This action might not be possible to undo. Are you sure you want to continue?
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 3.1 1.1 1.2.6 Degradation of SOFC caused by chromium from the interconnect The role of current load on electrical losses of degraded SOFC Impedance spectroscopy measurements and implications on the degradation process Microstructures in degraded SOFC Amounts of chromium in SOFC tested with and without current load Critical assessment of proposed mechanisms of chromium “poisoning” 1.2 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes New ways – alternative materials 2 3 Aim of study Method 3.2 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC Thermodynamic modeling 3.3.Table of Contents Table of Contents Summary Zusammenfassung 7 9 1 Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cralloy interconnects 1.1.1 3.4.1 Introduction 1.3 Principles of SOFC The problem of chromium “poisoning” 11 11 11 13 14 17 17 22 24 24 27 28 36 36 37 45 46 46 47 47 48 49 Volatilization of Cr2O3 Literature survey 1.4 1.1 3.4 Proposed strategies against chromium “poisoning” and their effectiveness 1.3 1.5 1.1.3 Stoichiometric solid oxides Solid solution phases – the Compound Energy Formalism (CEF) Vacancies and the concept of reciprocal reactions 4 .22.214.171.124.2 1.1 126.96.36.199.2 1.2 1.3.
188.8.131.52.1.3 4.4.5 Conclusions 5 Thermodynamic calculations of impacts of chromium on Sr-doped 5 .4 Literature review of the La-Cr system Literature review of the La-Cr-O system Thermodynamic modeling and optimization Results and discussion 4.4 4.3 4.1 Technology 4.3 4.3.3 Experimental Thermodynamic modeling Optimization of parameters Results Discussion 4.1 Calculation of defect chemistry using the Calphad approach 51 52 53 53 53 54 58 59 66 67 73 77 77 78 86 89 93 96 97 101 102 103 103 109 117 128 134 134 135 137 140 143 Optimization of model parameters Thermodynamic reassessment of the Cr-O system in the framework of SOFC research 4.7 Conclusions 4.2.5 4.1 Introduction 4.4.2 4.4.3 4 4.6 Experimental data Previous assessments of the Cr-O System Thermodynamic modeling Optimization of parameters Results and discussion Thermodynamic assessments 4.3.1 Introduction 4.5 184.108.40.206.1.1.4 4.3 4.7 Applications on SOFC Thermodynamic assessment of the La-Cr-O system 4.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials 4.3.4 220.127.116.11 Assessment of data from the literature Modeling and optimization Results and discussion 4.2 4.1 Introduction 4.2.6 4.6 Conclusions Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications 4.2 18.104.22.168 4.2.5 4.4 3.1.4.Table of Contents 3.2.
3.1MnO3-δ contaminated by chromium Thermodynamic calculations of (La0.Table of Contents manganite (LSM) cathodes for SOFC 5.9Sr0.8Sr0.3.2)0.4 5.1 5.2 5.9MnO3-δ contaminated by chromium Thermodynamic testing of LSM with Mn-deficiency Formation of Cr2O3 148 149 150 152 152 157 160 162 163 165 Discussion Conclusions Appendix Thermodynamic La-Cr database Thermodynamic La-Sr-Mn-Cr-O-(H) oxide database 170 169 172 Curriculum Vitae 190 6 .3.4 5.3 5.3.5 Thermodynamic calculations of La0.1 5.3 Introduction Method Results 5.2 5.
even if the system is in a thermodynamic non-equilibrium state. The associated chemical changes of the LSM phase. A key role is played by the adsorption of gaseous CrO3(g) (g = gaseous) and chromiumoxyhydroxides stemming from the interconnect on LSM and reaction of chromium with LSM. and the modeling approach used in this study is presented. In the third chapter the reader learns. and the aim of this study (chapter 2) is to gather a deeper understanding of these unsolved problems by using thermodynamics. and some are kinetically controlled. Based on the findings from the literature it gets clear that several questions about the key mechanisms of the chromium “poisoning” have not been answered yet. In chapter 1 the basics of planar SOFC are briefly explained. This has calamitous consequences for the electrochemical properties of the cathode. and previous findings of chromium “poisoning” of SOFC are critically reviewed. Furthermore spinel blocks pores and thus impedes the oxygen 7 . The chromium is known to deteriorate the electrical performance of the cathodes. 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. Some of these processes are governed by thermodynamics. as well as the formation of a new spinel phase occur under thermodynamic control: decreasing concentrations of vacancies in LSM that contains chromium are calculated at decreased oxygen partial pressure reflecting SOFC operation at high current load. It is shown that chromium “poisoning” of SOFC cathodes is a rather complex process consisting of several steps. Chapter 4 deals with the construction of the La-SrMn-Cr-O oxide database based on the assessments of subsystems. some of them probably occurring simultaneously. 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. how thermodynamic calculations can lead to a better understanding of a system.Summary Summary The thermodynamic La-Sr-Mn-Cr-O oxide database is established by assessing oxide subsystems using the CALPHAD (Calculation of phase diagrams) approach.
8 . Appropriate measures can be foreseen preventing the long-term degradation of SOFC cathodes in combination with high-chromium containing interconnects. which of the phenomena in a chromium-“poisoned” LSM cathode are governed by thermodynamics.Summary reduction required for the function of the cell. Cr2O3(s) (s = solid) that hampers the diffusion of oxygen into the electrolyte is a metastable phase in LSM contaminated by chromium. With this contribution the prevailing question is resolved.
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).
forming a cell stack to obtain higher voltage and power. The direct-current electricity is produced by the electron flow through the external electric circuit.1. At the anode the oxygen ions react with hydrogen of the fuel to form water and release electrons.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. supplied at the cathode reacts with electrons from the external electric circuit to form oxygen ions. In an SOFC. a = anode. White circles symbolize pores. A single cell produces a voltage of 0. The oxygen. as shown in Fig. 1. The electrodes are required to have high reactivity and the electrolyte must allow high oxygen ion diffusion. and ceramicmetal composites are used for the anode. cathode and electrolyte consist of refractory solid oxide ceramics. These ions migrate through the electrolyte to the anode. The materials for the cell components need to have a sufficient chemical and structural stability at rather high temperatures up to 1273 K that occur during cell production as well as during cell operation.5 to 1 W cm-2. e = electrolyte. Normally many cells are electrically connected in series by an interconnect.1 Scheme of the electrochemical processes in a fuel cell with O2 oxidant and H2 fuel.2 (next page) for the widely used planar-design SOFC.7 to 1 V and power around 0.1. c = cathode. 1. The electrons flow from the anode through the external electric circuit to the cathode. All the components of the cell need to be matched in their thermal expansion in order to minimize mechanical stresses. 12 .
1.2 Planar design of SOFC The interconnect separates the fuels and oxidants in adjacent cells. difficulties in sintering and manufacturing and low mechanical strength required the development of alternative interconnect materials. the electronic conductivity of several LaCrO3-based ceramics under SOFC operating conditions is high. and chemical compatibility (no reactions) with other cell materials. 1. as the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. 13 . However high costs of these materials.2 The problem of chromium “poisoning” In the 1990is LaCrO3-based ceramics were intensively investigated for interconnect applications in SOFC.1. as chromium alloys come close to all desired properties. low permeability for oxygen and hydrogen to minimize direct combination of oxidant and fuel during cell operation. stability in both oxidizing and reducing atmospheres at the high cell operating temperature (from about T = 973 K to 1273 K). a thermal expansion coefficient close to that of the cathode and the anode. and their thermal and redox-stability is satisfying. 1. However high-valent gaseous Cr-oxide and Cr-oxyhydroxides diffuse from the Cr2O3(s) scale covering the interconnect into the cathode up to the cathode-electrolyte interface and cause the degradation that results in the strong deterioration of the electrical performance of SOFC. a low ionic conductivity. Nowadays the state-of-the-art interconnect is commonly a chromiumcontaining metal plate[3-5]. It is the most demanding component in a planar SOFC as it should have a high electronic conductivity.
the volatile species must be a higher oxide of chromium. and -diffusion processes. Volatilization of Cr2O3(s) was neither observed in dry nor in wet argon.3-2. Appreciable volatilization occurred in dry oxygen. 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.6 mg at T = 1473 K at a gas flow rate of 200 ml min-1 after 20 h. 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. Caplan and Cohen investigated the evaporation of Cr2O3(s) by measuring the weight loss when Cr2O3(s) pellets with 1. But when it was learned that Cr2O3(s). or at discontinuities such as fractures in the film and would then evaporate.2 cm in diameter and height were heated at T = 1273 K in stagnant air.2 Volatilization of Cr2O3 Early investigations[6-9] revealed that oxidation of Cr-containing alloys at high temperatures leads to the redeposition of Cr2O3(s) crystals at cooler parts of the experimental apparatus from the gas phase. it became evident that a volatile Cr-oxide was being formed.6 mg at T = 1473 K. but its formation by the reaction Cr2 O3(s) + 3 2O2(g) → 2CrO3(g) (1. Furthermore. The volatilization in wet oxygen was significantly higher after 20 h at the same gas flow rate: 2.6 mg at T = 1373 K and 2. lost weight when heated in oxygen. -reduction. and at T = 1373 and 1473 K in flowing dry and wet oxygen as well as in dry and wet argon. This was a surprising result. In stagnant air the volatilization was 0. 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.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 weight loss being 0. in the absence of metal. 1.2. neither the vapour pressure of Cr2O3(s) nor its dissociation pressure is high enough to account for the quantities of deposits observed. A known volatile oxide of Cr is CrO3.1) 14 .3 mg at T = 1273 K after 72 h. and it was suggested that high-valent gaseous Cr-oxide and Cr-oxyhydroxides detrimentally affect the O2 -adsorbtion. Since weight loss takes place under oxidizing conditions.1 mg at T = 1373 K and 5.
