plotted above the composition square. and its molar Gibbs energy can be defined by optimization of model parameters by experiments. denoted with A in Fig.)3 .1 The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . a 2+ )2 (O2. the reference should favorably be a highly charged compound. thus far off neutral compositions that can really exist. Fig. 3.)3 .2. It thus can exist. The composition square of the phase can be seen in Fig. For the example of the reciprocal solid solution phase (a3+ . The 2+ charged center composition of the square.. Va)3 is a reciprocal phase. 50 . 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. and (a3+ .1 that is redrawn from Hillert.1.Method of the phase.2. with the neutral line and the reduced compound. but a line of neutral compositions connects (a3+ )2 (O2. (a3+ a 2+ )2 (3 2O2.Va)3 . and its Gibbs energy can be optimized with experiments that are related to the reduction of the phase. a 2+ )2 (O2. The three other endmembers are charged and cannot exist. A system that obeys this relation is called a reciprocal system. the only neutral endmember is (a3+ )2 (O2.2. is theoretically obtained by mixing equal amounts of either (a3+ )2 (O 2.)3 with the reduced compound (a 2+ )2 (2 3O2.)3 and (a 2 + )2 (Va)3 or (a3+ )2 (Va)3 and (a 2 + )2 (O 2. denoted with R. Va)3 approximating its overall Gibbs energy for Δ°Grec > 0 and Δ°Grec = 0.3 2 Va)3 . included. 3.. As the chosen molar Gibbs energy of the reference is unlikely the true value. for instance oxygen nonstoichiometry data.
Va)3 at very low temperatures (to make the configurational entropic contribution negligible). b 2 + .Method The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . as long as these endmembers are charged and away from the existing composition range of the phase. the Gibbs energy surface is flat and no tendency of demixing of A exists. Va)(O 2. d 3+ .. site fractions and oxygen content.) 3 − °G ( 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.)3 − (a3+ )2 (O 2.)3 − (a 2 + )2 (Va)3 : Δ °G rec = °G ( a 3+ ) 2 (Va)3 + °G ( a 2+ ) 2 (O 2. temperature.)3 and the reference (a 3+ )2 (Va)3 are fixed. and no experiments define a proper value of the reciprocal reaction parameter. a 2+ )2 (O2. for instance (a 3+ . 51 . As no tendency of demixing was reported for the nonstoichiometric oxide solid solutions that are treated in this study. Va)3 for a Cr-doped LSM perovskite as a function of composition. 3.1 (page 50) only the edge of this plane is seen as bold line. Δ°Grec is positive. Anyway. and the theoretic compound A will tend to demix to (a3+ )2 (O2.2. For this purpose model parameters of the reduced and oxidized compounds are optimized with experimental information on charge carriers.1 (page 50) and approximates the whole Gibbs energy of the phase.4 Calculation of defect chemistry using the Calphad approach The Calphad approach is very powerful for the calculation of the defect chemistry of highorder nonstoichiometric reciprocal solid solution oxide phases such as (A)(B)O3-δ perovskite with a complex sublattice formula. the Gibbs energy surface is curved. when the Gibbs energies of the endmember (a 3+ )2 (O 2. if Δ°Grec is zero.8) If Δ°G of the reciprocal reaction. The morphology of the Gibbs energy surface depends on Δ°G of the reciprocal reaction (a3+ )2 (Va)3 + (a 2 + )2 (O 2.) 3 − °G ( a 2+ ) 2 (Va)3 (3. the Gibbs energies of the remaining endmembers are significantly different for Δ°Grec > 0 and Δ°Grec = 0.2.2. This is not a problem for the description of a reciprocal oxide phase. d 4+ . Va)(c 2 + . 3. On the other hand. 3. In Fig. c 4 + .)3 and (a 2+ )2 (Va)3 by only slightly oxidizing or reducing it.2. it is legitimate to define Δ°Grec = 0. c3+ .. the true surface shape of a reciprocal oxide phase with charged endmembers is not known. and without excess terms for the Gibbs energy is visualized in Fig. and oxygen partial pressure.
M. J. 3. 4. J. Alloy.. 153-90.. Ivas. References 1. 81-87. pp. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. Z.P. 1985. L. 6. Calculation of Defect Chemistry Using the CALPHAD Approach. Andersson. Jansson. M. Saunders. pp. pp. Sundman. Grundy. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously. pp. B. Hillert.-O. 437-445. 2006. M. 5. Calphad Calculation of Phase Diagrams. 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. Miodownik. 1988. pp. 34. B. The program minimizes the sum of squared errors between calculated and experimentally determined phase diagram and thermodynamic data. 320.3 Optimization of model parameters The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system.F. Elsevier Science Ltd. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. Application of the Compound-Energy Model to Oxide Systems..J. This weighting process is based on the accurate assessment of experimental thermodynamic and phase diagram data. Calphad. 1986. Povoden. 9(2).N. 33-41. Vol. A. Guillermet. Sundman. Hillert. Pergamon Materials Series. 30. N. Andersson. B.O. Gauckler. Jansson. E. Metallkd. The Thermo-Calc databank system. Jansson.Method 3. 161-76. Calphad. Hillert. B. Sundman.. 2. Cmpd. 52 . A. 1. B. 79(2). T. B. J. 479 p. 2001. A. Acta Metall. 1998. The Compound Energy Formalism.
Also the magnetic transition in Cr2O3 and the oxygen solubility in Cr are modeled. Grundy. For the planar design SOFC. 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 block active sites as well as pores.J. pp.1 Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research E. a consistent set of thermodynamic model parameters is optimized based on new experiments.1 Technology SOFC offers high fuel conversion efficiencies and. combined heat. thus substantially reducing the triple- 53 .% 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.% Cr. A comprehensive compilation and evaluation of experimental and thermodynamic data for the Cr-O system is presented and. A.1. Loss of performance caused by the migration of Cr originating from the alloy interconnect is well documented by several investigators. low manufacturing costs and high thermal conductivity. Namely a Cr5Fe1Y2O3 oxide dispersion strengthened alloy with the composition 94 wt. Nonstoichiometry of eskolaite (Cr2+xO3) is described using the compound energy model. 2006.N. Microstructural analyses of the cathode of SOFC show the formation of Cr2O3 and (CrMn)3O4. and L. Meanwhile the use of Cr-based alloy interconnect materials has gained popularity due to their relative ease of fabrication. 353-62.% Fe and 1 wt. Cr3O4 is described as a stoichiometric compound. Gauckler J. 4. Povoden. Phase Equilib. which offers low fabrication costs. and the liquid is described using the two-sublattice model for ionic liquids.. ceramic and metal interconnect materials have been tested and evaluated over the years.Thermodynamic assessments 4 Thermodynamic assessments 4. However. 5 wt.and power-generation capability. due to the high operating temperature (>1173 K). by application of the CALPHAD method. 27. Diff.
These authors document the existence of a large miscibility gap between the metallic and the oxide melt.1.2 Experimental data Phase diagram data: Experimental investigations of phase diagrams in the Cr-O system were made by Ol’shanskii and Shlepov and Toker.Thermodynamic assessments phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. T (K) T (K) 2257 2317 2603 ---- 2543 ± 25 -- 54 . Results of special points in the Cr-O phase diagram from several studies are summarized in Table 4. Eskolaite (Cr2O3) is the dominating stable oxide phase over a wide temperature range.1.1 Special points in the Cr-O system Eutectic Melting of Cr2O3 in Eutectic composition.1. 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.1. X(O) ----Cr3O4 detected ----Stability range Mono- of Cr3O4. experimental Bunting experimental air. 4. Table 4. tectic T (K) ----T (K) ----Reference Kanolt experimental Wilde and Rees experimental McNally et al.
Thermodynamic assessments --2571 ---2539 1933 1918 1941 1929 1937 1938 ± 2 1938 0. The question of the existence of a crystalline Cr3O4 phase was discussed controversially by several authors.496 0. The monotectic reaction of Cr (bcc) metal and liquid was found at T = 2083 K by Grube and Knabe and by Ol’shanskii and Shlepov. 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. who measured T = 2543 ± 25 K also in air.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. Concerning the pure Cr-O system. Lam reported the existence of molten chromium with oxygen impurities of 1400 ppm at T = 2133 K. This value significantly deviates from the result of Bunting. experimental This work.499 0. Microstructures of a quenched 55 .52 0. Investigations made by Hilty et al.513 0.% Cr2O3 lowers the melting point of metallic Cr from T = 2163 K to between T = 2043 K and 2063 K. experimental Johnson and Muan experimental Degterov and Pelton calculated Kowalski and Spencer calculated Taylor and Dinsdale calculated Toker et al. Grube and Knabe found that 1 wt. calculated Note: Itallicized data were used for optimization The melting temperatures of eskolaite in air reported from Kanolt and Wilde and Rees can be discarded as being too low.523 0. whereas Toker et al. Mc Nally measured a melting temperature of 2603 K in air using an induction furnace. Ol’shanskii and Shlepov and Johnson and Muan did not find Cr3O4 up to the eutectic temperature of chromium oxide.497 0. and Hook and Adair led them to postulate the existence of a crystalline Cr3O4 phase in the Cr-Fe-O system.
These authors used a flow method where thermal diffusion problems were suppressed by inserting corundum bushes into the reaction tube.. Holzheid and O’Neill noted a deviation from the well-established trend from T = 900 K to 1300 K for high-temperature data caused by finite electronic conductivity at elevated temperatures. that is. The independent results of corrected cell potentials of the two measurement series are excellent. and 1373 K. as well as transport of oxygen ions from the cathode to the Cr/Cr2O3 anode.. Thermodynamic data: Oxygen Potentials: Grube and Flad measured log( pO2 ) values for the Cr-Cr2O3 equilibrium between T = 1053 K and 1573 K by both oxidizing Cr to Cr2O3 and reducing Cr2O3 to Cr in a flowing H2-H2O atmosphere. used two separate series of emf measurements employing the solid oxide electrolyte galvanic cell technique from T = 1148 K to 1548 K. 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.. days for T < 1100 K. Disagreement between the emf results from Pehlke et al. and Lam. Davies and Smeltzer determined log( pO2 ) values of Cr2O3 at T=1173 K. Novokhatskii and Lenev studied the equilibrium of the reduction of Cr2O3 to Cr with hydrogen from T=1493 K to 1893 K. Toker et al. The obtained 56 . 1273 K. and Tretjakow and Schmalzried were assigned to possible electronic conduction in the zirconia electrolyte used by the latter authors. thus at these temperatures log( pO2 ) values were determined solely from the reduction of Cr2O3. Pugliese and Fitterer. Pehlke et al. The data are in close agreement with the gas-solid equilibrium measurements by Jeannin et al. as well as the importance of sufficient time to attain equilibrium. Appreciable sublimation of metallic chromium was not observed. Applying the same technique as Pehlke et al. At T ≥ 1573 K they were confronted with the loss of a quarter of Cr in the case of oxidation.Thermodynamic assessments chromium melt with maximum oxygen impurities of about 2930 ppm lately investigated by Lam document an inner Cr3O4 phase and an outer Cr2O3 phase in dispersed oxides in large chromium grains and grain boundaries. Thus in this study the authors accept the findings of Toker et al. causing transfer of oxygen through the cell. 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. 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.
15 K Chase et al..736 ×105 T −2 (4. The accuracy of this study is evident from excellent data reproduction by performing two runs in the entire temperature range.1.84 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 .43 K.736 ×105 T −1 − 9759 (4.17 ± 0. relied on the results from Anderson. and fitting procedure are worked out very carefully. The latter authors measured a consistent data set of heat capacities of synthetic eskolaite from T = 1. Resulting Cp data correspond nicely to the most recent calorimetric results from Klemme et al.53T + 1.20 ×10−3 T − 3. heat Contents.1. and entropies: Anderson’s calorimetric data set of Cp-values lacks detailed documentation of the experimental procedure.5 K to 340 K with mean increments of 0.68 ≤ T ≤ 323.3) For ° S298K (Cr2O3) Chase et al.. Documentation of the experiments. 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. and fitted the data to the heat of diffusion equation that considers some material properties employing a least-mean-squares fit. 4. who calculated ° S298K (Cr2O3) = 81. Heat Capacities.1.4 % for Cp (20 K < T < 200 K) and 0.53 + 2. Bruce and Cannell applied a two-dimensional temperature wave method using a single crystal of Cr2O3 to calculate specific heat in the temperature range 290.1) yielding ° H T − ° H 298K = 28.1.2 results in C p = 28. relied on the calculated results from heat content measurements performed by Kelley et al. For Cp(Cr2O3) = 120. data presentation.7 % for Cp (T < 20 K) were estimated.2) Temperature derivation of Eq.56 K..Thermodynamic assessments dissociation pressures of Cr2O3 are in agreement with average values derived from emf studies using an yttria-doped thoria electrolyte worked out by Jacob and a very high temperature gas-mixing study of Toker et al.10 ×10−3 T 2 + 3. Uncertainties of 0.37 J mol-1 K-1 at T = 298.
 evaluated Δ f.72 kJ mol-1 from Wagman et al.98 ± 1.el° H 298K (Cr2O3) =–1140. Klemme et al. This procedure was critically documented by other authors. Dellien et al. adopted their ° S298K (Cr2O3) value from Wagman et al. Shirokov estimated Δ f. were used.el° H 298K (Cr2O3) = –1122.74 ± 1. Navrotsky cited Garrels and Christ for Δ f.4 kJ mol-1 by evaluating emf data from Holzheid and O’Neill. The latter authors proposed a 58 .1 J K-1mol-1 by reevaluating emf data from Holzheid and O’Neill.06 kJ mol-1. Kowalski and Spencer used the associated solution model for the liquid phase based on the experimental data used by Taylor and Dinsdale. which is in good agreement with an early finding by Bunting who measured T = 2543 ± 25 K. who calculated ° S298K (Cr2O3) = 85.3 Previous assessments of the Cr-O system Banik et al. Degterov and Pelton reassessed the CrO-Cr2O3 subsystem for the molten slag database using a modified quasi-chemical model for the liquid phase. Mah. using a bomb calorimetric combustion technique at 1323 K and 30 atm oxygen pressure.7 kJ mol-1. calculated Δ f.4 kJ mol-1 for metastable CrO.. This was circumvented by heating the combustion products to T = 1323 K. Enthalpies of Formation: Roth and Wolf found Δ f.5 kJ mol-1 (el=elements) by applying a calorimetric technique. Chase et al. thermodynamic data for Cr-Cr2O3 from Fromm and Gebhardt. for example. recommended Δ f. recommend ° S298K (Cr2O3) = 83..el° H 298K (CrO) = –305.42 kJ mol-1.4 kJ mol-1 from several earlier studies.2 ± 0.3 J K-1 mol-1 from their measurements.86 J K-1 mol-1. while Dellien et al. Some difficulty caused by moisture adsorption was encountered in weighing the combustion products.7 ± 8.1. Klemme et al.el° H 298K (Cr2O3) the heat content data given by Kelley et al. Ramsey et al.Thermodynamic assessments functions. used heat capacity and entropy data from tabulations of Coughlin to obtain Δ f.el° H 298K (Cr2O3) = –1134. adopted Δ f.el° H 298K (Cr2O3) = –1139. For the calculation of Δ f..8 ± 2.el° H 298K (Cr2O3) = –1128. Their calculated liquidus temperature of Cr2O3 in air is T = 2571. 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.el° H 298K (Cr2O3) = –1125.16 K. Klemme et al. 4.el° H 298K (Cr2O3) = –1128. Shirokov estimated ° S298K of a metastable CrO phase to be 46. and thermodynamic estimates for CrO from Shirokov.
space group R3c . The magnetic properties of eskolaite can be described using a magnetic ordering model proposed by Inden. 4. and only few thermodynamic data of the Cr3O4 phase and the liquid phase exist. Kelley et al. Experimental information on phase relations for their assessment was taken from Ol’shanskii and Shlepov. This is reflected by significant variations of the position of the eutectics.4) 59 . at elevated temperatures as a sum of magnetic and nonmagnetic contributions. 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 the temperature of the monotectic reaction of Cr(bcc) and liquid between the assessments of the Cr-O system. There is a large uncertainty concerning the exact melting point of Cr2O3. Toker.4 Thermodynamic modeling Solid phases: The crystal structure of eskolaite is α-Al2O3 type. and simplified by Hillert and Jarl.1. and Grube and Knabe. the stability field of Cr3O4. Their calculated values for the enthalpy of formation and the entropy of Cr3O4 are in agreement with an estimate done by Chipman. Eskolaite shows an antiferromagnetic to paramagnetic transition at T = 305.1. 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. Taylor and Dinsdale fitted Cp data from Anderson close to the antiferromagnetic to paramagnetic transition and data from Chase et al.Thermodynamic assessments phase diagram in good agreement with the experimental data obtained by Toker. 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 ) (4.5 K. The use of six parameters for the description of the Cr3O4 phase is somewhat incommensurate with the scanty experimental information of this phase. In this model.. using the same thermodynamic models as the authors use in this work. The heat capacity of Cr3O4 was taken as 7/5 times the nonmagnetic value for Cr2O3 according to Neumann and Kopp’s rule.
Tc and β are both dependent on the composition. it is important to submit the experimental data to a defect-chemistry analysis.1..6) ' Assuming small defect concentrations all concentrations except [CrCr ] and [Cri••• ] are ~ 1 and ' can be ignored. Due to charge neutrality the relation [Cri••• ] = 3[CrCr ] must hold. 4. When modeling nonstoichiometry in an oxide phase. The magnetic parameter p equals 0. and Cri•••• giving a slope of pO −3 20 2 . Both are unlikely: the former because it is unlikely to get Cr4+ on reduction.1.1. however.1. Tc is the critical temperature for magnetic ordering.Cr3+)2 (Cr3+.Thermodynamic assessments where β is a parameter related to the total magnetic entropy.Va)1 (O2-)3 can be modeled using experimental data from Matsui and Naito. Assuming the defect reaction that describes the formation of oxygen vacancies: x x ' CrCr + 1 2OO → CrCr + 1 2 Va •• + 1 4O2(g) O (4.7) 60 . In the case of Cr2+xO3 modeled with interstitial Cr3+ the defect reaction reads x x ' x 2CrCr + Va ix + 3OO → 3 2CrCr + 1 2Cri••• + 1 4 Va ix + 9 4OO + 3 8O 2(g) (4. which is in agreement with Young et al. the latter because of the large size of Cr2+. 4. their equation violates the fundamentals of defect chemistry and must be rejected in favor of the defect reaction given above (Eqs.5 and 4.28. To explain their experimental results Matsui and Naito proposed a defect reaction that leads to the same proportionality. and τ = T/Tc.6 gives the proportionalities [Cri••• ] ∝ pO2 −3 16 and [CrCr ] ∝ pO2 −3 16 .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. The defect chemistry of Cr2+xO3 with the sublattice occupation (Cr2+.1. This means that reduction is accomplished by the formation of interstitial Cr3+ and not by the formation of oxygen vacancies. Inserting this ' into Eq. The following other interstitial defects could be assumed: Cri•• giving a slope of pO2 −1 4 .6).1.
The present authors didn’t consider this by their defect chemistry model. This slope does not correspond O to the experimental findings of Matsui and Naito. The low nonstoichiometry data from Matsui and Naito show a different slope than their higher nonstoichiometry data.1. for example charge disproportionation. where each corner of the composition square represents a °G parameter.1.1 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 present authors believe that the different slopes are caused by a competing defect reaction. As the most reasonable way to model reduction is to use the reduced neutral endpoint 61 . Fig. Only compounds along the neutral line can exist on their own. In contrast to Matsui and Naito who explain this assuming that neutral Cr forms interstitially.Thermodynamic assessments ' leads to a proportionality of [Va •• ] ∝ PO2 −1 6 and [CrCr ] ∝ PO2 −1 6 . The three other corner compositions present charged compounds. 4. Cr3+ → Cr2+ + Cr4+.1 is a graphic representation of the model the authors use to describe the oxygen nonstoichiometry of eskolaite. Fig. The corner Cr3+:Va:O2corresponds to stoichiometric Cr2O3. as it would make the description quite complex. similar to the case of LaMnO3 perovskites. 4. Also the defects cannot explain the electrical properties measured by Young et al.
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 (4.1.1. 4.1. labeled A in Fig.10) This means that without introducing interaction parameters one gets an ideal description between Cr2O3 and Cr2+xO3.1. 4. and by defining a reciprocal reaction giving four equations with which all °Gs at the corners can be expressed. pp. by choosing an arbitrary reference.2. This is done by using the two equations for the stoichiometric and the reduced endpoints.10 are listed in Table 4. The expressions for all °Gs at the corners resulting from Eq.8) The last term describes the configurational entropy due to mixing of Cr3+ and Va on the interstitial site.63-64. which leads to ° G Cr3+ :Cr3+ + °G Cr 2+ :Va − °G Cr3+ :Va − °G Cr 2+ :Cr3+ =0 (4.1.1.Thermodynamic assessments (Cr2+)2 (Cr3+2/3Va1/3)1 (O2-)3. 62 .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.8 to 4. one has to find functions of °G of three charged corners expressed solely in terms of the neutral compositions.1. °G of the 3+ charged endmember (Cr3+)2 (Cr3+)1 (O2-)3 is chosen as reference and given the value °GCr3+ :Cr3+ .1.
= 121000 Solid Cr (bcc_A2) (Cr)1 (O.2923T 3 Cr O3 SER SER GCr 22+ :Va:O 2.543 102.6 β = 3.− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.52 mol O2 0 LCr 2+ :O2.− 2 H Cr − 2H O = 2GCR1O1_L Reference Cr (bcc_A2) 1 2 Mass 51.Va q. Cr 3+ ) 2 (Cr 3+ ..2923T 3 p = 0.008 CrO ° Cr1O SER SER GCr:O1 − H Cr − H O = GCR1O1 Cr2O3 (Cr 2+ .Cr 3+ ) p (O 2. q = 2 yCr 2+ + 3 yCr3+ ° ° ° ° L SER GCr 2+ :Va q.− 3H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.Thermodynamic assessments Table 4.4 β = −0.1.+ qyVa .28 Tc = 308.996 15.H0 4050.− H Cr = GCR_L L SER GCr3+ :Va q.− 2 H Cr − 3H O = GCR2O3_L L SER SER GCr 2+ :O2.Va)1 (O 2.− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L L SER SER GCr3+ :O2.2 Thermodynamic description of the Cr-O System Element Element Cr O Liquid (Cr 2+ .Va)3 ° ° bcc SER GCr:Va − H Cr = GHSERCR  bcc SER SER GCr:O − H Cr − 3H O = GHSERCR + 3GHSEROO + 243T 0 bcc Cr:O.Va L = −709542 Tc = −311.0 Cr3O4 ° Cr3O SER SER GCr:O 4 − 3H Cr − 4 H O = GCR3O4 Functions 63 .0 4341.Va q.5 p = 0...− 3H Cr − 3H O = GCR2O3 + GHSERCR  3+ Cr O3 SER SER GCr 22+ :Cr3+ :O 2.)3 ° ° ° ° Cr 3 SER SER GCr 2O:Va:O 2.= 0 LCr3+ :O2.Va q.)q p = 2 yO2.999 H298 .− 2 H Cr -3H O = GCR2O3 3+ Cr 3 SER SER GCr 2O:Cr3+ :O 2.0 S298 23.
Its heat capacity is given by Neumann and Kopp’s rule.82T GCR3O4 = 1. the number of parameters is kept as low as possible.5GHSEROO + 339673 − 121.5GCR2O3 − 0. and gaseous O are from Dinsdale In contrast to Taylor and Dinsdale.8T ln T −4. Therefore a large value is given to the endmember °GCr:O (in this case 0 was a large number) and the oxygen stability is modeled with the temperature dependence of °GCr:O and a regular interaction parameter 0 LCr:O. 4. mol.5GHSEROO + 255269 − 53.56T − 119. Pa: R = 8. K.5GHSEROO + 280045 − 93.51] is selected to describe the ionic liquid. As the experimental data on the liquid phase are scarce. literature data from Caplan and Fraser are used.Cr2+)p(O2-.2 (next page) is a graphic expression of the model. The oxygen solubility in solid Cr(bcc) can be described by an interstitial solution model of the form (Cr)1(O. The Cr3O4 phase is based on the eskolaite phase. liquid Cr. The descriptions for solid and liquid chromium metal and gaseous O2 are from Dinsdale.. the latter constraint is not needed in the model..4T Note: All parameters are in SI units: J. Metastable CrO is described in the same way.Thermodynamic assessments GCR2O3 = −1164542 + 728.5GCR2O3 − 0.97 × 10-3T 2 + 1050000T -1 GCR1O1 = 0. 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. Fig.76T GCRO0 = 108305 + GCR2O3 + 2 GHSERCR  3 GCR2O3_L = GCR2O3 + 439078 − 169T GCR1O1_L = 0. With this expression one is able to obtain reasonable results for the liquid phase using the positive interaction parameters. 64 . 0 LCr2+ :O2.5GCR2O3 − 0. Parameters for solid Cr. For the optimization of model parameters.Va)3.Va and 0 LCr3+ :O2. Ionic liquid: The two-sublattice ionic liquid model[50.Vaq-)q is chosen. where each corner of the composition square represents a °G parameter of the liquid phase. The sublattice occupation (Cr3+.1.Va that must of course be negative. 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.31451 J mol-1 K-1.Va that are required to give the miscibility gap. and one can reduce the number of parameters to only two.
Hallstedt and Gauckler recently reoptimized the Cu-O liquid.1. One way of doing this would be to simply say that Cr3+:Va equals Cr2+:Va plus a large positive term. The liquid composition changes along the hyperbolic curves in Fig.1. This considerably improved the description of the Cu-O liquid and removed the inverted 65 . In this model description of the liquid phase metallic Cr-liquid can be described by both the corners Cr2+:Va and Cr3+:Va. 4. for example +600000 as given to °GCu2+ :Va by Hallstedt et al. This is however problematic for reciprocal systems. 4. The °GL of liquid Cr is taken from Dinsdale. Cr3+:Va must be metastable compared to Cr2+:Va. The eutectic temperature is mainly determined by the value of the corner Cr2+:O2-.Thermodynamic assessments Fig. One derives the °GL functions of the oxide compositions (Cr3+:O2-) and (Cr2+:O2-) from the eskolaite phase.2. in his original assessment of the Cu-O system. obtaining the parameter °GCu2+ :Va from the reciprocal relation and giving it a reciprocal energy of 0. 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.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. A special feature of the Cr-O system is the occurrence of a eutectic very close to the composition of CrO.
and.The ° G L 3+ Cr :Va = 2 °G L 2+ Cr :Va + °G L 3+ Cr :O2- − 3 °G L 2+ Cr :O2- + ΔGr .2 (pp. To determine the parameters describing the enthalpy and entropy of Cr2O3 log( pO2 ) data from Jeannin et al.Thermodynamic assessments miscibility gap found at high temperatures in the original assessment. An identical strategy is employed here. ΔGr = 0 (4. and experimental data on the liquidus at the oxygen rich side of the miscibility gap from Ol’shanskii and Shlepov. The melting temperature of eskolaite in air was taken from Bunting. Δ f. 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.5 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Cr-O system is given in Table 4. and Cp data from Klemme et al.el° H 298. The authors optimized Tc and β using Cp data from Klemme et al. The data used were heat content data from Kelley et al. at T = 290 K and from T = 335 K to 338 K with a low relative weight.1. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. In the next step the authors optimized the nonstoichiometry of Cr2+xO3 using data from Matsui and Naito. The program minimizes the sum of squared errors between the calculated and experimentally determined phase diagram and thermodynamic data. In principle. experimental data on the liquidus at the oxygen poor side from Toker et al.. They assessed Cr3O4 and the liquid simultaneously. The first parameters to be optimized were the Cp-parameters of Cr2O3. The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system.1. 63-64). PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously.1.11) 4. high temperature emf data from Holzheid and O’Neill  .. and Toker et al. with low relative weight. Finally the solubility of O in solid Cr was optimized using data 66 . close to the antiferromagnetic to paramagnetic transition temperature. using experimental phase equilibria data from Toker et al. These parameters were then kept fixed during the rest of the optimization.16 and ° S298. Thus metallic liquid is given by the corner L parameter °GCr3+ :Va is obtained by the reciprocal reaction given as ° G LCr2+ :Va ..16 data from Holzheid and O’Neill were used.
4 (next page). 54-55) values that were used for our optimization are written in italic letters.3 Calculated Cr-O phase diagram with oxygen isobars (Pa. logarithmic) given.3.Thermodynamic assessments from Caplan and Fraser.1. 67 .1.1. Fig.1 (p.6 Results and discussion Phase diagram: The calculated phase diagram with oxygen isobars is shown in Fig. The gas phase was not included in the calculation An enlargement of the phase diagram close to the CrO composition is presented in Fig.1.1. 4. 4. 4. 4. In Table 4.
1.4 Enlargement of the calculated Cr-O phase diagram close to the CrO composition.Thermodynamic assessments Fig. The calculated liquidus temperature of eskolaite in air is T = 2539 K.497 it decomposes in a peritectic reaction at T = 1973 K forming Cr2O3 and liquid. 4. in good agreement with the measurement from Bunting. For the monotectic temperature of the reaction of Cr (bcc) and liquid the present authors calculate T = 2117 K. 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. with experimental data and oxygen isobars (Pa.1. and an earlier experiment from Ol’shanskii and Shlepov is slightly deviating from former optimizations. Cr3O4 is formed at T = 1918 K by the eutectoid reaction Cr2 O3 + Cr + 1 2O2 → Cr3O4 . At a mole fraction of oxygen > 0. and for the eutectic one gets T=1938 K at a mole fraction of oxygen of 0. Fig.5 (next page) shows the calculated oxygen potential phase diagram of the Cr-O system with experimental log( pO ) data included. 2 68 . 4.
4.5 Calculated oxygen potential phase diagram of the Cr-O system. Fig. 4.1. The stability of Cr3O4 is shown in the log( pO2 ) versus temperature diagram in Fig.Thermodynamic assessments Fig.6. 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 . 4. are particularly well reproduced by the authors’ optimization. with experimental log( pO2 ) data as a function of temperature from different studies The experimentally determined phase stabilities from Toker et al.1.1.
If the commonly used – however grubby – notation “Cr2O3-δ” is applied.4. The maximum calculated δ = 0. 4. 70 .Thermodynamic assessments The solubility of oxygen in Cr(bcc) is shown in Fig.8 (next page). The comparison of the calculated nonstoichiometry in Cr2+xO3 with the experimental data by Matsui and Naito is given in Fig. but it results simply from the extrapolation of experimental data from Matsui and Naito on excess Cr as a function of pO down to the oxygen partial pressure at the Cr-Cr2O3 2 equilibrium following the proportionality given by the defect chemistry analysis in section 4.1. Fig.1. the total charge of Cr is given by 6+2δ.08 at.7. 4. logarithmic) included For the maximum solubility of oxygen in Cr(bcc) one calculates 0.% at T=1938 K. 4.098 at T = 1918 K.1.7 Calculated oxygen solubility in Cr(bcc) with experimental data and oxygen isobars (Pa. The cation overstoichiometry resulting from the presented optimization might seem somewhat high.1.
8) and leads to the reduced neutral endpoint being too stable at low temperatures. Solid lines result from our accepted optimization without considering temperature dependence. Considering a temperature dependence for the reduced neutral endpoint of the phase Cr2+xO3 gives values of GCRO0 = −202130 + 235T + GCR2O3 + 2 3GHSERCR (dotted lines in Fig. and due to existing data at only three different temperatures from a single author it was decided not to optimize a temperature dependence giving GCRO0 = 108305 + GCR2O3 + 2 3GHSERCR .1. The solid lines correspond to the optimization that is accepted in this work. 71 . The low nonstoichiometry data show a different slope than the higher nonstoichiometry data. 4.8 Optimized nonstoichiometry of Cr2+xO3 with the only available experimental data from Matsui and Naito included.Thermodynamic assessments Fig. Therefore. 4. Optimization of a temperature dependence is represented by dotted lines. Obviously the calculated results show a temperature dependence that is significantly stronger compared to the experiments. as the introduction of an additional defect species would be required to reproduce these. The data at low oxygen nonstoichiometries were not used.1.
1.555 J K-1 mol-1.el° H 298K = −306 kJ mol-1 . 4. Cp. which is very close to the results from Holzheid and O’Neill.9) are well represented by our assessment. 4. and for Tc we get 308.685 kJ mol-1. Fig.6. and ° S298K (Cr3O4) = 150. and for ° S298K (Cr2O3) we get 85 J K-1mol-1.9 Comparison of calculated heat capacities of Cr2O3 with experimental data For the magnetic parameter β we calculate 3.0. 72 . and for ° S298K (Cr3O4) we get 175 J K-1mol-1. For a metastable CrO phase we calculate Δ f. For Δ f. of the solid Cr2O3 phase (Fig.Thermodynamic assessments Thermodynamic Data: The heat capacities.el° H 298K (Cr3O4) we calculate –1402 kJ mol-1. and ° S298K = −79 J K -1 mol-1 based on the estimates of Shirokov.1. For Δ f. These values for Cr3O4 deviate significantly from the results of Taylor and Dinsdale who calculated Δ f ° H 298K (Cr3O4) = –1447.. which is in particularly good agreement with the data from Ramsey et al.el° H 298K (Cr2O3) we calculate –1123 kJ mol-1.
. 6. 42(11). Nauk.Thermodynamic assessments 4. 203(2). Ribbe. 9. Sci. Y. Ceram. R. 1955. 1936. J. E. 491-93.N. I.P. J.I. Shlepov. Sistema Cr-Cr2O3. Ol’shanskii. Melting and casting of high purity chromium with controlled oxygen content. 123-55. 8. 44(10).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. McNally. Nat. R. The ternary system MgO-Al2O3-Cr2O3.I. P. Min. Oxygen solubility and oxide phases in the FeCr-O system. R. 7. 793-804 (in German). Kanolt. Soc.K. Wash. D. G. 4. Wilde. Hilty. N. 2.. V. R. 561-64. S. The system palladium–chromium. Phase equilibria in the system Cr2O3-Al2O3. Foger. J. Am. Y. Trans. Grube. Toker.F. Solid State Ionics. K.. 1978. pp. Stand. R. 1913. Knabe. 253-68.T.K. 1997. it must be kept in mind that experimental data on the liquid miscibility gap are largely missing. 1931. 5. 297-310.. pp. Zhang.Y. and that a large variation of the measured melting points of eskolaite exists. Melting points of some refractory oxides. Forgeng. 6(6). 73 . T. 2000. Brit. Res. pp. pp. pp. Folkman. 315-18.. Badwal.P. Bur. F. 1953. 10.H. 1943. Dokl. Acad. Z. Eng. 947-49.N. SSSR.W.1. Deller. melting points of MgO in a N2 atmosphere and of Cr2O3 in N2 and in air atmospheres. 99. Bunting. However.L. J.J. Laboratory furnace for studies in controlled atmospheres. Lam. 3. United States Patent 6039788. W. 1961. 42(7). C. Rees. Metall. Ceram. Peters. pp. Ramprakash. pp. 91(3).S. Equilibrium phase relations and thermodynamics for the systems Cr-O and Fe-Cr-O in the temperature range 1500 to 1825 °C. W. Akad. 3. pp. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.D.. W. References 1. Pennsylvania State University. Elektrochem. Thesis. J.C.
