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Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells
DISSERTATION for the degree of DOCTOR OF SCIENCES of the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH
presented by ERWIN POVODEN-KARADENIZ Mag. rer. nat. born on March 18, 1973 Citizen of Austria
accepted on the recommendation of Prof. Dr. Ludwig J. Gauckler, examiner Prof. John T.S. Irvine, co-examiner Dr. Ming Chen, co-examiner
Dedicated to my parents
Whatever creates or increases happiness or some part of happiness, we ought to do; whatever destroys or hampers happiness, or gives rise to its opposite, we ought not to do.
I am deeply grateful to my supervisor Professor Gauckler. He gave me a great chance by taking me into the boat: a boat that is not only sailed to scientific success. It took me away from an insecure float wobbling in the surf and approaches a promising future. Endless gratitude belongs to my wife who stays by my side throughout highs, downs, and distances, preventing me from losing the way; she is my firm anchor. I am greatly indebted to Nicholas Grundy for open doors, his patience of a saint, great teaching, and picky reviewing. He catalyzed my way into the field of thermodynamic modeling, airing the “modeling is fun” approach at any time. I would further like to thank Ming Chen for continuing scientific support and advising; he was often motivating me to spin the wheel of accurate and fast modeling and publishing. I owe thanks to Franc and Flavia Dugal-Borsari who saved me from an unintentional outdoor adventure in Zurich during a time when it was extremely difficult to find a new accommodation. It was a very pleasant time in Zollikon. I thank Brandon Bürgler and Jennifer Rupp for their pleasing office companionship at the beginning of my work: they facilitated my jump into the ETH waters. I would also like to thank Toni Ivas for abiding collegiality, cooperation, and friendship. I thank the rest of the office crew, Thomas Ryll and Rene Tölke, for always enjoyable working hours.
Zurich, December 2008
2 1.2 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC Thermodynamic modeling 3.1 1.2 3.3.4 1.1 3.1 1.1.1 3.2 1.5 1.Table of Contents Table of Contents Summary Zusammenfassung 7 9 1 Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cralloy interconnects 1.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.1 Introduction 1.3 22.214.171.124.126.96.36.199.2 1.2 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes New ways – alternative materials 2 3 Aim of study Method 3.3.3 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 188.8.131.52.6 Degradation of SOFC caused by chromium from the interconnect The role of current load on electrical losses of degraded SOFC Impedance spectroscopy measurements and implications on the degradation process Microstructures in degraded SOFC Amounts of chromium in SOFC tested with and without current load Critical assessment of proposed mechanisms of chromium “poisoning” 1.1 1.3 Stoichiometric solid oxides Solid solution phases – the Compound Energy Formalism (CEF) Vacancies and the concept of reciprocal reactions 4 .
5 4.2 4.3.5 4.1.5 Conclusions 5 Thermodynamic calculations of impacts of chromium on Sr-doped 5 .7 Conclusions 4.1.4 184.108.40.206.6 Conclusions Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications 4.3 4.2.1 Introduction 4.6 Experimental data Previous assessments of the Cr-O System Thermodynamic modeling Optimization of parameters Results and discussion Thermodynamic assessments 4.2 4.1.1 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 4.1 Introduction 4.4 Literature review of the La-Cr system Literature review of the La-Cr-O system Thermodynamic modeling and optimization Results and discussion 220.127.116.11 4.Table of Contents 3.4 18.104.22.168 Assessment of data from the literature Modeling and optimization Results and discussion 4.2 4.2.3 4 4.2.4 22.214.171.124.3 4.1 Introduction 126.96.36.199.4 4.2 4.2.1 Technology 4.5 4.3.3 4.3 Experimental Thermodynamic modeling Optimization of parameters Results Discussion 188.8.131.52 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials 4.6 184.108.40.206 Applications on SOFC Thermodynamic assessment of the La-Cr-O system 4.
2 5.8Sr0.1MnO3-δ contaminated by chromium Thermodynamic calculations of (La0.9Sr0.4 5.5 Thermodynamic calculations of La0.2)0.3 5.9MnO3-δ contaminated by chromium Thermodynamic testing of LSM with Mn-deficiency Formation of Cr2O3 148 149 150 152 152 157 160 162 163 165 Discussion Conclusions Appendix Thermodynamic La-Cr database Thermodynamic La-Sr-Mn-Cr-O-(H) oxide database 170 169 172 Curriculum Vitae 190 6 .4 5.3.1 5.3.1 5.2 5.3.3 Introduction Method Results 5.Table of Contents manganite (LSM) cathodes for SOFC 5.3.
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. 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. The chromium is known to deteriorate the electrical performance of the cathodes. 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. Furthermore spinel blocks pores and thus impedes the oxygen 7 . The associated chemical changes of the LSM phase. and the aim of this study (chapter 2) is to gather a deeper understanding of these unsolved problems by using thermodynamics. Some of these processes are governed by thermodynamics. how thermodynamic calculations can lead to a better understanding of a system. and the modeling approach used in this study is presented. 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.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. In chapter 1 the basics of planar SOFC are briefly explained. 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. some of them probably occurring simultaneously. This has calamitous consequences for the electrochemical properties of the cathode. Chapter 4 deals with the construction of the La-SrMn-Cr-O oxide database based on the assessments of subsystems. It is shown that chromium “poisoning” of SOFC cathodes is a rather complex process consisting of several steps. even if the system is in a thermodynamic non-equilibrium state. and some are kinetically controlled. In the third chapter the reader learns. and previous findings of chromium “poisoning” of SOFC are critically reviewed.
which of the phenomena in a chromium-“poisoned” LSM cathode are governed by thermodynamics.Summary reduction required for the function of the cell. With this contribution the prevailing question is resolved. Cr2O3(s) (s = solid) that hampers the diffusion of oxygen into the electrolyte is a metastable phase in LSM contaminated by chromium. 8 . Appropriate measures can be foreseen preventing the long-term degradation of SOFC cathodes in combination with high-chromium containing interconnects.
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).
Normally many cells are electrically connected in series by an interconnect. 1.2 (next page) for the widely used planar-design SOFC. 12 . 1. a = anode. forming a cell stack to obtain higher voltage and power. The electrons flow from the anode through the external electric circuit to the cathode. These ions migrate through the electrolyte to the anode. The direct-current electricity is produced by the electron flow through the external electric circuit. All the components of the cell need to be matched in their thermal expansion in order to minimize mechanical stresses.5 to 1 W cm-2. White circles symbolize pores. e = electrolyte.7 to 1 V and power around 0.1 Scheme of the electrochemical processes in a fuel cell with O2 oxidant and H2 fuel. and ceramicmetal composites are used for the anode. At the anode the oxygen ions react with hydrogen of the fuel to form water and release electrons.1. as shown in Fig. The electrodes are required to have high reactivity and the electrolyte must allow high oxygen ion diffusion. In an SOFC. The oxygen.1. 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. A single cell produces a voltage of 0. supplied at the cathode reacts with electrons from the external electric circuit to form oxygen ions. 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. c = cathode.
as the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. a thermal expansion coefficient close to that of the cathode and the anode.2 The problem of chromium “poisoning” In the 1990is LaCrO3-based ceramics were intensively investigated for interconnect applications in SOFC. 1. as chromium alloys come close to all desired properties. Nowadays the state-of-the-art interconnect is commonly a chromiumcontaining metal plate[3-5]. low permeability for oxygen and hydrogen to minimize direct combination of oxidant and fuel during cell operation. a low ionic conductivity.1. However high costs of these materials.1. and their thermal and redox-stability is satisfying. difficulties in sintering and manufacturing and low mechanical strength required the development of alternative interconnect materials.2 Planar design of SOFC The interconnect separates the fuels and oxidants in adjacent cells. the electronic conductivity of several LaCrO3-based ceramics under SOFC operating conditions is high. It is the most demanding component in a planar SOFC as it should have a high electronic conductivity. 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. stability in both oxidizing and reducing atmospheres at the high cell operating temperature (from about T = 973 K to 1273 K).Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. and chemical compatibility (no reactions) with other cell materials. 1. 13 .
1) 14 . But when it was learned that Cr2O3(s). and at T = 1373 and 1473 K in flowing dry and wet oxygen as well as in dry and wet argon. Caplan and Cohen investigated the evaporation of Cr2O3(s) by measuring the weight loss when Cr2O3(s) pellets with 1.6 mg at T = 1473 K at a gas flow rate of 200 ml min-1 after 20 h. or at discontinuities such as fractures in the film and would then evaporate.3 mg at T = 1273 K after 72 h.6 mg at T = 1373 K and 2. The volatilization in wet oxygen was significantly higher after 20 h at the same gas flow rate: 2. and it was suggested that high-valent gaseous Cr-oxide and Cr-oxyhydroxides detrimentally affect the O2 -adsorbtion. the volatile species must be a higher oxide of chromium.2 cm in diameter and height were heated at T = 1273 K in stagnant air.2. Appreciable volatilization occurred in dry oxygen. 1. the weight loss being 0. but its formation by the reaction Cr2 O3(s) + 3 2O2(g) → 2CrO3(g) (1. and -diffusion processes. in the absence of metal. -reduction.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. 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. This was a surprising result. Volatilization of Cr2O3(s) was neither observed in dry nor in wet argon. 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. Since weight loss takes place under oxidizing conditions. neither the vapour pressure of Cr2O3(s) nor its dissociation pressure is high enough to account for the quantities of deposits observed.6 mg at T = 1473 K. A known volatile oxide of Cr is CrO3. it became evident that a volatile Cr-oxide was being formed. Furthermore.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. In stagnant air the volatilization was 0. lost weight when heated in oxygen.1 mg at T = 1373 K and 5.3-2.
18] cited above.2) Cr2 O3(s) + 1 2O2(g) + H 2 O(g) → 2CrO2 (OH)(g) (1.1 (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.3 is calculated to be +134 kJ at T = 1273 K using combined data from Kim and Belton and Ebbinghaus. This tendency is shown in Fig. These findings are supported by the higher volatilization of Cr2O3(s) in wet air. 15 .2..2.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects is thermodynamically unfavourable at high temperatures. and Ebbinghaus. 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. the formation of CrO3(g) occurs under kinetic control. 1.1 is calculated to be +321 kJ at T = 1273 K using assessed thermodynamic data for Cr2O3(s) from Povoden et al. The existence of gaseous Cr-oxyhydroxides as oxidation products (Eqs. 1. 1. Δ°G of Eq. However.3) Δ°G of reaction 1.2. As gaseous CrO3(g) was detected experimentally by mass spectrometry when Cr2O3(s) was heated under oxidizing conditions.2.3) in wet atmosphere was experimentally proven in several studies[14-17]. and for CrO3(g) from Ebbinghaus.2 is calculated to be −158 kJ at T = 1273 K using combined data from Opila et al. whereas at higher temperatures the gas phase mainly contains CrO3(g) and CrO2OH(g). 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.2 and 1. 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. and this was affirmed by thermodynamic modeling. data for O2(g) from Dinsdale. μ(O) being −300 J mol-1 referred to pure oxygen gas result from combined thermodynamic data[11-14.2. and Δ°G of reaction 1.
Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. the mass loss being higher at higher water content and higher temperature: the constant rate of mass loss was 0.2 μg h-1 for 3 mol% H2O in air at T = 1073 K. used a transpiration method proposed by Gindorf et al. The Cr-vaporization rate of Cr5Fe1Y2O3 exceeds that of Crofer22APU by about a factor of 3 in the temperature range from T = 1023 K to 1173 K. and the 16 .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 = 2.3 μg h-1 for 25 mol% H2O in air at T = 1073 K. 1. and 18.6 μg h-1 for 3 mol% H2O in air at T = 973 K. Mass loss of Cr2O3(s) at T = 973 K and 1073 K was measured in air with different amounts of water. to measure the vaporization rate of Cr from Cr5Fe1Y2O3 (Ducrolloy) and Crofer22APU (high-Cr ferritic steel). reaching pCr = 4.2. Cr-vaporization in SOFC: Konysheva et al. at T = 1073 K for a time period of about 500 h. two high-chromium alloy interconnects widely used in SOFC. 3.57x10-3 Pa at T = 1223 K.12x10-5 Pa at T = 673 K and increases as a function of increasing temperature.
17 .34. Badwal et al.220.127.116.11] of the degradation of SOFC with LSM cathodes caused by chromium are listed in Table 1. The amount of Cr in these degraded cells was 140 μg cm-2 with Cr5Fe1Y2O3. 1. 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. thus quantitative chromium “poisoning” rates affecting the cathode are difficult to determine.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects vaporization rate increases with increasing temperatures for both alloys.5 higher than with Crofer22APU. this value being by about a factor of 2. With increasing humidity the difference in the vaporization rates between the two alloys increases.1 Degradation of SOFC caused by chromium from the interconnect Considering the experimental data from Caplan and Cohen. pp. 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. However.3 Literature survey 1. Experimental results[21-29. 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. for an SOFC setup with a Cr5Fe1Y2O3 interconnect plate. 18-21.3.3. mentioned significant amounts of deposited Cr2O3(s) in the air exhaust of the cell. an LSM cathode.
3.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Table 1.1 Results of chromium poisoning of SOFC with and without Cr-containing interconnects with LSM cathodes collected from the literature 18 .
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 .
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. The cell was electrochemically tested at T = 1273 K under a current load of 300 mA cm-2 for 400 h..1MnO3-δ. and intensity measurements using electron probe microanalysis showed that Cr was concentrated at the cathode-electrolyte interface. These authors measured an increase of cathode polarization and decrease of cell voltage in an SOFC consisting of an LSM cathode with the compositions La0.7 V to about 0. The cell voltage decreased over this time from initially about 0. In a test of the same setup under open circuit conditions for 21 . a YSZ electrolyte and a NiO/YSZ anode with a piece of a Ni-Cr-Fe-alloy (Inconel 600) attached on top of a Pt mesh used as current collector.1 V.9Sr0.
All these experimental studies[22-29] unambiguously proved that chromium stemming from the alloy interconnect causes the degradation of SOFC.: these authors tested the cell performance of an SOFC with a Cr5Fe1Y2O3 interconnect plate. an LSM cathode. its power density decreasing from a maximum of 0.1 V during an operation time of 2500 h.48 W cm-2. a YSZ electrolyte and a Ni-zirconia cermet anode at T = 1273 K and a current density of 250 mA cm-2. whereas the opposite was observed for SOFC with Cr-alloy interconnect.3. 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. 1. ascribed the voltage decrease to increasing losses of cathodic overpotential. the voltage drop being 0. the cell performance was stable for 110 h. But using a Cr-Fe-alloy interconnect.4 V after only 16 h. and Cr was randomly distributed across the cathode. On the other hand the voltage of the cell with Cr-Fe-alloy interconnect decreased rapidly as a function of operation time. and to chromium deposited at the LSM-YSZ interface filling pores. Later these results were confirmed by Badwal et al.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 300 h no deterioration of the cell performance was observed. 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 . the cell started to degrade severely after 20 h of testing. 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. 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. Simner et al. presented cell performance data of an SOFC with LSM cathode. holding the cells at 0.2 The role of current load on electrical losses of degraded SOFC Badwal et al. thus linked the cell degradation to the time that the discharge current was applied. reported that the degradation rate of SOFC with a Cr5Fe1Y2O3 interconnect plate. Taniguchi et al.05 W cm-2 after 110 h. the power density being 0. an LSM cathode. The cell performance without interconnect plate deteriorated only little by less than 0. hindering the supply of oxygen gas and decreasing the number of reaction sites for the oxygen reduction. a Sm2O3-CeO2 interlayer between cathode and electrolyte.7 V: without the interconnect steel.2 W cm-2 to 0.
5 V potential.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.33]. 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. At the beginning of the cell tests.5 Ohm cm2 for a thickness of 23 . 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.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. with a tendency of stabilization of the cell performance after this testing period at much lower magnitude of output current. However the cell degraded rapidly again when the current was switched on again.4MnO3-δ cathode and a YSZ electrolyte at 300 mA cm-2 current density. La0.[24. in agreement with earlier findings[22. The total polarization resistance (Rpol) of a half-cell setup using a Cr-Fe-alloy interconnect.. using a half-cell with a Cr5Fe1Y2O3 interconnect. Zhen et al.32. In earlier studies using the same setup a rapid decrease from −360 to −560 mV after 10 minutes[25.25] at 1173 K and a current density of 200 mA cm-2.6 V.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 15.2)0.26] was observed.65Sr0. losses increased sharply and reached their maximum values after only 15 h of cell operation.28.8Sr0. a La0. Konysheva et al.23. Rpol being 0. whereas at 280 mA cm-1 the voltage dropped by 0.25.6Sr0. an LSM/LSM-YSZ cathode double layer and a YSZ electrolyte tested for 400 h was markedly dependent on the thickness of the LSM-YSZ layer. 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. 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. Konysheva et al. LSM cathode and a YSZ electrolyte tested 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 flow of electrons through the cathode) increased only insignificantly during the cell tests. The overpotential losses were higher and the cell deterioration was faster at higher current density. tested the reversibility of degradation in a half-cell setup with CrFe-alloy interconnect.31]. 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. A plateau of degradation was reached after about 400 h of testing.07 V.
 observed an increased size of the high frequency arc during the current passage in half-cell tests using a Cr5Fe1Y2O3 interconnect plate. Jiang et al. 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. 0. 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. and 2 Ohm cm2 for 7 μm. LSM cathode and YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2.32]. 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. a La0. Mazusaki and Yasuda concluded from the interpretation of impedance spectra of a half-cell with an Inconel 600 interconnect.3 Impedance spectroscopy measurements and implications on the degradation process Badwal et al.3.7 V.26. reflecting increasing cathode resistance. and from −800 to −1120 mV at T = 973 K after 10 minutes. This finding was confirmed 24 . The total polarization resistance was also higher at higher current load.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 50 μm. Zhen et al.4MnO3-δ cathode and a YSZ electrolyte operated at T=1073 K and 300 mA cm-2 current load that the degradation in the electrode caused by chromium was due to the increase in both charge-transfer resistance and surface diffusion resistance. but not due to the increase in ohmic resistance. were the first who reported the occurrence of Cr-Mn-spinel in Cr“poisoned” SOFC with an LSM cathode by using XRD analysis. observed less overpotential losses at lower temperatures in a half-cell with CrFe-alloy interconnect. reported the existence of a high frequency and a low frequency arc in impedance spectra of a half-cell with Cr-Fe-alloy interconnect.75 Ohm cm2 for 13 μm.4 Microstructures in degraded SOFC Cathodic polarization: Taniguchi et al.[24. 1. 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. from −900 to −1200 mV at T = 1073 K.3.6Sr0.33] and Jiang et al. 1. an LSM cathode and a YSZ electrolyte as a function of operation time. The degradation was higher at higher temperatures at 0.
an LSM cathode. Badwal et al.36] documented spinel formation at the LSM-YSZ interface already after 4 h. Jiang et al.[25. an LSM/LSM-YSZ cathode double layer and a YSZ electrolyte chromium-deposits were only found in the LSM layer under open circuit conditions. but further details on their spatial distribution and composition were not given. Under the same testing conditions as above.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects by Badwal et al. a YSZ electrolyte and a Nizirconia cermet anode at T = 1173 and 1273 K under current load.05 μm) of Cr2O3 towards the cathode-electrolyte interface. who detected small amounts of Cr-Mn spinel after 100 h of operation of SOFC with a Cr5Fe1Y2O3 interconnect plate. Using the same setup as above. Using the same setup.36]. but under anodic polarization very fine grains of Cr2O3 were forming exclusively at the LSM-YSZ interface. 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 Cr-Mn spinel formed already at 25 . The deposition zone broadened as the polarization time increased from about 60 μm after 50 h to 89 μm after 129 h. In some cases these authors also observed Cr2O3(s) at the cathode-electrolyte interface. Zhen et al. In the same setup without LSM-YSZ functional layer no chromium-deposits were detected without current at T = 1073 K over 393 h. For the same setup large quantities of spinel had formed after 2000 to 2500 h of cell operation. further observed spinel in the contact region between interconnect and cathode. The grain size of spinel was about 0. and the cell degradation was strong. and the cell-degradation was weak. The zone of these large faceted crystals was followed by a zone of very fine grains (about 0. 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.17 μm after 4 h of cell testing and increased to about 0.7 μm after 50 h. in some of the experiments forming a dense layer of several microns at the cathode-electrolyte interface. observed dense Cr-Mn spinel-deposits exclusively at the LSM-YSZ interface after a half-cell test of an SOFC with Cr-Fe-alloy interconnect operated for 20 h at T = 1173 K and a current density of 200 mA cm-2. 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 a half-cell setup with a Cr-Fe-alloy interconnect. unfortunately the specific conditions for its formation were not given in more detail. no Cr-deposits formed after 50 h of testing under open circuit conditions[25. Using a half-cell setup with Inconel 600. Very small grains of Cr-deposits formed at T = 1373 K under open circuit conditions.
2)0. reported the formation of very fine particles of Cr2O3. after the half-cell was tested by a sequence of 8 chronoamperometry experiments at −0.98MnO3-δ cathode that rested on a 144 mm2 square YSZ electrolyte. exclusively covering the YSZ surface.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. After 20 h spinel formation was observed forming a 40 to 50 μm wide band at the LSM-YSZ interface. and the density and size of deposits increased by time.21 % Cr attached on top of a 4 mm2 square (La0.8Sr0. and spinel crystals were found on the surface of a thin Cr2O3-layer adjacent to the electrolyte. Transmission electron microscopy analyses revealed the layered structure of the composites: a 0. These authors observed the formation of a 500 μm broad zone of 8 individual.. almost completely 26 . large gaps between YSZ grains formed. up to 10 μm away from the LSM-YSZ interface after 160 h of testing.5 V and T = 1073 K. dense Cr2O3-layers at the edge of LSM on the YSZ surface. After 5 minutes of testing at T = 1173 K very fine Cr-deposits (< 100 nm) already formed on the YSZ-surface.18MnO3-δ cathode and a YSZ electrolyte were systematically investigated as a function of time and temperature at a current load of 200 mA cm-2 by Jiang et al. a La0.5 μm thick layer directly adjacent to the YSZ containing mainly Cr2O3 is covered by a spinel layer. and the deposition was less pronounced at T = 1073 K and 973 K.72Sr0. The morphology of the particles was different than the morphology of the deposits under cathodic polarization. Cr2O3 completely filled gaps between YSZ grains. Influence of temperature: Microstructural changes during half-cell tests of a setup consisting of a Cr-Fe-alloy interconnect. After 160 h of testing at 100 mA cm-2 current load. Cr-deposits consisting of Cr2O3 and Cr-Mn-spinel were concentrated in an about 2 μm broad region at the LSM-YSZ interface. Cr2O3 was also found inside YSZ. and 30 μm from the LSM-YSZ contact after 940 h. A reference test without polarization did not lead to these features. Anodic polarization: After a half-cell test of an SOFC with Cr-Fe-alloy interconnect operated for 6 h at T = 1173 K and a current density of 200 mA cm-2. In direct contact with YSZ about 500 nm large Cr2O3-grains were detected. No spinel formation was observed in these experiments. Paulson and Birss investigated the microstructures in a half-cell setup with a stainless steel disk containing 15. Jiang et al.
5 Amounts of chromium in SOFC tested with and without current load Konysheva et al. associated with large grains (about 1 μm) of spinel. compared the total amounts of chromium in half-cells with Cr-Fe-alloy interconnects. measured about 2. This may lead to a dramatic drop of the oxygen diffusion coefficient in LSM by about 60% and pers.% of Cr at 10 μm distance from the cathode-electrolyte interface. a Sm2O3-CeO2 interlayer between cathode and electrolyte and a YSZ electrolyte with a Crofer22APU interconnect operated at T = 1073 K. although the degradation of the polarized cell was remarkably higher. measured 5 at.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects covering the YSZ surface. Simner et al. a La0. 27 . comm. Krumpelt et al.% Cr in the Sm2O3-CeO2 interlayer. holding the cell at 0. In a half-cell with LSM cathode. but no Cr in LSM using energy dispersive scanning electron microscopy.3MnO3-δ/LSM+YSZ double layer cathode and a YSZ electrolyte after tests without current showing very small degradation. The Cr-content dropped to about 0. 1.7 V. 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.7 V for 120 h.3.8 wt. 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.vacancy within about 10 Å around Cr3+. The amounts of chromium in the half-cell operated under a current was 100 μg cm-2 after 150 h and 150 μg cm-2 after 500 h. In SOFC with LSM cathodes and a Cr-Fe-steel interconnect that were tested at T=1073 K for 300 h at 0. It further decreased slightly towards the interconnectcathode interface.5 wt. The amount of Cr-deposits was significantly smaller after 20 h of testing and 200 mA cm-2 current load at T = 973 K: isolated fine particles (about 100 to 200 nm) were detected on the YSZ surface. The decreasing degradation at lower temperatures was ascribed to slower diffusion and lower partial pressure of gaseous Cr-species.65Sr0. By using molecular dynamics simulation techniques it was stated recently that only 890 ppm Cr3+ in LSM significantly increase the formation energy of O2. this is only 15 to 20 % higher than in the cell operated without current.
1) Several authors[21-23.3. and gas.37].33. Badwal et al. 1. 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.3. 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. 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. described by inverse Eq. 1.3. Both reduction and chemical dissociation processes reflect non-equilibrium conditions. 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. Badwal et al.1 when solid solubility of Cr in LSM is considered and spinel contains the molar fraction of Cr. 1.31.2) 28 .2.1. emphasized that chromium “poisoning” would consist of several processes. In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary (TPB) between LSM.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[21-23.230.2 is a possible reaction for the formation of spinel with a higher amount of Mn. where the reaction partners for the reduction.3. 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) (1.30-31.33]. YSZ. and 2) Chemical dissociation of Crspecies on the LSM surface[24-26. reduction of CrO3(g) at the cathode-electrode interface competing with the normal oxygen reduction reaction. and blocking of pores by Cr-Mn spinel and Cr2O3(s).Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1.1) Eq. electron-donating LSM and oxygen-accepting YSZ are available. including changes of the chemical composition of the LSM surface.32.33] ascribe the mechanism of chromium “poisoning” to the reduction of gaseous CrO3(g) and Cr-oxyhydroxides at the cathode-electrolyte interface. 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.
These assumptions would mean that fast reduction of Cr-gas to Cr2O3(s) occurs as one process.3. However the formation of spinel can also be interpreted as a direct solid-gas reaction.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects For equal y in Eqs.3. red = reduction.3.3. more oxygen is produced.1 Possible reaction paths for the spinel formation as a function of Gibbs energy. Fig. Ea of the concerning reaction.1 and 1. and the mobility of the gas phase is high. reactions of direct formation of spinel by the interaction between Cr-gas and LSM can be formulated (Eqs. 1. and the LSM-Cr-gas reaction occurs as a parallel process leading to the formation of spinel. sp-form = spinel formation. and this is not known. 1. Which of the possible reaction paths is realized.3. 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. The true shape of the curves depends on the activation energy Ea and is thus not known. Fig.1 is a simplified illustration of possible reaction paths that lead to the end product Cr-Mn spinel.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). thus assuming a lower activation energy for the LSM-Cr-gas reaction. 1. Oxygen production stems from the reduction of Mn3+ in perovskite to Mn2+ in spinel.5) considering the main chromium molecules that interact with LSM for spinel with X(Cr) = 2X(Mn). As it is not assured if spinel in fact forms in a solid-solid reaction. Such gas-solid reaction can be split into two reaction steps: formation of 29 .3.3. and LSM gets more deficient in Mn. depends on the activation energy. 1. 1.2 less Cr2O3 is needed for the formation of Mn2CrO4.3 to 1. The shape of the curves in Fig.
[24-27. opposite to the trend that would be expected under the control of the vacancy diffusion mechanism.3.32. Huang et al. and consequently to Cr-Mn spinel and Cr2O3(s).32.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. Yasuda et al.3. The ionic conductivity was lower at lower oxygen partial pressures.5 that oxygen is produced during the formation of spinel. concluded that 30 . 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. This in turn will also lead to less Mn2+ in LSM and consequently lower oxygen diffusion in LSM. 1.1 to 1.4) 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) (1.37]: 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.18.104.22.168] 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.3. 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) (1.3) 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. However they did not discuss the dependence of oxygen diffusion upon pO2 .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. Thus the pO2 at the locations of the spinel formation is expected to increase. 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.33. As Mn2+ is associated to vacancy formation in LSM that is necessary for the oxygen diffusion. It can be seen from Eqs.
Paulson and Birss.1 has a large negative value. η = −0. In an investigation of active sites for the oxygen reduction at the O2/LSM/YSZ interface for three different overvoltages of cathode polarization (η = −0.336 V corresponding to pO2 = 10-4 Pa. compared to δ = 3.32.336 V.9Sr0. This confirms the suggestion that the formation of oxygen vacancies in LSM contributes to the oxygen diffusion at high current loads. when the oxygen partial pressure at the cathode-electrolyte interface is decreased significantly.37].2MnO3-δ at 973 K and pO2 = 10-4 Pa is δ = 2.185 V. Based on the findings from the literature it can be summarized that in LSM oxygen diffuses through grain boundaries at high pO2 .1CoO3-δ in which oxygen ions are transported by the vacancy mechanism.8Sr0.2. 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. 1. Reduction of CrO3(g) to Cr2O3(s) was such predominant as to make sampling of gaseous CrO3(g) difficult. The calculated amount of oxygen vacancies (δ) in La0. This indicates that a vacancy diffusion mechanism also applies to LSM. as oxygen vacancies are simply not available under these conditions. 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. The electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach[24-27. as well as Konysheva et al. as Δ°G of the reduction being the inversion of reaction Eq. This phenomenon was well explained by continuous feeding of an initial 31 . as it was directly proven by isotopic and tracer diffusion experiments.94x10-9 in air. 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. observed the extension of dense Cr2O3layers into YSZ. The activation energy for the diffusion of oxygen for LSM is in the range of 250 to 300 kJ mol-1.33.090 V) using isotopic oxygen exchange and secondary ion mass spectrometry it was found that oxygen ions can only diffuse through dense LSM at the high overvoltage of η= − 0. We believe that the oxygen vacancy diffusion mechanism contributes to the oxygen diffusion under high current loads. It was also mentioned in the early paper of Caplan and Cohen that substantial precipitation of Cr2O3(s) from CrO3(g) occurred in the cooler part of the experimental setup. and η = −0.4x10-6.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. This is close to 270 kJ mol-1 for La0.
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. In this case no chromium will be deposited at the cathode-electrolyte interface under open-circuit conditions. and the normal charge transfer can take place by switching it on again. Also two different diffusion processes were distinguished. If CrO3(g) is electrochemically reduced to Cr2O3(s) in a cell. The region of spinel formation extends several microns from the TPB into the cathode. the latter becoming reduced at the new TPB consisting of YSZ and electron-donating Cr2O3(s)[21.33. Thus it is obvious that the explanation of the “poisoning” process by the chemical dissociation approach alone is not without doubt. thus the formation of nuclei by the proposed LSM-Cr interaction won’t occur.30.[24. This is in contrast with the complicated mechanism for the formation of Cr2O3(s) under anodic 32 . from impedance spectra analyses it was in fact possible to distinguish two distinctive depositions of Cr-species. which both seemed to be inhibited by chromium poisoning.32.26. whereas the phase that was most likely identified as Cr2O3 occurs in fine-grained. and the second with a higher rate on the YSZ electrolyte surface. partly layered structures.31]: by switching off the polarization the competing reduction of CrO3(g) no longer occurs.37]: the two phases formed in the scope of a polarized LSM cathode exhibit distinctive microstructures: spinel forms large grains. whereas an explanation by the chemical dissociation approach is not satisfying. In this case the contribution of reduction to the Cr-“poisoning” has to be rejected.34]. whereas in a polarized cathode the reduction of CrO3(g) takes place and competes with the oxygen reduction leading to Cr2O3(s) deposition.23. 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).28. and the degradation can be associated to the dissociation process[24-27. Cr2O3(s) deposition should also occur under open-circuit conditions.37] and subsequent formation of spinel. which does not seem to be the case for the spinel phase. Furthermore. Some indications for two independent chromium poisoning mechanisms can be found in the work from Jiang et al. which is increasing as a function of increasing polarization. whereas Cr2O3 is always located directly at the cathode-electrolyte interface. This explanation is in line with the microstructural features of tested cells both under open circuit voltage and under current load. 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. and it is also in line with the observed temporary reversibility of the cell deterioration[22. From the occurrence of finegrained Cr2O3 the existence of a large number of nuclei for its formation is concluded. one with a lower rate on the LSM surface.
and in LSM a pO2 gradient is expected under polarization. Alternatively. and thus lack of spinel formation. opposite to the situation with a platinum cathode. It was further mentioned that the existence of Cr-containing products away from the TPB would be in disagreement with the reduction approach. In this context experimental results of a half-cell test with Cr-Fe-alloy (RA446) interconnect. LSM cathode and a YSZ electrolyte at T = 1173 K and a current density of 200 mA cm-2 from Zhen et al. Oxygen deficiency is negligible in LSM under high pO2 .Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects polarization established by Jiang et al. contrary to an LSM electrode. based on an early finding that LSM behaves like a metallic electrode at low polarization potentials that was not quantified. which is indeed not the case in a platinum cathode. However. 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. In cell tests of a polarized platinum electrode using a Cr-containing interconnect no Cr was observed. This is a simple and consistent explanation for a strict localization of Cr2O3(s) formed by reduction of gaseous Cr-species even under anodic conditions. However this conclusion was not tested in the light of the oxygen partial pressure gradient towards the electrode-electrolyte interface: contrary to platinum. the following simple explanation for strictly localized Cr2O3(s) formation under anodic polarization can be given: in an LSM cathode the reduction of gaseous Cr-species is expected to be localized at the triple phase boundary. this apparent antagonism is abolished. the number of the latter being less than under cathodic polarization. This is an indication against one unique “poisoning” mechanism. and thus under these conditions LSM has no tendency at all to accept oxygen. 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. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. if both the chemical dissociation as well as the reduction of gaseous Cr-species is occurring with different proportions. 4 b) as a function of time reveals an inflection point after about 6 1/2 h. are particularly interesting: the slope of the cathode polarization curve (Fig. 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. This different behavior of Pt and LSM electrodes under Cr-poisoning was used as an evidence for the exclusive validity of the dissociation approach. where the reaction partners for the reduction. contrary to the situation of a strong pO2 gradient under cathodic polarization. that includes diffusion of Mn3+/Mn2+ driven by the oxygen evolution reaction at the cathode/electrolyte interface.
even though the decrease is expected to be less due to less LSM/YSZ active sites caused by the first degradation. 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. Under polarization. the lower is the oxygen partial pressure at the contact between LSM and YSZ. The higher the current density under SOFC operation. the LSMCr interaction is again favored in the region close to YSZ as pO2 decreases at the TPB. and oxygen cannot access the TPB. Reduction already takes place at higher pO2 at the beginning of the current load operation.. 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. 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. 34 . This results in a lower oxygen partial pressure at the interface as compared to that in air. 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.8 S m-1 at T = 1282 K and pO2 = 1 Pa. weak catalytic reaction diffuse into YSZ. The temporary reversibility of the deterioration by switching the cell off and on again can also be explained: in contrast to current load operation.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects performance. The deposition of chromium followed by its reduction near this interface blocks direct oxygen access to the electrochemically active sites.8 S m-1 in air). Oxygen is mainly reduced at the new TPB between Cr2O3(s) and YSZ. 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). the oxygen ions formed at this interface are transported from the cathodeelectrolyte interface through the electrolyte. Applying a current load. as electronic conductivity of Cr2O3 is significantly higher at higher pO2 (1. under open circuit the LSM-Cr interactions occur randomly throughout the cathode. As Cr2O3(s) has a small electronic conductivity of 0. give the following explanation. and their respective influence on the cell deterioration may vary as a function of time. the oxygen ions from this new. 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. thus the remaining TPB/YSZ active sites are almost unaffected under open current circuit. Konysheva et al.
5. Fig.3. or gas-solid reaction.2.2.2 is a visualisation of the microstructural consequences of chromium in an LSM cathode. but new oxygen is not supplied to the new TPB.3.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Oxygen ions diffuse into YSZ. and chromium content is schematized in the picture.2. Active LSM/YSZ sites further diminish by ongoing formation of spinel and Cr2O3 deposits.2.3 occurs. 1. 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. 1.3. current load. and number 3 denotes the reduction of gaseous Cr-species by the reverse of Eq.3 to 1.1 to 1.1 to 1. and the degradation increases as a function of time.1 leading to the redeposition of Cr2O3(s) at the cathode-electrolyte interface. Numbers refer to locations of processes that are decisive for the degradation Number 1 in Fig.3. 1. The reported dependence of structural features of the degraded cell on the operation temperature. Eqs.2 Model of chromium poisoning of an SOFC with Cr-interconnect and LSM cathode based on the findings in the literature. 35 . 1. Number 2 denotes the region of interactions between LSM and chromium leading to spinel formation by solid-solid reaction.3. 1. Eqs. followed by diffusion of the gaseous products into the cathode. 1.
2FeO3-δ. so far volatilization could not be suppressed completely.8Fe0.4 Proposed strategies against chromium “poisoning” and their effectiveness 1. or Cu-Mn. 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.4.Sr)CoO3.475O4.5Co0. La0. thereby improving the electrical conductivity of the interconnect-cathode interface[49-69].Co)3O4.8Sr0. La0. 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. Co-Mn. If the buffer layer contains an ionic conductor.4Mn1. Furthermore such a buffer layer may act as a sink for CrO3(g) thus diminishing nuclei formation on LSM. Co3O4.54].5O3. as well as (Ti.2O3.65].8Sr0.05Mn1. La0. La0. as Cr in the ppm range significantly influences the oxygen diffusion in the LSM cathode. or Mn2CrO4. coating alone does not solve the problems associated to chromium poisoning completely.Al)N. However. 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. Ni.15MnO3-δ. La. but a combination of the quoted strategies is advisable to further improve the long-time stability of SOFC performance.6Sr0. This was recently shown for a cell with a YSZ-LSM functional layer: a functional LSM-YSZ layer adjacent to the YSZ electrolyte led to a lower cell degradation: increasing the ionic conductivity of the LSM cathode that is predominantly electronically conducting down to pO2 = 10-7 Pa by admixture of YSZ results in an 36 .5Co0. La0. Ce0.8Sr0. MnCo2O4[54-61]. 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.67Sr0.5O3-δ. La0.6O4[53.475Co1. sputtered Co.3MnO3[58. or Cu. Mn.2Mn0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. (La.50].33MnO3. La0.4Co0.2Mn0.85Sr0. Cu1. more active sites for the oxygen reduction will result in a higher Cr-tolerance. two-segment Cr-Al-Y-O nanocomposite and (Mn.65Sr0.1 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes More than ten years ago Badwal et al. However.
4. and (La. Besides.4Co0.2Fe0.Ba)(Co.6Sr0.74]. 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. 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. La0. Thus the number of active sites is increased.Fe)O3-δ (LNF). The amount of Cr- 37 . whereas no proper nuclei were reported for LBCF.Ba)(Co. All these perovskites are mixed electronic-ionic conductors.2 New ways – alternative materials Badwal et al. La(Ni. La(Ni. contrary to LSM.2O1. In all these cathodes Cr-deposition was observed throughout the cathode both under polarization and without polarization. 1.Ni)FeO3-δ [71. In recent time it was found that new cathode materials such as La1-xSrxCo1-yFeyO3-δ (LSCF). LNF and LBCF revealed extraordinary high tolerance against chromium poisoning. and (La.72]. As for LSM these authors concluded that the mechanism of Cr poisoning can be explained by chemical dissociation of CrO3(g) to the perovskite-structured materials and nuclei formation in the cases of LSCF and LNF. which makes this material a promising candidate for a steady long-term SOFC performance.Fe)O3-δ (LBCF)[71.75] cathodes were investigated using impedance spectroscopy. 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.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.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. Based on these findings they predicted that highly Cr-tolerant cathodes can be developed. The ionic conductivity can be increased by doping the B-site of ABO3 perovskite with reducible cations. the reduction of gaseous chromium will not be restricted to the small area at the TPB due to a smaller oxygen partial pressure gradient. The highest tolerance against the effects of chromium under SOFC operating conditions combined with high electrical conductivity has been reported recently for (La.73].8Sm0. Effects of Cr upon the degradation of La1-xSrxCo1-yFeyO3-δ (LSCF)[26.8O3-δ (LSCF) cathode and Ce0.Fe)O3-δ (LBCF) are more tolerant against chromium “poisoning”. already considered alternative cathode materials to reduce or stop the formation of the spinel phase.Fe)O3-δ (LNF)[71. and the cell is more tolerant against chromium.71.