and this was affirmed by thermodynamic modeling. 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. 1. and for CrO3(g) from Ebbinghaus.2 and 1.18] cited above. The existence of gaseous Cr-oxyhydroxides as oxidation products (Eqs.2 is calculated to be −158 kJ at T = 1273 K using combined data from Opila et al. As gaseous CrO3(g) was detected experimentally by mass spectrometry when Cr2O3(s) was heated under oxidizing conditions. These findings are supported by the higher volatilization of Cr2O3(s) in wet air.3 is calculated to be +134 kJ at T = 1273 K using combined data from Kim and Belton and Ebbinghaus. data for O2(g) from Dinsdale.3) Δ°G of reaction 1. Δ°G of Eq.. and Δ°G of reaction 1.2) Cr2 O3(s) + 1 2O2(g) + H 2 O(g) → 2CrO2 (OH)(g) (1. μ(O) being −300 J mol-1 referred to pure oxygen gas result from combined thermodynamic data[11-14.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects is thermodynamically unfavourable at high temperatures.3) in wet atmosphere was experimentally proven in several studies[14-17].2.2. 1. 15 .2.1 (next page): the calculated amounts of main Cr-species in the gas phase as a function of temperature in humid air of pH2O = 2000 Pa at constant chemical potential of oxygen.1 is calculated to be +321 kJ at T = 1273 K using assessed thermodynamic data for Cr2O3(s) from Povoden et al. whereas at higher temperatures the gas phase mainly contains CrO3(g) and CrO2OH(g). 1. and Ebbinghaus. 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.2.2. 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. This tendency is shown in Fig. However.
12x10-5 Pa at T = 673 K and increases as a function of increasing temperature.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. 1. Cr-vaporization in SOFC: Konysheva et al.2. two high-chromium alloy interconnects widely used in SOFC. and the 16 .57x10-3 Pa at T = 1223 K.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.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Fig. 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.3 μg h-1 for 25 mol% H2O in air at T = 1073 K. used a transpiration method proposed by Gindorf et al. reaching pCr = 4. at T = 1073 K for a time period of about 500 h. to measure the vaporization rate of Cr from Cr5Fe1Y2O3 (Ducrolloy) and Crofer22APU (high-Cr ferritic steel). and 18.2 μg h-1 for 3 mol% H2O in air at T = 1073 K. the mass loss being higher at higher water content and higher temperature: the constant rate of mass loss was 0. 3.
for an SOFC setup with a Cr5Fe1Y2O3 interconnect plate. 1.3. this value being by about a factor of 2.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects vaporization rate increases with increasing temperatures for both alloys. an yttriumstabilized zirconia (YSZ) electrolyte and a Ni-zirconia cermet (ceramic-metallic composite) anode operated at T = 1173 K and 1273 K.34.1 Degradation of SOFC caused by chromium from the interconnect Considering the experimental data from Caplan and Cohen.5 higher than with Crofer22APU. pp. 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. 18-21. The amount of Cr in these degraded cells was 140 μg cm-2 with Cr5Fe1Y2O3.32. an LSM cathode. thus quantitative chromium “poisoning” rates affecting the cathode are difficult to determine. 17 . 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. mentioned significant amounts of deposited Cr2O3(s) in the air exhaust of the cell. However. and the chromium problem is restricted to the interconnect-cathodeelectrolyte region of SOFC.1. With increasing humidity the difference in the vaporization rates between the two alloys increases. Badwal et al.3.35] of the degradation of SOFC with LSM cathodes caused by chromium are listed in Table 1.3 Literature survey 1.31. Experimental results[21-29.
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 .
and intensity measurements using electron probe microanalysis showed that Cr was concentrated at the cathode-electrolyte interface.7 V to about 0. In a test of the same setup under open circuit conditions for 21 . The cell was electrochemically tested at T = 1273 K under a current load of 300 mA cm-2 for 400 h. These authors measured an increase of cathode polarization and decrease of cell voltage in an SOFC consisting of an LSM cathode with the compositions La0. 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.1MnO3-δ.9Sr0..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.1 V. The cell voltage decreased over this time from initially about 0.
 presented cell performance data of an SOFC with LSM cathode. 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.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.05 W cm-2 after 110 h.2 W cm-2 to 0.3. and Cr was randomly distributed across the cathode. an LSM cathode. the cell performance was stable for 110 h. the cell started to degrade severely after 20 h of testing. whereas ohmic losses (resistance to 22 . its power density decreasing from a maximum of 0. the voltage drop being 0. Simner et al.48 W cm-2. 1. reported that the degradation rate of SOFC with a Cr5Fe1Y2O3 interconnect plate. thus linked the cell degradation to the time that the discharge current was applied.: these authors tested the cell performance of an SOFC with a Cr5Fe1Y2O3 interconnect plate. 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. 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. Later these results were confirmed by Badwal et al. a Sm2O3-CeO2 interlayer between cathode and electrolyte. an LSM cathode. the power density being 0. and to chromium deposited at the LSM-YSZ interface filling pores. All these experimental studies[22-29] unambiguously proved that chromium stemming from the alloy interconnect causes the degradation of SOFC.2 The role of current load on electrical losses of degraded SOFC Badwal et al. Taniguchi et al. But using a Cr-Fe-alloy interconnect.1 V during an operation time of 2500 h. holding the cells at 0. 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. hindering the supply of oxygen gas and decreasing the number of reaction sites for the oxygen reduction. a YSZ electrolyte and a Ni-zirconia cermet anode at T = 1273 K and a current density of 250 mA cm-2. On the other hand the voltage of the cell with Cr-Fe-alloy interconnect decreased rapidly as a function of operation time.4 V after only 16 h. ascribed the voltage decrease to increasing losses of cathodic overpotential. The cell performance without interconnect plate deteriorated only little by less than 0. whereas the opposite was observed for SOFC with Cr-alloy interconnect.7 V: without the interconnect steel.
Zhen et al. The polarization behavior of SOFC with Crcontaining interconnect was explained by the strong inhibiting effect of gaseous Cr-species on the oxygen reduction in LSM.21 % Cr on top of a (La0.3MnO3-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. LSM cathode and a YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2.98MnO3-δ cathode and a YSZ electrolyte over 5 to 10 h at T = 1073 K applying a −0. 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. tested the reversibility of degradation in a half-cell setup with CrFe-alloy interconnect. Rpol being 0. using a half-cell with a Cr5Fe1Y2O3 interconnect. Paulson and Birss reported rapid deterioration of the performance of a half-cell setup with a stainless steel disk containing 15. losses increased sharply and reached their maximum values after only 15 h of cell operation.23. A plateau of degradation was reached after about 400 h of testing.32.6 V.5 V potential. whereas at 280 mA cm-1 the voltage dropped by 0. in agreement with earlier findings[22. 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.07 V. Konysheva et al.8Sr0. La0. 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.28.5 Ohm cm2 for a thickness of 23 . 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. a La0. In earlier studies using the same setup a rapid decrease from −360 to −560 mV after 10 minutes[25. with a tendency of stabilization of the cell performance after this testing period at much lower magnitude of output current. in general agreement with Jiang et al. 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 [24.31].[24.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..33].65Sr0.6Sr0.25. At the beginning of the cell tests. 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.25] at 1173 K and a current density of 200 mA cm-2.26] was observed. The overpotential losses were higher and the cell deterioration was faster at higher current density. Konysheva et al. The total polarization resistance (Rpol) of a half-cell setup using a Cr-Fe-alloy interconnect.2)0.
 reported the existence of a high frequency and a low frequency arc in impedance spectra of a half-cell with Cr-Fe-alloy interconnect.26. observed an increased size of the high frequency arc during the current passage in half-cell tests using a Cr5Fe1Y2O3 interconnect plate. and from −800 to −1120 mV at T = 973 K after 10 minutes. 1. from −900 to −1200 mV at T = 1073 K. a La0.32].4MnO3-δ cathode and a YSZ electrolyte operated at T=1073 K and 300 mA cm-2 current load that the degradation in the electrode caused by chromium was due to the increase in both charge-transfer resistance and surface diffusion resistance. LSM cathode and YSZ electrolyte tested at T = 1173 K and a current density of 200 mA cm-2. 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. reflecting increasing cathode resistance. The degradation was higher at higher temperatures at 0.33] and Jiang et al.6Sr0. This finding was confirmed 24 . an LSM cathode and a YSZ electrolyte as a function of operation time.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 50 μm. it deteriorated from 500 mA to 350 mA at T = 1073 K and from 300 mA to 150 mA at T = 973 K over the testing time of 200 h and then remained constant. Mazusaki and Yasuda concluded from the interpretation of impedance spectra of a half-cell with an Inconel 600 interconnect.3 Impedance spectroscopy measurements and implications on the degradation process Badwal et al. and 2 Ohm cm2 for 7 μm. were the first who reported the occurrence of Cr-Mn-spinel in Cr“poisoned” SOFC with an LSM cathode by using XRD analysis. 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. Zhen et al. 1. 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.[24.4 Microstructures in degraded SOFC Cathodic polarization: Taniguchi et al. The total polarization resistance was also higher at higher current load.3. observed less overpotential losses at lower temperatures in a half-cell with CrFe-alloy interconnect. Jiang et al.75 Ohm cm2 for 13 μm.7 V. but not due to the increase in ohmic resistance. 0.3.
unfortunately the specific conditions for its formation were not given in more detail. Jiang et al. Zhen et al. Badwal et al. an LSM cathode.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects by Badwal et al.[25. 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-2.36] documented spinel formation at the LSM-YSZ interface already after 4 h. On the other hand Cr-Mn spinel formed already at 25 . Using the same setup. a YSZ electrolyte and a Nizirconia cermet anode at T = 1173 and 1273 K under current load. Using the same setup as above. Using a half-cell setup with Inconel 600.17 μm after 4 h of cell testing and increased to about 0. In some cases these authors also observed Cr2O3(s) at the cathode-electrolyte interface. In the same setup without LSM-YSZ functional layer no chromium-deposits were detected without current at T = 1073 K over 393 h. Very small grains of Cr-deposits formed at T = 1373 K under open circuit conditions. 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. in some of the experiments forming a dense layer of several microns at the cathode-electrolyte interface. but under anodic polarization very fine grains of Cr2O3 were forming exclusively at the LSM-YSZ interface. For the same setup large quantities of spinel had formed after 2000 to 2500 h of cell operation. no Cr-deposits formed after 50 h of testing under open circuit conditions[25.36]. The amount of spinel at the cathode-electrolyte interface was much larger than within the LSM cathode particularly after a period of current load. 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. and the cell-degradation was weak.7 μm after 50 h. 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. The grain size of spinel was about 0. In a half-cell setup with a Cr-Fe-alloy interconnect. further observed spinel in the contact region between interconnect and cathode. and the cell degradation was strong. The zone of these large faceted crystals was followed by a zone of very fine grains (about 0. Under the same testing conditions as above.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. The deposition zone broadened as the polarization time increased from about 60 μm after 50 h to 89 μm after 129 h.