. 430-33. Aime. pp. pp. chromous chloride and chromic chloride at low temperatures. pp. Rev. 51(8). Adair. 24. Am. Russ. Soc.H. Muan.. M. Activities in iron–chromium alloys. J. J. Holzheid. Flad. Geochim. 20. 13. Tretjakow. 2000. C. Gmelin. 1991.. 1686-93. H. A.H. A. Muan. O’Neill. Thermodynamic properties of Cr2O3 and FeCr2O4 at high temperatures.E. pp. 23.D. 1827-31. R. Trans. Chem.. A. 74 . N. 377-89 (in German). T. 21. J.T. A. Mannerskantz. FeCr2O4. F. E. Mineral. 1997-2002. Cannell. 225-32. 12. Ceram. Hook. pp. Y. pp. 1977. 22.S. D. Jeannin. Soc. pp. 4451-59. A. Cosmochim. The Cr-Cr2O3 oxygen buffer and the free energy of formation of Cr2O3 from high-temperature electrochemical measurements. 300-5. Pugliese. Pehlke. Lenev. Soc. 15(9).Thermodynamic assessments 11. Affinity and enthalpy of the solid solution in the system Cr-Ni.E. F. Grube.R. Bunsen Gesell. B. 121(4). 15. Trans. Klemme. Toker. Jacob. Elektrochem. Ceram. L. W. 1970. O’Neill.W. 1965. K. H. S.. Solid oxide electrolyte emf cell determination of the standard free energy of Cr2O3 and applications to chromium–bearing mineral systems. C. R. 11(9). Soc. Mazandarany. 16. 124. pp. Ac.A. 1966. pp. Phys. R. Oxygen and metal activities of the chromium–nickel–oxygen system between 900° and 1100°C. pp. Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites. R.. Activities and phase boundaries in the Cr–Ni system using a solid electrolyte technique.S. Schnelle.T. J. 69(5). 230(6).. Berich. 396-402 (in German). 1942.. G. Bruce.D. pp.Y. 14. Metall. Electrochem. L. 1278-83. 1078-80. Schmalzried.S.M. Radzilowski. 1977. pp. Anderson. 1937. 1964. The heat capacity of MgCr2O4. Aime. aluminate). The thermodynamics of spinel phases (chromite. 59(3). G. 59. 1968. H. 1963. Am. pp.. 488-91. Electrochem. 25. Phase diagrams for the systems Si-O and Cr-O. 18. Soc.S. chromic oxide. Smeltzer. 1995. Am. The heat capacities of chromium. 833-45. J. Soc. L. 475-79. 22(2). 1(7). 39. pp.. Geochim. Richardson. Metall. Metall. 19. Ac. Davies. Z. 48(7). B. Equilibrium phase relations and thermodynamics of the Cr-O system in the temperature range of 1500 °C to 1825 °C. pp. ferrite. Metall.M. R. Fitterer. Johnson. Inorg.N. W. J.D. 1974. 85. 227(2). Specific heat of Cr2O3 near the Neel temperature.. Novokhatskii. Darken. 1975. 17. The formation and dissolution of chromium oxides in chromium. Cosmochim. T. 543-49. H. and Cr2O3 at low temperatures and derived thermodynamic properties.
T. 37.A. 1976. Thermodynamics of the oxidation of chromium. 80 pp. 38. 31. Downey.M.. F. Am. Soc. 46. J. Cosmochim. NBS Tech. Shirokov. 39. D. F. 29. G. Huffman. Z. W. A. Navrotsky. Flurip. I. A. pp. 410.M. 30. I. Lux. 17(6). Springer Verlag.M. 76(3). 32. D. E. New York. Degterov. Garrels and C.W. L. 1973. Nauk. 1944. Schmitt. 1956. Phys. 1980. Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3. M. 1969. J. S. B.I. Roth. Evans. S. Burr. The heat of formation of chromium oxide. J. Gebhardt: Gases and Carbon in Metals. Dellien. Data. Jr. 1975. 71(10): pp. p. R. Chem. Bur. Metal.. 940-42.. 43 pp. 102.3rd ed. Ref. especially oxides at high temperature. W. J. Fromm. Thermochemistry of chromium compounds. p. Geochim.J. D. Hall. pp. 1954. 45-46 (in German). 283-310. Christ: Solutions. V. Chase. 662. 542. 103(2). Phase Equilib. Minerals and Equilibria.N. pp. Pelton. Chem.A.B. Mines Tech.R. SSSR.. Chromium. Syverud. chemical equilibria. Ettmayer. Mines Bull.A. 33. 2. 14(Suppl. and standard potentials. Wolf. A. Z... 27. U. 1985.A. Banik. E. Ac.H.P. Elektrochem.H. R. 819-32. 75 . Tables for elements 35 through 53 in the standard order of arrangement. Selected values of chemical thermodynamic properties. Electrochem. 476-87. Halow. J. 39. Chem. P.D.H. Kelley. 1): pp. CrO-Cr2O3-Al2O3.. Bangert.G. 1954. pp. Bailey. 521-34 (in German). 34..S. Parker. pp. 1965.M. 35. 1996. and CrO-Cr2O3-CaO systems. Harper & Row. D. and tungsten: thermodynamic properties. E.K. Schumm. Berlin. Rev. 1940. N.. W. 36.L. Dokl. pp. Mah. Janaf thermochemical tables . Boericke. Thermodynamic consideration on the system Cr-Cr2O3.D. Davies.Thermodynamic assessments 26. 28. K. Metallkd. Notes. J. Hepler. Ramsey.. Heidelberg. 1976. Contributions to the data on theoretical metallurgy. Coughlin. 3363-65. Wagman. Heats of formation of chromium oxide and cadmium oxide from combustion calorimetry. pp. N. Paper. Thermodynamic properties of carbides of chromium. 644-45. Caplan. molybdenum. Thermodynamic properties of chromous oxide. R. 270(4). Akad. Bur. Soc. 135-38. McDonald. 76(13). C. A. J.
J.T. Grundy. Calculation of defect chemistry using the Calphad approach. 317-425. Hallstedt. D. L. General treatment. 47. 15. Soc.A. Hillert. M. 1978. 78-82. 51. Z. J. A.. Caplan. Cleveland. Trans. pp. Young. Risold. Thermodynamic reevaluation of the Cr-O. pp. M. Matsui. A. 45. B. Calphad. 42. 16A. Calphad.N. pp. P. 1994.. 50. pp. M.R. 1985. L. 1995. G. 1955. 97-106. 2001. J. Modification of the two-sublattice model for liquids. p. 2257-60. 136.W. T. Dinsdale.J. A thermodynamic assessment of the Ni-O. Burr: in Ductile Chromium. Sr-Cu-O. Fraser. Mater. Sundman. Naito. 66(10). Phase Equilib. M. Jansson.T. 227-38. Calphad. pp. 1957. 43. Sundman. Atomic interactions in molten alloy steels. 49. Gauckler. B. Determination of chemical and magnetic interchange energies in bcc alloys. 1991. Iron Steel Inst. Nucl. Revision of the thermodynamic descriptions of the Cu-O. Gauckler. Bi-Sr-O. B. 41. 483-99. 44.H.J. pp.. Calphad. Sundman. A. J.J.H. 76 . J. 261-66. pp. 134(9). B. Taylor. 1987. 180. 81(5). Kowalski. 577-82. 48. L. pp. J. A two-sublattice model of molten solutions with different tendency of ionization. B. T. pp. 53. pp. M. 33-41.W. 109-19. Chipman. pp.A. Metallkd.. Gerretson. pp. pp. Ca-Cu-O and Sr-Ca-Cu-O systems. J. Calphad. Calphad. SGTE data for pure elements. Inden. 15(5). 54. 177-91. J. 1975. Ag-Cu-O. Thermodynamic assessment of the copper-oxygen system. Ohio. J. The oxygen partial-pressure dependence of the defect structure of chromium(III)oxide. Calphad. A model of alloying effects in ferromagnetic metals. D. Electrochem. Ågren. 599-605. de Witt. 1990. J. Gauckler. ASM. Z. Predicting miscibility gaps in reciprocal liquids. 2(3). M. 1985. E. K. Ivas. Bi-Cu-O. 2005. Cr-O and Cr-Ni-O systems using the ionic liquid and compound energy models. A. Hillert. Existence of hypostoichiometric chromium sesquioxide at low oxygen partial pressures. A. Jarl. B. 1991. 196. 1994. 25(4). 46. Fe-O and Ni-O systems: 229-43. Metallkd. AgO. bcc and fcc phases.. 19(3). Metall. 15(4). E. 30. Povoden. Remodelling of the liquid. Spencer.J. Hillert.. Dinsdale. 354-66. 52. I. Hallstedt. pp. 2003.Thermodynamic assessments 40. 27(2).
B. Also solid solutions of the phases (Cr1-yMny)2+xO3. a consistent set of thermodynamic model parameters is optimized for the Cr-Mn-O system based on experimental data. and (Mn1-yCry)1-xO are considered.. 569-78. However.% Cr.8 wt. and the liquid is described using the two-sublattice model for ionic liquids. 97. 153-90. 1985.. By application of the CALPHAD method. Calphad.2.6 wt. The thermodynamic data of the pure elements are taken from Dinsdale. J..O.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. Grundy. 4. 22. We are contributing to the understanding of the underlying thermodynamics of these processes by assessing the MnCr-O system using the CALPHAD approach.% Mn resulted in an improvement of short-term SOFC operation. and the data for the Mn-O. pp. B. Cr-O. Simner et al. and Mn-Cr binaries from Grundy et al.J. 2006. Mater. Povoden.% Fe. mobilization predominantly via the gas phase of Cr originating from the alloy interconnect leads to the formation of Cr2+xO3 (eskolaite) and chromium manganese spinel MnyCr3-yO4 which block catalytically active sites as well as pores. Jansson. 4. Res. Chromium manganese spinel MnyCr3-yO4 and its tetragonally distorted polymorph are described using the compound energy model. thus substantially diminishing the triple phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. Andersson. Povoden et al. Sundman. pp.Thermodynamic assessments 55. The Thermo-Calc databank system. and 0. 9(2). Gauckler Int. J.45 wt. Relevance for solid oxide fuel cells is discussed. 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. 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. Mn2-yCryO3. A.N. and Lee  77 .2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials E. and L.2].
show varying degrees of mutual solid solubility. 78 . 4.1. Normal spinel is given by the formula [A2+](B3+)2O4. MnO2.2 Experimental Phase diagram data: Our calculated phase diagram of the MnOx-Cr2O3 system in air is shown in Figs. 4. In this work we use the following abbreviations: β-spl for cubic chromium manganese spinel solid solution. and 4. Fig. and liq for the liquid phase. bcc for chromium manganese alloy with bcc A2 structure. esk for Cr2+xO3 (eskolaite) with dissolved Mn. α-spl for tetragonally distorted polymorph spinel solid solution.2 (p.2. No new ternary phases are found in the Mn-Cr-O system. The most prominent oxide phase in the Mn-Cr-O system is cubic chromium manganese spinel with the formula MnyCr3-yO4. 80) shows the calculated phase diagram at pO2 = 1×10-4 Pa .2. however all the binary oxides except pyrolusite (prl).2. 4. 4. 79).3 (p.2. Spinel containing a large amount of Mn3+ becomes tetragonally distorted on lowering the temperature as a consequence of the macroscopic Jahn-Teller effect that is caused by the distortion of the octahedral sites occupied by Mn3+. In 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. 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.4 (p. β-hsm (βhausmannite) for the cubic and α-hsm (α-hausmannite) for the tetragonally distorted Mn3O4 endmember of the spinel solid solution. 80). bxb for Mn2O3 (bixbyite) with dissolved Cr.2.Thermodynamic assessments respectively. mgs for Mn1-xO (manganosite) with dissolved Cr.
The gas phase was not included in the calculation.1 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. 79 .Thermodynamic assessments Fig. The gas phase was not included in the calculation.2.2 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. Fig. 4. 4.2. with experimental data.
80 . with experimental data. Fig. 4.Thermodynamic assessments Fig.4 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 under strongly reducing conditions ( PO2 = 1×10-4 Pa ).3 Mn rich part of the calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. showing the expanded stability field of β-spl + mgs.2. 4.2.
p. but it is lower than the findings from Speidel and Muan.[14. p. Their data are shown in Figs.3. 79). 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. next page). 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. 4.2.14 at T = 1105 K in air. This value is in agreement with the result from Geller and Espinosa. 4. and β-spl + esk + liq in equilibrium at T = 2243 ± 20 K.42 at oxygen partial pressure >> 20000 Pa. They consider the solubility limit of Mn in (Cr1-yMny)2+xO3 to be negligible. 80. and Pollert et al..2. 81 .2. The solubility limit of Cr in Mn2-yCryO3 is measured by these authors to be y = 0.5.2.2. Their resulting phase diagram is in considerable disagreement with the findings of Speidel and Muan. 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-yCryO3.2. The Mn solubility in (Cr2-yMny)1+xO3 reported from Speidel and Muan is significantly higher than it is found by Golikov et al. report a solubility limit of y = 1. 79 and 4. Pollert et al. Golikov et al. They estimate a minimum temperature of T = 773 K for the stability of β-spl. 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.Thermodynamic assessments Speidel and Muan present a phase diagram of the MnOx-Cr2O3 system in air in the temperature range 873 K to 2253 K resulting from the determination of phase equilibria using quenching techniques and X-ray and microscopic examination (Fig. Pollert et al. p. 4. Tanahashi et al.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.
As the compositions of mgs 2 solid solution are located on the line connecting Mn1-xO with CrO in the ternary phase 82 . They found almost unchanging solubility of Cr in (Mn1-yCry)1-xO from pO = 2×10-6 to 2 ×102 Pa at T = 1873 K.2. esk in equilibrium with β-spl.5 Cr contents of β-spl in equilibrium with mgs. which increases slightly with increasing oxygen partial pressure. The compositions of β-spl are located on a line connecting MnCr2O4 with β-hsm in the ternary plot. each phase in the quenched specimens was subjected to electron probe microanalysis (EPMA). Experimental data are included.Thermodynamic assessments Fig. and 1873 K. 4. They found increasing Mn solubility in cubic MnyCr3-yO4 at oxygen partial pressure higher than 2 ×10-2 Pa .5). Phase relations were verified using X-ray diffraction.2. 1473 K. 4. 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. and significantly increasing Cr solubility in cubic MnyCr3-yO4 with decreasing oxygen partial pressure (Fig. In order to identify the equilibrium compositions. conclude that Mn is dissolved in cubic MnyCr3-yO4 in the form of Mn3O4. From this result Tanahashi et al. They report small solubility of Mn in (Cr1-yMny)2+xO3 at pO2 = 2×10-6 . β-spl in equilibrium with esk.
6). and 1273 ± 5 K in the oxygen partial pressure range from 0. Also the experimental result on the three phase equilibrium MnO + MnCr2O4 + bcc from Ranganathan is plotted.2. single solid solution phase equilibria (heavy lines). Fig.2 cat. 4. p. two-phase fields and three-phase fields. For the invariant three phase equilibrium mgs + β-spl + bcc Ranganathan and Hajra measured the Mn content in bcc to be 25. There are no data on oxygen nonstoichiometry of MnyCr3-yO4. Three-phase field boundaries are denoted with thin solid lines.2. 1173 K. 4.5. Dotted lines are tie lines.2.Thermodynamic assessments diagram.6 Ternary phase diagram of the system Cr-Mn-O with stoichiometric single phase equilibria (points). 83 . 4. investigated the composition changes of the two phase equilibrium β-spl + mgs at T = 1073 K. Bobov et al.1 to 10-13 Pa (Fig. these authors conclude that chromium oxide dissolves in (Mn1-yCry)1-xO in the form of CrO.% at T = 1323 K performing an isopiestic experiment (Fig. 82).
p.2.3) β-spl to be –10 kJ mol-1 at T = 1873 K. solid Cr and oxygen at T = 1873 K in the pO range from 2×10-6 to 1. investigated the martensitic α-spl → β-spl transition temperatures. derive Δ f °GMnCr2O4 = –958 ± 8 kJ mol-1 from liquid Mn. 79).5 + Mn0. 4.5AlO2 and AlO1.MnyAl3-yO4 solid solutions formed from Cr2O3-Al2O3 mixtures at T = 1873 K. which is equivalent to Δf G of 1 2(Δ f GMnCr2O4 − Δ f GMnAl2O4 ) .5AlO2 = AlO1.2.4 for the formation of α-spl. and remain β-spl.8 do not show Jahn–Teller distortion at room temperatures. From these data and the activities of CrO1. Giving α-spl the formula [Mn2+](Mn3+.Thermodynamic assessments Holba et al.2) (4.5CrO2 (4.5 + Mn0.2. enthalpies and entropies of MnyCr3-yO4 samples annealed at T = 1723 K using X-ray analysis and DTA measurement. Tanahashi et al. Thermodynamic data: Cubic spinel (β-spl): Only values for the standard Gibbs energy of formation of β-spl of the composition MnCr2O4 β-spl are published.5×10-4 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. Tsai and Muan experimentally determined compositions of coexisting MnyCr3-yO4 . With decreasing Mn-content the temperature for the transition decreases (Fig.5CrO2 obtained from a previous study they derive ΔG of the reaction CrO1.1) β-spl Using compiled Δf °GMnO and Δf °GCr2O3  they calculate Δ f °GMnCr2O4 from its oxides to be –59 ± 8 kJ mol-1.Cr3+)2O4 this corresponds to a minimum concentration of [Mn3+] = 0. We recalculate this value using the most recently assessed Δf °GMnO  and Δ f °GCr2O3  β-spl values at T = 1873 K giving Δ f °GMnCr2O4 = –66 ± 8 kJ mol-1.2.5 in Mn0.2.5 in Mn0. This means that the Gibbs energy of formation of β-spl of the composition MnCr2O4 from its 84 . Samples with y < 1.
Thermodynamic assessments oxides using this calculation technique depends on the value of Δf °GMnAl2O4 . with experimental data and error bars.6 kJ mol-1 β-spl giving Δ f °GMnCr2O4 = –52. unfilled symbols correspond to recalculated values. According to these authors the transition of pure α-hsm to β-hsm takes place at T=1445 K.2.2. and –36.1 kJ mol-1.7 Calculated Gibbs energy of formation of β-spl of the composition MnCr2O4 as a function of temperature. 4.0 kJ mol-1 at T=1523 K. Δ f °GMnAl2O4 = –32.  in the CoO- β-spl The spread of Δ f °GMnCr2O4 values resulting from different studies and our recalculations is shown in Fig.4 ± 10 kJ mol-1.7.1 kJ mol-1. Tetragonally distorted spinel (α-spl): Pollert et al. Using other values for Δ f °GMnAl2O4 reported β-spl in the literature[25-27] leads to deviating Δ f °GMnCr2O4 of –34. Biggers by using the same technique as Tsai and Muan β-spl MnO-Cr2O3 system found Δ f °GMnCr2O4 = –59.6 kJ mol-1 at T = 1873 K. ΔΗ α β = 18810 J mol-1. Tsai and Muan chose the value determined by Lenev and Novokhatskiy. Filled symbols correspond to originally reported literature data. Fig. 85 . 4. present thermodynamic data on the transition of α-spl to β-spl. –46. and ΔS α β = 13 J K-1 mol-1.
2. This state is denoted SER (Stable Element Reference). Thus the endmember ° β-spl β-spl G[Cr 2+ ](Mn3+ ) O becomes less stable the more stable °G[Mn 2+ ](Cr3+ ) O becomes. β-spl can therefore be described by the simple formula [Mn2+.30]. However there is no experimental data quantifying the amount of Mn4+ in β-spl. 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.Cr2+](Cr3+. They propose small polaron hopping between Mn3+ and Mn4+ on the octahedral sites as mechanism for the electrical conductivity. The Gibbs energies of the endmembers [Mn2+](Mn3+)2O4 that corresponds to β-hsm.Mn4+)2O4. As the degree of inversity of β-spl is very low.15 K and p = 105 Pa.Mn3+.2. Considering these findings an alternative description of β-spl would read [Mn2+.4) This endmember is considerably more stable than the endmember of the formula [Cr2+](Mn3+)2O4.5) The Gibbs energy of the reciprocal reaction is taken to be zero. To maintain electroneutrality Mn2+ is formed on the octahedral sites resulting in a charge disproportionation reaction.Mn3+)2O4 using the compound energy model[31–33].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. measured the electrical conductivity of β-spl. 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. Lu et al. 2 4 2 4 86 .Thermodynamic assessments 4.8]. 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.Cr2+](Cr3+. All endmembers of our model β-spl are neutral.Mn2+.2. In our description we further go along with the presumption that the amount of oxygen vacancies may be neglected. 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.
The incorporation of chromium of valencies other than three is mentioned nowhere in literature. (Mn2+. whereas for ordering due to Jahn–Teller distortion the opposite holds. as the degree of inversity is increasing with higher temperature. Due to these considerations we may write [Mn2+](Cr3+.34] show that α-spl is stabilized at high Mn contents.Mn3+. Manganosite (mgs): Based on the proposed incorporation of Cr into (Mn1-yCry)1-xO in the form of CrO we tested a description of mgs given by (Mn2+.6) Bixbyite (bxb): Geller and Espinosa postulate the incorporation of Cr into Mn2-yCryO3 by a simple substitution mechanism between Cr3+ and Mn3+.15].Mn3+)2O4 to describe α-spl.Cr3+. This is a reasonable assumption as the radii of these ions are very similar. the two endmembers of α-spl read [Mn2+](Mn3+)2O4 and [Mn2+](Cr3+)2O4. 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.Va)(O2-) leads to far more satisfactory 87 . Thus we may describe bxb as (Mn3+.14. Experiments[11.Va)(O2-).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. The Gibbs energy of [Mn2+](Mn3+)2O4 is equal to α-hsm.7) The experimental data could be reproduced without the optimization of a temperature dependent parameter. 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 2.2.Cr2+.Cr3+)2(O2-)3.15.2. and the Cr solubility in tetragonally distorted MnyCr3-yO4 does not extend beyond MnCr2O4. The Gibbs energy of the endmember (Mn3+)2(O2-)3 is taken from Grundy et al.) 3 + Abxb (4. Hence.Mn3+. It is very unlikely that trivalent cations are incorporated into the tetrahedral sites of α-spl. Using this description the solubility of Cr in function of oxygen partial pressure experimentally determined by Tanahashi could not be reproduced correctly..
The Gibbs energy of (Mn3+)2(Cr3+)1(O2-)3 is given by 88 .2.8) The Gibbs energies of the three other endmembers are taken from Grundy et al. postulate the incorporation of trivalent Mn ions into (Cr1-yMny)2+xO3.2. Eskolaite (esk): Pollert et al. Agreeing with these authors we model the solubility of Mn by (Cr3+. Fig. The model description of mgs is shown in Fig. 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. 4. With this description we are in agreement with O’Keefe and Valigi who observe a decrease in the lattice parameter of mgs compared to undoped Mn1-xO providing strong support for the assumption that it is Cr3+ that is substituting the much larger Mn2+ ion and which is forcing the lattice to contract.Cr2+.Va)1(O2-)3.Mn3+)2(Cr3+.)3 Gas − 1 3 °GO − 3 2 RT (1 3ln1 3 + 2 3ln 2 3) + Amgs 2 (4.8. 4. These experiments also provide evidence against Cr being incorporated interstitially. 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.Thermodynamic assessments reproduction of these data..8 Geometrical representation of the mgs phase described using the compound energy model.2.
4 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Mn-Cr-O system is given in Table 4. 90-92). Mn3+.Mn2+)p(O2-.2.2.. Assuming low oxygen solubility in bcc bcc manganese metal we give a large value to the endmember °GMn:O .)3 + °GCr SER + Aesk (4. Liquid: We model the liquid phase as (Cr3+. No data are reported for the oxygen solubility in pure bcc A2 manganese metal.1 (pp.10) We take the Gibbs energies of the other endmembers from Povoden et al.The binary interaction parameters are taken from Grundy et al.Va)3.9) and the Gibbs energy of (Mn3+)2(Va)1(O2-)3 by ° G esk3+ (Mn )2 (Va)1O3 = °G bxb3+ (Mn )2 (O2.Mn)1(O..2.Thermodynamic assessments ° G esk3+ (Mn )2 (Cr3+ )1O3 = °G bxb3+ (Mn )2 (O2.)3 + Aesk (4. 4. 89 . and Lee.2.39] . The descriptions of further alloy phases are taken from. The liquidus temperature is optimized using the interaction . Cr-Mn alloys: We describe the oxygen solubility in bcc by an interstitial solution model of the form (Cr.Cr2+.. Experimental data on the oxygen solubility in pure bcc A2 chromium metal were used for the description of (Cr)1(O.Vaq-)q using the two-sublattice model for ionic liquids parameter 0 Lliq3+ Cr .Va)3. Povoden et al.Mn3+ :O2- [38.
Mn 3+ :O 2.− H Mn = GMN_L liq SER GMn3+ :Va q..Mn 3+ :O 2- L Bcc A2 alloy (bcc) (Mn.0 23.2. q = 2 yCr 2+ + 2 yMn 2+ + 3 yCr3+ + 3 yMn3+ ° ° ° ° ° ° ° ° liq SER GCr 2+ :Va q.543 32..)q p = 2 yO2.Va q1 liq Mn 2+ :O 2.999 4050.− 2 H Mn − 2H O = 2GMN1O1_L 0 liq Cr 2+ :O2.Mn 3+ ) p (O 2.Mn 2+ :Va q1 liq Cr 2+ .938 15.1 Thermodynamic description of the Cr-Mn-O system a) Element Element Reference Mass H298 .Va q..− H Cr = GCR_L liq SER GCr3+ :Va q.Cr 3+ .996 54.6587T = 504 + 0.O)3 90 ..Va q- L 0 liq Mn 2+ .− 2 H Mn − 3H O = GMN2O3_L liq SER SER GMn 2+ :O2..008 102.− H Mn = 2GMN_L + GMN2O3_L − 3GMN1O1_L liq SER SER GMn3+ :O2.Cr)1 (Va.− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+ :O2.Va q- L L = 121000 = 129519 = −45459 = −33859  = −15009 + 13.− 2 H Cr − 3H O = GCR2O3_L liq SER SER GCr 2+ :O2.+ qyVa .0 4341.Thermodynamic assessments Table 4.Mn 2+ :Va q- L 0 liq Cr 3+ .6 0 liq Mn 2+ :O 2.0 4996.Va q- L L 0 liq Cr 2+ .52 (Cr 2+ .9479T = −188487.Mn 2+ .H0 S298 Cr Mn O Liquid (liq) BCC_A2 CBCC_A12 ½ mol O2 51.− 2 H Cr − 2H O = 2GCR1O1_L liq SER GMn 2+ :Va q.
2923T 3 esk SER SER GCr 2+ :Va:O 2.93845T mgs SER SER GMn 3+ :O2.− 2 H Mn − H Cr − 3H O = GMN2O3 + GHSERCR  + 39503 esk SER SER GMn 3+ :Va:O 2.)3 ° bxb SER SER GMn 3+ :O2.6 yCr 2+ :Cr3+ :O2esk Tcesk = 308.Mn:Va L 0 bcc Cr:O.− 2 H Mn − 3H O = GMN2O3 bxb SER SER GCr 3+ :O 2.− 2 H Mn − 3H O = GMN2O3 + 39503 ° ° ° Magnetic contribution p = 0.27 yMn + yCr yMn [0.− 2 H Cr − 3H O = GCR2O3 + 3459 ° Eskolaite (esk) (Cr 2+ .)1 ° ° ° mgs SER SER GMn 2+ :O 2.6 y esk Cr 3+ :Va:O 2- esk β esk = 3 yCr :Va:O esk β esk = 3 yCr :Cr 2+ 2+ 3+ esk Tcesk = 308.1533 1 mgs Mn 2+ .6 yCr3+ :Cr3+ :O2esk β esk = 3 yCr :Cr 3+ 3+ 3+ :O 22- T esk c = 308.5GCR2O3 + 71549.6 yCr 2+ :Va:O2- :O 22- esk β esk = 3 yCr :Va:O Cubic spinel (β-spl) 91 .− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.2923T 3 esk SER SER SER GMn 3+ :Cr3+ :O2.− 2 H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.4183T  1 bcc Cr.008 yCr − 0.8766 = 46513. Cr 3+ .117( yCr − yMn )8 ] β bcc = −0.93265( yCr − yMn ) 4 ] Manganosite (mgs) (Mn 2+ .− H Mn − H O = GMN1O1 mgs SER SER GCr 3+ :O 2.5 yCr − 580 yMn + yCr yMn [−1325 − 1133( yCr − yMn ) 2 − 10294( yCr − yMn ) 4 + 26706( yCr − yMn ) 6 − 28.Mn 3+ :O 2- L Bixbyite (bxb) (Mn 3+ .Thermodynamic assessments ° ° ° ° bcc SER GCr:Va − H Cr = GHSERCR  bcc SER GMn:Va − H Mn = GHSERMN bcc SER SER GCr:O − H Cr − 3H O = GHSERCR  + 3GHSEROO + 243T bcc SER SER GMn:O − H Mn − 3H O = GHSERMN + 3GHSEROO 0 bcc Cr.)3 ° ° ° esk SER SER GCr 3+ :Va:O 2.− H Mn − H O = GMN1O1 − 21883.Va L = −709542 p = 0.− 2 H Cr − 3H O = GCR2O3 esk SER SER GCr 3+ :Cr3+ :O 2.1853365T 0 mgs Mn 2+ .− H Cr − H O = 0.7339T  = −9162 + 4.Va)1 (O 2.Cr 3+ ) 2 (O 2.Mn 3+ :O 2- L = −42104.Mn 3+ .5213 − 22.Va)1 (O 2.28 esk Tcesk = 308. Cr 3+ .− 3H Cr − 3H O = GCR2O3 + GHSERCR  esk SER SER GCr 2+ :Cr3+ :O 2.3 − 7.Mn 3+ ) 2 (Cr 3+ .72035( yCr − yMn ) 2 − 1.Mn:Va L = −20328 + 18.4 Tcbcc = −311.48643 − 0.
As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.− H Cr − 2 H Mn − 4H O = GCR3O4+GMN3O4B -GSPINEL Tetragonally distorted spinel (α-spl) (Mn 2+ )1 (Cr 3+ . 4.7 cat. 4.69T GTSPINEL = 2 GCR3O4+ 1 GMN3O4 3 3 −200941. The temperature found from Speidel and Muan for Cr the two phase equilibrium of Mn rich β-spl (Mn = 94. PARROT takes into account all sorts of thermodynamic and phase diagram data simultaneously.− H Mn − 2 H Cr − 4H O = GSPINEL β-spl SER SER GCr 2+ :Cr 3+ :O 2.Mn3+ :O2.4 and 0 Lliq3+ .2.1T a) Note: All parameters are in SI units: J.4.9+75.) 4 ° α-spl SER SER SER GMn 2+ :Cr 3+ :O 2.− 3H Cr − 4H O = GCR3O4 β-spl SER SER GMn 2+ :Mn 3+ :O 2.2.2.Thermodynamic assessments (Mn 2+ . Further the melting temperature of β-spl in air found by Speidel and Muan is used to optimize Aβ-spl and Bβ-spl in Eq. All these data are given a high weight. The optimization of the thermodynamic parameters is performed using the PARROT module of the Thermo Calc database system. and we use data on the solubility of Cr in MnyCr3-yO4 at T=1873 K under varying 92 . Pa: R = 8.Mn 3+ ) 2 (O 2.2.Mn3+ :O2- .4 we use the Δ f °GMnCr2O4 value derived from Tsai and Muan using Δ f °GMnAl2O4 from Kim and McLean and the composition of bcc in equilibrium with β-spl and mgs reported by Ranganathan and Hajra.5+61.) 4 ° ° ° ° β-spl SER SER SER GMn 2+ :Cr 3+ :O2.4 and Aα-spl and Bα-spl in Eq.− H Mn − 2 H Cr − 4H O = GTSPINEL α-spl SER SER GMn 2+ :Mn 3+ :O 2. β-spl To optimize the parameters Aβ-spl and Bβ-spl in Eq. 4. 4. K.Cr 2+ )1 (Cr 3+ . 4. mol.. Further we use – with lower weights – the temperature of the two phase equilibrium β-spl + liq at X(Cr) = 0.31451 J mol-1 K-1. 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. The program minimizes the sum of squared errors between the experimentally determined phase diagram and thermodynamic data and the corresponding calculated data.Mn 3+ ) 2 (O 2.− 3H Mn − 4H O = GMN3O4 ° Functions GSPINEL = 2 GCR3O4+ 1 GMN3O4B 3 3 −210795.4 and 0 liq L Cr3+ .− 3H Mn − 4H O = GMN3O4B β-spl SER SER SER GCr 2+ :Mn 3+ :O 2.105 from Speidel and Muan to optimize Aβ-spl and Bβ-spl in Eq.2.%) and α-spl is used to optimize Aβ-spl and Bβ-spl in Eq.