J. nuclei might form in addition. However. 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”. pp. Fergus. 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. 1-15. Metallic interconnects for solid oxide fuel cells. Stimming. Advances. Materials Science and Engineering A. 2. and a typical mixed ionic-electronic conductor such as LSCF can take over both functions. Improved inhibition of the reduction of CrO3(g) is predicted for LNF. 2004. pp. Solid State Ionics. which was explained by a removing effect of nuclei for the chromium deposition under polarization conditions. U. Thus reduction of CrO3(g) takes place inside the whole cathode even without being promoted electrochemically by polarization of the cell. J. 38 . Fergus. The higher the contribution of the ionic conduction the less complete reduction is expected due to prolonged lack of an electron donator. 127. 171. The amount of deposited Cr in LSCF was even larger without polarization than under polarization. However under strong polarization one can expect that LSCF gets more and more ionic conducting towards the electrode-electrolyte interface. J. 271-83. 397. Even if the reduction reaction is considered to be the dominant mechanism of chromium poisoning. that is towards lower oxygen partial pressures. pp. aging mechanisms and lifetime in solid-oxide fuel cells. Tu. most likely resulting in retarding or inhibiting of the reduction reaction. Power Sources. References 1. but their influence on the Cr deposition compared to the reduction of CrO3(g) cannot be decided yet. Lanthanum chromite-based materials for solid oxide fuel cell interconnects.W. 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. 2004.W. As an alternative to the complicated nuclei mechanism. 2005. 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. 3. as this phase has a particularly high ionic conductivity. 284-93. H.
108 pp. Warshaw and M. pp. 1954. Allgem. Flame. J. 5. 1991. 317-425. Thermodynamics of gas phase chromium species: the chromium oxides. Belton. Bandel. Int. 11. Recent advances in metallic interconnects for solid oxide fuel cells. E. B. 37. Lond. Combust. 43-9.. Trans. pp. 16.J. Padley.. Soc. Srivastava. G. Soc. 1. 15. pp.S.. Müller. Z. 1993. 27. Wilms and T. Caplan and M. 1971. Dinsdale. N.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 4. 438-442. Ebbinghaus. Glemser and A. Metals. 1964. 1057-65. D. 13. J. 271-284 (in German). Chem. Farber and R. 2007. J. 53. Gaseous hydroxide. 1973. D.-W. 9. Species CrO3 and CrO2(OH). A. pp.W. Caplan and M. I. 108. Rea. M. Special high-temperature corrosion features of heat-resistant steels and alloys. Yang.L. 7. 1959. 377-400. Arch. I. Solid solution and chromium oxide loss in part of the system MgO-Al2O3-Cr2O3-SiO2. University of Pittsburgh. 2008. Res.D. Mass spectrometric investigation of reactions involving vanadium and chromium with potassium-seeded H2-O2 flames. Phase Equilib. M. 18. 1.J. pp. pp. pp. Nielsen. The oxidation of materials for interconnects in solid oxide fuel cells. The volatilization of chromium oxide. 6.R. Combust. Met. pp. the chromium oxyhydroxides. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Loss of metal from chromium at elevated temperatures in air. Thermodynamics of volatilization of chromic oxide. Bulewicz and P. Anorg. Mater. Olminsky. Calphad. pp. E. 10.N. Jacobson. D. J. 5. 334. 1952. 353-62. Z. 8.D. Flame.L. O. Proc. Cohen. pp. pp. Opila. Thesis. 8. Photometric investigations of behaviour of chromium additives in premixed H2+O2+N2 flames. Soc.R. 2006.B.M. On a gaseous hydroxide of chromium. Kim and G. Gauckler. Diff. Keith. Chem. 1974. Grundy. and volatility calculations in waste incineration processes. Povoden.F.. Am. 1811-16. 1961. Myers.T. 15(4). Eisenhüttenwesen. J. Electrochem. Cohen.K. 12. 151-4 (in German). Hammer. J. Ceram. 323. 14. 20. Allendorf.. 111. Y. pp. J. 93. Less Common Metals. pp.M. J. 39 . L. High temperature oxidation of some iron-chromium alloys. R. E.E. 411-12.J. 161-8. 284-93. 2005. Johnson. D. A. A. 1971-80. pp. Theroretical and experimental investigation of the thermochemistry of CrO2(OH)2(g).. 1941. 39-54. 4. A. Phys. G.B. pp. 119-37. SGTE data for pure elements. 15. J. 17.
K. Hilpert. 30. S. Solid State Ionics. K. M. 2000. Hilpert. Office of Fossil Energy Fuel Cell Program. Li.P. Matsuzaki. 271-278. II. B1252-B64. 3195-3205. Peck. pp. 162. Soc. Y. J. 22. Badwal.13. 27. 3642-7. K. Konysheva. Steel Res. pp.. Penkalla. M. Zhang. Taniguchi. S. Electrochem. Hilpert. K.. 297-310. 1997. Mertens. pp. 2001. R. Miller.-H. Y. 40 . Solid State Ionics. Y. J. J. J. J. Singheiser. Zhen. E. Power Sources. Chromium poisoning of the porous composite cathode. Use of gaseous Cr species to diagnose surface and bulk process for O2 reduction in solid oxide fuel cells. Penkalla. L. Power Sources 55 (1995) 73-79. Deller. Chromium vapor species over solid oxide fuel cell interconnect materials and their potential for degradation processes. S. Foger. J. Jiang. Singheiser.S. S. Saitoh. Electrochem. 528-33. 147(9). 2006. pp. SOFC cathode materials development at PNNL. 23. Stevenson.D. Apateanu. Hilpert.P. 20. 2007. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. D. 72. 143. Soc. Ceram. J. 26. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator. pp. K. Jiang.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 19. Weiβ. J. S. 22. Applied Electrochem. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. pp. J. III. H.G. Electrochem.P. Chromium vaporisation from Fe. S. T. S. 132. Y. Chromium poisoning of perovskite cathodes by the ODS alloy Cr5Fe1Y2O3 and the high chromium ferritic steel Crofer22APU. 24. J. Effect of cathode thickness and current density. 31. Miyake. Effect on O2 reduction reaction. Singheiser. R. Jiang. E. 1043-1052. J. Yasuo. Simner. Gindorf. H. 361-73. 2001. 2006. Konysheva. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. Soc. E.Cr base alloys used as interconnect in fuel cells. C. J. FY 2004 Annual Report. Zhang. Soc. 154 (12).. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.A. Anderson.P. Soc. Kadowaki. 28. Yasuda.. I. pp. pp. Wessel. A765-73. pp.. J. D. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. Electrochem. K. Das. Kawamura. 25. 2004. Zheng. 29. 21. Zhang. Foger. J.P.P. E. Jiang. L. J. 99. Europ.. Ramprakash. 2000.P. 93-6. L. Seeling. L. X. Mertens. 181-192.. 1996. 153. T. U. Y.P. pp. Akiyama. 2002. M. pp.
S. 887-90. Sci. Apateanu. 1-22. L. Paulson. A. 34. I. Yasuda. 2005. T. Hash.P. Zhen. Zhang. R. B. S. A. pp. 44. M. Gopalan.D. Electrochem. Steele. 148. Chromium poisoning of LSM-YSZ SOFC cathodes. S.N. 4013-22. Solid State Ionics. pp. Hishinuma. pp. 2008. pp. M. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes.J. T. I. 1996. Soc. J. Jiang.J. Kajda. 1151-60. Oxygen tracer diffusion coefficient of (La. S. V. 173. 53. 42. Chem. J. 43. Wu. Oxygen-transport in selected nonstoichiometric perovskite-structure oxides.. Solid State Ionics. Hallstedt. 2007.1. 2002. Grundy. M. Y. Carter. S. pp. Birss. J.Sr)MnO3±δ. FY 2004 Annual Report.Sr)MnO3 and (La. 146. B. A. Early interaction between Fe-Cr alloy metallic interconnect and Sr-doped LaMnO3 cathodes of solid oxide fuel cells.. Int. 1197-1201. A1961-68. J. Inorg. Chater. 2000. K. J. 20. T. Ogasawara.H. SOFC research and development. pp. Skaarup.. W. Filonova. Selcuk. 45. Soc.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 31.W. Krumpelt. 86-88. Jiang. Solid State Ionics. 38. Measurement of partial oxygen ion conductivity of Srdoped lanthanum manganite. Solid State Ionics. 28. Petrov. 2004. L.P. Electrochem. J. Pal. J. 2007. 4th international symposium on solid oxide fuel cells 37. I. Gauckler. A126-31. Hydrogen Energy. Fergus. 2001. S. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells.. pp. J. J. 35. 2007. Mater. 747-58. J. pp. 39. Kawada. U. 40. Cruse. Foger.P. Mechanisms and kinetics. Assessment of the La-Sr-Mn-O system.A. Yasuda. pp. E. M. S.A. Development of lanthanum strontium manganite perovskite cathode materials of solid oxide fuel cells: a review. Zhang. 3664-71. Calphad.Fe)O3 electrodes. 191-201. Kinetic and geometric aspects of solid oxide fuel cell electrodes. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Jiang. 39-43. Mater.P. 52. Russ.I. 33. Y.A. A. Jiang. J. 597-605.N. 2004. S.Sr)(Co. Matsuzaki. 771-74. Huang. M. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. A comparison of O2 reduction reactions on porous (La. Soc. Demina. Electrochem. Res. Mogensen. pp. 2004. pp. K. Kilner. 43. 41 . 36. Dokiya. pp. Kaun. 32. J.C. S.A.N. Zheng and P. 6799-6833.P.. 151(11). Power Sources. 86-88. III. pp. 41.C. pp. J.C. 1996. 1992. 147.. 32. Office of Fossil Energy Fuel Cell Program.
Tietz.9Sr0. Power Sources. 164. Virkar. M.. pp. T. T. pp. Tech. K. Fuel Cell Sci. Protective coatings on stainless steel interconnect for SOFCs: oxidation kinetics and electrical properties. Stanislowski. Quadakkers. 127. 4467-70. 47. Bertoldi. Hou.. 201.V. Surf. 138. pp. 176. De Jonghe. 1991. K.R. J. P. X. D.R. R. pp. A. Petric. L. Garcia-Vargas. 56.-J. A. FY 2004 Annual Report. Wei. M. 011001-1 – 011001-5 54. T. K. Stevens. H. Lavacchi. Soc. J. D. Sakai. M. T. A. J. Deng. 2008. C. Smith.. Hilpert. 578-89. Giolli. Sglavo. X.P. Tech. Session B08. A. Matsui. 49.J. Cobalt plating of high temperature stainless steel interconnects. 2006. pp. Electrochem. M. Horita.J. J. Gannon. Naito. Spinel coatings for UNS 430 stainless steel interconnects. A. M. Coat. Kiefer. L. M.E. 7th European SOFC Forum. Montinaro. Protective coatings of metallic interconnects for IT-SOFC application. Petric. 1225-29. Niewolak. File No. Bateni. P. Kawada. Collins. Kayani. Bateni. pp. 529-36. 425-33. P. L. 4677-84. 50. 5. Protection of SOFC interconnects against Cr-evaporation using atmospheric plasma-sprayed spinel layers. Kleitz. 160. 289-93. Froitzheim. Kopczyk. T. Nucl. Fossati. Reduction of chromium vaporization from SOFC interconnectors by highly effective coatings. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. 1984. pp. T. Wei. W. T. Hammou. M. Bateni. M. Lucas. A. M. Tech.. 57. B081. Smith.M. V. 55. Homel.C. 51. A. Deibert. V. Kato. S. 201. pp. Markus. Yamaji.L. Oxidation and electrical conductivity behavior of spinel coatings for metallic interconnects of solid oxide fuel cells. E. 1212-16. Mater. J.-S. Bardi. P. Office of Fossil Energy Fuel Cell Program. Petric. P. Solid State Ionics. C. Armstrong. Zanonella. Deng. T.J. Solid State Ionics. Coat.1MnO3-x/yttria-stabilized zirconia interface for different cathodic overvoltages by secondary-ion mass spectrometry. 42 . pp. U. J. Siebert. M. 53. Yokokawa. A. Gorokhovsky.R. Electrical conductivity anomaly of nonstoichiometric chromium sesquioxide. 120. Oxygen reduction sites and diffusion paths at La0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 46. Buchanan. Jacobson. P. Chen.C. T. Zahid. J. 48. 2000. N. pp. Power Sources. F. 2007. Vaβen. 2007. M. X. Deng. M. 115-118.. 55-65.J. Visco. Singheiser. A. X. Caneiro. A. Chromium volatility of coated and uncoated steel interconnects for SOFCs. Corrosion 63 (2007) pp. R. Surf. 52. Wei. Hammouche. 2006.Y.I. 2005. Choi. C.
Kayani. Int. N. 177. Electrochem. G. 2008. H. Zhang. Evaluation of lanthanum ferrite coated interconnect for intermediate temperature solid oxide fuel cells.33MnO3 protective coating on SOFC interconnect by plasma-sputtering. Z. Hydrogen Energ. B. 287-96. J. Z. Norby.-G.% Fe-1 wt. Gannon. White. B140-43. 11. J. Visco. Li. 3251-56. (Mn.W.65Sr0. Evaluation of interconnect alloys and cathode contact coatings for SOFC stacks.67Sr0. 60. T. pp. Coat. Enabling inexpensive metallic alloys as SOFC interconnects: An investigation into hybrid coating technologies to deposit nanocomposite functional coatings on ferritic stainless steels. pp.. 32. Stevenson.3MnO3 and Fe/Cr-based steels. Smith.15)0. 1857-63. P. Nie. Effects of La0. Ce-modified (Mn. Hydrogen Energ. Yang. Dejonghe. J. Sakurai. Int. D. Z. 62. C.-H. Rietveld. Singheiser. Spinel and perovskite functional layers between Plansee metallic interconnect (Cr-5 wt. Power Sources. K. Stevenson.-G. 61. Jacobson.Co)3O4 spinel coatings on ferritic stainless steels for SOFC interconnect applications. Maupin. Xia. 923-30. pp.. Wang. Proceedings of the 6th European Solid oxide Fuel Cell Forum. Lucerne/Switzerland. Thin Solid Films. K. Y. J. 32. M. 319. C.B. J. Kurokawa. 43 .Co)3O4 spinel coatings on ferritic stainless steels for SOFC interconnect applications. Tech. Int. pp. Chen. 67. Solid St. 2008. 2007. Templeton. Konysheva. P.% Y2O3) and ceramic (La0. Deibert. Solid State Ionics.Q. N.91MnO3 cathode materials for solid oxide fuel cells. 64.W.D.J. Zhou. Visco. X. Jacobson. pp. E. pp. Z. Larring. 2006. Sun. Solid State Ionics.85Sr0. Yang. Wessel. 63.W. N. Gorokhovsky. Hydrogen Energ. C. Tietz. Conductive protection layers on oxidation resistant alloys for SOFC interconnect applications. J. 33. 66. Surf. McCready. L.I. 2536-46. G.R. Kurokawa. p.N. 261-69. Xia. 68. V. Prevention of SOFC cathode degradation in contact with Cr-containing alloy. F. L. pp. 178. Fu. S. 2000. Y. pp. Tietz. 516. K. Fujita. 201. E. Hilpert.T. Laatsch. 147.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 58. Z. J. 59.J. pp. X. G.-G. Dekker.-L.. Stevenson. Matsuzaki. F. 2007. 2006. P. Electrochem. 3672-81.. S. Xia. Chu.C. Yang. Sofie. 131. 4476-83. J.. H. Ogasawara. Chromium vaporization of bare and of coated iron-chromium alloys at 1073 K. J. Christiansen. K. Influence of different perovskite interlayers on the electrical conductivity between La0. J. S. Laatsch. J. J. R. D.E. A. S. T. 65.-Y. 3648-54. G. Soc.. C. J. Lee. 2004. C. Yang. 2007. pp. 2004. 2008.
Zhen. P. Jiang. S. E. pp. 78. 2007. Xu. 17. Viskup.-H. V. 61-6. pp. Mixed conductivity and electrochemical behavior of (La0. 72. Y. and D. 2008. 178. S. J. 82-89. Solid State Ionics. Chiba. Zhen. 2008.75Sr0.P. D. K. Electroceram. Cr Poisoning suppression in solid oxide fuel cells using LaNi(Fe)O3 electrodes.D. Peck. Boey. 170. 77. Jiang. A127-A134.-G. pp. Jiang. pp. Jiang.C. 2008. C. A.-H.T. G.Y. M. Liu. A9-12. Properties of Cu. Y. Soc. Kim. J. 71. Zhao. L. R. 101-13. Zhang. Jiang. pp. Characterization and performance of (La. J. C. 33. Liu. J. 451-56.P. J. Cross. Ni. Int.P. J. Developing TiAlN coatings for intermediate temperature solid oxide fuel cell interconnect applications. A. 189-96. Arai. Power Sources. Power Sources. pp. S. 695-703. 176. Ong. La(Ni.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 69.Fe)O3 as a cathode material with high tolerance to chromium poisoning for solid oxide fuel cells. Shin. Electrochem. 2007. H.S. T.P. Solid St.. 76. F.. Nozawa. Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells. F. L.. K.-H. Li.Y.-R. Li. Lim. 9. Electrochem.5Mn0.R. S. 75. 153. Boey. pp.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect.Y. X. Diwu. Tsipis.I.P. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. pp. Lee.P.Fe)O3 cathodes of solid oxide fuel cells. 2008. Wang. 2006. J. Tok.. J. C. Wu. 180.D. Frade. Electrochem. J. Kharton. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. Dong. A. pp.Y. Liu.C. I.-H. and V doped-LaCrO3 interconnect materials prepared by Pechini.V. J. Development of Cr-tolerant cathodes for solid oxide fuel cells. M. Y. SolidState Lett. 70. Irvine..95Cr0.Sr)(Co. Meng. Zhen. Power Sources.Ba)(Co. J.P. 2006. 177. S. 44 . T. Liu. D.V.P.25)0. Power Sources. Marozau. X. 2008. Zhen. K. 723-27. Song.I. Arakawa. J. Hydrogen Energ.-Y. 2006. Y. Shul. B42-6. J. pp. G. J. Sato.D. Y. R. 74. Deposition of Cr species at (La. 73.5O3-δ. 11. Komatsu. Johnson. Pu. Tok. S. S.
this behaviour would not be expected. So far it was not possible to define unambiguously. it seems that strategies against the cell degradation have been mostly established in a rather random way so far. The causes and consequences of chromium poisoning are clear. 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. which further retards the diffusion process of oxygen into the electrolyte. Previous experiments have shown that the following factors: -) High temperature -) Decrease of oxygen partial pressure at the TPB under current load of SOFC and processes: -) Interaction of chromium with LSM leading to Mn-Cr-O nuclei and/or spinel formation -) Reduction of CrO3(g) to Cr2O3(s) at the TPB -) Blocking of pores at the TPB by Cr2O3 and/or spinel govern the degradation of SOFC caused by chromium. 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. which of these processes play a dominant role for the degradation and which don’t. 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. but the effects of chromium would be observed only after thermodynamic equilibrium is obtained. This means that the kinetic control on the mechanisms of chromium 45 . If the process of chromium “poisoning” were completely governed by thermodynamics. However. Reduction of CrO3(g) at the TPB leads to the formation of electrically low conducting Cr2O3.Aim of study 2 Aim of study Chromium poisoning of planar SOFC with LSM cathodes and Cr-alloy interconnects is a complex process consisting of several steps that may occur simultaneously inside the cell. For a more systematic and thus more efficient combination of strategies a strong knowledge about the mechanisms of chromium poisoning of SOFC is required. and some strategies against cell degradation caused by chromium have already been successfully applied.
in this study the author focuses on the effects of Cr on the degradation of SOFC with LSM cathodes.1 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC A thermodynamic La-Sr-Mn-Cr-O oxide database is highly desirable to enable fundamental understanding of the mechanisms of chromium “poisoning” of LSM cathodes for SOFC. The following questions have remained unsolved so far: -) Does spinel form by a solid (LSM)-solid (Cr2O3) reaction or directly in a solid (LSM)-gas (gaseous Cr) reaction? -) Can the concentration of deposits at the cathode-electrolyte interface under current load be explained by thermodynamics? -) How does the LSM phase chemically change due to the interaction with chromium. and as LSM cathodes are still considered to serve as promising cathodes due to their high electrical conductivity and stability at SOFC operating conditions. and a degrading cell is in a non-equilibrium state particularly at the early stages of the degradation. and can this change be explained by thermodynamics? -) Which of the phases observed in LSM contaminated by chromium form under thermodynamic control. 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. 3 Method 3. As a degrading cell is in a non-equilibrium state. Therefore the thermodynamic La-Sr-Mn-Cr-O oxide database needs to be established based on the assessments of low-order subsystems.Aim of study is high. Thus. 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. the obvious question why the results of thermodynamic calculations should be feasible for a deeper understanding of the mechanisms 46 .
one can draw conclusions on the evolution of the phase chemistry of degraded LSM cathodes. C can be predicted for changing cathode compositions. Hence. 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. The presented thermodynamic database of the La-Sr-Mn-Cr-O oxide system is constructed using the CALPHAD approach.1.1 Stoichiometric solid oxides The stoichiometric ternary phase α.equilibrium (A) ⎯⎯ equilibrium (B) → (3. For instance. The optimization of model parameters is based on the accurate assessment of experimental thermodynamic and phase diagram data of oxide subsystems. a with the positive electrical charge r and b with the positive electrical charge q.2 Thermodynamic modeling 3.1 reflects the path the system takes towards its equilibrium state.1. and oxygen partial pressures. 3.1) By calculating thermodynamic equilibria for a LSM cathode that is affected by chromium (A) in the relation above. can be calculated using the thermodynamic La-Sr-Mn-Cr-O oxide database: C non . 3. the theoretical final state of chromium poisoning after a very long time is found by thermodynamic equilibrium calculations (B). using the thermodynamic database one can calculate the expected thermodynamic equilibrium.2. and the rate of chromium diffusion the equilibrium state of chromium “poisoning”. for instance under reducing oxygen partial pressures reflecting the situation at the TPB under current load. 47 . taking into account experimental data on the chromium “poisoning” of SOFC and using a thermodynamic La-Sr-Mn-Cr-O oxide database. and for solid solution phases as a function of temperature and composition. From A and B. It contains the optimized Gibbs energy functions of solid oxide phases: for stoichiometric phases as a function of temperature. by choosing the starting conditions composition of LSM and defined amount of Cr at a specific temperature. temperatures. containing m and n moles of two different sorts of cations. composition of LSM. including the operating temperature. C in Eq.
)u containing cation a with the positive charge r.2. c with the negative electrical charge s.2. 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. 3.2 Solid solution phases – the Compound Energy Formalism (CEF) If in the binary oxide Ox1: (a r )t (O2. C. To account for the charge neutrality criterion. v. D. Eq. the three types of ions sitting in three distinctive crystallographic sublattices. b q )t (O2. the sublattice formula of the resulting solid solution phase β(ss) reads (a r .1 is true. As Cp(α) is defined by C p = −C − 2 DT − 6 ET 2 − 2 FT −2 (3.2.)u and Ox2: (b q )v (O2. 3.2.5 is the criterion for charge neutrality: 48 .1) α The molar Gibbs energy of α.2) A.)u n ° (b G + Gm t m v r ° α Gm = °Gm ( a r )m (bq )n (O2. E and F are optimized to heat capacity data only. B.Method respectively.)w + ptv − muv − nwt ° O (g) Gm + A + BT 2tv 2 (3. A and B are optimized by thermodynamic and phase diagram data.) p = q )v (O2. °Gm can be based on the molar Gibbs energies of existing binary oxides Ox1: (a r )t (O2. 3. 3. Eq. another sort of cation with the positive charge q. E. w ∈ N ). bq can sit in the same sublattice as a. and F are model parameters to be optimized by thermodynamic and phase diagram data. u. mr + nq + 2 p = 0 (3.4) ° α Gm is the Gibbs energy of formation of the phase α relative to the oxide components.3) α C.2. For oxides c = O and charge s = −2.) w ( t .2.2. D. °Gm at constant pressure is given by ° α Gm = A + BT + CT ln T + DT 2 + ET 3 + FT ( −1) (3. and p moles of one sort of anions. can be described by the sublattice formula (a r )m (b q )n (c s ) p .4: m ° ( a )t (O2.2.)u .
7) Once again the molar Gibbs energies of all the 4 endmember compounds (a3+ )2 (O2. 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. a 2+ )2 (O2. a 2+ )2 (O2. For β(ss) the two compounds read (a r )t (O2.)3 ( + ya2+ yO2.)3 .. with only one cation a accepting the charge 3+ or 2+ in the cation sublattice. the molar Gibbs energy of the solid solution phase contains the Gibbs energies of the compounds. 3..31451 J mol-1 K-1. a 2+ )2 (O2.ln yO2.2.Va )3 (3.6) where yar is the site fraction of cation a on the cation sublattice. In the sublattice form the phase can be written as (a3+ . and ybq is the site fraction cation b on the cation sublattice.)u β + tRT yar ln yar + ybq ln yar + EGmss ( ) (3.)u and (bq )t (O2.5) Using the Compound Energy Formalism (CEF)[2-4]. (a 2 + )2 (O 2. The oxygen nonstoichiometry is denoted “O3-δ”. and B denoting the anion sublattice. The Gibbs energy of β(ss) at constant pressure reads ° β Gmss = yar °G ( a r) t (O2.3 Vacancies and the concept of reciprocal reactions Let us consider the case of a binary oxide phase (A)2(B)3. (a 3+ )2 (Va)3 .)u .)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. 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. Va)3 .2. the charge neutrality criterion is no longer obeyed by an anionic sublattice that is completely filled with oxygen. If the cation is reduced.)3 .Method u= t ( ya q + yb q ) 2 (3.+ yVa ln yVa + EGma ( ) ( ) .)u + ybq °G (b q )t (O2.Va )3 ( = ya3+ yO2.2.. The second-last term accounts for the configurational entropy of mixing of t moles of a and b.°Gma 2+ )2 (O2.°Gma 3+ )2 (O2. A standing for the cation sublattice. The molar Gibbs energy of the phase at constant pressure reads 3+ ° A ( Gm 2 O3−δ = °Gma 2+ .2. R=8. and (a 2 + )2 (Va)3 of the phase are required for the molar Gibbs energy 49 .
included. the only neutral endmember is (a3+ )2 (O2. A system that obeys this relation is called a reciprocal system. 3.. It thus can exist. As the chosen molar Gibbs energy of the reference is unlikely the true value. for instance oxygen nonstoichiometry data.. thus far off neutral compositions that can really exist. However.)3 . The 2+ charged center composition of the square. Va)3 is a reciprocal phase.)3 with the reduced compound (a 2+ )2 (2 3O2. The composition square of the phase can be seen in Fig.1 that is redrawn from Hillert. Va)3 the 6+ charged compound (a3+ )2 (Va)3 is chosen as reference. and its molar Gibbs energy can be defined by optimization of model parameters by experiments. the reference should favorably be a highly charged compound. with the neutral line and the reduced compound.)3 and (a 2 + )2 (Va)3 or (a3+ )2 (Va)3 and (a 2 + )2 (O 2. and (a3+ .)3 . a 2+ )2 (O2. 50 .2.2.Method of the phase. (a3+ a 2+ )2 (3 2O2. is theoretically obtained by mixing equal amounts of either (a3+ )2 (O 2. denoted with A in Fig. 3.3 2 Va)3 . For the example of the reciprocal solid solution phase (a3+ . a 2+ )2 (O2.Va)3 . Va)3 approximating its overall Gibbs energy for Δ°Grec > 0 and Δ°Grec = 0. but a line of neutral compositions connects (a3+ )2 (O2. For an unambiguous definition of the molar Gibbs energy of the reciprocal phase it is necessary to give an arbitrary molar Gibbs energy to a reference. denoted with R. The three other endmembers are charged and cannot exist. plotted above the composition square. a 2+ )2 (O2. 3.1 The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . Fig.. and its Gibbs energy can be optimized with experiments that are related to the reduction of the phase.2.1.
On the other hand.)3 − (a3+ )2 (O 2.4 Calculation of defect chemistry using the Calphad approach The Calphad approach is very powerful for the calculation of the defect chemistry of highorder nonstoichiometric reciprocal solid solution oxide phases such as (A)(B)O3-δ perovskite with a complex sublattice formula. 3.)3 − (a 2 + )2 (Va)3 : Δ °G rec = °G ( a 3+ ) 2 (Va)3 + °G ( a 2+ ) 2 (O 2.)3 and the reference (a 3+ )2 (Va)3 are fixed. d 4+ . for instance (a 3+ .)3 and (a 2+ )2 (Va)3 by only slightly oxidizing or reducing it.) 3 − °G ( a 3+ ) 2 (O 2. site fractions and oxygen content. 51 . when the Gibbs energies of the endmember (a 3+ )2 (O 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. and without excess terms for the Gibbs energy is visualized in Fig. c3+ . a 2+ )2 (O2. For this purpose model parameters of the reduced and oxidized compounds are optimized with experimental information on charge carriers. Va)3 at very low temperatures (to make the configurational entropic contribution negligible). This is not a problem for the description of a reciprocal oxide phase.. it is legitimate to define Δ°Grec = 0. Va)3 for a Cr-doped LSM perovskite as a function of composition.2.) 3 − °G ( a 2+ ) 2 (Va)3 (3. c 4 + . and the theoretic compound A will tend to demix to (a3+ )2 (O2.1 (page 50) only the edge of this plane is seen as bold line.1 (page 50) and approximates the whole Gibbs energy of the phase. and no experiments define a proper value of the reciprocal reaction parameter. As no tendency of demixing was reported for the nonstoichiometric oxide solid solutions that are treated in this study. Δ°Grec is positive. Anyway. and oxygen partial pressure. The morphology of the Gibbs energy surface depends on Δ°G of the reciprocal reaction (a3+ )2 (Va)3 + (a 2 + )2 (O 2. Va)(O 2. the Gibbs energy surface is curved.. the Gibbs energy surface is flat and no tendency of demixing of A exists. 3. temperature. Note that in order to obtain the same Gibbs energy of the reduced compound R for Δ°Grec > 0 and Δ°Grec = 0. Va)(c 2 + . In Fig. if Δ°Grec is zero.2.8) If Δ°G of the reciprocal reaction. d 3+ .2. the true surface shape of a reciprocal oxide phase with charged endmembers is not known. 3.2. b 2 + . the Gibbs energies of the remaining endmembers are significantly different for Δ°Grec > 0 and Δ°Grec = 0.
B. Calphad Calculation of Phase Diagrams. 1986. 34. Sundman. 2001. J. Gauckler. 1998. 6. Andersson. Acta Metall. Alloy. Hillert. Z. Elsevier Science Ltd. 2. E. 153-90. Guillermet. 1988. 479 p. The Thermo-Calc databank system.P. 52 . T. 81-87. pp. B. 79(2). This weighting process is based on the accurate assessment of experimental thermodynamic and phase diagram data. B. Hillert.. Jansson. 161-76. Jansson. Jansson.N. B. pp. Hillert. J. A. M. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers.F. pp. A. 5. Pergamon Materials Series.O. J. Application of the Compound-Energy Model to Oxide Systems. Andersson. 2006. 1. B. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously. 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. B.Method 3. Sundman. 437-445. 320. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.. Vol.. Povoden. Calphad. 4. M. 33-41. Miodownik. Calphad. M. L. pp. Metallkd. The program minimizes the sum of squared errors between calculated and experimentally determined phase diagram and thermodynamic data. 9(2). A. Calculation of Defect Chemistry Using the CALPHAD Approach. pp.3 Optimization of model parameters The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system. N. 30. Saunders.. The Compound Energy Formalism. Sundman. References 1.J. Grundy. Cmpd. Ivas. 3. 1985.-O.
Cr3O4 is described as a stoichiometric compound. 2006. ceramic and metal interconnect materials have been tested and evaluated over the years. Gauckler J. However. and the liquid is described using the two-sublattice model for ionic liquids.and power-generation capability.1.1 Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research E.J. thus substantially reducing the triple- 53 . Microstructural analyses of the cathode of SOFC show the formation of Cr2O3 and (CrMn)3O4. which block active sites as well as pores. Diff. due to the high operating temperature (>1173 K).N. 5 wt. combined heat. Grundy. low manufacturing costs and high thermal conductivity..% Fe and 1 wt.% Cr.Thermodynamic assessments 4 Thermodynamic assessments 4. Nonstoichiometry of eskolaite (Cr2+xO3) is described using the compound energy model. pp. 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. A comprehensive compilation and evaluation of experimental and thermodynamic data for the Cr-O system is presented and. For the planar design SOFC. a consistent set of thermodynamic model parameters is optimized based on new experiments. A. Namely a Cr5Fe1Y2O3 oxide dispersion strengthened alloy with the composition 94 wt.1 Technology SOFC offers high fuel conversion efficiencies and. and L. which offers low fabrication costs. Meanwhile the use of Cr-based alloy interconnect materials has gained popularity due to their relative ease of fabrication. 27. 4. Also the magnetic transition in Cr2O3 and the oxygen solubility in Cr are modeled.% 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. Loss of performance caused by the migration of Cr originating from the alloy interconnect is well documented by several investigators. 353-62. Povoden. Phase Equilib. by application of the CALPHAD method.
X(O) ----Cr3O4 detected ----Stability range Mono- of Cr3O4. 4. Results of special points in the Cr-O phase diagram from several studies are summarized in Table 4.2 Experimental data Phase diagram data: Experimental investigations of phase diagrams in the Cr-O system were made by Ol’shanskii and Shlepov and Toker. tectic T (K) ----T (K) ----Reference Kanolt experimental Wilde and Rees experimental McNally et al. T (K) T (K) 2257 2317 2603 ---- 2543 ± 25 -- 54 .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.Thermodynamic assessments phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. experimental Bunting experimental air.1. These authors document the existence of a large miscibility gap between the metallic and the oxide melt. Eskolaite (Cr2O3) is the dominating stable oxide phase over a wide temperature range.1.1. Table 4.1 Special points in the Cr-O system Eutectic Melting of Cr2O3 in Eutectic composition.
who measured T = 2543 ± 25 K also in air. The question of the existence of a crystalline Cr3O4 phase was discussed controversially by several authors. This value significantly deviates from the result of Bunting.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. Grube and Knabe found that 1 wt. Lam reported the existence of molten chromium with oxygen impurities of 1400 ppm at T = 2133 K. Microstructures of a quenched 55 . whereas Toker et al. Investigations made by Hilty et al. experimental Johnson and Muan experimental Degterov and Pelton calculated Kowalski and Spencer calculated Taylor and Dinsdale calculated Toker et al. Ol’shanskii and Shlepov and Johnson and Muan did not find Cr3O4 up to the eutectic temperature of chromium oxide. Concerning the pure Cr-O system. 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.497 0.496 0. Mc Nally measured a melting temperature of 2603 K in air using an induction furnace. calculated Note: Itallicized data were used for optimization The melting temperatures of eskolaite in air reported from Kanolt and Wilde and Rees can be discarded as being too low.499 0.52 0.% Cr2O3 lowers the melting point of metallic Cr from T = 2163 K to between T = 2043 K and 2063 K. and Hook and Adair led them to postulate the existence of a crystalline Cr3O4 phase in the Cr-Fe-O system.523 0.Thermodynamic assessments --2571 ---2539 1933 1918 1941 1929 1937 1938 ± 2 1938 0. 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. experimental This work.513 0.
. Applying the same technique as Pehlke et al. as well as transport of oxygen ions from the cathode to the Cr/Cr2O3 anode. The data are in close agreement with the gas-solid equilibrium measurements by Jeannin et al. Pehlke et al. and 1373 K. Novokhatskii and Lenev studied the equilibrium of the reduction of Cr2O3 to Cr with hydrogen from T=1493 K to 1893 K. as well as the importance of sufficient time to attain equilibrium..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. used two separate series of emf measurements employing the solid oxide electrolyte galvanic cell technique from T = 1148 K to 1548 K. Appreciable sublimation of metallic chromium was not observed. Davies and Smeltzer determined log( pO2 ) values of Cr2O3 at T=1173 K. thus at these temperatures log( pO2 ) values were determined solely from the reduction of Cr2O3. days for T < 1100 K. and Lam. causing transfer of oxygen through the cell. 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. 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. that is. At T ≥ 1573 K they were confronted with the loss of a quarter of Cr in the case of oxidation. Toker et al. Disagreement between the emf results from Pehlke et al. The reversibility and accuracy of the yttria-doped thoria electrolyte and the electrode was tested by measurements of a standard iron-chromium alloy at 1326 K. using an electrochemical cell with a calcia-zirconia electrolyte and a Fe/FeO reference electrode. This indicates that the first phase to crystallize on solidification is Cr3O4 giving strong evidence for the stability of this phase. and Tretjakow and Schmalzried were assigned to possible electronic conduction in the zirconia electrolyte used by the latter authors.. These authors used a flow method where thermal diffusion problems were suppressed by inserting corundum bushes into the reaction tube. Pugliese and Fitterer. The obtained 56 . 1273 K. Thus in this study the authors accept the findings of Toker et al. The independent results of corrected cell potentials of the two measurement series are excellent. 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.
37 J mol-1 K-1 at T = 298. relied on the results from Anderson.1) yielding ° H T − ° H 298K = 28. relied on the calculated results from heat content measurements performed by Kelley et al.2) Temperature derivation of Eq.56 K. Heat Capacities.1.5 K to 340 K with mean increments of 0. Uncertainties of 0.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. 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 ° (4.1. and fitting procedure are worked out very carefully.4 % for Cp (20 K < T < 200 K) and 0.. data presentation.17 ± 0.1.3) For ° S298K (Cr2O3) Chase et al. Resulting Cp data correspond nicely to the most recent calorimetric results from Klemme et al. The accuracy of this study is evident from excellent data reproduction by performing two runs in the entire temperature range.736 ×105 T −2 (4.53 + 2.7 % for Cp (T < 20 K) were estimated. who calculated ° S298K (Cr2O3) = 81. and fitted the data to the heat of diffusion equation that considers some material properties employing a least-mean-squares fit.68 ≤ T ≤ 323. Bruce and Cannell applied a two-dimensional temperature wave method using a single crystal of Cr2O3 to calculate specific heat in the temperature range 290.10 ×10−3 T 2 + 3. heat Contents..20 ×10−3 T − 3.1.53T + 1. and entropies: Anderson’s calorimetric data set of Cp-values lacks detailed documentation of the experimental procedure.43 K.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 . The latter authors measured a consistent data set of heat capacities of synthetic eskolaite from T = 1. For Cp(Cr2O3) = 120.736 ×105 T −1 − 9759 (4.2 results in C p = 28.15 K Chase et al.. 4. Documentation of the experiments.
1 J K-1mol-1 by reevaluating emf data from Holzheid and O’Neill. Their calculated liquidus temperature of Cr2O3 in air is T = 2571.el° H 298K (Cr2O3) = –1122. Ramsey et al. which is in good agreement with an early finding by Bunting who measured T = 2543 ± 25 K.el° H 298K (Cr2O3) = –1134.el° H 298K (Cr2O3) = –1139.4 kJ mol-1 by evaluating emf data from Holzheid and O’Neill. adopted their ° S298K (Cr2O3) value from Wagman et al.3 Previous assessments of the Cr-O system Banik et al.el° H 298K (Cr2O3) the heat content data given by Kelley et al. Kowalski and Spencer used the associated solution model for the liquid phase based on the experimental data used by Taylor and Dinsdale.3 J K-1 mol-1 from their measurements..42 kJ mol-1.1. Mah. Chase et al. for example. Some difficulty caused by moisture adsorption was encountered in weighing the combustion products. Enthalpies of Formation: Roth and Wolf found Δ f. adopted Δ f.72 kJ mol-1 from Wagman et al. The latter authors proposed a 58 . 4. who calculated ° S298K (Cr2O3) = 85.el° H 298K (Cr2O3) = –1128. Dellien et al. For the calculation of Δ f. Degterov and Pelton reassessed the CrO-Cr2O3 subsystem for the molten slag database using a modified quasi-chemical model for the liquid phase. Shirokov estimated Δ f. Klemme et al.el° H 298K (Cr2O3) = –1128. thermodynamic data for Cr-Cr2O3 from Fromm and Gebhardt.74 ± 1. 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. Shirokov estimated ° S298K of a metastable CrO phase to be 46. Klemme et al. recommended Δ f.7 ± 8.86 J K-1 mol-1. Klemme et al. Navrotsky cited Garrels and Christ for Δ f. while Dellien et al. This was circumvented by heating the combustion products to T = 1323 K. using a bomb calorimetric combustion technique at 1323 K and 30 atm oxygen pressure. were used.4 kJ mol-1 for metastable CrO.el° H 298K (Cr2O3) =–1140.el° H 298K (CrO) = –305.2 ± 0.4 kJ mol-1 from several earlier studies.5 kJ mol-1 (el=elements) by applying a calorimetric technique. and thermodynamic estimates for CrO from Shirokov.06 kJ mol-1. used heat capacity and entropy data from tabulations of Coughlin to obtain Δ f. This procedure was critically documented by other authors.98 ± 1. recommend ° S298K (Cr2O3) = 83. evaluated Δ f..8 ± 2. calculated Δ f.7 kJ mol-1.16 K.Thermodynamic assessments functions.