2)0. Cr-deposits consisting of Cr2O3 and Cr-Mn-spinel were concentrated in an about 2 μm broad region at the LSM-YSZ interface. These authors observed the formation of a 500 μm broad zone of 8 individual. almost completely 26 . and the deposition was less pronounced at T = 1073 K and 973 K. The morphology of the particles was different than the morphology of the deposits under cathodic polarization. A reference test without polarization did not lead to these features.72Sr0.8Sr0. After 5 minutes of testing at T = 1173 K very fine Cr-deposits (< 100 nm) already formed on the YSZ-surface. and the density and size of deposits increased by time. Cr2O3 completely filled gaps between YSZ grains. after the half-cell was tested by a sequence of 8 chronoamperometry experiments at −0. After 20 h spinel formation was observed forming a 40 to 50 μm wide band at the LSM-YSZ interface. 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. exclusively covering the YSZ surface. and 30 μm from the LSM-YSZ contact after 940 h. Influence of temperature: Microstructural changes during half-cell tests of a setup consisting of a Cr-Fe-alloy interconnect. large gaps between YSZ grains formed. and spinel crystals were found on the surface of a thin Cr2O3-layer adjacent to the electrolyte.5 V and T = 1073 K. After 160 h of testing at 100 mA cm-2 current load.. No spinel formation was observed in these experiments.21 % Cr attached on top of a 4 mm2 square (La0. In direct contact with YSZ about 500 nm large Cr2O3-grains were detected.98MnO3-δ cathode that rested on a 144 mm2 square YSZ electrolyte. Paulson and Birss investigated the microstructures in a half-cell setup with a stainless steel disk containing 15. Cr2O3 was also found inside YSZ.5 μm thick layer directly adjacent to the YSZ containing mainly Cr2O3 is covered by a spinel layer. a La0. dense Cr2O3-layers at the edge of LSM on the YSZ surface. up to 10 μm away from the LSM-YSZ interface after 160 h of testing. reported the formation of very fine particles of Cr2O3. Transmission electron microscopy analyses revealed the layered structure of the composites: a 0.18MnO3-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. Jiang et al.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.
8 wt. this is only 15 to 20 % higher than in the cell operated without current. Simner et al. holding the cell at 0. In SOFC with LSM cathodes and a Cr-Fe-steel interconnect that were tested at T=1073 K for 300 h at 0. a Sm2O3-CeO2 interlayer between cathode and electrolyte and a YSZ electrolyte with a Crofer22APU interconnect operated at T = 1073 K.5 Amounts of chromium in SOFC tested with and without current load Konysheva et al. measured about 2. 1. but no Cr in LSM using energy dispersive scanning electron microscopy. compared the total amounts of chromium in half-cells with Cr-Fe-alloy interconnects. This may lead to a dramatic drop of the oxygen diffusion coefficient in LSM by about 60% and pers.5 wt. 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.7 V.65Sr0.% of Cr at 10 μm distance from the cathode-electrolyte interface. measured 5 at. Krumpelt et al. comm. 27 . The Cr-content dropped to about 0. In a half-cell with LSM cathode. 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.vacancy within about 10 Å around Cr3+.% at 14 μm distance from the contact to the electrolyte. The decreasing degradation at lower temperatures was ascribed to slower diffusion and lower partial pressure of gaseous Cr-species.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects covering the YSZ surface. although the degradation of the polarized cell was remarkably higher. a La0.% Cr in the Sm2O3-CeO2 interlayer. associated with large grains (about 1 μm) of spinel.3MnO3-δ/LSM+YSZ double layer cathode and a YSZ electrolyte after tests without current showing very small degradation.7 V for 120 h.3. and under 200 mA cm-2 current density showing strong degradation as a function of testing time at T = 1073 K. By using molecular dynamics simulation techniques it was stated recently that only 890 ppm Cr3+ in LSM significantly increase the formation energy of O2. The amount of Cr-deposits was significantly smaller after 20 h of testing and 200 mA cm-2 current load at T = 973 K: isolated fine particles (about 100 to 200 nm) were detected on the YSZ surface. It further decreased slightly towards the interconnectcathode interface.
30-31. 22.214.171.124 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. 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. 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. emphasized that chromium “poisoning” would consist of several processes.1.33. 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. 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.2 is a possible reaction for the formation of spinel with a higher amount of Mn. where the reaction partners for the reduction. 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) (1.230.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. 1.33]. and 2) Chemical dissociation of Crspecies on the LSM surface[24-26. 1. 1) Several authors[21-23.33] ascribe the mechanism of chromium “poisoning” to the reduction of gaseous CrO3(g) and Cr-oxyhydroxides at the cathode-electrolyte interface. reduction of CrO3(g) at the cathode-electrode interface competing with the normal oxygen reduction reaction.31. and blocking of pores by Cr-Mn spinel and Cr2O3(s). Both reduction and chemical dissociation processes reflect non-equilibrium conditions.3.37].3. and gas.32. 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”. including changes of the chemical composition of the LSM surface.3.1) Eq. electron-donating LSM and oxygen-accepting YSZ are available. In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary (TPB) between LSM.3. Badwal et al. YSZ.2) 28 . Badwal et al.1 when solid solubility of Cr in LSM is considered and spinel contains the molar fraction of Cr. described by inverse Eq.
Which of the possible reaction paths is realized. and the mobility of the gas phase is high.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.5) considering the main chromium molecules that interact with LSM for spinel with X(Cr) = 2X(Mn). 1.2 less Cr2O3 is needed for the formation of Mn2CrO4. sp-form = spinel formation. Oxygen production stems from the reduction of Mn3+ in perovskite to Mn2+ in spinel. thus assuming a lower activation energy for the LSM-Cr-gas reaction.1 and 1.1 is a simplified illustration of possible reaction paths that lead to the end product Cr-Mn spinel. 1. Ea of the concerning reaction. and the LSM-Cr-gas reaction occurs as a parallel process leading to the formation of spinel.3.3 to 1.3. However the formation of spinel can also be interpreted as a direct solid-gas reaction.3. Fig. The shape of the curves in Fig. and this is not known. As it is not assured if spinel in fact forms in a solid-solid reaction. Fig. red = reduction. reactions of direct formation of spinel by the interaction between Cr-gas and LSM can be formulated (Eqs.3. 1. 1.3. depends on the activation energy. Such gas-solid reaction can be split into two reaction steps: formation of 29 .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). and LSM gets more deficient in Mn. These assumptions would mean that fast reduction of Cr-gas to Cr2O3(s) occurs as one process.3. more oxygen is produced. The true shape of the curves depends on the activation energy Ea and is thus not known. 1.1 Possible reaction paths for the spinel formation as a function of Gibbs energy.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects For equal y in Eqs.
It can be seen from Eqs. Yasuda et al.3. concluded that 30 . The ionic conductivity was lower at lower oxygen partial pressures. and consequently to Cr-Mn spinel and Cr2O3(s). 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. However they did not discuss the dependence of oxygen diffusion upon pO2 .37] oxygen diffusion is inhibited by the nuclei-formation.33. opposite to the trend that would be expected under the control of the vacancy diffusion mechanism.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Cr2O3(s) from the gas and subsequent spinel formation from Cr2O3 + LSM.5 that oxygen is produced during the formation of spinel.[24-27. Huang et al.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. 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. 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. confirmed these early suggestions by evaluating the ionic conductivity of LSM from pure oxygen to pO2 = 300 Pa at temperatures from 953 K to 1153 K using YSZ as blocking electrode.1 to 1. Thus the pO2 at the locations of the spinel formation is expected to increase.3) La1− xSrx MnO3−δ + 3 yCrO2 (OH)2(g) → La1− xSrx Mn1− y Cry O3−δ + yMnCr2O4 + 3 yH 2O(g) + 5 2 y O2(g) (1.3. As Mn2+ is associated to vacancy formation in LSM that is necessary for the oxygen diffusion.33.32.5) 2) The chemical dissociation of gaseous Cr-species on the LSM surface for the cell degradation was proposed as the key process for the degradation of SOFC caused by chromium by another research group[24-27. 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.3.3.32. This in turn will also lead to less Mn2+ in LSM and consequently lower oxygen diffusion in LSM.3.