2. and Aα-spl and Bα-spl in Eq.2.2. 4. prl coexists with esk at T < 513 K 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.% at T = 668 K in air. 79 and Fig. In Fig. p. Abxb in Eq. 79 shows the temperature dependence of the diffusionless transformation of α-spl to β-spl.4. 4.2.8 data on the solubility of Cr in (Mn1-yCry)1-xO from Tanahashi et al. 82 are used. Temperature data from Speidel and Muan and Pollert et al.4. bxb is stable from T = 694 K to 1154 K in air. 82. p.220.127.116.11. 4. 4. β-spl and esk coexist from X(Cr) = 0. p.2 cat. The maximum Mn solubility in (Cr1-yMny)2+xO3 is 0.2. and Aα-spl and Bα-spl in Eq.23 in air. mgs is not stable in air.5.2. 79. 4. 80) to optimize Aβ-spl and Bβ-spl in Eq. prl + bxb is stable in a small area from T = 668 K to 694 K and X(Cr) = 0 to 0. shown in Fig.2.2. 4. p. 4. αspl coexists with β-spl from X(Cr) = 0 at T = 1441 K to X(Cr) = 0. p.7 is optimized using data on the solubility of Cr in Mn2-yCryO3 from Pollert. We use data from Holba et al.2. This two-phase field expands under more reducing conditions which can be seen in the calculated phase diagram of 93 .2.175 at T = 1156 K.67 in air.5.2.2. 4. 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. 4.2.65 prl and β-spl coexist in air. 4. are used (Fig.4.% at 2243 K in air. The maximum Cr solubility in Mn2-yCryO3 is 23 cat.6. p.2. shown in Fig.2.66 to 0. 4.2. The dotted line in Fig. p. on the two phase equilibrium β-spl + bxb in air (Fig.2. 80 the Mn rich part of the diagram is shown in detail.5. 4.992 at 1203 K in air. From T = 513 K to 668 K and maximum X(Cr) = 0. The two-phase field bxb + α-spl is only found in a very small area at about 1150 K. 4.9 and 4. At pO2 = 400 Pa it starts to form in equilibrium with β-spl in a small area at the Mn-rich side of the MnOx-Cr2O3 system around T = 1840 K. on the phase equilibria α-spl + β-spl and α-spl + β-spl + bxb are used to optimize Aβ-spl and Bβ-spl in Eq.10 data on the solubility of Mn in (Cr1-yMny)2+xO3 from Pollert et al.2. and for Aesk in Eq.2.Thermodynamic assessments oxygen partial pressures from Tanahashi et al. p. p.2. 4. for Amgs in Eq. 82). on the temperature dependence of the diffusionless transformation of α-spl to β-spl shown in Fig. and data from Pollert et al.3. 4. 4. 4.1 and 4. 4.2. 79 to optimize Aβ-spl and Bβ-spl in Eq.054 in air.5 Results Phase diagram data: The calculated phase diagram of the pseudo-binary system MnOx-Cr2O3 in air is shown in Figs.
2.9 (next page). 4. 1173 K. and from Bobov et al. Experimental data from Tanahashi et al. 4.6. 4. and 1273 K in function of log(pO2 ) are compared to the calculated results from this work. 82 experimental and calculated solubility data of Cr in mgs + β-spl. and Mn in esk + β-spl are presented. 94 . In Fig.Thermodynamic assessments the pseudo-binary MnOx-Cr2O3 system at an oxygen partial pressure of 1×10-4 Pa in Fig.4. on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl and esk + β-spl at 1873 K. 80. 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.5. were not used for the optimization. The data from Bobov et al. p. on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl at T = 1073 K.2. p. Isothermal sections of the Cr2O3-MnO-MnO2 system at different temperatures are plotted in Fig.2. 4.2. In the isothermal phase diagram of the Mn-Cr-O system at T = 1323 K of Fig. p.
Thermodynamic assessments Fig. Three-phase field boundaries are denoted with thin lines. 4. 95 .9 Isothermal sections of the ternary system Cr2O3-MnO-MnO2 showing oxide and liquid evolution as a function of temperature and composition.2. Dotted lines are tielines. Stoichiometric single phase equilibria are points. and single solid solution phase equilibria are heavy lines.
15] and Ranganathan et al.9 a) disappear. The calculated dependence of β-spl solid solubility on oxygen partial pressures shown in Fig.2.2.2 (p.6 Discussion Phase diagram data: Our assessed phase diagram is in rough agreement with the findings from Speidel and Muan. 82 agrees well with the results from Tanahashi et al. 4. and Δf °G α-spl = –1625681 J mol-1 at T = 298.9 a to c). ° α-spl S = 98 J mol-1K-1.3 (p. 4.2. 4.2.2.[14. At this temperature small oxygen nonstoichiometry of esk is apparent.9 (p. 4.2. 4. 4.2. and Fig. and the two-phase fields prl + bxb.2. At T = 1873 K we get Δ f °GMnCr2O4 = –34388 J mol-1. For both cases Speidel and Muan mention the speculative character of their phase diagram due to the lack of experimental data.2.5. 4.15 K.Thermodynamic assessments Thermodynamic data: The calculated enthalpy. 79). 79). °SMnCr2O4 = 116 J mol-1 K-1. At T=1700 K α-spl is no longer stable and the three-phase regions mgs + α-spl + β-spl and bxb + α-spl + β-spl (Fig. p. 4. 4. 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. The three-phase regions prl + esk + bxb and bxb + esk + β-spl. 83). β-spl + bxb.9 b). on the other hand cannot be reproduced. The results from Bobov et al. Our assessed phase diagram is in excellent agreement with the findings of Pollert et al. For α-spl of the composition MnCr2O4 we calculate Δ f °H α-spl = –1596517 J mol-1. 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-1.2. (Fig. Our calculated T0 line for the diffusionless transformation of α-spl → β-spl is in perfect agreement with experiments by Holba et al.. 85. In the β-spl temperature range from 1050 to 1800 K Δ f °GMnCr2O4 from the oxides is given by the term –89167 + 29. and β-spl Δ f °GMnCr2O4 = –1634017 J mol at T = 298.15 K. p. Fig. 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. but it increases at elevated 96 . p. and mgs + β-spl dominate the system in a wide temperature range from T=1200 K to 1900 K (Figs.6 (p.2.338 T with an error of ± 0. as shown in Figs. 4. 95) represents the phase relations of the oxides and the evolution of liquid formation. 4.21 %. The oxygen nonstoichiometry of mgs is yet insignificant (Fig.2.7. 80).
9 d).2.9 c).2.2. 83. and ΔSα β values for the transformation of α-spl to β-spl are very small. Hence.2. This is obvious from Fig. At T = 1900 K phase relations become more complex due to incipient melting (Fig. 4.2. At T = 2400 K the only remaining stable solid phases are esk and prl (Fig. found that the electrical conductivity of chromium manganese spinel increases with increasing Mn-content. 4.2. 4. The calculated ΔHα needed for the transformation to take place. 83 associated with decreasing 97 .2. 4. and the-three phase fields bxb + β-spl + liq and mgs + β-spl + liq emerge (Fig.2.9 f). The composition of Crofer22 APU alloy is close to the Cr-corner of the Mn-Cr-O phase diagram. p. indicating that only very little energy is 4.6. 4. The occurrence of other Cr-Mn phases in the protective scales formed during thermal exposure of Crofer 22 APU interconnects is not expected thermodynamically. 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..2.9 c). 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.Thermodynamic assessments temperatures becoming apparent at T = 2000 K (Fig. 4. 4.9 d).6.6. 4. 84) on Crofer22 APU alloy is expected under SOFC operating conditions. p. Thermodynamic data: β-spl β-spl Our calculated Δ f °GMnCr2O4 value at T = 1873 K is in agreement with the Δ f °GMnCr2O4 value spl derived from Tsai and Muan using Δ f °GMnAl2O4 from Kim and McLean. must be kinetically controlled. which is at point A in Fig. At T = 1900 K liquid is formed at the Mn-rich side of the system.7 Applications on SOFC Due to the large stability range of β-spl and esk in air it is not realistic to prevent the formation of these unwanted phases under oxidizing conditions at the cathode side of SOFC operated with high Cr alloy interconnects and LSM cathode. p. In a thermodynamic view the formation of β-sp with the composition MnCr2O4 (Point A in Fig. Recently Qu et al. 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. Even more three phase regions due to increasing liquid formation start to exist at T = 2000 K (Fig.
Bossel (Ed. °S. H. Nickel.Thermodynamic assessments electrical conductivity.). Kinzel.). K. Fergus. W. 2003. Singheiser. Druckerei J. pp. S. Badwal. Ramprakash. 2004. D. 1997. Zhang. pp. and we present well-founded Δf°H. Hilpert. R. p. which is very close to the experimental findings of several authors. 99.P. 4. M. Hilpert. 1037.A. Deller. 1-15. 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. in: U. Göttingen. 2. Chichester. References 1.P. J. Technology and Applications.2. and Δf°G data for β-spl and α-spl. There is a surprising lack of thermodynamic data on β-spl. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. in: W. 3. John Wiley & Sons. Das. Handbook of Fuel Cells – Fundamentals. compositions and transformations of unwanted MnxCr3-xO4 spinel solid solution and eskolaite phases in solid oxide fuel cells under any desired temperature and oxygen partial pressure conditions.S. Y. 2. J. A.W. 171. K. 98 . L. Miller. 4.J. Gasteiger (Eds. and the only available -1 β-spl Δ f °GMnCr2O4 values are spread over a range of 31 kJ mol . Foger. Lamm. First European Solid Oxide Fuel Cell Forum Proceedings. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Vielstich. Recalculating old experiments using new thermodynamic data together with phase diagram data we achieved a description. 297-310. Vol.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. H. Quadakkers. K. p. Solid State Ionics. 703. Our Thermo Calc dataset resulting from the presented CALPHAD modeling of the Mn-CrO system allows the calculation of phase stabilities. Solid State Ionics. All features of the system are well described with the optimization of only 8 additional optimization parameters. 1994.
Corliss.H. 10. 71.. SGTE Data for Pure Elements. S. 750-751 (in Russian). 562-65.D. 1987.J. 1963.P. Chem. P. Sci. Phys. Geller. Fujisawa. Zh. Alloy oxide equilibria in the Cr-Mn-O system.J.V. Simner.M. Ceram. Res. 1919-1933. 353-62.. 1975. ISIJ Int. B-J. Magnetic structure of manganese chromite. V. Soc. M. 149-58. J. Muan. pp. Peculiarities of phase-diagram in the reduction of Me0. 24. pp. Y. 15(4). Res. 15. pp. 1970. pp. L. Nevriva. 19. 853-60.. Lee. Khim. pp. 15. 16. Golikov. 1145-47. 1987. 9. 1309-1315. Holba. J. 317-425. 7. Tetragonal distortion of spinel solid-solutions MnCr2O4Mn3O4. 1977. C. J. Calphad. 126. Metall.P.. pp. Phase Equilib. G.Thermodynamic assessments 5. Trans. D. L. J. Rev. Nevriva. Solids.25Mn2.V. 3763-69. Electrochem.. Nevřiva. pp. J. Chufarov.. E. L.. S. Grundy. 1962. Anderson. 38.F. A. Soc. pp.N. Pollert. 41. Diff. Miscibility gap of MnxCr3-xO4 spinels. Phase Equilib. Stevenson. 1980. 2005. pp. Ranganathan. Rev.N. 58. 17. Assessment of the Mn-O system.P. 556-65. Novak. Magnetic and crystallographic transitions in Sc3+. 2003. N. A. J. Phys. Balakirev. Mater. Phase equilibria of the MnO-SiO2CrOx system at 1873 K under controlled oxygen partial pressure. Golikov. B. 1991. J. M. Hajra. Furuta. Balakirev. Novak.-G. 1984. Mater. Bobov. Hallstedt. Xia. V. The system manganese oxide-Cr2O3 in air.. Solid State Chem.P. 9. M. Gauckler. Yang.. Phase equilibrium diagram of the system Mn-Cr-O. 27.. 2006. 8. Gauckler.M. Pollert. 1993.R. Grundy. Bull. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. G. Tanahashi. A 24. pp. J.. E. Mater. 10. and Ga3+ substituted Mn2O3. M. 2001. M. A740-45. Am. pp. 12. J. L.W. Pederson. Povoden. Phys. 577-78. 99 . S. Zalazinsky. Bull. Fiz.F. T.I. pp. Yamauchi. 6. A. 46. 21-39. A thermodynamic evaluation of the Cr-Mn and Fe-Cr-Mn systems. SOFC performance with Fe-Cr-Mn alloy interconnect. pp. J. 14. E. E. A.75O4 solid-solutions. J.G.. 1453-56. pp. A. 152. Y. 13. Espinosa. A. G. 18. 11. Cr3+. Phase diagram of the Mn2O3-Cr2O3 system in air.. pp. Dinsdale. Z. Pollert. Bull. T. B 1. Speidel. Hastings.
Lenev.P. L. Weyl. S. N.A. 10B. Trans. Taniguchi. 1988.D. 1981. ISIJ Int. 87-92. Soc. A. 20.T. 225-232.S.A. 437-445. Q. pp. A. Izv. E. Jansson. Pennsylvania State University. Muan. 81-87. Alloy. 25. Phase diagram of system MnO-Al2O3 and thermodynamic properties of MnAl2O4. J. Trans. Z. 2000. J. pp. Ceram. pp. Thermodynamics of iron-manganese aluminate spinel inclusions in steel. Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides.F. Shannon. Activity composition relations in refractory oxide solid-solutions at high-temperatures – the system Cr2O3-Al2O3. 100 . Sundman. Payzant. Guillermet. Jansson. J. Equilibrium phase-relations and thermodynamics of the Cr-O system in the temperature-range of 1500°C to 1825°C. Z. Parts I and II. B. B.. 1412-15. Metall.. pp. Am.. 3. Electrical conductivity of the manganese chromite spinel solid solution. Novokhatskiy... Thesis. Standard Gibbs free energy of formation of MnO-saturated MnO. Janke. Acta Crystallogr. Zhu. 31. Hillert. 30. pp. Lu. pp. A. A. 1966. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. J. 1995. 1407-11. T. Application of the Compound-Energy Model to Oxide Systems. I. 27. 1966. Revision of thermodynamic data on MnO-Al2O3 melts. Barin: Thermochemical Data of Pure Substances. T. Sundman. 2001. 1993. The Compound Energy Formalism.T. 23. Control of the manganese-oxygen reaction in pure iron melts. 1986. Weinheim. M. 26. C. M. Activity composition relations in FeCr2O4-FeAl2O4 and MnCr2O4MnAl2O4 solid-solutions at 1500°C and 1600 °C. 1050-53. pp. 88. Tsai. 1979.V.K. Tanahashi.Y. Am.. Nauk SSSR.(in Russian). Cmpd. 1992. Hillert. Metall. H. 1991. M. C. A. Soc.. University Park. 79(2). L. 320..K. 161-76.T. J. 2nd Ed. Acta Metall.-O. N. Ceram. Can. Muan. Metall. 22. B. PA. VCH Verlagsgesellschaft mbH.Thermodynamic assessments 20. 66. J. 22. Darken. pp. D. Met. McLean.Cr2O3 solid solution at 1873 K. Furuta. I. B. pp. Steel Res. 89-92. Yamauchi. Jacob. 32. 33. A 32. pp. K. Lam: United States Patent 6039788. R. Akad. Paranthaman. Ceram.D. 75. pp.. Soc. pp. A. 73.. Tsai. Fujisawa. J. Metallkd.. Muan. 43. 1992. 2003. B. 575-84. 2005. Dimitrov. 29. Toker. 28. 21. Am. M. Hillert. Kim. 1976. 34. 75.. 35. 34. R. M. Andersson. 751-67. Biggers: Ph. H. 7-13. pp.F. B.M. 24.
Sundman. Eremenko. L.M. Grundy. Modification of the Two-sublattice Model for Liquids. Diff. Chem. G. M.3 Thermodynamic assessment of the La-Cr-O system E. D. Ivas. O’Keefe. pp. M. Trans. J.. 153.-O.Thermodynamic assessments 36. 1970. Andersson. 2006. T. Lukashenko. and L. Ohio. Calphad. ASM. Qu. Phys. Sundman. Fraser. The electrical properties and defect structure of pure and chromium-doped MnO. V. pp. M. 1985. Gauckler J. Jansson. 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. M. B. Solids. Phase equilibria of the La-Cr-O system are calculated at T = 1273 K as a function of oxygen partial pressure. A. A. 37. 31. 38. Burr. Sidorko. B. 9(2).N. M. Jian. B. In the La-Cr system reported solubility of lanthanum in bcc chromium is considered in the modeling. D. Valigi. p. 261-66. 1991.J. The Thermo-Calc Databank System. V. 4. 947-962. J. Caplan. 1957. 39. Ivey. Povoden. (accepted) The La-Cr and the La-Cr-O systems are assessed using the Calphad approach.M. 42. Chen . Hill. J. B. 16A.5-CrO1.J. and oxygen solubilities in bcc and fcc metals are modeled. The calculated La-Cr phase diagram as well as LaO1. 153-90. air. J. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. 109-19.A. pp. Thermodynamic properties of alloys of manganese with transition elements of fourth period (Cr Fe Co Ni) and with copper. Hillert. Power sources. Chem. In the La-Cr-O system the Gibbs energy functions of La2CrO6. Calphad. pp. W. Cleveland. Jansson. 343-. and under reducing conditions are presented. J. pp. The following standard data of 101 . 1985. La2(CrO4)3. 196. 41.M. Phys. Ågren. Metall. Sundman. pp. B. 114-24. Russ.G. 15. and perovskitestructured LaCrO3 are presented.R. 42. J.5 phase diagrams in pure oxygen. A. 40. Phase Equilib. in: Ductile Chromium. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. 1968.
The assessment of the La-Cr-O system using the Calphad approach is based on the recently reassessed La-O and Cr-O subsystems. thermodynamic. Cation nonstoichiometry of La1-xCrO3 perovskite is described using the compound energy formalism (CEF). pO2 (decomp) = 10-20. 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. All available experimental phase diagram. 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.oxides° H 298 K (LaCrO3 ) = −73. the thermodynamic stability of the cathode is particularly important for efficient long-term operation. Furthermore earth alkaline-containing LaCrO3 has been proposed as a cathode material in a recent study by Jiang et al.1 Introduction In SOFC.Thermodynamic assessments stoichiometric perovskite are The calculated: Δf. As the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. Sr-doped lanthanum manganites (LSM) with the perovskite structure are used as cathode materials in SOFC. The liquid phase is modeled using the two-sublattice model for ionic liquids. The lattice stabilities of elements are adopted from Dinsdale. and Crdiffusion into the cathode from LaCrO3-based interconnects is significantly lower than from Cr-containing metallic interconnects.oxides G(LaCrO3 ) = –72. oxides.3. V-doped and Zn-doped La1-xCaxCrO3-δ have been considered as promising alternative interconnect materials for SOFC. aiming on minimizing the squared errors between 102 . Δf. Diffusion of chromium from the metallic interconnect with high chromium content into the cathode leads to the formation of Mn(Cr. Gibbs energy of formation from the and ° S 298 K (LaCrO3 ) = 109.7 kJ mol-1 . 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.2 J mol-1 K -1 . 4.Mn)2O4 spinel and Cr2O3 along with a severe cell voltage decrease[1-4].97 Pa.0034 T (kJ mol-1) (T = 1273 K to 2673 K) is calculated.403–0. and the model is submitted to a defect chemistry analysis. and structurechemical data are critically assessed. recently Sr-.
26]. from T = 1073 K up to the melting of Cr using metallographic and microhardness techniques to be 2. denoted as αCrss . No intermetallic phases were found in the La-Cr system[12.% Cr2O3 (T = 2473±20 K) in argon atmosphere on either side of the congruently melting perovskitestructured lanthanum chromite[18-20] (in this study oxides containing Cr(III) and Cr with higher valencies than three are denoted as chromite and chromate respectively).4 at. The solubility of La in αCrss decreases towards lower temperatures.% or 99.% Cr2O3 (T = 2323±20 K).% at 1983 K. Tm(air) = 2773 K was determined by Foëx and by Coutures using a thermal analysis technique described in more detail in earlier publications.[22-24] The melting temperature was measured with optical pyrometers.3 Literature review of the La-Cr-O system In the LaO1. 4.2 Literature review of the La-Cr system The La-Cr system has a eutectic at T = 1138 K[12.04 at.% Cr and a monotectic at T = 1983 K or T = 2103 K and 96 at. Experimentally determined special points in the LaO1. and the exact value of the oxygen partial pressure was not specified.1 at.. determined the partial enthalpy of mixing in La-Cr liquid with infinite dilution of Cr. Berezutskii et al.% Cr2O3 (T = 2248 K) or 80 at. Small solubility of La in αCrss was reported [12. and Berjoan 103 .5. but in the graphic presentation of the phase diagram in the same paper Tm(argon) ≈ 2600 K. whereas Cr is almost insoluble in La. found La < 0.68 at. As small additions of rare-earth metals essentially increase the high-temperature corrosion resistance of chromium.Thermodynamic assessments experiments and calculation during the optimization of model parameters using the PARROT module of the Thermocalc software. modeling of the La-solubility in bcc-structured Cr.14. reported a La solubility of 0.13] and 3. Tm(argon) = 2703 K was reported by Tresvjatskiy et al. Furthermore deviations between the data from Tresvjatskiy et al.CrO1.% in αCrss at T = 1533 K.5-CrO1. as well as a large liquidliquid miscibility gap[12. Svechnikov et al. ΔH Cr at T = 1700 K using high-temperature calorimetry.3. and at 84 at.5 quasibinary system reveal a considerable spread.17] . This is not surprising as experiments are complicated due to the high investigation temperatures and evaporation of predominantly Cr[25.% Cr.% Cr2O3 (T = 2243 K) or 12 at.3.% at T = 2103 K. The melting temperature of lanthanum chromite in air. is of technological interest. 4.13]. The solubility of La in αCrss was determined in investigations by Savitskii et al. and Epstein et al.5 at.13].5 system two eutectics were found at 19 at.
46-53]. Experimental oxygen solubilities in pure Cr and La were considered in thermodynamic assessments by Povoden et al. thermodynamics[30. The peritectic phase diagram proposed by Cassedanne is in gross conflict with the phase diagram data from the other groups. solubilities in αCrss are missing. and nonstoichiometry[55-56] along with the investigation techniques used are listed in Table 4.25O2(g) ↑ → (4.Thermodynamic assessments may partly originate from differences of the oxygen partial pressure. However these were in significant disagreement with later results obtained by the same author.7 kJ mol-1.31].33-35. The perovskite phase: Existing experimental data of lanthanum chromite perovskite structure[33-45]. Stoichiometries and thermal stability ranges of lanthanum chromates with complex formulae were reported by Berjoan et al. to be −3961±11. 104 . The enthalpy of formation of La2(CrO4)3 from the elements at T = 298 K was proposed by Tsyrenova et al.43. whereas experiments on oxygen Lanthanum chromates: The following lanthanum chromates were documented: Berjoan reported that orthorhombic La2CrO6 forms at T > 923 K.. and Grundy et al.3. 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 (4.3. 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. LaCrO4 has been interpreted as a mixed-valent intermediate decomposition product of La2(CrO4)3[30. which in both studies was not exactly specified. phase stability.1 (next page).5Cr2 O3 + 2.2) An enthalpy change of 231 kJ mol-1 was determined for this reaction at the average temperature of T = 960 K.  .
this work. calculated = −73.1× 10−5 Knudsen mass spectrometry La CrO6 = −73. calculated ° 2 S 298K La CrO6 = 330 Jmol-1K -1 this work.calorimetry Activity of Cr2 O3 in LaCrO3 T = 2100 K T = 2100 K La 2 CrO6 Enthalpy of the formation reaction La 2 O3 + 0.2 HT .758 + 0.elements ° H 298K = −3845 kJmol−1 this work. calculated 2 Δ f.06 ± 2. calculated La (CrO4 )3 La (CrO4 )3 La 2 (CrO 4 )3 2 Δ f.2 Jmol-1K -1 this work. calculated Enthalpy of the dissociation reaction La 2 (CrO 4 )3 → 2LaCrO3 + 0.52 kJmol −1 this work.9 ± 1. calculated T = 1273 K T = 1273 K T = 2100 K T = 2100 K ° Δ °G = −30.38 kJmol −1 CaF2 . 700 . calculated 94.11 × 10−4 this work.1 ± 1.emf Δ °G = −42.oxides ° H 975K LaCrO3 = −1368.5Cr2 O3 + 2. calculated 139.29 ± 0.0034T (kJmol−1 ).based emf Δ °G = −79. calculated = −73.1 Calculated and experimental thermodynamic data of La-Cr oxides Rhombohedral LaCrO3 Standard enthalpy Δ f.5 kJmol −1 solid oxide electrolyte .08530T (kJmol−1 ).35 kJmol-1 this work. 1273 . calculated Enthalpy of the formation reaction La 2 O3 +1.0 kJmol−1 this work. fitted 105 . calculated = −3961 ± 11.7 kJmol−1 .5Cr2 O3 +1. calculated aCr2O3 = 1.oxides ° H 298K aCr2O3 = 1.based emf Enthalpy increments H − H 298 K .5O 2(g) → La 2 CrO6 2 Δ f.elements ° H 298K Δ f.based emf Δ °G = −94.4(kJmol −1 ).25O 2(g) → La 2 (CrO 4 )3 2 Δ f.oxides ° H 298K Δ f.oxides ° H 1078K ° LaCrO3 Standard entropy S 298K LaCrO3 = 109. calculated Δ °G = −78.79 kJmol-1 Drop solution calorimetry in 2PbO × B2 O3 LaCrO3 LaCrO3 Δ f. calculated Gibbs energy of formation by 1 3 La 2 O3 + Cr2 O3 → LaCrO3 2 4 T = 1273 K Δ °G = −76.19.7 kJmol-1 this work.002115T ± 0.calorimetry T = 1350 K 133.25O 2(g) 2 ΔH 298K La (CrO4 )3 = 231 kJmol−1 and this work. calculated = −62.1 kJmol −1 Knudsen mass spectrometry Δ G = −72.5Cr2 O3 + 2. (kJmol−1 ) T = 1090 K 98.885 K CaF2 .75 kJmol−1 this work. calculated Δ °G = −44.2 kJmol-1 this work. 855 -1073 K CaF2 .2673 K this work.403 − 0.3.1 × 10−4 ± 1.oxides ° H 298K La (CrO4 )3 = −372 kJmol−1 this work.elements ° H 298K ° 2 S 298K La (CrO4 )3 = 516 Jmol−1K −1 this work.Thermodynamic assessments Table 4.45 + 0.4 HT (high temperature) .05 this work.
3. calculated 0. thermogravimetry. dilatometry 545 heating.XRD.40) at 533 ± 5 a) DSC 380 at 550 K DSC 310 at 509 K DSC Entropy change of transition (Jmol-1K −1 ) 0. DSC 535 cooling. HT . dilatometry 536  a) adiabatic shield calorimetry.XRD 528 − 533 a) HT .08 J mol-1 and 0.microscopy.XRD 533 ± 3 a) DTA 543 XRD 533 HT . The temperatures.75 a) calculated from adiabatic shield calorimetry a) used for optimization The reported transformation temperatures lie between T = 503 K and 583 K. HT .XRD 540 ± 2 a) HT .ray photography 550 HT . DSC 550 HT .x .33-42].25 at 536 K a) calculated from adiabatic shield calorimetry 340 ± (10 .2 along with the investigation techniques used. calculated 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. Table 4. HT .3.96 at 503 − 583K calculated from adiabatic calorimetry 0. this work. DSC 533 ± 5 a) HT . XRD Enthalpy change of transition (Jmol−1 ) 340.5 J mol-1 to 106 . HT . simultaneous DSC . this work.XRD (air and vacuum) 563 ± 5 DTA.XRD. simultaneous DSC .84 at 503 − 583 K  calculated from adiabatic calorimetry 277 at 544 ± 1 K a) DSC 403.XRD 533 estimated from neutron powder diffraction 509 DSC. DSC.XRD.2 Calculated and experimental data of the orthorhombic to rhombohedral transition of LaCrO3 Transition temperature (K) 540. calculated 503 − 583 adiabatic calorimetry 544 ± 1 a) DTA.63.5 a) calculated from DSC 0.XRD 541 a) completed transition. The determined enthalpy and entropy changes vary from 277 J mol-1 to 502. enthalpy and entropy changes of this first-order transition taken from the literature are listed in Table 4. this work.XRD 523 a) starting transition. dilatometry.08 ± 41.
Heat capacity and enthalpy increment data: the heat capacities of LaCrO3 were measured by Korobeinikova and Reznitskii from T = 340 K to 900 K using adiabatic calorimetry. measured emf of Pt. Enthalpy of formation: Cheng and Navrotsky determined the enthalpy of formation of LaCrO3 by oxide melt solution calorimetry at T = 1078 K. Single phase lanthanum chromite with 0.28 cat. 289 K. and Momin et al. On the other hand Geller and Raccah as well as Höfer and Kock did not observe the rhombohedral to cubic transition up to T = 1873 K and T = 1823 K respectively using differential thermal analysis (DTA). T = 700 to 885 K. A transformation from rhombohedral to cubic structure at a temperature close to T = 1300 K was reported by Ruiz et al. or 295 K. LaF3/CaF2/LaF3. reported T = 1923 K using high-temperature x-ray diffraction (HT-XRD). (T = 77 K to 280 K) using alternating current calorimetry.% in furnace-cooled LaCrO3 annealed at T = 1773 K in air was reported from Khattak and Cox. Peck et al.% to 1.. A magnetic order-disorder transition was documented to occur at T ≈ 287 K.38 cat. Cation nonstoichiometry and defect chemistry: Maximum excess Cr in single-phase La1-xCrO3 of 0. Cr2O3/O2. This means that the perovskite phase does not decompose within this oxygen partial pressure range. reported no weight loss of lanthanum chromite at T=1273 K from pure oxygen to pO2 =10-16. and Sakai and Stølen (T = 272 K to 1000 K) using adiabatic shield calorimetry. Chen et al. whereas Coutures et al. Enthalpy increments of LaCrO3 at T = 1090 K and 1350 K were measured by Suponitskii using a high-temperature heat-conducting calorimeter. Satoh et al. Azad et al.% excess 107 . O2/La2O3.. Pt in pure oxygen from T = 855 K to 1073 K. Sakai et al. LaCrO3/MgO-stabilized ZrO2/Cr2O3. Chemical stability: Nakamura et al. and T = 1273 K respectively. LaCrO3. Chen et al. Gibbs energy of formation: in order to obtain the Gibbs energy of formation of LaCrO3. (T=100 K to 1000 K) using laser-flash calorimetry.76 cat. Cr/Pt at 1273 K.Thermodynamic assessments 0. and Dudek et al.1 Pa using thermogravimetry combined with X-ray diffraction (XRD). 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. Berjoan further reported prevailing of the cubic structure at T = 2173 K..96 J mol-1 K-1. (150 to 450 K) using DSC. measured electromotive force (emf) of the solid oxide galvanic cell Pt/Cr. La2O3. Höfer and Kock (480 to 610 K) and Satoh et al. and its oxgen nonstoichiometry is negligible. in agreement with Berjoan (T = 1923 ± 20 K) using dilatometry.
 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. 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. is inconsistent with the findings from Akashi et al. thus the presence of interstitial Cr in reduced chromite was proposed.59] agree that the electrical neutrality is maintained by holes and lanthanum vacancies. The transition from reduced to stoichiometric chromite was accompanied by a decrease of about 0. 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. Akashi et al. Ruiz et al. resistivity and thermo-emf at pO2 = 1Pa and pO = 102 Pa . deduced n-type conductivity from measurements of transport number. measured the isothermal electrical conductivity of an equilibrated La1-xCrO3-Cr2O3 mixture with 5 vol.0 ×104 Pa . reported that the ionic transport number in lanthanum chromite is less than 0. in line with the results from thermogravimetry. the electrical conductivity being 2 proportional to pO2 −3 8 . 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. the same as reported in an earlier study. In contrast to the other authors Shvaiko-Shvaikovskii et al. The conductivity was proportional to pO2 3 16 .58-60]. Iliev et al. and Meadowcroft proposed the occurrence of chromium vacancies instead of lanthanum vacancies. affirming the lack of oxygen vacancies in the structure.0 ×103 Pa to pO2 = 2. 108 . 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.57]. and that the carrier is the hole in lanthanum chromite[25.05 % up to T = 1250 K.1% in weight. Several groups[58. However n-type conductivity was not approved by any further study. ShvaikoShvaikovskii et al.Thermodynamic assessments Cr was prepared at T = 1773 K in a pure oxygen atmosphere. reported that concentrations of lanthanum vacancies and holes slightly increase from T = 1550 K to 1700 K.% excess Cr2O3 from T = 1573 K to 1673 K from pO2 = 1.
mixedvalent chromates mentioned above. we reassess the oxygen-solubility in Cr(bcc) using the model (Cr)(O. Eq.5 is defined as 3 2 3 ° gas G + A + BT 4 O2 ° SER SER G(Cr)(O)1.5 − H Cr − H O = °GCr(bcc) + (4. the zeroth-order. Solid oxides: Lanthanum chromates: The Gibbs energy function of La2CrO6 was based on the sum of the Gibbs energy functions of La2O3.3.Cr)(Va. 4. and O2 in proper stoichiometries and A + BT parameters that were fitted to the enthalpy of formation from the oxides.4 Thermodynamic modeling and optimization Metal phases: In order to account for the solubility of La in αCrss . Cr2O3. compositionindependent interaction parameter 0 Lbcc Cr.Va were optimized with the same experimental data. We chose the solubility values from Svechnikov et al. and αCrss is then given by the two-sublattice description (La.Va)1.15 K and 10 Pa. In order to refine the model parameters of La2CrO6.O)3. for its optimization.3.O)1. using the PARROT module of the Thermocalc software A was given the fix value 0 for the reasons discussed in an earlier paper. 5  A and B are adjustable parameters.1 as well as thermal stability data. For the reasons discussed recently. as these data are more comparable to solubilities in other rare earths-transition elements systems.5. The Gibbs energy of the end-member (Cr)(O)1. Povoden et al. 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.3. The formation of chromates that contain mixed Cr valences may be explained by gradual reduction of Cr6+ in La2CrO6 as the temperature increases.5. and to optimize their model parameters with phase diagram data[19. These chromates can be interpreted as intermediate products in the 109 .La:Va was given a positive value. 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. described the solubility of oxygen in Cr(bcc) using the model Cr(Va.3) SER H x is the standard enthalpy of the stable state of element x at 298. The thermal stability of La2CrO6 is slightly influenced by the thermodynamics of the intermediate.32]. and B and a regular interaction parameter 0 LCr:O.Thermodynamic assessments 4.
activity-data of Cr2O3 in LaCrO3 from Peck et al. The simplified decomposition reaction reads 1+ x 1.32] (4.32] and is completed at T = 1473 K or 1523 K.5) The parameters A. Stoichiometric perovskite: The Gibbs energy function of stoichiometric rhombohedral r-prv LaCrO3 with the sublattice formula (La3+)(Cr3+)(O2-). The enthalpy of formation from the elements was not used as it is a calculated value.(1. °GLaCrO3 is given by ° r-prv SER SER SER GLaCrO3 − HLa − H Cr − 3H O = °GLa3+ :Cr3+ :O2− = GRPRV = 1° 1 GCr2O3  + °GLa2O3  + Gmag + A + BT + CT ln T 2 2 (4.4) Slight differences of the oxygen partial pressure during experiments may be reflected by a variable extent of Cr-reduction.5 .3. We go along with the interpretation of LaCrO4 being an intermediate reaction product during the decomposition of La2(CrO4)3 by Eq. and C are optimized using the enthalpy of formation from Cheng and Navrotsky. 4.32] are not included in the presented thermodynamic database. The model parameters were fitted to the experimental enthalpy and temperature of decomposition. and enthalpy increment-data 110 . B. and consequently ambiguous stoichiometries of mixed-valent intermediate chromates. GRPRV denotes the Gibbs energy function for stoichiometric rhombohedral perovskite. The Gibbs energy function of La2(CrO4)3 was formulated using the same strategy as for La2CrO6. which starts at T = 1153 K[19. GVCR4O and GLCR4O are set equal for orthorhombic and rhombohedral perovskite. 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.3.3. heat capacity-data obtained by adiabatic calorimetry from Sakai and Stølen. These lanthanum chromates with conflicting stoichiometries[19..2 and do not include this phase in the modeling. GVCR4O and GLCR4O stand for the Gibbs energy functions of the completely oxidized neutral endmember.5 x) La 2 O3 + La1.Thermodynamic assessments scope of a sluggish decomposition of La2CrO6. The superscripts o-prv and r-prv stand for Gibbs energy expressions that have different values for orthorhombic and rhombohedral perovskite.x CrO3 + O2 (g) ↑ 2 2 mixed-valent chromates → La 2 CrO6 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ [19.