In this model. Kelley et al. 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. This is reflected by significant variations of the position of the eutectics. especially as their miscibility gap does not close on increasing temperature. The use of six parameters for the description of the Cr3O4 phase is somewhat incommensurate with the scanty experimental information of this phase. Experimental information on phase relations for their assessment was taken from Ol’shanskii and Shlepov.4) 59 . 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.1. The magnetic properties of eskolaite can be described using a magnetic ordering model proposed by Inden. Eskolaite shows an antiferromagnetic to paramagnetic transition at T = 305. The heat capacity of Cr3O4 was taken as 7/5 times the nonmagnetic value for Cr2O3 according to Neumann and Kopp’s rule. and simplified by Hillert and Jarl. Their calculated values for the enthalpy of formation and the entropy of Cr3O4 are in agreement with an estimate done by Chipman. 4. the stability field of Cr3O4. There is a large uncertainty concerning the exact melting point of Cr2O3.5 K. and the temperature of the monotectic reaction of Cr(bcc) and liquid between the assessments of the Cr-O system.1. which are the two-sublattice ionic model for the liquid and the compound energy model for the Cr2+xO3 phase. Toker. and Grube and Knabe.Thermodynamic assessments phase diagram in good agreement with the experimental data obtained by Toker. space group R3c . at elevated temperatures as a sum of magnetic and nonmagnetic contributions.. Taylor and Dinsdale fitted Cp data from Anderson close to the antiferromagnetic to paramagnetic transition and data from Chase et al.4 Thermodynamic modeling Solid phases: The crystal structure of eskolaite is α-Al2O3 type. and only few thermodynamic data of the Cr3O4 phase and the liquid phase exist. using the same thermodynamic models as the authors use in this work.
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) (22.214.171.124) 60 .5 and 4.28.1. This means that reduction is accomplished by the formation of interstitial Cr3+ and not by the formation of oxygen vacancies.1. The defect chemistry of Cr2+xO3 with the sublattice occupation (Cr2+. however.6).6 gives the proportionalities [Cri••• ] ∝ pO2 −3 16 and [CrCr ] ∝ pO2 −3 16 . The magnetic parameter p equals 0.5) 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. Tc and β are both dependent on the composition. which is in agreement with Young et al. and Cri•••• giving a slope of pO −3 20 2 .6) ' Assuming small defect concentrations all concentrations except [CrCr ] and [Cri••• ] are ~ 1 and ' can be ignored. and τ = T/Tc. When modeling nonstoichiometry in an oxide phase. Due to charge neutrality the relation [Cri••• ] = 3[CrCr ] must hold. Inserting this ' into Eq. it is important to submit the experimental data to a defect-chemistry analysis.Va)1 (O2-)3 can be modeled using experimental data from Matsui and Naito. Tc is the critical temperature for magnetic ordering.1. Both are unlikely: the former because it is unlikely to get Cr4+ on reduction. their equation violates the fundamentals of defect chemistry and must be rejected in favor of the defect reaction given above (Eqs.Cr3+)2 (Cr3+.. the latter because of the large size of Cr2+. 4. To explain their experimental results Matsui and Naito proposed a defect reaction that leads to the same proportionality.1.Thermodynamic assessments where β is a parameter related to the total magnetic entropy. 4. The following other interstitial defects could be assumed: Cri•• giving a slope of pO2 −1 4 . 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.
Thermodynamic assessments ' leads to a proportionality of [Va •• ] ∝ PO2 −1 6 and [CrCr ] ∝ PO2 −1 6 .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. Only compounds along the neutral line can exist on their own. The low nonstoichiometry data from Matsui and Naito show a different slope than their higher nonstoichiometry data. similar to the case of LaMnO3 perovskites. where each corner of the composition square represents a °G parameter. the present authors believe that the different slopes are caused by a competing defect reaction.1 is a graphic representation of the model the authors use to describe the oxygen nonstoichiometry of eskolaite. 4.1. The present authors didn’t consider this by their defect chemistry model. Also the defects cannot explain the electrical properties measured by Young et al. Cr3+ → Cr2+ + Cr4+.. In contrast to Matsui and Naito who explain this assuming that neutral Cr forms interstitially. Fig. 4.1. This slope does not correspond O to the experimental findings of Matsui and Naito. The three other corner compositions present charged compounds. Fig. As the most reasonable way to model reduction is to use the reduced neutral endpoint 61 . as it would make the description quite complex. The corner Cr3+:Va:O2corresponds to stoichiometric Cr2O3. for example charge disproportionation.
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 (4.8 to 4.1.10 are listed in Table 4. 62 .Thermodynamic assessments (Cr2+)2 (Cr3+2/3Va1/3)1 (O2-)3.8) The last term describes the configurational entropy due to mixing of Cr3+ and Va on the interstitial site.1.1. 4. The expressions for all °Gs at the corners resulting from Eq.1. pp. °G of the 3+ charged endmember (Cr3+)2 (Cr3+)1 (O2-)3 is chosen as reference and given the value °GCr3+ :Cr3+ . by choosing an arbitrary reference. Then the reciprocal relation reads ° G Cr3+ :Cr3+ + °G Cr 2+ :Va = °G Cr3+ :Va + °G Cr 2+ :Cr3+ = ΔGr (4.63-64.1. and by defining a reciprocal reaction giving four equations with which all °Gs at the corners can be expressed. labeled A in Fig. This is done by using the two equations for the stoichiometric and the reduced endpoints.1.2.9) In order to avoid the inevitable formation of miscibility gaps if the energy of the reciprocal relation is large we set this energy zero.10) This means that without introducing interaction parameters one gets an ideal description between Cr2O3 and Cr2+xO3. one has to find functions of °G of three charged corners expressed solely in terms of the neutral compositions. 4.1. which leads to ° G Cr3+ :Cr3+ + °G Cr 2+ :Va − °G Cr3+ :Va − °G Cr 2+ :Cr3+ =0 (4.1.
Va L = −709542 Tc = −311.− 2 H Cr − 3H O = GCR2O3_L L SER SER GCr 2+ :O2.4 β = −0..Va q.− 3H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.)q p = 2 yO2.+ qyVa .6 β = 3.543 102.)3 ° ° ° ° Cr 3 SER SER GCr 2O:Va:O 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.52 mol O2 0 LCr 2+ :O2.Va)1 (O 2.Va q.5 p = 0.0 S298 23.996 15.Cr 3+ ) p (O 2.− 2 H Cr − 2H O = 2GCR1O1_L Reference Cr (bcc_A2) 1 2 Mass 51.2 Thermodynamic description of the Cr-O System Element Element Cr O Liquid (Cr 2+ .999 H298 .008 CrO ° Cr1O SER SER GCr:O1 − H Cr − H O = GCR1O1 Cr2O3 (Cr 2+ .− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.0 Cr3O4 ° Cr3O SER SER GCr:O 4 − 3H Cr − 4 H O = GCR3O4 Functions 63 .− H Cr = GCR_L L SER GCr3+ :Va q..0 4341.Thermodynamic assessments Table 4.2923T 3 Cr O3 SER SER GCr 22+ :Va:O 2.Va q.= 121000 Solid Cr (bcc_A2) (Cr)1 (O.1.− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L L SER SER GCr3+ :O2. q = 2 yCr 2+ + 3 yCr3+ ° ° ° ° L SER GCr 2+ :Va q. Cr 3+ ) 2 (Cr 3+ .28 Tc = 308.− 2 H Cr -3H O = GCR2O3 3+ Cr 3 SER SER GCr 2O:Cr3+ :O 2.= 0 LCr3+ :O2.− 3H Cr − 3H O = GCR2O3 + GHSERCR  3+ Cr O3 SER SER GCr 22+ :Cr3+ :O 2.H0 4050..2923T 3 p = 0.
For the optimization of model parameters.5GCR2O3 − 0.76T GCRO0 = 108305 + GCR2O3 + 2 GHSERCR  3 GCR2O3_L = GCR2O3 + 439078 − 169T GCR1O1_L = 0.. mol.2 (next page) is a graphic expression of the model. It was not possible to model the oxygen solubility using the endmember °GCr:O as this endmember turned out to be too stable and CrO3 appeared in the stability diagram at high oxygen partial pressures.5GHSEROO + 339673 − 121.82T GCR3O4 = 1. As the experimental data on the liquid phase are scarce. liquid Cr. Parameters for solid Cr.Va and 0 LCr3+ :O2. Metastable CrO is described in the same way.5GHSEROO + 280045 − 93. and one can reduce the number of parameters to only two.. With this expression one is able to obtain reasonable results for the liquid phase using the positive interaction parameters.Vaq-)q is chosen. The sublattice occupation (Cr3+.8T ln T −4.97 × 10-3T 2 + 1050000T -1 GCR1O1 = 0.5GHSEROO + 255269 − 53.Va that are required to give the miscibility gap. and gaseous O are from Dinsdale In contrast to Taylor and Dinsdale.Va that must of course be negative.5GCR2O3 − 0.56T − 119. the number of parameters is kept as low as possible. 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. The Cr3O4 phase is based on the eskolaite phase. 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.Cr2+)p(O2-. literature data from Caplan and Fraser are used.51] is selected to describe the ionic liquid. 0 LCr2+ :O2.Va)3.31451 J mol-1 K-1. The oxygen solubility in solid Cr(bcc) can be described by an interstitial solution model of the form (Cr)1(O. 4. where each corner of the composition square represents a °G parameter of the liquid phase. Pa: R = 8. Fig.5GCR2O3 − 0. The descriptions for solid and liquid chromium metal and gaseous O2 are from Dinsdale. Ionic liquid: The two-sublattice ionic liquid model[50.4T Note: All parameters are in SI units: J.1. Its heat capacity is given by Neumann and Kopp’s rule.Thermodynamic assessments GCR2O3 = −1164542 + 728. 64 . the latter constraint is not needed in the model. K.
4.1. 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. 4. This is however problematic for reciprocal systems. for example +600000 as given to °GCu2+ :Va by Hallstedt et al.Thermodynamic assessments Fig. The liquid composition changes along the hyperbolic curves in Fig. One derives the °GL functions of the oxide compositions (Cr3+:O2-) and (Cr2+:O2-) from the eskolaite phase. in his original assessment of the Cu-O system.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.1. The °GL of liquid Cr is taken from Dinsdale. Cr3+:Va must be metastable compared to Cr2+:Va.2. A special feature of the Cr-O system is the occurrence of a eutectic very close to the composition of CrO. The eutectic temperature is mainly determined by the value of the corner Cr2+:O2-. Hallstedt and Gauckler recently reoptimized the Cu-O liquid. In this model description of the liquid phase metallic Cr-liquid can be described by both the corners Cr2+:Va and Cr3+:Va. This considerably improved the description of the Cu-O liquid and removed the inverted 65 . One way of doing this would be to simply say that Cr3+:Va equals Cr2+:Va plus a large positive term. obtaining the parameter °GCu2+ :Va from the reciprocal relation and giving it a reciprocal energy of 0.
16 and ° S298.16 data from Holzheid and O’Neill were used. The melting temperature of eskolaite in air was taken from Bunting. The authors optimized Tc and β using Cp data from Klemme et al. 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.11) 4. close to the antiferromagnetic to paramagnetic transition temperature.el° H 298. To determine the parameters describing the enthalpy and entropy of Cr2O3 log( pO2 ) data from Jeannin et al. 63-64). and. and experimental data on the liquidus at the oxygen rich side of the miscibility gap from Ol’shanskii and Shlepov. An identical strategy is employed here. In the next step the authors optimized the nonstoichiometry of Cr2+xO3 using data from Matsui and Naito.. and Toker et al. The first parameters to be optimized were the Cp-parameters of Cr2O3.2 (pp. at T = 290 K and from T = 335 K to 338 K with a low relative weight. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. experimental data on the liquidus at the oxygen poor side from Toker et al.5 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Cr-O system is given in Table 4. The program minimizes the sum of squared errors between the calculated and experimentally determined phase diagram and thermodynamic data. with low relative weight.1.. using experimental phase equilibria data from Toker et al. The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system.1. The data used were heat content data from Kelley et al. Δ f.Thermodynamic assessments miscibility gap found at high temperatures in the original assessment. and Cp data from Klemme et al. Thus metallic liquid is given by the corner L parameter °GCr3+ :Va is obtained by the reciprocal reaction given as ° G LCr2+ :Va . Finally the solubility of O in solid Cr was optimized using data 66 . ΔGr = 0 (4. In principle.The ° G L 3+ Cr :Va = 2 °G L 2+ Cr :Va + °G L 3+ Cr :O2- − 3 °G L 2+ Cr :O2- + ΔGr .1.. high temperature emf data from Holzheid and O’Neill  . They assessed Cr3O4 and the liquid simultaneously. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously. These parameters were then kept fixed during the rest of the optimization.
4.1.4 (next page). logarithmic) given.Thermodynamic assessments from Caplan and Fraser.1. Fig. 4.6 Results and discussion Phase diagram: The calculated phase diagram with oxygen isobars is shown in Fig. 4.1.1 (p. 54-55) values that were used for our optimization are written in italic letters.1.1.3 Calculated Cr-O phase diagram with oxygen isobars (Pa. In Table 4.3. 4. The gas phase was not included in the calculation An enlargement of the phase diagram close to the CrO composition is presented in Fig. 67 .
with experimental data and oxygen isobars (Pa.4 Enlargement of the calculated Cr-O phase diagram close to the CrO composition.Thermodynamic assessments Fig. 4.1. and for the eutectic one gets T=1938 K at a mole fraction of oxygen of 0.1.497 it decomposes in a peritectic reaction at T = 1973 K forming Cr2O3 and liquid. Cr3O4 is formed at T = 1918 K by the eutectoid reaction Cr2 O3 + Cr + 1 2O2 → Cr3O4 . 2 68 . For the monotectic temperature of the reaction of Cr (bcc) and liquid the present authors calculate T = 2117 K. 4. At a mole fraction of oxygen > 0. Fig. in good agreement with the measurement from Bunting.497. 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.5 (next page) shows the calculated oxygen potential phase diagram of the Cr-O system with experimental log( pO ) data included. and an earlier experiment from Ol’shanskii and Shlepov is slightly deviating from former optimizations. The calculated liquidus temperature of eskolaite in air is T = 2539 K.
with experimental log( pO2 ) data as a function of temperature from different studies The experimentally determined phase stabilities from Toker et al.5 Calculated oxygen potential phase diagram of the Cr-O system. Fig.6 Stability of Cr3O4 in the log( pO2 ) versus temperature diagram 69 .1.1.6. are particularly well reproduced by the authors’ optimization. 4. The stability of Cr3O4 is shown in the log( pO2 ) versus temperature diagram in Fig. 4. The shape and size of the miscibility gap is speculative due to the lack of experimental data.1. 4.Thermodynamic assessments Fig.
1. 70 . 4.1. 4. If the commonly used – however grubby – notation “Cr2O3-δ” is applied. The comparison of the calculated nonstoichiometry in Cr2+xO3 with the experimental data by Matsui and Naito is given in Fig.7.7 Calculated oxygen solubility in Cr(bcc) with experimental data and oxygen isobars (Pa.1.4.098 at T = 1918 K. 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. logarithmic) included For the maximum solubility of oxygen in Cr(bcc) one calculates 0.Thermodynamic assessments The solubility of oxygen in Cr(bcc) is shown in Fig. The maximum calculated δ = 0. 4.8 (next page).% at T=1938 K.08 at. Fig. The cation overstoichiometry resulting from the presented optimization might seem somewhat high. the total charge of Cr is given by 6+2δ.1.
1. 4. Therefore. 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 . The data at low oxygen nonstoichiometries were not used. as the introduction of an additional defect species would be required to reproduce these.Thermodynamic assessments Fig. 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. 4.1. The solid lines correspond to the optimization that is accepted in this work. The low nonstoichiometry data show a different slope than the higher nonstoichiometry data. 71 .8 Optimized nonstoichiometry of Cr2+xO3 with the only available experimental data from Matsui and Naito included. Solid lines result from our accepted optimization without considering temperature dependence.8) and leads to the reduced neutral endpoint being too stable at low temperatures.
685 kJ mol-1. 72 . of the solid Cr2O3 phase (Fig. For a metastable CrO phase we calculate Δ f. and ° S298K (Cr3O4) = 150.9 Comparison of calculated heat capacities of Cr2O3 with experimental data For the magnetic parameter β we calculate 3. which is very close to the results from Holzheid and O’Neill.el° H 298K (Cr2O3) we calculate –1123 kJ mol-1. which is in particularly good agreement with the data from Ramsey et al. and ° S298K = −79 J K -1 mol-1 based on the estimates of Shirokov.1. These values for Cr3O4 deviate significantly from the results of Taylor and Dinsdale who calculated Δ f ° H 298K (Cr3O4) = –1447.el° H 298K = −306 kJ mol-1 .9) are well represented by our assessment. For Δ f.Thermodynamic assessments Thermodynamic Data: The heat capacities. Cp. Fig..0.555 J K-1 mol-1. and for ° S298K (Cr2O3) we get 85 J K-1mol-1. 4.6.1. For Δ f. and for ° S298K (Cr3O4) we get 175 J K-1mol-1.el° H 298K (Cr3O4) we calculate –1402 kJ mol-1. 4. and for Tc we get 308.
Min. pp. Solid State Ionics. Forgeng.1. S. Eng. 1955. Metall. Folkman.T. Zhang. Shlepov. 6. 1978.7 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.S. Pennsylvania State University. 1943. J.. 9. Grube. 2. The ternary system MgO-Al2O3-Cr2O3. T. Bur. pp. 315-18. Am. Wash. pp. Nauk. 561-64. 793-804 (in German). Deller. Rees. Brit. 44(10). Ramprakash. Peters. Wilde. Sci. Bunting. 1961. J. F. P. V. 7. Akad. Laboratory furnace for studies in controlled atmospheres. R.. K. 297-310.H. D. R. 203(2). N. pp. 8.Y. Sistema Cr-Cr2O3. R. Nat.J.P. Foger. Knabe. Equilibrium phase relations and thermodynamics for the systems Cr-O and Fe-Cr-O in the temperature range 1500 to 1825 °C. Y. Phase equilibria in the system Cr2O3-Al2O3. Ol’shanskii.P.C. SSSR. and that a large variation of the measured melting points of eskolaite exists.L. 1913. Kanolt. 99. 5. 1931. Ribbe.F.. 3. McNally. 1997.Thermodynamic assessments 4.N. However. C. 42(7). 947-49.K. Z. R. Oxygen solubility and oxide phases in the FeCr-O system. R. Stand. pp. G. melting points of MgO in a N2 atmosphere and of Cr2O3 in N2 and in air atmospheres. 253-68.. Hilty. 73 .I. J.N. 123-55. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. 91(3). W. I.D. Trans. it must be kept in mind that experimental data on the liquid miscibility gap are largely missing. 1953.K. The system palladium–chromium. Elektrochem. Melting points of some refractory oxides. Thesis. E. J.. Toker. Melting and casting of high purity chromium with controlled oxygen content. United States Patent 6039788. Ceram.W. 10.I. 42(11). 4. pp. Res. 491-93.. 1936. W. pp. Lam. Soc. Acad. 6(6). Badwal. Ceram. 3. Dokl. Y. pp. J. 2000. References 1. W.
1937. Ac. pp. Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites. pp. Berich. Fitterer. R. L. Muan. O’Neill. 1968. Jeannin. Darken. pp. FeCr2O4.. 85. Gmelin. pp. 227(2). Adair. Soc. Ceram. D. F. Mannerskantz.S. N. G. R. Davies. T. 833-45. J. Equilibrium phase relations and thermodynamics of the Cr-O system in the temperature range of 1500 °C to 1825 °C. 13. 25. M. Geochim.H. 1991. Elektrochem. 20. 488-91.N. C. chromous chloride and chromic chloride at low temperatures. Jacob. 39. Soc. Aime. chromic oxide. G. H.S. Johnson. Flad. 1966.. pp. Metall. Am. 230(6). Phase diagrams for the systems Si-O and Cr-O. A. Am. Klemme. Oxygen and metal activities of the chromium–nickel–oxygen system between 900° and 1100°C.D. 15(9). A. Activities and phase boundaries in the Cr–Ni system using a solid electrolyte technique.. Phys. J. E. 300-5. Schmalzried. 1965.E. Soc. 1686-93.R. O’Neill.. Electrochem. 16. 1(7). 1977. Anderson. Rev. R. H. Am. Activities in iron–chromium alloys. 543-49. pp. 1995. Z. Mineral. Metall. 18. 19. and Cr2O3 at low temperatures and derived thermodynamic properties. 69(5). The formation and dissolution of chromium oxides in chromium. Thermodynamic properties of Cr2O3 and FeCr2O4 at high temperatures. 23.W. 2000. Russ. Bunsen Gesell.S. The heat capacities of chromium.. Metall. W. Affinity and enthalpy of the solid solution in the system Cr-Ni. A. 11(9). K. 1974. 74 .Y. 1078-80.. 1942. 121(4). 1827-31. aluminate). Lenev.. 48(7). 377-89 (in German). Solid oxide electrolyte emf cell determination of the standard free energy of Cr2O3 and applications to chromium–bearing mineral systems. 1964. C. Soc. Electrochem. L.. 430-33. Geochim. 22(2). J. F. W. Cannell. Chem. pp. 1977.H.A. Trans.. S. R. J. Smeltzer. pp. 22. 1997-2002. Hook. 51(8). The heat capacity of MgCr2O4. Soc. B. 1970. Tretjakow.E. 1975. Holzheid. J. 1278-83. 225-32. 14. Trans. 1963. A. H.T.D. 24. Bruce. Inorg. pp.M. pp.D. Grube. pp.M. J. Ceram. pp. Ac.. Radzilowski. Y. 15. Schnelle. Soc. 12.. Pugliese. A. L.S. H. Toker. Pehlke. 124. Cosmochim. The thermodynamics of spinel phases (chromite. 475-79. Mazandarany. Muan. 59(3). Richardson. T. Cosmochim. Novokhatskii. 59. Specific heat of Cr2O3 near the Neel temperature. 21. B. pp. 4451-59.Thermodynamic assessments 11. ferrite. Metall. The Cr-Cr2O3 oxygen buffer and the free energy of formation of Cr2O3 from high-temperature electrochemical measurements. Aime. R.T. 17. pp. pp. 396-402 (in German).
.A. J. M. NBS Tech..H. Soc.L.. Chem. Burr. Syverud.M. 75 . 1976. Bailey.B. Downey. Fromm. 1954. 1): pp. D. Wagman. pp. Paper. 36. 29.D. and CrO-Cr2O3-CaO systems.I. N.M. 2.K. 14(Suppl. 1985. 1976. W. D. Berlin. 819-32. 542. Contributions to the data on theoretical metallurgy. 283-310. Hepler. Cosmochim. Notes. Selected values of chemical thermodynamic properties. Am. 1973. Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3. F. pp. especially oxides at high temperature. 28. pp. 35. Mines Bull. 1956. molybdenum. A. Data. Evans. Heidelberg. Bur.. Elektrochem. pp. 80 pp. Boericke. Kelley. S. G. Garrels and C. Banik. Chromium. R. 1965. 102.A. Bangert.. Coughlin. Ref. 1969. SSSR. Roth. Phys. 76(3). Z. 30.W. Thermodynamic consideration on the system Cr-Cr2O3. Chase. Z.S. pp.A. The heat of formation of chromium oxide. 476-87.. 940-42. U. D. Soc. 644-45. and standard potentials. Ettmayer. N. Springer Verlag. Minerals and Equilibria. Chem. Metal. 76(13). Harper & Row. New York. Akad. E. Halow. Nauk. R. J. P. S. 1996.. 1944. J. Chem.. Hall. 1975. Davies. Thermodynamic properties of carbides of chromium. 17(6).G. 71(10): pp. F. pp. Phase Equilib. I. A. L. p. Wolf. E. 37.H. Gebhardt: Gases and Carbon in Metals. Thermochemistry of chromium compounds. Ramsey.A. 1954.P.M. 410. C. Christ: Solutions. J.D. Tables for elements 35 through 53 in the standard order of arrangement.. 31.3rd ed. p..J. 521-34 (in German). V. 103(2). Lux. W. Mah. T. Navrotsky. Jr. 39. J. 135-38. Dellien. 662. pp. Caplan. 270(4). 33. Huffman. Electrochem. E. Heats of formation of chromium oxide and cadmium oxide from combustion calorimetry. 32. Bur. Metallkd. 38.M. J. CrO-Cr2O3-Al2O3. B. 27. Degterov. and tungsten: thermodynamic properties.R. I. 43 pp. W.Thermodynamic assessments 26. Schmitt. Janaf thermochemical tables . A.N. Thermodynamic properties of chromous oxide. J. Flurip. 39. Geochim. 45-46 (in German). Parker. D. Thermodynamics of the oxidation of chromium. 3363-65. 34. A. 1980. 46. Schumm. K. Rev. 1940. Mines Tech. R. Ac. Dokl. chemical equilibria. Shirokov. McDonald. Pelton.H.
Gauckler. pp. Calculation of defect chemistry using the Calphad approach. M. Metall. pp. Risold. Ag-Cu-O. Sundman. pp. 15(5). pp. Sundman. J. 45. Taylor. 19(3). Hillert. 1985. Dinsdale.J. 1955. Z. 51. D. 1990.. M. Thermodynamic reevaluation of the Cr-O. 43. 2001. Calphad. bcc and fcc phases. A. A. M. 109-19. 30. pp. Jarl. ASM. 48. pp. Determination of chemical and magnetic interchange energies in bcc alloys.T. p. Ivas. 1995.. Hallstedt. Mater. E. Revision of the thermodynamic descriptions of the Cu-O. A. B. Calphad. 2(3). J. Trans.Thermodynamic assessments 40. 1991. Calphad. 52. 2005.R. B. A two-sublattice model of molten solutions with different tendency of ionization. Hallstedt. Ågren. 136. Sr-Cu-O. Thermodynamic assessment of the copper-oxygen system. pp.H. Ca-Cu-O and Sr-Ca-Cu-O systems. B. Matsui. Hillert. 47. 50. SGTE data for pure elements. pp. pp. Hillert. The oxygen partial-pressure dependence of the defect structure of chromium(III)oxide. M. 1987. 78-82. Electrochem. Fe-O and Ni-O systems: 229-43. pp.. B.H. 1978. 1985. 227-38.J. E. L. Iron Steel Inst. Existence of hypostoichiometric chromium sesquioxide at low oxygen partial pressures. Cleveland.J. I. Fraser. Jansson. Calphad. 46. 196. 599-605. Remodelling of the liquid. Povoden. Calphad. 76 . 1975.. D. L. Inden. Bi-Cu-O. A. 25(4). A model of alloying effects in ferromagnetic metals. Gauckler. Sundman. M. Ohio. T.N. Modification of the two-sublattice model for liquids. 42. 354-66. 177-91. 2257-60.J. Young. 49. 180. 1994. pp. M. J. Naito.. Atomic interactions in molten alloy steels. Nucl. 261-66. Caplan. General treatment. G. 15. K. T. A thermodynamic assessment of the Ni-O. Spencer. Metallkd. J. pp. pp. L. 54. 97-106. 483-99. Gerretson. 41. 33-41. J. 1994. 44. 317-425. P. J. 134(9). 577-82. 27(2). 2003. de Witt.W. Cr-O and Cr-Ni-O systems using the ionic liquid and compound energy models.. AgO. Calphad. Bi-Sr-O. 1991.J. 16A.T. 53. B.W. 81(5). Dinsdale. Phase Equilib. Predicting miscibility gaps in reciprocal liquids. Kowalski. Soc.A. J. 66(10). Burr: in Ductile Chromium. B. 15(4). pp. Chipman. J. 1957. J.A. Grundy. Metallkd. Z. Gauckler. Calphad. A.
Calphad. thus substantially diminishing the triple phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. 569-78. Chromium manganese spinel MnyCr3-yO4 and its tetragonally distorted polymorph are described using the compound energy model. A. Res. Relevance for solid oxide fuel cells is discussed. 2006.2]. 153-90. Also solid solutions of the phases (Cr1-yMny)2+xO3. and L. pp.O. and Lee  77 . 4.6 wt. B. J. We are contributing to the understanding of the underlying thermodynamics of these processes by assessing the MnCr-O system using the CALPHAD approach. Povoden. J. 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. 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. Simner et al. and (Mn1-yCry)1-xO are considered.% Cr..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. 4.8 wt. 97.. B. The thermodynamic data of the pure elements are taken from Dinsdale.. The Thermo-Calc databank system. By application of the CALPHAD method. Povoden et al. 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.N. 22.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials E. 1985. a consistent set of thermodynamic model parameters is optimized for the Cr-Mn-O system based on experimental data. and Mn-Cr binaries from Grundy et al.45 wt. However. 9(2). Cr-O. Mater. Andersson. and the liquid is described using the two-sublattice model for ionic liquids.2.Thermodynamic assessments 55.% Mn resulted in an improvement of short-term SOFC operation. and the data for the Mn-O.% Fe. Grundy.J. Gauckler Int. pp. Sundman. Mn2-yCryO3. Jansson. and 0.
however all the binary oxides except pyrolusite (prl).2. No new ternary phases are found in the Mn-Cr-O system.4 (p. 80) shows the calculated phase diagram at pO2 = 1×10-4 Pa . 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. 4. 79).Thermodynamic assessments respectively. MnO2.2. 4. In this work we use the following abbreviations: β-spl for cubic chromium manganese spinel solid solution. 4. 80). bcc for chromium manganese alloy with bcc A2 structure. bxb for Mn2O3 (bixbyite) with dissolved Cr. Fig. Normal spinel is given by the formula [A2+](B3+)2O4. and 4. and liq for the liquid phase.2. mgs for Mn1-xO (manganosite) with dissolved Cr.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+. 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. α-spl for tetragonally distorted polymorph spinel solid solution. β-hsm (βhausmannite) for the cubic and α-hsm (α-hausmannite) for the tetragonally distorted Mn3O4 endmember of the spinel solid solution. esk for Cr2+xO3 (eskolaite) with dissolved Mn.2 Experimental Phase diagram data: Our calculated phase diagram of the MnOx-Cr2O3 system in air is shown in Figs.1.3 (p. 4. show varying degrees of mutual solid solubility.2.2 (p. 78 . The most prominent oxide phase in the Mn-Cr-O system is cubic chromium manganese spinel with the formula MnyCr3-yO4.
Fig. 4. The gas phase was not included in the calculation.1 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. The gas phase was not included in the calculation. with experimental data. 79 .Thermodynamic assessments Fig.2 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air.2.2. 4.
Thermodynamic assessments Fig. with experimental data. 80 .2. showing the expanded stability field of β-spl + mgs.4 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 under strongly reducing conditions ( PO2 = 1×10-4 Pa ). 4. Fig. 4.3 Mn rich part of the calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air.2.
80.2.14 at T = 1105 K in air.[14. This value is in agreement with the result from Geller and Espinosa. Their data are shown in Figs. 4.2. and β-spl + esk + liq in equilibrium at T = 2243 ± 20 K. Their resulting phase diagram is in considerable disagreement with the findings of Speidel and Muan. They estimate a minimum temperature of T = 773 K for the stability of β-spl.. 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. The Mn solubility in (Cr2-yMny)1+xO3 reported from Speidel and Muan is significantly higher than it is found by Golikov et al. p. 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.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.42 at oxygen partial pressure >> 20000 Pa. but it is lower than the findings from Speidel and Muan.3.2. p. report a solubility limit of y = 1. 79). Pollert et al. 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. 81 . p. They find β-spl + α-spl + bxb coexisting in equilibrium at T = 1183 ± 5 K. Golikov et al. 4. 79 and 4.2. From the absence of changes of the lattice parameters of esk in equilibrium with β-spl annealed at T = 1105 K and 1620 K in air compared to pure Cr2O3 they conclude that the solubility of Mn in (Cr2-yMny)1+xO3 is low and does not depend significantly on temperature. next page).2. Tanahashi et al. and Pollert et al.2. They consider the solubility limit of Mn in (Cr1-yMny)2+xO3 to be negligible. Pollert et al. 4.15] studied phase stabilities in the MnOx-Cr2O3 system in the temperature range from T = 1100 K to 1620 K in air by means of X-ray measurement of annealed samples. The solubility limit of Cr in Mn2-yCryO3 is measured by these authors to be y = 0.5.
As the compositions of mgs 2 solid solution are located on the line connecting Mn1-xO with CrO in the ternary phase 82 . which increases slightly with increasing oxygen partial pressure. Phase relations were verified using X-ray diffraction. In order to identify the equilibrium compositions.5 Cr contents of β-spl in equilibrium with mgs. 1473 K. 4.Thermodynamic assessments Fig. conclude that Mn is dissolved in cubic MnyCr3-yO4 in the form of Mn3O4. each phase in the quenched specimens was subjected to electron probe microanalysis (EPMA). and 1873 K. and significantly increasing Cr solubility in cubic MnyCr3-yO4 with decreasing oxygen partial pressure (Fig. 4. They found increasing Mn solubility in cubic MnyCr3-yO4 at oxygen partial pressure higher than 2 ×10-2 Pa . 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. 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.5). The compositions of β-spl are located on a line connecting MnCr2O4 with β-hsm in the ternary plot. They report small solubility of Mn in (Cr1-yMny)2+xO3 at pO2 = 2×10-6 . Experimental data are included. β-spl in equilibrium with esk. From this result Tanahashi et al. esk in equilibrium with β-spl.2.2.
and 1273 ± 5 K in the oxygen partial pressure range from 0. Dotted lines are tie lines. There are no data on oxygen nonstoichiometry of MnyCr3-yO4.2 cat. Also the experimental result on the three phase equilibrium MnO + MnCr2O4 + bcc from Ranganathan is plotted. 4.6 Ternary phase diagram of the system Cr-Mn-O with stoichiometric single phase equilibria (points).2. two-phase fields and three-phase fields. Fig. For the invariant three phase equilibrium mgs + β-spl + bcc Ranganathan and Hajra measured the Mn content in bcc to be 25. Bobov et al. p.% at T = 1323 K performing an isopiestic experiment (Fig. these authors conclude that chromium oxide dissolves in (Mn1-yCry)1-xO in the form of CrO. 4. 4. 83 . 1173 K.Thermodynamic assessments diagram. single solid solution phase equilibria (heavy lines). Three-phase field boundaries are denoted with thin solid lines.5. investigated the composition changes of the two phase equilibrium β-spl + mgs at T = 1073 K. 82).6).1 to 10-13 Pa (Fig.2.2.
Giving α-spl the formula [Mn2+](Mn3+. 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.5 in Mn0.5CrO2 obtained from a previous study they derive ΔG of the reaction CrO1. 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-1.1) β-spl Using compiled Δf °GMnO and Δf °GCr2O3  they calculate Δ f °GMnCr2O4 from its oxides to be –59 ± 8 kJ mol-1. which is equivalent to Δf G of 1 2(Δ f GMnCr2O4 − Δ f GMnAl2O4 ) .5AlO2 and AlO1.Cr3+)2O4 this corresponds to a minimum concentration of [Mn3+] = 0. enthalpies and entropies of MnyCr3-yO4 samples annealed at T = 1723 K using X-ray analysis and DTA measurement. From these data and the activities of CrO1. Tanahashi et al.Thermodynamic assessments Holba et al.5AlO2 = AlO1. and remain β-spl. derive Δ f °GMnCr2O4 = –958 ± 8 kJ mol-1 from liquid Mn. With decreasing Mn-content the temperature for the transition decreases (Fig.MnyAl3-yO4 solid solutions formed from Cr2O3-Al2O3 mixtures at T = 1873 K.4 for the formation of α-spl.5 + Mn0.2) (4.2. 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. Tsai and Muan experimentally determined compositions of coexisting MnyCr3-yO4 .3) β-spl to be –10 kJ mol-1 at T = 1873 K.2.5 in Mn0. This means that the Gibbs energy of formation of β-spl of the composition MnCr2O4 from its 84 .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 (4.5 + Mn0.5CrO2 (4.2. 79).2. 4. Samples with y < 1.2.8 do not show Jahn–Teller distortion at room temperatures. p.
0 kJ mol-1 at T=1523 K. 85 . Fig.1 kJ mol-1.  in the CoO- β-spl The spread of Δ f °GMnCr2O4 values resulting from different studies and our recalculations is shown in Fig. Using other values for Δ f °GMnAl2O4 reported β-spl in the literature[25-27] leads to deviating Δ f °GMnCr2O4 of –34. Δ f °GMnAl2O4 = –32. Tsai and Muan chose the value determined by Lenev and Novokhatskiy. unfilled symbols correspond to recalculated values.6 kJ mol-1 at T = 1873 K. and ΔS α β = 13 J K-1 mol-1. 4. present thermodynamic data on the transition of α-spl to β-spl.1 kJ mol-1. –46. Filled symbols correspond to originally reported literature data.Thermodynamic assessments oxides using this calculation technique depends on the value of Δf °GMnAl2O4 .4 ± 10 kJ mol-1. Biggers by using the same technique as Tsai and Muan β-spl MnO-Cr2O3 system found Δ f °GMnCr2O4 = –59. According to these authors the transition of pure α-hsm to β-hsm takes place at T=1445 K.2. and –36. 4.7 Calculated Gibbs energy of formation of β-spl of the composition MnCr2O4 as a function of temperature.7.6 kJ mol-1 β-spl giving Δ f °GMnCr2O4 = –52. ΔΗ α β = 18810 J mol-1.2. Tetragonally distorted spinel (α-spl): Pollert et al. with experimental data and error bars.
To maintain electroneutrality Mn2+ is formed on the octahedral sites resulting in a charge disproportionation reaction.4) This endmember is considerably more stable than the endmember of the formula [Cr2+](Mn3+)2O4.2. In our description we further go along with the presumption that the amount of oxygen vacancies may be neglected. This state is denoted SER (Stable Element Reference).30].Mn2+.Mn4+)2O4. 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. As the degree of inversity of β-spl is very low. Thus the endmember ° β-spl β-spl G[Cr 2+ ](Mn3+ ) O becomes less stable the more stable °G[Mn 2+ ](Cr3+ ) O becomes. so we stick to the less complex description without Mn2+ and Mn4+ on the octahedral sites. 2 4 2 4 86 .Mn3+)2O4 using the compound energy model[31–33]. and [Cr2+](Cr3+)2O4 that corresponds to Cr3O4 are taken from the assessed binaries[7.2.Cr2+](Cr3+.Mn3+. 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. 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. Considering these findings an alternative description of β-spl would read [Mn2+.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[29.5) The Gibbs energy of the reciprocal reaction is taken to be zero.15 K and p = 105 Pa. All endmembers of our model β-spl are neutral.Thermodynamic assessments 4. measured the electrical conductivity of β-spl. Lu et al. β-spl can therefore be described by the simple formula [Mn2+.2.8]. The Gibbs energies of the endmembers [Mn2+](Mn3+)2O4 that corresponds to β-hsm. They propose small polaron hopping between Mn3+ and Mn4+ on the octahedral sites as mechanism for the electrical conductivity.Cr2+](Cr3+. However there is no experimental data quantifying the amount of Mn4+ in β-spl.
Cr3+.7) The experimental data could be reproduced without the optimization of a temperature dependent parameter.) 3 + Abxb (4.15]. The incorporation of chromium of valencies other than three is mentioned nowhere in literature.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.Cr3+)2(O2-)3. and the Cr solubility in tetragonally distorted MnyCr3-yO4 does not extend beyond MnCr2O4. Hence. the two endmembers of α-spl read [Mn2+](Mn3+)2O4 and [Mn2+](Cr3+)2O4.Mn3+. The Gibbs energy of the endmember (Mn3+)2(O2-)3 is taken from Grundy et al. (Mn2+. 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. Experiments[11.15. 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. Due to these considerations we may write [Mn2+](Cr3+. 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. This is a reasonable assumption as the radii of these ions are very similar.6) Bixbyite (bxb): Geller and Espinosa postulate the incorporation of Cr into Mn2-yCryO3 by a simple substitution mechanism between Cr3+ and 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+. Thus we may describe bxb as (Mn3+. whereas for ordering due to Jahn–Teller distortion the opposite holds.Cr2+.Va)(O2-) leads to far more satisfactory 87 .Mn3+.Mn3+)2O4 to describe α-spl.34] show that α-spl is stabilized at high Mn contents.2.14.2. as the degree of inversity is increasing with higher temperature. The Gibbs energy of [Mn2+](Mn3+)2O4 is equal to α-hsm..
Agreeing with these authors we model the solubility of Mn by (Cr3+. 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. Eskolaite (esk): Pollert et al. 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.Va)1(O2-)3.8) The Gibbs energies of the three other endmembers are taken from Grundy et al. 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.2. 4. 4.. postulate the incorporation of trivalent Mn ions into (Cr1-yMny)2+xO3.Mn3+)2(Cr3+.8.Cr2+.)3 Gas − 1 3 °GO − 3 2 RT (1 3ln1 3 + 2 3ln 2 3) + Amgs 2 (4. The Gibbs energy of (Mn3+)2(Cr3+)1(O2-)3 is given by 88 . The model description of mgs is shown in Fig.8 Geometrical representation of the mgs phase described using the compound energy model.2. Fig.Thermodynamic assessments reproduction of these data. These experiments also provide evidence against Cr being incorporated interstitially.2.
1 (pp. Cr-Mn alloys: We describe the oxygen solubility in bcc by an interstitial solution model of the form (Cr. Experimental data on the oxygen solubility in pure bcc A2 chromium metal were used for the description of (Cr)1(O.9) and the Gibbs energy of (Mn3+)2(Va)1(O2-)3 by ° G esk3+ (Mn )2 (Va)1O3 = °G bxb3+ (Mn )2 (O2.)3 + °GCr SER + Aesk (4.4 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Mn-Cr-O system is given in Table 4. Assuming low oxygen solubility in bcc bcc manganese metal we give a large value to the endmember °GMn:O . Povoden et al.. and Lee.39] ..2.Cr2+.Mn)1(O. Mn3+.Va)3. Liquid: We model the liquid phase as (Cr3+.10) We take the Gibbs energies of the other endmembers from Povoden et al..Vaq-)q using the two-sublattice model for ionic liquids parameter 0 Lliq3+ Cr .2.2.Thermodynamic assessments ° G esk3+ (Mn )2 (Cr3+ )1O3 = °G bxb3+ (Mn )2 (O2. The liquidus temperature is optimized using the interaction .Mn2+)p(O2-. 89 . 90-92).The binary interaction parameters are taken from Grundy et al.Va)3.2.)3 + Aesk (4. The descriptions of further alloy phases are taken from.Mn3+ :O2- [38. 4. No data are reported for the oxygen solubility in pure bcc A2 manganese metal.