as Δ°G of the reduction being the inversion of reaction Eq.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects oxygen ions in the bulk of LSM diffuse by the vacancy diffusion mechanism. 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. compared to δ = 3.94x10-9 in air. when the oxygen partial pressure at the cathode-electrolyte interface is decreased significantly.1 has a large negative value. The electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach[24-27. This confirms the suggestion that the formation of oxygen vacancies in LSM contributes to the oxygen diffusion at high current loads. The activation energy for the diffusion of oxygen for LSM is in the range of 250 to 300 kJ mol-1.33. 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.9Sr0. 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. We believe that the oxygen vacancy diffusion mechanism contributes to the oxygen diffusion under high current loads. This phenomenon was well explained by continuous feeding of an initial 31 . observed the extension of dense Cr2O3layers into YSZ. Based on the findings from the literature it can be summarized that in LSM oxygen diffuses through grain boundaries at high pO2 .4x10-6.336 V corresponding to pO2 = 10-4 Pa. Paulson and Birss.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. and η = −0.185 V.32. as well as Konysheva et al.37]. 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. η = −0.336 V. as oxygen vacancies are simply not available under these conditions.1CoO3-δ in which oxygen ions are transported by the vacancy mechanism. 1.2MnO3-δ at 973 K and pO2 = 10-4 Pa is δ = 2.2. 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. as it was directly proven by isotopic and tracer diffusion experiments. 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. This indicates that a vacancy diffusion mechanism also applies to LSM.8Sr0. This is close to 270 kJ mol-1 for La0.
which was definitively not observed.26.28. Cr2O3(s) deposition should also occur under open-circuit conditions. which does not seem to be the case for the spinel phase. partly layered structures. and the normal charge transfer can take place by switching it on again. Furthermore.31]: by switching off the polarization the competing reduction of CrO3(g) no longer occurs. If CrO3(g) is electrochemically reduced to Cr2O3(s) in a cell. which both seemed to be inhibited by chromium poisoning. From the occurrence of finegrained Cr2O3 the existence of a large number of nuclei for its formation is concluded. which is increasing as a function of increasing polarization. whereas in a polarized cathode the reduction of CrO3(g) takes place and competes with the oxygen reduction leading to Cr2O3(s) deposition.37] and subsequent formation of spinel.30. But how can one explain the strictly localized deposition of Cr2O3 that also occurs under anodic polarization? Under oxidizing conditions little Mn2+ is expected to be present in LSM. thus the formation of nuclei by the proposed LSM-Cr interaction won’t occur.37]: the two phases formed in the scope of a polarized LSM cathode exhibit distinctive microstructures: spinel forms large grains.33. In this case the contribution of reduction to the Cr-“poisoning” has to be rejected. one with a lower rate on the LSM surface. In this case no chromium will be deposited at the cathode-electrolyte interface under open-circuit conditions. whereas Cr2O3 is always located directly at the cathode-electrolyte interface. The region of spinel formation extends several microns from the TPB into the cathode. This is in contrast with the complicated mechanism for the formation of Cr2O3(s) under anodic 32 . Also two different diffusion processes were distinguished.34].32. and the second with a higher rate on the YSZ electrolyte surface. 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. the latter becoming reduced at the new TPB consisting of YSZ and electron-donating Cr2O3(s)[21. and it is also in line with the observed temporary reversibility of the cell deterioration[22. whereas an explanation by the chemical dissociation approach is not satisfying. whereas the phase that was most likely identified as Cr2O3 occurs in fine-grained.[24. from impedance spectra analyses it was in fact possible to distinguish two distinctive depositions of Cr-species. Thus it is obvious that the explanation of the “poisoning” process by the chemical dissociation approach alone is not without doubt. and the degradation can be associated to the dissociation process[24-27. This explanation is in line with the microstructural features of tested cells both under open circuit voltage and under current load.23. Some indications for two independent chromium poisoning mechanisms can be found in the work from Jiang et al.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Cr2O3-layer with CrO3(g).
if both the chemical dissociation as well as the reduction of gaseous Cr-species is occurring with different proportions. This is indeed true for the case of CrO3(g) and Cr-oxyhydroxide reduction being the only Cr-poisoning mechanism. based on an early finding that LSM behaves like a metallic electrode at low polarization potentials that was not quantified. In this context experimental results of a half-cell test with Cr-Fe-alloy (RA446) interconnect. 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. are particularly interesting: the slope of the cathode polarization curve (Fig. again with Mn2+ acting as agent for the formation of Cr-Mn-O nuclei.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects polarization established by Jiang et al. However this conclusion was not tested in the light of the oxygen partial pressure gradient towards the electrode-electrolyte interface: contrary to platinum. LSM cathode and a YSZ electrolyte at T = 1173 K and a current density of 200 mA cm-2 from Zhen et al. In cell tests of a polarized platinum electrode using a Cr-containing interconnect no Cr was observed. contrary to the situation of a strong pO2 gradient under cathodic polarization. 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. and thus under these conditions LSM has no tendency at all to accept oxygen. where the reaction partners for the reduction. 4 b) as a function of time reveals an inflection point after about 6 1/2 h. It was further mentioned that the existence of Cr-containing products away from the TPB would be in disagreement with the reduction approach. Alternatively. this apparent antagonism is abolished. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. but several processes may lead to the deterioration of cell 33 . and in LSM a pO2 gradient is expected under polarization. This different behavior of Pt and LSM electrodes under Cr-poisoning was used as an evidence for the exclusive validity of the dissociation approach. This is an indication against one unique “poisoning” mechanism. which is indeed not the case in a platinum cathode. that includes diffusion of Mn3+/Mn2+ driven by the oxygen evolution reaction at the cathode/electrolyte interface. 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. opposite to the situation with a platinum cathode. the number of the latter being less than under cathodic polarization. vacancies are expected to form in LSM under increasing polarization. However. Oxygen deficiency is negligible in LSM under high pO2 . and thus lack of spinel formation. contrary to an LSM electrode.
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. 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. the LSMCr interaction is again favored in the region close to YSZ as pO2 decreases at the TPB. This results in a lower oxygen partial pressure at the interface as compared to that in air. under open circuit the LSM-Cr interactions occur randomly throughout the cathode. the oxygen ions from this new. Oxygen is mainly reduced at the new TPB between Cr2O3(s) and YSZ. and their respective influence on the cell deterioration may vary as a function of time. give the following explanation. thus the remaining TPB/YSZ active sites are almost unaffected under open current circuit. Konysheva et al. 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. the lower is the oxygen partial pressure at the contact between LSM and YSZ. as electronic conductivity of Cr2O3 is significantly higher at higher pO2 (1. Applying a current load. weak catalytic reaction diffuse into YSZ. 34 . The deposition of chromium followed by its reduction near this interface blocks direct oxygen access to the electrochemically active sites.. Under polarization. Reduction already takes place at higher pO2 at the beginning of the current load operation. and oxygen cannot access the TPB.8 S m-1 in air). thereby still more decreasing the oxygen partial pressure at a newly formed Cr2O3(s)/electrolyte interface: the TPB between LSM and YSZ diminishes more and more by the blocking of Cr2O3(s).8 S m-1 at T = 1282 K and pO2 = 1 Pa. The important role of decreased oxygen activity at the LSM-YSZ interface under current load for the cell degradation was already suggested by Taniguchi et al. The temporary reversibility of the deterioration by switching the cell off and on again can also be explained: in contrast to current load operation. The higher the current density under SOFC operation. the oxygen ions formed at this interface are transported from the cathodeelectrolyte interface through the electrolyte. From the considerations in this chapter we conclude that no sustainable arguments exist for the rejection of the reduction of gaseous Cr-species as one of the controlling mechanisms of Cr-“poisoning” of SOFC. As Cr2O3(s) has a small electronic conductivity of 0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects performance.
3 occurs. 1. Numbers refer to locations of processes that are decisive for the degradation Number 1 in Fig. current load.2 is a visualisation of the microstructural consequences of chromium in an LSM cathode.1 to 1.2 Model of chromium poisoning of an SOFC with Cr-interconnect and LSM cathode based on the findings in the literature. Fig.2. 1. Eqs. 1. and chromium content is schematized in the picture.3. Fig.1 to 1. or gas-solid reaction. 1. followed by diffusion of the gaseous products into the cathode. Number 2 denotes the region of interactions between LSM and chromium leading to spinel formation by solid-solid reaction.3.3 to 1. but new oxygen is not supplied to the new TPB.2 denotes the interconnect-cathode interface region where oxidation of Cr2O3(s) to gaseous Cr-oxides and Cr-oxyhydroxides by Eqs.2. 1.3. The reported dependence of structural features of the degraded cell on the operation temperature.3. Eqs. 1. 1.1 leading to the redeposition of Cr2O3(s) at the cathode-electrolyte interface.126.96.36.199.3. and the degradation increases as a function of time. Active LSM/YSZ sites further diminish by ongoing formation of spinel and Cr2O3 deposits.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects Oxygen ions diffuse into YSZ.2. and number 3 denotes the reduction of gaseous Cr-species by the reverse of Eq. 35 .