The rhombohedral to cubic transformation at high temperatures is not considered in the model.5-CrO1.42]. and oxygen nonstoichiometry can be excluded from thermogravimetry and electrical conductivity[37. A+BT parameters of the low-temperature orthorhombic perovskite phase were optimized with those temperatures[34.Va)(O2-. A phase diagram with congruent melting of lanthanum chromite and two eutectics[18. 112-114) resulted in negligible concentrations of Va on the B-site and the anion sublattice. The optimization of selective model parameters listed in Table 4.Va)(Cr3+.3. These are solved by allowing Va on the B-site and the anion sublattice of lanthanum chromite just like in lanthanum manganite leading to the appropriate sublattice formula (La3+. Thus these data were excluded from the optimization.Cr4+. enthalpies[34. and the perovskite formula essentially remains La1-xCrO3.40. 111 .64].40] and entropies[34. 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.38.5-MnO1.35.Va)3.35. This means that the simplest sublattice model to describe cation nonstoichiometric La1-xCrO3 reads (La3+.3 (pp.58] measurements. B-site vacancies are energetically less favored than A-site vacancies in the perovskite structure[63. as there is no existing thermodynamic data for this transition.Thermodynamic assessments measured at high temperatures.Va)(Cr3+.5 system required for SOFC applications due to diversities between the model descriptions of lanthanum chromite and lanthanum manganite. While this model results in a satisfying reproduction of experimental data. irreconcilable trouble is encountered at the extension to the LaO1. Thus the defects in n-type conducting lanthanum chromite are ambiguous and were not considered in the model.35] of transition having been obtained by combined investigation techniques and being internally most consistent.Cr4+)(O2-)3.19] cannot be reproduced by using the emf-experiments[49-52]. is unlikely due to the densely-packed perovskite structure.
O)1.923T  liq SER SER GCr 2+ :O2. q = 3 yLa3+ + 2 yCr 2+ + 3 yCr3+ ° ° ° ° ° ° liq SER GLa3+:Vaq.5 yCr  β bcc = −0.5T  2 4 Lbcc Cr:Va.23T + (65393 − 23T )( yCr 2+ − yLa3+ ) Cr Lliq 2+ .− H Cr = 2GCRLIQ − GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+:O2.Vaq..− 2 H Cr − 2H O = 2GCR1O1_L Interaction terms Lliq 2+ :O2.422 ° Lbcc Cr. Cr)(Va.− H Cr = GCRLIQ liq SER GCr3+:Vaq. Va q. Cr 2+ .− 2 HLa − 3H O = GLA2O3LIQ liq SER GCr 2+ :Vaq.− HLa = GLALIQ liq SER SER GLa3+:O2.008 yCr  112 .− 2 H Cr − 3H O = 5GCROLIQ − 179638 + 79.La3+ :Vaq.= Lliq 3+ :O2.La3+ :O2.5 ° ° bcc SER GCr:Va − HFe = GHSERCR  bcc SER GLa:Va − HLa = GLABCC 3 SER 3° bcc SER GCr:O − H Cr − H O = GHSERCR  + G (O 2(g) ) + 113.= −101850 − 39016( yCr 2+ − yLa3+ ) Cr Lliq 3+.)q p = 2 yO2.= 61397 − 5.La3+:O2.17755T 2 4 3 SER 3° SER ° bcc GLa:O − HLa − H O = GLABCC + G (O 2(g) ) − 855000 + 142.Vaq..= 121000 Cr Cr Lliq 2+ .3.= −101850 − 39016( yCr3+ − yLa3+ ) Cr Bcc A2 phase (La.La:Va = 83500 p = 0. Cr 3+ ) p (O 2.O = −355151.3 Model descriptions and Gibbs energy functionsa) Liquid (liq) (La 3+ .4 Tcbcc = −311..Thermodynamic assessments Table 4.+ qyVa .
75 °G(O2(g) ) − 1.41263T + Gmag ° r-prv SER SER GVa:Cr3+:O2. Va La .Va:O2.5 °G(O2(g) ) + 4. Va)(O2.Va)(Cr 4+ .− HLa − HCr − 3HO = 5 6 GS4O +GOPRV − GS3V + 1 6GS4V + Gmag ° r-prv SER SER SER GLa3+ :Cr4+:O2.− 2HLa − 3HCr − 12HO = GLA2CR3O12 La (CrO ) 113 .35056T + Gmag ° o-prv SER r-prv SER GVa:Cr4+:Va − HCr = °GVa:Cr4+:Va − HCr = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O − °G(O2(g) ) + 4.75 °G(O2(g) ) − 1.= Lprv3+:Cr4+.894 yi:j:k SER SER SER 2 GLa3+ :Cr6 :O2.41263T + Gmag ° o-prv SER SER r-prv SER SER GVa:Cr4+:O2.5GVCR4O +0.5GVCR4O +0.− HLa − HCr − 3HO = GOPRV + Gmag r-prv SER SER SER GLa3+ :Cr3+:O2.= 250000 La La Magnetic contribution Tco-prv = Tcr-prv = 291.)12 ° SER SER SER 4 3 2 GLa3+ :Cr6+:O2.41263T + Gmag ° r-prv SER GVa:Cr3+:Va − HCr = GRPRV + 1.41263T + Gmag ° o-prv SER GVa:Cr3+:Va − HCr = GOPRV + 1.Va:O2.− HCr − 3HO = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O + 0.Va j = Cr 4+ .Chromates La 2CrO6 (La 3+ )2 (Cr 6+ )(O2.5 °G(O2(g) ) + Gmag o-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GOPRV − 1.− HLa − HCr − 3HO = 5 6GS4O +GRPRV − GS3V + 1 6GS4V + Gmag ° ° ° o-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GOPRV − 1.5GVVV − 2GLCR4O + 0.− HLa − HCr − 3HO = GRPRV + Gmag o-prv SER SER SER GLa3+ :Cr4+:O2.5GVCR4O +0.)6 ° prv β o-prv = β r-prv = 0.− 2HLa − HCr − 6HO = GLA2CRO6 6+ La CrO La 2 (CrO4 )3 (La 3+ )2 (Cr 6+ )3 (O2.35 yi:j:k i = La 3+ .5GVVV − 2GLCR4O − 0.Thermodynamic assessments La1-xCrO3 perovskite (La 3+ .5GVVV − 2GLCR4O + 0.75 °G(O2(g) ) − 1.35056T + Gmag Interaction term Lprv3+:Cr3+.Cr3+ k = O-2..5 °G(O2(g) ) + Gmag r-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GRPRV − 1.− HCr − 3HO = GRPRV + 1.− HCr − 3HO = GOPRV + 1.− HCr − 3HO = °GVa:Cr4+:O2.5 °G(O2(g) ) + Gmag ° r-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GRPRV − 1.Cr3+ .5 °G(O2(g) ) + Gmag ° o-prv SER SER GVa:Cr3+:O2.5GVCR4O +0. Va)3 ° ° ° o-prv SER SER SER GLa3+ :Cr3+:O2.5GVVV − 2GLCR4O − 0.75 °G(O2(g) ) − 1.
5GCR2O3 − 1.38T − 0.01T − 0.68T ln T Neutral nonstoichiometric perovskite endmembers GS4O = −597648 + 213.56T ln(T ) − 0.00307T 2 + 190000T −1 +0.5GLA2O3A + 0.75 °G(O2(g) ) − 72615 − 4.25 °G(O2(g) ) − 371557 + 205T a) All parameters are in SI units : J.68T ln T Stoichiometric rhombohedral perovskite GRPRV = 0.00307T 2 + 190000T −1 +0. K.5GCR2O3 − 73591 + 2.38T − 47.5GCR2O3 GVCR4O = 0.6) i j k i j k where yi is the site fraction of Va and La3+ on the A-sublattice. Cr4+ and Va on the B-sublattice.25 °G(O2(g) ) GS3O = −472704 + 191. R = 8. mol.25 °G(O2(g) ) La 2CrO6 GLA2CRO6 = GLA2O3A + 0.31451 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 (4.5T La 2 (CrO4 )3 GLA2CR3O12 = GLA2O3A + 1. and yk is the site fraction of O2. The second-last term describes the excess Gibbs energy of mixing due to interactions of ions in the mixture.56T ln(T ) − 0.5GCR2O3 + 0.5GCR2O3 + 2.5GCR2O3 + 0.7186T − 47.25 °G(O2(g) ) − 291802 − 250T GLCR4O =1 3GLA2O3A + 0.and Va on the anion sublattice of the perovskite A1-xBO3. yj is the site fraction of Cr3+.5GLA2O3A + 0.5GCR2O3 − 73931 + 3.56T ln(T ) − 0. R = 8. The third-last term accounts for the configurational entropy of mixing.3.31451 J mol-1 K-1.9T − 47.00307T 2 + 190000T −1 +0. These are accounted for by the 114 .Thermodynamic assessments Functions Perovskite Stoichiometric orthorhombic perovskite GOPRV = 0.25 °G(O2(g) ) − 200000 Perovskite reference GS4V = −607870 + 268.5GCR2O3 + 0.5GCR2O3 + 0.
The neutral compounds used for the optimization are marked by the black spots. 4.1 is a visualization of the Cr-containing part of the model the authors use to describe the cation nonstoichiometry of lanthanum chromite.3.1 Representation of the Cr-containing part of the model for nonstoichiometric lanthanum chromite.) and °G(La3+ )(Cr 4+ )(Va) are given in Table 4.3 (pp. The thin lines margin the neutral plane. 115 . 4. Fig.5-SrO-CrO1. with the 8 Cr-containing compounds being the corners of the cube. 112-114).) and °G(La3+ )(Cr 4+ )(Va) from Povoden et al.3. The last term designates the magnetic contribution to the Gibbs energy. Only compounds inside the neutral plane can exist on their own. 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 LaO1.3. ° prv prv G(La3+ )(Cr 4+ )(O2. The magnetic parameters Tc and β were fitted to the C p data around the magnetic transition temperature from Sakai and Stølen. For the magnetic part of the Gibbs energy a magnetic ordering-model proposed by Inden and simplified by Hillert and Jarl was used..5 3 system  .Thermodynamic assessments optimization of interaction parameters. A short summary of this model can be found in Chen et al. Thus the authors prv prv adopted °G(La3+ )(Cr 4+ )(O2.
The parameters A and B of Eq. and °G(Va)(Va)(Va)3 from Grundy et al. The configurational entropy3 3 3 3 term in Eq.3.) .3. In Eq.) .Thermodynamic assessments The neutral Cr4+ -containing endmembers 2° 1 ⎛ 2 2 1 1⎞ GVa:Cr 4+ :O2− + °GVa:Cr 4+ :Va + 3RT ⎜ ln + ln ⎟ 3 3 ⎝ 3 3 3 3⎠ 1 1 gas = GVCR4O = °GCr2O3  + °GO2  + Gmag + A + BT 2 4 prv SER SER GVaCrO2 − H Cr − 2 H O = ° (4.8 and adopting the Gibbs energies of the remaining endmembers ° prv prv prv prv G(La3+ )(Va)(O2.) . °G(La3+ )(Va)(Va) . °G(Va)(Cr3+ )(Va) .) . 4. Furthermore the temperature dependence of lanthanum vancancy and hole concentrations from Akashi et al. 4.r-prv GLaCrVa3 − HLa − H Cr = °GLa3+ :Cr3+ :Va = GLaCrO3 − (4.8 it describes random mixing of La3+ and Va on the A-site.3. °G(Va)(Va)(O2.r-prv SER SER o-prv.8 are optimized using experimental data of excess Cr in perovskite.7 describes random mixing of O2. the Croverstoichiometry in a furnace-cooled specimen reported by Khattak and Cox does most likely not represent the overstoichiometry at an intermediate temperature and was not used for the optimization.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 ⎠ (4.7 and A of Eq.9) Using Eqs. the 12 endmembers of the compound energy formalism of the perovskite phase are defined. was considered in the optimization.3. 4.3. °G(Va)(Cr 4+ )(O2. ° prv G(La3+ )(Cr3+ )(Va) results from a reciprocal relation which was set zero in analogy to Grundy et 3 al. and °G(Va)(Cr 4+ )(Va) . The 116 .3.  : 3° G (O2(g) ) 2 ° o-prv.3.8) 1 1 1 gas = GLCR4O = °GCr2O3  + °GLa2O3  + °GO2  + Gmag + A 2 3 4 prv GLa2 3CrO3 − ° and reciprocal relations which were set zero in analogy to Grundy et al.5 to 4.3. 3 3 3  . 4. 4. As cation diffusion in La1-xCrO3 is extremely slow even at high temperatures.3.with Va on the anion sublattice. were used to obtain ° prv prv prv prv G(Va)(Cr3+ )(O2.
As a value of the oxygen partial pressure is required for the optimization.. The chromium species considered in the liquid are Cr2+ and Cr3+. together with experimental phase diagram data[12.Va:Cr3+ :O2.Va:Cr4+ :O2.14.La3+ :Va and subregular 1Lliq 2+ . 4.La3+ :O2- L were optimized. It was assumed that the interactions between Cr2+-La3+ and Cr3+-La3+ are of the same order of magnitude in the oxide melt. we defined pO2 = 1 Pa. 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 LaO1.5 Results and Discussion The La-Cr system: The calculated phase diagram of the La-Cr system is presented in Fig.5. thus the two regular interaction parameters were set equal to each other. did not specify the value of the prevailing oxygen partial pressure during their phase diagram experiments conducted in an argon atmosphere.3. The liquid is thus given by the model description (La3+.and the two subregular 1Lliq 3+ .2 (next page).= Cr Cr Cr 1 liq Cr 2+ .and 0Lprv3+ .Thermodynamic assessments introduction of positive interaction parameters 0Lprv3+ . and Foëx. The experimentally determined temperatures and liquid compositions[13.5 system from Tresvjatskiy et al. 4.17]. It was based on the liquid descriptions of the binary subsystems.La3+ :O2. as were the two sub-regular interaction parameters.Cr2+. Furthermore the two regular interaction parameters 0 Lliq 3+ . the temperature of the eutectic at the Cr-rich side from Berjoan.Cr3+)p(O2-. 117 .14] at the eutectic and monotectic in the metallic La-Cr system and the partial enthalpy of mixing of Cr.13.that were given La La the same values circumvents too high Cr4+ contents at low temperatures that would be in conflict with the experiments. Higher oxidation states are unlikely to exist in the liquid at normal oxygen partial pressures.La3+ :O2.74] was used for the description of the liquid phase of the La-Cr-O system.La3+ :Va Cr Cr interaction parameters to account for interactions between La and Cr.= 0 Lliq 2+ .Vaq-)q.CrO1.3. Berjoan and Tresvjatskiy et al. ΔH Cr  in La-Cr liquid were used to optimize the temperature-dependent regular 0 Lliq 2+ . and the congruent melting temperature of the perovskite phase from Coutures et al.La3+ :O2. The liquid phase: The two-sublattice model for ionic liquids[73.
% at 1134 K. of 2 ×10-3 at.17] .3 (next page) together with the experimentally determined value that is well reproduced by the calculation. the lowest temperature of stable γ La ss . The model description of the bcc phase results in a tiny solubility of Cr in La(bcc).3. 4. The calculated enthalpies of mixing are shown in Fig. which further decreases as a function of increasing temperature. denoted as γ La ss .3. 4.Thermodynamic assessments Fig.La:Va used to model the bcc phase results in a large miscibility gap between the La-rich and Cr-rich metals. which is tantamount to a small solubility of La in αCrss in agreement with the experiments [14. The positive value of 0Lbcc Cr. 118 .2 Calculated phase diagram of the La-Cr system with data from the literature included (symbols).
3. at T = 1700 K included (symbol with error-bar). A satisfying reproduction of the experimental data was obtained by considering a moderate temperature dependence of 0 liq Cr 2+ . This is unfortunately associated with Cr an inverse liquid-liquid miscibility gap with a minimum at X(Cr) = 0. The La-Cr-O system: Phase equilibria: Calculated LaO1.3 Calculated partial enthalpies of mixing of La and Cr in La-Cr liquid.La3+ :Va L and 1Lliq 2+ . 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.5 phase diagrams in pure oxygen at pO2 =105 Pa. and integral enthalpies of mixing as a function of composition. which are T = 2180 K and 2130 K.25 and T ≈ 5000 K that is of course unphysical.Thermodynamic assessments Fig.CrO1. in air at 119 .. The higher value was favored by Dinsdale and is adopted in this study. with the experiment from Berezutskii et al. 4. and Svechnikov et al. whereas the lower melting temperature was chosen by Savitskii et al.La3+ :Va .5.
and under reducing conditions representing argon atmosphere at pO2 = 1 Pa with experimental data included (symbols).19] and the conflicting data on the melting temperature of lanthanum chromite in argon atmosphere the presented liquid description is rather tentative. Fig.3.4 Calculated phase diagrams of the LaO1.5 system in pure oxygen. Excess Cr in lanthanum chromite is favored at high oxygen partial pressures. La2CrO6 is stable within a wide temperature-range in pure oxygen. On the other hand a significant amount of Cr3+ in the ionic liquid is reduced to Cr2+ under reducing conditions. reflected by the disappearance of Cr overstoichiometry. lanthanum chromite is expected to be metastable at room temperature. and under reducing conditions at pO2 = 1 Pa representing the typical oxygen partial pressure in argon atmosphere are shown in Fig. whereas it does not form in air and argon atmosphere.5-CrO1. Be it that the reported thermodynamic data of La2CrO6 and La2(CrO4)3 are correct. air atmosphere. This is in line with the interpretations of Raman spectra from Iliev et al.3. A decrease of Cr4+ during annealing of an originally lanthanum-deficient perovskite phase under reducing conditions is predicted by the model. Analogous to Fe in the La-Fe-O system this oxidation of Cr2+ to Cr3+ governs shifts of eutectic compositions and temperatures and the increase of the melting temperature of the perovskite phase on increasing the oxygen partial pressure.4 together with experimental data[18-21]. 4. Under oxidizing conditions Cr3+ is favored over Cr2+ in the liquid. and orthorhombic perovskite is stable only at pO2 ≤102 Pa. 4.Thermodynamic assessments pO2 = 21278 Pa. and the liquid stability increases considerably at the Cr-rich part of the system 120 . Due to the ambiguous oxygen partial pressure of phase diagram experiments[18.
3. 105). Table 4. The same oxygen solubility in Cr as in the assessment by Povoden et al. 4. Thermodynamic data: Calculated thermodynamic data of solid oxides are listed together with experimental data from the literature in Table 4.3. 121 . 105-107) is a compilation of the Gibbs energy functions and model descriptions of the phases in the La-Cr-O system obtained in this study.3 (pp. In Fig.5.5 calculated phase equilibria of the La-Cr-O system at T = 1273 K are shown as a function of oxygen partial pressure.5 Calculated phase equilibria of the La-Cr-O system at T = 1273 K as a function of oxygen partial pressure. Fig.3. 4. Calculated and experimental data on the orthorhombic to rhombohedral transition of LaCrO3 are listed in Table 4. 106). It is obvious that no mutual solubilities of La and Cr in bcc metal in equilibrium with oxides are expected. Despite this discrepancy we did not go for an alternative liquid model for the sake of consistency with our previously assessed systems.2 (p. was obtained using the new model description (Cr)(O. 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. At pO2 = 10-34.3.04 Pa metallic liquid forms at the lanthanum-rich side of the phase diagram.Va)1.3.Thermodynamic assessments leading to a considerably lowered eutectic temperature.1 (p.
4. The calculated C p -curve extrapolates well to high temperatures. Anyway the model parameters were fitted to the experimental data. bearing in mind the high degree of uncertainty of the resulting description.31] resulted in gross disagreement between optimized and reported values. whereas the calculated standard enthalpy of formation from the elements was rejected.3.6. The perovskite phase: the calculated heat capacities of LaCrO3 are compared with experiments from the literature in Fig.6 Calculated heat capacities of LaCrO3 (solid curve) as a function of T with experimental data included (symbols). The use of C p -data from Sakai and Stølen along with enthalpy increment-data from Suponitskii to optimize the 122 . 4. The dashed line marks the temperature of the o-prv ↔ r-prv transition.3.Thermodynamic assessments Lanthanum chromates: Testing an optimization of model parameters of La2(CrO4)3 by using all available thermodynamic data[29. and/or by significant deviations between the thermodynamic standard data used for the calculation of the enthalpy of formation from the elements and assessed values[8-10]. Fig. The considerable error might be explained by experimental difficulties to reach equilibrium at the low investigation temperatures.
The calculated C p -peak at T = 290 K reflects the temperature of the magnetic order-disorder transition. as it unavoidably leads to emf that are too low. 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.28 or p = 0. The calculated transition temperature of T = 540 K is shown by the broken line in Fig.28 and p=0. and hcp is not available in the literature. p.4. 4. fcc. their C p is the same.or oxygen-containing atmosphere. In this case the emf depends on the activity 123 .3. Two values for the magnetic parameter p are possible depending on the crystal structure.1.70] using p = 0. 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. The C p -anomaly is equally well reproduced by the model[69. 105). Experimental enthalpy increments are well reproduced by the calculation (see Table 4. p=0. For the sake of compatibility with the recent assessment of the La-Fe-O system we chose p = 0.28. As CTlnT was set equal for o-prv and r-prv. A possible explanation is found in a study by Akila and Jacob: Fine precipitates of CaO can form on the surface of CaF2 in water.4.3. Yet it is obvious that the CaF2based emf-technique is neither suitable for the determination of thermodynamic data of lanthanum chromite. 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. The resulting Gibbs energies of formation from emf-measurements are remarkably less negative than the Gibbs energies of formation derived from Knudsen mass spectrometry. A small peak which was found around 855 K can be explained most likely by the decomposition of an undetected impurity phase. 105.6. It needs to be clarified why all of the emf-measurements are problematic: Azad et al.10) are listed as a function of temperature together with data from the literature [49-53] in Table 4.Thermodynamic assessments parameter CTlnT of the Gibbs energy of stoichiometric perovskite resulted in the lowest error between experiments and calculation.1. whereby the proper p-value for structures other than bcc.3. 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.35] the term CTlnT is fixed firmly. Due to the consistency between both groups of calorimetric experiments[30. the transition temperature being in agreement with the experiments.3. p.
3.3.7. 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. The calculated decomposition of the perovskite phase by Eq.3.11) is pO2 = 10-20. 4. Defect chemistry of the perovskite phase: 124 . 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.97 at 1273 K.3.11 is plotted as a function of temperature and oxygen partial pressure in Fig. Fig.7 Calculated decomposition of lanthanum chromite as a function of temperature and oxygen partial pressure.Thermodynamic assessments of CaO at the electrode/electrolyte interface. 4.
and charge neutrality is maintained by 1 • [Va ′′′ ]= [CrCr ] La 3 (18.104.22.168.)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. yprv .14) x x x For small oxidation extent [La La ] . yprv 3+ . and yprv 4+ in the compound energy formalism. 4. yprv 3+ . CrCr . yprv .: 1 (La 3+ )(Cr 3+ )(O2. 4.Thermodynamic assessments Applying a defect chemistry analysis of La1-xCrO3 in equilibrium with Cr2O3 the following defect reaction for its oxidation can be written in the sublattice form. yprv 3+ .14 gives the proportionalities [Va ′′′ ].3. A La 125 .15) • Substituting this into Eq.3.)3 2 4 (4. Va La . and [OO ] can be considered to be ~ 1.12) 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 (4.3.13) 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. and CrCr in La1-xCrO3 correspond to the site 3 fractions yprv 3+ . [CrCr ] . if [Va ′′′ ] and [Va •• ] are O Cr assumed to be negligible according to Akashi et al. The line for yprv 3+ at 1073 K cannot be seen as it is very close to 1. [CrCr ] ∝ PO2 16 .8 (next page) for lanthanum chromite in equilibrium with Cr2O3. La x x • ′′′ The concentrations of the defects LaLa .
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. 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. is calculated from very high to very low oxygen partial pressures. may be explained by problems of reaching equilibrium due to extraordinarily slow cation diffusion in • ′′′ lanthanum chromite.12. 4..3. In Fig.Thermodynamic assessments Fig. 4. The conflicting data from Shvaiko-Shvaikovskii et al. 4.9 (next page) the calculated slopes of VaLa and CrCr are 126 .0 ×103 Pa and pO2 = 2. This slope is • fixed by the defect reaction Eq. 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.0 ×104 Pa determined by Akashi et al.3. The slope • At T=1073 K a constant slope of 3/16 of the defect concentrations [Va ′′′ ] and [CrCr ] shown in La the triangle. pO 2 .3.8 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.
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. broken lines). as a function of La reciprocal temperatures.15.Thermodynamic assessments • compared with slopes of [Va ′′′ ] and [CrCr ] determined by Akashi et al. The presented defect chemistry calculations are still rather tentative. as calculated [Va ′′′ ] and [Va •• ] are very small. derived from electrical conductivity measurements (symbols with error-bars. The calculated concentrations agree well with the data derived from electrical conductivity • measurements. The calculated amount of [Va ′′′ ] relative to [CrCr ] is fixed by the criterion for La charge neutrality. 4.3.. Eq. Fig.3. 127 . 4. as the temperature and oxygen partial pressure dependence of excess Cr in La1-xCrO3 has not been investigated systematically so far. The calculated O Cr relative defect concentrations are in line with those proposed by Akashi et al.
pp. 3. U. Das. Kinzel. 2000. R. K. 147(11). Ramprakash and J. 2. Deller. Göttingen. Carlsson. 1997. Foger.-M. 2. Proceedings of the 26th Risoe International Syposium on 128 . S. Cr-Mn deposition at the three-phase boundary observed by TEM. A. Mechanism and kinetics. D. as the use of these data for the optimization of model parameters resulted in a proper reproduction of the phase equilibria derived from experiments. pp. p. Using the new database the stability limits of lanthanum chromite in function of temperature and oxygen partial pressure can be quantified. Zhang. Soc. P.6 Conclusions Model parameters of the presented thermodynamic La-Cr-O database were optimized with assessed thermodynamic and phase diagram data. I. 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.G. Solid State Ionics. 4013-22. Miller. J.. Foger. K. 1994. and Cheng and Navrotsky. S. Kjaer and J.P. Electrochem. 4. Hilpert. M. P. 703. Nickel. Jiang. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells. J.Thermodynamic assessments 4. The orthorhombic to rhombohedral transition in lanthanum chromite and the magnetic order-disorder transformation are well reproduced by the model. Badwal. References 1. Larsen. The proposed existence of lanthanum vacancies and holes to maintain charge neutrality in lanthanum chromite with excess Cr is reproduced by the model.P. Y. 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. and K. 99.3.). The thermodynamic descriptions of lanthanum chromates and the liquid phase are rather tentative due to humble or sketchy experimental information. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Druckerei J. Vol. The thermodynamic modeling of lanthanum chromite was based on experimental thermodynamic data reported by Peck et al. Zhang. 297-310. First European Solid Oxide Fuel Cell Forum Proceedings. H. Bossel (Ed. S. However the amounts of excess Cr in La1-xCrO3 used for the optimization of the cation nonstoichiometry are preliminary. A.H.
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Allg. Neorg. 1246-48. N. 1995. Zonov. Coutures.. Soc. 36. P. Yu. 276. Pavlikov. J. Acad. Chim. Geller. Crystal Chemistry and Thermal Behavior in the La(Cr. Traverse. Mathews. Heat Capacity and Thermodynamic Properties of Lanthanum(III) Chromate(III): LaCrO3. 43. 322(1-2).. R. A. J. Analysis of Crystal Structure and Phase Transition of LaCrO3 by Various Diffraction Measurements. pp. Phase Transformations of Certain Chromites of the Rare Earth Elements. Electrochem. Mirza. Yoshida. 132. Ruiz. 32. A. 140(10). Evaluation of the Thermal Conductivity. Thermodyn.. Kamiyama.P. 2000. 1973. and Entropy of Lanthanum Chromite between 298 and 900 °K. Nauk SSSR. pp. S. Kishi. Some Observations on the Formation and Structure of Lanthanum Chromite. Tagawa. M. Chem. 23(9). High Temp. Reznitskii. 2889-94. pp. Akad. Oikawa. 1-14 (in German). Rev. 1985. Terao. Shimojyo.P. 1966. Morii. pp. 1973. 1167-72. Lopato. Akad. Y. Hashimoto. Anthony. C. pp.E. 2(4). H. 679-82 (in Russian). N.. Solid State Ionics. Y. D. LaCrO4. K.G.A. Neorg. Ni)O3 Perovskite System. 5-8 (in French). Schwarz. Höfer. Kononyuk. K. pp. K. 183-90.N. Miner. 1271-74 (in French). Tsuzuki. A. I lanthanum chromate(V). 524-29. Hashimoto. Lyutsko. Tolochko. B. Sc. pp.M. Enthalpy..R..B.V. S. 1963. H. Kock. Lett.M. Chem. Izv. Takagi. 1967.. 805-06. 42. T. Tanaka. Structural study and thermal decomposition of lanthanum based chromate.F. Mater. J. L. Berjoan. 27(5).Thermodynamic assessments 31. Mater. Phys. T. S. Paris C. pp.. 10. J.F. Foëx. 35. M. H. J. 264. Solid State Chem.G. 41. 309-16 (in French).S. 154.R. pp. 33. Sci. Momin. at Temperatures from 298.-M. pp. On the Semiconducting Properties of Lanthanum Chromite. Acad. Sc. High-Temperature X-ray Diffractometric Studies of LaCrO3. Phase Transitions in Solid Solutions Based on Lanthanum Chromite. I.C. Z.P. Tresvyatskii. Sakai K. Paris B. 1976.15 K. Mater. 10. J. Structural Phase Transition of Orthorhombic LaCrO3 Studied by Neutron Powder Diffraction.. J. 14(4). Stølen. 131 . E. 39. V. Kamiyama. 34. 1993. pp. K. A. Oikawa. T. 1991. 2(4). Sakai. V. LaCrO3 at Room Temperature. Nauk SSSR. Dokiya. 493-506. Izv. 1970. S. Rev. Raccah. 1520-24 (in Russian). N. 40. pp. Tsuda. On the chromates(V) of the rare earths. Korobeinikova. Anorg. W. N. A. M. 38. 37. Phase Transitions in Perovskitelike Compounds of the Rare Earths. pp. T. Specific Heat. C. 2000.
Heat Capacity Measurement of Lanthanum Chromite by Laser Flash Method. 23-29. 562-66. Less-Common Met.-Q. Gauckler. I. 166(1). Li. Litvinchuk. J. Nature. Hashimoto. Miller. Hao. Res. 1996. H. 1990. 1998. Sun. Dokiya. Dudek. Fe. M. Kolev. J. J. pp. Li. Sudha. Co. pp. B. Y. pp.P.. 192(4). Y. N. pp. Sakai. M. X. Method. Res. Z. 79(12). 7677 (in Japanese). pp. 53. 108(9). 49. T. Azad. H. Mater. 2006. 214301-1214301-7. Peck. S. N. Kawada. 259. Fe. T..E. Mn. Bull. 132 . Petzow. Nickel. 1997.Y. A. J. L. Ni) in Reducing Atmosphere I. pp. M. Zhou. Rare Metals. Huang. 1961. Rev. Mat. 1979. A. K. F. Japan. pp. Iliev. Phys. Alloys Compt. M. T. 2006. K. T. W. Chung. Chen. Koseki. Cheng.P. 45. Takahashi. pp.Sr)CrO3 System. Raman Spectroscopy of Low-Temperature (Pnma) and High-Temperature (R 3 c) Phases of LaCrO3. 74. C. and Ni). 48. Hadjiev. Yokokawa. Murakami. 176-82. 55. M. 1987.. Thermodynamic Properties of LaCrO3. 12. Weinberg. Co.-H. D. Structural Studies of the (La. S. Cr. 3266-72. Y. pp. Sreedharan. 191-200. N. Solid State Commun.Thermodynamic assessments 44. M. G. 57-62. Z. Abrashev. 47. Meng. N. X.-Y. Dokiya. 20(1). Kobertz. G. Zhongguo Xitu Xuebao. 2005. Res.G. 1977.V. V. Wang.N. 19-24 (in Chinese). Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties. 46. N. 56. Satoh. Róg. November 1991. Pressure-Induced Structural Phase Transition of LaCrO3.. 463-72. M. Xing. pp. O. Navrotsky. Stability of the Perovskite Phase LaBO3 (B=V. J. pp. Chem. 649-59. Kozlowska-Róg. Mater. Thermodynamic Stability of LaCrO3 and CaZrO3 Using a Solid-State Galvanic Cell Method.J. A. D. Matsushita. Ceram. J. R.M. 54. W. Electron Paramagnetic Resonance and Antiferromagnetism in LaCrO3.-L. H. Kikegawa.. Takagi. Soc. pp. Bull. 14.. 445-46. Yoshida. Experimental Results. 50. A. Khattack and D. Am. 5(3). 81. Tagawa.F. Enthalpies of Formation of LaMO3 Perovskites (M=Cr. pp. Kyoto. 52. 2007. P. 25(5). Determination of the Standard Free Energy of Formation of LaCrO3 at 1273 K. 691-94. Yuan. Hilpert. Nakamura. R. Cox. Thermodynamic Stability of LaCrO3 by a CaF2Based E. 51. Chen. M. Abstracts of the 27th Symposium on Thermal Analysis and Calorimetry.M... H. Y. Larssen. Heat Capacities of LnCrO3 (Ln=Rare Earth). Kamegashira. Polish J. G. Cmaidalka. Kojima. H.
pp. A. 2006. 64. Transport of Lanthanum Ion and Hole in LaCrO3 Determined by Electrical Conductivity Measurements. L. M. Jarl. Goto. pp. 1978. Determination of Chemical and Magnetic Interchange Energies in BCC Alloys. Akad.. Application of the Compound-Energy Model to Oxide Systems. 70. G. pp. A.G. 2(3). pp. 61. L. 68. 65. J. Inden. 24(3).J. 36. 94-96. Nauk SSSR. pp. 81-87. pp. 1595-1609. Gauckler. B. Andersson. 1984. Z. J. Solid State Ionics. J. N. Calculation of Defect Chemistry Using the CALPHAD Approach. 23A. 69. 66. Calphad Calculation of Phase Diagrams. E.J. Z. B. V. Chem.Thermodynamic assessments 57. Tripathi. Gauckler.F. Indian J. Vidyasagar. V. A.N. Povoden-Karadeniz. E. 265-84. H.R. Hillert. Chem.. A. L.L. accepted 63. 212-27. 59.E. Hillert. V. Thermodynamic Assessment of the La-Fe-O System. Pergamon Materials Series. 15(8). 71. B. Alloy. p 227-38. Maruyama. Jansson. 1979. 133 . Akashi. Shvaiko-Shvaikovskii. 320.P. pp. Electrical Transport in Rare Earth OrthoChromites. Saunders. 243-. Hillert. Guillermet. Gordon. T. C. Phys. J. Gopalakrishnan. 1986. I.R. Miodownik. T.B. Mater.G. p 161-76. 345-58.... 437-45. Rao. Cmpd. Gauckler. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. M. Calphad. Izv. Metallkd. 2003. 164. Ivas. 58. pp. 1971. The Compound Energy Formalism. 1989. pp. -Manganites and -Ferrites. J.V. T. J. Fierro. Phase Equilib. 1441-45 (in Russian). pp. M. M. Tejuca. Influence of the Synthesis Conditions on the Electrical Properties of LaCrO3. Sundman. 2003. Thermodynamic Assessment of the Co-O System. 1988. C. A. T. 577-82. Acta Metall. 79(2). Neorg.. L. Advances in Catalysis. Elsevier Science Ltd. 67. M. B. Grundy.-O. G. A Model of Alloying Effects in Ferromagnetic Metals. 66(10). Metallkd.N. Superstructures. Povoden. Hillert. 33-41. Wanklyn. Mater. 1982. T. Chen.K. K. 17. Diff. Rao. Hallstedt. pp. M. Sundman. 1.M. Solids. pp. Jansson. 2001. Calphad.N. Grundy. Ivas. Sci. Rao. B. M. Vol. Popov. 1998. Lal. Phase Equilib.. Ordered Defects & Nonstoichiometry in Metal Oxides of Perovskite & Related Structures.N. Chen.. J. J.P. Structure and Reactivity of Perovskite-Type Oxides. 34. 60. General Treatment. 30..S. Electrical Transport in Light Rare-Earth Orthochromites. 32.J. 62.G. 177-83. B.. 1975.