Thermodynamic assessments Table 4.Mn 2+ .0 4996.6587T = 504 + 0.Va q1 liq Mn 2+ :O 2.996 54.Va q- L L = 121000 = 129519 = −45459 = −33859  = −15009 + 13.0 4341.− H Mn = 2GMN_L + GMN2O3_L − 3GMN1O1_L liq SER SER GMn3+ :O2.9479T = −188487.52 (Cr 2+ .999 4050.Mn 3+ :O 2- L Bcc A2 alloy (bcc) (Mn..− 2 H Cr − 3H O = GCR2O3_L liq SER SER GCr 2+ :O2.− H Mn = GMN_L liq SER GMn3+ :Va q.− 2 H Mn − 2H O = 2GMN1O1_L 0 liq Cr 2+ :O2.938 15.Va q. q = 2 yCr 2+ + 2 yMn 2+ + 3 yCr3+ + 3 yMn3+ ° ° ° ° ° ° ° ° liq SER GCr 2+ :Va q.H0 S298 Cr Mn O Liquid (liq) BCC_A2 CBCC_A12 ½ mol O2 51.Cr 3+ .0 23.2.O)3 90 .008 102.6 0 liq Mn 2+ :O 2.1 Thermodynamic description of the Cr-Mn-O system a) Element Element Reference Mass H298 .Cr)1 (Va.)q p = 2 yO2..543 32.− 2 H Cr − 2H O = 2GCR1O1_L liq SER GMn 2+ :Va q.Va q- L L 0 liq Cr 2+ .Mn 2+ :Va q- L 0 liq Cr 3+ .Va q- L 0 liq Mn 2+ .Mn 3+ :O 2.Mn 3+ ) p (O 2..− H Cr = GCR_L liq SER GCr3+ :Va q..− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+ :O2.Mn 2+ :Va q1 liq Cr 2+ ..− 2 H Mn − 3H O = GMN2O3_L liq SER SER GMn 2+ :O2.+ qyVa .
2923T 3 esk SER SER SER GMn 3+ :Cr3+ :O2.72035( yCr − yMn ) 2 − 1.3 − 7.− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.8766 = 46513.008 yCr − 0.7339T  = −9162 + 4.)3 ° bxb SER SER GMn 3+ :O2.− H Cr − H O = 0.6 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 = 308.6 yCr 2+ :Va:O2- :O 22- esk β esk = 3 yCr :Va:O Cubic spinel (β-spl) 91 .− 2 H Mn − 3H O = GMN2O3 bxb SER SER GCr 3+ :O 2.− 2 H Mn − H Cr − 3H O = GMN2O3 + GHSERCR  + 39503 esk SER SER GMn 3+ :Va:O 2.− 2 H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.Mn:Va L 0 bcc Cr:O.Mn 3+ . Cr 3+ .− 2 H Cr − 3H O = GCR2O3 esk SER SER GCr 3+ :Cr3+ :O 2.Cr 3+ ) 2 (O 2.6 yCr3+ :Cr3+ :O2esk β esk = 3 yCr :Cr 3+ 3+ 3+ :O 22- T esk c = 308.Va)1 (O 2.− 2 H Mn − 3H O = GMN2O3 + 39503 ° ° ° Magnetic contribution p = 0.− H Mn − H O = GMN1O1 − 21883.48643 − 0.93845T mgs SER SER GMn 3+ :O2.Mn:Va L = −20328 + 18.28 esk Tcesk = 308.27 yMn + yCr yMn [0.)1 ° ° ° mgs SER SER GMn 2+ :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+ .− H Mn − H O = GMN1O1 mgs SER SER GCr 3+ :O 2.4183T  1 bcc Cr.− 3H Cr − 3H O = GCR2O3 + GHSERCR  esk SER SER GCr 2+ :Cr3+ :O 2.1533 1 mgs Mn 2+ .)3 ° ° ° esk SER SER GCr 3+ :Va:O 2.93265( yCr − yMn ) 4 ] Manganosite (mgs) (Mn 2+ .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.Mn 3+ :O 2- L = −42104.− 2 H Cr − 3H O = GCR2O3 + 3459 ° Eskolaite (esk) (Cr 2+ .Va L = −709542 p = 0.6 yCr 2+ :Cr3+ :O2esk Tcesk = 308.4 Tcbcc = −311.1853365T 0 mgs Mn 2+ .117( yCr − yMn )8 ] β bcc = −0.2923T 3 esk SER SER GCr 2+ :Va:O 2. Cr 3+ .Mn 3+ ) 2 (Cr 3+ .5213 − 22.Va)1 (O 2.5GCR2O3 + 71549.
Mn3+ :O2- .105 from Speidel and Muan to optimize Aβ-spl and Bβ-spl in Eq.7 cat. The program minimizes the sum of squared errors between the experimentally determined phase diagram and thermodynamic data and the corresponding calculated data. β-spl To optimize the parameters Aβ-spl and Bβ-spl in Eq. 4. PARROT takes into account all sorts of thermodynamic and phase diagram data simultaneously.4.Mn 3+ ) 2 (O 2. The temperature found from Speidel and Muan for Cr the two phase equilibrium of Mn rich β-spl (Mn = 94.2.− 3H Cr − 4H O = GCR3O4 β-spl SER SER GMn 2+ :Mn 3+ :O 2.2.− 3H Mn − 4H O = GMN3O4 ° Functions GSPINEL = 2 GCR3O4+ 1 GMN3O4B 3 3 −210795. The optimization of the thermodynamic parameters is performed using the PARROT module of the Thermo Calc database system.69T GTSPINEL = 2 GCR3O4+ 1 GMN3O4 3 3 −200941. 4. mol.Thermodynamic assessments (Mn 2+ . 4.4 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. Further we use – with lower weights – the temperature of the two phase equilibrium β-spl + liq at X(Cr) = 0.− H Mn − 2 H Cr − 4H O = GTSPINEL α-spl SER SER GMn 2+ :Mn 3+ :O 2.1T a) Note: All parameters are in SI units: J.− H Mn − 2 H Cr − 4H O = GSPINEL β-spl SER SER GCr 2+ :Cr 3+ :O 2.Mn3+ :O2.2. 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.Cr 2+ )1 (Cr 3+ .2.Mn 3+ ) 2 (O 2.5+61. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.4 and 0 liq L Cr3+ . 4. K.) 4 ° α-spl SER SER SER GMn 2+ :Cr 3+ :O 2.− 3H Mn − 4H O = GMN3O4B β-spl SER SER SER GCr 2+ :Mn 3+ :O 2. and we use data on the solubility of Cr in MnyCr3-yO4 at T=1873 K under varying 92 .. Pa: R = 8.) 4 ° ° ° ° β-spl SER SER SER GMn 2+ :Cr 3+ :O2. 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.4 and Aα-spl and Bα-spl in Eq.31451 J mol-1 K-1. 4.2.− H Cr − 2 H Mn − 4H O = GCR3O4+GMN3O4B -GSPINEL Tetragonally distorted spinel (α-spl) (Mn 2+ )1 (Cr 3+ .4 and 0 Lliq3+ .%) and α-spl is used to optimize Aβ-spl and Bβ-spl in Eq.9+75.
2. shown in Fig. 4. 4.2.2. 4. on the two phase equilibrium β-spl + bxb in air (Fig. Single phase α-spl is stable in a small T–X(Cr) range from T = 1153 K to 1441 K and X(Cr) = 0 to 0.2.65 prl and β-spl coexist in air.2.2.5. The maximum Cr solubility in Mn2-yCryO3 is 23 cat. 80) to optimize Aβ-spl and Bβ-spl in Eq. and for Aesk in Eq.126.96.36.199 data on the solubility of Mn in (Cr1-yMny)2+xO3 from Pollert et al. 4. 4. p.% at T = 668 K in air. 82. 82).2. β-spl is stable in a large temperature range from T = 513 K to 2243 K and from X(Cr) = 0 to X(Cr) = 0. The two-phase field bxb + α-spl is only found in a very small area at about 1150 K.2.67 in air. The maximum Mn solubility in (Cr1-yMny)2+xO3 is 0.054 in air. 82 are used. We use data from Holba et al.2.Thermodynamic assessments oxygen partial pressures from Tanahashi et al. From T = 513 K to 668 K and maximum X(Cr) = 0. 4.5 Results Phase diagram data: The calculated phase diagram of the pseudo-binary system MnOx-Cr2O3 in air is shown in Figs. The dotted line in Fig.% at 2243 K in air. 4.66 to 0. on the temperature dependence of the diffusionless transformation of α-spl to β-spl shown in Fig.2.1 and 4. 4. shown in Fig.23 in air. 4. 4. p.2.4.2. αspl coexists with β-spl from X(Cr) = 0 at T = 1441 K to X(Cr) = 0. p.2.2. and data from Pollert et al.2 cat.3. 4. prl coexists with esk at T < 513 K in air.2. p. p. prl + bxb is stable in a small area from T = 668 K to 694 K and X(Cr) = 0 to 0. p. 4. and Aα-spl and Bα-spl in Eq. In Fig. and Aα-spl and Bα-spl in Eq. 79. 79 to optimize Aβ-spl and Bβ-spl in Eq. 79 shows the temperature dependence of the diffusionless transformation of α-spl to β-spl.2.175 at T = 1156 K. 4. 4. p.5. This two-phase field expands under more reducing conditions which can be seen in the calculated phase diagram of 93 . β-spl and esk coexist from X(Cr) = 0. 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.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. 79 and Fig.4.2.2. p. 4. for Amgs in Eq. p. Abxb in Eq.8 data on the solubility of Cr in (Mn1-yCry)1-xO from Tanahashi et al.2. are used (Fig.2. Temperature data from Speidel and Muan and Pollert et al.7 is optimized using data on the solubility of Cr in Mn2-yCryO3 from Pollert.6. 80 the Mn rich part of the diagram is shown in detail.6.992 at 1203 K in air. 4.3. bxb is stable from T = 694 K to 1154 K in air. mgs is not stable in air. 4. 188.8.131.52.
p. Isothermal sections of the Cr2O3-MnO-MnO2 system at different temperatures are plotted in Fig. were not used for the optimization. 4. 94 . on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl and esk + β-spl at 1873 K. 4.2. and from Bobov et al.6. on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl at T = 1073 K. p. 4.5.4. 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.2.2. and 1273 K in function of log(pO2 ) are compared to the calculated results from this work.2. and Mn in esk + β-spl are presented. Experimental data from Tanahashi et al. The data from Bobov et al. p. In the isothermal phase diagram of the Mn-Cr-O system at T = 1323 K of Fig.Thermodynamic assessments the pseudo-binary MnOx-Cr2O3 system at an oxygen partial pressure of 1×10-4 Pa in Fig. In Fig. 82 experimental and calculated solubility data of Cr in mgs + β-spl. 1173 K. 4.9 (next page). 80.
Stoichiometric single phase equilibria are points. and single solid solution phase equilibria are heavy lines. Three-phase field boundaries are denoted with thin lines.2. 95 .Thermodynamic assessments Fig.9 Isothermal sections of the ternary system Cr2O3-MnO-MnO2 showing oxide and liquid evolution as a function of temperature and composition. 4. Dotted lines are tielines.
°SMnCr2O4 = 116 J mol-1 K-1.9 (p. on the other hand cannot be reproduced. In the β-spl temperature range from 1050 to 1800 K Δ f °GMnCr2O4 from the oxides is given by the term –89167 + 29.[14. At T = 1873 K we get Δ f °GMnCr2O4 = –34388 J mol-1. 4.9 b).15] and Ranganathan et al.2. and β-spl Δ f °GMnCr2O4 = –1634017 J mol at T = 298.15 K. Fig. 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. Our calculated T0 line for the diffusionless transformation of α-spl → β-spl is in perfect agreement with experiments by Holba et al. 4.2. 4. 4. The results from Bobov et al.6 (p. 82 agrees well with the results from Tanahashi et al. The oxygen nonstoichiometry of mgs is yet insignificant (Fig. At this temperature small oxygen nonstoichiometry of esk is apparent. as shown in Figs. The three-phase regions prl + esk + bxb and bxb + esk + β-spl. Our assessed phase diagram is in excellent agreement with the findings of Pollert et al. 4.2. 95) represents the phase relations of the oxides and the evolution of liquid formation. p. and Δf °G α-spl = –1625681 J mol-1 at T = 298.15 K. 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-1.2.3 (p. 85. p.2.9 a) disappear.2. p. 4. 80).5. For both cases Speidel and Muan mention the speculative character of their phase diagram due to the lack of experimental data. 4. and the two-phase fields prl + bxb. For α-spl of the composition MnCr2O4 we calculate Δ f °H α-spl = –1596517 J mol-1.9 a to c)..2. The calculated dependence of β-spl solid solubility on oxygen partial pressures shown in Fig. 4. but it increases at elevated 96 . 79). and Fig. 79). 4. 83).2.7.21 %. 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.338 T with an error of ± 0.Thermodynamic assessments Thermodynamic data: The calculated enthalpy. (Fig.2 (p. ° α-spl S = 98 J mol-1K-1.2. 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. 4.2.2. 4.2.6 Discussion Phase diagram data: Our assessed phase diagram is in rough agreement with the findings from Speidel and Muan. β-spl + bxb. and mgs + β-spl dominate the system in a wide temperature range from T=1200 K to 1900 K (Figs.
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.9 d). 4.2.2. p. 4. 4. which is at point A in Fig. At T = 1900 K phase relations become more complex due to incipient melting (Fig. Hence. indicating that only very little energy is 4. 4. 83 associated with decreasing 97 .9 f). Even more three phase regions due to increasing liquid formation start to exist at T = 2000 K (Fig. This is obvious from Fig. 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. p.2.9 d). Recently Qu et al. the formation of a protective Cr2O3 single phase layer followed by a chromium manganese spinel on Mn bearing interconnects as it is observed by Simner et al.2. 84) on Crofer22 APU alloy is expected under SOFC operating conditions.9 c). found that the electrical conductivity of chromium manganese spinel increases with increasing Mn-content. The occurrence of other Cr-Mn phases in the protective scales formed during thermal exposure of Crofer 22 APU interconnects is not expected thermodynamically.2. 4. The calculated ΔHα needed for the transformation to take place.. In a thermodynamic view the formation of β-sp with the composition MnCr2O4 (Point A in Fig. Thermodynamic data: β-spl β-spl Our calculated Δ f °GMnCr2O4 value at T = 1873 K is in agreement with the Δ f °GMnCr2O4 value spl derived from Tsai and Muan using Δ f °GMnAl2O4 from Kim and McLean.6. 4. and ΔSα β values for the transformation of α-spl to β-spl are very small. must be kinetically controlled.2. The composition of Crofer22 APU alloy is close to the Cr-corner of the Mn-Cr-O phase diagram. and the-three phase fields bxb + β-spl + liq and mgs + β-spl + liq emerge (Fig. At T = 1900 K liquid is formed at the Mn-rich side of the system.6. 83. At T = 2400 K the only remaining stable solid phases are esk and prl (Fig.6.2.9 c). 4.2.Thermodynamic assessments temperatures becoming apparent at T = 2000 K (Fig. p.2. 4. 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.
Thermodynamic assessments electrical conductivity. Ramprakash. Foger. 2003. 3. A. K. Our Thermo Calc dataset resulting from the presented CALPHAD modeling of the Mn-CrO system allows the calculation of phase stabilities. 1997. Badwal. Y. Quadakkers. 297-310. 1037.). Bossel (Ed. 98 . and Δf°G data for β-spl and α-spl. and the only available -1 β-spl Δ f °GMnCr2O4 values are spread over a range of 31 kJ mol . Kinzel.P. Lamm. p. Solid State Ionics. S. J. L. 1994. K. Hilpert. 2. Handbook of Fuel Cells – Fundamentals. p.J. 703. 4. M.W. Hilpert. pp. 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. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. in: W. Miller. Zhang. D. Recalculating old experiments using new thermodynamic data together with phase diagram data we achieved a description. First European Solid Oxide Fuel Cell Forum Proceedings. Das.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. J. W. and we present well-founded Δf°H. 4. References 1.2. pp.). 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. Druckerei J. H. 99. Singheiser. All features of the system are well described with the optimization of only 8 additional optimization parameters. K. R. in: U.A. 2. H. 171. 1-15.S. Deller. Gasteiger (Eds. Nickel. Göttingen. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. Chichester. Fergus. Vol. °S. Solid State Ionics. Technology and Applications. John Wiley & Sons. 2004.P. There is a surprising lack of thermodynamic data on β-spl. Vielstich. which is very close to the experimental findings of several authors.
S. Zalazinsky. J. Hajra. SGTE Data for Pure Elements. Phase Equilib. Yang. Mater. V. Y. Solids.. 16. M. Xia. 3763-69. 15. and Ga3+ substituted Mn2O3. 99 . V. Phase equilibria of the MnO-SiO2CrOx system at 1873 K under controlled oxygen partial pressure. 15(4). Phys. Phys. pp. T.J. N. Ceram. pp.. Assessment of the Mn-O system. Bobov. L. Balakirev. 2001. Dinsdale. Pederson. Tanahashi. S. Pollert. Fiz. Yamauchi. Fujisawa. J. 149-58.. pp. 1309-1315. G. Zh. Peculiarities of phase-diagram in the reduction of Me0. 10. Electrochem. Mater. Metall. Mater. 1919-1933.. Espinosa. 46. Khim. T. A. 152. J. Magnetic and crystallographic transitions in Sc3+.. 1970. 853-60. 8. pp.P. L. A. pp. D. pp. 1987.. E. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 58. 577-78. Cr3+. 1977. Grundy. Hallstedt. Nevriva. J.H. 1991.V. pp. Res. 18. 1962. 19. 2003. Bull. Y.P. 9. Trans. A.. 13. Rev. J. pp. 1975. Corliss.. Bull. Pollert.75O4 solid-solutions. Gauckler. A thermodynamic evaluation of the Cr-Mn and Fe-Cr-Mn systems. Gauckler.. Am. Grundy. pp. Muan. 15.G. P.N. 12. Geller. 1963. 317-425. Miscibility gap of MnxCr3-xO4 spinels. Stevenson. Golikov. Sci. A740-45. A. 750-751 (in Russian). Balakirev. Bull. Anderson. Solid State Chem. 14. Simner. 1993. Soc. A. Novak. 6. Alloy oxide equilibria in the Cr-Mn-O system. pp.N. Chufarov. 41. Holba. E.25Mn2. M. Nevřiva. Lee.D. 126.F. 1980. Phase diagram of the Mn2O3-Cr2O3 system in air. Z. Magnetic structure of manganese chromite.. A 24. E. 2005. 353-62.. 1984. S. Phase Equilib.-G. pp. pp. 24.F. B. 21-39. L. SOFC performance with Fe-Cr-Mn alloy interconnect. E. M. Pollert.V.M. Povoden. 1987. Novak. 10. pp. The system manganese oxide-Cr2O3 in air.. 7. A. Tetragonal distortion of spinel solid-solutions MnCr2O4Mn3O4. ISIJ Int.W. pp. pp. Res. M. J. J. Chem. 38. 17. J. Phys. J. 2006. Hastings. B 1. J. L. Diff. 11. Phase equilibrium diagram of the system Mn-Cr-O. J.J. 71. Furuta.. Rev. 556-65.P. 1145-47.P. M.M.R. 1453-56. Speidel. 27. C. Ranganathan. B-J.I. Nevriva. Golikov. Soc. 562-65. G.Thermodynamic assessments 5. G. 9. Calphad.
66. 26. Hillert. Revision of thermodynamic data on MnO-Al2O3 melts. 1992.Cr2O3 solid solution at 1873 K. Control of the manganese-oxygen reaction in pure iron melts. Activity composition relations in FeCr2O4-FeAl2O4 and MnCr2O4MnAl2O4 solid-solutions at 1500°C and 1600 °C. Soc.P. 1979. A. 25. Trans. Akad. H. J. Guillermet. J. Nauk SSSR. McLean. 43. M. Thesis. Yamauchi.F. 1976.S. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. Electrical conductivity of the manganese chromite spinel solid solution. A. Lenev. Can. Am. Acta Crystallogr. Tsai. A. 100 . J. 28. Activity composition relations in refractory oxide solid-solutions at high-temperatures – the system Cr2O3-Al2O3. Pennsylvania State University. Ceram. M. Novokhatskiy. pp. L. 1966...D. pp..K.A. University Park..Thermodynamic assessments 20. 7-13. Jansson... Muan. Toker. 1050-53. Kim. Tsai. 31. B. Ceram. Paranthaman. Soc.. Acta Metall.D. 23. pp. Metall.. Jansson.T. Janke. Soc. 1988. A 32. Muan. 81-87.. 87-92. 1966. VCH Verlagsgesellschaft mbH. L. 225-232.T.F. N. ISIJ Int. S. 1991. M. 24. T. Parts I and II. pp. Equilibrium phase-relations and thermodynamics of the Cr-O system in the temperature-range of 1500°C to 1825°C. Steel Res. 88. 32. pp.(in Russian). 20. Thermodynamics of iron-manganese aluminate spinel inclusions in steel. Z. Taniguchi. R. 320. 22. PA. A. C. Cmpd.T. Phase diagram of system MnO-Al2O3 and thermodynamic properties of MnAl2O4. pp. Sundman. 10B. J. H.. Hillert.-O. Andersson. N. Sundman. Weyl. Z. Standard Gibbs free energy of formation of MnO-saturated MnO. D. 2005. Fujisawa. 2nd Ed. 1993. 89-92. C. Hillert. 75. A. pp. 75. Izv. B. Metall. 79(2). A.A. I. Shannon. Biggers: Ph. E. 30. M. 3. Payzant. Trans. I. Muan.M. Alloy.Y. Zhu. 34.V. 1407-11. Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides. Barin: Thermochemical Data of Pure Substances. 575-84. 34. 1995. 1412-15. 21. pp. T. Am. 22. pp. 27. pp. 33. Darken. Metallkd. B. K. 2003. B. 1986. 437-445. 751-67. 2000. B. 161-76. pp. pp. 29. M. J. J.. 1981. 35. Jacob. 1992. Ceram. 2001. Weinheim. Q. Application of the Compound-Energy Model to Oxide Systems. Dimitrov. Am. Metall. B. R. pp. 73. Furuta. J.K. Met. Tanahashi. Lu. The Compound Energy Formalism.. Lam: United States Patent 6039788.
J.M.M. O’Keefe. Sundman. Valigi. 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. 261-66. Ohio. D. Russ. L. 947-962. Caplan. Solids. M. 153. Chen . Ågren. J. 9(2). B. 109-19. 114-24.A. In the La-Cr system reported solubility of lanthanum in bcc chromium is considered in the modeling. The following standard data of 101 . 38. Calphad. G. B. Sundman. 42. 196. Jansson. In the La-Cr-O system the Gibbs energy functions of La2CrO6. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. Phase equilibria of the La-Cr-O system are calculated at T = 1273 K as a function of oxygen partial pressure. and L. A. Thermodynamic properties of alloys of manganese with transition elements of fourth period (Cr Fe Co Ni) and with copper. 16A. Calphad. B. pp. 1957.J. 39. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. B. (accepted) The La-Cr and the La-Cr-O systems are assessed using the Calphad approach.3 Thermodynamic assessment of the La-Cr-O system E. 31. M.M. J. 40. Burr. ASM. and perovskitestructured LaCrO3 are presented. M. Fraser. Metall. and under reducing conditions are presented. pp. Chem. Phys. pp. 1991.5 phase diagrams in pure oxygen. Diff. Ivas. Phys. J. Gauckler J. Andersson. V. Jian. 41. Jansson. 2006. Povoden. 1968. J. 1985. Hillert. p.Thermodynamic assessments 36. W.J. A.R.5-CrO1. D. Cleveland. 4. T. air. A. 343-. La2(CrO4)3. The electrical properties and defect structure of pure and chromium-doped MnO. J. in: Ductile Chromium. pp. pp. Eremenko. Power sources. Chem. Sundman. V. 15. Phase Equilib. 1985. M. Lukashenko. Grundy. B. The Thermo-Calc Databank System. and oxygen solubilities in bcc and fcc metals are modeled. pp. 37.. Hill. Modification of the Two-sublattice Model for Liquids. 153-90. Trans.-O.N. Qu. 1970. Ivey. Sidorko.G. M. The calculated La-Cr phase diagram as well as LaO1. 42.
1 Introduction In SOFC. Furthermore earth alkaline-containing LaCrO3 has been proposed as a cathode material in a recent study by Jiang et al.7 kJ mol-1 . As the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. Δf. recently Sr-. The presented thermodynamic assessment of the La-Cr-O system is laying the grounding for extensions to the thermodynamic La-Sr-Mn-Cr-O oxide database that is required to understand the thermodynamics of SOFC degradation by chromium. and structurechemical data are critically assessed. oxides. pO2 (decomp) = 10-20. 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.2 J mol-1 K -1 . thermodynamic.Thermodynamic assessments stoichiometric perovskite are The calculated: Δf. the thermodynamic stability of the cathode is particularly important for efficient long-term operation. The liquid phase is modeled using the two-sublattice model for ionic liquids. Gibbs energy of formation from the and ° S 298 K (LaCrO3 ) = 109.oxides G(LaCrO3 ) = –72. 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.0034 T (kJ mol-1) (T = 1273 K to 2673 K) is calculated. Cation nonstoichiometry of La1-xCrO3 perovskite is described using the compound energy formalism (CEF).97 Pa. All available experimental phase diagram.oxides° H 298 K (LaCrO3 ) = −73. The lattice stabilities of elements are adopted from Dinsdale.Mn)2O4 spinel and Cr2O3 along with a severe cell voltage decrease[1-4]. Diffusion of chromium from the metallic interconnect with high chromium content into the cathode leads to the formation of Mn(Cr. 4.403–0. Sr-doped lanthanum manganites (LSM) with the perovskite structure are used as cathode materials in SOFC. aiming on minimizing the squared errors between 102 . and Crdiffusion into the cathode from LaCrO3-based interconnects is significantly lower than from Cr-containing metallic interconnects. V-doped and Zn-doped La1-xCaxCrO3-δ have been considered as promising alternative interconnect materials for SOFC. The assessment of the La-Cr-O system using the Calphad approach is based on the recently reassessed La-O and Cr-O subsystems. and the model is submitted to a defect chemistry analysis.3.
5-CrO1.4 at.% or 99.% Cr. The solubility of La in αCrss decreases towards lower temperatures. whereas Cr is almost insoluble in La.13] and 3.% Cr2O3 (T = 2323±20 K). reported a La solubility of 0.% in αCrss at T = 1533 K.17] . Svechnikov et al. The solubility of La in αCrss was determined in investigations by Savitskii et al.68 at.5 at. as well as a large liquidliquid miscibility gap[12.% at 1983 K.% 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).5. is of technological interest.% Cr2O3 (T = 2248 K) or 80 at. and the exact value of the oxygen partial pressure was not specified. found La < 0. This is not surprising as experiments are complicated due to the high investigation temperatures and evaporation of predominantly Cr[25. determined the partial enthalpy of mixing in La-Cr liquid with infinite dilution of Cr.2 Literature review of the La-Cr system The La-Cr system has a eutectic at T = 1138 K[12. 4.13]. but in the graphic presentation of the phase diagram in the same paper Tm(argon) ≈ 2600 K.14. Tm(air) = 2773 K was determined by Foëx and by Coutures using a thermal analysis technique described in more detail in earlier publications. No intermetallic phases were found in the La-Cr system[12.3. 4. Tm(argon) = 2703 K was reported by Tresvjatskiy et al.% Cr and a monotectic at T = 1983 K or T = 2103 K and 96 at.Thermodynamic assessments experiments and calculation during the optimization of model parameters using the PARROT module of the Thermocalc software..[22-24] The melting temperature was measured with optical pyrometers.13].5 system two eutectics were found at 19 at. and at 84 at. and Epstein et al.3 Literature review of the La-Cr-O system In the LaO1. ΔH Cr at T = 1700 K using high-temperature calorimetry. The melting temperature of lanthanum chromite in air. Experimentally determined special points in the LaO1.% Cr2O3 (T = 2243 K) or 12 at. As small additions of rare-earth metals essentially increase the high-temperature corrosion resistance of chromium.5 quasibinary system reveal a considerable spread.3.26].04 at.CrO1.1 at. Small solubility of La in αCrss was reported [12. from T = 1073 K up to the melting of Cr using metallographic and microhardness techniques to be 2. denoted as αCrss . and Berjoan 103 . Berezutskii et al. Furthermore deviations between the data from Tresvjatskiy et al.% at T = 2103 K. modeling of the La-solubility in bcc-structured Cr.
 to be −3961±11..31].Thermodynamic assessments may partly originate from differences of the oxygen partial pressure. and Grundy et al.3.3. and nonstoichiometry[55-56] along with the investigation techniques used are listed in Table 4. Experimental oxygen solubilities in pure Cr and La were considered in thermodynamic assessments by Povoden et al. The enthalpy of formation of La2(CrO4)3 from the elements at T = 298 K was proposed by Tsyrenova et al. Stoichiometries and thermal stability ranges of lanthanum chromates with complex formulae were reported by Berjoan et al.2) An enthalpy change of 231 kJ mol-1 was determined for this reaction at the average temperature of T = 960 K. La2(CrO4)3 decomposes by 890 −1030 K La 2 (CrO4 )3 ⎯⎯⎯⎯⎯ 2LaCrO3 + 0.5Cr2 O3 + 2.33-35.43. which in both studies was not exactly specified. However these were in significant disagreement with later results obtained by the same author. 104 . thermodynamics[30. 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 (4.7 kJ mol-1.1 (next page). The perovskite phase: Existing experimental data of lanthanum chromite perovskite structure[33-45].1) at T=1055 K and pO2 =83000 Pa to be −151±8 kJ mol-1.25O2(g) ↑ → (4. whereas experiments on oxygen Lanthanum chromates: The following lanthanum chromates were documented: Berjoan reported that orthorhombic La2CrO6 forms at T > 923 K. LaCrO4 has been interpreted as a mixed-valent intermediate decomposition product of La2(CrO4)3[30. solubilities in αCrss are missing.46-53]. The peritectic phase diagram proposed by Cassedanne is in gross conflict with the phase diagram data from the other groups. phase stability.  .3.
calculated 139. calculated = −73. calculated T = 1273 K T = 1273 K T = 2100 K T = 2100 K ° Δ °G = −30.oxides ° H 298K aCr2O3 = 1.75 kJmol−1 this work. calculated = −73. calculated aCr2O3 = 1.2 Jmol-1K -1 this work. fitted 105 .elements ° H 298K = −3845 kJmol−1 this work.oxides ° H 975K LaCrO3 = −1368.9 ± 1.oxides ° H 298K Δ f.1× 10−5 Knudsen mass spectrometry La CrO6 = −73.5Cr2 O3 + 2. 700 .7 kJmol-1 this work.25O 2(g) → La 2 (CrO 4 )3 2 Δ f. calculated 94.5 kJmol −1 solid oxide electrolyte .1 kJmol −1 Knudsen mass spectrometry Δ G = −72. calculated Enthalpy of the dissociation reaction La 2 (CrO 4 )3 → 2LaCrO3 + 0. calculated Enthalpy of the formation reaction La 2 O3 +1.5O 2(g) → La 2 CrO6 2 Δ f. 1273 .5Cr2 O3 +1.29 ± 0.1 × 10−4 ± 1. (kJmol−1 ) T = 1090 K 98.oxides ° H 298K La (CrO4 )3 = −372 kJmol−1 this work. calculated = −3961 ± 11.758 + 0. calculated Gibbs energy of formation by 1 3 La 2 O3 + Cr2 O3 → LaCrO3 2 4 T = 1273 K Δ °G = −76.based emf Δ °G = −94.2 HT .calorimetry T = 1350 K 133.1 Calculated and experimental thermodynamic data of La-Cr oxides Rhombohedral LaCrO3 Standard enthalpy Δ f.elements ° H 298K ° 2 S 298K La (CrO4 )3 = 516 Jmol−1K −1 this work. 855 -1073 K CaF2 .45 + 0.4 HT (high temperature) .5Cr2 O3 + 2. calculated Δ °G = −44. this work.19. calculated ° 2 S 298K La CrO6 = 330 Jmol-1K -1 this work.3.885 K CaF2 .oxides ° H 1078K ° LaCrO3 Standard entropy S 298K LaCrO3 = 109.7 kJmol−1 .0034T (kJmol−1 ).52 kJmol −1 this work.79 kJmol-1 Drop solution calorimetry in 2PbO × B2 O3 LaCrO3 LaCrO3 Δ f.08530T (kJmol−1 ).emf Δ °G = −42.002115T ± 0.1 ± 1.25O 2(g) 2 ΔH 298K La (CrO4 )3 = 231 kJmol−1 and this work.11 × 10−4 this work.35 kJmol-1 this work. calculated La (CrO4 )3 La (CrO4 )3 La 2 (CrO 4 )3 2 Δ f.based emf Δ °G = −79.4(kJmol −1 ).0 kJmol−1 this work. calculated = −62.2 kJmol-1 this work.38 kJmol −1 CaF2 .elements ° H 298K Δ f.2673 K this work. calculated 2 Δ f.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.based emf Enthalpy increments H − H 298 K .Thermodynamic assessments Table 4.403 − 0.05 this work.06 ± 2. calculated Δ °G = −78.
HT .5 J mol-1 to 106 .XRD 541 a) completed transition. dilatometry 545 heating. simultaneous DSC .XRD (air and vacuum) 563 ± 5 DTA. DSC.40) at 533 ± 5 a) DSC 380 at 550 K DSC 310 at 509 K DSC Entropy change of transition (Jmol-1K −1 ) 0. this work.2 Calculated and experimental data of the orthorhombic to rhombohedral transition of LaCrO3 Transition temperature (K) 540.XRD.08 J mol-1 and 0.25 at 536 K a) calculated from adiabatic shield calorimetry 340 ± (10 .33-42]. thermogravimetry.XRD.XRD. this work.08 ± 41.XRD 540 ± 2 a) HT .5 a) calculated from DSC 0. dilatometry 536  a) adiabatic shield calorimetry.63.96 at 503 − 583K calculated from adiabatic calorimetry 0. HT . simultaneous DSC . calculated 502. DSC 535 cooling. Table 4. this work.ray photography 550 HT . DSC 550 HT . The temperatures. HT .x . The determined enthalpy and entropy changes vary from 277 J mol-1 to 502.microscopy.XRD 533 ± 3 a) DTA 543 XRD 533 HT . XRD Enthalpy change of transition (Jmol−1 ) 340. calculated 0.2 along with the investigation techniques used.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. dilatometry. DSC 533 ± 5 a) HT .3.84 at 503 − 583 K  calculated from adiabatic calorimetry 277 at 544 ± 1 K a) DSC 403. enthalpy and entropy changes of this first-order transition taken from the literature are listed in Table 4.XRD 533 estimated from neutron powder diffraction 509 DSC.75 a) calculated from adiabatic shield calorimetry a) used for optimization The reported transformation temperatures lie between T = 503 K and 583 K. calculated 503 − 583 adiabatic calorimetry 544 ± 1 a) DTA.XRD 523 a) starting transition. HT .XRD 528 − 533 a) HT .3.
 measured emf of Pt.. and Sakai and Stølen (T = 272 K to 1000 K) using adiabatic shield calorimetry. and Momin et al.38 cat. LaF3/CaF2/LaF3.% to 1. Gibbs energy of formation: in order to obtain the Gibbs energy of formation of LaCrO3. Cr2O3/O2.% excess 107 . This means that the perovskite phase does not decompose within this oxygen partial pressure range. La2O3. Chemical stability: Nakamura et al. O2/La2O3. (T=100 K to 1000 K) using laser-flash calorimetry.1 Pa using thermogravimetry combined with X-ray diffraction (XRD).% in furnace-cooled LaCrO3 annealed at T = 1773 K in air was reported from Khattak and Cox.96 J mol-1 K-1. Satoh et al. A magnetic order-disorder transition was documented to occur at T ≈ 287 K.. reported T = 1923 K using high-temperature x-ray diffraction (HT-XRD). LaCrO3.28 cat. Chen et al. reported no weight loss of lanthanum chromite at T=1273 K from pure oxygen to pO2 =10-16. Single phase lanthanum chromite with 0. Peck et al. or 295 K.76 cat. and its oxgen nonstoichiometry is negligible. 289 K. in agreement with Berjoan (T = 1923 ± 20 K) using dilatometry. Berjoan further reported prevailing of the cubic structure at T = 2173 K. Höfer and Kock (480 to 610 K) and Satoh et al. derived the Gibbs energy of formation of LaCrO3 from the determination of the thermodynamic activity of Cr2O3 in LaCrO3 for the Cr2O3-poor phase boundary of LaCrO3 in the temperature range from T = 1887 K to 2333 K using Knudsen effusion mass spectrometry. 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. Pt in pure oxygen from T = 855 K to 1073 K. LaCrO3/MgO-stabilized ZrO2/Cr2O3. Cation nonstoichiometry and defect chemistry: Maximum excess Cr in single-phase La1-xCrO3 of 0. Chen et al. and Dudek et al. whereas Coutures et al.. Cr/Pt at 1273 K. Enthalpy increments of LaCrO3 at T = 1090 K and 1350 K were measured by Suponitskii using a high-temperature heat-conducting calorimeter. A transformation from rhombohedral to cubic structure at a temperature close to T = 1300 K was reported by Ruiz et al. Enthalpy of formation: Cheng and Navrotsky determined the enthalpy of formation of LaCrO3 by oxide melt solution calorimetry at T = 1078 K. T = 700 to 885 K. and T = 1273 K respectively. (150 to 450 K) using DSC. Sakai et al. Azad 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). measured electromotive force (emf) of the solid oxide galvanic cell Pt/Cr.Thermodynamic assessments 0. (T = 77 K to 280 K) using alternating current calorimetry.
The transition from reduced to stoichiometric chromite was accompanied by a decrease of about 0. the same as reported in an earlier study.58-60]. is inconsistent with the findings from Akashi et al. deduced n-type conductivity from measurements of transport number. reported that concentrations of lanthanum vacancies and holes slightly increase from T = 1550 K to 1700 K. the electrical conductivity being 2 proportional to pO2 −3 8 . In contrast to the other authors Shvaiko-Shvaikovskii et al. and Meadowcroft proposed the occurrence of chromium vacancies instead of lanthanum vacancies. ShvaikoShvaikovskii et al. 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. 108 . resistivity and thermo-emf at pO2 = 1Pa and pO = 102 Pa .0 ×104 Pa . 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. in line with the results from thermogravimetry. and that the carrier is the hole in lanthanum chromite[25.1% in weight. Ruiz et al.59] agree that the electrical neutrality is maintained by holes and lanthanum vacancies. measured the isothermal electrical conductivity of an equilibrated La1-xCrO3-Cr2O3 mixture with 5 vol.Thermodynamic assessments Cr was prepared at T = 1773 K in a pure oxygen atmosphere. reported that the ionic transport number in lanthanum chromite is less than 0.% excess Cr2O3 from T = 1573 K to 1673 K from pO2 = 1. Several groups[58. thus the presence of interstitial Cr in reduced chromite was proposed. However n-type conductivity was not approved by any further study. The conductivity was proportional to pO2 3 16 . Akashi et al.57]. This feature was assigned to a reduced number of Cr4+ due to partial removal of oxygen during the annealing of the originally lanthanum-deficient perovskite phase. On the other hand a slope of pO2 1 4 from T=700 K to 1300 K and purely intrinsic conductivity > 1600 K stated by Shvaiko-Shvaikovskii et al.05 % up to T = 1250 K.0 ×103 Pa to pO2 = 2. 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. affirming the lack of oxygen vacancies in the structure. Iliev et al.
using the PARROT module of the Thermocalc software A was given the fix value 0 for the reasons discussed in an earlier paper.15 K and 10 Pa. These chromates can be interpreted as intermediate products in the 109 .3.La:Va was given a positive value.5 − H Cr − H O = °GCr(bcc) + (4. We chose the solubility values from Svechnikov et al. The Gibbs energy of the end-member (Cr)(O)1.5.Va)1. Cr2O3. as these data are more comparable to solubilities in other rare earths-transition elements systems.3.Va were optimized with the same experimental data. the zeroth-order. for its optimization.4 Thermodynamic modeling and optimization Metal phases: In order to account for the solubility of La in αCrss .3) SER H x is the standard enthalpy of the stable state of element x at 298. Eq. 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.5.O)3. and αCrss is then given by the two-sublattice description (La. 5  A and B are adjustable parameters.Thermodynamic assessments 4. compositionindependent interaction parameter 0 Lbcc Cr.5 is defined as 3 2 3 ° gas G + A + BT 4 O2 ° SER SER G(Cr)(O)1. The formation of chromates that contain mixed Cr valences may be explained by gradual reduction of Cr6+ in La2CrO6 as the temperature increases.32]. and O2 in proper stoichiometries and A + BT parameters that were fitted to the enthalpy of formation from the oxides.O)1.1 as well as thermal stability data. The thermal stability of La2CrO6 is slightly influenced by the thermodynamics of the intermediate. 4. Povoden et al. Solid oxides: Lanthanum chromates: The Gibbs energy function of La2CrO6 was based on the sum of the Gibbs energy functions of La2O3. 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. mixedvalent chromates mentioned above. In order to refine the model parameters of La2CrO6.3. we reassess the oxygen-solubility in Cr(bcc) using the model (Cr)(O. and B and a regular interaction parameter 0 LCr:O.Cr)(Va. For the reasons discussed recently. and to optimize their model parameters with phase diagram data[19.