2Mn0. La. However.50]. as Cr in the ppm range significantly influences the oxygen diffusion in the LSM cathode.54].4Co0.15MnO3-δ.85Sr0. La0. La0. Co-Mn. Cu1. Furthermore such a buffer layer may act as a sink for CrO3(g) thus diminishing nuclei formation on LSM.5Co0. MnCo2O4[54-61]. as well as (Ti. Ni. proposed that coating of the Cr-interconnect with a protective electrically conductive dense layer would be an effective strategy against the diffusion of Cr-species into the cathode. or Cu.8Sr0. Co3O4.475O4. 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. La0. sputtered Co. La0. but a combination of the quoted strategies is advisable to further improve the long-time stability of SOFC performance.65Sr0.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 1. 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.05Mn1. 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.1 Increasing the Cr-tolerance of conventional SOFC with Cr-interconnects and LSM cathodes More than ten years ago Badwal et al. La0.2FeO3-δ.6Sr0.65].5O3-δ.67Sr0. more active sites for the oxygen reduction will result in a higher Cr-tolerance. La0.Co)3O4. thereby improving the electrical conductivity of the interconnect-cathode interface[49-69]. 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 . or Cu-Mn.Sr)CoO3.8Sr0. or Mn2CrO4.475Co1.4Mn1. (La.33MnO3. If the buffer layer contains an ionic conductor. coating alone does not solve the problems associated to chromium poisoning completely. so far volatilization could not be suppressed completely. two-segment Cr-Al-Y-O nanocomposite and (Mn.5O3.4.Al)N. Ce0.4 Proposed strategies against chromium “poisoning” and their effectiveness 1. La0.6O4[53.8Fe0.2O3.5Co0. However.3MnO3[58.2Mn0. Mn.8Sr0.
71. particularly LSCF and LNF show rather high ionic contributions to the total electrical conductivity. 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. already considered alternative cathode materials to reduce or stop the formation of the spinel phase.8O3-δ (LSCF) cathode and Ce0.75] cathodes were investigated using impedance spectroscopy. The highest tolerance against the effects of chromium under SOFC operating conditions combined with high electrical conductivity has been reported recently for (La. Based on these findings they predicted that highly Cr-tolerant cathodes can be developed. La(Ni.Fe)O3-δ (LNF).Fe)O3-δ (LBCF) are more tolerant against chromium “poisoning”. In recent time it was found that new cathode materials such as La1-xSrxCo1-yFeyO3-δ (LSCF). the reduction of gaseous chromium will not be restricted to the small area at the TPB due to a smaller oxygen partial pressure gradient. Thus the number of active sites is increased.2 New ways – alternative materials Badwal et al. contrary to LSM.Fe)O3-δ (LNF)[71.Ba)(Co. which makes this material a promising candidate for a steady long-term SOFC performance. Matsuzaki and Yasuda concluded from insignificant Crdeposits in tested SOFC with Cr-Fe-alloy interconnect.73].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.6Sr0.Ba)(Co. 1.2O1. La0. All these perovskites are mixed electronic-ionic conductors. and (La. La(Ni. The amount of Cr- 37 . The ionic conductivity can be increased by doping the B-site of ABO3 perovskite with reducible cations.74]. whereas no proper nuclei were reported for LBCF. In all these cathodes Cr-deposition was observed throughout the cathode both under polarization and without polarization. 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.72].Fe)O3-δ (LBCF)[71. Effects of Cr upon the degradation of La1-xSrxCo1-yFeyO3-δ (LSCF)[26.4.8Sm0.2Fe0.Ni)FeO3-δ [71. and (La. LNF and LBCF revealed extraordinary high tolerance against chromium poisoning. Besides. and the cell is more tolerant against chromium.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. 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.4Co0.
171. most likely resulting in retarding or inhibiting of the reduction reaction. pp. As an alternative to the complicated nuclei mechanism. 397. 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. 284-93. Solid State Ionics. 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”. Advances. J. J. 2005. However. Metallic interconnects for solid oxide fuel cells. Power Sources.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects poisoning of LSCF was considerable. The amount of deposited Cr in LSCF was even larger without polarization than under polarization. H. 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. 2004. which was explained by a removing effect of nuclei for the chromium deposition under polarization conditions. Fergus. that is towards lower oxygen partial pressures. as this phase has a particularly high ionic conductivity. nuclei might form in addition. References 1. Fergus. Thus reduction of CrO3(g) takes place inside the whole cathode even without being promoted electrochemically by polarization of the cell. 127.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. 271-83. pp. Materials Science and Engineering A. Lanthanum chromite-based materials for solid oxide fuel cell interconnects. U. aging mechanisms and lifetime in solid-oxide fuel cells. 38 . Improved inhibition of the reduction of CrO3(g) is predicted for LNF. 2. pp.W. The higher the contribution of the ionic conduction the less complete reduction is expected due to prolonged lack of an electron donator. but their influence on the Cr deposition compared to the reduction of CrO3(g) cannot be decided yet. Stimming. Even if the reduction reaction is considered to be the dominant mechanism of chromium poisoning. However under strong polarization one can expect that LSCF gets more and more ionic conducting towards the electrode-electrolyte interface. 2004. Tu. and a typical mixed ionic-electronic conductor such as LSCF can take over both functions. J. 1-15.
Anorg.S. A. 2007. 9. 317-425. 17. Kim and G. Chem. E. pp. University of Pittsburgh. 16. A. 12.. Jacobson. Warshaw and M. pp.L. pp. Soc. 15. 1954.D. 108. Species CrO3 and CrO2(OH). Gauckler. 20. Johnson.. J. Less Common Metals. R. 53.M.E. Calphad. Rea.T. The oxidation of materials for interconnects in solid oxide fuel cells. 1964. 14. 334.B. 1991. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research.J. Photometric investigations of behaviour of chromium additives in premixed H2+O2+N2 flames. 108 pp. 2005. Thesis. Myers. Yang. Combust. 2006. 27. Flame. Arch.R. Loss of metal from chromium at elevated temperatures in air. 93. G. 1971-80. 8. Bulewicz and P. pp. pp. 1. M. L. Special high-temperature corrosion features of heat-resistant steels and alloys. J. D.R. 5. 1993. B. Nielsen. Thermodynamics of volatilization of chromic oxide.W. 39-54. Caplan and M. Chem. Thermodynamics of gas phase chromium species: the chromium oxides.M. Caplan and M. pp. E. 2008. Lond. M. 1973... 15. Proc. 284-93. 161-8. Phys. Dinsdale. Int.B.N.J. Z. J. 377-400. G. Trans. 151-4 (in German). pp. 1811-16. Gaseous hydroxide. 15(4).L. 271-284 (in German). Farber and R. D. pp. Srivastava. 438-442. pp. On a gaseous hydroxide of chromium. 1057-65. Povoden. 13. Belton. Mass spectrometric investigation of reactions involving vanadium and chromium with potassium-seeded H2-O2 flames. Opila. Metals. Olminsky. I. pp. 323. A. E. 1. Bandel. Y. The volatilization of chromium oxide. Recent advances in metallic interconnects for solid oxide fuel cells. pp. Ceram. J. 5. 4. 7. 1941. D. 353-62. I. Glemser and A. and volatility calculations in waste incineration processes. Res. Met. 6. Soc. 18. Wilms and T. 39 . Ebbinghaus. 1971. J. Allendorf. Combust. 43-9. the chromium oxyhydroxides. High temperature oxidation of some iron-chromium alloys. J. D. A. J. Flame. Phase Equilib. Solid solution and chromium oxide loss in part of the system MgO-Al2O3-Cr2O3-SiO2. 119-37. Am. J. Hammer. N. 37. Diff.-W. Z. pp. 8. 111. Allgem. Keith. Theroretical and experimental investigation of the thermochemistry of CrO2(OH)2(g). pp.F. 11. pp.. SGTE data for pure elements.J.. Electrochem. Padley. 1959. 411-12. 1961. Cohen. Cohen. Soc. Mater. 10. O. Grundy. Eisenhüttenwesen.D.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 4.K. J. 1974. pp. Müller. 1952.
Hilpert.G. 27. 23.. D.. Hilpert. Singheiser. Jiang. 147(9). 162. 2002. S. 22. J. Anderson. L. Penkalla. 143.P.. 2006. 132. J. A765-73. Konysheva.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 19. K. Solid State Ionics. Applied Electrochem. K. Hilpert. Zhang. Chromium poisoning of perovskite cathodes by the ODS alloy Cr5Fe1Y2O3 and the high chromium ferritic steel Crofer22APU. Electrochem. Ramprakash. Foger. II. Chromium vaporisation from Fe. 20. 528-33. Singheiser. U. Yasuo.P. 30. pp.. M. 1997. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Office of Fossil Energy Fuel Cell Program. J. 2000. T. Yasuda. 1043-1052. L. S. S. Apateanu. Konysheva. Soc.. Chromium poisoning of the porous composite cathode. Gindorf. Badwal. Seeling. Electrochem. 361-73. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. J. Electrochem. Mertens. Kadowaki. K. 154 (12)..D.-H. pp. Kawamura. K. S. 29.P. SOFC cathode materials development at PNNL. Miller. E. J. J. Zhen. 1996. Y. Stevenson. 22. 2007. Use of gaseous Cr species to diagnose surface and bulk process for O2 reduction in solid oxide fuel cells. Simner.13. 28. S. D. R. K. pp. E. 2000. Hilpert. pp. J. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. Electrochem. Soc. S. Singheiser. Matsuzaki. Zhang. L. J. 24. 72. T. Europ. Soc. Soc. Deller. 25. 31. Saitoh. H. Y. Weiβ. 297-310. Y. J. Jiang.Cr base alloys used as interconnect in fuel cells. J.P.P. M. III. Mertens.P. M. Y.S. X. pp. pp. Solid State Ionics. Soc. 153. J. Jiang. 271-278. 3642-7. R. E. L. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator.. Foger. 21. K. 99. I. pp.P.A. 93-6. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Steel Res. 40 . Chromium vapor species over solid oxide fuel cell interconnect materials and their potential for degradation processes. J. Effect on O2 reduction reaction. Peck. 3195-3205. Taniguchi. Li. Das. 181-192. Effect of cathode thickness and current density. Power Sources 55 (1995) 73-79. S. Ceram. Penkalla. Zheng. Akiyama. 2001. pp. 26.P. 2004. H. C. pp. 2006. J. Power Sources. B1252-B64. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. FY 2004 Annual Report. J. 2001. Y. Jiang. Wessel. Zhang. J. Miyake. E. pp. pp.