1 Introduction Sr-doped lanthanum manganite (LSM) with the perovskite structure ABO3-δ is used as cathode materials in SOFC. 20. A. Sundman.N. 294-300. B. pp. Trans. 74. Grundy. Metall. Sundman. Hillert.2]. 15. L. These requirements are conformed by using the CALPHAD approach. A. The Mobility of Oxygen Ions in CaF2. submitted to Scripta Mater. 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. as well as defect concentrations of the cathode contaminated by Cr at different temperatures and oxygen partial pressures.4 Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications E. Jacob. B. Modification of the Two-sublattice Model for Liquids. Gauckler.J. pp.Thermodynamic assessments 72. 1985. 261-66. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. Appl. thermodynamic driving forces and activities. E. 73. and SrCr2O4 are presented. M. 1991. The database should meet the demand to calculate stable and metastable phase equilibria.T. Povoden. M.J.N. M. pp. 1990. Electrochem. Sr2CrO4. K. 4. Akila.4. Jansson. Experimental solid solubilities and nonstoichiometries in La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ are reproduced by the model. Ågren. and L. Povoden. 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. B. R. Calphad. Chen. Chen. 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. 109-19..67Cr2O8. A. J. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. 4. J. For the construction of the 134 . Grundy. 16A. Sr2. Gibbs energy functions of SrCrO4. 75.
67Cr2O8 by using microprobe analysis. in agreement with Hartl and Braungart. whereas emf measurements using CaF2-based emftechnique led to conflicting results likely caused by competing reactions. Limited solution of Sr in La1-xSrxCrO3-δ perovskite was confirmed by a later investigation.785 Å for at maximum 6-fold coordinated Mn3+) we omit Mn3+ on the A-site. allowed Mn3+ on the A-site of LSM to reproduce experimental oxygen nonstoichiometries under low oxygen partial pressures. Calculation of the oxygen nonstoichiometry of perovskite + MnO instead of metastable single phase perovskite leads to a good agreement between experimental and calculated nonstoichiometries.Thermodynamic assessments La-Sr-Mn-Cr-O oxide database La-Mn-Cr-O oxide and La-Sr-Cr-O oxide systems are assessed. No quaternary phases or solid solutions were found in the Sr-Mn-Cr-O oxide system. and La-Cr-O databases are adopted[3-5].4. 0. and the LaSr-Mn-O oxide database is taken from Grundy et al.5 Å for 12-fold coordinated La3+. with a slight modification: Grundy et al. 4.12]. which is in agreement with Negas and Roth.2 Assessment of data from the literature Previous assessments of the La-O.15-19]: for the stabilities of SrCr2O4 and Sr2CrO4 we trust the accurate study of Jacob. 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. Sr-Mn-Cr-O oxide is treated as ideal extension from the subsystems. Sr-Cr-O oxide: Thermodynamic functions for Sr-Cr-oxides in the SSUB database are based on estimates. Cr-O. On the other hand the conflicting phase equilibria presented by Kisil 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. Due to large differences between the ionic radii of La3+ and Mn3+ and possible coordination numbers (1.12. The 135 . The stoichiometry of a phase defined as Sr3Cr2O8 was later corrected to be essentially Sr2. Sr3Cr2O7 was approved as high pressure phase only. Differences concern the reported stabilities of further compounds[11. 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.
Sr)CrO4 were stable in air. In contrast to Peck et al. La-Mn-Cr-O oxide: In the La-Mn-Cr-O oxide system no quaternary stoichiometric compounds were reported.8Sr0.5Cr0.25. and 0.3.5O3-δ with x = 0. Cheng and Navrotsky measured enthalpies of formation of La1-xSrxCrO3-δ with x = 0. and 0. and the solubility of Cr is unknown.2.1. and 0. 136 .3 using Knudsen mass spectrometry. and La0. thermodynamic data are missing.8Sr0.Thermodynamic assessments existence of several Ruddlesden-Popper phases is restricted to reducing conditions. Myoshi et al.Sr)CrO4 is ambiguous. 0.11 using drop calorimetry at T = 1080 K. and −0. it was proposed earlier that Sr(La.3 as a function of temperature and oxygen partial pressure using XRD analysis. and 1573 K.3 at T = 1173 K that Cr4+ were absent in the latter. 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.1. −0. Nonstoichiometry data for La1-xSrxCrO3-δ with x=0. 1473K. The exact temperature and oxygen partial pressure range of Sr(La. investigated the single phase region of La1-xSrxCrO3 with x = 0.Sr)CrO4 is omitted in the modeling. Sr(La. 0. Plint et al.3 at T = 1273K. and 0. 0.1. Thus its extension to the quinary database would not be reliable.24]. 1373 K.22.214.171.124MnO3 and Cr2O3 at 1073 K was reported after 1000 h of heat treatment in air. 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.9Cr0. and δ = 0.1.2. and 0.1O3-δ was measured using thermogravimetry. 0. concluded from the similarity between X-ray absorbtion spectra of Cr K of LaCrO3 and La1-xSrxMn0. As Ruddlesden-Popper phases have not been reported to form during SOFC operation with LSM cathodes. solely Sr(La.09.Sr)CrO4 showed reproducible stoichiometry. 0. Complete solid solution between the LaMnO3 and the LaCrO3 perovskites was affirmed. Perovskite+MnCr2O4 spinel equilibrium of a powdered mixture of La0. δ of LaMn0. whereas negative δ essentially stands for cation nonstoichiometriy. Positive δ in the perovskite formula reflects oxygen deficiency.2CrO3-δ at 1273 K were measured as a function of oxygen partial pressure using thermogravimetry. Cr4+ and oxygen vacancies are regarded as the major defects[23. Peck et al. −0. determined the Gibbs energy of formation of La1-xSrxCrO3 with x = 0.04.
Thermodynamic assessments The perovskite phase: Magnetic and structural transitions of La1-xSrxCrO3-δ [29−35].4. their modeling was omitted without consequences for the applicability of the database for SOFC. Magnetic transitions have been well reproduced by an ordering-model[42. accounting for the structural feature of alternating rocksalt. and La1-xSrxMn1-yCryO3-δ [8.3 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. Thus.67Cr2O8. H a is the standard enthalpy of the stable state of element a at 298. composition and oxygen partial pressure.1) SER v = 0.4.25 for SrCrO4. in terms of the applicability of the new database for SOFC the authors omit structural transitions in the modeling. As the magnetic transitions are low temperature features. LaMn1-xCrxO3-δ [26.and perovskite layers of the latter. 0.43] for LaCrO3. All 137 . Consistency among transition data for La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ prevails.12] and phase stabilities of SrCr2O4 and Sr2CrO4 investigated by equilibration experiments of different mixed oxide compositions under controlled atmospheres.41] were reported.36−40]. most likely due to interactions that cannot be reproduced by the model. and Sr2CrO4 respectively.75. 7/6.67Cr2O8 following the proposed formula and for the Ruddlesden-Popper phase Sr2CrO4. their optimization with the following experimental phase diagram and thermodynamic data using the PARROT module of the Thermocalc software resulted in the lowest error between model and experiments: Gibbs energies of formation of SrCrO4[11.15 K and 105 Pa.67Cr2O8+SrCrO4+Cr2O3 as a function of temperature and oxygen partial pressure[11. SrCr2O4. A and B are adjustable parameters. Sr2. Gibbs energy functions of Sr-Croxides were formulated as 1 2 ° SER SER SER gas G(Sr)x(Cr)y(O)z − xH Sr − yH Cr − zH O = x °GSrO + y °GCr2O3 + v °GO2  + A + BT (4. Transitions of LaMn1-xCrxO3-δ are complex as they depend on temperature. (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 the equilibrium Sr2. 4. However we did not obtain satisfying results in higher-order perovskites. and 0. whereas diversities exist regarding the transitions in La1-xSrxMn1-yCryO3-δ .12].
15 kJmol-1 x = 0. Δ H = −65.851 − 1116 K Δ °G = −273.88 kJmol-1 x = 0.825 ± 0.106904T kJmol-1 . δ = 0.1080 − 1380 K (1 − x) 2 La 2 O3 + xSrO + 1 2 Cr2 O3 + x 4 O 2 − δ 2 O2 = La1− xSrx CrO3−δ x = 0.3. δ = 0.4.1. calc. δ = 0. calc.54 kJmol-1 x = 0. Δ °G = −93.67 Cr2 O8 + SrCrO 4 + Cr2 O3 Δμ O 2 = −265. BSr2CrO4 = 50 J ASrCr2O4 = 98000 J.48 kJmol -1 138 .2. ° Δ ° H = −36.5 J ASr2.340 + 0.09. T = 2000 K.767 + 0.2.1073 − 1473 K Δμ O 2 = −276. BSrCr2O4 = −95. Table 4. Δ °G = −109.5 kJmol-1 x = 0.4. calc.1. Δ ° H = −50.8 kJmol-1 this work.4 kJmol-1 this work.774 + 0.= 5 6GS4O − GS3V + 1 6GS4V + GRPRV GSr 2+ :Cr 3+ :O2. δ = 0. T = 298 K. Δ °G = −85.67Cr2O8 = 219 J La1 − xSrxCrO3 − δ ° gas GLa3+ :Cr 4+ :Va = 5 6GS4O − GS3V + 1 6GS4V + GRPRV − 1.4. calc. Δ ° H = −56. Δμ O 2 = −262. Δ °G = −102.2 Calculated and experimental thermodynamic data SrO +1 2 Cr2 O3 + 3 4 O 2 = SrCrO 4 Δ °G = −273.= GS3V + 1 6GS4O − 1 6GS4V GSr 2+ :Cr 3+ :Va = GS3V − 5 6GS4O + 5 6GS4V Table 4.13152T kJmol-1 this work.1.11. Δ ° H = −20.1 and 4. calc.4 kJmol-1 this work. T = 2000 K.2 kJmol-1 this work. Δ H = −48. T = 298 K.13157T kJmol-1 . ° Δ ° H = −67.15832T kJmol-1 this work. T = 2000 K.0 kJmol-1 this work. Optimized parameters and calculated and experimental thermodynamic data are listed in Table 4. calc. calc.15553T kJmol-1 . BSrCrO4 = 131.4.2. BSr2. δ = 0. δ = 0. Δ °G = −93.67Cr2O8 = −508507 J.950 − 1280 K Sr2. δ = 0. T = 298 K.5 °GO2  ° ° ° GLa3+ :Cr 4+ :O2.166T kJmol-1 .76 kJmol -1 x = 0. calc.3. Δ ° H = −59.6 J ASr2CrO4 = −145000 J. Δ ° H = −20. Δ ° H = −34.050 + 0.3 kJmol-1 this work.3.859 + 0. δ = 0. T = 298 K.6 kJmol-1 this work. Δ °G = −213. T = 298 K.7 kJmol-1 x = 0.2 + 0. calc.1 Optimized model parameters Sr .Cr oxides ASrCrO4 = −273771 J. δ = 0.Thermodynamic assessments reported phase equilibria are correctly reproduced by the model.3 kJmol-1 this work.1 kJmol-1 this work.72 kJmol-1 x = 0.2. Δ ° H = −55.04.7 kJmol-1 x = 0. calc. Δ ° H = −34. T = 298 K. Δ °G = −88. calc.
°G(Sr2+)(Cr4+)(Va)3 1° 5 gas GCr2O3  − °GO2  2 4 ° SER SER GSrCrVa3 − H Sr − H Cr = °GSr2+ :Cr 4+ :Va = GS4V = °GSrO + (4. (Sr2+)(Va)(Va)3.31451 J mol-1 K-1. The molar Gibbs energy °G of La1-xSrxCrO3-δ is uniquely defined as follows: °Gs of the endmembers (La3+)(Cr3+)(O2-)3. The second-last term accounts for the configurational entropy of mixing. The last term describes the excess Gibbs energy of mixing.Sr2+.g. yj is the site fraction of each cation and Va on the B-sublattice.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. and small amounts of Cr brought into the cathode unlikely lead to a change of the structure. (La3+)(Va)(Va)3. this is achieved by using the same model. Typical compositions of Sr-doped lanthanum manganites used for SOFC cathodes.3) is chosen as reference.4. The parameters of the compound energy formalism are the Gibbs energies of the end-member compounds °Gi: j:k . (Sr2+)(Va)(O2-)3.Va)3 with A. Using the above model and the proposed defect chemistry[22-24] the sublattice formula for La1-xSrxCrO3-δ reads (La3+. B = cations and Va = vacancies using the compound energy formalism.Va)(B. and (Va)(Va)(Va)3 and ternary interaction parameters are adopted[5. 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.Va)(O-2. La0.and Va on the anion sublattice.Cr4+. (La3+)(Va)(O2-)3. Thus it is reliable to take the Gibbs energies of the compounds of rhombohedral perovskite from  for the model. and A and B parameters of °G of two neutral compounds 139 . R = 8.8Sr0.4.6.2MnO3-δ are rhombohedral at SOFC operating temperatures (T=1073 K to 1273 K).Va)(Cr3+. It can be accounted for by introducing interaction parameters. (La3+)(Cr3+)(Va)3.Va)(O2-. We adopt the description (A.48].Va)3.2) where yi is the site fraction of each cation and Va on the A-sublattice. and yk is the site fraction of O2. (Va)(Va)(O2-)3. e.
4 Results and discussion The reproduction of experimentally determined Gibbs energies and enthalpies of formation.Mn4+. The regular interaction parameter 0L(La3+:Cr3+.5 in Eq.Mn3+.Cr .20]. (Sr2+)(Cr3+)(O2-)3.4. it is reliable to allow Cr4+ on the B-site: as Cr4+ exists in nonstoichiometric lanthanum chromite perovskite.Sr .2 (next page).Va)(Mn .4.1 (p.6. with A = 27027 and B = −69.5) are optimized with all available experimental data of the perovskite phase.4 denotes °G (Sr2+)(Cr4+)(O2-)3.4. 140 .Va)3.4. °Gs of the remaining endmembers (La )(Cr )(Va)3. 4.4.5Va0. and nonstoichiometries[23. 0L(La3+:Cr3+. Eq. All endmembers have been defined in the assessed subsystems. All endmember compounds have been defined in the assessed subsystems.Va)(O2-.2 (p.Mn3+:O2-) = +9421 J. 3+ 4+ (La3+)(Cr4+)(O2-)3.Cr3+.4) ° SER SER SER GSrCrO2. solid solubilities[18.Mn .24] of La1-xSrxCrO3-δ.5Va0. 4.5. The 3+ 2+ sublattice 2+ 3+ formula 4+ 3+ of 4+ the 2- quinary perovskite reads (La .5H O = GS3V = 5° 1 1 ⎛5 5 1 1⎞ GSr2+ :Cr3+ :O2− + °GSr2+ :Cr3+ :Va + RT ⎜ ln + ln ⎟ = °GSrO + °GCr2O3  + A + BT 6 6 2 ⎝6 6 6 6⎠ (4. 4.Cr .4.5 − H Sr − H Cr − 2. Thus for LaMn1-xCrxO3-δ we propose the sublattice formula (La3+.Thermodynamic assessments ° SER SER SER GSrCrO3 − H Sr − H Cr − 3H O = °GSr2+ :Cr 4+ :O2− = GS4O = °GSrO + 1° 1 gas  G + °GO2  + A + BT 2 Cr2O3 4 (4. 4. it is expected that it is not removed from the structure if the phase is doped.Va)3.4.Va)(Mn2+. Though structure-chemical information of site occupancies in LaMn1-xCrxO3-δ perovskite is missing. 138).Cr4+.4. A = 136453 and B = −91. and phase equilibria in the La-Sr-Cr-O oxide system by the modeling is satisfying as shown in Table 4.4. and in Figs.Va)(O . 138).1 and 4.Mn .Mn3+:O2-) accounting for interactions between Cr and Mn cations is fitted to experimental nonstoichiometries.2 for ° GSrCrO2. and (Sr2+)(Cr3+)(Va)3 are obtained by conversions of reciprocal equations that are set zero and are listed in Table 4.
141 . prv = La1-xSrxCrO3-δ. two phase. Filled circles. and circles with crosses denote single phase. Calculated phase equilibria are the same as in. and three phase equilibria. blank circles.5-SrO-CrO1.Thermodynamic assessments Fig.5 system calculated at T = 1223 K in air atmosphere (solid lines) with experimental data included (symbols).4.1 LaO1. 4.
4. p. prv = LaMn1-xCrxO3-δ.4.4.4. Fig.2. 142 .23] nonstoichiometries of La1-xSrxCrO3-δ at different temperatures for x = 0. as shown in Fig.5 system calculated at T = 1273 K in air atmosphere. The calculated nonstoichiometries of La1-xSrxCrO3-δ are in good agreement with the experimental values at higher temperatures.3.Thermodynamic assessments Fig.3 LaO1. β-spl = cubic Cr-Mn-spinel. α-spl = tetragonally distorted Cr-Mn-spinel.4 (next page). and 0. 0. 141 Calculated (lines) and experimental (symbols)[22. The calculated isothermal section of the La-Mn-Cr-O oxide system at T = 1273 K in air is presented in Fig. 4. 0. 4.2.4. possibly caused by equilibration difficulties due to slow diffusion.1.25. However it was not possible to reproduce the nonstoichiometries at T = 1073 K and 973 K. Deducing from the change of δ from T = 1273 K to 1173 K the measured increase of δ from T = 1173 K to 1073 K might be too small.3 as a function of oxygen partial pressure.5-MnOx-CrO1. 4.
Experimental findings[8. To approximate the absence of Cr4+ in quinary perovskite. temperature.28] are in line with our calculations.Cr3+.4 Calculated (lines) and experimental (symbols) nonstoichiometries of LaMn0. and the conclusion of missing Cr4+ is not based on a direct chemical analysis of Cr valencies.Mn4+. 4. We propose the model (La3+.5 Conclusions The thermodynamic La-Sr-Mn-Cr-O oxide database has been obtained by combining thermodynamic assessments of oxide subsystems. 4.Sr2+.Va)(O2-.Va)(Mn2+.Va)3 for the quinary perovskite phase.Mn3+.Thermodynamic assessments Fig. Optimized by experiments in pseudoternary and pseudoquaternary oxide subsystems.Cr4+.4. We believe that complete removal of Cr4+ from the perovskite structure is unlikely.4.1O3-δ at different temperatures as a function of oxygen partial pressure. The new database is adapted for quantitative calculations of 143 . this model allows the quantitative calculation of defects as a function of composition.Mn3+:O2-) and L(Sr2+:Cr4+. Experimentally determined nonstoichiometry of LaCrO3 indicates the existence of some Cr4+.Mn3+:O2-). and oxygen partial pressure.9Cr0. Thus we stick to a model without interaction parameters. it would be necessary to give large positive values to the regular interaction parameters 0 0 L(Sr2+:Cr3+.
Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research.N. M. 138..P. 5. London. Mechanism and kinetics. Badwal. Kawada. Phase relations in the system Sr-Cr-O and thermodynamic properties of SrCrO4 and Sr3Cr2O8. K.T. pp.T. Hack (ed. Abraham. 1997. S. Grundy. S. S. E. Diff.N. Y. 1991. J. J. Jacob. Z. J. L.-K. K. 4013-4022. Solid State Ionics. J.J. Chemical thermodynamic considerations in sintering of LaCrO3-based perovskites. Zhang. Ivas. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells I.J. Phase Equilib. T. Saxena. Petrov. 925-. Solids. pp. 11. E.N. Povoden. The SGTE casebook: thermodynamics at work. T. Phys. Diff. Durygin. Gauckler. Electrochem. Gauckler. P. Russ. 9. S. 2007. K. 2000.P.A. Effective ionic radii in oxides and fluorides. 297-310. Grundy. 2004. pp. 21. S. Electrochem Soc. L. B25. Prewitt. Hallstedt. Zhang. M. N. 144 . Povoden. Solid State Ionics. Filonova. M. Yang. C. 1721. 2000. pp. 99. Shannon. pp. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. Gauckler. 52. 1018-27.. Foger. Sakai. Chem... Institute of Materials. and L. 147. References 1. A. 67.J. K. Liu.. 1996. Ramprakash and J. A.. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. 1901-07. 8. Grundy. 173. Acta Crystall. Phase Equilib. J. A. pp. Aldinger. J. Jiang. A.Thermodynamic assessments phase equilibria and defect chemistry in a Sr-doped lanthanum manganite SOFC cathode poisoned by chromium. J. 4. 7. H. Geupel. Phase Equilib. F.P. P..N. J. E. pp. 10. R. Thermodynamic assessment of the La-Cr-O system.N. Soc. La1-xMn1-yO3-z perovskites modelled with and without antisite defects using the Calphad approach. 46-53. 2006. Chen. R. 2006. Yokokawa. Deller. pp. Dokiya. Foger.K. Chem. Inorg. K. B. 771-774. pp.). B- Stru. 27(4). 1969. M. 2. accepted 6. A. Demina. Zinkevich. 353-62.D. 3. A. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.
1998. 23. Boroomand. 1989. 59-65. Ceram. Defect formation and mechanical stability of perovskites based on LaCrO3 for solid oxide fuel cells (SOFC). 2004. pp. 1984. Alario-Franco. T. A.. 15. 194. 2005.W. Hartl. H. 19.K. pp. 21. Mizusaki. 1978. The mobility of oxygen ions in CaF2. Navrotsky. Braungart. 401-12. Kaimai. M. Steinbrech. B.T. 33. Matsumoto. E. S. Hilpert. 129-36. Naturforsch. R. A. pp. 143. 300920.M. Mater. 119-24. K.H. K. Solid State Chem.G. a hightemperature compound with defect-bariumphosphate-structure. D. A. B. Azad.V. E. K. Hilpert. Sudha. 20.M. pp. Hilpert. 18. 177.67Va0.. F. 123. Solid State Sci. T. Thermochim. Teller.. Energetics of La1-xAxCrO3-δ perovskites (A = Ca or Sr). J. O. F. Sr2. A. R. J. Ishikawa. 39. The standard Gibbs energies of formation of ACrO4 (A=Ca. 1990. Meschke. K. 1158-61. 9. 1969. A. 2003. Sr or Ba) from emf-measurements. Roth.33(CrO4)1. Onuma. 4112-. 952-953 (in German). H. R. VI). Miller. Kisil. S. 1992. 145 .67. pp. Jacob. Fueki. Castillo-Martínez. 22. 16. Peck. 23. Standard Gibbs energies of formation of SrCrO4 and Sr3Cr2O8. pp. 2007. T.. Akila and K.Thermodynamic assessments 12.. Singheiser. pp. Jim. J. 234-44. 20. Phase formation in the system SrO-CrO3-Cr2O3. Solid State Chem. Kawada.33(CrO4)0. Peck. Ch. Solid State Ionics. Solid State Ionics. Y. J. Nickel. Europ.. Z.-H. 2001. M.. H. J. 1999. Sharova. Inoue. Nonstoichiometry of the perovskitetype oxide La1-xSrxCrO3-δ. L. Slobodin.S. R. Electrochem. pp. J. 431-42. 178. T. 17. S. Inorg. Res. Miller. Revisiting the Sr-Cr(IV)-O system at high pressure and temperature with special reference to Sr3Cr2O7. Negas. NBS A Phys. Strontiumchromate(V. N. 564-73. Cheng.A. J. R. 12. 13. K. 25. 73A. 1490-91. 24. K. pp. Acta. D. Solid State Ionics. Phase diagram studies in the SrO-Cr2O3-La2O3 system in air and under low oxygen pressure. Myoshi. System SrO-chromium oxide in air and oxygen. pp. Pt. Appl. pp. O. Mater. J. Sreedharan. Soc. Yokokawa. Yamauchi. 294-300. pp. Vaporization and thermodynamics of La1-xSrxCrO3-δ investigated by Knudsen effusion mass spectrometry.. Maruyama. pp. 14. M. Zuev. Wessel. T. Akashi. T. Yashiro. Mizusaki.
T. N. 28. D. Morii. Yokokawa. Shimojo. Greaves. T. Magnetic and neutron diffraction study on perovskites La1-xSrxCrO3. 404-10. Hashimoto.E. Sato. S.. T. Yusuf. Cabeza.S. A.G. H. Y. Matsunaga. K. Chiba.A. Mat. Y. 222-29. 0.R. Muirhead. Structural studies of (La. Sakai.Sr)CrO3 system. C. H. Solid State Ionics. Takahashi. T. Thermodynamic considerations on Cr poisoning in SOFC cathodes.. R. V. Arai. H. 145. xSrxCrO3 Analysis of magnetic and structural phase transition behaviors of La1- for preparation of phase diagram. J. Evolution of crystal structure with the oxygen content in the LaMn0. Matter.A. Res.. C. Ohba. 1998.R. 170. 34. pp. Ramanadham. Solid State Chem. Takahashi. 18. P. Francesconi. 176. L. K. Morii. Matter.Thermodynamic assessments 25. Tao.1O3+δ (3. Phys. A. Studies on magnetic properties of La0. Y.13. H. Power Sources. 57-. 2000. Hinatsu. M. Komatsu. Tyagi. J. 177. Phys. 8661-72. Matsubara. 26. Cox. 474. Caneiro.15). Brito. Magnetization and resistivity in chromium doped manganites. 2003. Y. 2569-78. Horita. Chakraborty. J. H. Hashimoto. H.M. 27. Solid State Comm. Y. Solid State Ionics. 463-71.5Mn0. pp. 4151-60. 12. K. S.25CrO3 at high temperatures.85Sr0. K. Pomjakushin. 32. K.9Cr0. 141.75Sr0. 2008. 11. Connor. 1977. Khattak. Nakamura. J. M.5O3±δ. Bull. Tezuka. Electronic transport in the novel SOFC anode material La1-xSrxCr0.05CrO3 and La0. C. P. Acta. 435. Y. 30. S. O. Morales. T. Y.95Sr0.15CrO3 by means of powder neutron diffraction. 2008. Kishimoto. J. J. K. Oikawa. Inami. Xiong. pp. M. Yamaji. 1999. H. pp.T. Structural study of La0. Kawaji. 132-. 35. Solid State Chem.K. Nakamura. Y. Acta. Matsunaga. Hinatsu. Irvine.M. 12. F. Tezuka. Nakamura. 2006. M. H. Shimojo. Plint. 2005-08. pp. Thermochim. 33. Matter. 29.S. 404-10. N. Bari. pp.: Condens. Analysis of relationship between magnetic property and crystal structure of La1-xSrxCrO3 (x=0. Arai. Atake. 2006. Phys. A. 2008.E. Takahashi. J. 146 . Y.. 2005. T. Y. Thermochim.-P.: Condens. Long.M.P. 502-06. T. F. K. 31. 177. 2006. pp. M.: Condens.12) compound. 3193-98. Hashimoto. Krishna.00 ≤ 3+δ ≤ 3. 36. Matsunaga. pp.
Calphad. Kallel. 46. Soc. Ghedira. 320. P. SGTE data for pure elements. B. Alloy Compd. Hrovat. Preliminary data on solid solubility between LaCrO3 and LaFeO3 or LaMnO3. M. I. H. Vincent. 1985. Dhahri.25) using the Rietveld method of analysis. pp. A. 42. Cmpd. Mater. Nordblad. Howard. Effect of Cr doping in La0.-K.3Mn1-xCrxO3 with 0 ≤ x ≤ 0. 20. D.A. Lett. 2008. 2(3). D. Gauckler.7Sr0. Sci.. Rundlöf. Anderson.U. 319-25. Chen. 317-425. Sapiña. 40. L. J. Dhahri. Am.. 1991. Synthesis. E. 47. R. J. Ceram. 66(10). 1978. pp. 2005. Beltrán. F. 9. D. J. Holc. B. Zemni. Sundman. Hallstedt. J. Diff. Martinez. 437-43. A. J. F. (a).R. S. Phase Equilib. 16. J. Gauckler. J. 0. 153-90. E. J. N. A model of alloying effects in ferromagnetic metals. M. El-Fadli.. Tellgren. pp. Risold. 2000. 353-61. B. B. Phys.2. X-ray-powder diffraction structural phasetransition study of La(Cr1-xMnx)O3 (x=0 to 0. and magnetic properties of LaCr1-yMnyO3 (y=0. Kuscer. 2001. Stat.N. 457. Andersson. Jansson. 26. Inden.J. pp. 1685-87. M. J. 1975. Metni. 0.Thermodynamic assessments 37. Chem. G. Folgado. H. L. pp. Determination of chemical and magnetic interchange energies in bcc alloys. Dinsdale. 161-76. Mater. M. 577-82. The thermo-calc databank system. Jarl. Z. 532-40. M. Oumezzine. 1992. A.-O. 10. The strontium-oxygen system. Tseggai. 131-51 147 . 227-38. 39.. Metallkd. G. Bourèe. Alloy. 45.J. Calphad. Calphad. 15(4). M. Calphad. Beltrán. H.. pp. Kolar. 75. Andrè. Hallstedt. S. 1996. S. Hillert.1.V. Assessment of the La-Mn-O system. Z. 38..5. pp. Bernik. Hillert and M. and 0. Sol. 143-46. 44. 48. nuclear structure. D. The compound energy formalism. Structural effects of Co and Cr substitution in LaMnO3+δ.T. 43. 1997. J. 184. Yau. General treatment.. Grundy. 41. 2001. pp.3). M. M. J. pp.
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.J. 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. Proper strategies to prevent the problem of chromium “poisoning” are proposed.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. 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. Chen. 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. the deterioration of the cell performance is expected to be less pronounced when the cell is operated at lower temperatures and current loads. whereas Cr2O3 is metastable. 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. Gauckler. T. Even though the chromium problem cannot be solved satisfactorily by varying the cathode composition or the SOFC operating conditions. and L. This has consequences for the electrochemical properties of the cell: the electronic conductivity of the cathode will decrease. M. 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. The spinel formation goes along with increasing Mn2+ in LSM under decreasing oxygen partial pressures. 148 . Ivas. Povoden.
thermal stability. and -diffusion process. 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]. 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. as well as low fabrication costs. Consequently Cr-Mn spinel and Cr2O3(s) would form. 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. Ad 1) In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary. mechanical strength. The chemical dissociation approach is coherently based on the interpretation of a large number of impedance spectra. where they cause the degradation of the cell by detrimentally affecting the O2adsorbtion. though partly with conflicting results. Consequences of Cr poisoning have been investigated specifically in (La1-xSrx)MnO3-δ (LSM) perovskite-structured cathodes. -reduction. 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. On the other hand the electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach. 149 . electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. This reduction reaction would compete with the oxygen reduction and lead to blocking of the active sites at the triple phase boundary (TPB). good electronic and negligible ionic conductivity. 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.1 Introduction Chromium-containing metallic interconnects are commonly used in planar-design solid oxide fuel cells (SOFC) due to their high oxidation resistance. where the reaction partners for the reduction. and no Cr2O3(s) is formed. 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.Thermodynamic calculations of impacts of Cr on LSM cathodes 5. associated to these nuclei.
Thermodynamic calculations of impacts of Cr on LSM cathodes
In the critical assessment in chapter 1.3.6 it was concluded that doubtless reasons to reject the reduction approach do not exist. One critical point concerns the extension of dense Cr2O3layers into the YSZ electrolyte: this phenomenon can be explained best by continuous feeding of an initial Cr2O3-layer with CrO3(g), the latter becoming reduced at a new TPB consisting of YSZ and electron-donating Cr2O3(s). On the other hand this process cannot be explained satisfactorily by using the chemical dissociation approach. Even though particularly the early stages of chromium “poisoning” occur in thermodynamic non-equilibrium, the system SOFC develops towards thermodynamic equilibrium by time. This is reflected by a flattening of the curves that reflect the performance deterioration as a function of time, such as the curves of voltage drop and overpotential loss. Thus thermodynamic calculations allow interpretations of the phase equilibria that result from the interactions between LSM and chromium, as well as changes of the phase chemistry that are associated with the chromium contamination of LSM cathodes.
The La-Sr-Mn-Cr-O oxide database is used for the following thermodynamic calculations: phase equilibria in Cr-contaminated LSM (in the following denoted as LSM(Cr)), phase compositions of LSM(Cr) and Cr-Mn spinel, defect concentrations of LSM(Cr), as well as driving forces for the formation of Cr2O3 were calculated with the poly-module of the ThermoCalc software. The following model descriptions were used: for the Cr-contaminated cathode perovskite with the
2+ 4+ 3+
sublattice for cubic
(La ,Sr ,Va)(Mn ,Mn ,Mn ,Cr ,Cr ,Va)(O ,Va)3, for tetragonally distorted spinel (Mn2+)(Mn3+,Cr3+)2(O2-)4 was chosen, (Mn2+,Cr2+)(Mn3+,Cr3+)2(O2-)4 was used, and for Cr2O3 (Cr2+,Cr3+)2(Cr3+,Va)(O2-)3 was taken. Uptake of Cr in LSM is expected, as a complete solid solubility of Cr in LSM has been shown experimentally. For proper thermodynamic calculations of phase equilibria thermodynamic conditions need to be set that reflect the conditions of the chromium contamination of SOFC: the bulk pressure (room pressure, 101325 Pa), the operation temperature (typically from T = 1073 K to 1273 K), the oxygen partial pressure, the cathode composition, and the amount of chromium.