GVCR4O and GLCR4O are set equal for orthorhombic and rhombohedral perovskite. 4. The Gibbs energy function of La2(CrO4)3 was formulated using the same strategy as for La2CrO6. and enthalpy increment-data 110 . and C are optimized using the enthalpy of formation from Cheng and Navrotsky..5) The parameters A. °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 (4.2 and do not include this phase in the modeling. Stoichiometric perovskite: The Gibbs energy function of stoichiometric rhombohedral r-prv LaCrO3 with the sublattice formula (La3+)(Cr3+)(O2-). which starts at T = 1153 K[19. GRPRV denotes the Gibbs energy function for stoichiometric rhombohedral perovskite.x CrO3 + O2 (g) ↑ 2 2 mixed-valent chromates → La 2 CrO6 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ [19.32] (4.3. and consequently ambiguous stoichiometries of mixed-valent intermediate chromates.3.32] and is completed at T = 1473 K or 1523 K. The simplified decomposition reaction reads 1+ x 1. heat capacity-data obtained by adiabatic calorimetry from Sakai and Stølen. 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.32] are not included in the presented thermodynamic database. The enthalpy of formation from the elements was not used as it is a calculated value.Thermodynamic assessments scope of a sluggish decomposition of La2CrO6. GVCR4O and GLCR4O stand for the Gibbs energy functions of the completely oxidized neutral endmember. We go along with the interpretation of LaCrO4 being an intermediate reaction product during the decomposition of La2(CrO4)3 by Eq. The superscripts o-prv and r-prv stand for Gibbs energy expressions that have different values for orthorhombic and rhombohedral perovskite. The model parameters were fitted to the experimental enthalpy and temperature of decomposition. B.5 x) La 2 O3 + La1.4) Slight differences of the oxygen partial pressure during experiments may be reflected by a variable extent of Cr-reduction.3. activity-data of Cr2O3 in LaCrO3 from Peck et al.5 . These lanthanum chromates with conflicting stoichiometries[19.(1.
Va)3. Thus the defects in n-type conducting lanthanum chromite are ambiguous and were not considered in the model. 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.Va)(O2-. Thus these data were excluded from the optimization.5-CrO1.Thermodynamic assessments measured at high temperatures.42].19] cannot be reproduced by using the emf-experiments[49-52].Va)(Cr3+. enthalpies[34. The rhombohedral to cubic transformation at high temperatures is not considered in the model. and the perovskite formula essentially remains La1-xCrO3. The optimization of selective model parameters listed in Table 4.Cr4+)(O2-)3.35.40. 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. is unlikely due to the densely-packed perovskite structure. 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+. irreconcilable trouble is encountered at the extension to the LaO1.Cr4+. as there is no existing thermodynamic data for this transition.40] and entropies[34.3. B-site vacancies are energetically less favored than A-site vacancies in the perovskite structure[63.3 (pp. This means that the simplest sublattice model to describe cation nonstoichiometric La1-xCrO3 reads (La3+.5 system required for SOFC applications due to diversities between the model descriptions of lanthanum chromite and lanthanum manganite.64].38. While this model results in a satisfying reproduction of experimental data. 112-114) resulted in negligible concentrations of Va on the B-site and the anion sublattice.58] measurements.Va)(Cr3+.5-MnO1.35] of transition having been obtained by combined investigation techniques and being internally most consistent. A phase diagram with congruent melting of lanthanum chromite and two eutectics[18.35. 111 .
= 121000 Cr Cr Lliq 2+ .= 61397 − 5.Vaq.− 2 H Cr − 3H O = 5GCROLIQ − 179638 + 79.3.923T  liq SER SER GCr 2+ :O2.− H Cr = GCRLIQ liq SER GCr3+:Vaq.= −101850 − 39016( yCr 2+ − yLa3+ ) Cr Lliq 3+.− 2 HLa − 3H O = GLA2O3LIQ liq SER GCr 2+ :Vaq.Vaq..008 yCr  112 .La3+:O2.5 yCr  β bcc = −0.− 2 H Cr − 2H O = 2GCR1O1_L Interaction terms Lliq 2+ :O2.− HLa = GLALIQ liq SER SER GLa3+:O2.+ qyVa . Cr 3+ ) p (O 2.La3+ :O2. Cr)(Va.)q p = 2 yO2. Cr 2+ . O)1.= −101850 − 39016( yCr3+ − yLa3+ ) Cr Bcc A2 phase (La.= Lliq 3+ :O2. Va q..3 Model descriptions and Gibbs energy functionsa) Liquid (liq) (La 3+ .O = −355151.17755T 2 4 3 SER 3° SER ° bcc GLa:O − HLa − H O = GLABCC + G (O 2(g) ) − 855000 + 142.La:Va = 83500 p = 0.422 ° Lbcc Cr. q = 3 yLa3+ + 2 yCr 2+ + 3 yCr3+ ° ° ° ° ° ° liq SER GLa3+:Vaq.− H Cr = 2GCRLIQ − GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+:O2.4 Tcbcc = −311.23T + (65393 − 23T )( yCr 2+ − yLa3+ ) Cr Lliq 2+ .Thermodynamic assessments Table 4.5 ° ° 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..La3+ :Vaq.5T  2 4 Lbcc Cr:Va.
5GVVV − 2GLCR4O + 0.= Lprv3+:Cr4+.− HLa − HCr − 3HO = GRPRV + Gmag o-prv SER SER SER GLa3+ :Cr4+:O2.5 °G(O2(g) ) + Gmag r-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GRPRV − 1.75 °G(O2(g) ) − 1. Va)(O2.5GVCR4O +0.75 °G(O2(g) ) − 1.5 °G(O2(g) ) + Gmag ° o-prv SER SER GVa:Cr3+:O2.Chromates La 2CrO6 (La 3+ )2 (Cr 6+ )(O2.75 °G(O2(g) ) − 1.894 yi:j:k SER SER SER 2 GLa3+ :Cr6 :O2.− HCr − 3HO = GRPRV + 1.− 2HLa − HCr − 6HO = GLA2CRO6 6+ La CrO La 2 (CrO4 )3 (La 3+ )2 (Cr 6+ )3 (O2.35056T + Gmag ° o-prv SER r-prv SER GVa:Cr4+:Va − HCr = °GVa:Cr4+:Va − HCr = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O − °G(O2(g) ) + 4.Cr3+ k = O-2.− HLa − HCr − 3HO = 5 6GS4O +GRPRV − GS3V + 1 6GS4V + Gmag ° ° ° o-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GOPRV − 1.. Va)3 ° ° ° o-prv SER SER SER GLa3+ :Cr3+:O2.5GVVV − 2GLCR4O + 0.Va:O2.5GVCR4O +0.− HCr − 3HO = GOPRV + 1.41263T + Gmag ° o-prv SER GVa:Cr3+:Va − HCr = GOPRV + 1.5GVCR4O +0.Cr3+ .75 °G(O2(g) ) − 1.)6 ° prv β o-prv = β r-prv = 0.− HCr − 3HO = °GVa:Cr4+:O2.5 °G(O2(g) ) + 4.= 250000 La La Magnetic contribution Tco-prv = Tcr-prv = 291.− HCr − 3HO = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O + 0.Thermodynamic assessments La1-xCrO3 perovskite (La 3+ .− HLa − HCr − 3HO = GOPRV + Gmag r-prv SER SER SER GLa3+ :Cr3+:O2.35056T + Gmag Interaction term Lprv3+:Cr3+.5GVVV − 2GLCR4O − 0.41263T + Gmag ° r-prv SER SER GVa:Cr3+:O2.5GVCR4O +0.Va)(Cr 4+ .41263T + Gmag ° o-prv SER SER r-prv SER SER GVa:Cr4+:O2.− 2HLa − 3HCr − 12HO = GLA2CR3O12 La (CrO ) 113 .5 °G(O2(g) ) + Gmag ° r-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GRPRV − 1.41263T + Gmag ° r-prv SER GVa:Cr3+:Va − HCr = GRPRV + 1.35 yi:j:k i = La 3+ .5GVVV − 2GLCR4O − 0. Va La .Va j = Cr 4+ .Va:O2.− HLa − HCr − 3HO = 5 6 GS4O +GOPRV − GS3V + 1 6GS4V + Gmag ° r-prv SER SER SER GLa3+ :Cr4+:O2.)12 ° SER SER SER 4 3 2 GLa3+ :Cr6+:O2.5 °G(O2(g) ) + Gmag o-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GOPRV − 1.
31451 J mol-1 K-1.31451 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. R = 8. Cr4+ and Va on the B-sublattice.5GCR2O3 + 0.5GCR2O3 − 1.5GCR2O3 GVCR4O = 0.01T − 0.56T ln(T ) − 0.5GCR2O3 + 0.00307T 2 + 190000T −1 +0.25 °G(O2(g) ) GS3O = −472704 + 191.68T ln T Neutral nonstoichiometric perovskite endmembers GS4O = −597648 + 213.and Va on the anion sublattice of the perovskite A1-xBO3.5T La 2 (CrO4 )3 GLA2CR3O12 = GLA2O3A + 1. yj is the site fraction of Cr3+.56T ln(T ) − 0.25 °G(O2(g) ) − 371557 + 205T a) All parameters are in SI units : J.68T ln T Stoichiometric rhombohedral perovskite GRPRV = 0.75 °G(O2(g) ) − 72615 − 4.Thermodynamic assessments Functions Perovskite Stoichiometric orthorhombic perovskite GOPRV = 0.25 °G(O2(g) ) − 200000 Perovskite reference GS4V = −607870 + 268. The third-last term accounts for the configurational entropy of mixing.00307T 2 + 190000T −1 +0.56T ln(T ) − 0.25 °G(O2(g) ) La 2CrO6 GLA2CRO6 = GLA2O3A + 0. R = 8.5GCR2O3 + 0. K.5GCR2O3 − 73931 + 3. These are accounted for by the 114 .3.38T − 47. and yk is the site fraction of O2.00307T 2 + 190000T −1 +0.5GLA2O3A + 0.25 °G(O2(g) ) − 291802 − 250T GLCR4O =1 3GLA2O3A + 0.7186T − 47.6) i j k i j k where yi is the site fraction of Va and La3+ on the A-sublattice.38T − 0. The second-last term describes the excess Gibbs energy of mixing due to interactions of ions in the mixture.9T − 47.5GCR2O3 + 0.5GCR2O3 − 73591 + 2.5GLA2O3A + 0.5GCR2O3 + 2. mol.
with the 8 Cr-containing compounds being the corners of the cube. These endmembers of 3 3 nonstoichiometric perovskite have been fixed firmly by a sufficient number of consistent experiments in 3 the LaO1. A short summary of this model can be found in Chen et al. ° prv prv G(La3+ )(Cr 4+ )(O2.3. The thin lines margin the neutral plane. For the magnetic part of the Gibbs energy a magnetic ordering-model proposed by Inden and simplified by Hillert and Jarl was used. Only compounds inside the neutral plane can exist on their own. 115 .) and °G(La3+ )(Cr 4+ )(Va) from Povoden et al.1 Representation of the Cr-containing part of the model for nonstoichiometric lanthanum chromite. Fig.. The parameters of the compound energy formalism are the Gibbs energies of the not necessarily neutral 12 end-member compounds °Gi: j:k .Thermodynamic assessments optimization of interaction parameters.5-SrO-CrO1. The neutral compounds used for the optimization are marked by the black spots.3.3.3 (pp. 4.1 is a visualization of the Cr-containing part of the model the authors use to describe the cation nonstoichiometry of lanthanum chromite.5 3 system  . The last term designates the magnetic contribution to the Gibbs energy. 4. The magnetic parameters Tc and β were fitted to the C p data around the magnetic transition temperature from Sakai and Stølen. 112-114).) and °G(La3+ )(Cr 4+ )(Va) are given in Table 4. Fig. Thus the authors prv prv adopted °G(La3+ )(Cr 4+ )(O2.
°G(Va)(Va)(O2.9) Using Eqs.3.8 it describes random mixing of La3+ and Va on the A-site.3. the 12 endmembers of the compound energy formalism of the perovskite phase are defined. The parameters A and B of Eq. 3 3 3  . 4.3. 4. the Croverstoichiometry in a furnace-cooled specimen reported by Khattak and Cox does most likely not represent the overstoichiometry at an intermediate temperature and was not used for the optimization.7 and A of Eq. 4. and °G(Va)(Cr 4+ )(Va) .8 are optimized using experimental data of excess Cr in perovskite. and °G(Va)(Va)(Va)3 from Grundy et al.3.3.5 to 4.) .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. The configurational entropy3 3 3 3 term in Eq.7) and 2 SER 2 1 ⎛ 2 2 1 1⎞ SER SER H = °GLa3+ :Cr 4+ :O2− + °GVa:Cr 4+ :O2− + RT ⎜ ln + ln ⎟ − H Cr − 3H O 3 La 3 3 ⎝ 3 3 3 3 ⎠ (4.) .3.3. were used to obtain ° prv prv prv prv G(Va)(Cr3+ )(O2.3.r-prv GLaCrVa3 − HLa − H Cr = °GLa3+ :Cr3+ :Va = GLaCrO3 − (4.7 describes random mixing of O2. As cation diffusion in La1-xCrO3 is extremely slow even at high temperatures.8 and adopting the Gibbs energies of the remaining endmembers ° prv prv prv prv G(La3+ )(Va)(O2. Furthermore the temperature dependence of lanthanum vancancy and hole concentrations from Akashi et al.  : 3° G (O2(g) ) 2 ° o-prv.3.r-prv SER SER o-prv. °G(Va)(Cr3+ )(Va) . The 116 . °G(Va)(Cr 4+ )(O2.Thermodynamic assessments The neutral Cr4+ -containing endmembers 2° 1 ⎛ 2 2 1 1⎞ GVa:Cr 4+ :O2− + °GVa:Cr 4+ :Va + 3RT ⎜ ln + ln ⎟ 3 3 ⎝ 3 3 3 3⎠ 1 1 gas = GVCR4O = °GCr2O3  + °GO2  + Gmag + A + BT 2 4 prv SER SER GVaCrO2 − H Cr − 2 H O = ° (4. 4. 4.with Va on the anion sublattice. In Eq.) . ° prv G(La3+ )(Cr3+ )(Va) results from a reciprocal relation which was set zero in analogy to Grundy et 3 al. °G(La3+ )(Va)(Va) . was considered in the optimization.) .
as were the two sub-regular interaction parameters. the temperature of the eutectic at the Cr-rich side from Berjoan.La3+ :Va and subregular 1Lliq 2+ . The liquid phase: The two-sublattice model for ionic liquids[73.5 system from Tresvjatskiy et al. Furthermore the two regular interaction parameters 0 Lliq 3+ .La3+ :Va Cr Cr interaction parameters to account for interactions between La and Cr.Va:Cr3+ :O2. and the congruent melting temperature of the perovskite phase from Coutures et al.. 117 . The liquid is thus given by the model description (La3+.Va:Cr4+ :O2.Cr3+)p(O2-. The experimentally determined temperatures and liquid compositions[13.and 0Lprv3+ . 4.Thermodynamic assessments introduction of positive interaction parameters 0Lprv3+ .La3+ :O2.and the two subregular 1Lliq 3+ . As a value of the oxygen partial pressure is required for the optimization.= Cr Cr Cr 1 liq Cr 2+ . together with experimental phase diagram data[12.La3+ :O2.74] was used for the description of the liquid phase of the La-Cr-O system. The chromium species considered in the liquid are Cr2+ and Cr3+.5 Results and Discussion The La-Cr system: The calculated phase diagram of the La-Cr system is presented in Fig. 4. did not specify the value of the prevailing oxygen partial pressure during their phase diagram experiments conducted in an argon atmosphere. and Foëx. we defined pO2 = 1 Pa.17]. It was based on the liquid descriptions of the binary subsystems. It was assumed that the interactions between Cr2+-La3+ and Cr3+-La3+ are of the same order of magnitude in the oxide melt. Higher oxidation states are unlikely to exist in the liquid at normal oxygen partial pressures.La3+ :O2- L were optimized.CrO1.13.3. ΔH Cr  in La-Cr liquid were used to optimize the temperature-dependent regular 0 Lliq 2+ .5. 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. thus the two regular interaction parameters were set equal to each other.Cr2+.Vaq-)q.14] at the eutectic and monotectic in the metallic La-Cr system and the partial enthalpy of mixing of Cr.2 (next page).14.= 0 Lliq 2+ .3.La3+ :O2. Berjoan and Tresvjatskiy et al.that were given La La the same values circumvents too high Cr4+ contents at low temperatures that would be in conflict with the experiments.
The model description of the bcc phase results in a tiny solubility of Cr in La(bcc). denoted as γ La ss . the lowest temperature of stable γ La ss .2 Calculated phase diagram of the La-Cr system with data from the literature included (symbols).% at 1134 K.Thermodynamic assessments Fig. of 2 ×10-3 at.17] . which is tantamount to a small solubility of La in αCrss in agreement with the experiments [14.La:Va used to model the bcc phase results in a large miscibility gap between the La-rich and Cr-rich metals.3. The positive value of 0Lbcc Cr. which further decreases as a function of increasing temperature.3. 4.3 (next page) together with the experimentally determined value that is well reproduced by the calculation. 4. The calculated enthalpies of mixing are shown in Fig. 118 .
whereas the lower melting temperature was chosen by Savitskii et al. The higher value was favored by Dinsdale and is adopted in this study.3 Calculated partial enthalpies of mixing of La and Cr in La-Cr liquid.La3+ :Va L and 1Lliq 2+ .5 phase diagrams in pure oxygen at pO2 =105 Pa. and Svechnikov et al. and integral enthalpies of mixing as a function of composition. The La-Cr-O system: Phase equilibria: Calculated LaO1. 4.5. at T = 1700 K included (symbol with error-bar). This is unfortunately associated with Cr an inverse liquid-liquid miscibility gap with a minimum at X(Cr) = 0.. with the experiment from Berezutskii et al.25 and T ≈ 5000 K that is of course unphysical.Thermodynamic assessments Fig. A satisfying reproduction of the experimental data was obtained by considering a moderate temperature dependence of 0 liq Cr 2+ .CrO1. Considerable deviations of the calculated liquidus from experiments at the Cr-rich side of the system can be ascribed to the problem of two different melting temperatures for Cr cited in the literature.3. which are T = 2180 K and 2130 K. in air at 119 .La3+ :Va .
This is in line with the interpretations of Raman spectra from Iliev et al. Be it that the reported thermodynamic data of La2CrO6 and La2(CrO4)3 are correct.19] and the conflicting data on the melting temperature of lanthanum chromite in argon atmosphere the presented liquid description is rather tentative.4 together with experimental data[18-21]. 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.3. Under oxidizing conditions Cr3+ is favored over Cr2+ in the liquid.Thermodynamic assessments pO2 = 21278 Pa. A decrease of Cr4+ during annealing of an originally lanthanum-deficient perovskite phase under reducing conditions is predicted by the model.3.5-CrO1. reflected by the disappearance of Cr overstoichiometry. air atmosphere. Fig. and the liquid stability increases considerably at the Cr-rich part of the system 120 .5 system in pure oxygen. lanthanum chromite is expected to be metastable at room temperature. 4.4 Calculated phase diagrams of the LaO1. On the other hand a significant amount of Cr3+ in the ionic liquid is reduced to Cr2+ under reducing conditions. and under reducing conditions at pO2 = 1 Pa representing the typical oxygen partial pressure in argon atmosphere are shown in Fig. and under reducing conditions representing argon atmosphere at pO2 = 1 Pa with experimental data included (symbols). 4. Excess Cr in lanthanum chromite is favored at high oxygen partial pressures. La2CrO6 is stable within a wide temperature-range in pure oxygen. Due to the ambiguous oxygen partial pressure of phase diagram experiments[18. whereas it does not form in air and argon atmosphere. and orthorhombic perovskite is stable only at pO2 ≤102 Pa.
3.3 (pp. Despite this discrepancy we did not go for an alternative liquid model for the sake of consistency with our previously assessed systems.5 Calculated phase equilibria of the La-Cr-O system at T = 1273 K as a function of oxygen partial pressure. In Fig. 121 .2 (p. 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. 4.5.Thermodynamic assessments leading to a considerably lowered eutectic temperature.04 Pa metallic liquid forms at the lanthanum-rich side of the phase diagram. 105).5 calculated phase equilibria of the La-Cr-O system at T = 1273 K are shown as a function of oxygen partial pressure. Table 4. was obtained using the new model description (Cr)(O. The same oxygen solubility in Cr as in the assessment by Povoden et al. Fig. 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. Calculated and experimental data on the orthorhombic to rhombohedral transition of LaCrO3 are listed in Table 4.3.3. 106). 4. Thermodynamic data: Calculated thermodynamic data of solid oxides are listed together with experimental data from the literature in Table 4.3.1 (p. At pO2 = 10-34.3.Va)1. It is obvious that no mutual solubilities of La and Cr in bcc metal in equilibrium with oxides are expected.
The dashed line marks the temperature of the o-prv ↔ r-prv transition.3. 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]. The perovskite phase: the calculated heat capacities of LaCrO3 are compared with experiments from the literature in Fig.6.Thermodynamic assessments Lanthanum chromates: Testing an optimization of model parameters of La2(CrO4)3 by using all available thermodynamic data[29. bearing in mind the high degree of uncertainty of the resulting description.31] resulted in gross disagreement between optimized and reported values. The considerable error might be explained by experimental difficulties to reach equilibrium at the low investigation temperatures. Anyway the model parameters were fitted to the experimental data. whereas the calculated standard enthalpy of formation from the elements was rejected. 4. Fig. The calculated C p -curve extrapolates well to high temperatures. The use of C p -data from Sakai and Stølen along with enthalpy increment-data from Suponitskii to optimize the 122 .3.6 Calculated heat capacities of LaCrO3 (solid curve) as a function of T with experimental data included (symbols). 4.
3. The calculated transition temperature of T = 540 K is shown by the broken line in Fig. Experimental enthalpy increments are well reproduced by the calculation (see Table 4.6. It needs to be clarified why all of the emf-measurements are problematic: Azad et al.3.28 and p=0.4. 105. 105). The resulting Gibbs energies of formation from emf-measurements are remarkably less negative than the Gibbs energies of formation derived from Knudsen mass spectrometry.4. Yet it is obvious that the CaF2based emf-technique is neither suitable for the determination of thermodynamic data of lanthanum chromite. 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. 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. 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. as it unavoidably leads to emf that are too low.1.10) are listed as a function of temperature together with data from the literature [49-53] in Table 4. fcc.or oxygen-containing atmosphere.28. their C p is the same.Thermodynamic assessments parameter CTlnT of the Gibbs energy of stoichiometric perovskite resulted in the lowest error between experiments and calculation. A small peak which was found around 855 K can be explained most likely by the decomposition of an undetected impurity phase.70] using p = 0.1.3. The C p -anomaly is equally well reproduced by the model[69.35] the term CTlnT is fixed firmly. whereby the proper p-value for structures other than bcc. p. Two values for the magnetic parameter p are possible depending on the crystal structure.28 or p = 0. and hcp is not available in the literature. As CTlnT was set equal for o-prv and r-prv. 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 calculated C p -peak at T = 290 K reflects the temperature of the magnetic order-disorder transition. 4.3. The calculated Gibbs energies of the formation of LaCrO3 from the oxides 1 La O + 1 Cr O → LaCrO 3 2 2 3 2 2 3 (4. p=0. Due to the consistency between both groups of calorimetric experiments[30. For the sake of compatibility with the recent assessment of the La-Fe-O system we chose p = 0. p. the transition temperature being in agreement with the experiments. In this case the emf depends on the activity 123 .
11) is pO2 = 10-20.3. Defect chemistry of the perovskite phase: 124 . 4. 4. The calculated decomposition of the perovskite phase by Eq.7.7 Calculated decomposition of lanthanum chromite as a function of temperature and oxygen partial pressure. 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. Fig.3. 4.3.3.Thermodynamic assessments of CaO at the electrode/electrolyte interface. 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 (4.11 is plotted as a function of temperature and oxygen partial pressure in Fig.
[CrCr ] . and [OO ] can be considered to be ~ 1. The line for yprv 3+ at 1073 K cannot be seen as it is very close to 1. A La 125 . and CrCr in La1-xCrO3 correspond to the site 3 fractions yprv 3+ . [CrCr ] ∝ PO2 16 . yprv 3+ .3. CrCr . 4.: 1 (La 3+ )(Cr 3+ )(O2. if [Va ′′′ ] and [Va •• ] are O Cr assumed to be negligible according to Akashi et al.3.3.)3 2 4 (4.3. Va La .3.12) Using Kröger-Vink notation this defect reaction reads 1 2 x 1 x x x • x La La +CrCr +3OO + O2(g) → La La + Va ′′′ + CrCr +3OO 4 3 3 La (4.15) • Substituting this into Eq. and charge neutrality is maintained by 1 • [Va ′′′ ]= [CrCr ] La 3 (4.3.)3 + O2(g) → (La 3+3 Va1 3 )(Cr 4+ )(O2.13) 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. La x x • ′′′ The concentrations of the defects LaLa . yprv . 4. and yprv 4+ in the compound energy formalism. yprv 3+ .8 (next page) for lanthanum chromite in equilibrium with Cr2O3.14 gives the proportionalities [Va ′′′ ].Thermodynamic assessments Applying a defect chemistry analysis of La1-xCrO3 in equilibrium with Cr2O3 the following defect reaction for its oxidation can be written in the sublattice form. yprv . yprv 3+ . A La A Va B Cr B Cr A La A Va B Cr y prv 4+ and the tiny fractions y prv and y prv are plotted logarithmically as a function of B Cr B Va O Va log pO2 at T = 1073 K and 1673 K in Fig.14) x x x For small oxidation extent [La La ] .
The slope • At T=1073 K a constant slope of 3/16 of the defect concentrations [Va ′′′ ] and [CrCr ] shown in La the triangle.3.0 ×104 Pa determined by Akashi et al. This slope is • fixed by the defect reaction Eq.12.3.Thermodynamic assessments Fig.0 ×103 Pa and pO2 = 2. 4. 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. may be explained by problems of reaching equilibrium due to extraordinarily slow cation diffusion in • ′′′ lanthanum chromite. 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.. In Fig. is calculated from very high to very low oxygen partial pressures. 4. The conflicting data from Shvaiko-Shvaikovskii et al.9 (next page) the calculated slopes of VaLa and CrCr are 126 . pO 2 . 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. 4.3.8 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.
as calculated [Va ′′′ ] and [Va •• ] are very small.. as the temperature and oxygen partial pressure dependence of excess Cr in La1-xCrO3 has not been investigated systematically so far.9 Calculated defect concentrations in La1-xCrO3 in thermodynamic equilibrium with Cr2O3 (solid lines) logarithmically plotted as a function of reciprocal temperature along with the data from Akashi et al.15. 127 .Thermodynamic assessments • compared with slopes of [Va ′′′ ] and [CrCr ] determined by Akashi et al. The calculated O Cr relative defect concentrations are in line with those proposed by Akashi et al.3. 4. as a function of La reciprocal temperatures. The calculated amount of [Va ′′′ ] relative to [CrCr ] is fixed by the criterion for La charge neutrality. The calculated concentrations agree well with the data derived from electrical conductivity • measurements. The presented defect chemistry calculations are still rather tentative. 4. Fig. derived from electrical conductivity measurements (symbols with error-bars.3. Eq. broken lines).
M.G. A. Zhang. Nickel. 2. H.P.. pp. The thermodynamic modeling of lanthanum chromite was based on experimental thermodynamic data reported by Peck et al. However the amounts of excess Cr in La1-xCrO3 used for the optimization of the cation nonstoichiometry are preliminary. S. D. and Cheng and Navrotsky. Bossel (Ed. Solid State Ionics. I. 297-310. S.3. p. K. Hilpert. Electrochem. Zhang. K. Proceedings of the 26th Risoe International Syposium on 128 . R. 4013-22. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. and K. Cr-Mn deposition at the three-phase boundary observed by TEM. Ramprakash and J.-M. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells. Mechanism and kinetics. P. Jiang.6 Conclusions Model parameters of the presented thermodynamic La-Cr-O database were optimized with assessed thermodynamic and phase diagram data. pp. 2000.). Foger. J. Carlsson. Göttingen. U. A.P. Deller. 3. Using the new database the stability limits of lanthanum chromite in function of temperature and oxygen partial pressure can be quantified. The thermodynamic descriptions of lanthanum chromates and the liquid phase are rather tentative due to humble or sketchy experimental information. S. Das. The orthorhombic to rhombohedral transition in lanthanum chromite and the magnetic order-disorder transformation are well reproduced by the model.Thermodynamic assessments 4. 1997. 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. Kjaer and J. 2. Miller. 1994. References 1. 147(11). as the use of these data for the optimization of model parameters resulted in a proper reproduction of the phase equilibria derived from experiments. Larsen. J. Druckerei J. 99. Badwal. First European Solid Oxide Fuel Cell Forum Proceedings. The proposed existence of lanthanum vacancies and holes to maintain charge neutrality in lanthanum chromite with excess Cr is reproduced by the model. 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. Foger. 703. Soc. 4.H. P. Kinzel. Vol. Y.
L. 1991.-H. and D.-Y. 2006.). G. V.M. E. Lim. Ong. Gauckler. 129 . 1986. Tavadze. Solids. B. D. Powder Metall Met. Calphad. Akad. 13. 2006. Lee. G. J. A. F. 2005. Denmark. pp. pp. Li.G. Jansson. Ivancenko. 82-89. J. Diwu.-H. Ni. M. 9. 7. Berezutskii. 25(5-6). A. Chem. Linderoth. Geupel.. Kim. Power Sources. 9(2). Russian J.. J. Shin. 167-71 (in Ukrainian).P. J.N. pp. Kireev. 2006. 17. Ceram.F. Y. 27(4). J. J. Saxena. J.P. 14. Z. S. Electroceram. F. 264 (in Russian). O. 335-350. Oxid. A. 16. Liu. O. B. S. S. Kobal. A. 1901-07. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. 353-362.N. M. High-temperature corrosion of dilute chromium-lanthanum alloys. 2008. Zhao. Risø National Laboratory. Yttrium and lanthanum solubility in chromium. Met. Povoden. p. V. Peck. 67.V. L. pp.P. Svechnikov. R.-H. Shul. Keshelava. S. pp. B. Properties of Cu. pp. Phase diagram for alloys in the chromium-lanthanum system.N. pp. X. 266271.I. N. 5. Roskilde. and V doped-LaCrO3 interconnect materials prepared by Pechini. 177. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. Usenko.J.-G. Kiev. S. L. Savitskii. A. Meng. Zinkevich. Barabash and Y. Crystal structures of metals and alloys.M. 5(3). 1985. Grundy. Phys. Calphad.. Liu. D. pp. Aldinger. Terekhova. 176. 2008. Pu. 451-56. Diff. Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells.. Andersson. 10. Thermochemistry of binary alloys of lanthanum with 3d-transition metals.F. 15(4). E. Smith et al.M. M. J. 1986. J. Yang.T. K. 153-90. M. A. pp. Dopov. Dinsdale. Song. G. Kobzenko. 6. N.V. 12. 45(5-6). Wu. 317-425.I. (Eds. J. Durygin. 11..I. M. Nauk. Sundman. Ivanov.-K. Mikadze. Dong. V. 2006. Liu. Chem. Liu. pp. Inorg. pp. Wang. Kholopov. T. V. 1973. Jiang.-H. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. The Thermo-Calc databank system.Thermodynamic assessments Materials Science: Solid State Electrochemistry. 1960. 723-27.-R.K. 8.-O. 155-62.P. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. pp. Power Sources. Naukova Dumka. SGTE data for pure elements.V. P. Bulia. 2. 15. Phase Equilib. 362-63.
Temp. 2004.M. Acad. J. Gr. Stability and thermodynamic properties of rare earth perovskites. 1974. V.A. or lanthanum chromite. Int. M. Thermochemical properties of lanthanum chromates(VI). 1976. Coutures.Thermodynamic assessments 17. 45-50. 1980. Z. pp.K.A. 5.J. 28. Karapetyants. Suponitskii. pp. Brit. A. Foёx.G.. pp. Coutures... S. J.L. M. A. B. Ceram. Phase Equilib.. 105-13. Tsyrenova. Gauckler. An. 1965. 19. Paris.F. Cienc. Acad. 23. 309-26 (in French). 54(2). 294-99. pp. Sc. Khim.S. 45(2). Shevchenco. 2(2). Tresvjatskiy. 8. 337. A. R.. 1969. Phys. 61-67. Shevchik. 40(1). R. 27. 25. Int. C. 29. pp. Measurement of the solidification points of several refractory oxides.. 13. Appl. Badie. 2705-07. pp.. 22. A. Measurement of the freezing points of refractory oxides.R. 21. Temp. 260. Energy. Suponitskii. Rev. Lopato. Int. Solubility limits of yttrium and the lanthanide rare-earth elements in chromium and chromium-iron alloys.. 313-24 (in German).P. 130 . J. Fiz. B. Pavlivov. J. pp. High Temp. BMI-1376. Ed. Contribution to the study of interactions between oxygen and mixed lanthanum oxide and chromium oxide(III). Phase correlation in the systems formed by oxides of rare earths and by oxide of chromium.. Rev.B. Hautes. L. Thermal properties and thermochemistry of lanthanide chromates. Sol. 1959. 1966. Ind. J. 26. 3. pp. Suvorov. Comments on the allotropic transformations of the rare earth sesquioxides. 18. 1225-33. Bauer. 48(11). S. S. Hautes. M. 1968.. O. D. pp. scandium and yttrium. Yu. 2005. Y. Energy Comm. M. 6389-92 (in French). 1963. 119-35 (in French). Zh. Foёx. R. 2001.. 33136. Rouanet. Refract. Sci. Russ. 13. Chemical equilibria involving lanthanum chromite. Berjoan. U. pp. Thermodynamic assessment of the lanthanumoxygen system. 24. M. pp.B. Cassedanne.N.L. Hautes. Meadowcroft. 2. Temp. Some properties of strontium-doped lanthanum chromite. 94-99. Flamand. Hallstedt. 22(2). Examination of freezing points of rare earth oxides and chromites. 9(1).N. At.. Anorg. Rev. Foёx. Chem. Examination of the equilibrium diagram La2O3-Cr2O3. 30. pp. Berjoan. S. R. J. Comparison of thermal properties of oxygen-containing compounds of rare-earth elements. pp.G. Foёx.-P. 57-60 (in French). Allg. 20. Grundy. Dickerson. 1965.M. Int. L. 1968. Chem. Epstein. A.V.. Bras.
Soc.M. T. N. Pavlikov. Nauk SSSR. pp. J. pp. 36. H. 1993. D. 5-8 (in French). Phase Transitions in Perovskitelike Compounds of the Rare Earths. Kononyuk. Dokiya. Chim. Zonov. Coutures. I. Akad. Lyutsko. Y. 43. Mater.G.E.-M. Nauk SSSR. 1966. 34. W. pp. P. 1985. 40. 33. K. Phase Transformations of Certain Chromites of the Rare Earth Elements. Acad. K. 1995. V. 1-14 (in German). Chem. Mater.. N. Kishi. On the chromates(V) of the rare earths. J. Ruiz. 131 . H.G. B. M. Tsuda. Yu. 1991. 322(1-2). Sakai K. 27(5). Stølen. Tanaka. Rev. T. 41. 1970. at Temperatures from 298. pp. 524-29. pp. Analysis of Crystal Structure and Phase Transition of LaCrO3 by Various Diffraction Measurements. and Entropy of Lanthanum Chromite between 298 and 900 °K. Thermodyn. 1963. Reznitskii. Shimojyo. H. S. Rev. 38. pp. 805-06. J. Neorg. 154. Kock. J. Sc. LaCrO3 at Room Temperature. 23(9). Chem. Kamiyama.. 1973.15 K. 1967. 39. K. Allg. Structural study and thermal decomposition of lanthanum based chromate. Evaluation of the Thermal Conductivity. On the Semiconducting Properties of Lanthanum Chromite. Anorg. 2000. 2000. Yoshida. Akad. A. Enthalpy. 264. 1271-74 (in French).. Berjoan.R. 183-90. Raccah. 1976. N..M. S. T. M. LaCrO4. 1246-48.F. Mirza.F. Specific Heat. 1520-24 (in Russian). Lett. pp. N. Paris C. Takagi. Hashimoto. Tsuzuki. Paris B. S. Mathews.. 37.V. 1167-72. Oikawa. Crystal Chemistry and Thermal Behavior in the La(Cr. I lanthanum chromate(V). Terao. High-Temperature X-ray Diffractometric Studies of LaCrO3. Sc. Izv. pp.C. 140(10).R. T. C. Acad. 132. 309-16 (in French). S. High Temp. Ni)O3 Perovskite System. L.P.S. Lopato. pp. 276. Sci. Tagawa. Structural Phase Transition of Orthorhombic LaCrO3 Studied by Neutron Powder Diffraction. 10. Oikawa.P. A. pp. Kamiyama.. Korobeinikova. 10. 35.. Izv. Phase Transitions in Solid Solutions Based on Lanthanum Chromite. A.N. 1973. Neorg.P. J. C. E. Z. Foëx. M. A. R. Some Observations on the Formation and Structure of Lanthanum Chromite. Traverse. Höfer. Sakai.B. Tolochko. Electrochem. 679-82 (in Russian). pp. Solid State Chem. pp. K. 493-506. Y. A. Hashimoto..Thermodynamic assessments 31. Tresvyatskii. Schwarz. Miner. Morii. Heat Capacity and Thermodynamic Properties of Lanthanum(III) Chromate(III): LaCrO3. pp. 2(4). 2889-94.A. Phys. Mater. Momin. Geller. J. 14(4). 32. V. Anthony. J. 42. Solid State Ionics.. 2(4).
N. Kamegashira. Polish J. Soc. pp. H. Fe. Determination of the Standard Free Energy of Formation of LaCrO3 at 1273 K. pp. J. Mater. Heat Capacities of LnCrO3 (Ln=Rare Earth). 50. 46. Chen. Kojima. G. 166(1). 1979. 1987. Experimental Results. K. Kyoto. 445-46. Thermodynamic Stability of LaCrO3 and CaZrO3 Using a Solid-State Galvanic Cell Method.M. W. M. Miller. 2005. 12. Peck. Structural Studies of the (La. Rare Metals. 49. Phys. M. 3266-72. Nickel. Sudha. 48. Solid State Commun. Satoh. Zhongguo Xitu Xuebao.J. 5(3). Kawada. Abrashev. pp. pp. D. pp. Mat. Takahashi.. K. 79(12). Thermodynamic Properties of LaCrO3. 74. 132 . 176-82. Dokiya. 55. Yoshida. Res. M. 25(5). O. Res. Bull. Enthalpies of Formation of LaMO3 Perovskites (M=Cr. Yokokawa. 192(4). pp. 259. 108(9).F. A. Hilpert. Litvinchuk. Yuan. 51. Azad. G. Li. Nakamura. Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties. 1996.. Alloys Compt. T. T. P. R. Matsushita.M.. 1961.. Cr. Chem. Method. Iliev. M. A. Kozlowska-Róg. 191-200. Weinberg. M. 54. Y. L. 45.Y. 81. 1990. Huang. Róg. Mn. 47. H. pp. H. 691-94. 23-29. 562-66.. Y. H. 2006. A. Xing.G. Hadjiev. Murakami. 57-62. Raman Spectroscopy of Low-Temperature (Pnma) and High-Temperature (R 3 c) Phases of LaCrO3. Koseki. Bull. Cox.P. Am. T. Chung. Hashimoto. F. November 1991. N. M. 53. Kolev. Sreedharan. 463-72.-Q. 2006. 19-24 (in Chinese). Pressure-Induced Structural Phase Transition of LaCrO3.V. pp. Thermodynamic Stability of LaCrO3 by a CaF2Based E. Kikegawa. Cheng. Y. A. Li. Co. Gauckler. N. G. M. 1998. Y. Co. N. Nature.. T. pp. X. Takagi. X.P. Ceram. Z. 7677 (in Japanese). 2007. 1997. Stability of the Perovskite Phase LaBO3 (B=V. Less-Common Met. pp. Kobertz. 56. Wang. Res. Fe.. Khattack and D.-H. J. Mater.N. Electron Paramagnetic Resonance and Antiferromagnetism in LaCrO3. Sakai. B. Sun. V.E. J. Petzow. J. 214301-1214301-7. Zhou. 14. Dudek. J. W. N. Japan. Dokiya. S. Heat Capacity Measurement of Lanthanum Chromite by Laser Flash Method. 649-59. pp. Navrotsky. Larssen.-Y.Sr)CrO3 System. Cmaidalka.Thermodynamic assessments 44.-L. S. Hao. Chen. pp. Z. Tagawa. M. 52. Meng. J. 1977. H. Abstracts of the 27th Symposium on Thermal Analysis and Calorimetry. R. C. D. Rev.. Ni) in Reducing Atmosphere I. 20(1). pp. I. and Ni).