I. Ogasawara. 148. 173. 1-22. 34. 597-605.A. 1996. 2007. B. Chater. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Fergus. Chem. K.W.C. Jiang. J. V. Sci. T. pp. Jiang.N. 4th international symposium on solid oxide fuel cells 37. K. 4013-22.D. 40. M. Hydrogen Energy. 2001. Oxygen tracer diffusion coefficient of (La. S. Kilner. 39. Kaun. 3664-71. Electrochem. S. 36. A126-31. 39-43. pp. 747-58. Apateanu. Solid State Ionics. M. Electrochem. pp. A comparison of O2 reduction reactions on porous (La. Zhang. Wu.A. Inorg. Yasuda. A.Fe)O3 electrodes. A. Petrov.P. Kawada.P. pp..P. FY 2004 Annual Report. 32. Chromium poisoning of LSM-YSZ SOFC cathodes. Gauckler. S. Solid State Ionics. 2005. Calphad. Demina. Oxygen-transport in selected nonstoichiometric perovskite-structure oxides. J.J.C. Assessment of the La-Sr-Mn-O system.A. pp. Zhang.. 33. S.P. Solid State Ionics. Carter. Early interaction between Fe-Cr alloy metallic interconnect and Sr-doped LaMnO3 cathodes of solid oxide fuel cells. Dokiya. 35. 86-88. M. 2007. 2000.P. Foger. 38. Kinetic and geometric aspects of solid oxide fuel cell electrodes.C. pp. J. 2002. Filonova. Jiang. Power Sources. Development of lanthanum strontium manganite perovskite cathode materials of solid oxide fuel cells: a review. Int. R. Skaarup. 1992. 1197-1201. L. SOFC research and development. 28. 151(11). Steele. Mechanisms and kinetics. I. 86-88. J. S. Hash. Y. J.Sr)MnO3±δ. Zhen. pp.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 31. A. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes. Mater. S. J. Grundy. Russ. S. 44. M. J. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. Birss. Mogensen. Pal. Electrochem. 2008. 146. pp. 42. A. 771-74. 53. III.I. J. I. A1961-68. Huang. 6799-6833. Mater. T. B. J. J. Soc. Office of Fossil Energy Fuel Cell Program.N. Measurement of partial oxygen ion conductivity of Srdoped lanthanum manganite. Kajda. pp. 43. pp. 2004. Soc. 887-90. S. Y. Selcuk.H. J. Matsuzaki. Soc. Res. 2004. Zheng and P.. 191-201. Cruse. J..A.Sr)MnO3 and (La. pp. Paulson. E. pp. 1996. Krumpelt. Yasuda. 1151-60. 41. Solid State Ionics. 32. 41 . 2004. Jiang. J. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells.J.1.. W. Hishinuma.N. 2007. L. 45. T.Sr)(Co. 147. pp. U. pp.. Gopalan. 20. 43. S. 52. Hallstedt. M.
Soc. Protective coatings on stainless steel interconnect for SOFCs: oxidation kinetics and electrical properties. Mater. 176. Tech. Deng. P.C. 48. 138. Deng. R.. 2008. Garcia-Vargas. J.Y. Petric. Hammou. Tech. 53. R. J. Kayani.L.. Power Sources. 2000. A. Kleitz. 127.. P. Surf. K. Protection of SOFC interconnects against Cr-evaporation using atmospheric plasma-sprayed spinel layers. 57. 2007. Electrical conductivity anomaly of nonstoichiometric chromium sesquioxide. A. Vaβen. K. T. Smith. Lavacchi. T. A. Oxidation and electrical conductivity behavior of spinel coatings for metallic interconnects of solid oxide fuel cells. pp. N. Fossati. 115-118.. C. 289-93. Gorokhovsky.9Sr0. 011001-1 – 011001-5 54. A. L.R. pp. 49. 120. pp. De Jonghe. T. 1212-16. File No. Collins. A. Power Sources. M. M. Choi. 5. Reduction of chromium vaporization from SOFC interconnectors by highly effective coatings. T.1MnO3-x/yttria-stabilized zirconia interface for different cathodic overvoltages by secondary-ion mass spectrometry.-S. Office of Fossil Energy Fuel Cell Program. T. 42 . Bateni. Buchanan. Kato. M. Kawada. Bateni. P. FY 2004 Annual Report.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 46. K. J.-J. M. Deibert. Corrosion 63 (2007) pp. 52. Solid State Ionics. Stevens. M. Tietz. Homel. Yamaji.J. Quadakkers. pp. Cobalt plating of high temperature stainless steel interconnects. 47. Surf. Visco. Zanonella. A. Lucas. Horita. pp. 160. 4677-84. Fuel Cell Sci. C. S. V. H. Wei.V. pp. Petric. W. 578-89. 55. M. J. Wei. Bateni. C. Session B08. L. Chen. pp. D. J. T.R. Markus. M. Montinaro. Wei. T. 2007. E. D. M. Nucl. M. Sakai. pp.M. Spinel coatings for UNS 430 stainless steel interconnects. Armstrong. 7th European SOFC Forum. pp. A.E. 50. P.J. X. Yokokawa. Oxygen reduction sites and diffusion paths at La0.P. Caneiro. Siebert. Kiefer. Zahid. Hou. 1225-29. Smith. V. Virkar. X.I.J. Electrochem.J. T.R. 2006. P. Matsui. Froitzheim. Giolli. pp. 2005. Hilpert. Jacobson. M. Chromium volatility of coated and uncoated steel interconnects for SOFCs. X. J. Kopczyk. P. Bardi. Bertoldi.C. Deng. Niewolak. Naito. Singheiser. A. M. 1984. Petric. 164. Hammouche. Coat. 56. Tech. Protective coatings of metallic interconnects for IT-SOFC application. 2006. 425-33. A. 1991. U. 201. X. M. 201. Gannon. A. 55-65. T. 4467-70. 529-36. Stanislowski. Solid State Ionics. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. L. Sglavo.. 51. B081. F. Coat. J.
J. Fujita..-L. 261-69. 2000. J. 131. Stevenson. S. J. 60. Effects of La0. 2004. Fu. Xia. Visco. Kurokawa. 2007. Z. (Mn. Tech. L.R. Spinel and perovskite functional layers between Plansee metallic interconnect (Cr-5 wt.C. Z. Prevention of SOFC cathode degradation in contact with Cr-containing alloy. 2007. Yang. 33. Kurokawa. 177. T. 66. Li.91MnO3 cathode materials for solid oxide fuel cells. 67.-G. Smith.W. 11. Solid State Ionics.Co)3O4 spinel coatings on ferritic stainless steels for SOFC interconnect applications. Templeton. 65. Yang. Maupin. J. C.Q. 63. Coat. J. Sofie. 516. K. Hydrogen Energ. Lee.% Y2O3) and ceramic (La0. Deibert. Ce-modified (Mn. Electrochem. Int. Z. S. V. Wessel..85Sr0. pp.I. Chu. Matsuzaki. 3648-54. M. Thin Solid Films. Int. Solid St. J. K. Y. B140-43. pp.D. P. Z. 147. pp. H. pp. 61. Tietz. White. 2006.T. E. Laatsch. Lucerne/Switzerland. pp. Nie. C. Enabling inexpensive metallic alloys as SOFC interconnects: An investigation into hybrid coating technologies to deposit nanocomposite functional coatings on ferritic stainless steels. J. 2008. F. Hilpert. 3672-81. Yang. Sakurai. R. Chen. Norby. Jacobson. Influence of different perovskite interlayers on the electrical conductivity between La0. S.E.W.J. N. Jacobson. X. P.15)0. L. Zhang. N.. pp.Co)3O4 spinel coatings on ferritic stainless steels for SOFC interconnect applications. Dekker. Int. 62. 32. G.N. 287-96. J.. Conductive protection layers on oxidation resistant alloys for SOFC interconnect applications. K. 2008.. 4476-83. Tietz. D. 32. A.67Sr0. Ogasawara. pp.33MnO3 protective coating on SOFC interconnect by plasma-sputtering. X.-G. E. Rietveld. Solid State Ionics. 3251-56. Hydrogen Energ. J.3MnO3 and Fe/Cr-based steels. Konysheva. Gorokhovsky. 43 . G.B.-H. 2004. J.% Fe-1 wt. p. Power Sources. Kayani. Soc. G. K. Laatsch. Xia. 1857-63. Zhou. pp. 201. Xia.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 58. C. 319. 923-30. H.. 2007. Electrochem. Gannon.-Y. S. Wang. Evaluation of lanthanum ferrite coated interconnect for intermediate temperature solid oxide fuel cells. P. Christiansen. 64. Chromium vaporization of bare and of coated iron-chromium alloys at 1073 K. 2008. J. McCready. Sun. 2536-46. F. B. G. D. Hydrogen Energ. Stevenson. Y. Visco. 178. Evaluation of interconnect alloys and cathode contact coatings for SOFC stacks. C. C. 2006.W. Proceedings of the 6th European Solid oxide Fuel Cell Forum. 59. J. J. pp. Z. N. Stevenson. J. 68. Surf. T. Yang.65Sr0.-G. Singheiser. Larring. pp. Dejonghe.