Thermodynamic calculations of impacts of Cr on LSM cathodes
The oxygen partial pressure at the interconnect-cathode interface is air. Under current load it is expected that the oxygen partial pressure will strongly decrease close to the cathodeelectrolyte interface in the triple phase boundary (TPB) region where the oxygen reduction in LSM takes place: the oxygen partial pressure at the cathode-electrolyte interface, pO2(i) can be approximated from the measured cell voltage of a Pt/LSM/YSZ/Ni-Cermet/Pt solid oxide cell and the fuel composition by using the equation for the overall electromotive force E of the cell:
pO RT 2(i) ln 4 F pO
R = 8.31451 J mol-1 K-1, F = 96485.309 C mol-1 and pO2(an) is given by the ratio of H2-H2O in
the fuel. From a measured cell voltage of 0.7 V at T = 1173 K (fuel: 97 vol.% H2, 3 vol.% H2O) and a high current load of 300 mA cm-2 a strong decrease of the oxygen partial pressure at the oxygen reduction sites is expected, pO2(i) ≈ 0.01 Pa. As we are interested in the influences of chromium throughout a cathode under realistic operation conditions of SOFC, results of the thermodynamic calculations are presented for pO ≤ 21278 Pa ≥ 0.01 Pa.
Several LSM cathode compositions can be found in the literature. Part of them is cation stoichiometric, and part of them has excess Mn that is known to prevent unwanted formation of electrochemically isolating zirconate at the cathode/electrolyte interface. In this study two cathode compositions are used for the thermodynamic calculations: La0.9Sr0.1MnO3-δ and (La0.8Sr0.2)0.9MnO3-δ. The sublattice model for this perovskite phase allows the formation of vacancies on each site and changing valencies of Mn as a function of temperature and oxygen partial pressure. The amount of chromium in the system is defined by the partial pressure of the Cr-gas phase:
⎛ μ Cr ⎞ ⎟ ⎝ RT ⎠
pCr = exp ⎜
This means that by knowing the partial pressure of the Cr-gas phase in the TPB region, it is possible to calculate the thermodynamics of the chromium contamination. The problem is that the definite amount of gas that contributes to the degradation phenomena is not known
Thermodynamic calculations of impacts of Cr on LSM cathodes
exactly, as only a fraction of the Cr-gas that evaporates from the Cr2O3 scale on the Cr-alloy interconnect interacts with LSM or is reduced. Fortunately the amount of deposited Cr in a degraded LSM cathode has been analyzed as a function of distance from the cathode/YSZ electrolyte interface, and the combined data of X(Cr) and the oxygen partial pressure at the TPB fix the chemical potential of Cr. The amount of deposited Cr close to the LSM(Cr)/YSZ interface was about 3 wt.% after a long cell test of 300 h at T = 1073 K. If one assumes that the pO2 under the test conditions was 1 Pa at the the LSM(Cr)/YSZ interface (normal cell performance), the chemical potential of the Cr-gas phase can be calculated. Even though it is clear that the chemical potential of Cr will change if the amount of evaporated Cr from different interconnect materials is different, the Cr-gas reservoir is assumed to be in a saturated state due to “unlimited” supply from the interconnect during the cell performance, and thus its chemical potential is fixed in the thermodynamic calculations. This simplification is reasonable, as in all investigated cell tests with LSM and Cr-alloy interconnects the degradation was similar, so that changing chromium amounts due to different interconnect alloys are obviously not detrimental for the cell degradation. H2O (operation of SOFC in humid air) is not considered in the calculations, as neither hydroxides nor solubilities of hydrogen or OH− were included in the La-Sr-Mn-Cr-O oxide database.
Thermodynamic calulcations of La0.9Sr0.1MnO3 contaminated by chromium
Fig. 5.3.1 (next page) shows phase fractions in Cr-“poisoned” La0.9Sr0.1MnO3-δ at constant chemical potential of CrO3, μ(CrO3) = −300000 J mol-1 referred to 100000 Pa of CrO3(g) as a function of oxygen partial pressure at T = 1273 K and 1073 K, and in Figs. 5.3.2 (next page) and 5.3.3 (p. 153) phase equilibria are indicated: the cathode remains single phase at pO2 > 102.75 Pa. By decreasing the oxygen partial pressure, tetragonally distorted Mn3O4 spinel (t-sp), the manganese endmember of the Cr-Mn spinel solid solution phase forms.
1MnO3-δ as a function of oxygen partial pressure at T=1273 K and 1073 K at μ(CrO3) = −300000 J mol-1 Fig. Vertical lines indicate boundaries between different phase equilibria 153 .3. B. and C denote sublattices of the perovskite phase.1MnO3-δ and defect concentrations of La0.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.2 Phase equilibria in Cr-“poisoned” La0.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1. A.9Sr0. 5.1(Mn. 5.9Sr0. with A and B standing for the cation sublattices and C standing for the oxygen sublattice.3.1 phase fractions in Cr-“poisoned” La0.9Sr0.
Thermodynamic calculations of impacts of Cr on LSM cathodes
Fig. 5.3.3 Phase equilibria in Cr-“poisoned” La0.9Sr0.1MnO3-δ and defect concentrations of
La0.9Sr0.1(Mn,Cr)O3-δ as a function of oxygen partial pressure at T = 1073 K and
μ(CrO3)= −300000 J mol-1. The vertical line indicates the boundary between phase equilibria
At T = 1273 K (Figs. 5.3.1, p. 153 and 5.3.2, p. 153), tetragonally distorted spinel remains stable to pO2 = 10-0.4 Pa. At lower pO2 cubic Mn-Cr spinel forms. At 1073 K (Figs. 5.3.1, p. 152 and 5.3.3), tetragonally distorted spinel remains stable to pO2 = 100.75 Pa, followed by the formation of cubic spinel at lower pO2 . This means that by decreasing the oxygen partial pressure from pO2 = 104.3, the pressure of air, to 10-1.5 Pa, the amount of spinel in the contaminated cell increases. At 1073 K Cr-Mn spinel formation is less pronounced, and CrMn spinel formation starts at lower pO2 than at 1273 K. To find out about the structural chemical changes in the cathode perovskite caused by reaction with chromium, the fractions of species in a specific sublattice (site fractions) are calculated at
T=1273 K and 1073 K (plots in Figs. 5.3.2, p. 152 and 5.3.3) as a function of pO2 The results .
are compared with the calculated site fractions in a cathode with a very small chemical
Thermodynamic calculations of impacts of Cr on LSM cathodes
potential of Cr, μ(CrO3) = −106 J mol-1 that means with practically no Cr (Figs. 5.3.4 to 5.3.5).
Fig. 5.3.4 Defect concentrations in La0.9Sr0.1MnO3-δ
as a function of oxygen partial pressure at T=1273 K.
Fig. 5.3.5 Defect concentrations in La0.9Sr0.1MnO3-δ
as a function of oxygen partial pressure at T = 1073 K. 155
Thermodynamic calculations of impacts of Cr on LSM cathodes
In general defect concentrations of the Cr-contaminated LSM differ from the defect concentrations in LSM without Cr at a high temperature of 1273 K: with Cr the concentrations of vacancies on the A- and B-sublattices decrease stronger by decreasing the oxygen partial pressure. The increase of oxygen vacancies by decreasing the oxygen partial pressure on the other hand is weaker when chromium is present. At T = 1273 K and pO2 = 1 Pa, which is the expected pO2 at the LSM/YSZ interface at 250 mA cm-2 current load, the site fractions of cation vacancies on the A- and B-sublattices for LSM(Cr) are y(Va)A = 1.98x10-6, y(Va)B=4.3x10-6, whereas in LSM y(Va)A = 3.086x10-6 and y(Va)B = 7.096x10-6 are calculated. The concentration of oxygen vacancies at 1 Pa and T = 1273 K in LSM(Cr) is slightly higher than in LSM, y(Va)C = 3.01x10-5 in LSM(Cr),compared to y(Va)C = 2.57x10-5 in LSM. A pronounced drop of cation and oxygen vacancies is calculated at 1273 K and pO2 = 10-1 Pa, the expected oxygen partial pressure at the TPB under a high current load of 300 mA cm-2: the concentration of oxygen vacancies in LSM(Cr) is y(Va)C = 3.39x10-5, compared to
y(Va)C = 9.48x10-5 in LSM. This means that if the oxygen partial pressure at the LSM/YSZ
interface strongly decreases the vacancy concentrations will drop significantly. The concentrations of Cr3+ and Cr4+ in LSM(Cr) increase when the temperature increases and the oxygen partial pressure decreases. The calculated compositions of tetragonally distorted spinel (Fig. 5.3.6 a, next page) and cubic spinel (Fig. 5.3.6 b) formed during chromium “poisoning” show a strong dependence upon the oxygen partial pressure: only under low oxygen partial pressures a significant amount of chromium is found in the spinel phase, whereas at higher oxygen partial pressures the spinel phase has a composition close to Mn3O4. At T = 1073 K the spinel phase contains less chromium than at T = 1273 K.
3.3.8Sr0.2 Thermodynamic calculations of (La0.3.9MnO3-δ contaminated by chromium From Fig. tetragonally distorted Mn3O4 (t-sp) is expected to form. Fig.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.7 phase fractions in Cr-“poisoned” (La0.9MnO3-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. 5.6 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. 5.8Sr0.2)0. 5.2)0. At T = 1073 K Mn2O3 is stable in a Cr-contaminated LSM cathode with excess Mn in air.3.
2)0. In general.Thermodynamic calculations of impacts of Cr on LSM cathodes In Fig.3. 5.8 the compositional changes of cubic spinel are plotted as a function of oxygen partial pressure at T = 1273 K. as in the case of cation-stoichiometric LSM. 158 . Fig.9 (next page).9MnO3-δ cathode are shown in Fig. the compositions of the spinel phases formed during chromium “poisoning” become richer in Cr under more reducing conditions.8Sr0. 5.8 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 (La0.3. 5.3.
5. In LSM(Cr) the concentrations of these cation vacancies drop strongly at low pO2 .8Sr0.10) and without Cr (solid lines in Fig. 5.3.8Sr0. Mn2+ is higher in LSM(Cr) than in LSM at higher pO2 .Cr)O3-δ and defect concentrations in (La0. 159 .2)0.9(Mn. 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.3.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 and μ(CrO3) = −300000 J mol-1.8Sr0.9 Phase equilibria in Cr-“poisoned” (La0. The vertical line indicates the boundary between different phase equilibria Fig.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.3. 5.9(Mn.10) at 1273 K.2)0. and the concentration of oxygen vacancies is lower in LSM(Cr) than in LSM at relatively high and low pO2 .2)0.3. 5.10 (next page) is a comparison of defect concentrations of (La0.9MnO3-δ with Cr (broken lines in Fig.
10 Defect concentrations in (La0.Cr)O3-δ (dashed lines) and (La0.148Mn0.8Sr0.11.3.1. 5. next page.3. Table 5.9(Mn.2)0. as it is illustrated in Fig.9MnO3-δ (solid lines) as a function of oxygen partial pressure at T = 1273. Calculated concentrations of all species in LSM(Cr) and tetragonally distorted spinel in equilibrium are listed in Table 5.1 Pa.8Sr0. 5.1 Compositions of LSM(Cr) and spinel in equilibrium at different T at pO2=1 Pa with and without Cr.871Sr0.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.3. 5.947O3-δ spinel formation becomes important only at pO2 < 0.2)0. 160 .3.3.3 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.
5.11 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-1.2)0.8Sr0.871Sr0.8Sr0.3. and the concentration of oxygen vacancies is almost an order of magnitude lower then in (La0. 5.Cr)0.9MnO3-δ at pO2 = 10-1 Pa.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.12.9MnO3-δ at high oxygen partial pressures. y(Va)C even decrease slightly towards lower pO2 . after reaching a plateau at pO2 = 103 Pa.3. The influence of chromium on defect concentrations in La0. However.2)0.947O3-δ is illustrated in Fig.Cr)0. next page: The concentration of oxygen vacancies in La0.148(Mn.871Sr0. 161 .148(Mn.947O3-δ is half of an order of magnitude higher than in (La0.
If the driving force is 0. The more negative the driving force. In Fig.3. the phase is thermodynamically stable. 5. One can get an idea about the degree of metastability of a phase by calculating its thermodynamic driving force.947O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1 (solid lines).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”.148(Mn. Dashed lines indicate the defect concentrations in (La0.2)0. and thus its formation is kinetically controlled. Vertical lines indicate boundaries between different phase equilibria 5. 162 .12 Phase equilibria in Cr-“poisoned” Mn-deficient LSM and defect concentrations in La0.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.3.4 Formation of Cr2O3 This phase was not found in the thermodynamic calculations.871Sr0. 5. This is the amount of energy that is needed to bring the phase to its stable state.8Sr0.Cr)0. the more energy is needed to stabilize the phase.9MnO3 without chromium. and the driving force for the formation of the phase is low.3.
Thermodynamic calculations of impacts of Cr on LSM cathodes
Fig. 5.3.13 Driving force of Cr2O3 as a function of temperature
at different pO2 at μ(CrO3) = −300000 J mol-1. The driving force for the formation of Cr2O3 is less negative at higher oxygen partial pressures.
In the following the results of the thermodynamic calculations are compared to experimental findings on chromium poisoning from the literature. Interpretations are given, which of the chromium poisoning mechanisms occur under thermodynamic control. By carrying out equilibrium calculations of state-of-the-art LSM cathodes with the compositions La0.9Sr0.1MnO3-δ and (La0.8Sr0.2)0.9MnO3-δ at constant chromium in the gas phase it was tested if spinel formation would be favored thermodynamically under low oxygen partial pressure, i.e. close to the electrode-electrolyte interface under polarization conditions. The calculations showed that this is indeed the case. As the A-sublattice of the spinel is completely filled by Mn2+ under the cell operation conditions, and the only source for this species is LSM, it is obvious that spinel formation will be associated with increasing Mn2+ in LSM. Thus, as Mn2+ in LSM increases as a function of decreasing pO2 , also the amount of
Thermodynamic calculations of impacts of Cr on LSM cathodes
spinel formed is higher at low oxygen partial pressure. Cr-gas reveals increasing affinity to LSM towards the electrode-electrolyte interface: both Cr solid solution in LSM and spinel formation increase under decreasing the oxygen partial pressure. From the calculation it is interpreted that the spinel phase that forms under Cr-“poisoning” of the cathode will contain a high amount of Mn, if the oxygen partial pressure at the cathode/electrolyte interface is about 1 Pa. Only at lower pO2 significant Cr is incorporated in the spinel phase, with the stoichiometric MnCr2O4 phase forming at about pO2 = 10-1 Pa. Though spinel formation is thermodynamically driven in Cr-contaminated SOFC, it seems that spinel formation per se is not one of the keys of severe cell degradation due to chromium, but the affinity of Cr-gas to the LSM surface, as even very small Cr contamination in the ppm range apparently leads to a dramatic decrease of the oxygen diffusion in LSM. From impedance spectroscopy analyses it was consistently concluded that the oxygen diffusion is severely influenced by chromium. The thermodynamic calculations showed that Cr interacting with LSM leads to a change of the defect chemistry of the perovskite phase, and particularly to a decreasing amount of oxygen vacancies at high temperatures and low oxygen partial pressures. As the formation of oxygen vacancies in LSM is inhibited, oxygen diffusion to the triple phase boundary is retarded. The results of the thermodynamic defect chemistry calculations of LSM(Cr) thus indicate that the deterioration of the oxygen diffusion is higher under at decreased oxygen partial pressures reflecting high current loads. Cr2O3 is found in degraded SOFC, particularly under high current load. However this phase was not found in the thermodynamic calculations, and its driving force remains negative under SOFC operating conditions. This means that its formation is kinetically controlled. Even though Cr2O3 is not a thermodynamically stable phase in Cr-contaminated SOFC, a strong tendency exists for CrO3(g) to be reduced to Cr2O3(s) at the TPB, as the reduction reaction has a large negative ΔG. It was also mentioned earlier that a high tendency for the precipitation of Cr2O3(s) from CrO3(g) exists. In addition to the adsorption process it is expected that a great many of Cr-gas molecules are driven further to the energy valley for their reduction, namely the TPB. Thus it is non-contradictory that coupling of Cr-gas to LSM and subsequent spinel formation at the LSM surface, and the reduction of CrO3 (g) at the TPB leading to the metastable reduction product Cr2O3(s) occur simultaneously. An alternative way to form Cr2O3 was discussed by Konysheva et al.: The kinetic decomposition of the spinel phase may occur in an oxgen partial pressure gradient due to different mobilities of Mn2+ and Cr3+.
Thermodynamic calculations of impacts of Cr on LSM cathodes
In addition to the inhibiting of oxygen diffusion to the TPB and blocking of active triple phase boundary sites by the thermodynamically controlled formation of spinel and the kinetically driven formation of Cr2O3(s) and thus retarded diffusion of oxygen ions into the electrolyte, further unwanted consequences of chromium poisoning can be ascribed to the low electrical conductivity of Cr2O3. Also Cr-Mn-spinel and Cr-doped LSM are significantly less conductive than pure LSM[26-29]. The electrical conductivity of Cr-Mn spinel decreases as its Cr-content increases. From the thermodynamic calculations it can be predicted that increasing the current load will lead to the formation of a spinel phase with a low electrical conductivity. The ohmic resistance of spinel will also increase due to more Cr dissolved in spinel as the amount of deposits of chromium in the cathode increases as a function of time. Furthermore it is expected that the electrical conductivity of LSM is influenced by chromium particularly under high current loads, as chromium leads to decreased concentrations of cation and oxygen vacancies in LSM(Cr) relative to LSM under such operating conditions of SOFC.
Thermodynamic calculations of LSM contaminated by chromium showed that the formation of spinel is thermodynamically driven, whereas Cr2O3 is a metastable phase that forms under kinetic control in degraded SOFC. The formation of spinel is favored under low oxygen partial pressures, thus in an SOFC under current load this phase is found predominantly at the LSM/YSZ interface. The interaction between chromium and LSM leads to changes of the defect chemistry of the LSM perovskite phase. Particularly diminished concentration of oxygen vacancies relative to LSM without chromium may be a reason for the inhibited oxygen diffusion in degraded SOFC at high temperatures and high current loads . This is also true for Mn-deficient LSM compositions, though the formation of spinel can be restricted to lower oxygen partial pressures. Its defect chemistry is particularly problematic at low oxygen partial pressures, the concentration of oxygen vacancies being strongly diminished relative to LSM with excess Mn. Anyway the use of a Mn-deficient LSM cathode for SOFC is not recommended due to the formation of electrically isolating zirconate.
M. Kawamura. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator. K. J. J. 271-278. Electrochem. Advances.P. 284-93. pp. Stimming. J. Jiang. pp. Mechanisms and kinetics. 127. S. pp.P. 7. 132. 5. 2004.. 1995. 2. Thus it is expected that in this case the consequences of Crpoisoning will persist particularly at high current loads. Kadowaki. pp. Matsuzaki. interaction between Mn from LSM with Cr may be cumbered by proper doping of the perovskite with further B-site cations. Solid State Ionics. L. pp. H.C. 2001. J. 3. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. J. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. Y. 2004. Y. Electrochem. V. 2000. Furthermore.P. Yasuda. Soc. S. Chromium poisoning of LSM-YSZ SOFC cathodes.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. Power Sources. 3195-3205. U. 1997. Matsuzaki. Electrochem. Power Sources. Birss. A126-31. K. Saitoh. Deller. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells I. 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. Yasuda. Taniguchi. Apateanu. References 1. aging mechanisms and lifetime in solid-oxide fuel cells.. Tu. 99. I. Y. T. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes. J. I. 166 .P. Ramprakash. A1961-68. 4. 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. 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. S. Soc. Foger. Yasuo. 73-9. H.I. R. Foger. Badwal. Solid State Ionics. Zhang.. Y. 148. 55. J. 6.S. Paulson. 2000. S. T. Akiyama. pp. Miyake. 297-310. Zhang. pp. 151(11). Y. Soc. 147(9).
pp. J. J. 17. 97. Y. J. Jiang.. Diff. 19. E.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. Power Sources.J. Calphad. Foger..A. 52. Res. Cohen. J. Characterization and performance of (La. Int. 771-774. Li. pp. Jiang. 3664-71. Gauckler.. pp. Electrochem. Ceam. J. E. Petrov. Calphad. Filonova... B. J. A. 13. Y. 1985. Applied Electrochem. Fergus. 21. L. Sundman.D. 10. Grundy. The volatilization of chromium oxide. Grundy. 167 . J. 9. M. I. 4013-22. 695-703. X. Inorg. Mechanisms and kinetics. 191-201. Chem. pp. 12. Povoden. 153-190. pp. J. J. E. Y. Europ. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. S.Ba)(Co. J. J. S. L. pp. 147. 18. 438-442. 162. Mater. 2006. Jiang. 353-62. 16. Jansson. 31. L. J. 27. Jiang. Jiang.Sr)(Co. 2001. Grundy. 1-22. S. Povoden. Electrochem.P. 180.Thermodynamic calculations of impacts of Cr on LSM cathodes 8. Solid State Ionics. Soc. Apateanu.N.. A. 15. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Gauckler. S. 20. Wu.P. FY Annual report. 32. S. 11. 23. L.Sr)MnO3 and (La. Use of gaseous Cr species to diagnose surface and bulk process for O2reduction in solid oxide fuel cells. comm. Zhen. Int. 146.J.D. J.G.P. B. 1043-1052. Soc. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. Phase Equilib. Krumpelt et al.P.N. Zhang.P. Zhang. Russ. D. 22. pp. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. Zhang.P.W. 39-43. Zheng and P. S.P. pp. 2000. 2007. B (119) (2005) 80-86. pp. 22. Hydrogen Energy. 2002.J. 1961. pp. 28. 2008. 9.-O. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Demina. Jiang. A comparison of O2 reduction reactions on porous (La. Power Sources.N. 56978. pp. 2004.N. A.Fe)O3 electrodes. 2002. K. The Thermo-Calc databank system. A. Sci. Jiang. Assessment of the La-Sr-Mn-O system. Mater. Andersson. S.N. B. pp. J. Hallstedt. 14. 2007. 2004. Eng. A. Gauckler. Zhen.. Soc. Zheng. 181-192. 2006. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. J. 361-73. J. Zhen. 2006. Caplan and M.P.P. 4th international symposium on solid oxide fuel cells and pers. S. pp. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells.. pp. 108.
J. T.. 27.B. E. E. pp. 1212-16. Hill. pp. B1252-B64. H. Pennington. W. Hammou. 2006. Kleitz. J.E. M. R.M. pp. Konysheva. Siebert. Brito. p. 154 (12). H.Thermodynamic calculations of impacts of Cr on LSM cathodes 24. 29.. 168 . N. in SOFC-1. Singheiser. K. H. Kishimoto. 26. S.U. Koc. Howard. 220. pp. O. 681-686. Solid State Ionics. A. Phillips. 1991. L. A. Soc. Y. Caneiro. The Electrochemical Society Proceedings Series.P. Ivey. Effect of cathode thickness and current density. NJ (1995). Yamamoto. Singhal. 114-24. NJ (1989).. A.A. Hammouche. Soc. Xiong. Singhal. Chromium poisoning of the porous composite cathode. S. Power sources. 153.C. Yamaji. Maruyama. Structure and transport property of manganese-chromium-iron oxide as main compound in oxide scales of alloy interconnects for SOFCs.M. M. N. Anderson. PV 89-11. Qu. 25. J.G. J. Horita. Eds. 2005. Tagawa. 2007. J. 138. D.C. in SOFC-IV. Hilpert. Ed. Sammes. 472. Yokokawa. 176. Jian. Electrochem. K. M. Pennington. Mertens. Penkalla. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. M. H. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. L. Sakai. Dokiya. T. H. The Electrochemical Society Proceedings Series. Electrochem. p.. 28. S. PV 95-01.
284604*T-26.908*t*LN(T)+0.403+120.004045175*T**2 -5.. fcc ENTER-SYMBO FUNCTION GLAFCC 298. Dinsdale 1991 @@ La. bcc ENTER-SYMBO FUNCTION GLABCC 298.3891E+02 5.1996E+01 2.0*T*LN(T)-2.3088*T*LN(T).894+218.988+174.06113*T-17.94+157.00189435*T**2 -1.15 -3952.34*T*LN(T)-. 4000 N @@ Cr. Dinsdale 1991 @@ La.413+59.344+344.008371705*T**2 +6.7919*T*LN(T)-0.88526E+32*T**(-9).1659411*T*LN(T)-.25865E-07*T**3.91+1123.072353*T-21.053968535*T**2 -4. 2180 Y -34869. @@ ---------------------------------------------------------@@ Functions @@ ---------------------------------------------------------@@ Standard data for elements.413074*T*LN(T)+0. 1193 Y -136609. STATE ATOMIC MASS AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1. AMEND-ELEMENT VA VACUUM 0 H0 6.387295093*T**2 +4.440708*T*LN(T)-0.6902E+01. 2000 Y -15608.. 550 Y -3381.3088*T*LN(T). 800 Y +321682. 1134 Y -16377.492988*T-39. Povoden-Karadeniz 2008 @@ GO G ENTER-ELEMENT LA CR VA @@ELEMENT NAME REF.. double hcp ENTER-SYMBO FUNCTION GHSERLA 298. bcc ENTER-SYMBO FUNCTION GHSERCR 298.0500E+03 0 S0 0.15 -8856.5388*T*LN(T).882+181.673-3565.9547989E-05*T**3-36581228*T**(-1).15 -7968.390071*T-34.35429E+01.15 169 . 6000 N @@------------------------------------------------------------------@@ Solid metals.056395E-06*T**3+21167204*T**(-1).47721E-06*T**3+139250*T**(-1).Appendix Appendix La-Cr databasea) @@ Database La-Cr.001295165*T**2.08252*T+513.34397*T-163.48*T-26.161+88.8932E-07*T**3-399448*T**(-1).6651E+03 4.836315*T-34. AMEND-ELEMENT CR BCC_A2 5.18*T-50. 4000 N @@ La. 2000 Y -8205.
042032405*T**2 -3.47721E-06*T**3+139250*T**(-1)+2.797+89. 4000 N @@ ---------------------------------------------------------------------@@ Liquid metal functions. 2180 Y -16459.791973*T*LN(T)-0.0037094435*T**2 -2.00189435*T**2 -1.70261E-07*T**3+2891891*T**(-1). from SGTE @@ La(g) ENTER-SYMBO FUNCTION F12026T 298.908*T*LN(T)+.28626*T+17.37615E-21*T**7.5192158*T-21.0188191*T*LN(T)-0.15 +422273.1074654*T-19.059775*T-26. 1134 Y -124598.7643*T*LN(T)-.232-104.006002155*T**2 +1.843-369.36083*T*LN(T)+7.878761*T-21. 2000 Y -12599. 1100 Y +393886. 8200 Y -92343.653+18.403+41.2*T**(-1).69883E-07*T**3-1738066.5*T**(-1).020171603*T**2 +2.018431*T-34.015+146.3088*T*LN(T).61216717E-06*T**3+154422.016725*T-42.976+955.955-30.93775E-06*T**3-133541*T**(-1).386+178. 3200 Y +497751.17+114.96003*T*LN(T)+.54399*T-34. 1300 Y +404460.984+335. 4000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.004961847*T**2 -1.0188*T*LN(T)+0.0037862445*T**2 -2.5353212*T-40.06299*T*LN(T)-0.004045175*T**2 -5.85*T**(-1).71447833E-07*T**3+102710. from SGTE ENTER-SYMBOL FUNCTION F7763T 298.64743*T*LN(T)-.33826017E-06*T**3-312130.15 +390765.7919*T*LN(T)-0.4786162*T-13.085237*T+2.007085085*T**2 -4.878375*T-139. 600 Y +426628.338363*T-111. 6000 N @@-----------------------------------------------------------@@ Gas functions @@ La gas. 1400 Y +642608. 6000 N @@ Cr2 gas.207991*T-19.15*T**(-1).0441+773.25865E-07*T**3.3088*T*LN(T).928-44.066199E-06*T**3+20994153*T**(-1).747-246.83676*T*LN(T)-0.004+171.588679E-07*T**3+10285.616317*T-50*T*LN(T).23012*T-11. 1134 Y -3942.Appendix -6109.1*T**(-1).15 +5332.011938995*T**2 +1. 10000 N @@ Cr gas.346741*T*LN(T)+0.00406*T*LN(T)+0.02767321*T**2 170 . 800 Y +613345. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.3347881*T-22.253215E-04*T**2 -1.23648333E-07*T**3-722515*T**(-1).001513089*T**2 -4.82257667E-08*T**3+5.56798*T*LN(T)+.418475E+08*T**(-1).15 +598511.30043383E-07*T**3-34158815*T**(-1). from SGTE ENTER-SYMBO FUNCTION F7491T 298.15 +15483.005444405*T**2 +4.331-31.905-85.
...LA. set-interactive a) databases scripts can be used in Thermocalc with the extension ..tcm 171 ..CR2.. 2 1 1 LA...895+159. ENTER-PAR G(GAS..LA.135805E+08*T**(-1).0) 298. AMEND-PHASE LIQ COMP 2..0) 298..CR:VA...9699545E-04*T**2 +1.055+2598.97520167E-07*T**3+7.25559*T-334.004229401*T**2 +1.. 2 1 3 LA CR..CR:VA.51783483E-07*T**3+1...5 LA .CR:VA..CR:VA.0428*T*LN(T)+3...15 +GHSERLA.. ENTER-PAR L(LIQ.Appendix +1.... VA.0) 298.0) 298.0) 298.LA:VA..07969*T*LN(T)-.1) 298. VA.LA..15 +F12026T+RTLNP...15 +GLALIQ..0) 298.49*t. ENTER-PAR G(LADHCP. 6000 N @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Metals @@ La. VA.LA:VA.137623*T-105.... dhcp ENTER-PHASE LADHCP.15 +F7763T+RTLNP...0) 298.15 64573-23*t. ENTER-PAR G(LIQ.LA:VA.. ENTER-PAR G(GAS. @@-----------------------------------------------------------@@ Gas ENTER-PHASE GAS G 1 LA CR CR2. ENTER-PAR G(BCC. ENTER-PAR G(LAFCC. @@ ----------------------------------------------------------------@@ Alloys @@ BCC_A2 ALLOY ENTER-PHASE BCC.4843765E+08*T**(-1)..008.0) 298.LA:VA.0) 298..LA..4 ENTER-PAR TC(BCC.15 83500. 2300 Y +553119..CR:VA..15 +GLAFCC.0) 298. 3900 Y +347492..34+623.. N..CR:VA. @@ ------------------------------------------------------------------------@@ Liquid....CR:VA.0) 298. fcc ENTER-PHASE LAFCC..5.15 +GLABCC.15 -311. 2 1 0.5939925E-07*T**3+14793625*T**(-1).15 +GHSERCR...188555*T-52..15 60713-5...605906E-06*T**3-5831655*T**(-1). ENTER-PAR G(GAS. ENTER-PAR BMAGN(BCC..028597625*T**2 -4.. AMEND-PHASE-DESC BCC MAGN -1 0..15 +GCR_L.15 +F7491T+RTLNP.. @@ La.. ideal extension from lower-order systems ENTER-PHASE LIQ. 2 1 1 LA CR.. VA.CR.... @@ GO PAR SET-OUT-LEVEL....15 -0...7145*T*LN(T)+. @@ Interaction parameters from binaries ENTER-PAR L(LIQ...0) 298. ENTER-PAR L(BCC. ENTER-PAR G(BCC......0) 298.. ENTER-PAR G(LIQ. 5800 Y -484185.
as only few phase @@ diagram data exist! @@ -------------------------------------------------------------------GO G ENTER-ELEMENT LA SR MN CR O VA H @@ELEMENT NAME REF.6651E+03 5. AMEND-ELEMENT SR SR_FCC_A1 8..Appendix La-Sr-Mn-Cr-O-(H) oxide database @@ LA-SR-Mn-CR-O-(H) oxide.7620E+01 6..3891E+02 6. @@ @@ -------------------------------------------------------------------@@ 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 .6902E+01. AMEND-ELEMENT CR BCC_A2 5.5694E+01. AMEND-ELEMENT MN CBCC_A12 5. @@ Actual version: Dec2008 by Povoden-Karadeniz @@ @@ COMMENTS @@ @@ Sr-Cr-O liquid: simple description.9960E+03 3. associate at composition SrCrO4 can @@ help for better fit to experiments – future work @@ @@ No data exist for Sr-Mn-Cr-O. 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. AMEND-ELEMENT O 1/2_MOLE_O2(G) 1.1008E+01 0 0. AMEND-ELEMENT H 1/2_MOLE_H2(G) 0.5999E+01 4.2008E+01.) considered @@ @@ Quinary Ruddlesden popper phase is very tentative.... Povoden-Karadeniz @@ @@ Database La-Sr-Mn-Cr-O-(H).5680E+03 5. STATE ATOMIC MASS H0 S0 AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1..3410E+03 1. first version: Feb2006 by Povoden.4938E+01 4.0500E+03 2. AMEND-ELEMENT VA VACUUM 0 0 0.1996E+01 4.35429E+01..0252E+02.65340E+02.
3000 N @@ Mn.27966+130.00189435*T**2 -1.15 -3480.5028601*T-11.656847E30*T**(-9).872255-25.008371705*T**2 +6. 550 Y -3381.390071*T-34. 1000 Y 173 .8742*T**(-1).4582*T*LN(T)-0.15 -8856.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.47721E-06*T**3+139250*T**(-1).1355068*T*LN(T)-0.0*T*LN(T)-2.61225E-3*T**2 -1.18*T-50.3088*T*LN(T).196104*T-30.1*T**(-1). bcc ENTER-SYMBO FUNCTION GHSERCR 298.413+59.0905432*T*LN(T)-3.8932E-07*T**3-399448*T**(-1).001295165*T**2. 820 Y -13380.344+344. 6000 N @@ O1.908*t*LN(T)+0. cbcca12 ENTER-SYMBO FUNCTION GHSERMN 298.41+312. double hcp ENTER-SYMBO FUNCTION GHSERLA 298.005098873*T**2 +6.84189E-07*T**3+850134*T**(-1).905*T*LN(T)-4. (1/2 O2) ENTER-SYMBO FUNCTION GHSEROO 298.88526E+32*T**(-9).367+107.183879*T-23. 4000 N @@ Sr.34*T*LN(T)-. 2180 Y -34869.94+157.2648*T-48*T*LN(T)+1.284604*T-26.6184604E-07*T**3-38364.059572*T-23.403+120.15 -8115.00734768*T**2 +69827.67477E-07*T**3-2055*T**(-1).06113*T-17. 1519 Y -28733.15 -7968.48*T-26.1659411*T*LN(T)-.251266E-3*T**2 +1.102+153.882+181. Dinsdale 1991 @@ La.15 -7532. fcc ENTER-SYMBO FUNCTION GHSERSR 298. 2000 N @@ Cr. 2000 Y -15608.