. 2006. T. Maruyama. Structure and Reactivity of Perovskite-Type Oxides. Chen. L.R. J. Povoden. pp. J. Hillert. A. Calphad. A. 133 ..J. N. 1978.. Calphad Calculation of Phase Diagrams. L. Gopalakrishnan. 65. Hillert. Sundman. Tripathi.P. J. 58. A. pp. Jansson. B. G. Influence of the Synthesis Conditions on the Electrical Properties of LaCrO3. p 161-76. 36. Grundy. B. 1975. Acta Metall. Pergamon Materials Series. 64. 1595-1609. pp. 1986. T. B. Jansson. Alloy.N.M.G. The Compound Energy Formalism. Metallkd. 68. L. Shvaiko-Shvaikovskii. H. J. 1989. 17. Guillermet. 67. pp. Advances in Catalysis. 62. Chen. pp. B. Grundy. Gauckler. 32. 60. Goto. pp. Povoden-Karadeniz. M. Vidyasagar. Wanklyn. 1. M. 320.J. Hillert. Indian J. Calphad. Chem. Phase Equilib. G. 81-87. I.L.V. M. Transport of Lanthanum Ion and Hole in LaCrO3 Determined by Electrical Conductivity Measurements. Solid State Ionics. 66(10). 69. Superstructures. A. Hallstedt. 71. 61. 24(3). pp. 1979. C. Ivas. 2(3). Metallkd. Fierro. -Manganites and -Ferrites. Andersson. 1998. Gordon. 30. Mater. J. 577-82.N.. E. Thermodynamic Assessment of the Co-O System. Elsevier Science Ltd. 345-58. C. pp. Sci.. Jarl. V. A. Miodownik. 243-. M.F. 66. 33-41.G. p 227-38. Saunders. Ordered Defects & Nonstoichiometry in Metal Oxides of Perovskite & Related Structures. T. Gauckler. 2003. 177-83.. 2003.. Determination of Chemical and Magnetic Interchange Energies in BCC Alloys. T.-O. pp. Chem. Solids. 212-27.Thermodynamic assessments 57. 79(2). Rao. Application of the Compound-Energy Model to Oxide Systems. 1441-45 (in Russian). pp. 1984. 23A.R. Diff. Vol. Rao. Popov. 1971.J. Nauk SSSR. Izv. 2001. B. pp. 59. Sundman. Hillert. E. Calculation of Defect Chemistry Using the CALPHAD Approach. M. Z. A Model of Alloying Effects in Ferromagnetic Metals. pp. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers.B. Thermodynamic Assessment of the La-Fe-O System.S. V.G.. B. 94-96. 1988. accepted 63. T. 34. Lal. 70. Electrical Transport in Rare Earth OrthoChromites. Akad. Tejuca. 1982. 437-45. 265-84. Cmpd. M. M.E. Phys. Mater. K. Gauckler. General Treatment. Electrical Transport in Light Rare-Earth Orthochromites. 164. J. Inden. L. Akashi. Rao. V. Phase Equilib. Neorg. J. 15(8).K..N. Ivas. J. Z..N.P.
Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. Calphad. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. R. Gibbs energy functions of SrCrO4. 1990. Povoden.. B. and L.1 Introduction Sr-doped lanthanum manganite (LSM) with the perovskite structure ABO3-δ is used as cathode materials in SOFC.J. Jansson. as well as defect concentrations of the cathode contaminated by Cr at different temperatures and oxygen partial pressures. 73. 75. Trans.N. 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. Electrochem. 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. 16A. and SrCr2O4 are presented. A.2]. Modification of the Two-sublattice Model for Liquids. submitted to Scripta Mater. For the construction of the 134 . J. thermodynamic driving forces and activities. B. Chen. J. Akila.67Cr2O8. Sundman. 261-66. 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.N. Ågren. A. Experimental solid solubilities and nonstoichiometries in La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ are reproduced by the model. 4. Appl.J.4. K. Sr2CrO4. A. M. These requirements are conformed by using the CALPHAD approach. E. The Mobility of Oxygen Ions in CaF2. L. 15. M.4 Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications E. Povoden. 74. Jacob. B. 1985. The database should meet the demand to calculate stable and metastable phase equilibria. 294-300. Metall. 4.Thermodynamic assessments 72.T. 1991. pp. pp. Gauckler. M. pp. Hillert. Sr2. Grundy. Chen. Grundy. 109-19. Sundman. 20.
Calculation of the oxygen nonstoichiometry of perovskite + MnO instead of metastable single phase perovskite leads to a good agreement between experimental and calculated nonstoichiometries. Limited solution of Sr in La1-xSrxCrO3-δ perovskite was confirmed by a later investigation.12]. which is in agreement with Negas and Roth. 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.12. Differences concern the reported stabilities of further compounds[11. The 135 . whereas emf measurements using CaF2-based emftechnique led to conflicting results likely caused by competing reactions. allowed Mn3+ on the A-site of LSM to reproduce experimental oxygen nonstoichiometries under low oxygen partial pressures. 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.785 Å for at maximum 6-fold coordinated Mn3+) we omit Mn3+ on the A-site.Thermodynamic assessments La-Sr-Mn-Cr-O oxide database La-Mn-Cr-O oxide and La-Sr-Cr-O oxide systems are assessed.15-19]: for the stabilities of SrCr2O4 and Sr2CrO4 we trust the accurate study of Jacob. Cr-O. 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. in agreement with Hartl and Braungart. 0. Due to large differences between the ionic radii of La3+ and Mn3+ and possible coordination numbers (1.5 Å for 12-fold coordinated La3+. Sr3Cr2O7 was approved as high pressure phase only. and La-Cr-O databases are adopted[3-5]. On the other hand the conflicting phase equilibria presented by Kisil lack experimental details. The stoichiometry of a phase defined as Sr3Cr2O8 was later corrected to be essentially Sr2.67Cr2O8 by using microprobe analysis. No quaternary phases or solid solutions were found in the Sr-Mn-Cr-O oxide system. 4.4. Sr-Cr-O oxide: Thermodynamic functions for Sr-Cr-oxides in the SSUB database are based on estimates.2 Assessment of data from the literature Previous assessments of the La-O. with a slight modification: Grundy et al. and the LaSr-Mn-O oxide database is taken from Grundy et al.
1.Sr)CrO4 is omitted in the modeling. and the solubility of Cr is unknown. and 0. and 0. La-Mn-Cr-O oxide: In the La-Mn-Cr-O oxide system no quaternary stoichiometric compounds were reported.1. 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. 0.Sr)CrO4 is ambiguous. Cr4+ and oxygen vacancies are regarded as the major defects[23. In contrast to Peck et al. Nonstoichiometry data for La1-xSrxCrO3-δ with x=0.3 at T = 1173 K that Cr4+ were absent in the latter. investigated the single phase region of La1-xSrxCrO3 with x = 0. thermodynamic data are missing.24]. 0. As Ruddlesden-Popper phases have not been reported to form during SOFC operation with LSM cathodes.3 using Knudsen mass spectrometry.3 at T = 1273K.Sr)CrO4 were stable in air.25.3.3 as a function of temperature and oxygen partial pressure using XRD analysis. Complete solid solution between the LaMnO3 and the LaCrO3 perovskites was affirmed. it was proposed earlier that Sr(La.09.2.8Sr0. Myoshi et al.2. Perovskite+MnCr2O4 spinel equilibrium of a powdered mixture of La0.2CrO3-δ at 1273 K were measured as a function of oxygen partial pressure using thermogravimetry. The exact temperature and oxygen partial pressure range of Sr(La.5Cr0. 1473K.Sr)CrO4 showed reproducible stoichiometry. and 0. 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. Thus its extension to the quinary database would not be reliable.1. Cheng and Navrotsky measured enthalpies of formation of La1-xSrxCrO3-δ with x = 0. determined the Gibbs energy of formation of La1-xSrxCrO3 with x = 0. 0. and δ = 0.2.2. Peck et al.1O3-δ was measured using thermogravimetry. Plint et al. −0.2MnO3 and Cr2O3 at 1073 K was reported after 1000 h of heat treatment in air.1. −0.8Sr0. 0. concluded from the similarity between X-ray absorbtion spectra of Cr K of LaCrO3 and La1-xSrxMn0.04.11 using drop calorimetry at T = 1080 K. Sr(La.9Cr0.5O3-δ with x = 0. δ of LaMn0. Positive δ in the perovskite formula reflects oxygen deficiency. and La0. and 1573 K. and −0. and 0. 136 .2.Thermodynamic assessments existence of several Ruddlesden-Popper phases is restricted to reducing conditions. and 0. solely Sr(La. 1373 K. whereas negative δ essentially stands for cation nonstoichiometriy. 0.
Thermodynamic assessments The perovskite phase: Magnetic and structural transitions of La1-xSrxCrO3-δ [29−35].43] for LaCrO3. Magnetic transitions have been well reproduced by an ordering-model[42. Consistency among transition data for La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ prevails. However we did not obtain satisfying results in higher-order perovskites. most likely due to interactions that cannot be reproduced by the model.1) SER v = 0.36−40].3 Modeling and optimization Sr-Cr-O oxide: The sublattice models (Sr2+)(Cr6+)(O2-)4 and (Sr2+)(Cr3+)2(O2-)4 are employed for the descriptions of SrCrO4 and SrCr2O4.41] were reported. 4.15 K and 105 Pa. and the equilibrium Sr2.25 for SrCrO4. Transitions of LaMn1-xCrxO3-δ are complex as they depend on temperature. whereas diversities exist regarding the transitions in La1-xSrxMn1-yCryO3-δ . in terms of the applicability of the new database for SOFC the authors omit structural transitions in the modeling. and La1-xSrxMn1-yCryO3-δ [8. As the magnetic transitions are low temperature features.12]. Sr2. LaMn1-xCrxO3-δ [26. composition and oxygen partial pressure.4. Thus. and 0. and Sr2CrO4 respectively.67Cr2O8+SrCrO4+Cr2O3 as a function of temperature and oxygen partial pressure[11. (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 perovskite layers of the latter.4. 0.67Cr2O8. H a is the standard enthalpy of the stable state of element a at 298.67Cr2O8 following the proposed formula and for the Ruddlesden-Popper phase Sr2CrO4. All 137 .12] and phase stabilities of SrCr2O4 and Sr2CrO4 investigated by equilibration experiments of different mixed oxide compositions under controlled atmospheres. 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. A and B are adjustable parameters. SrCr2O4. 7/6. accounting for the structural feature of alternating rocksalt.75. 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. their modeling was omitted without consequences for the applicability of the database for SOFC.
calc. Δ ° H = −34. δ = 0. BSr2CrO4 = 50 J ASrCr2O4 = 98000 J.11.1 Optimized model parameters Sr . δ = 0. Optimized parameters and calculated and experimental thermodynamic data are listed in Table 4. Δμ O 2 = −262. δ = 0. Δ ° H = −20.851 − 1116 K Δ °G = −273.4. T = 298 K. δ = 0.13152T kJmol-1 this work. Δ °G = −93.Thermodynamic assessments reported phase equilibria are correctly reproduced by the model.04.1.72 kJmol-1 x = 0.4.= GS3V + 1 6GS4O − 1 6GS4V GSr 2+ :Cr 3+ :Va = GS3V − 5 6GS4O + 5 6GS4V Table 4. ° Δ ° H = −36. ° Δ ° H = −67.340 + 0.3 kJmol-1 this work. calc. Δ H = −48.48 kJmol -1 138 . calc.8 kJmol-1 this work.2. calc.15 kJmol-1 x = 0. Δ °G = −109. δ = 0. calc. T = 298 K.4. Δ ° H = −50.88 kJmol-1 x = 0. Δ ° H = −55.2. 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. calc.7 kJmol-1 x = 0. Δ °G = −102.6 kJmol-1 this work.5 J ASr2.2 + 0. δ = 0.106904T kJmol-1 . T = 298 K.= 5 6GS4O − GS3V + 1 6GS4V + GRPRV GSr 2+ :Cr 3+ :O2.67 Cr2 O8 + SrCrO 4 + Cr2 O3 Δμ O 2 = −265.5 °GO2  ° ° ° GLa3+ :Cr 4+ :O2.825 ± 0.4.67Cr2O8 = −508507 J.3.15553T kJmol-1 .0 kJmol-1 this work.950 − 1280 K Sr2. calc.1 kJmol-1 this work. BSrCrO4 = 131.Cr oxides ASrCrO4 = −273771 J. calc.13157T kJmol-1 . T = 2000 K. T = 298 K. T = 2000 K. T = 298 K. calc. Δ H = −65.2 kJmol-1 this work.5 kJmol-1 x = 0. Δ ° H = −34.1 and 4.3. Δ °G = −93. calc.2.2 Calculated and experimental thermodynamic data SrO +1 2 Cr2 O3 + 3 4 O 2 = SrCrO 4 Δ °G = −273.767 + 0.15832T kJmol-1 this work. δ = 0.2.67Cr2O8 = 219 J La1 − xSrxCrO3 − δ ° gas GLa3+ :Cr 4+ :Va = 5 6GS4O − GS3V + 1 6GS4V + GRPRV − 1. Table 4.3. T = 298 K. Δ ° H = −56.54 kJmol-1 x = 0.859 + 0. Δ ° H = −59.1.7 kJmol-1 x = 0. Δ ° H = −20.3 kJmol-1 this work.774 + 0. Δ °G = −213. BSr2.050 + 0.4 kJmol-1 this work.6 J ASr2CrO4 = −145000 J. Δ °G = −85. δ = 0.4 kJmol-1 this work.1.166T kJmol-1 . T = 2000 K. calc. BSrCr2O4 = −95.1073 − 1473 K Δμ O 2 = −276.76 kJmol -1 x = 0.09. Δ °G = −88.
yj is the site fraction of each cation and Va on the B-sublattice. (Va)(Va)(O2-)3.4.Sr2+. Typical compositions of Sr-doped lanthanum manganites used for SOFC cathodes.Va)3.Va)3 with A. La0.4. (La3+)(Va)(O2-)3.3) is chosen as reference. and yk is the site fraction of O2.Va)(O2-.Cr4+. Using the above model and the proposed defect chemistry[22-24] the sublattice formula for La1-xSrxCrO3-δ reads (La3+. (La3+)(Cr3+)(Va)3. Thus it is reliable to take the Gibbs energies of the compounds of rhombohedral perovskite from  for the model. 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)(B. (La3+)(Va)(Va)3. B = cations and Va = vacancies using the compound energy formalism. (Sr2+)(Va)(O2-)3. R = 8. It can be accounted for by introducing interaction parameters. this is achieved by using the same model. (Sr2+)(Va)(Va)3.g. The molar Gibbs energy °G of La1-xSrxCrO3-δ is uniquely defined as follows: °Gs of the endmembers (La3+)(Cr3+)(O2-)3. The parameters of the compound energy formalism are the Gibbs energies of the end-member compounds °Gi: j:k .2) where yi is the site fraction of each cation and Va on the A-sublattice. We adopt the description (A. The last term describes the excess Gibbs energy of mixing. and A and B parameters of °G of two neutral compounds 139 .2MnO3-δ are rhombohedral at SOFC operating temperatures (T=1073 K to 1273 K).48]. and (Va)(Va)(Va)3 and ternary interaction parameters are adopted[5.31451 J mol-1 K-1. °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. e.8Sr0.Va)(Cr3+.Va)(O-2. The second-last term accounts for the configurational entropy of mixing.6. and small amounts of Cr brought into the cathode unlikely lead to a change of the structure.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 Va on the anion sublattice.
with A = 27027 and B = −69. 4. The regular interaction parameter 0L(La3+:Cr3+. Thus for LaMn1-xCrxO3-δ we propose the sublattice formula (La3+.Cr4+.5 in Eq. solid solubilities[18. 4.5Va0. 138).Mn .5.4. The 3+ 2+ sublattice 2+ 3+ formula 4+ 3+ of 4+ the 2- quinary perovskite reads (La .4. All endmembers have been defined in the assessed subsystems.2 (p. 140 .6. (Sr2+)(Cr3+)(O2-)3.Sr .1 (p.Va)(O .2 (next page).4) ° SER SER SER GSrCrO2.2 for ° GSrCrO2. and phase equilibria in the La-Sr-Cr-O oxide system by the modeling is satisfying as shown in Table 4. °Gs of the remaining endmembers (La )(Cr )(Va)3. A = 136453 and B = −91. and nonstoichiometries[23. and (Sr2+)(Cr3+)(Va)3 are obtained by conversions of reciprocal equations that are set zero and are listed in Table 4.4. 4.Cr3+. 138).Mn3+. it is expected that it is not removed from the structure if the phase is doped.4.4. Eq. and in Figs.4 Results and discussion The reproduction of experimentally determined Gibbs energies and enthalpies of formation.24] of La1-xSrxCrO3-δ.Va)(O2-. All endmember compounds have been defined in the assessed subsystems.1 and 4.Cr .Mn4+.4.Mn3+:O2-) accounting for interactions between Cr and Mn cations is fitted to experimental nonstoichiometries.5) are optimized with all available experimental data of the perovskite phase.4 denotes °G (Sr2+)(Cr4+)(O2-)3.4. 3+ 4+ (La3+)(Cr4+)(O2-)3.4.Va)3. it is reliable to allow Cr4+ on the B-site: as Cr4+ exists in nonstoichiometric lanthanum chromite perovskite.Va)(Mn .Cr .Mn3+:O2-) = +9421 J.Mn .5Va0.5 − H Sr − H Cr − 2.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.Va)3. Though structure-chemical information of site occupancies in LaMn1-xCrxO3-δ perovskite is missing. 0L(La3+:Cr3+.Va)(Mn2+.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⎠ (4.20].4. 4.
Thermodynamic assessments Fig. and three phase equilibria.5-SrO-CrO1.5 system calculated at T = 1223 K in air atmosphere (solid lines) with experimental data included (symbols).1 LaO1. 4. two phase. Calculated phase equilibria are the same as in. blank circles. and circles with crosses denote single phase.4. prv = La1-xSrxCrO3-δ. 141 . Filled circles.
However it was not possible to reproduce the nonstoichiometries at T = 1073 K and 973 K.4. 141 Calculated (lines) and experimental (symbols)[22.2. 0.25. and 0. 4. as shown in Fig.5 system calculated at T = 1273 K in air atmosphere. 4.1. 4. possibly caused by equilibration difficulties due to slow diffusion.3 as a function of oxygen partial pressure.23] nonstoichiometries of La1-xSrxCrO3-δ at different temperatures for x = 0.2.4.4. 142 . The calculated nonstoichiometries of La1-xSrxCrO3-δ are in good agreement with the experimental values at higher temperatures. Deducing from the change of δ from T = 1273 K to 1173 K the measured increase of δ from T = 1173 K to 1073 K might be too small.4 (next page).4. Fig. prv = LaMn1-xCrxO3-δ. α-spl = tetragonally distorted Cr-Mn-spinel. 0.5-MnOx-CrO1.3 LaO1. The calculated isothermal section of the La-Mn-Cr-O oxide system at T = 1273 K in air is presented in Fig. 4. p.Thermodynamic assessments Fig. β-spl = cubic Cr-Mn-spinel.3.
and oxygen partial pressure.1O3-δ at different temperatures as a function of oxygen partial pressure. We believe that complete removal of Cr4+ from the perovskite structure is unlikely.Thermodynamic assessments Fig.Mn3+:O2-).4. We propose the model (La3+.Sr2+.Cr3+.4. 4. this model allows the quantitative calculation of defects as a function of composition. Optimized by experiments in pseudoternary and pseudoquaternary oxide subsystems. The new database is adapted for quantitative calculations of 143 .Mn3+.Va)3 for the quinary perovskite phase. Thus we stick to a model without interaction parameters. Experimental findings[8. Experimentally determined nonstoichiometry of LaCrO3 indicates the existence of some Cr4+.Cr4+.28] are in line with our calculations. temperature.Mn3+:O2-) and L(Sr2+:Cr4+. it would be necessary to give large positive values to the regular interaction parameters 0 0 L(Sr2+:Cr3+. 4.Va)(Mn2+. To approximate the absence of Cr4+ in quinary perovskite. and the conclusion of missing Cr4+ is not based on a direct chemical analysis of Cr valencies.9Cr0.Mn4+.Va)(O2-.5 Conclusions The thermodynamic La-Sr-Mn-Cr-O oxide database has been obtained by combining thermodynamic assessments of oxide subsystems.4 Calculated (lines) and experimental (symbols) nonstoichiometries of LaMn0.
Abraham. J. Diff. J. Foger. 925-. 1997. Ivas. Diff. 147. 2006. A. Grundy. 353-62. 1996. Chem. 9. K. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. 27(4). F. accepted 6. Chemical thermodynamic considerations in sintering of LaCrO3-based perovskites. Phase Equilib. 771-774. J. London. Gauckler.. E. 138. Hallstedt. 2007. Yang. Povoden. La1-xMn1-yO3-z perovskites modelled with and without antisite defects using the Calphad approach. R. S. 297-310. N. Electrochem Soc. P. A. E. Petrov. A. Acta Crystall. Electrochem. 1901-07. K. Phase Equilib. References 1.. Y. J. H. B. 8.T. 144 . Solid State Ionics.. T. P. 4. 2000.. Foger. Zhang. Geupel. Institute of Materials. pp. 11. pp.T. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells I. Mechanism and kinetics. pp. J. Chem. 5. Thermodynamic assessment of the La-Cr-O system. M. Jiang. 10. 7. Deller. 2000. Phase Equilib. E. B25. J.N. 2. Demina. pp. Gauckler. Aldinger. The SGTE casebook: thermodynamics at work. 2004. Liu.N.K.P.N. Inorg. Grundy. 1018-27. K. pp. pp. M. S. 99. Prewitt.D. 1721.J. S. 1969. M. Badwal. S. M. 2006. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. Soc. Effective ionic radii in oxides and fluorides. B- Stru. 67.N. Saxena. 3.P. L. Povoden. J.-K. Chen. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 21.J.). Shannon.. L.N.. Jacob. Ramprakash and J. Gauckler.Thermodynamic assessments phase equilibria and defect chemistry in a Sr-doped lanthanum manganite SOFC cathode poisoned by chromium. Zhang. Dokiya. Hack (ed. R. pp. Grundy. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.P. C. J. A. Russ. Sakai. 173. Zinkevich. 52. A. K. Solids. and L. pp.J. Filonova. Durygin.. pp. 1991. K. Kawada. Z. Phase relations in the system Sr-Cr-O and thermodynamic properties of SrCrO4 and Sr3Cr2O8. A. Yokokawa. S. 46-53.A. T. 4013-4022. Solid State Ionics. Phys.
J. 20. 23. Electrochem. The mobility of oxygen ions in CaF2.33(CrO4)0. Fueki. Hilpert.S. 15.. Strontiumchromate(V. R. Ishikawa. 2004. Inoue. 21. 1978. M. 33. Mater. pp. F. S. Thermochim. T. D. L. E. Solid State Ionics. M. 294-300. Peck. pp. Phase formation in the system SrO-CrO3-Cr2O3.. J. Y. pp. O. Sr or Ba) from emf-measurements. 9. Sudha. 1999. Azad. Peck. T. 1989. 143. J. F. pp. Akashi. 73A. 17. pp. Yokokawa. 2003. Inorg. Singheiser. Hilpert. Energetics of La1-xAxCrO3-δ perovskites (A = Ca or Sr).. pp. Boroomand.M. 39. R.Thermodynamic assessments 12. 177. Standard Gibbs energies of formation of SrCrO4 and Sr3Cr2O8. Negas. J. Mizusaki. 1984. M. Meschke. 20. Pt.H. 1969.33(CrO4)1. J.67. Solid State Chem. 25. Castillo-Martínez. Vaporization and thermodynamics of La1-xSrxCrO3-δ investigated by Knudsen effusion mass spectrometry. Maruyama. Revisiting the Sr-Cr(IV)-O system at high pressure and temperature with special reference to Sr3Cr2O7. Steinbrech. A. Soc. 19. 1998. R. pp. Sr2. 178. 194. T. Wessel. 22. Nonstoichiometry of the perovskitetype oxide La1-xSrxCrO3-δ. 59-65. System SrO-chromium oxide in air and oxygen. B. E. pp. NBS A Phys. 234-44. pp. 564-73. Acta. 13. T. 431-42. Zuev. 129-36. Jim. A. Teller. Navrotsky. Z. J. pp. pp. Miller..-H. Jacob. Kaimai.T. 16. Kisil. Kawada. 2007. Braungart. Yamauchi. Matsumoto. 24. 23. Hartl. 145 . Slobodin. A. 12. D. T. Sharova. K. Mater. 18. R. Onuma. a hightemperature compound with defect-bariumphosphate-structure. Appl. Solid State Ionics.A. Solid State Sci. S. The standard Gibbs energies of formation of ACrO4 (A=Ca. H. K. 4112-. Myoshi. K. K. Yashiro. 1990. 119-24. Akila and K. VI). J. B. Hilpert. Miller. J.. Mizusaki.G. K. H.. H. Sreedharan. 952-953 (in German). 14.67Va0.. 1992. Phase diagram studies in the SrO-Cr2O3-La2O3 system in air and under low oxygen pressure. Ceram. 2005. A. 1158-61. S. R. Alario-Franco. Europ.. pp. Res. 300920. 1490-91.V. Ch. 401-12. Defect formation and mechanical stability of perovskites based on LaCrO3 for solid oxide fuel cells (SOFC). O. Solid State Chem. pp. Roth.W. Naturforsch.M. A. N. 2001. Cheng.K. Solid State Ionics. Nickel. 123. T. K.
J. M. Arai. Francesconi. 0.9Cr0. 11. J. H. Y. Brito.S.-P. Y. Tezuka. 18.E.: Condens. O. 32. Hinatsu. M. 12. 141. K. Yamaji. V. 404-10. Acta.Sr)CrO3 system. Electronic transport in the novel SOFC anode material La1-xSrxCr0. Takahashi. 30. Irvine. 2005. C. Magnetization and resistivity in chromium doped manganites. 2006. Ramanadham.K.S.85Sr0. 2008. 57-. A. Mat. 34. Takahashi. 1999. J. Analysis of relationship between magnetic property and crystal structure of La1-xSrxCrO3 (x=0. Studies on magnetic properties of La0. Sato. F. Tyagi.A. 27. 12. J. 4151-60. 2006. T. L. Phys.. Takahashi. Plint.M. 33. xSrxCrO3 Analysis of magnetic and structural phase transition behaviors of La1- for preparation of phase diagram. Cabeza. Cox.95Sr0. Pomjakushin. S. D. Komatsu. Magnetic and neutron diffraction study on perovskites La1-xSrxCrO3.M. Y. T. Horita. Matter. 132-. Sakai. Nakamura.5O3±δ. Morii. Chiba. N. K. T. Shimojo. 26. 176.75Sr0. Evolution of crystal structure with the oxygen content in the LaMn0. H. Solid State Ionics. Yokokawa. A. Hashimoto. Morales.1O3+δ (3. 222-29. 2000. 1977. pp. Thermochim. R. 2569-78. H. J. Bull. Tao. 2008.. Khattak. M. Y. 2003. Matsubara. pp. K. 31.15). Atake. F. J. 146 . Solid State Ionics. pp.: Condens.15CrO3 by means of powder neutron diffraction. Arai. Thermodynamic considerations on Cr poisoning in SOFC cathodes. C. 463-71. M.13. K. Acta. Solid State Chem.R. 3193-98. K.. T. Yusuf. P. Oikawa. Y. Structural studies of (La. 145. Y. Long. M. Muirhead. pp.E. Hinatsu. Y. Chakraborty. Ohba. Morii. Matsunaga. pp. S.R. 2008. Y. Matter.Thermodynamic assessments 25. Thermochim. Bari. K. Nakamura. J. T.12) compound. 404-10. 8661-72. Caneiro. N. S. Power Sources.G.5Mn0. 474. Matsunaga.25CrO3 at high temperatures. P. 29.A. 177. pp. Solid State Chem.P. Inami. 2005-08. 170. Structural study of La0. 1998. T.00 ≤ 3+δ ≤ 3. Kishimoto. 28. Matsunaga.. H. 435. A. Matter.05CrO3 and La0. T.M. pp. Solid State Comm. Y. 36. H. H. Phys. Greaves. Hashimoto. pp. 177. Tezuka. Nakamura. 35. Xiong.: Condens. 2006. Phys. Krishna. 502-06. Connor. Hashimoto. Res. Kawaji. Y. K. Shimojo. C.T. H. H.
J. Effect of Cr doping in La0. Kuscer.7Sr0. Yau. M.3Mn1-xCrxO3 with 0 ≤ x ≤ 0. (a). Kolar. 66(10). Bourèe. Calphad. Ceram. M. nuclear structure.. 0. 48. 320. Holc.25) using the Rietveld method of analysis. Folgado.A. F. The thermo-calc databank system. X-ray-powder diffraction structural phasetransition study of La(Cr1-xMnx)O3 (x=0 to 0. 16. Gauckler. Chem. Calphad. 317-425.U. Synthesis.J. pp.-K. 1978. A. N. Sapiña. A model of alloying effects in ferromagnetic metals. H. 20. 38.N. 1975. 153-90. M. M. Z. Sundman. M. G. B. Preliminary data on solid solubility between LaCrO3 and LaFeO3 or LaMnO3. 46. J. Inden. Mater.3). Hillert and M. 161-76.. Am. 1996.. H. F. Chen. 26. D. Beltrán. 1997. Oumezzine. 1991. 2005. Grundy. 227-38. and magnetic properties of LaCr1-yMnyO3 (y=0. 1992. Vincent. Calphad. Anderson. Bernik. J. Jarl. pp. pp. Sci.. Hrovat. Dhahri.Thermodynamic assessments 37. pp. J. S. J. Lett. J.. M.V. Gauckler. P. 39.2. J. Andersson. J. Hallstedt. L. pp. 9. L. E. A. 44. Beltrán. Metallkd. pp. M. 184.. B. D. Jansson. 577-82. Z. Alloy.J. 0. 2008. Metni. Tellgren. Rundlöf. 457. 42. 131-51 147 . Diff. S. Martinez. B. pp. D. G. 45. R. A. Mater. Cmpd. 143-46. Phase Equilib. J. J. M. 41. pp. 2(3). I. Tseggai. E. J. 2001. 43. Howard. 437-43. Determination of chemical and magnetic interchange energies in bcc alloys. Dinsdale. 1685-87. 532-40. Phys. Kallel. SGTE data for pure elements.. Zemni. 319-25. Risold. 10. Sol. Ghedira. 40. Calphad. Hillert. Stat. 2001. Assessment of the La-Mn-O system.1. Soc. General treatment.T.-O.R. pp. 47. El-Fadli. 2000. 353-61. Dhahri. Structural effects of Co and Cr substitution in LaMnO3+δ. H. 75. The compound energy formalism. Nordblad. 15(4). The strontium-oxygen system. Alloy Compd. Andrè.5. and 0. B. S. D. Hallstedt. 1985.
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. and L.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. 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. 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. 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. Povoden. 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. Proper strategies to prevent the problem of chromium “poisoning” are proposed. Chen. This has consequences for the electrochemical properties of the cell: the electronic conductivity of the cathode will decrease. the deterioration of the cell performance is expected to be less pronounced when the cell is operated at lower temperatures and current loads. 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. T. Even though the chromium problem cannot be solved satisfactorily by varying the cathode composition or the SOFC operating conditions. 148 . M. Ivas.J. whereas Cr2O3 is metastable. The spinel formation goes along with increasing Mn2+ in LSM under decreasing oxygen partial pressures.
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. mechanical strength.1 Introduction Chromium-containing metallic interconnects are commonly used in planar-design solid oxide fuel cells (SOFC) due to their high oxidation resistance. Consequences of Cr poisoning have been investigated specifically in (La1-xSrx)MnO3-δ (LSM) perovskite-structured cathodes. though partly with conflicting results. This reduction reaction would compete with the oxygen reduction and lead to blocking of the active sites at the triple phase boundary (TPB). and -diffusion process. and no Cr2O3(s) is formed. In the last decade a lot of efforts were made to elucidate the degradation mechanisms. as well as low fabrication costs. Consequently Cr-Mn spinel and Cr2O3(s) would form. 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. where they cause the degradation of the cell by detrimentally affecting the O2adsorbtion. Ad 2) In contrast to 1) it was proposed that gaseous Cr-species would be chemically dissociated to LSM under the polarization of the cell. where the reaction partners for the reduction. -reduction. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available.Thermodynamic calculations of impacts of Cr on LSM cathodes 5. Both groups of researchers agree that without polarization Cr is randomly deposited inside the cathode. associated to these nuclei. good electronic and negligible ionic conductivity. 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]. The chemical dissociation approach is coherently based on the interpretation of a large number of impedance spectra. 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. On the other hand the electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach. Ad 1) In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary. thermal stability. 149 .
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. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. and C denote sublattices of the perovskite phase.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1.9Sr0. Vertical lines indicate boundaries between different phase equilibria 153 .1MnO3-δ and defect concentrations of La0.1 phase fractions in Cr-“poisoned” La0.3. B.9Sr0.1(Mn. with A and B standing for the cation sublattices and C standing for the oxygen sublattice.2 Phase equilibria in Cr-“poisoned” La0.9Sr0. A.3. 5.
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.
184.108.40.206.6 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.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. tetragonally distorted Mn3O4 (t-sp) is expected to form. Fig. At T = 1073 K Mn2O3 is stable in a Cr-contaminated LSM cathode with excess Mn in air.3.7 phase fractions in Cr-“poisoned” (La0. 5.2 Thermodynamic calculations of (La0.2)0.8Sr0.2)0.9MnO3-δ as a function of oxygen partial pressure at T = 1273 K and 1073 K and μ(CrO3) = −300000 J mol-1 157 .7 it is obvious that in this widely used LSM composition Cr-“poisoning” leads to the formation of additional phases already at high oxygen partial pressures: A small amount of about 5 mol% of the pure spinel endmember.9MnO3-δ contaminated by chromium From Fig.8Sr0. 5.
Fig. 5.8Sr0. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes In Fig.3.2)0. 158 .9 (next page).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. as in the case of cation-stoichiometric LSM.3.9MnO3-δ cathode are shown in Fig.8 the compositional changes of cubic spinel are plotted as a function of oxygen partial pressure at T = 1273 K. 5. In general. the compositions of the spinel phases formed during chromium “poisoning” become richer in Cr under more reducing conditions.3.
9MnO3-δ with Cr (broken lines in Fig. The vertical line indicates the boundary between different phase equilibria Fig.3.8Sr0.3.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 and μ(CrO3) = −300000 J mol-1. 159 . 5.10 (next page) is a comparison of defect concentrations of (La0. 5.10) and without Cr (solid lines in Fig.10) at 1273 K.Cr)O3-δ and defect concentrations in (La0.9 Phase equilibria in Cr-“poisoned” (La0.3. In LSM(Cr) the concentrations of these cation vacancies drop strongly at low pO2 . 5.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. The vacancy concentrations on the A-sites and B-sites of the Cr-contaminated perovskite phase are basically in the middle between these vacancy concentrations in LSM.2)0.8Sr0.9(Mn.8Sr0. Mn2+ is higher in LSM(Cr) than in LSM at higher pO2 .3.2)0. 5. and the concentration of oxygen vacancies is lower in LSM(Cr) than in LSM at relatively high and low pO2 .2)0.9(Mn.
as it is illustrated in Fig.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.148Mn0. Table 5.2)0. Calculated concentrations of all species in LSM(Cr) and tetragonally distorted spinel in equilibrium are listed in Table 5.8Sr0.3.1 Pa.11.1 Compositions of LSM(Cr) and spinel in equilibrium at different T at pO2=1 Pa with and without Cr.8Sr0. 160 .9(Mn.9MnO3-δ (solid lines) as a function of oxygen partial pressure at T = 1273. next page. 5. 5.Cr)O3-δ (dashed lines) and (La0.3. 5.10 Defect concentrations in (La0.3.3.3 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 La0.947O3-δ spinel formation becomes important only at pO2 < 0.3.871Sr0.2)0.1.
2)0.Cr)0.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.12. 5.947O3-δ is illustrated in Fig.871Sr0. y(Va)C even decrease slightly towards lower pO2 .Cr)0.2)0. 5.148(Mn. and the concentration of oxygen vacancies is almost an order of magnitude lower then in (La0.8Sr0.947O3-δ is half of an order of magnitude higher than in (La0. after reaching a plateau at pO2 = 103 Pa.9MnO3-δ at high oxygen partial pressures.3. However. The influence of chromium on defect concentrations in La0.871Sr0.11 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-1.9MnO3-δ at pO2 = 10-1 Pa.8Sr0.3. 161 . next page: The concentration of oxygen vacancies in La0.148(Mn.
5.947O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1 (solid lines).Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.3. One can get an idea about the degree of metastability of a phase by calculating its thermodynamic driving force.148(Mn.2)0.3. and thus its formation is kinetically controlled.871Sr0.8Sr0.Cr)0.4 Formation of Cr2O3 This phase was not found in the thermodynamic calculations. If the driving force is 0. and the driving force for the formation of the phase is low. This is the amount of energy that is needed to bring the phase to its stable state.12 Phase equilibria in Cr-“poisoned” Mn-deficient LSM and defect concentrations in La0. Vertical lines indicate boundaries between different phase equilibria 5.3. 5. The more negative the driving force. Dashed lines indicate the defect concentrations in (La0. 162 . In Fig.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”. the phase is thermodynamically stable. the more energy is needed to stabilize the phase.9MnO3 without chromium.
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.
Taniguchi. 2004. pp. T. Birss. Thus it is expected that in this case the consequences of Crpoisoning will persist particularly at high current loads.P. Matsuzaki. I. 3195-3205. V. 73-9. Yasuo. Y. T. U. 55. Apateanu. 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. Chromium poisoning of LSM-YSZ SOFC cathodes. 7. 1997. Power Sources. Electrochem. S. pp. L. Ramprakash. Electrochem. J. interaction between Mn from LSM with Cr may be cumbered by proper doping of the perovskite with further B-site cations. Akiyama. Zhang. H. Saitoh.. pp. Yasuda. Solid State Ionics. 2000. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells I. 127. K. aging mechanisms and lifetime in solid-oxide fuel cells. 271-278. 2000. 3.. pp. References 1. 2001.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. 2004. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. J. pp. 147(9). 1995. Jiang. 297-310. Y. 6. J.C. Y. 132. Miyake. Kadowaki. J. S. 284-93. Mechanisms and kinetics. Y.P.P. R. 2. 5. H. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator. 148. S. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes. Tu. Badwal. Foger. S.P. Solid State Ionics. 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. Foger. 166 . 99. Paulson.. Y.S. Furthermore. Advances. J. 151(11). pp. Electrochem. Soc. 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. Deller. Soc. Matsuzaki. Yasuda.I. Kawamura. M. 4. J. Soc. pp. A1961-68. Stimming. Power Sources. J. A126-31. K. Zhang. I.
Zheng.J. pp. J. pp.J. K. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials.P. J. pp.. J.. B. Wu. 2007. FY Annual report.. L.N. pp. Li. Sci. 2006. 28.J. Solid State Ionics. Povoden. Jiang.Fe)O3 electrodes.D. 108. S. Power Sources. J. B. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3.A. 9.Ba)(Co. J.P. Electrochem. Jiang. Applied Electrochem. pp. J. S.P. Assessment of the La-Sr-Mn-O system. Krumpelt et al. 2002. Apateanu. Diff. 19. Soc. Mater.P. pp. 162. Mechanisms and kinetics. 771-774. Grundy.P.. Gauckler. A. D. E. 191-201. L. Soc. pp. 27. Mater. 1961. 10. Inorg. Electrochem. Eng. Sundman. 23. 2007.N. S. The Thermo-Calc databank system. A comparison of O2 reduction reactions on porous (La. Hydrogen Energy. 13.G. 4th international symposium on solid oxide fuel cells and pers. 18. 695-703. J. Characterization and performance of (La. S.N.Thermodynamic calculations of impacts of Cr on LSM cathodes 8. 3664-71. Int. 56978. 438-442. Soc. Zhang. 21. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 17. Zhen. Jiang. Gauckler. pp. L. pp. Y. Chem.. 2001. Power Sources. Res. S. 153-190.W. Ceam. 31. E. Zhang. 1-22. comm. Povoden. Jiang. Use of gaseous Cr species to diagnose surface and bulk process for O2reduction in solid oxide fuel cells. Jansson. 1043-1052.. S.D. Int. Zheng and P. Y.N. S. M. Cohen. 2002. Y. A.P. 52. J..-O. E. 9.. 181-192. Grundy. 39-43. J. 16. 2004. pp. J. 14. 167 . Jiang. Phase Equilib. 2008. 146. pp. 20. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. 22. 4013-22. Demina. L. 2006. J. Europ. J. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells. Fergus. Caplan and M.Sr)MnO3 and (La. Jiang. 353-62.Sr)(Co. Foger. A. Jiang. Russ. J. 147. A. Zhang. The volatilization of chromium oxide. Gauckler. J. J. 32. 2000. S. 180.P.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Grundy.P. B. Filonova. pp. 22. 1985. 2006. Petrov. Zhen.P. 12. I. Zhen. Hallstedt. J. pp. 97. Calphad. B (119) (2005) 80-86. X. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. A. 361-73. 11. 2004. pp. Andersson. 15. Calphad.N.