K. Arakawa. 153. Tok. Jiang. A.-H.P. 11. pp. Hydrogen Energ.D.Sr)(Co. G.Y. F. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. 451-56. J.V. C. and V doped-LaCrO3 interconnect materials prepared by Pechini.75Sr0. J. 77. Power Sources. 17. 2006. E. Solid State Ionics. A.C. Deposition of Cr species at (La. Shul. 2008. 61-6. 72.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect. Shin. A127-A134. Boey. Li. 2008. Diwu. J. 2008. 723-27. Tsipis. Development of Cr-tolerant cathodes for solid oxide fuel cells.I. S. Properties of Cu. Kim.P. 71. Sato. Zhang. 2007. Y. pp. R. B42-6. J. Dong. S. 75. 2007.. Kharton.V..P. J. Zhen. 78. 70. 9. 33. 44 . 76. Frade. C. Int.P. S. K. Developing TiAlN coatings for intermediate temperature solid oxide fuel cell interconnect applications. T. Peck. J.25)0. Marozau. Arai.-H. 695-703. Liu. Zhen.5Mn0. 2008. pp.Fe)O3 as a cathode material with high tolerance to chromium poisoning for solid oxide fuel cells.Y. C. Electrochem.. H.T. Electroceram. Xu. Nozawa. Viskup. Cr Poisoning suppression in solid oxide fuel cells using LaNi(Fe)O3 electrodes. Mixed conductivity and electrochemical behavior of (La0. Jiang. Meng. Power Sources.-Y. 74. Chiba. S. S. 177. P. X. Zhen.P. Jiang. T. pp. D. M. Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells. pp. Y.Y.Fe)O3 cathodes of solid oxide fuel cells. Liu.-H.S. 2008. M.Ba)(Co. Zhao. A. J. La(Ni. 101-13. pp. Zhen. L. 178. F.P. Irvine. G.-G.5O3-δ. X. A9-12. Ni. Wu. 2006. Electrochem. 176. J. Y. L. 82-89.D. and D. K. Komatsu. SolidState Lett.. 2006. Wang.R.C. R. Johnson.Degradation of planar solid oxide fuel cells (SOFC) with LSM cathodes and Cr-alloy interconnects 69. Liu. 189-96. J.-H. Ong. 170. Pu. S.P. I. Lee. Y. Lim. V. pp.P. D. Soc. pp. Power Sources.Y. J. J. Li. Jiang. J. Boey. J. pp. Jiang. Y.. pp. 73. Characterization and performance of (La. Cross.D.I. Liu. Solid St. S.95Cr0. Tok. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. Song.-R. J. Electrochem. 180. Power Sources.
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. For a more systematic and thus more efficient combination of strategies a strong knowledge about the mechanisms of chromium poisoning of SOFC is required. Mn2+ in LSM plays an important role for the adsorption of gaseous CrO3(g) and Croxyhydroxide on LSM resulting in blocked oxygen transport from the cathode to the electrolyte.Aim of study 2 Aim of study Chromium poisoning of planar SOFC with LSM cathodes and Cr-alloy interconnects is a complex process consisting of several steps that may occur simultaneously inside the cell. and some strategies against cell degradation caused by chromium have already been successfully applied. this behaviour would not be expected. 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. This means that the kinetic control on the mechanisms of chromium 45 . but the effects of chromium would be observed only after thermodynamic equilibrium is obtained. severe degradation has been observed after several hours of testing under current load at state-of-the-art SOFC operating temperatures: from the literature findings it is obvious that the degradation of SOFC caused by chromium starts immediately after starting SOFC tests under current load. However. Previous experiments have shown that the following factors: -) High temperature -) Decrease of oxygen partial pressure at the TPB under current load of SOFC and processes: -) Interaction of chromium with LSM leading to Mn-Cr-O nuclei and/or spinel formation -) Reduction of CrO3(g) to Cr2O3(s) at the TPB -) Blocking of pores at the TPB by Cr2O3 and/or spinel govern the degradation of SOFC caused by chromium. So far it was not possible to define unambiguously. Reduction of CrO3(g) at the TPB leads to the formation of electrically low conducting Cr2O3. which of these processes play a dominant role for the degradation and which don’t. which further retards the diffusion process of oxygen into the electrolyte. If the process of chromium “poisoning” were completely governed by thermodynamics.
3 Method 3. and what are the conditions that favour their formation? This work aims to answer these questions by the application of thermodynamic calculations. Thus. the obvious question why the results of thermodynamic calculations should be feasible for a deeper understanding of the mechanisms 46 .Aim of study is high. In particular LSM cathodes have been intensively investigated over the last decade. in this study the author focuses on the effects of Cr on the degradation of SOFC with LSM cathodes. 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 several studies can be found regarding the degradation of LSM cathodes caused by chromium. As a degrading cell is in a non-equilibrium state. 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. In recent times many materials have been tested for SOFC cathodes.1 Benefits of the thermodynamic La-Sr-Mn-Cr-O oxide database for the understanding of Cr-poisoning of SOFC A thermodynamic La-Sr-Mn-Cr-O oxide database is highly desirable to enable fundamental understanding of the mechanisms of chromium “poisoning” of LSM cathodes for SOFC. The following questions have remained unsolved so far: -) Does spinel form by a solid (LSM)-solid (Cr2O3) reaction or directly in a solid (LSM)-gas (gaseous Cr) reaction? -) Can the concentration of deposits at the cathode-electrolyte interface under current load be explained by thermodynamics? -) How does the LSM phase chemically change due to the interaction with chromium. Therefore the thermodynamic La-Sr-Mn-Cr-O oxide database needs to be established based on the assessments of low-order subsystems.
2 Thermodynamic modeling 3. one can draw conclusions on the evolution of the phase chemistry of degraded LSM cathodes. From A and B. composition of LSM.1 reflects the path the system takes towards its equilibrium state. C can be predicted for changing cathode compositions. the theoretical final state of chromium poisoning after a very long time is found by thermodynamic equilibrium calculations (B). temperatures. 47 .1. For instance. 3. The presented thermodynamic database of the La-Sr-Mn-Cr-O oxide system is constructed using the CALPHAD approach. It contains the optimized Gibbs energy functions of solid oxide phases: for stoichiometric phases as a function of temperature. 3.1) By calculating thermodynamic equilibria for a LSM cathode that is affected by chromium (A) in the relation above. taking into account experimental data on the chromium “poisoning” of SOFC and using a thermodynamic La-Sr-Mn-Cr-O oxide database. containing m and n moles of two different sorts of cations. a with the positive electrical charge r and b with the positive electrical charge q. The optimization of model parameters is based on the accurate assessment of experimental thermodynamic and phase diagram data of oxide subsystems. and the rate of chromium diffusion the equilibrium state of chromium “poisoning”.Method of chromium “poisoning” needs some explanation: from the conditions of the non-equilibrium state at the beginning of the degradation process. 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. and oxygen partial pressures. by choosing the starting conditions composition of LSM and defined amount of Cr at a specific temperature. C in Eq.1 Stoichiometric solid oxides The stoichiometric ternary phase α.1. Hence. and for solid solution phases as a function of temperature and composition. including the operating temperature. using the thermodynamic database one can calculate the expected thermodynamic equilibrium.equilibrium (A) ⎯⎯ equilibrium (B) → (3.2. can be calculated using the thermodynamic La-Sr-Mn-Cr-O oxide database: C non . for instance under reducing oxygen partial pressures reflecting the situation at the TPB under current load.
2. the sublattice formula of the resulting solid solution phase β(ss) reads (a r . u. C. 3. D. and p moles of one sort of anions.)u containing cation a with the positive charge r.)u .Method respectively. w ∈ N ). E.2. b q )t (O2.2. Eq.2.5 is the criterion for charge neutrality: 48 . E and F are optimized to heat capacity data only. A and B are optimized by thermodynamic and phase diagram data.4: m ° ( a )t (O2. D.4) ° α Gm is the Gibbs energy of formation of the phase α relative to the oxide components. 3. v.1 is true. Eq. and F are model parameters to be optimized by thermodynamic and phase diagram data. 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. °Gm at constant pressure is given by ° α Gm = A + BT + CT ln T + DT 2 + ET 3 + FT ( −1) (3.) p = q )v (O2.)u n ° (b G + Gm t m v r ° α Gm = °Gm ( a r )m (bq )n (O2. For oxides c = O and charge s = −2.) w ( t .)w + ptv − muv − nwt ° O (g) Gm + A + BT 2tv 2 (3. °Gm can be based on the molar Gibbs energies of existing binary oxides Ox1: (a r )t (O2.2.2. another sort of cation with the positive charge q. As Cp(α) is defined by C p = −C − 2 DT − 6 ET 2 − 2 FT −2 (3. B. To account for the charge neutrality criterion. bq can sit in the same sublattice as a.)u and Ox2: (b q )v (O2. the three types of ions sitting in three distinctive crystallographic sublattices. mr + nq + 2 p = 0 (3.1) α The molar Gibbs energy of α.3) α C.2.2) A.2 Solid solution phases – the Compound Energy Formalism (CEF) If in the binary oxide Ox1: (a r )t (O2. 3. can be described by the sublattice formula (a r )m (b q )n (c s ) p . c with the negative electrical charge s.2.