52766201E+01*T*LN(T) -7.66666666667*GHSERCR.15 +GSROSOL+GHSEROO-43740+70*T.15 -5...629*T*LN(T)-0.Appendix -6568.15 -607870+268.15 32350-13. @@ ALPHA-HAUSMANNITE. Risold 1996 @@ SrO ENTER-SYMBO FUNCTION GSROSOL 298.. Grundy 2003 @@ MANGANOSITE.9579637E-04*T**2 +6.15 +108305+GCR2O3+0.5*GCR2O3-0.... @@ ESKOLAITE.. @@ Mn-oxides. @@ reduced neutral endmember of CR2O3 ENTER-SYMBO FUNCTION GCRO0 298.45091278E+05+3.12922234E+05*T**(-1).41618912E+06+8.259625*T-18.97E-03*T**2 +1. optimized @@ La-oxides.164542E+06+7.. 3300 Y -13986.80284521E-03*T**2+6.5*GHSEROO+280045-93...54747566E+02*T*LN(T) -1..00307*T**2 +190000*T**(-1). ENTER-SYMBO FUNCTION GLA2O3H 298..... @@ -------------------------------------------------------------- 174 .15 +1. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3D 298... Grundy 2006 ENTER-SYMBO FUNCTION GMN2O3 298. BETA-MN3O4 (CUBIC) ENTER-SYMBO FUNCTION GCMN3O4 298..9536*T*LN(T)-4. ENTER-SYMBO FUNCTION GLA2O3X 298.15 -4.. MODIFIED.778*T**(-1). Cr2O3 ENTER-SYMBO FUNCTION GCR2O3 298..25243E-04*T**2 +1..15 -1.15 -1.. MN1O2 ENTER-SYMBO FUNCTION GMN1O2 298..76015+12.54747566E+02*T*LN(T) -1. MNO ENTER-SYMBO FUNCTION GMN1O1 298.. @@ Cr-O oxides.15 -9.59355626E+02*T-4.9664*T-120.82*T.555*T+GLA2O3D.8*T*LN(T)-4.728+31.66000166*T-16.96393E+05+5.9*T-47.02477557E+05+2. Povoden 2005 @@ METASTABLE CRO ENTER-SYMBO FUNCTION GCR1O1 298.56*T*LN(T)-0.5*GHSEROO+255269-53.6846E+02*T-9.. ALPHA-MN3O4 (DISTORTED) ENTER-SYMBO FUNCTION GTMN3O4 298.. @@ PYROLYSITE.43703676E+06+8.. @@ SrO2 ENTER-SYMBO FUNCTION GSRO2SOL 298.15 -1..68352649E+01*T*LN(T) -3.85001409E-03*T**2+2.006854*T**2 +808000*T**(-1)-1E7*T**(-2)....74079033E-02*T**2+9.0822E+05*T**(-1)..15 +0.75120338E+02*T-1.911E+01*T*LN(T)-2.. @@ BETA-HAUSMANNITE..2856E+02*T-119.95379396E+02*T-6.78055555E-09*T**3+262904. @@ Sr-oxides.64955386E+05*T**(-1). @@ @@ MN2O3-FUNCTION.86138663E+05*T**(-1).89567858E+02*T-1..05E+06*T**(-1).74079033E-02*T**2+9..986*T+GLA2O3D..5*GCR2O3-0.8138015*T*LN(T)-5.15 -1833257+692..0721E-08*T**3+4383200*T**(-1).76*T.86138663E+05*T**(-1). 6000 N @@-----------------------------------------------------------@@ Binary oxides..056E-02*T**2 +6. @@ CR-SPINEL CR3O4 ENTER-SYMBO FUNCTION GCR3O4 298...15 43192-18..
.15 0.15 @@ 3.15 @@ 8*GLA2O3D+3. @@ @@ Functions of the Sr-Mn-O system.15 GLA2O3D+0.15 +GMN2O3+GSM3_HEX-2. @@ LA7 @@ ENTER-SYMBO FUNCTION GLA7 298..15 +GSROSOL+GMN1O2-1.15 +GSROSOL+0.5*GLA2O3D+0. ENTER-SYMBO FUNCTION GSM3OZ 298. ENTER-SYMBO FUNCTION SRH_ALPH 298..... ENTER-SYMBO FUNCTION LA_BETA 298..799*T..15 +GSROSOL+GLA2O3D+GMN2O3-137400..5*GHSEROO-371557+205*T..32830000E+05.19200000E+04.15 +2*GSROSOL+GMN1O2-1. optimized (except perovskite functions) @@ @@ Functions of the La-Sr-O system. ENTER-SYMBO FUNCTION GL3O_RP1 298.15 0..15 +GSROSOL+0.78500000E+05....15 +GMN2O3+GSM4_HEX-8..15 +4*GSROSOL+3*GMN1O2-3......11300000E+05..79100000E+03....5E+04... ENTER-SYMBO FUNCTION GSM3_HEX 298..15 +3*GSROSOL+2*GMN1O2-8.5*GCR2O3+9..26029731E+04-3...5E+04. Grundy 2004 ENTER-SYMBO FUNCTION SR_ALPHA 298. Povoden 2008 @@ LA2CRO6 ENTER-SYMBO FUNCTION GLA2CRO6 298. Grundy 2004 @@ HEX Phase ENTER-SYMBO FUNCTION GSM4_HEX 298..99100000E+04-90*T... ENTER-SYMBO FUNCTION RE_ALPHA 298.5E+04..5*GHSEROO-154101-2.. ENTER-SYMBO FUNCTION GL3O_RP2 298.5*GCR2O3+1.. @@ Sr7Mn4O1 175 ..15 +GLA2O3D+GMN1O1+6. @@ RP1 ENTER-SYMBO FUNCTION GS4O_RP1 298. @@ @@ Functions of the La-Mn-O system. @@ RP3 ENTER-SYMBO FUNCTION GSM4_RP3 298....15 +2*GSROSOL+2....71704891E+01*T. Grundy et al.15 +2*GSROSOL+2..Appendix @@ Ternary oxides. ENTER-SYMBO FUNCTION SRX_ALPH 298... @@ SrMn3Oz as SrMnO3_Mn2O3 ENTER-SYMBO FUNCTION GSM4OZ 298.5*GMN2O3-68300....158E+04. @@ @@ Functions of the La-Cr-O system. @@ intermediate La-chromates @@ LA16 @@ ENTER-SYMBO FUNCTION GLA16 298..5*GMN2O3-7..5*GCR2O3+4.. 2005 ENTER-SYMBO FUNCTION GL2MNO4 298.. @@ RP2 ENTER-SYMBO FUNCTION GS4O_RP2 298..15 GLA2O3D+1.14*T..15 +2*GSROSOL+2..70000000E+01*T.5*GLA2O3D+GCR2O3+2. ENTER-SYMBO FUNCTION RE_BETA 298.5*GHSEROO-540404-9. @@ LA2CR3O12 ENTER-SYMBO FUNCTION GLA2CR3 298.55*T..5*GHSEROO-73045-4.73000000E+03 -1....15 +GLA2O3D+2.
333333*GLA2O3D+GMN1O2-53760.....666666667*GCR3O4+.15 +0..31*T.15 2*GSROSOL+0.44550000E+04 176 . @@ @@ Functions of the Mn-Cr-O system..19*T*LN(T) +232934*T**(-1)-3429+4..5*GCR2O3+0.77*T-7...5*GMN2O3-63367+51. Povoden 2008 @@ Ruddlesden Popper phase ENTER-SYMBO FUNCTION GREFRP 298..6*T..5*GLA2O3D+0....5*T.15 +0.5*GLA2O3D+GMN1O1+27672.5*GLA2O3D+0.15 +0.333333333333*GHSEROO -508507+219*T.19*T*LN(T) +232934*T**(-1). @@ SRCR2O7 ENTER-SYMBO FUNCTION GSC2O7 298..72*t.15 0.5*GCR2O3+1. ENTER-SYMBO FUNCTION GMS3O 298.4*t.5*GLA2O3D+0. ENTER-SYMBO FUNCTION GV4O 298. @@ ENTER-SYMBO FUNCTION GL3OR 298..15 +GSROSOL+GCR2O3+3*GHSEROO-325047+196*T....Appendix ENTER-SYMBO FUNCTION GS7M4 298.. @@ @@ Functions of the Sr-Cr-O system.666666667*GCR3O4+.15 +0.. ENTER-SYMBO FUNCTION GLCR3O_RP1 298..15 0.19*T*LN(T) +232934*T**(-1)+400-0.. Povoden 2008 @@ SRCR2O4 ENTER-SYMBO FUNCTION GSC2O4 298..15 +0. @@ TETRAGONALLY DISTORTED SPINEL ENTER-SYMBO FUNCTION GTSPINEL 298..77*T-7..... @@ @@ Functions of the La-Sr-Cr-O oxide system..5*GCR2O3+0. @@ SR2CRO4 ENTER-SYMBO FUNCTION GS2CO4 298.75*GMN1O2-91857+20.15 +0. @@ ENTER-SYMBO FUNCTION GL3OL 298.3+61.5*GHSEROO.5*GMN2O3-7.5*GLA2O3D+0.5*GHSEROO-273771 +131.15 +6*GL2O+4*GL4O+3*GV4O-12*GL3O-254212...5*GHSEROO-145000+50*T. Povoden 2005 @@ CUBIC SPINEL ENTER-SYMBO FUNCTION GSPINEL 298.15 +2.1*T..33333333334*GCMN3O4-210795.... @@ SR3CR2O8 ENTER-SYMBO FUNCTION GS3C2O8 298.15 +GSROSOL+0.15 +GSROSOL+GCR2O3+98000-95...5*GMN2O3-63367+51.15 +2*GSROSOL+0. @@ SRCRO4 ENTER-SYMBO FUNCTION GSCO4 298.66666667*GSROSOL+GCR2O3+2.33333333334*GTMN3O4-200942+75..77*T-7.....69*T. ENTER-SYMBO FUNCTION GVVV 298.15 +7*GSROSOL+4*GMN1O2-6. ENTER-SYMBO FUNCTION GL4O 298. @@ ---------------------------------------------------------------@@ Perovskite functions @@ Grundy 2005 @@ Charge compensated by Mn+4 (correct) ENTER-SYMBO FUNCTION GL3O 298. ENTER-SYMBO FUNCTION GL2O 298.12450000E+05+50*T.5*GMN2O3-63367+51..15 +GLACRO3+GSROSOL+7000-25*t.15 +GSROSOL+0........73000000E+03-1.
15 +15483.5*GHSEROO-200000.5*GLA2O3D+0.0188191*T*LN(T)-0.6208*T-4.15 +GLACRO3-340+0.93775E-06*T**3-133541*T**(-1)..11300000E+05+2. 4000 N @@ Sr ENTER-SYMBO FUNCTION GSRLIQ 298.00189435*T**2 -1.15 +GHSERMN+17859.908*T*LN(T)+.5*GHSEROO-291802-250*t..52*t.29+213.981237E-06*T**3-265559*T**(-1).15 +547422.997-10. 3000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.653+18...Appendix -1. 1134 Y -3942.5*GHSEROO+10222-55..018431*T-34.15 GSROSOL+0.984+335..15 +GSROSOL+0..2288*T-1.5*GCR2O3-73591+2.2386*T+135166-88.42*t.406219*T-39. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.... @@ Reciprocals: all 0!!!!! @@ @@ Povoden 2008 @@ LaCrO3-PEROVSKITE ENTER-SYMBO FUNCTION GLACRO3 298.51-13.15 0. 2180 Y -16459. @@ Function for neutral endmember SrCrO3 ENTER-SYMBO FUNCTION GS4O 298.33333*GLA2O3D+...020171603*T**2 +2..118994*T-5..23012*T-11..69000000E+00*T.15 0.0668978*T*LN(T)-3.5*GHSEROO.. @@ Functions for defect chemistry ENTER-SYMBO FUNCTION GVCR4O 298.5*GCR2O3+0.68*T* LN(T). ENTER-SYMBO FUNCTION GALACRO3 298.15 GSROSOL+0...3088*T*LN(T)...47721E-06*T**3+139250*T**(-1)+2.5*GCR2O3+11. 1050 Y -10855. 1519 Y +GHSERMN+18739.5*GCR2O3+0.656847E30*T**(-9).26500000E+04 -7.. @@ (LaSr)CrO3+/-delta-Perovskite @@ Reference SrCrVa3 ENTER-SYMBO FUNCTION GS4V 298... @@ ---------------------------------------------------------------------@@ LIQUID FUNCTIONS @@ ---------------------------------------------------------------------@@ Liquid metal functions...37615E-21*T**7.059775*T-26. 3000 N @@ Mn ENTER-SYMBO FUNCTION GMN_L 298.70000000E+01*T. @@ Function for neutral endmember SR(CR+3. 6000 N @@ --------------------------------------------------------------------- 177 .63*t.1840595E-2*T**2 +4.15 0....91-12.015+146.616317*T-50*T*LN(T)..VA)O3 ENTER-SYMBO FUNCTION GN 298. ENTER-SYMBO FUNCTION GLACR4O 298.5*GCR2O3-2. ENTER-SYMBO FUNCTION GMS4O 298.15 +5332.5*GCR2O3+0.41929E-21*T**7. ENTER-SYMBO FUNCTION ANTI 298.004+171.463*T*LN(T).38*T-0.15 +GSROSOL+GMN1O2-1..15 +2194.
.1074654*T-19.135*T**(-1).S).C. Povoden ENTER-SYMBO FUNCTION GCR1O1_L 298.15 GCR2O3+439078-169*T.S Class: 5) ENTER-SYMBO FUNCTION F7705T 298.36845867E-08*T**3+6.588679E-07*T**3+10285.35563E+08*T**(-1)...00119977*T**2 -1. 10000 N @@ CR1O1 Gas.69E-7*T**3. REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCR1O1_G 298..15 -1833257+692.6220*T.23648333E-07*T**3-722515*T**(-1).15 GMN1O1+4..253215E-04*T**2-1. 1100 Y +393886. Class: 4 @@ SGTE=scientific group thermodata Europe @@ ENTER-SYMBO FUNCTION F7491T 298. @@ liquid SrO.708+805.06284295E+01*T.722975E-07*T**3-64209900*T**(-1).001513089*T**2 -4.31*T-40.A. ENTER-SYMBO FUNCTION GCR2O3_L 298. 900 Y +170853.15 +173449. ENTER-SYMBO FUNCTION GMN2O3_L 298.928-44.A.917665E-05*T**3-18523425*T**(-1).8669*T*LN(T) +.63356E+08*T**(-1).15 +2*GMN1O1+GHSEROO-6.S.237405*T+14.R.869-31.59563*T-186.003139382*T**2 -1.19*T*LN(T) +27.178604*T-117.671+1078.74749*T*LN(T)+..3+37.097*T*LN(T)-0..15 +390765.502-414.C..1684007*T-39. 8400 Y -403765.C.48744*T*LN(T)-.8788-3288. from T.224944*T-121.52515733E-07*T**3+682877*T**(-1).Appendix @@ Liquid oxide functions.4*T.006854*T**2 +808000*T**(-1)-1E7*T**(-2)+141329-56. source: Thermocenter of russian academy @@ of science (T.0 (1998).41*T*LN(T).48508*T**2-.5567E-7*T**3.....9513659*T-30.2320948*T**2-9..9664*T-120.629*T*LN(T)-0..083*T-30.36083*T* LN(T) +7. 540 Y -8528143.15 +176483.5*GHSEROO+339673-121.008463125*T**2 +1. 600 Y -331037.18729*T+495.R. from T.15*T**(-1).62+32. Risold ENTER-SYMBO FUNCTION GSROLIQ 298. 500 Y -62418.555*T*LN(T)+0. 601 N @@ -----------------------------------------------------------------------@@ GAS FUNCTIONS @@ --------------------CHROMIUM GAS---------------------------------------@@ CR Gas: SGTE v 3.00607059*T**2 +9.49525609E+04+4. 4000 Y +307209.5329*T*LN(T)+.00631160667*T**3+5.282+741.0063*T**2 +31300*T**(-1)+9.5192158*T-21..R.5*GCR2O3-0.1*T*LN(T). @@ liquid Mn oxides. 1000 Y +167489.229905E-07*T**3+35263. @@ liquid Cr oxides..00148*T**2 +873600*T**(-1)+1.A.15 -332319.14296167E-05*T**3+978019*T**(-1).. optimized @@ liquid La2O3. 178 .39465890E+04-2.4-33.2897*T*LN(T)-.1304*T*LN(T) -.331-31. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3LIQ 298.96003*T*LN(T)+.15 -566346+449*T-73.9+142414. 6000 N @@ CR1O1 Gas (SGTE 1998.31437957E+01*T.15 0.45*T-22596.. Grundy ENTER-SYMBO FUNCTION GMN1O1_L 298. Class: 4 ENTER-SYMBO FUNCTION GH2O_L 298. @@------------------------------------------------------------------@@ LIQUID WATER.504926*T**2+4.
01283575*T**2 -3. 6000 N @@ O3 Gas (SGTE 1998.15 +211801.A.526*T*LN(T)-0.5*T**(-1). 3000 N @@ CR1O3 Gas. from T.494-20.0847281*T-17.C. 3000 N @@-------------------OXYGEN GAS------------------------------------@@ O Gas (JANAF 1982.00623741*T**2-6.05535833E-07*T**3+1246309.10286*T*LN(T)+.798361*T-149.0010728235*T**2 +1.17486667E-07*T**3+1572175*T**(-1).15 -341231. 2800 Y +409416.1894682*T-31.423-52.13383*T-764.09852775*T**2 -2.108664-15. reassessed by Ming Chen 2006.5*T**(-1).01555*T*LN(T)+1.15 -109942.45*T**(-1). 6000 N @@ H Gas (JANAF 1982.569*T*LN(T)-0.15 -9522.0216*T**2 +428900*T**(-1)+3.40916*T*LN(T) -. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O2_G 298.039707355*T**2 -4.S Class: 4) ENTER-SYMBO FUNCTION F14021T 298.00016*T**2 +1814700*T**(-1)+7.10457667E-06*T**3+12362250*T**(-1).15 +243206.14618667E-07*T**3-1280036*T**(-1).0155*T**2 +245800*T**(-1)+2. 6000 N @@ H2O1 Gas (SGTE 1998.8435*T*LN(T)+.944-37.3120249*T-32.4437*T*LN(T)-. 2950 Y +252301.555105E-07*T**3-2.00206456*T**2 -5.S Class: 4) ENTER-SYMBO FUNCTION F10963T 298.35707*T*LN(T)+0.6128262*T-17.0922361*T**2 +4.59*T-39.99+130.2687055E-04*T**2 -1. 6000 N @@ -------------O-H GAS----------------------------------@@ H2 Gas (JANAF THERMOCHEMICAL TABLES SGTE) ENTER-SYMBO FUNCTION H2GAS 298.2*T*LN(T)-.610855E+08*T**(-1).5*T**(-1).3956+710.89*T-82.9096643*T-27. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION F13349T 298.09482*T-134. 1000 Y -354716.43E-6*T**3.623+176.58118*T*LN(T)-. 2100 Y +866367.00584168*T**2 +3.15 +130696.15 -250423.2001*T*LN(T)-. 1300 Y +49468.64520667E-09*T**3-3973170. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION HGAS 298. 3500 Y -1866338.621+24. from T.696*T*LN(T)-0.413565E-04*T**2 +7.23131283E-08*T**3-42897.78611*T*LN(T).A.21188*T*LN(T)-5. 2800 Y 179 .09+299.1699975E+08*T**(-1).45*T**(-1).4989821*T-20.44768833E-06*T**3-2.8612582*T-21.5273873*T-31.01526167E-08*T**3-64163.6+6101.434+4.9608*T*LN(T)+.043+890.C.3696*T*LN(T)+. 1100 Y -256145.R.306855E-06*T**3-21589870*T**(-1).78+10.05082*T*LN(T)-0.02763076*T**2 +4.80563*T+421.1663+92.43044*T*LN(T) -.401E-6*T**3. 700 Y +114760.00012*T**2 +932050*T**(-1)-8.81*T-56.Appendix 3000 N @@ CR1O2 Gas.33E-9*T**3.1304835E+08*T**(-1).R.007055445*T**2+3.59784667E-06*T**3+9.075-3566.14281783E-08*T**3+3561002.1284109*T**2 +5.45470312*T-28. 2100 Y -18840. reassessment Chen 2006.626737*T-60. 4900 Y +97590.60539333E-06*T**3+99530.3*T**(-1).01667E-8*T**3.879+30.46390667E-07*T**3+56582.09*T**(-1).0027589925*T**2 -7. 1000 Y -118120+123.84857*T*LN(T)-0.97393+78. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O3_G 298. 1000 Y +180.61*T-57.70834*T+223.383-1950.
4077*T*LN(T) +.47*T-96.122915E-07*T**3+925845*T**(-1).86*T-75.771+239.94271*T*LN(T) -.5127-12.573855E-09*T**3+26048030*T**(-1).75E-7*T**3.9*T*LN(T) -. 20000 N @@ H1O2 Gas (SGTE 1998.36297E-06*T**3-29469.10636*T*LN(T) -.724*T*LN(T) -0.551*T*LN(T) +0.C.0023107985*T**2+5.418+116. 1000 Y 180 .64106-55.S Class: 4) ENTER-SYMBO FUNCTION F10729T 298. 6000 N @@ H2O2 Gas (JANAF SECOND EDIT SGTE) ENTER-SYMBO FUNCTION F10983T 298.15 +1075.24542*T*LN(T) +.0146*T**2+715900*T**(-1)+2.6898+15.0015*T**2+938850*T**(-1)+5.007931945*T**2+4.15 +68260+52.77872*T*LN(T) +2.34404917E-07*T**3+116618.799205E-07*T**3-25503. 800 Y -7932.259882*T-92.1173*T*LN(T) +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 298.0792741*T-24. 18000 Y -165728. +326722.7343256*T-24.334E-8*T**3.82*T**(-1).15 +30698.1931655E+08*T**(-1). 8400 Y -489068. 1000 Y 56684+136.1497212*T-26.R.9096451*T-29. 1500 N @@-------------------CR-O-H GAS---------------------------------------@@ CR(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O1_G 298.2921095E-09*T**3-4.003069987*T**2+6.S Class: 1) ENTER-SYMBO FUNCTION F10666T 298.406716*T-68.036948065*T**2+6.953+370.971-37.52*T-74.7*T-72.5*T**(-1).191295*T-50.0007*T**2+243850*T**(-1)-9.8961+275.0019361405*T**2-1.4+195. 700 Y -156470.77*T-83.326117*T-69.91863E-08*T**3-6415210*T**(-1).53*T-57.42186*T*LN(T) -. 3600 Y -67875. 3000 Y +31735.97594167E-08*T**3+2458230.4391015E+08*T**(-1).94216*T*LN(T) -.292415E+08*T**(-1).A.15 -274384.018507875*T**2+2.96842*T*LN(T) -.97699*T*LN(T) +.0783-20.053*T*LN(T) -0.686636*T-25.05*T**(-1).003149545*T**2+1. 18000 Y -154907.65*T**(-1). 1000 Y -492562+351.2E-7*T**3.645643*T-59.002*T**2+185600*T**(-1)-1.00501027*T**2+2.52+180.505+120.15 -497678+273.690197*T-42. 3000 N @@ CRO2(OH) Gas.277-65.29733833E-07*T**3+684985.99164+54. 3000 N @@ CR(OH)2 Gas.0018*T**2+1338300*T**(-1)+9. from T. 20000 N @@ H1O1 Gas (SGTE 1998.Appendix -268423.2016233*T-40.242048*T-24.927*T*LN(T) -0.C.32+190.87*T-46.0031*T**2+266750*T**(-1)-9.0016703495*T**2-1. 8600 Y +41016.2768*T*LN(T) +6. 1000 Y -276268.175*T*LN(T) +0.213599E-04*T**2-1.15 -147258.30298483E-10*T**3-8.15 -351288.A.39E-6*T**3.42189E-05*T**2-1.15E-8*T**3.12331E-04*T**2-6.0018*T**2+2218000*T**(-1)-2.45435*T*LN(T) -. 3000 N @@ CRO(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O2_G 298. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O2_G 298.765625E+08*T**(-1).135E-7*T**3.R. assessment Chen 2006.65*T**(-1).47539017E-08*T**3+1.5*T**(-1).001713168*T**2-6.32333233E-08*T**3+1.51E-7*T**3.659505E-06*T**3+65357.882+553. from T.775*T*LN(T) -.257*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 298.014*T**2+6008850*T**(-1)+7.15 -578683+391.65*T*LN(T) -0.545E-7*T**3. assessment Chen 2006.12+967. 3000 N @@ CRO2(OH)2 Gas.97*T-180. 3000 N @@ CR(OH)6 Gas.18913267E-06*T**3-77266.83+534.2*T-109.0099*T**2+770750*T**(-1)+5.25*T*LN(T) -0.1+867.019*T**2+513600*T**(-1)+1.00056*T**2+663150*T**(-1)-5.945E-07*T**3+4671850*T**(-1).97*T-79.006*T**2+2525450*T**(-1)+2. 3000 N @@ CR(OH)5 Gas. 1000 Y -909897.0065*T**2+2669300*T**(-1)+3.13133917E-07*T**3+1368173*T**(-1).4+51. 3000 N @@ CR(OH)3 Gas.36214*T+18.006*T**2+498450*T**(-1)-2.15 -787712+400*T-107. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH4O4_G 298.Appendix -359644+228.67833E-07*T**3.3*T-137.15 -902751. 3000 N @@ CRO(OH)3 Gas.15 +432449.004*T**2+785800*T**(-1)-2. assessment Chen 2006. from T. assessment Chen 2006 based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O3_G 298. 5500 Y +1270342.6+712. 3000 N @@ CR(OH)4 Gas.3E-7*T**3.15 -650064.819*T*LN(T) -0.6*T-195. 1000 Y -991549. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH6O6_G 298.91E-7*T**3.7467E-7*T**3.6022*T*LN(T) -.014*T**2+1.35E-07*T**3+665100*T**(-1). 1000 Y -861477.386334*T-22.026-56.R.S Class: 4) ENTER-SYMBO FUNCTION F7586T 298. 1000 Y -806262+567*T-131.0049*T**2+3311450*T**(-1)+2. assessment Chen 2006.15 -976204+672.0086*T**2+3058600*T**(-1)+4.378E-6*T**3.8867E-7*T**3.8967E-07*T**3+1688150*T**(-1).002*T*LN(T) -0.349852E-04*T**2-1.05*T**(-1).713-424. 1000 Y -997791.049*T*LN(T) -0.37019*T*LN(T) -.15 -978211.45*T-229. 1000 Y -1053466+1080. 1000 Y +421602.A.874*T*LN(T) -0.9*T-190.6*T-109. 3000 N @@ CRO(OH)2 Gas.0054*T**2+1023500*T**(-1)-1.05+820. 3000 N @@ CRH1 Gas (SGTE 1998. 3500 Y +587860. assessment Chen 2006.5*T*LN(T) +0.7+464.37*T-125.9865812*T-37.004*T**2+2094950*T**(-1)+1.008*T**2+840600*T**(-1)-1.457*T*LN(T) -0.60191*T+219.C.99681*T*LN(T) +3.76+600. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O4_G 298.46-2142.004*T**2+1.93E-7*T**3.9958E-06*T**3.355E-6*T**3.41*T*LN(T) -0.74*T-146.973194012145*T-158.35E-7*T**3. assessment Chen 2006.86+694.34E-7*T**3.5*T-163*T*LN(T) +0.15 -1029121. 3000 N @@ CRO(OH)4 Gas.2*T*LN(T) -0.16*T*LN(T) -0. assessment Chen 2006.8+813.3*T-121. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH5O5_G 298.11767E-6*T**3.6*T-162. 1000 Y -656538+448.0096*T**2+4. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O3_G 298.86*T*LN(T) -0.99444833E-08*T**3-86705500*T**(-1).15 -851590.77E-6*T**3.89*T-216.455*T*LN(T) -0.007723995*T**2+7.9391*T*LN(T) 181 .098*T*LN(T) -0.00994042*T**2+1.01*T**2+4151100*T**(-1)+5. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION G_CRH4O5 298.524*T*LN(T) -0.525*T*LN(T) -0. 1000 Y -582354+394.
87691*T.33333333*RE_BETA +15. ENTER-PAR G(LA2O3SS. ENTER-PAR G(LA2O3_CUBSS.. ENTER-PAR G(BETA.. +GLA2O3H-3*GHSEROO..MN:O.. Risold @@ ENTER-PHASE SRO2. ENTER-PAR L(LA2O3_CUBSS.0). ENTER-PAR G(LA2O3SS....LA+3:VA... O-2 VA.0)....0) 298..87691*T...SR+2:O-2. ENTER-PAR L(LA2O3SS..LA+3.149E+05-7.SR+2:VA....20451E+08*T**(-1).SR+2:O-2..0)..1*T.LA+3.15 +193600-78.1) 298. +GLA2O3X-3*GHSEROO. +SRX_ALPH2*GHSEROO+15. ENTER-PAR L(LA2O3_HEXSS...0) 298.. O-2 VA. +SR_ALPHA+GHSEROO +15.. 2 2 3 LA+3 SR+2.15 -20000..277845E-07*T**3-5....0)..0) 298.. @@ ---------------------------------------------------------------------@@ Ternary oxides @@ @@ LA-SR-O... 182 .15 +GSRO2SOL.SR+2:VA. @@ La4SrO7 as BETA phase ENTER-PHASE BETA..1*T. ENTER-PAR G(LA2O3SS. +LA_BETA.. ENTER-PAR G(LA2O3_HEXSS.1*T...LA+3:O-2..87691*T.0). +SRH_ALPH+GHSEROO+15. ENTER-PAR G(LA2O3_HEXSS... ENTER-PAR G(LA2O3SS.SR+2:VA.LA+3:VA... 6000 N @@ @@ @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Binary oxides @@ @@ Sr oxides. Grundy @@ @@ STOICHIOMETRIC PYROLYSITE.81E+01*T. +SRH_ALPH-2*GHSEROO +15.. ENTER-PAR G(BETA.LA+3.. ENTER-PAR G(LA2O3_HEXSS..15 +2.149E+05-7....81E+01*T.87691*T. MN1O2 ENTER-PHASE MN1O2.0)...0) 298..SR+2:O-2.0) 298...034109635*T**2+7.87691*T. +LA_BETA-3*GHSEROO.. ENTER-PAR G(SRO2. +GLAO-GHSEROO.Appendix -...LA+3..LA+3:O-2...SRO2.. ENTER-PAR G(BETA. +SR_ALPHA-2*GHSEROO +15.0) 298... ENTER-PAR G(LA2O3_CUBSS.. ENTER-PAR G(MN1O2.LA+3.15 +GMN1O2.SR+2:VA.... ENTER-PAR G(LA2O3_CUBSS.SR+2:VA.0)..0)..0)... 2 1 2 MN.SR+2:O-2..LA+3:O-2.15 -20000.LA+3. +GLA2O3H.0)..87691*T..15 +193600-78. ENTER-PAR L(LA2O3SS... ENTER-PAR L(LA2O3_CUBSS...15 +GLAO. O-2 VA.SR+2:VA. @@ ENTER-PHASE LA2O3_CUBSS..15 +2... ENTER-PAR G(LA2O3SS. O-2 VA. O... 2 2 3 LA+2 LA+3 SR+2...LA+3:VA.0)... +SRX_ALPH+GHSEROO+15..LA+3:VA.. ENTER-PAR L(LA2O3_CUBSS..LA+3:O-2..SR+2:VA.. @@ ENTER-PHASE LA2O3_HEXSS.. ENTER-PAR G(LA2O3SS..SR+2:O-2. +SR_ALPHA+416100+GHSEROO -0. 2 2 3 LA+3 SR+2. Chen @@ ENTER-PHASE LA2O3SS. 1 SRO2.15 +168700-78.. ENTER-PAR G(LA2O3_HEXSS...0)... +GLA2O3D-3*GHSEROO..0). ENTER-PAR G(LA2O3_CUBSS..SR+2:O-2.0).. 2 2 3 LA+3 SR+2.LA+3..LA+2:O-2.0).15 +168700-78. ENTER-PAR L(LA2O3_HEXSS..0) 298..LA+3.1) 298. Grundy...........0) 298.0) 298.1*T.LA+2:VA.SR+2:O-2..SR+2:O-2.0) 298.. @@ @@ Mn oxides. ENTER-PAR L(LA2O3_CUBSS..87691*T.15 +GLA2O3D. +GLA2O3X....