G. 25. 28. Singhal. Hammou.. NJ (1989). Siebert. Howard.M. Dokiya. 154 (12). Singheiser. Power sources. The Electrochemical Society Proceedings Series. Konysheva. in SOFC-1. 138. W. H. Yamamoto. M. Penkalla. 114-24. Qu.. 681-686.U. M.P. PV 89-11. E. PV 95-01. NJ (1995). S. 1212-16. H. Kleitz. Xiong. Hill. Hilpert. Sammes. L. Koc. pp. Mertens. Hammouche. in SOFC-IV. Solid State Ionics. K. 176. p. Structure and transport property of manganese-chromium-iron oxide as main compound in oxide scales of alloy interconnects for SOFCs. K. Yokokawa. 220. J.C.Thermodynamic calculations of impacts of Cr on LSM cathodes 24. pp.. 27. M. Phillips.A. J. Soc. 2007. Kishimoto. Horita. Maruyama. Sakai. Pennington. Electrochem. 26. Tagawa. B1252-B64. Jian. H. 2006. Ivey. J. L. S. 153. 168 .B.E. Effect of cathode thickness and current density. 29. pp. J.M. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. H. A. Eds. S. 472. Caneiro. O. Singhal. T. R.. A. Electrochem. p. J. D. T. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects. The Electrochemical Society Proceedings Series. Y. A. N. Yamaji. M. Soc. N. Pennington. Brito. Chromium poisoning of the porous composite cathode. 1991. pp. 2005.C. H. Anderson. E. Ed.
004045175*T**2 -5.91+1123.15 -8856. fcc ENTER-SYMBO FUNCTION GLAFCC 298. AMEND-ELEMENT VA VACUUM 0 H0 6.. Povoden-Karadeniz 2008 @@ GO G ENTER-ELEMENT LA CR VA @@ELEMENT NAME REF. 4000 N @@ Cr.25865E-07*T**3.3088*T*LN(T).9547989E-05*T**3-36581228*T**(-1).8932E-07*T**3-399448*T**(-1). double hcp ENTER-SYMBO FUNCTION GHSERLA 298.35429E+01.94+157.08252*T+513.Appendix Appendix La-Cr databasea) @@ Database La-Cr.387295093*T**2 +4.5388*T*LN(T). 4000 N @@ La.403+120. Dinsdale 1991 @@ La.492988*T-39.6651E+03 4. 1134 Y -16377. STATE ATOMIC MASS AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1. @@ ---------------------------------------------------------@@ Functions @@ ---------------------------------------------------------@@ Standard data for elements. 800 Y +321682.18*T-50.344+344.988+174.34*T*LN(T)-. 2000 Y -15608.06113*T-17.413+59.00189435*T**2 -1.34397*T-163.. AMEND-ELEMENT CR BCC_A2 5.3891E+02 5.836315*T-34.882+181.673-3565.284604*T-26.88526E+32*T**(-9).056395E-06*T**3+21167204*T**(-1).390071*T-34.908*t*LN(T)+0.3088*T*LN(T). bcc ENTER-SYMBO FUNCTION GLABCC 298.1659411*T*LN(T)-. bcc ENTER-SYMBO FUNCTION GHSERCR 298.440708*T*LN(T)-0. 2000 Y -8205.1996E+01 2.47721E-06*T**3+139250*T**(-1). Dinsdale 1991 @@ La.15 169 .053968535*T**2 -4.413074*T*LN(T)+0.0*T*LN(T)-2.894+218. 6000 N @@------------------------------------------------------------------@@ Solid metals.7919*T*LN(T)-0.0500E+03 0 S0 0.001295165*T**2.15 -3952.48*T-26. 550 Y -3381.072353*T-21.161+88. 2180 Y -34869.008371705*T**2 +6.6902E+01. 1193 Y -136609..15 -7968.
976+955.47721E-06*T**3+139250*T**(-1)+2.02767321*T**2 170 .7643*T*LN(T)-.0441+773. 1134 Y -3942. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.83676*T*LN(T)-0.64743*T*LN(T)-.15 +15483.5192158*T-21.54399*T-34.928-44.1*T**(-1). 2000 Y -12599.020171603*T**2 +2.418475E+08*T**(-1).878761*T-21. 6000 N @@ Cr2 gas.5*T**(-1).004+171.00189435*T**2 -1.56798*T*LN(T)+.006002155*T**2 +1.0037862445*T**2 -2.00406*T*LN(T)+0.15 +390765.25865E-07*T**3.3088*T*LN(T).1074654*T-19.30043383E-07*T**3-34158815*T**(-1). from SGTE @@ La(g) ENTER-SYMBO FUNCTION F12026T 298.0188*T*LN(T)+0.15 +598511.878375*T-139. 10000 N @@ Cr gas.06299*T*LN(T)-0.96003*T*LN(T)+.338363*T-111.984+335.Appendix -6109. 6000 N @@-----------------------------------------------------------@@ Gas functions @@ La gas.28626*T+17.005444405*T**2 +4.253215E-04*T**2 -1. 3200 Y +497751.386+178.018431*T-34.588679E-07*T**3+10285.15*T**(-1).37615E-21*T**7.4786162*T-13. 8200 Y -92343.042032405*T**2 -3.71447833E-07*T**3+102710.905-85.346741*T*LN(T)+0.23648333E-07*T**3-722515*T**(-1).36083*T*LN(T)+7. 1300 Y +404460.15 +422273.2*T**(-1).0037094435*T**2 -2.61216717E-06*T**3+154422.007085085*T**2 -4.843-369.011938995*T**2 +1.616317*T-50*T*LN(T). 800 Y +613345.69883E-07*T**3-1738066.653+18.059775*T-26.23012*T-11.791973*T*LN(T)-0.004961847*T**2 -1. from SGTE ENTER-SYMBOL FUNCTION F7763T 298. 1100 Y +393886.015+146.797+89.85*T**(-1).908*T*LN(T)+.3088*T*LN(T). 2180 Y -16459.232-104.085237*T+2.33826017E-06*T**3-312130.955-30.15 +5332. 4000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298. 1400 Y +642608.0188191*T*LN(T)-0. 600 Y +426628. from SGTE ENTER-SYMBO FUNCTION F7491T 298.066199E-06*T**3+20994153*T**(-1).5353212*T-40.403+41.747-246.17+114.207991*T-19.3347881*T-22. 4000 N @@ ---------------------------------------------------------------------@@ Liquid metal functions.016725*T-42.82257667E-08*T**3+5.331-31.93775E-06*T**3-133541*T**(-1).001513089*T**2 -4.7919*T*LN(T)-0.70261E-07*T**3+2891891*T**(-1).004045175*T**2 -5. 1134 Y -124598.
fcc ENTER-PHASE LAFCC. ENTER-PAR G(LAFCC.. VA. AMEND-PHASE-DESC BCC MAGN -1 0..605906E-06*T**3-5831655*T**(-1).. ENTER-PAR G(GAS.5939925E-07*T**3+14793625*T**(-1).7145*T*LN(T)+. VA..028597625*T**2 -4.. 6000 N @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Metals @@ La.0) 298.. ENTER-PAR L(BCC. dhcp ENTER-PHASE LADHCP.25559*T-334....0) 298..15 +GCR_L.0) 298..CR2...CR:VA.LA.LA.tcm 171 .008. 2 1 3 LA CR. ENTER-PAR G(LIQ...CR:VA...LA:VA. ENTER-PAR BMAGN(BCC.. @@ Interaction parameters from binaries ENTER-PAR L(LIQ.15 +F12026T+RTLNP.15 +GHSERCR.. VA.07969*T*LN(T)-.. N.15 +GHSERLA. ENTER-PAR G(BCC.0) 298.... AMEND-PHASE LIQ COMP 2. @@ ------------------------------------------------------------------------@@ Liquid..CR. 2 1 1 LA CR.0) 298.... VA..137623*T-105...97520167E-07*T**3+7.0428*T*LN(T)+3. @@ ----------------------------------------------------------------@@ Alloys @@ BCC_A2 ALLOY ENTER-PHASE BCC.0) 298.4843765E+08*T**(-1)... 5800 Y -484185... 2300 Y +553119.. ENTER-PAR G(LADHCP..004229401*T**2 +1. ideal extension from lower-order systems ENTER-PHASE LIQ.9699545E-04*T**2 +1.1) 298..CR:VA...LA. @@ GO PAR SET-OUT-LEVEL... 2 1 0.0) 298.15 60713-5. ENTER-PAR G(LIQ.LA:VA.5... @@-----------------------------------------------------------@@ Gas ENTER-PHASE GAS G 1 LA CR CR2.15 -0..15 64573-23*t.51783483E-07*T**3+1. ENTER-PAR G(GAS..LA:VA....135805E+08*T**(-1).CR:VA... 3900 Y +347492. @@ La..Appendix +1.895+159. ENTER-PAR G(BCC.0) 298.055+2598...0) 298.15 +GLALIQ.0) 298.15 +GLABCC.15 +F7491T+RTLNP.49*t..0) 298. ENTER-PAR G(GAS..CR:VA.4 ENTER-PAR TC(BCC.0) 298..5 LA . set-interactive a) databases scripts can be used in Thermocalc with the extension ..CR:VA....15 -311...0) 298...34+623.15 83500.188555*T-52.CR:VA. ENTER-PAR L(LIQ....15 +F7763T+RTLNP.LA...... 2 1 1 LA..15 +GLAFCC..LA:VA.
6902E+01.4938E+01 4.7620E+01 6.5694E+01. associate at composition SrCrO4 can @@ help for better fit to experiments – future work @@ @@ No data exist for Sr-Mn-Cr-O. AMEND-ELEMENT SR SR_FCC_A1 8. AMEND-ELEMENT O 1/2_MOLE_O2(G) 1. @@ Actual version: Dec2008 by Povoden-Karadeniz @@ @@ COMMENTS @@ @@ Sr-Cr-O liquid: simple description.3410E+03 1.0500E+03 2..9960E+03 3..0252E+02.3891E+02 6.. 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 H 1/2_MOLE_H2(G) 0. as only few phase @@ diagram data exist! @@ -------------------------------------------------------------------GO G ENTER-ELEMENT LA SR MN CR O VA H @@ELEMENT NAME REF. Povoden-Karadeniz @@ @@ Database La-Sr-Mn-Cr-O-(H). AMEND-ELEMENT VA VACUUM 0 0 0. AMEND-ELEMENT CR BCC_A2 5.) considered @@ @@ Quinary Ruddlesden popper phase is very tentative..65340E+02. STATE ATOMIC MASS H0 S0 AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1.5680E+03 5.1008E+01 0 0.. first version: Feb2006 by Povoden. @@ @@ -------------------------------------------------------------------@@ 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 .35429E+01.1996E+01 4.5999E+01 4.6651E+03 5.Appendix La-Sr-Mn-Cr-O-(H) oxide database @@ LA-SR-Mn-CR-O-(H) oxide. AMEND-ELEMENT MN CBCC_A12 5..2008E+01..
0*T*LN(T)-2.059572*T-23.00734768*T**2 +69827.15 -8856.251266E-3*T**2 +1.0905432*T*LN(T)-3. 3000 N @@ Mn. fcc ENTER-SYMBO FUNCTION GHSERSR 298.67477E-07*T**3-2055*T**(-1).413+59. 2180 Y -34869.06113*T-17. double hcp ENTER-SYMBO FUNCTION GHSERLA 298. bcc ENTER-SYMBO FUNCTION GHSERCR 298.284604*T-26. 820 Y -13380.15 -7532.15 -7968.84189E-07*T**3+850134*T**(-1).001295165*T**2.3088*T*LN(T). (1/2 O2) ENTER-SYMBO FUNCTION GHSEROO 298.196104*T-30.47721E-06*T**3+139250*T**(-1).905*T*LN(T)-4.18*T-50.390071*T-34.102+153.4582*T*LN(T)-0.1*T**(-1).27966+130.15 -3480.6184604E-07*T**3-38364.8742*T**(-1).403+120.1659411*T*LN(T)-.183879*T-23. Dinsdale 1991 @@ La.2648*T-48*T*LN(T)+1.5028601*T-11. 4000 N @@ Sr. cbcca12 ENTER-SYMBO FUNCTION GHSERMN 298.88526E+32*T**(-9).367+107.008371705*T**2 +6.1355068*T*LN(T)-0.34*T*LN(T)-.41+312.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.872255-25.908*t*LN(T)+0. 2000 Y -15608.8932E-07*T**3-399448*T**(-1).61225E-3*T**2 -1.94+157. 550 Y -3381.005098873*T**2 +6.00189435*T**2 -1.344+344.882+181.656847E30*T**(-9). 1519 Y -28733. 6000 N @@ O1. 2000 N @@ Cr.48*T-26. 1000 Y 173 .15 -8115.
.. 3300 Y -13986.97E-03*T**2 +1. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3D 298.78055555E-09*T**3+262904.96393E+05+5.02477557E+05+2...728+31. @@ @@ MN2O3-FUNCTION...80284521E-03*T**2+6.56*T*LN(T)-0.45091278E+05+3.9664*T-120.15 43192-18.. MN1O2 ENTER-SYMBO FUNCTION GMN1O2 298. @@ ESKOLAITE.86138663E+05*T**(-1)..76015+12.74079033E-02*T**2+9.0822E+05*T**(-1). 6000 N @@-----------------------------------------------------------@@ Binary oxides.68352649E+01*T*LN(T) -3. @@ Mn-oxides...Appendix -6568..15 -1.. Grundy 2006 ENTER-SYMBO FUNCTION GMN2O3 298..15 32350-13.25243E-04*T**2 +1.86138663E+05*T**(-1).9579637E-04*T**2 +6.9536*T*LN(T)-4.. @@ Cr-O oxides. MNO ENTER-SYMBO FUNCTION GMN1O1 298.15 +108305+GCR2O3+0.15 -4..15 -5..15 -607870+268.66000166*T-16. Povoden 2005 @@ METASTABLE CRO ENTER-SYMBO FUNCTION GCR1O1 298.15 +0. Risold 1996 @@ SrO ENTER-SYMBO FUNCTION GSROSOL 298..259625*T-18.8*T*LN(T)-4.629*T*LN(T)-0.43703676E+06+8. @@ BETA-HAUSMANNITE. Grundy 2003 @@ MANGANOSITE..8138015*T*LN(T)-5.15 -1833257+692.. optimized @@ La-oxides. @@ SrO2 ENTER-SYMBO FUNCTION GSRO2SOL 298..85001409E-03*T**2+2.9*T-47. Cr2O3 ENTER-SYMBO FUNCTION GCR2O3 298. @@ Sr-oxides.6846E+02*T-9....76*T.2856E+02*T-119.. MODIFIED.00307*T**2 +190000*T**(-1).95379396E+02*T-6. @@ PYROLYSITE.12922234E+05*T**(-1).05E+06*T**(-1).5*GHSEROO+255269-53.52766201E+01*T*LN(T) -7. BETA-MN3O4 (CUBIC) ENTER-SYMBO FUNCTION GCMN3O4 298.5*GHSEROO+280045-93.164542E+06+7.056E-02*T**2 +6. ENTER-SYMBO FUNCTION GLA2O3X 298.911E+01*T*LN(T)-2.89567858E+02*T-1... ENTER-SYMBO FUNCTION GLA2O3H 298. @@ -------------------------------------------------------------- 174 .66666666667*GHSERCR. @@ ALPHA-HAUSMANNITE.41618912E+06+8..5*GCR2O3-0.82*T..0721E-08*T**3+4383200*T**(-1).....006854*T**2 +808000*T**(-1)-1E7*T**(-2). ALPHA-MN3O4 (DISTORTED) ENTER-SYMBO FUNCTION GTMN3O4 298..64955386E+05*T**(-1).986*T+GLA2O3D.54747566E+02*T*LN(T) -1.15 -9.74079033E-02*T**2+9.15 +GSROSOL+GHSEROO-43740+70*T.778*T**(-1).59355626E+02*T-4...15 +1.. @@ reduced neutral endmember of CR2O3 ENTER-SYMBO FUNCTION GCRO0 298.5*GCR2O3-0....75120338E+02*T-1. @@ CR-SPINEL CR3O4 ENTER-SYMBO FUNCTION GCR3O4 298.15 -1..555*T+GLA2O3D..15 -1..54747566E+02*T*LN(T) -1.
.5*GHSEROO-540404-9.... ENTER-SYMBO FUNCTION GSM3OZ 298. ENTER-SYMBO FUNCTION GL3O_RP1 298. @@ Sr7Mn4O1 175 .5*GCR2O3+9. @@ RP1 ENTER-SYMBO FUNCTION GS4O_RP1 298.15 GLA2O3D+1.. ENTER-SYMBO FUNCTION SRX_ALPH 298...15 +GSROSOL+GLA2O3D+GMN2O3-137400....5E+04. optimized (except perovskite functions) @@ @@ Functions of the La-Sr-O system.15 +GSROSOL+0..55*T... @@ LA2CR3O12 ENTER-SYMBO FUNCTION GLA2CR3 298.15 0...... @@ intermediate La-chromates @@ LA16 @@ ENTER-SYMBO FUNCTION GLA16 298.15 @@ 3.15 @@ 8*GLA2O3D+3.14*T. Grundy et al.5*GLA2O3D+0.5*GCR2O3+4.15 +GSROSOL+0..11300000E+05.. @@ RP2 ENTER-SYMBO FUNCTION GS4O_RP2 298...79100000E+03..15 +GMN2O3+GSM3_HEX-2.. ENTER-SYMBO FUNCTION SRH_ALPH 298. @@ @@ Functions of the Sr-Mn-O system.15 +2*GSROSOL+2. 2005 ENTER-SYMBO FUNCTION GL2MNO4 298.....15 +4*GSROSOL+3*GMN1O2-3...15 +GLA2O3D+2. ENTER-SYMBO FUNCTION RE_ALPHA 298. @@ LA7 @@ ENTER-SYMBO FUNCTION GLA7 298..71704891E+01*T.15 0.73000000E+03 -1. Povoden 2008 @@ LA2CRO6 ENTER-SYMBO FUNCTION GLA2CRO6 298.5*GHSEROO-73045-4....15 +3*GSROSOL+2*GMN1O2-8.15 GLA2O3D+0...99100000E+04-90*T. Grundy 2004 @@ HEX Phase ENTER-SYMBO FUNCTION GSM4_HEX 298.26029731E+04-3..158E+04.. @@ SrMn3Oz as SrMnO3_Mn2O3 ENTER-SYMBO FUNCTION GSM4OZ 298. Grundy 2004 ENTER-SYMBO FUNCTION SR_ALPHA 298.5E+04.32830000E+05.70000000E+01*T..15 +2*GSROSOL+2. @@ @@ Functions of the La-Cr-O system.15 +GLA2O3D+GMN1O1+6...19200000E+04.5*GHSEROO-154101-2... ENTER-SYMBO FUNCTION GSM3_HEX 298..5E+04..5*GCR2O3+1.5*GMN2O3-7. ENTER-SYMBO FUNCTION RE_BETA 298. ENTER-SYMBO FUNCTION GL3O_RP2 298..15 +GMN2O3+GSM4_HEX-8... ENTER-SYMBO FUNCTION LA_BETA 298..5*GLA2O3D+GCR2O3+2.....15 +2*GSROSOL+2...78500000E+05..5*GMN2O3-68300.15 +2*GSROSOL+GMN1O2-1. @@ @@ Functions of the La-Mn-O system. @@ RP3 ENTER-SYMBO FUNCTION GSM4_RP3 298...Appendix @@ Ternary oxides..15 +GSROSOL+GMN1O2-1..799*T.5*GHSEROO-371557+205*T.
.15 +0.66666667*GSROSOL+GCR2O3+2.6*T.....15 +GSROSOL+GCR2O3+3*GHSEROO-325047+196*T.5*GHSEROO-273771 +131.5*GMN2O3-63367+51.44550000E+04 176 .19*T*LN(T) +232934*T**(-1)-3429+4.5*GCR2O3+0.15 2*GSROSOL+0.5*GLA2O3D+0.15 +GSROSOL+0.3+61...5*GHSEROO. Povoden 2008 @@ SRCR2O4 ENTER-SYMBO FUNCTION GSC2O4 298.. @@ ENTER-SYMBO FUNCTION GL3OL 298..15 0. ENTER-SYMBO FUNCTION GL4O 298.5*GLA2O3D+0.5*GLA2O3D+0.15 +0..5*GCR2O3+0.15 +7*GSROSOL+4*GMN1O2-6...Appendix ENTER-SYMBO FUNCTION GS7M4 298. ENTER-SYMBO FUNCTION GLCR3O_RP1 298..15 +2*GSROSOL+0. ENTER-SYMBO FUNCTION GMS3O 298....15 +GSROSOL+GCR2O3+98000-95.15 +GSROSOL+0.... ENTER-SYMBO FUNCTION GL2O 298.72*t.15 0.15 +0. @@ @@ Functions of the Sr-Cr-O system.77*T-7.. @@ SR3CR2O8 ENTER-SYMBO FUNCTION GS3C2O8 298. @@ SR2CRO4 ENTER-SYMBO FUNCTION GS2CO4 298.12450000E+05+50*T.5*GMN2O3-63367+51.5*GLA2O3D+GMN1O1+27672.19*T*LN(T) +232934*T**(-1)+400-0. Povoden 2008 @@ Ruddlesden Popper phase ENTER-SYMBO FUNCTION GREFRP 298....69*T. @@ SRCR2O7 ENTER-SYMBO FUNCTION GSC2O7 298... ENTER-SYMBO FUNCTION GVVV 298... @@ ENTER-SYMBO FUNCTION GL3OR 298.333333*GLA2O3D+GMN1O2-53760.666666667*GCR3O4+. @@ TETRAGONALLY DISTORTED SPINEL ENTER-SYMBO FUNCTION GTSPINEL 298.75*GMN1O2-91857+20.77*T-7.....15 +GLACRO3+GSROSOL+7000-25*t.19*T*LN(T) +232934*T**(-1).5*GHSEROO-145000+50*T.666666667*GCR3O4+..33333333334*GTMN3O4-200942+75.15 +0.5*GLA2O3D+0.. @@ ---------------------------------------------------------------@@ Perovskite functions @@ Grundy 2005 @@ Charge compensated by Mn+4 (correct) ENTER-SYMBO FUNCTION GL3O 298. @@ @@ Functions of the Mn-Cr-O system..15 +6*GL2O+4*GL4O+3*GV4O-12*GL3O-254212.31*T. ENTER-SYMBO FUNCTION GV4O 298.... Povoden 2005 @@ CUBIC SPINEL ENTER-SYMBO FUNCTION GSPINEL 298.. @@ SRCRO4 ENTER-SYMBO FUNCTION GSCO4 298.15 +2.5*T.15 +0..77*T-7.4*t.......73000000E+03-1...5*GMN2O3-63367+51.. @@ @@ Functions of the La-Sr-Cr-O oxide system.333333333333*GHSEROO -508507+219*T.15 +0.33333333334*GCMN3O4-210795...5*GMN2O3-7..5*GCR2O3+1.1*T.
5*GCR2O3+11.15 +GHSERMN+17859. ENTER-SYMBO FUNCTION ANTI 298.908*T*LN(T)+.15 +5332.616317*T-50*T*LN(T).018431*T-34....463*T*LN(T)..5*GLA2O3D+0..2386*T+135166-88..15 +15483.Appendix -1.15 0.15 GSROSOL+0.5*GCR2O3+0...15 +GSROSOL+GMN1O2-1. @@ (LaSr)CrO3+/-delta-Perovskite @@ Reference SrCrVa3 ENTER-SYMBO FUNCTION GS4V 298.91-12.51-13.38*T-0. @@ Reciprocals: all 0!!!!! @@ @@ Povoden 2008 @@ LaCrO3-PEROVSKITE ENTER-SYMBO FUNCTION GLACRO3 298. 1134 Y -3942.41929E-21*T**7.406219*T-39. ENTER-SYMBO FUNCTION GLACR4O 298.93775E-06*T**3-133541*T**(-1). 2180 Y -16459. 4000 N @@ Sr ENTER-SYMBO FUNCTION GSRLIQ 298.3088*T*LN(T)...5*GCR2O3+0. 1050 Y -10855.6208*T-4.0188191*T*LN(T)-0.29+213.00189435*T**2 -1. ENTER-SYMBO FUNCTION GALACRO3 298..68*T* LN(T)...653+18.42*t.015+146.69000000E+00*T.118994*T-5.VA)O3 ENTER-SYMBO FUNCTION GN 298...059775*T-26.020171603*T**2 +2..11300000E+05+2..15 +547422.70000000E+01*T.23012*T-11.004+171.5*GCR2O3+0.37615E-21*T**7.52*t....15 0. 3000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.1840595E-2*T**2 +4.15 +GLACRO3-340+0.5*GHSEROO-291802-250*t.0668978*T*LN(T)-3.15 +GSROSOL+0.997-10.26500000E+04 -7.2288*T-1.5*GHSEROO+10222-55.5*GHSEROO.5*GHSEROO-200000. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.5*GCR2O3-2.... 1519 Y +GHSERMN+18739..656847E30*T**(-9).. @@ Functions for defect chemistry ENTER-SYMBO FUNCTION GVCR4O 298.15 0. 3000 N @@ Mn ENTER-SYMBO FUNCTION GMN_L 298..5*GCR2O3-73591+2.33333*GLA2O3D+.47721E-06*T**3+139250*T**(-1)+2.981237E-06*T**3-265559*T**(-1).. @@ ---------------------------------------------------------------------@@ LIQUID FUNCTIONS @@ ---------------------------------------------------------------------@@ Liquid metal functions. 6000 N @@ --------------------------------------------------------------------- 177 ..984+335. @@ Function for neutral endmember SrCrO3 ENTER-SYMBO FUNCTION GS4O 298.15 +2194..15 GSROSOL+0.. ENTER-SYMBO FUNCTION GMS4O 298. @@ Function for neutral endmember SR(CR+3.63*t.
00119977*T**2 -1..3+37.59563*T-186.14296167E-05*T**3+978019*T**(-1).083*T-30.001513089*T**2 -4. Class: 4 @@ SGTE=scientific group thermodata Europe @@ ENTER-SYMBO FUNCTION F7491T 298.9+142414.. Risold ENTER-SYMBO FUNCTION GSROLIQ 298.224944*T-121.45*T-22596.928-44..C.35563E+08*T**(-1).0063*T**2 +31300*T**(-1)+9. 178 .555*T*LN(T)+0.00148*T**2 +873600*T**(-1)+1.504926*T**2+4.6220*T.2897*T*LN(T)-.15 +2*GMN1O1+GHSEROO-6..74749*T*LN(T)+.9664*T-120. 4000 Y +307209..15*T**(-1).869-31.69E-7*T**3. Grundy ENTER-SYMBO FUNCTION GMN1O1_L 298. optimized @@ liquid La2O3. REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCR1O1_G 298.48744*T*LN(T)-.36083*T* LN(T) +7. 600 Y -331037.135*T**(-1).8788-3288.49525609E+04+4.A..237405*T+14. source: Thermocenter of russian academy @@ of science (T.C. 10000 N @@ CR1O1 Gas.1074654*T-19.15 -1833257+692.. 601 N @@ -----------------------------------------------------------------------@@ GAS FUNCTIONS @@ --------------------CHROMIUM GAS---------------------------------------@@ CR Gas: SGTE v 3.00607059*T**2 +9.629*T*LN(T)-0.1304*T*LN(T) -. 8400 Y -403765. from T..588679E-07*T**3+10285. 1100 Y +393886.253215E-04*T**2-1.15 0.63356E+08*T**(-1).5*GCR2O3-0.15 +173449.708+805.1684007*T-39.62+32.4-33.5329*T*LN(T)+.Appendix @@ Liquid oxide functions.18729*T+495.00631160667*T**3+5.006854*T**2 +808000*T**(-1)-1E7*T**(-2)+141329-56. @@ liquid SrO..502-414. 900 Y +170853.15 +176483.41*T*LN(T).31437957E+01*T. 1000 Y +167489.. Povoden ENTER-SYMBO FUNCTION GCR1O1_L 298. ENTER-SYMBO FUNCTION GMN2O3_L 298..06284295E+01*T.331-31.96003*T*LN(T)+.671+1078.15 GCR2O3+439078-169*T.5567E-7*T**3.36845867E-08*T**3+6.52515733E-07*T**3+682877*T**(-1).15 +390765.S..31*T-40.A.15 GMN1O1+4. Class: 4 ENTER-SYMBO FUNCTION GH2O_L 298.722975E-07*T**3-64209900*T**(-1).5*GHSEROO+339673-121...39465890E+04-2.003139382*T**2 -1.15 -566346+449*T-73.9513659*T-30..282+741. @@------------------------------------------------------------------@@ LIQUID WATER.178604*T-117.917665E-05*T**3-18523425*T**(-1). 500 Y -62418. 6000 N @@ CR1O1 Gas (SGTE 1998.097*T*LN(T)-0. @@ liquid Mn oxides. @@ liquid Cr oxides.2320948*T**2-9.23648333E-07*T**3-722515*T**(-1).229905E-07*T**3+35263.008463125*T**2 +1.1*T*LN(T)...S Class: 5) ENTER-SYMBO FUNCTION F7705T 298.0 (1998). 540 Y -8528143. from T. ENTER-SYMBO FUNCTION GCR2O3_L 298.R.5192158*T-21.48508*T**2-.15 -332319.A..8669*T*LN(T) +.R.4*T.C.R.S). Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3LIQ 298.19*T*LN(T) +27.
45*T**(-1).2001*T*LN(T)-.4437*T*LN(T)-. 1000 Y +180. 6000 N @@ H Gas (JANAF 1982.526*T*LN(T)-0.A.2687055E-04*T**2 -1.33E-9*T**3.0155*T**2 +245800*T**(-1)+2.00584168*T**2 +3.21188*T*LN(T)-5.84857*T*LN(T)-0.43044*T*LN(T) -.59*T-39. 2800 Y +409416.14618667E-07*T**3-1280036*T**(-1).555105E-07*T**3-2.A.R.35707*T*LN(T)+0.3956+710.13383*T-764.5*T**(-1). 1000 Y -354716.8612582*T-21.944-37.44768833E-06*T**3-2. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O2_G 298.0922361*T**2 +4.01667E-8*T**3.9608*T*LN(T)+.3120249*T-32.1894682*T-31.879+30.15 +211801. reassessed by Ming Chen 2006.1284109*T**2 +5.1699975E+08*T**(-1).494-20.15 -250423.23131283E-08*T**3-42897.383-1950.043+890. 2950 Y +252301.5*T**(-1).15 -341231.15 +130696. 3000 N @@-------------------OXYGEN GAS------------------------------------@@ O Gas (JANAF 1982.0027589925*T**2 -7.623+176. reassessment Chen 2006.01283575*T**2 -3. 3500 Y -1866338.46390667E-07*T**3+56582. 700 Y +114760.00623741*T**2-6.S Class: 4) ENTER-SYMBO FUNCTION F10963T 298.423-52.5273873*T-31.45470312*T-28.3696*T*LN(T)+.1304835E+08*T**(-1).434+4.00012*T**2 +932050*T**(-1)-8. 4900 Y +97590.09482*T-134.14281783E-08*T**3+3561002.306855E-06*T**3-21589870*T**(-1). based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O3_G 298.10286*T*LN(T)+.0847281*T-17.1663+92.6+6101.626737*T-60.99+130.01555*T*LN(T)+1.R. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION F13349T 298.621+24.78+10.40916*T*LN(T) -.696*T*LN(T)-0.15 +243206.C.075-3566. 1300 Y +49468.0010728235*T**2 +1.4989821*T-20. 1000 Y -118120+123.09852775*T**2 -2.05082*T*LN(T)-0.70834*T+223.3*T**(-1).15 -9522.58118*T*LN(T)-.09*T**(-1).5*T**(-1). 6000 N @@ H2O1 Gas (SGTE 1998. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION HGAS 298.81*T-56.05535833E-07*T**3+1246309.798361*T-149.45*T**(-1).6128262*T-17.9096643*T-27.60539333E-06*T**3+99530.610855E+08*T**(-1). from T. 2100 Y +866367.80563*T+421. 3000 N @@ CR1O3 Gas.97393+78. from T. 6000 N @@ -------------O-H GAS----------------------------------@@ H2 Gas (JANAF THERMOCHEMICAL TABLES SGTE) ENTER-SYMBO FUNCTION H2GAS 298.61*T-57. 6000 N @@ O3 Gas (SGTE 1998.0216*T**2 +428900*T**(-1)+3.43E-6*T**3.039707355*T**2 -4.2*T*LN(T)-.15 -109942.569*T*LN(T)-0.02763076*T**2 +4.108664-15.10457667E-06*T**3+12362250*T**(-1). 1100 Y -256145. 2800 Y 179 .8435*T*LN(T)+.S Class: 4) ENTER-SYMBO FUNCTION F14021T 298.01526167E-08*T**3-64163.64520667E-09*T**3-3973170. 2100 Y -18840.00016*T**2 +1814700*T**(-1)+7.C.09+299.413565E-04*T**2 +7.78611*T*LN(T).59784667E-06*T**3+9.Appendix 3000 N @@ CR1O2 Gas.17486667E-07*T**3+1572175*T**(-1).007055445*T**2+3.00206456*T**2 -5.89*T-82.401E-6*T**3.
724*T*LN(T) -0.971-37.326117*T-69.573855E-09*T**3+26048030*T**(-1).42189E-05*T**2-1.4391015E+08*T**(-1).6898+15.97699*T*LN(T) +.99164+54.A.12331E-04*T**2-6. combined assessment Chen 2006 @@ based on Ebbinghaus 1995 @@ and from Povoden based on Kim and Belton 1974 @@ (data suggested by Opila 2007) ENTER-SYMBO FUNCTION GCRH1O3_G 298.259882*T-92.551*T*LN(T) +0.05*T**(-1).94271*T*LN(T) -.799205E-07*T**3-25503.4077*T*LN(T) +.52*T-74.765625E+08*T**(-1).24542*T*LN(T) +. 3600 Y -67875.C.0016703495*T**2-1. 700 Y -156470.927*T*LN(T) -0.77872*T*LN(T) +2.15 -147258. 20000 N @@ H1O2 Gas (SGTE 1998. 3000 N @@ CR(OH)2 Gas. 8600 Y +41016.9*T*LN(T) -.47*T-96. 3000 N @@ CRO(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O2_G 298.418+116.953+370.42186*T*LN(T) -. 1500 N @@-------------------CR-O-H GAS---------------------------------------@@ CR(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O1_G 298.0007*T**2+243850*T**(-1)-9.94216*T*LN(T) -.5*T**(-1).87*T-46. 1000 Y 180 .7343256*T-24.52+180.32+190. 3000 N @@ CRO2(OH) Gas.191295*T-50.S Class: 1) ENTER-SYMBO FUNCTION F10666T 298. 18000 Y -165728.213599E-04*T**2-1.645643*T-59.R.A.771+239.47539017E-08*T**3+1.053*T*LN(T) -0. 1000 Y 56684+136.257*T*LN(T) -0.018507875*T**2+2.8961+275. 8400 Y -489068.15 -274384.5*T**(-1).002*T**2+185600*T**(-1)-1.1173*T*LN(T) +6. assessment Chen 2006.00501027*T**2+2.30298483E-10*T**3-8.686636*T-25. 20000 N @@ H1O1 Gas (SGTE 1998.75E-7*T**3.7*T-72. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O2_G 298.277-65.65*T**(-1).505+120.135E-7*T**3.9096451*T-29.0031*T**2+266750*T**(-1)-9.15 -351288.34404917E-07*T**3+116618.15 -497678+273.406716*T-68.0146*T**2+715900*T**(-1)+2. 1000 Y -492562+351.36297E-06*T**3-29469.659505E-06*T**3+65357. 6000 N @@ H2O2 Gas (JANAF SECOND EDIT SGTE) ENTER-SYMBO FUNCTION F10983T 298.122915E-07*T**3+925845*T**(-1).1931655E+08*T**(-1).0783-20.29733833E-07*T**3+684985.0018*T**2+1338300*T**(-1)+9.15 +30698.R.C.2016233*T-40.036948065*T**2+6.Appendix -268423. from T.882+553.1497212*T-26.91863E-08*T**3-6415210*T**(-1). from T.0023107985*T**2+5.82*T**(-1).53*T-57.003069987*T**2+6.15 +68260+52.001713168*T**2-6.2921095E-09*T**3-4.2E-7*T**3.0018*T**2+2218000*T**(-1)-2. 800 Y -7932.0019361405*T**2-1.690197*T-42.775*T*LN(T) -.334E-8*T**3.0015*T**2+938850*T**(-1)+5.51E-7*T**3.292415E+08*T**(-1). 1000 Y -276268. +326722.5127-12.32333233E-08*T**3+1.39E-6*T**3.15E-8*T**3.175*T*LN(T) +0.97594167E-08*T**3+2458230.4+195.S Class: 4) ENTER-SYMBO FUNCTION F10729T 298.003149545*T**2+1.45435*T*LN(T) -.15 +1075.007931945*T**2+4.2768*T*LN(T) +6.77*T-83.86*T-75. 3000 Y +31735. 18000 Y -154907.0792741*T-24.65*T**(-1).10636*T*LN(T) -.64106-55.96842*T*LN(T) -.242048*T-24.
1000 Y -582354+394.45*T-229.026-56. 3000 N @@ CRO2(OH)2 Gas.6022*T*LN(T) -. 3000 N @@ CRO(OH)2 Gas. 1000 Y -997791.97*T-79.7+464.378E-6*T**3.37*T-125. 1000 Y -806262+567*T-131.004*T**2+1. assessment Chen 2006.006*T**2+498450*T**(-1)-2.6*T-109. assessment Chen 2006.874*T*LN(T) -0.004*T**2+785800*T**(-1)-2.8867E-7*T**3.9958E-06*T**3.16*T*LN(T) -0. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION G_CRH4O5 298.973194012145*T-158.65*T*LN(T) -0. 3000 N @@ CRO(OH)3 Gas.5*T-163*T*LN(T) +0.349852E-04*T**2-1. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH4O4_G 298. assessment Chen 2006.0086*T**2+3058600*T**(-1)+4.00056*T**2+663150*T**(-1)-5.35E-7*T**3.545E-7*T**3. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O3_G 298. 1000 Y +421602.6+712.8+813.004*T**2+2094950*T**(-1)+1.93E-7*T**3. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH5O5_G 298.R.76+600.0065*T**2+2669300*T**(-1)+3.4+51.77E-6*T**3.37019*T*LN(T) -.819*T*LN(T) -0.01*T**2+4151100*T**(-1)+5.15 -787712+400*T-107. combined assessment Chen 2006 @@ based on Ebbinghaus 1995 @@ and from Povoden-Karadeniz based on Opila 2007 ENTER-SYMBO FUNCTION GCRH2O4_G 298. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH6O6_G 298.15 +432449.014*T**2+1.97*T-180.0096*T**2+4. 1000 Y -656538+448.6*T-162.15 -578683+391.455*T*LN(T) -0.1+867. 3000 N @@ CRH1 Gas (SGTE 1998.2*T*LN(T) -0.15 -978211. 5500 Y +1270342. 1000 Y -861477. assessment Chen 2006.18913267E-06*T**3-77266.002*T*LN(T) -0. assessment Chen 2006.9*T-190.86*T*LN(T) -0.86+694. 3000 N @@ CR(OH)5 Gas.3*T-121. 3000 N @@ CR(OH)6 Gas.019*T**2+513600*T**(-1)+1.2*T-109.0099*T**2+770750*T**(-1)+5. 3500 Y +587860. 1000 Y -909897.15 -851590.05*T**(-1).5*T*LN(T) +0.098*T*LN(T) -0. 1000 Y -1053466+1080. assessment Chen 2006 based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O3_G 298.05+820.9391*T*LN(T) 181 .007723995*T**2+7.15 -650064. 3000 N @@ CR(OH)3 Gas.S Class: 4) ENTER-SYMBO FUNCTION F7586T 298. 1000 Y -991549. 3000 N @@ CR(OH)4 Gas.91E-7*T**3.99681*T*LN(T) +3.008*T**2+840600*T**(-1)-1.15 -1029121.386334*T-22.12+967.0054*T**2+1023500*T**(-1)-1.67833E-07*T**3.C.713-424.9865812*T-37.524*T*LN(T) -0.8967E-07*T**3+1688150*T**(-1).3*T-137.60191*T+219.3E-7*T**3.014*T**2+6008850*T**(-1)+7.006*T**2+2525450*T**(-1)+2.41*T*LN(T) -0.34E-7*T**3.00994042*T**2+1. 3000 N @@ CRO(OH)4 Gas.89*T-216.15 -902751.15 -976204+672.457*T*LN(T) -0.Appendix -359644+228.355E-6*T**3.99444833E-08*T**3-86705500*T**(-1).049*T*LN(T) -0. from T.6*T-195.36214*T+18.525*T*LN(T) -0.46-2142. assessment Chen 2006.945E-07*T**3+4671850*T**(-1). based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O4_G 298.35E-07*T**3+665100*T**(-1).83+534.13133917E-07*T**3+1368173*T**(-1).0049*T**2+3311450*T**(-1)+2.7467E-7*T**3.A.25*T*LN(T) -0.74*T-146.11767E-6*T**3.