+2*GLA2O3D+3*GSROSOL+229800 -136.. MN+3 MN+4........ O. Povoden @@ @@ STOICHIOMETRIC LA2CRO6 ENTER-PHASE LA2CRO6.0). 3 2 1 6 LA+3.. O-2. Stoichiometric ENTER-PHASE LA4SR3O9.LA+3:CR+6:O-2.. @@ STOICHIOMETRIC LA7 @@ ENTER-PHASE LA7..0).... ENTER-PAR G(SR4MN3O10.......SR+2:MN+3:O-2:MN+4:VA...LA+3:MN+2:O-2.. O-2.8*T.VA:O-2... +GSROSOL.23859*T. O-2..0)... +0.0). 5 1 2 3 1 3 SR+2.. ENTER-PAR L(BETA.0) 298.15 +GLMN2O5....15 -121000-237. CR+6. O.5*GHSEROO +11.. ENTER-PAR G(SRMN3O6. +GSM3OZ-2...0)... 4 1 1 1 5 LA+3. @@ intermediate La-chromates @@ STOICHIOMETRIC LA16 @@ ENTER-PHASE LA16.0).SR+2:MN+3:O-2:MN+3:O-2. @@ @@ LA-CR-O.......15 -121000-237.15 +GLA7. ENTER-PAR G(SR7MN4O15.Appendix ENTER-PAR G(BETA......LA+3.75*T.0) 298.LA+3:O-2. O-2. MN+4. ENTER-PAR G(SRMN3O6.... +GS7M4..LA+3:MN+3:MN+4:O-2.LA+3:SR+2:O-2.5*GHSEROO +11.SR+2:O-2. +GSM4_RP3. ENTER-PAR G(LA2CR3. @@ @@ SR-MN-O.15 +GL2MNO4. +GSM4OZ. +GSM3_HEX+0. ENTER-PAR G(SRMN3O6. 3 4 3 10 SR+2.15 +GLA2CR3.. O-2.. 3 1 1 3 SR+2..5*GHSEROO +11.0) 298. ENTER-PAR G(LMN2O5.0) 298.. O-2. 3 2 3 12 LA+3.. ENTER-PAR G(LA2CRO6... ENTER-PAR G(SRMN3O6. O-2 VA. 0.LA+3.. ENTER-PAR L(BETA.SR+2:MN+3:O-2.. MN+3 MN+4.. ENTER-PAR G(SRMNO3_HEX.8*T..LA+3:CR+6:O-2.. ENTER-PAR G(SRO..0). MN+4.LA:CR:O.. Grundy @@ ENTER-PHASE L2MNO4.SR+2:MN+4:O-2. ENTER-PAR G(SRO. 183 .. +SR_ALPHA+416100-2*GHSEROO +0......SR+2:O-2.....SR+2:MN+3:O-2:MN+3:VA.5*GLA2O3D+113700... O-2 VA.0).. @@ SrO Solid Solution ENTER-PHASE SRO..... Grundy @@ ENTER-PHASE SR7MN4O15. 3 7 4 15 SR+2..23859*T. CR. @@ @@ LA-MN-O... @@ ENTER-PHASE SRMNO3_HEX..SR+2:MN+3:O-2:MN+4:O-2. MN+2. 3 16 7 44 LA.. +GSM4OZ-3*GHSEROO.0).. SR+2. 3 4 3 9 LA+3.SR+2:VA. MN+3.SR+2:MN+4:O-2. @@ ENTER-PHASE SR4MN3O10.. 3 7 2 16 LA... @@ ENTER-PHASE LMN2O5.. ENTER-PAR G(LA4SR3O9. O-2. CR.15 +GLA16.23859*T.... MN+3.0) 298.. +GSM3_HEX-2..66666667*RE_BETA+15..SR+2:MN+3:VA.....0).. @@ @@ STOICHIOMETRIC LA2CR3O12 ENTER-PHASE LA2CR3.. 3 2 1 4 LA+3.SR+2:VA. MN+4.0) 298. +GSM3OZ+0.0).. ENTER-PAR G(SRMNO3_HEX.. @@ ENTER-PHASE SRMN3O6.. O-2. CR+6..... 2 1 1 LA+3 SR+2 VA.... @@ ENTER-PAR G(LA7.LA:CR:O.0).87691*T..5*GHSEROO +11..0) 298. O-2.15 +GLA2CRO6. ENTER-PAR G(SRO. @@ La4Sr3O9..0).. @@ ENTER-PAR G(LA16....0) 298. ENTER-PAR G(L2MNO4...23859*T.
. O-2.1853365*T. +GSM4_HEX.0) 298. ENTER-PAR L(MNO_HALIT.15 +GSC2O4.15 +GS2CO4.28 ENTER-PAR TC(MN2O3. MN+3 MN+4. ENTER-PAR G(MN2O3..0). @@ @@ SR2.MN+3:O-2:VA..1) 298.. Povoden @@ @@ NONSTOICHIOMETRIC MANGANOSITE (MNO) SOLID SOLUTION. O-2...93845*T +71549.0) 298..MN+2... ENTER-PAR G(MN2O3.MN+3:O-2:VA. 2 1 1 MN+2 MN+3 CR+3 VA.MN+3:VA:O-2. ..15 +GMN1O1-21883.SR+2:SR+2:MN+4:O-2.0) 298..21048766E+04.0) 298.. 3 2 1 4 SR+2..... O-2 VA... ENTER-PAR G(SCO4.87691*T.0).SR+2:SR+2:MN+3:O-2. @@ SRCR2O7. 3 2..CR+3:O-2:VA. NONSTOICHIOMETRIC CR2O3 SOLID SOLUTION. CR+4. @@ @@ Mn2O3 (Compatible with C-Y2O3...15 -4..67CR2O8 ENTER-PHASE S3C2N. O-2.0) 298.. O.59.. doubtful phase @@ ENTER-PHASE SC2O7.0) 298. 3 2 3 1 MN+3 CR+3......CR+3:O-2:VA.. ENTER-PAR G(SRMNO3_HEX..87691*T.. Povoden-K..... O-2..87691*T. CR. ENTER-PAR G(MN2O3. @@ @@ ESKOLAITE.. Povoden-Karadeniz ENTER-PHASE SCO4..15 +308. 4 1 2 2 7 SR+2.MN+3:O-2..MN+2. ENTER-PAR G(S2CO4.. O-2.0) 298. @@ ENTER-PAR G(SC2O7.MN+3:O-2:O-2. CR+6. O-2 VA.... +GSM4_HEX-3*GHSEROO.. SR+2.. ENTER-PAR G(SC2O4. ENTER-PAR G(MN2O3.0) 298... @@ SRCRO4.0) 298.0) 298.0) 298.MN+2:O-2.. ENTER-PAR G(MN2O3..15 +GCR2O3-3*GHSEROO. Povoden-Karadeniz 184 .. ENTER-PAR G(MNO_HALIT.. ENTER-PAR G(MNO_HALIT.MN+3:O-2. O-2.. ENTER-PHASE MNO_HALIT. @@ SR2CRO4 ENTER-PHASE S2CO4.MN+3:VA:VA.87691*T..15 +GCR2O3+GHSEROO +100000+15....Appendix ENTER-PAR G(SRMNO3_HEX. ENTER-PAR G(RP2.15 +GMN1O1..15 +GMN2O3-3*GHSEROO... ENTER-PAR G(MN2O3....15 +GMN2O3+GHSEROO +100000+15..SR+2:CR+3:O-2.15 +GCR2O3-2*GHSEROO +100000+15...15 +3*GSROSOL+GMN2O3+GHSEROO.SR+2:CR+6:O-2....15 +3.5213 -22.. @@ @@ CR-MN-O. @@ @@ RP2. Grundy. Chen.5*GCR2O3-7.15 +GSC2O7.15 +309.0) 298. 3 1 1 4 SR+2. ENTER-PAR G(S3C2N..3. 3 1 2 4 SR+2.SR+2:MN+4:VA..0) 298...SR+2:MN+4:O-2..CR+3:O-2:O-2.0) 298. CR+3. ENTER-PAR G(MN2O3.MN+3:O-2.SR:CR:O.0) 298..CR+3:O-2.0) 298.15 +4. ENTER-PAR TC(MN2O3.CR+3:VA:O-2.0) 298.. ENTER-PAR BMAGN(MN2O3......0) 298....SR+2:CR+4:O-2..0) 298. AMEND-PHASE MN2O3 MAGN..15 +GS4O_RP2.15 +GMN2O3-2*GHSEROO +100000+15. Grundy modified it in LSM modeling ENTER-PHASE RP2.6...0) 298.0) 298.65131533E+04. ENTER-PAR G(MNO_HALIT.15 0..15 +GMN2O3..0) 298.0) 298. ENTER-PAR G(MNO_HALIT.MN+3:O-2:VA. ENTER-PAR L(MNO_HALIT........ Povoden-Karadeniz) ENTER-PHASE MN2O3. CR+6.. ENTER-PAR G(RP2. 3 1 2 7 SR+2..15 +0.15 +GCR2O3+3459..CR+3:O-2:VA..SR+2:CR+6:O-2..... ENTER-PAR BMAGN(MN2O3.15 +GSCO4...0) 298.15 +GS3C2O8.VA:O-2... @@ @@ SR-CR-O.CR+3:VA:VA...15 +0.. Grundy.666667 2 8 SR.... ENTER-PAR G(MN2O3. Povoden @@ @@ SRCR2O4 ENTER-PHASE SC2O4.
ENTER-PAR G(CR2O3.15 +3. ENTER-PAR TC(CR2O3.15 +GCRO0 +. ENTER-PAR G(RPEROV. ENTER-PAR BMAGN(CR2O3.47717*T.47717*T.28 ENTER-PAR TC(CR2O3...15 +GL3O_RP2.15 +GCR2O3+GHSERCR...15 +308.. ENTER-PAR G(CR2O3.MN+2:CR+3:O-2...MN+3:VA:O-2..15 +0. O-2 VA... +GMS3O+0... ENTER-PAR G(LS3MN2O7..15 +GCRO0 -0.15 +309....15 +GSPINEL.0) 298.15 +GCR3O4+GCMN3O4-GSPINEL..MN+2:MN+3:O-2... 3 1 1 3 LA+3 SR+2 VA.CR+2:VA:O-2.0) 298.. ENTER-PAR G(CR2O3..0) 298.. ENTER-PAR BMAGN(CR2O3.15 +GCR3O4. MN+2 MN+3 MN+4 CR+3 CR+4 VA... 4 1 2 2 7 SR+2. Povoden-Karadeniz ENTER-PHASE TMNCR2O4..CR+2:MN+3:O-2......SR+2:MN+2:O-2.. Grundy.0) 298. CR+3 VA. O-2. ENTER-PAR G(CR2O3.MN+3:VA:O-2.666666666667*GHSERCR -5...SR+2:MN+3:O-2.CR+2:CR+3:O-2..2923*T...SR+2:LA+3:MN+3:O-2.CR+2:CR+3:O-2..0) 298. ENTER-PAR G(TMNCR2O4..... ENTER-PAR G(LS3MN2O7.0) 298.CR+2:VA:O-2.. @@ -----------------------------------------------------------------------@@ Quinary phases. LA+3 SR+2.33333333334*GHSERCR -5. 3 1 2 4 MN+2.5*GHSEROO+11. Grundy @@ ENTER-PHASE LS3MN2O7. +GMS3O+GL2O-GL3OR+GHSEROO +22. ENTER-PAR G(RPEROV.... .6.0) 298. @@ @@ CUBIC SPINEL.. MN+3 CR+3..CR+3:VA:O-2.. ENTER-PAR G(CMNCR2O4....15 +GCR2O3.CR+3:CR+3:O-2. Povoden-Karadeniz ENTER-PHASE CMNCR2O4. O-2... O-2..6. @@ -----------------------------------------------------------------------@@ Quaternary oxides @@ @@ La-Sr-Mn-O..6.MN+3:CR+3:O-2.SR+2:LA+3:MN+4:O-2.0) 298.CR+3:VA:O-2..15 +GL3O_RP2+GS4O_RP2 -3*GSROSOL -GMN2O3-GHSEROO-R_RP2.Appendix ENTER-PHASE CR2O3. ENTER-PAR G(RPEROV. MN+3 MN+4.0) 298.0) 298. ideal extensions from lower-order systems @@ @@ high temperature rhombohedral perovskite..59. ENTER-PAR BMAGN(CR2O3.0) 298.CR+2:CR+3:O-2.CR+3:CR+3:O-2..0) 298... ENTER-PAR G(LS3MN2O7.SR+2:SR+2:MN+3:O-2....0) 298.6.0) 298...2923*T.. +GMS3O+GL2O-GL3OR2*GHSEROO+22..0). ENTER-PAR G(CR2O3.. Grundy..0) 298..MN+3:CR+3:O-2...CR+2:CR+3:O-2.15 +GS4O_RP2..15 +0... 3 2 1 3 MN+3 CR+2 CR+3. @@ DISTORTED_SPINEL. Povoden-Karadeniz ENTER-PHASE RPEROV.. ENTER-PAR G(CMNCR2O4.. ENTER-PAR G(CMNCR2O4. 3 1 2 4 MN+2 CR+2.. AMEND-PHASE CR2O3 MAGN..0) 298.15 +3.0) 298....15 +3*GSROSOL+GMN2O3 +GHSEROO.MN+3:VA:O-2....CR+3:VA:O-2..0) 298.SR+2:MN+4:O-2. ENTER-PAR G(LS3MN2O7. ENTER-PAR G(TMNCR2O4..... ENTER-PAR TC(CR2O3..CR+3:CR+3:O-2.15 +GMN2O3+39503..15 +3. ENTER-PAR TC(CR2O3. ENTER-PAR BMAGN(CR2O3. MN+3 CR+3..0) 298..15 +3.0) 298.MN+3:CR+3:O-2..15 +308.15 +308.MN+2:MN+3:O-2. @@ ENTER-PAR G(RPEROV. 185 ..15 +GTMN3O4. O-2.0) 298.. +GMS4O.SR+2:SR+2:MN+4:O-2.15 +309.0) 298.0).23859*T. ENTER-PAR TC(CR2O3.0) 298.. Grundy.. ENTER-PAR G(CMNCR2O4...15 +GTSPINEL..0) 298......SR+2:MN+2:VA.0) 298... ENTER-PAR G(CR2O3..15 +308.. ENTER-PAR BMAGN(CR2O3...0) 298..0). ENTER-PAR TC(CR2O3.MN+2:CR+3:O-2....0)..15 +GMN2O3+GSERCR+39503.CR+2:VA:O-2.59. ENTER-PAR BMAGN(CR2O3.15 +GCMN3O4...0) 298.0) 298..
.LA+3:MN+4:O-2.0).VA:CR+3:VA.5*GVVV-1.....0)...33333*GL4O +GHSEROO+4.0)... +GL2O+1..0)...33333*GLACR4O +GHSEROO+4..5*GVVV-GL3OR -GHSEROO+12.5*GHSEROO+11..0)..62121*T.5*GHSEROO+1. G(RPEROV.5*GV4O+0..5*GVCR4O+0.0)..5*GVVV +2*GHSEROO+12... ENTER-PAR G(RPEROV..16666667*GS4V+GLACRO3 -3*GHSEROO.0).5*GV4O +0.0). ENTER-PAR G(RPEROV.LA+3:VA:O-2.. +GLACRO3+1.2386*T.. +GL2O+0. G(RPEROV.. ENTER-PAR G(RPEROV..VA:VA:VA...5*GV4O+0.. +GLACRO3+1... ENTER-PAR G(RPEROV. ENTER-PAR G(RPEROV. +GN+0......LA+3:CR+4:VA.33333*GVVV-1.SR+2:CR+4:VA.5*GVVV -2*GLACR4O-1.1666667*GS4O -0.41263*T. +GL2O-2..0).0). +GVVV.VA:MN+4:O-2.0)... ENTER-PAR G(RPEROV... +GL3OR+1...76318*T..16666667*GS4V. ENTER-PAR G(RPEROV... +0. G(RPEROV. +GMS4O-3*GHSEROO.1666667*GS4O +0..5*GV4O+0.LA+3:MN+3:O-2.41263*T..LA+3:MN+2:VA.. +2*GVCR4O+0....VA:MN+4:VA. +2*GV4O+0.23859*T...5*GV4O+0.1666667*GS4O +0.0).. +GL3OR. ENTER-PAR G(RPEROV.76318*T.5*GVVV-2*GL4O -GHSEROO+9.5*GVVV +1.5*GHSEROO+5...5*GHSEROO -1...2386*T.0). ENTER-PAR G(RPEROV...LA+3:MN+3:VA. ENTER-PAR G(RPEROV. +GS4V.3333*GVVV -1.5*GV4O+0..41263*T..333*GLACR4O -2*GHSEROO+4.166667*GVVV -3.41263*T.35057*T. ENTER-PAR G(RPEROV.333*GL4O -2*GHSEROO+4. +GL3OR-3*GHSEROO. +2*GV4O+0.5*GVVV-2*GL4O -1.0).Appendix ENTER-PAR G(RPEROV..VA:MN+2:VA....5*GHSEROO-1..0)... @@ Optimized interactions 186 .0).VA:CR+4:O-2..5*GHSEROO -1.SR+2:MN+3:VA.VA:VA:O-2.LA+3:MN+2:O-2.SR+2:CR+3:O-2..8333333*GS4V... ENTER-PAR G(RPEROV. +2*GL4O+0.62121*T.0).35057*T. ENTER-PAR G(RPEROV..0).LA+3:MN+4:VA.VA:CR+3:O-2. G(RPEROV..5*GVCR4O+0.. G(RPEROV.SR+2:CR+3:VA.0).0).0). +GLACRO3-3*GHSEROO.. +GN-0. G(RPEROV.. ENTER-PAR G(RPEROV..3333*GVVV-1..166667*GVVV -0. ENTER-PAR G(RPEROV.82596*T.35056*T.LA+3:CR+3:O-2..0)..VA:MN+3:VA.. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV...5*GV4O -0.0).8333333*GS4O +0...0). G(RPEROV..0). +2*GL4O-1.41263*T.. +GMS3O-GL3OR+2*GL4O -1..SR+2:VA:O-2.5*GHSEROO-1.. ENTER-PAR G(RPEROV. ENTER-PAR G(RPEROV.5*GHSEROO+11.LA+3:CR+3:VA..5*GV4O -0...0)..LA+3:VA:VA....5*GHSEROO+11.SR+2:CR+4:O-2...0). +GVVV+3*GHSEROO. G(RPEROV.33333*GVVV -1.0).0).5*GHSEROO +1. +GMS3O+2*GL4O-1. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.. +GMS3O-2.66667*GL4O+0. GS4O-GN-0. ENTER-PAR G(RPEROV.35056*T... ENTER-PAR G(RPEROV..5*GHSEROO+5.5*GVVV-2*GL4O +1. +GL3OR+1.VA:CR+4:VA....VA:MN+3:O-2.. ENTER-PAR G(RPEROV.5*GVVV -2*GLACR4O+1.LA+3:CR+4:O-2.. +0.66667*GL4O+0. +2*GVCR4O+0...0).41263*T. +GS4O..5*GV4O -1.... +GLACRO3..... GS4O+GLACRO3-GN-0....SR+2:MN+4:VA..16666667*GS4V...0).SR+2:VA:VA.
.SR+2:LA+3:MN+3:O-2:O-2.LA+3:CR+3.. @@ O-2.. ENTER-PAR G(ION..0) 298.. ENTER-PAR L(RPEROV.15 +2*GCR_L+GCR2O3_L-3*GCR1O1_L.. ENTER-PAR L(ION. @@ @@ Ruddlesden-Popper phase.SR+2:MN+2:O-2..SR+2:LA+3:CR+4:O-2:O-2.SR+2:VA. @@ ENTER-PAR G(RP.. ENTER-PAR G(ION. @@ ENTER-PAR L(RP..VA. ENTER-PAR L(RPEROV.. 20.38590000E+04..LA+3:CR+3. @@ ENTER-PAR L(RP.15 +GCR2O3_L..0) 298...15 +GL3O_RP1... -117000.0) 298...VA:O-2.CR+2:VA.LA+3:CR+3. ENTER-PAR L(RPEROV. @@ Interaction parameters from binaries ENTER-PAR L(ION..0) 298.15 -119062.15 +2*GSROLIQ.15 +GLALIQ. ENTER-PAR G(ION.. ENTER-PAR G(ION..MN+2:O-2.15 +GSRLIQ.. ENTER-PAR G(ION..LA+3.54590000E+04.SR+2:SR+2..15 +121000..1) 298......0) 298. ENTER-PAR L(ION.....MN+3:VA.LA+3..SR+2:SR+2:CR+3:O-2:O-2. ENTER-PAR L(RPEROV..15 GS2CO4+GLCR3O_RP1 @@ -GREFRP.6.MN+2:O-2.SR+2:MN+2:VA..0) 298.0) 298..CR+3:VA....SR+2:O-2.15 0...LA+3. O-2. ENTER-PAR L(ION..15 +GLA2O3LIQ.....0) 298.....0) 298. O-2 VA. ENTER-PAR G(ION. Povoden-Karadeniz ENTER-PHASE IONIC_LIQUID Y LA+3 SR+2 MN+2 MN+3 CR+2 CR+3.5*GHSEROO. -2...Appendix ENTER-PAR L(RPEROV. ENTER-PAR L(RPEROV. scarce experimental data @@ ENTER-PHASE RP.0) 298.1).MN+3:O-2.LA+3:MN+4.15 +2*GSROSOL+0.0) 298..SR+2:SR+2:CR+4:O-2:O-2.........0) 298.0) 298...15 100000.VA.15 GREFRP...15 +GMN_L.. @@ Interaction parameters from ternaries ENTER-PAR L(ION. ENTER-PAR G(ION.MN+3:O-2.15 +121000.15 1.1) 298.CR+2:O-2.. @@ -----------------------------------------------------------------------@@ Liquid.0) 298. @@ ENTER-PAR G(RP.LA+3. ENTER-PAR G(ION.0) 298.CR+3:O-2...0) 298. @@ ENTER-PAR G(RP.. ENTER-PAR L(ION.LA+3.15 +GMN2O3_L. ENTER-PAR G(ION.MN+2:VA.15 -1297.1). LA+3 SR+2.LA+3:CR+4. ENTER-PAR G(ION.. 5 1 1 1 3 1 SR+2..0).15 +2*GMN_L+GMN2O3_L-3*GMN1O1_L.LA+3:CR+3:O-2:O-2.SR+2:MN+3:O-2. @@ next two interaction parameters can be used to fit @@ Cr4+ amount in perovskite ENTER-PAR L(RPEROV..5*t...MN+3:O-2..LA+3:CR+3..15 0..0) 298..CR+2:O-2...VA:MN+4:O-2. ENTER-PAR L(ION...5*GMN2O3 @@ -0.15 +11368. @@ ENTER-PAR G(RP.. ENTER-PAR L(RPEROV. 9248...CR+3:O-2. ENTER-PAR G(ION.. AMEND-PHASE IONIC_LIQUID COMP 2.0) 298....MN+2:VA.LA+3:MN+4..MN+3:O-2..SR+2:CR+4..VA..SR+2:SR+2:MN+4:O-2:O-2. preliminary.LA+3:O-2.SR+2:MN+4:VA.0) 298.5*GHSEROO....1).5*GMN2O3 @@ +0... @@ ENTER-PAR G(RP. ideal extension from lower-order systems...LA+3.. -136600..0) 298..0)..SR+2:SR+2:MN+3:O-2:O-2.MN+4:O-2.SR+2:CR+4..LA+3:CR+4:O-2:O-2.15 3766.MN+3:O-2.. ENTER-PAR G(ION. ENTER-PAR L(RPEROV.15 -3..15 +GL3O_RP1+GS4O_RP1 @@ -2*GSROSOL-0..MN+2...LA+3..0) 298..15 +2*GMN1O1_L.0) 298..29519000E+05.. 250000.1).LA+3:VA... ENTER-PAR L(RPEROV. MN+3 MN+4 CR+3 CR+4..LA+3..0) 298..MN+3:O-2...... @@ ENTER-PAR G(RP.... ENTER-PAR L(RPEROV.. ENTER-PAR L(ION..15 +GS4O_RP1.15 +GCR_L.. -117000.VA:O-2.0).4..15 2*GCR1O1_L.SR+2:LA+3:MN+4:O-2:O-2..1) 298. ENTER-PAR L(RPEROV.. 187 . ENTER-PAR L(RPEROV..MN+2:O-2.. ENTER-PAR L(RPEROV.0) 298.VA:O-2.LA+3.0).0) 298. @@ ENTER-PAR G(RP.SR+2:LA+3:CR+3:O-2:O-2.15 -4.0) 298.0) 298..0) 298.....SR+2:MN+4:O-2..MN+2:O-2.1) 298.. 250000... -136600.VA.15 -11316.15 100000....MN+2:VA..15 GS2CO4. ENTER-PAR L(RPEROV.0) 298..0) 298.15 -1..MN+3:O-2.0) 298..15 +GLCR3O_RP1.SR+2:SR+2....0) 298.0).15 185. @@ ENTER-PAR G(RP..
ENTER-PAR L(IONIC.. ENTER-PAR G(CRGAS.. ENTER-PAR G(GAS..CR+2:O-2.15 +F7586T+RTLNP. 1500 N ENTER-PAR G(GAS.. ENTER-PAR L(IONIC..O3.CRH4O5.H1O1.. ENTER-PAR L(ION.CRH2O4. @@ @@ H2O reference gas ENTER-PHASE STEAM...MN+2:VA..15 +46000.CRH1.....CR+2:VA...0) 298....4) 298..15 +GCRH1O1_G+RTLNP. ENTER-PAR L(ION.0) 298..0) 298.LA+3.SR+2.7.15 +GCRH2O4_G+RTLNP. 6000 N ENTER-PAR G(GAS.. ENTER-PAR L(IONIC...15 -188487.0) 298.0) 298. ENTER-PAR G(GAS. SGTE and reassessments by Chen.15 +GCRH1O3_G+RTLNP.MN+3:O-2. @@-----------------------------------------------------------@@ Cr-GAS..0) 298.SR+2.CR1O2. ENTER-PAR L(ION.CR1O3.0) 298..15 +GCR1O1_G+RTLNP..15 +H2GAS+RTLNP.15 +GCRH2O3_G+RTLNP. 20000 N ENTER-PAR G(GAS..15 +F10963T+RTLNP..0) 298.CR+3:O-2. ENTER-PAR G(GAS. ENTER-PAR G(GAS.1) 298.15 +F10983T+RTLNP..CR+2:O-2....0) 298.. ENTER-PAR G(GAS. 20000 N ENTER-PAR G(GAS.15 -119062... 6000 N ENTER-PAR G(GAS. @@ @@ CRO3 reference gas ENTER-PHASE CRGAS.H2O1. 6000 N ENTER-PAR G(GAS.LA+3.0) 298..0) 298...CRH3O4...MN+3.0) 298.MN+2:VA....15 +GCRH2O2_G+RTLNP.15 +GCRH1O2_G+RTLNP.LA+3..CR+3:O-2..LA+3.. 1 O2.0) 298..0) 298..CR+2:VA..15 -179575...MN+2.15 +GCRH3O4_G+RTLNP. 20000 N ENTER-PAR G(GAS.0) 298.SR+2..CR+2:VA.LA+3.SR+2.1) 298.CRH1O3.CRH6O6...0) 298. 6000 N ENTER-PAR G(GAS.0) 298... 1 CR1O3.15 +GCRH5O5_G+RTLNP.0) 298.. ENTER-PAR L(IONIC..1) 298..MN+3:O-2. 20000 N @@ @@ O2 reference gas ENTER-PHASE O2GAS. 1 H2O1.. ENTER-PAR G(GAS. ENTER-PAR L(ION.. ENTER-PAR L(IONIC.15 +GCRH4O5_G+RTLNP.15 -101850.15 -179575.H.0) 298.CR+2:O-2.0) 298..15 +F13349T+RTLNP.. ENTER-PAR L(ION.6587*T.15 -9111.15 +F10729T+RTLNP.. ENTER-PAR L(ION.15 +504+0.15 +GCRH6O6_G+RTLNP...0) 298.CR1O3..9479*T.....15 +60713-5.. ENTER-PAR G(GAS.SR+2.CRH5O5.CR+3:O-2.CR+2:VA.H1O2.. ENTER-PAR L(ION.SR+2....0) 298.15 +F13704T+RTLNP..0) 298.0) 298..0) 298. ENTER-PAR G(STEAM.CRH2O2.....MN+2.H2O1.H2.15 +GCRH3O3_G+RTLNP.SR+2..15 -15009+13. 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 +HGAS+RTLNP.CR+3:O-2. ENTER-PAR L(ION.15 +GCR1O2_G+RTLNP. ENTER-PAR L(ION... ENTER-PAR G(GAS.CRH1O1..0) 298.. ENTER-PAR G(GAS.15 +GCRH4O4_G+RTLNP.0) 298.LA+3..15 +F10666T+RTLNP..CR+2:VA.15 +F14021T+RTLNP..15 +F10963T+RTLNP....LA+3.SR+2.CRH4O4.CR+3:O-2.0) 298.O. ENTER-PAR G(GAS.CRH2O3.O2.....15 -619869.0) 298.0) 298.15 -39016.15 +GCR1O3_G+RTLNP.CR+2:O-2..... ENTER-PAR G(GAS.15 +64573-23*T...15 -176300...1) 298.MN+2:O-2..LA+3..Appendix ENTER-PAR L(ION. ENTER-PAR G(GAS..0) 298. 188 .. ENTER-PAR L(IONIC.15 -176300.0) 298.. 6000 N ENTER-PAR G(GAS..15 +GCR1O3_G+RTLNP.0) 298. ENTER-PAR G(GAS.0) 298. ENTER-PAR G(GAS.0) 298.. ENTER-PAR L(ION.49*T.1) 298...15 -619869. ENTER-PAR L(ION. 6000 N ENTER-PAR G(GAS.0) 298..CRH1O2..0) 298.15 -39016.. ENTER-PAR L(ION...CRH3O3..15 -101850. ENTER-PAR G(GAS.0) 298.15 200000.1) 298.0) 298.CR1O1.H2O2.
. set-interactive +2*GHSEROO+RTLNP..O2.0) 298. N.... 189 ...Appendix ENTER-PAR G(O2GAS..15 @@ GO PAR @@ SET-OUT-LEVEL.
thesis: „ Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells“. Oxygen. carbon and strontium isotope systematics in two profiles across the Glarus thrust: implications for fluid flow. Graz 1979-1983 Elementary School. Berliner Ring. Miner.. Abart. Austria Education 01/2005 – 12/2008 Ph. Ludwig J. ETH Zurich. Prof. Department of Materials. Graz. Badertscher. Prof. Georg Hoinkes and Prof. Dr. pp. 1992-1999 Geoscience Studies. Rainer Abart 1983-1991 Realistisches Gymnasium. Petrol. Povoden. 190 . Nonmetallic Inorganic Materials. Contr. 143. Pestalozzistrasse 5. Erwin Date and place of birth: March 18. 1973. Graz Publications R.Curriculum vitae Curriculum Vitae Personal data Povoden-Karadeniz. Karl-Franzens University Graz Master thesis: „Kontaktmetamorphose und Fluid-Gestein-Interaktion in der östlichen Monzoni Kontaktaureole“. M. Switzerland. Dr. Dr. Burkhard. and E. 192-208. 2002. D. N. Gauckler.
to be submitted. Calphad. pp. Grundy. Gauckler. Presentations Assessment of the Cr-O system in the frame of SOFC research E. A.N. Grundy. M.N. J. and L. E. Horacek. A. T. Thermodynamic assessment of the La-Cr-O system. Povoden. A. Gauckler. Povoden. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. Povoden.. Ivas. Povoden. 76. Povoden-Karadeniz. J. Phase Equilib. E. and R. Phase Equilib. E.N. to be submitted. Grundy. T.. Res. Int. J.. Gauckler. Ivas. M. 30. Degradation of planar solid oxide fuel cells with (La1-xSrx)1-yMnO3 cathodes and Cr-alloy interconnects. Ivas. T.J. 99-120. Povoden. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials.J. Thermodynamic assessment of the La-Fe-O system. Gauckler. and L. E. 2006. Thermodynamic calculations of impacts of chromium on Sr-doped Lanthanum manganite (LSM) cathodes for solid oxide fuel cells (SOFC). Povoden. Chen. Povoden.Curriculum vitae E.N. Miner.J. Chen. 569-78. and L. Gauckler. Abart. 2002.J. and L. Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole. Ivas. and L. Gauckler. (accepted) E. and L. E. 1. Petrol.J. pp. Grundy. E. 2009. M.N. M. and L. 353-62. pp. Gauckler 191 . A. M. J. 12-27.N.Diff. 27. 33-41. Calculation of defect chemistry using the CALPHAD approach.J. Povoden. Chen. 97. Chen.J. Gauckler. pp. and L. Povoden. Mater. Diff.J. to be submitted. 2006. Grundy. A. Phase Equilib. A. Gauckler. A. Grundy. T.N. 2006.. Diff. E. Grundy. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. and L. pp.J.
Maastricht. 2005 Thermodynamic Assessment of the Cr-Mn-O System for Solid Oxide Fuel Cell (SOFC) Materials E. EMPA Dübendorf. USA. Grundy. Grundy. Gauckler Oral Presentation 3rd Fuel Cell Research Symposium. Z. and L. Boulder. Gauckler Oral Presentation Thermo 2006. August 4th.N.J. USA. and L. Pennsylvania State University.J. Povoden. and L. Peng. students. 2007 Thermodynamic assessment of the La-Cr-O and LaO3/2-MnOx-CrO3/2 Systems 192 . September 18th – 22nd. Switzerland. March 16th. 2006 The BiO3/2-SbO3/2-ZnO Phase Diagram at 1115°C in air E. Grundy. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fel cell (SOFC) materials E. Netherlands.N. Gauckler Oral Presentation HTMC XII. Povoden Oral Presentation 1st EMPA symposium for Ph. Povoden. Vienna. A.D. Switzerland. Colorado.N. May 6th – 11th. A.J.Curriculum vitae Poster Presentation CALPHAD XXXIV. Pennsylvania. Gauckler Poster Presentation CALPHAD XXXVI. A. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fuel cell (SOFC) materials using the CALPHAD approach E. Povoden. 2005 Thermodynamic assessment of the Cr-Mn-O system for solid oxide fuel cell (SOFC) materials E. Povoden. May 06th -11th. Austria. and L.J. October 20th. EMPA Dübendorf.
June 27th.The La-Sr-Mn-Cr-O system E. M.5-SrO-MnO1. 2007 The thermodynamic LaO1. Chen. Pennsylvania. and L. Povoden Oral Presentation Guest Talk. Finland.N. June 16th – 21st.J. Povoden. Lehrstuhl für physikalische Chemie. 2008 Thermodynamic LaO1.5-SrO-FeO1. A.5-CrO1.5 and LaO1.5-SrO-MnO1. Monatnuniversität Leoben. March 28th. 2008 193 .5-CrO1. USA. Povoden. Gauckler Oral Presentation CALPHAD XXXVI. Saariselkä.5-CrO1. Grundy. ETH Zurich. Gauckler Oral Presentation CALPHAD XXXVII. Grundy.5-CrO1.J.5 databases for SOFC applications using the CALPHAD approach E.N.5 databases for solid oxide fuel cells (SOFC) applications E.Curriculum vitae E.5-SrO-FeO1. May 6th – 11th. A.5 and LaO1. Pennsylvania State University. 2007 Thermodynamic modeling for solid oxide fuel cell research . Povoden Oral Presentation 2nd MRC Graduate Symposium . and L.
(Me)1(Va. J. In previous papers the authors have proposed the model Me(Va. For these reasons.3.Cr)(O.. otherwise the disordered model for interstitials in bcc. p.3. 2007. 31(1). accepted.Va)1. Phase Equilib. 109. p.O)1.5….Cr)(O. Hallstedt et al. Diff. 112 According to the latest discussion by B.X)3 is to be used…” Thus the model was also corrected in the thermodynamic assessment of the La-Fe-O system. 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. lines 7-14 and Table 4. Calphad. Povoden-Karadeniz et al.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. 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.” .Erratum.. p 2837 the correct model is (La.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. 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.. The following argumentation for modeling of the oxygen solubility in bcc using (physically wrong!) Me(O.Va)3 and not (La.5 based on the argument.Va)1.O)3 is undoubtedly a reasonable model description for the oxygen solubility in bcc.