..LA+3.0)....0).LA+3:O-2.. +SR_ALPHA+GHSEROO +15.0)........LA+3.. 6000 N @@ @@ @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Binary oxides @@ @@ Sr oxides.. @@ @@ Mn oxides.87691*T... 2 2 3 LA+3 SR+2.LA+3:O-2.SR+2:O-2.81E+01*T..15 +193600-78. ENTER-PAR G(LA2O3SS.. 1 SRO2.. ENTER-PAR L(LA2O3_HEXSS.15 +193600-78... O-2 VA..87691*T.SR+2:VA. Chen @@ ENTER-PHASE LA2O3SS.277845E-07*T**3-5. ENTER-PAR G(LA2O3_HEXSS.LA+3.. ENTER-PAR L(LA2O3SS..0) 298..SR+2:O-2. Risold @@ ENTER-PHASE SRO2.15 +GLA2O3D. +GLA2O3H-3*GHSEROO.. +GLAO-GHSEROO....0).. +SRH_ALPH-2*GHSEROO +15...0).0).LA+3.SR+2:O-2... ENTER-PAR L(LA2O3_CUBSS..... ENTER-PAR G(BETA. +SR_ALPHA+416100+GHSEROO -0. O...1*T. ENTER-PAR G(LA2O3_HEXSS.... ENTER-PAR G(SRO2... ENTER-PAR G(LA2O3_CUBSS. Grundy @@ @@ STOICHIOMETRIC PYROLYSITE..0) 298.LA+2:VA. ENTER-PAR L(LA2O3_CUBSS.... 2 2 3 LA+3 SR+2.. @@ ---------------------------------------------------------------------@@ Ternary oxides @@ @@ LA-SR-O.1*T..LA+3....SR+2:VA.15 +GSRO2SOL.15 +GLAO. ENTER-PAR G(LA2O3_CUBSS. ENTER-PAR G(LA2O3SS.. @@ ENTER-PHASE LA2O3_CUBSS. +GLA2O3X-3*GHSEROO. ENTER-PAR L(LA2O3_CUBSS. MN1O2 ENTER-PHASE MN1O2.0) 298. Grundy..LA+3:VA.0) 298. +SRX_ALPH+GHSEROO+15.0).1) 298. ENTER-PAR G(MN1O2.LA+3.SR+2:O-2..SR+2:VA.LA+3.LA+3....SR+2:O-2.. +SR_ALPHA-2*GHSEROO +15.. 2 2 3 LA+3 SR+2.. +GLA2O3H. O-2 VA.... 2 1 2 MN..87691*T..0) 298..SR+2:VA...SR+2:O-2. 2 2 3 LA+2 LA+3 SR+2...33333333*RE_BETA +15. @@ ENTER-PHASE LA2O3_HEXSS..149E+05-7.....0).0) 298.. +GLA2O3D-3*GHSEROO.SR+2:VA. +SRH_ALPH+GHSEROO+15.... 182 .15 +168700-78.LA+3:VA. ENTER-PAR G(LA2O3SS.0) 298. ENTER-PAR G(LA2O3_HEXSS.87691*T.20451E+08*T**(-1). ENTER-PAR G(LA2O3_CUBSS..SRO2. +LA_BETA..... ENTER-PAR G(LA2O3_HEXSS.0) 298.0).... ENTER-PAR G(LA2O3SS.LA+2:O-2.. ENTER-PAR G(LA2O3_CUBSS..87691*T.034109635*T**2+7.0) 298...15 -20000.0) 298...1) 298.0). ENTER-PAR G(BETA..0).15 +GMN1O2.MN:O.Appendix -.15 -20000....15 +168700-78.... @@ La4SrO7 as BETA phase ENTER-PHASE BETA.. ENTER-PAR L(LA2O3_HEXSS. +GLA2O3X.. O-2 VA.0).81E+01*T. ENTER-PAR G(LA2O3SS. +SRX_ALPH2*GHSEROO+15..87691*T..SR+2:O-2. ENTER-PAR L(LA2O3_CUBSS.. ENTER-PAR L(LA2O3SS...LA+3:VA.. ENTER-PAR G(LA2O3SS...149E+05-7.0).87691*T..LA+3:O-2. +LA_BETA-3*GHSEROO.. O-2 VA.SR+2:O-2..15 +2.1*T.LA+3:O-2..SR+2:VA.15 +2.SR+2:VA.0).LA+3:VA. ENTER-PAR G(BETA...0).1*T.
... ENTER-PAR G(SRO. ENTER-PAR G(LA4SR3O9.. @@ STOICHIOMETRIC LA7 @@ ENTER-PHASE LA7.SR+2:MN+3:VA.0) 298..... O-2 VA.. 3 1 1 3 SR+2. O-2 VA... ENTER-PAR G(SRMNO3_HEX... ENTER-PAR G(SRMN3O6. 3 4 3 10 SR+2.... O-2. @@ ENTER-PAR G(LA7...SR+2:MN+4:O-2.0).. +GSROSOL.... MN+4......23859*T..0) 298... @@ @@ LA-CR-O. 3 7 2 16 LA.15 +GLMN2O5.. 2 1 1 LA+3 SR+2 VA..0).... @@ ENTER-PHASE SRMNO3_HEX..0). MN+3. O-2........SR+2:VA.0) 298.0). @@ @@ SR-MN-O. ENTER-PAR G(SRMNO3_HEX... MN+3 MN+4..0).. @@ ENTER-PHASE SR4MN3O10......SR+2:VA.75*T.15 +GLA2CRO6..SR+2:MN+4:O-2. ENTER-PAR G(SRMN3O6. ENTER-PAR G(L2MNO4.23859*T. ENTER-PAR G(SRMN3O6. 3 7 4 15 SR+2.. O.. 0.15 +GLA7. @@ ENTER-PAR G(LA16..0)... @@ @@ STOICHIOMETRIC LA2CR3O12 ENTER-PHASE LA2CR3.15 -121000-237.LA+3..0).. @@ intermediate La-chromates @@ STOICHIOMETRIC LA16 @@ ENTER-PHASE LA16.5*GHSEROO +11.LA+3:SR+2:O-2...SR+2:O-2. ENTER-PAR G(LA2CR3.... O-2.LA+3:O-2. +GSM3OZ+0. ENTER-PAR G(SRMN3O6.LA:CR:O.0) 298..0) 298. MN+3. @@ @@ LA-MN-O.. 5 1 2 3 1 3 SR+2.0) 298.... O-2.0).. @@ ENTER-PHASE SRMN3O6. +SR_ALPHA+416100-2*GHSEROO +0..15 -121000-237. CR+6. ENTER-PAR L(BETA.. Grundy @@ ENTER-PHASE SR7MN4O15..Appendix ENTER-PAR G(BETA. +GSM4OZ. 4 1 1 1 5 LA+3.23859*T. Stoichiometric ENTER-PHASE LA4SR3O9..VA:O-2. ENTER-PAR G(SR4MN3O10...5*GLA2O3D+113700.... MN+3 MN+4..5*GHSEROO +11..5*GHSEROO +11.SR+2:MN+3:O-2:MN+4:O-2. O. +GS7M4.0) 298. +GSM4OZ-3*GHSEROO..LA+3.0). ENTER-PAR G(SRO..0).LA+3:CR+6:O-2. 3 16 7 44 LA.... +GSM3_HEX+0. SR+2..LA+3:MN+3:MN+4:O-2....8*T. O-2.LA+3:CR+6:O-2..8*T.. ENTER-PAR G(LA2CRO6... ENTER-PAR L(BETA. MN+4..0)... 3 2 1 6 LA+3.... ENTER-PAR G(LMN2O5. +GSM4_RP3. @@ SrO Solid Solution ENTER-PHASE SRO. CR. +0... +GSM3_HEX-2. @@ La4Sr3O9.. O-2..15 +GLA2CR3. Povoden @@ @@ STOICHIOMETRIC LA2CRO6 ENTER-PHASE LA2CRO6.SR+2:MN+3:O-2:MN+4:VA.87691*T.... ENTER-PAR G(SRO. MN+4.0). +2*GLA2O3D+3*GSROSOL+229800 -136... O-2. CR.SR+2:O-2. O-2.. 3 2 3 12 LA+3.. CR+6. 183 ..SR+2:MN+3:O-2:MN+3:O-2..23859*T. 3 4 3 9 LA+3.5*GHSEROO +11.SR+2:MN+3:O-2..LA+3:MN+2:O-2.0).15 +GLA16.0) 298. @@ ENTER-PHASE LMN2O5. +GSM3OZ-2... O-2. 3 2 1 4 LA+3. Grundy @@ ENTER-PHASE L2MNO4..15 +GL2MNO4..66666667*RE_BETA+15. MN+2..LA:CR:O.. ENTER-PAR G(SR7MN4O15...SR+2:MN+3:O-2:MN+3:VA..
59.. Grundy. Povoden-K.CR+3:O-2:VA. 3 2 3 1 MN+3 CR+3. 3 2 1 4 SR+2.0) 298.Appendix ENTER-PAR G(SRMNO3_HEX. ENTER-PAR BMAGN(MN2O3.. O-2. ENTER-PAR BMAGN(MN2O3.0) 298.....15 +GMN2O3+GHSEROO +100000+15.15 +GSCO4.MN+3:O-2:VA.MN+3:O-2:O-2.. ENTER-PAR G(MN2O3.15 +GMN1O1..87691*T...0) 298..666667 2 8 SR.0) 298.MN+3:O-2. O-2.87691*T.. ENTER-PAR G(MN2O3. 3 1 2 7 SR+2... O-2 VA..0) 298..0) 298.0) 298. NONSTOICHIOMETRIC CR2O3 SOLID SOLUTION.. O-2 VA....SR+2:MN+4:O-2. ENTER-PAR G(MNO_HALIT. 3 1 2 4 SR+2.15 +3*GSROSOL+GMN2O3+GHSEROO...0)..65131533E+04... CR+6...21048766E+04...SR+2:CR+6:O-2.. 3 1 1 4 SR+2......28 ENTER-PAR TC(MN2O3.15 +0... @@ @@ SR-CR-O.VA:O-2.3. ENTER-PAR G(MN2O3. O-2..0) 298. ENTER-PAR G(MN2O3. ENTER-PAR G(RP2.. AMEND-PHASE MN2O3 MAGN. Povoden @@ @@ NONSTOICHIOMETRIC MANGANOSITE (MNO) SOLID SOLUTION. ENTER-PAR G(SCO4... ENTER-PAR G(MN2O3.....0) 298... 2 1 1 MN+2 MN+3 CR+3 VA...15 +GMN2O3-3*GHSEROO. O-2..15 +GCR2O3+3459.....87691*T.... MN+3 MN+4.15 +0. ENTER-PAR G(S3C2N..15 +308.MN+3:O-2:VA.SR+2:CR+3:O-2. @@ SR2CRO4 ENTER-PHASE S2CO4.0) 298.0) 298. @@ @@ ESKOLAITE.MN+3:O-2:VA.....0) 298. O-2..15 +GS3C2O8. Grundy modified it in LSM modeling ENTER-PHASE RP2. ENTER-PAR G(MNO_HALIT.15 +GSC2O4.0). CR+4. +GSM4_HEX-3*GHSEROO.. ENTER-PAR G(MNO_HALIT.. ENTER-PAR TC(MN2O3.15 +309.. @@ @@ SR2. ENTER-PAR G(S2CO4. @@ ENTER-PAR G(SC2O7.SR+2:SR+2:MN+4:O-2.. Povoden @@ @@ SRCR2O4 ENTER-PHASE SC2O4. SR+2..0) 298. +GSM4_HEX.. @@ @@ CR-MN-O..15 +GSC2O7.MN+3:O-2... doubtful phase @@ ENTER-PHASE SC2O7.CR+3:O-2:VA..0) 298. Povoden-Karadeniz) ENTER-PHASE MN2O3...15 +GMN1O1-21883.MN+3:VA:O-2.CR+3:O-2:O-2... O-2...0) 298... 3 2. @@ SRCRO4..15 -4..1853365*T.5213 -22..93845*T +71549.0) 298.. ENTER-PAR G(MNO_HALIT.15 +GCR2O3-3*GHSEROO.15 +GCR2O3+GHSEROO +100000+15.CR+3:O-2:VA..MN+3:O-2.1) 298.6. 4 1 2 2 7 SR+2.CR+3:VA:O-2.. ENTER-PAR L(MNO_HALIT.... ENTER-PAR G(SRMNO3_HEX.15 +GCR2O3-2*GHSEROO +100000+15.CR+3:VA:VA. ENTER-PAR G(SC2O4... CR+3..MN+2.MN+2:O-2.15 +GS4O_RP2. ENTER-PAR G(MN2O3.0) 298. ENTER-PAR G(MN2O3.67CR2O8 ENTER-PHASE S3C2N.15 +GS2CO4.SR+2:SR+2:MN+3:O-2. @@ @@ Mn2O3 (Compatible with C-Y2O3.5*GCR2O3-7.. ENTER-PHASE MNO_HALIT.0) 298....15 +3. CR+6..0) 298. @@ SRCR2O7... Grundy..CR+3:O-2.SR+2:MN+4:VA.0) 298.MN+3:VA:VA.0) 298.SR+2:CR+4:O-2.... CR..15 +GMN2O3-2*GHSEROO +100000+15.0) 298.. ENTER-PAR G(MN2O3.15 +4. .87691*T.. Chen... O..15 0.0) 298.. @@ @@ RP2.. ENTER-PAR G(RP2...SR+2:CR+6:O-2.15 +GMN2O3.0) 298..MN+2.SR:CR:O.. Povoden-Karadeniz ENTER-PHASE SCO4. Povoden-Karadeniz 184 . ENTER-PAR L(MNO_HALIT.
.MN+3:CR+3:O-2.... ENTER-PAR BMAGN(CR2O3.. ideal extensions from lower-order systems @@ @@ high temperature rhombohedral perovskite..0) 298.0) 298. +GMS3O+GL2O-GL3OR2*GHSEROO+22. AMEND-PHASE CR2O3 MAGN..0). ENTER-PAR TC(CR2O3....CR+2:VA:O-2.0) 298. Grundy @@ ENTER-PHASE LS3MN2O7.MN+2:MN+3:O-2.15 +3.SR+2:LA+3:MN+4:O-2..666666666667*GHSERCR -5. MN+3 CR+3. ENTER-PAR G(TMNCR2O4..0) 298..15 +GMN2O3+39503..47717*T.CR+2:CR+3:O-2.. @@ @@ CUBIC SPINEL.0).CR+2:VA:O-2.15 +GCR2O3.MN+3:VA:O-2.6.15 +GCRO0 +.15 +GTMN3O4.0) 298..0) 298.0) 298..Appendix ENTER-PHASE CR2O3...MN+3:VA:O-2.15 +3. ENTER-PAR BMAGN(CR2O3. CR+3 VA.15 +3*GSROSOL+GMN2O3 +GHSEROO. O-2.0) 298.. ENTER-PAR G(LS3MN2O7. 3 1 1 3 LA+3 SR+2 VA..MN+3:VA:O-2.. Povoden-Karadeniz ENTER-PHASE TMNCR2O4...0) 298..6. ENTER-PAR G(LS3MN2O7. O-2...15 +3.15 +GCR2O3+GHSERCR.2923*T..59. 3 1 2 4 MN+2 CR+2..... @@ DISTORTED_SPINEL.0) 298...0) 298..0) 298. Povoden-Karadeniz ENTER-PHASE RPEROV.0) 298.SR+2:SR+2:MN+3:O-2.... . ENTER-PAR G(CR2O3.59..0) 298.SR+2:LA+3:MN+3:O-2.15 +309..15 +308. ENTER-PAR TC(CR2O3. ENTER-PAR G(LS3MN2O7.15 +GL3O_RP2+GS4O_RP2 -3*GSROSOL -GMN2O3-GHSEROO-R_RP2..0) 298.CR+2:CR+3:O-2.CR+2:VA:O-2.. ENTER-PAR G(CR2O3..28 ENTER-PAR TC(CR2O3. 185 .. ENTER-PAR G(CR2O3.0) 298... @@ -----------------------------------------------------------------------@@ Quinary phases. @@ -----------------------------------------------------------------------@@ Quaternary oxides @@ @@ La-Sr-Mn-O. ENTER-PAR G(RPEROV....0). O-2.SR+2:SR+2:MN+4:O-2.SR+2:MN+3:O-2... Grundy.MN+2:CR+3:O-2.. MN+3 MN+4.. ENTER-PAR BMAGN(CR2O3.....15 +3.0) 298.MN+3:CR+3:O-2.23859*T.CR+3:VA:O-2....15 +GS4O_RP2... Povoden-Karadeniz ENTER-PHASE CMNCR2O4.15 +GL3O_RP2.6..... +GMS3O+GL2O-GL3OR+GHSEROO +22..SR+2:MN+2:VA. +GMS3O+0.. Grundy. ENTER-PAR G(CMNCR2O4..33333333334*GHSERCR -5.15 +308. 3 2 1 3 MN+3 CR+2 CR+3.15 +308..... 3 1 2 4 MN+2.CR+3:CR+3:O-2.MN+2:CR+3:O-2. ENTER-PAR G(RPEROV..15 +GMN2O3+GSERCR+39503... MN+2 MN+3 MN+4 CR+3 CR+4 VA. ENTER-PAR G(RPEROV.0) 298.0) 298..CR+3:CR+3:O-2....SR+2:MN+2:O-2. ENTER-PAR TC(CR2O3. O-2 VA.15 +GTSPINEL.. ENTER-PAR BMAGN(CR2O3...0) 298. ENTER-PAR G(CR2O3.6.0) 298. ENTER-PAR G(CMNCR2O4....0) 298. ENTER-PAR G(CR2O3.15 +GSPINEL.MN+2:MN+3:O-2.15 +GCMN3O4....CR+2:CR+3:O-2. 4 1 2 2 7 SR+2.0) 298.CR+3:CR+3:O-2. LA+3 SR+2.0) 298.. MN+3 CR+3. Grundy.0) 298.CR+2:CR+3:O-2... ENTER-PAR G(LS3MN2O7..CR+3:VA:O-2.0).15 +GCR3O4+GCMN3O4-GSPINEL.2923*T. ENTER-PAR TC(CR2O3.CR+3:VA:O-2.... ENTER-PAR G(CR2O3..15 +309.. ENTER-PAR G(CMNCR2O4..SR+2:MN+4:O-2. ENTER-PAR G(TMNCR2O4..MN+3:CR+3:O-2...15 +0.. O-2. ENTER-PAR BMAGN(CR2O3.5*GHSEROO+11... @@ ENTER-PAR G(RPEROV.0) 298...0) 298. ENTER-PAR TC(CR2O3...15 +GCRO0 -0. ENTER-PAR G(CMNCR2O4..15 +GCR3O4..CR+2:MN+3:O-2.. +GMS4O....47717*T.....15 +0.. ENTER-PAR BMAGN(CR2O3..15 +308.0) 298.
LA+3:MN+4:O-2..LA+3:CR+3:VA.0)..5*GVCR4O+0.5*GV4O -0.33333*GVVV -1.SR+2:CR+4:O-2. ENTER-PAR G(RPEROV. +GN-0..SR+2:MN+3:VA. +GS4O..41263*T..66667*GL4O+0. ENTER-PAR G(RPEROV. @@ Optimized interactions 186 .0)..35057*T. ENTER-PAR G(RPEROV.5*GHSEROO+11.5*GVVV-GL3OR -GHSEROO+12..0).5*GHSEROO-1..5*GV4O+0.5*GVVV -2*GLACR4O+1.. +GVVV.. ENTER-PAR G(RPEROV..0)... +GMS3O-2. G(RPEROV.0)..5*GHSEROO -1.SR+2:CR+3:VA. ENTER-PAR G(RPEROV..... +2*GV4O+0.5*GVCR4O+0.0).VA:CR+3:O-2.. +GL3OR+1. +2*GL4O-1...1666667*GS4O +0.0). ENTER-PAR G(RPEROV. GS4O-GN-0.....LA+3:CR+4:O-2. ENTER-PAR G(RPEROV..1666667*GS4O +0..0).3333*GVVV -1...SR+2:CR+4:VA..VA:CR+3:VA.5*GHSEROO+11. +GL2O+0. +GL2O-2..5*GV4O+0.166667*GVVV -3.. +GL3OR-3*GHSEROO.5*GV4O+0.166667*GVVV -0.. ENTER-PAR G(RPEROV.. +GL2O+1. +0....LA+3:MN+2:O-2..LA+3:CR+4:VA.VA:CR+4:O-2....LA+3:CR+3:O-2... +GLACRO3-3*GHSEROO.8333333*GS4O +0.SR+2:CR+3:O-2..0)...... ENTER-PAR G(RPEROV. +GLACRO3+1.5*GHSEROO+5. ENTER-PAR G(RPEROV..0). +GS4V. G(RPEROV. ENTER-PAR G(RPEROV.333*GLACR4O -2*GHSEROO+4...35057*T.0).0)...0)..33333*GL4O +GHSEROO+4. G(RPEROV..... +GMS4O-3*GHSEROO.. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.66667*GL4O+0.35056*T.. +GL3OR+1. GS4O+GLACRO3-GN-0.... G(RPEROV...0)..0).62121*T..SR+2:VA:O-2..VA:MN+3:VA..82596*T.5*GV4O -0.SR+2:MN+4:VA.41263*T.0).0)....VA:CR+4:VA.. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.16666667*GS4V+GLACRO3 -3*GHSEROO.. G(RPEROV..5*GVVV-2*GL4O +1.41263*T..2386*T. G(RPEROV.23859*T.0)..0).0). +2*GV4O+0.8333333*GS4V.5*GHSEROO +1.VA:MN+4:VA.VA:MN+2:VA.5*GVVV +2*GHSEROO+12... ENTER-PAR G(RPEROV.VA:MN+4:O-2.VA:VA:O-2..0).1666667*GS4O -0. +2*GL4O+0.5*GHSEROO+5.0).5*GVVV-2*GL4O -GHSEROO+9...VA:MN+3:O-2.62121*T.LA+3:MN+3:O-2...VA:VA:VA.. ENTER-PAR G(RPEROV...333*GL4O -2*GHSEROO+4.41263*T. ENTER-PAR G(RPEROV.2386*T.5*GV4O -1. +GL3OR. +GMS3O-GL3OR+2*GL4O -1.. ENTER-PAR G(RPEROV.5*GV4O+0. +2*GVCR4O+0.Appendix ENTER-PAR G(RPEROV..41263*T...3333*GVVV-1.LA+3:VA:O-2.41263*T. +GLACRO3+1..5*GVVV -2*GLACR4O-1.. ENTER-PAR G(RPEROV.76318*T..5*GHSEROO -1. ENTER-PAR G(RPEROV.....0)...76318*T.5*GV4O +0.0).5*GHSEROO+1... G(RPEROV..... ENTER-PAR G(RPEROV.16666667*GS4V.0).33333*GVVV-1.LA+3:MN+2:VA. +0..5*GV4O+0...0)...5*GVVV-2*GL4O -1.LA+3:MN+4:VA. ENTER-PAR G(RPEROV.5*GVVV +1.SR+2:VA:VA.0)..5*GHSEROO-1....35056*T.. +GMS3O+2*GL4O-1..5*GVVV-1. +2*GVCR4O+0.16666667*GS4V. +GLACRO3.. +GVVV+3*GHSEROO.0).33333*GLACR4O +GHSEROO+4..LA+3:MN+3:VA.5*GHSEROO+11. G(RPEROV.. +GN+0...LA+3:VA:VA.0).0).0). ENTER-PAR G(RPEROV..
0) 298. ENTER-PAR L(RPEROV.CR+2:O-2.CR+2:O-2....MN+3:VA.15 +GCR2O3_L.0) 298. ENTER-PAR G(ION. ENTER-PAR G(ION.15 0.CR+3:O-2.LA+3:CR+4. 5 1 1 1 3 1 SR+2..15 -1297...SR+2:SR+2:MN+4:O-2:O-2.5*GMN2O3 @@ +0.15 185...15 -119062....MN+2.....1).MN+3:O-2.LA+3.SR+2:LA+3:CR+3:O-2:O-2..5*GHSEROO.0) 298..SR+2:LA+3:MN+3:O-2:O-2...0) 298.0) 298.LA+3:MN+4..LA+3:CR+3:O-2:O-2.SR+2:LA+3:MN+4:O-2:O-2. 9248.SR+2:LA+3:CR+4:O-2:O-2.VA:O-2. @@ @@ Ruddlesden-Popper phase. Povoden-Karadeniz ENTER-PHASE IONIC_LIQUID Y LA+3 SR+2 MN+2 MN+3 CR+2 CR+3.15 +11368..SR+2:SR+2:MN+3:O-2:O-2.. ENTER-PAR L(RPEROV..0) 298.0).0) 298. ENTER-PAR L(RPEROV.VA:MN+4:O-2...MN+2:O-2. -117000.VA:O-2......15 +2*GSROSOL+0.LA+3. -136600. ENTER-PAR L(ION.MN+4:O-2..15 -1. @@ ENTER-PAR L(RP.0) 298..15 -3.5*GHSEROO. @@ ENTER-PAR G(RP......LA+3....LA+3... @@ ENTER-PAR G(RP... ENTER-PAR L(RPEROV. @@ ENTER-PAR G(RP...SR+2:SR+2. ENTER-PAR G(ION. ENTER-PAR G(ION.. @@ next two interaction parameters can be used to fit @@ Cr4+ amount in perovskite ENTER-PAR L(RPEROV.15 GS2CO4+GLCR3O_RP1 @@ -GREFRP.. @@ Interaction parameters from binaries ENTER-PAR L(ION.29519000E+05. ENTER-PAR L(ION. ENTER-PAR L(RPEROV.LA+3.CR+3:O-2.....0) 298...SR+2:CR+4..VA:O-2.... ENTER-PAR L(ION.15 +GCR_L.0). ENTER-PAR L(RPEROV. scarce experimental data @@ ENTER-PHASE RP. ENTER-PAR L(ION.15 GREFRP.. ENTER-PAR G(ION.0) 298.5*GMN2O3 @@ -0... ENTER-PAR L(ION. ENTER-PAR L(RPEROV.MN+2:VA.. -2. ENTER-PAR G(ION.MN+2:O-2.0) 298.....LA+3:CR+3.38590000E+04.SR+2:VA.Appendix ENTER-PAR L(RPEROV.. ENTER-PAR L(RPEROV.0) 298.. @@ O-2.MN+2:O-2.VA. 187 .0) 298... @@ ENTER-PAR L(RP.15 +GMN_L.15 100000.15 1... ENTER-PAR L(ION.1)..0) 298.. 250000.LA+3:CR+3. O-2...0) 298.. ENTER-PAR L(RPEROV..0) 298.0) 298.....SR+2:MN+3:O-2...5*t.. ideal extension from lower-order systems....LA+3:O-2...15 100000....SR+2:MN+2:O-2.. @@ ENTER-PAR G(RP..0) 298.. ENTER-PAR L(RPEROV..15 +2*GMN1O1_L.. ENTER-PAR G(ION.15 +2*GMN_L+GMN2O3_L-3*GMN1O1_L.MN+3:O-2.0) 298....15 +GLCR3O_RP1.MN+2:VA.15 +121000. 20.0) 298.1) 298.CR+3:VA..MN+3:O-2. ENTER-PAR L(RPEROV.15 +GMN2O3_L...15 +GLALIQ..15 +2*GCR_L+GCR2O3_L-3*GCR1O1_L... preliminary. @@ Interaction parameters from ternaries ENTER-PAR L(ION..1).1) 298.... ENTER-PAR G(ION... ENTER-PAR G(ION.0) 298.15 2*GCR1O1_L.0) 298... -117000....0). @@ ENTER-PAR G(RP.. @@ -----------------------------------------------------------------------@@ Liquid..LA+3:CR+3.LA+3.15 +GS4O_RP1. @@ ENTER-PAR G(RP....15 +GL3O_RP1+GS4O_RP1 @@ -2*GSROSOL-0.SR+2:MN+2:VA.0)...0) 298.LA+3.0) 298.MN+3:O-2..0) 298.MN+3:O-2..VA..LA+3:MN+4.15 GS2CO4..LA+3:VA.. -136600.0) 298... ENTER-PAR L(RPEROV.0) 298.MN+3:O-2.SR+2:SR+2:CR+4:O-2:O-2...LA+3..4.SR+2:O-2. AMEND-PHASE IONIC_LIQUID COMP 2.1)..MN+2:VA.LA+3:CR+4:O-2:O-2..1) 298.0) 298...VA..15 +121000.SR+2:CR+4.SR+2:SR+2...VA...6.SR+2:SR+2:CR+3:O-2:O-2. @@ ENTER-PAR G(RP.MN+3:O-2..LA+3:CR+3. ENTER-PAR G(ION.15 0. ENTER-PAR G(ION.15 3766... MN+3 MN+4 CR+3 CR+4.SR+2:MN+4:VA.1) 298.MN+2:O-2...15 +2*GSROLIQ.0) 298.54590000E+04.0).15 -11316..LA+3..0) 298.0) 298.. LA+3 SR+2..15 -4.... ENTER-PAR G(ION..15 +GL3O_RP1. ENTER-PAR L(RPEROV.SR+2:MN+4:O-2. O-2 VA.. 250000.0) 298.CR+2:VA.15 +GLA2O3LIQ. @@ ENTER-PAR G(RP.15 +GSRLIQ.
ENTER-PAR G(GAS...H1O2..15 +GCRH1O3_G+RTLNP....0) 298.. 1 H2O1..CR+2:O-2.0) 298..0) 298..1) 298..CRH1O3. 1 CR1O3. ENTER-PAR L(ION. 1500 N ENTER-PAR G(GAS.15 +GCR1O3_G+RTLNP.0) 298.0) 298..0) 298. 6000 N ENTER-PAR G(GAS.. ENTER-PAR G(GAS..15 -39016.15 +504+0.15 -101850.0) 298..CRH4O5.15 +GCRH6O6_G+RTLNP..CR+2:VA... ENTER-PAR G(GAS.0) 298.0) 298. @@-----------------------------------------------------------@@ Cr-GAS.15 +GCRH3O4_G+RTLNP. @@ @@ CRO3 reference gas ENTER-PHASE CRGAS.LA+3..O.15 +F10983T+RTLNP. ENTER-PAR L(ION.CR+2:O-2.0) 298. ENTER-PAR L(ION.. ENTER-PAR G(GAS. ENTER-PAR G(GAS...15 +GCRH3O3_G+RTLNP. ENTER-PAR G(GAS.CR1O1.0) 298.0) 298..0) 298.15 +F10666T+RTLNP.. 188 ..15 +F14021T+RTLNP. ENTER-PAR L(IONIC.0) 298.LA+3..0) 298.CR1O3.15 -39016..0) 298....49*T. ENTER-PAR G(GAS.1) 298.15 +F10963T+RTLNP.. 1 O2.SR+2. 20000 N ENTER-PAR G(GAS.15 -9111.O3.....0) 298.. ENTER-PAR L(IONIC.MN+2.1) 298.7. ENTER-PAR L(IONIC.. SGTE and reassessments by Chen.0) 298.CRH4O4. 6000 N ENTER-PAR G(GAS...SR+2..0) 298.15 +F7586T+RTLNP.H2..LA+3.SR+2..15 +46000.H2O2.0) 298.CRH1O2...15 +60713-5.MN+2:VA.0) 298..CR+3:O-2.15 -176300..SR+2....H..MN+2:VA. 20000 N ENTER-PAR G(GAS..0) 298.15 +GCR1O1_G+RTLNP.15 +F10963T+RTLNP..1) 298.. ENTER-PAR L(ION.. 6000 N ENTER-PAR G(GAS.0) 298. ENTER-PAR L(ION. @@ @@ H2O reference gas ENTER-PHASE STEAM..CRH5O5.LA+3..15 -188487...15 +F13704T+RTLNP.6587*T... ENTER-PAR G(STEAM...CRH1O1.CR+3:O-2.0) 298.O2.CR+2:VA.0) 298..CRH2O3.. 6000 N ENTER-PAR G(GAS.15 +GCRH2O3_G+RTLNP.15 -619869. ENTER-PAR G(GAS... ENTER-PAR G(CRGAS...LA+3.CRH1.. ENTER-PAR G(GAS.15 +GCRH2O4_G+RTLNP.15 +GCRH2O2_G+RTLNP.Appendix ENTER-PAR L(ION....CR+2:VA.CR1O2..1) 298..15 -619869...15 200000...CR+2:O-2. ENTER-PAR L(ION..0) 298.CR+2:O-2...9479*T...0) 298.0) 298..0) 298...SR+2...15 +GCRH1O2_G+RTLNP.15 +GCRH1O1_G+RTLNP.H2O1.LA+3.15 -179575.15 +64573-23*T....0) 298..15 +H2GAS+RTLNP. ENTER-PAR L(IONIC.SR+2...15 -119062..0) 298.CR+2:VA...0) 298.CR+3:O-2.CRH3O3..MN+2:O-2.MN+3:O-2.1) 298..15 -176300.15 -15009+13.0) 298. 20000 N @@ @@ O2 reference gas ENTER-PHASE O2GAS..CRH2O2.0) 298. ENTER-PAR G(GAS.SR+2.4) 298. ENTER-PAR G(GAS.. ENTER-PAR L(IONIC. 6000 N ENTER-PAR G(GAS. ENTER-PAR G(GAS.CR+3:O-2....MN+3:O-2.MN+2.15 +GCR1O2_G+RTLNP.15 +GCR1O3_G+RTLNP.LA+3.SR+2. ENTER-PAR L(ION.0) 298. 6000 N ENTER-PAR G(GAS.0) 298.15 +HGAS+RTLNP.15 +F10729T+RTLNP.LA+3.0) 298..... Povoden-Karadeniz ENTER-PHASE GAS G 1 CR CR1O1 CR1O2 CR1O3 O O2 O3 H2 H H2O1 H1O1 H1O2 H2O2 CRH1 CRH1O1 CRH1O2 CRH1O3 CRH2O2 CRH2O3 CRH2O4 CRH3O3 CRH3O4 CRH4O4 CRH4O5 CRH5O5 CRH6O6.15 +GCRH4O4_G+RTLNP.0) 298.. ENTER-PAR L(ION.15 +GCRH4O5_G+RTLNP.15 +F13349T+RTLNP.CR+2:VA.CRH3O4.CRH2O4. ENTER-PAR G(GAS....15 -101850..CRH6O6. ENTER-PAR L(ION.. ENTER-PAR G(GAS..H2O1. ENTER-PAR L(IONIC.15 -179575.. ENTER-PAR L(ION.MN+3.. ENTER-PAR G(GAS. ENTER-PAR L(ION.0) 298...CR+3:O-2.15 +GCRH5O5_G+RTLNP.CR1O3.H1O1. ENTER-PAR L(ION.. 20000 N ENTER-PAR G(GAS.
..0) 298..... N. set-interactive +2*GHSEROO+RTLNP. 189 ..15 @@ GO PAR @@ SET-OUT-LEVEL.Appendix ENTER-PAR G(O2GAS..O2.
Pestalozzistrasse 5. thesis: „ Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells“. Graz 1979-1983 Elementary School. 143. Ludwig J. 1992-1999 Geoscience Studies. N.Curriculum vitae Curriculum Vitae Personal data Povoden-Karadeniz. pp. Graz Publications R. Rainer Abart 1983-1991 Realistisches Gymnasium. Abart. 2002. Oxygen. Karl-Franzens University Graz Master thesis: „Kontaktmetamorphose und Fluid-Gestein-Interaktion in der östlichen Monzoni Kontaktaureole“. Gauckler. Dr. Petrol. Dr. Erwin Date and place of birth: March 18. ETH Zurich. Dr. and E. Burkhard. Graz. Department of Materials. Switzerland. Georg Hoinkes and Prof. Berliner Ring. 1973. Nonmetallic Inorganic Materials. Prof. 192-208. 190 . Badertscher. Prof. carbon and strontium isotope systematics in two profiles across the Glarus thrust: implications for fluid flow. D. Miner.. Povoden. Austria Education 01/2005 – 12/2008 Ph. Contr. M.
Ivas. Gauckler. Thermodynamic calculations of impacts of chromium on Sr-doped Lanthanum manganite (LSM) cathodes for solid oxide fuel cells (SOFC).J. Grundy. Diff.J. 76. Povoden.Diff. Res.Curriculum vitae E. 2002. Calphad. 12-27. Phase Equilib. Chen. Povoden. Phase Equilib. Gauckler. Gauckler 191 . E. Grundy. A.J. and L. Povoden-Karadeniz. 33-41. Grundy. Gauckler. and L. 569-78. to be submitted.N. Ivas. E. Grundy. Povoden.. Povoden. Gauckler. M. Presentations Assessment of the Cr-O system in the frame of SOFC research E. 2006. A. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. 97..N. Povoden. and L. Grundy. and L. 27. and L. pp. Grundy. and L.J. and L. M. Thermodynamic assessment of the La-Cr-O system. 2009. Phase Equilib. Mater. 30. Gauckler. Thermodynamic assessment of the La-Fe-O system. T. A. A. M. Diff. pp.N.J. Ivas. Gauckler. Ivas. E. Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole. E.N. to be submitted. to be submitted. Degradation of planar solid oxide fuel cells with (La1-xSrx)1-yMnO3 cathodes and Cr-alloy interconnects. A. J.N. Grundy. Povoden. M. E. J. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Chen. pp.N. Povoden. Chen.J. pp. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. Abart. and R. T. Calculation of defect chemistry using the CALPHAD approach. (accepted) E.N. T.J. J.. M. E. A.J. Horacek.. Miner. Chen. T. 1. pp. 99-120. A. and L.J. Povoden. Int. Gauckler. 353-62. Povoden. and L. Petrol. E. Gauckler. 2006. J. 2006.
students. 2005 Thermodynamic assessment of the Cr-Mn-O system for solid oxide fuel cell (SOFC) materials E. Maastricht. Povoden Oral Presentation 1st EMPA symposium for Ph.D.Curriculum vitae Poster Presentation CALPHAD XXXIV. USA. A.J. Gauckler Oral Presentation Thermo 2006.J.N. March 16th.N. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fuel cell (SOFC) materials using the CALPHAD approach E. EMPA Dübendorf. and L. 2006 The BiO3/2-SbO3/2-ZnO Phase Diagram at 1115°C in air E. Grundy.J. Povoden. Colorado. and L. A. Peng. A. and L. Pennsylvania. Austria. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fel cell (SOFC) materials E. Povoden. Povoden. Boulder. Grundy.N. October 20th. Vienna. 2005 Thermodynamic Assessment of the Cr-Mn-O System for Solid Oxide Fuel Cell (SOFC) Materials E. EMPA Dübendorf. Gauckler Poster Presentation CALPHAD XXXVI. Z. Povoden. and L. Pennsylvania State University. 2007 Thermodynamic assessment of the La-Cr-O and LaO3/2-MnOx-CrO3/2 Systems 192 . September 18th – 22nd. Netherlands. May 06th -11th. Switzerland.J. Grundy. Gauckler Oral Presentation HTMC XII. Switzerland. Gauckler Oral Presentation 3rd Fuel Cell Research Symposium. August 4th. May 6th – 11th. USA.
5 and LaO1. Gauckler Oral Presentation CALPHAD XXXVI. Pennsylvania. 2008 Thermodynamic LaO1. March 28th.5-SrO-FeO1. Grundy. May 6th – 11th. Chen. Lehrstuhl für physikalische Chemie.5-CrO1. Povoden. Pennsylvania State University.Curriculum vitae E. Grundy. 2007 The thermodynamic LaO1. A. Saariselkä. 2008 193 .5 databases for SOFC applications using the CALPHAD approach E. Povoden Oral Presentation 2nd MRC Graduate Symposium .5 databases for solid oxide fuel cells (SOFC) applications E.J.5-SrO-MnO1.5-CrO1.5-CrO1.The La-Sr-Mn-Cr-O system E.N. A. Finland. Povoden Oral Presentation Guest Talk. and L. Povoden. Monatnuniversität Leoben.5-CrO1.N. June 27th.5 and LaO1. Gauckler Oral Presentation CALPHAD XXXVII. M. ETH Zurich.5-SrO-FeO1. and L. June 16th – 21st. 2007 Thermodynamic modeling for solid oxide fuel cell research .J. USA.5-SrO-MnO1.
. A further reason why we use this description is that for SOFC applications we are primarily interested in the oxide portion of the phase diagram and we have found that the endmember Me(O)3 used to describe oxygen solubility in the metallic phase can inadvertently appear in the oxide portion of the phase diagram.5 based on the argument. J. Phase Equilib. 109.Erratum. 112 According to the latest discussion by B. p.Cr)(O. For these reasons.Cr)(O.O)1. p.” .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.Va)1.5…. lines 7-14 and Table 4. 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)3 and not (La. The following argumentation for modeling of the oxygen solubility in bcc using (physically wrong!) Me(O. Diff. accepted. (Me)1(Va. Hallstedt et al.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.Va)1.3. 2007. Povoden-Karadeniz et al. otherwise the disordered model for interstitials in bcc..3.X)3 is to be used…” Thus the model was also corrected in the thermodynamic assessment of the La-Fe-O system. p 2837 the correct model is (La.. 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.Va)1. 31(1).O)3 is undoubtedly a reasonable model description for the oxygen solubility in bcc. Calphad. In previous papers the authors have proposed the model Me(Va.
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