In the sublattice form the phase can be written as (a3+ . R=8.3 Vacancies and the concept of reciprocal reactions Let us consider the case of a binary oxide phase (A)2(B)3..Va )3 ( = ya3+ yO2.5) Using the Compound Energy Formalism (CEF)[2-4].)u β + tRT yar ln yar + ybq ln yar + EGmss ( ) (3. 3. with only one cation a accepting the charge 3+ or 2+ in the cation sublattice. the charge neutrality criterion is no longer obeyed by an anionic sublattice that is completely filled with oxygen. a 2+ )2 (O2. Charge neutrality under such reducing conditions can be remained by the formation of zero-charged vacancies (Va) in the anionic sublattice resulting in the phase becoming oxygen-nonstoichiometric.)u + ybq °G (b q )t (O2. A standing for the cation sublattice. 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.7) Once again the molar Gibbs energies of all the 4 endmember compounds (a3+ )2 (O2. The Gibbs energy of β(ss) at constant pressure reads ° β Gmss = yar °G ( a r) t (O2.6) where yar is the site fraction of cation a on the cation sublattice.)u and (bq )t (O2. For β(ss) the two compounds read (a r )t (O2.. The oxygen nonstoichiometry is denoted “O3-δ”.Method u= t ( ya q + yb q ) 2 (3.)3 .+ yVa ln yVa + EGma ( ) ( ) . and ybq is the site fraction cation b on the cation sublattice. The molar Gibbs energy of the phase at constant pressure reads 3+ ° A ( Gm 2 O3−δ = °Gma 2+ .2. a 2+ )2 (O2.2. and B denoting the anion sublattice.31451 J mol-1 K-1.Va )3 (3.)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.)3 ( + ya2+ yO2. The second-last term accounts for the configurational entropy of mixing of t moles of a and b. a 2+ )2 (O2. (a 2 + )2 (O 2.2. the molar Gibbs energy of the solid solution phase contains the Gibbs energies of the compounds. and (a 2 + )2 (Va)3 of the phase are required for the molar Gibbs energy 49 .°Gma 3+ )2 (O2.)3 .°Gma 2+ )2 (O2. If the cation is reduced..)u . Va)3 .2.ln yO2. (a 3+ )2 (Va)3 .
and its Gibbs energy can be optimized with experiments that are related to the reduction of the phase..)3 .1. for instance oxygen nonstoichiometry data. For the example of the reciprocal solid solution phase (a3+ . 50 . thus far off neutral compositions that can really exist.Method of the phase. the reference should favorably be a highly charged compound. As the chosen molar Gibbs energy of the reference is unlikely the true value. Va)3 approximating its overall Gibbs energy for Δ°Grec > 0 and Δ°Grec = 0. 3.2. The 2+ charged center composition of the square. 3. Fig.1 that is redrawn from Hillert. a 2+ )2 (O2. denoted with R. Va)3 is a reciprocal phase. the only neutral endmember is (a3+ )2 (O2. (a3+ a 2+ )2 (3 2O2. is theoretically obtained by mixing equal amounts of either (a3+ )2 (O 2.)3 .1 The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . a 2+ )2 (O2.)3 with the reduced compound (a 2+ )2 (2 3O2. The composition square of the phase can be seen in Fig. The three other endmembers are charged and cannot exist.. denoted with A in Fig. However.)3 and (a 2 + )2 (Va)3 or (a3+ )2 (Va)3 and (a 2 + )2 (O 2. and (a3+ . It thus can exist. plotted above the composition square. with the neutral line and the reduced compound. and its molar Gibbs energy can be defined by optimization of model parameters by experiments..3 2 Va)3 . but a line of neutral compositions connects (a3+ )2 (O2. Va)3 the 6+ charged compound (a3+ )2 (Va)3 is chosen as reference. a 2+ )2 (O2. included.2. A system that obeys this relation is called a reciprocal system.Va)3 . 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.2. 3.
2. d 3+ . As no tendency of demixing was reported for the nonstoichiometric oxide solid solutions that are treated in this study. Note that in order to obtain the same Gibbs energy of the reduced compound R for Δ°Grec > 0 and Δ°Grec = 0. Δ°Grec is positive. it is legitimate to define Δ°Grec = 0.2. The morphology of the Gibbs energy surface depends on Δ°G of the reciprocal reaction (a3+ )2 (Va)3 + (a 2 + )2 (O 2.Method The surface of reference for the Gibbs energy of the reciprocal phase (a3+ . and oxygen partial pressure. In Fig.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. On the other hand. b 2 + .1 (page 50) and approximates the whole Gibbs energy of the phase. This is not a problem for the description of a reciprocal oxide phase. and no experiments define a proper value of the reciprocal reaction parameter. and the theoretic compound A will tend to demix to (a3+ )2 (O2. Va)3 for a Cr-doped LSM perovskite as a function of composition.. Va)3 at very low temperatures (to make the configurational entropic contribution negligible). the true surface shape of a reciprocal oxide phase with charged endmembers is not known.2.) 3 − °G ( a 2+ ) 2 (Va)3 (3. 51 .1 (page 50) only the edge of this plane is seen as bold line. 3. the Gibbs energy surface is flat and no tendency of demixing of A exists. 3..)3 and (a 2+ )2 (Va)3 by only slightly oxidizing or reducing it. site fractions and oxygen content.8) If Δ°G of the reciprocal reaction. if Δ°Grec is zero. For this purpose model parameters of the reduced and oxidized compounds are optimized with experimental information on charge carriers. temperature. c 4 + .)3 and the reference (a 3+ )2 (Va)3 are fixed. a 2+ )2 (O2. as long as these endmembers are charged and away from the existing composition range of the phase. Anyway. Va)(c 2 + .) 3 − °G ( a 3+ ) 2 (O 2. when the Gibbs energies of the endmember (a 3+ )2 (O 2.)3 − (a 2 + )2 (Va)3 : Δ °G rec = °G ( a 3+ ) 2 (Va)3 + °G ( a 2+ ) 2 (O 2. c3+ .2. the Gibbs energies of the remaining endmembers are significantly different for Δ°Grec > 0 and Δ°Grec = 0. Va)(O 2. and without excess terms for the Gibbs energy is visualized in Fig. 3. the Gibbs energy surface is curved. for instance (a 3+ . d 4+ .)3 − (a3+ )2 (O 2.
The Thermo-Calc databank system. M. 79(2). A. Vol.P. Pergamon Materials Series. B.Method 3. 437-445. Hillert. L. Sundman. Jansson. T. Jansson. Ivas.F. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. 4. B. Jansson. pp. This weighting process is based on the accurate assessment of experimental thermodynamic and phase diagram data. 2. B. Hillert.. B. pp. pp.. Alloy. 1998. J. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.-O. Application of the Compound-Energy Model to Oxide Systems. 320.O. M. pp. M. Miodownik.. Saunders. 81-87. Calculation of Defect Chemistry Using the CALPHAD Approach. PARROT can take into account all sorts of thermodynamic and phase diagram data simultaneously. 3. 33-41. Acta Metall. Gauckler. J.3 Optimization of model parameters The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system. 1. Guillermet. 52 . Povoden.. 1988. Cmpd. B. Elsevier Science Ltd. References 1. A. Andersson. Sundman. 6. Z. Hillert. Calphad. 1986. N. B. Grundy.N. E. 153-90. A. J. 2001.J. Sundman. 34. 161-76. pp. Andersson. 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. 479 p. The Compound Energy Formalism. 2006. 1985. The program minimizes the sum of squared errors between calculated and experimentally determined phase diagram and thermodynamic data. 5. Calphad Calculation of Phase Diagrams. 9(2). Calphad. 30. Metallkd.
Povoden.1.% Fe and 1 wt. A. combined heat. low manufacturing costs and high thermal conductivity. Microstructural analyses of the cathode of SOFC show the formation of Cr2O3 and (CrMn)3O4. 5 wt.% 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. 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. and the liquid is described using the two-sublattice model for ionic liquids.1 Technology SOFC offers high fuel conversion efficiencies and.Thermodynamic assessments 4 Thermodynamic assessments 4. by application of the CALPHAD method. and L. ceramic and metal interconnect materials have been tested and evaluated over the years.1 Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research E. which offers low fabrication costs. Namely a Cr5Fe1Y2O3 oxide dispersion strengthened alloy with the composition 94 wt. However. Cr3O4 is described as a stoichiometric compound. Phase Equilib.. Grundy. which block active sites as well as pores. Meanwhile the use of Cr-based alloy interconnect materials has gained popularity due to their relative ease of fabrication.and power-generation capability. due to the high operating temperature (>1173 K). Also the magnetic transition in Cr2O3 and the oxygen solubility in Cr are modeled.% Cr. Gauckler J. A comprehensive compilation and evaluation of experimental and thermodynamic data for the Cr-O system is presented and.N. 2006. a consistent set of thermodynamic model parameters is optimized based on new experiments. For the planar design SOFC.J. 353-62. Loss of performance caused by the migration of Cr originating from the alloy interconnect is well documented by several investigators. 27. Nonstoichiometry of eskolaite (Cr2+xO3) is described using the compound energy model. Diff. 4. thus substantially reducing the triple- 53 . pp.
tectic T (K) ----T (K) ----Reference Kanolt experimental Wilde and Rees experimental McNally et al. 4.1. T (K) T (K) 2257 2317 2603 ---- 2543 ± 25 -- 54 .2 Experimental data Phase diagram data: Experimental investigations of phase diagrams in the Cr-O system were made by Ol’shanskii and Shlepov and Toker. Eskolaite (Cr2O3) is the dominating stable oxide phase over a wide temperature range. These authors document the existence of a large miscibility gap between the metallic and the oxide melt.1. Results of special points in the Cr-O phase diagram from several studies are summarized in Table 4. X(O) ----Cr3O4 detected ----Stability range Mono- of Cr3O4. experimental Bunting experimental air. The influence of Cr from the interconnect alloy on the strontium-doped lanthanum manganite (LSM) cathode can be modelled in terms of an equilibrium thermodynamic view to contribute to strategies for reducing the SOFC chromium poisoning process by optimizing SOFC operating conditions and refining SOFC material compositions.1.1 Special points in the Cr-O system Eutectic Melting of Cr2O3 in Eutectic composition.1.Thermodynamic assessments phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. Table 4.
499 0. Concerning the pure Cr-O system.% 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.513 0. Ol’shanskii and Shlepov and Johnson and Muan did not find Cr3O4 up to the eutectic temperature of chromium oxide. who measured T = 2543 ± 25 K also in air.Thermodynamic assessments --2571 ---2539 1933 1918 1941 1929 1937 1938 ± 2 1938 0. Investigations made by Hilty et al. The question of the existence of a crystalline Cr3O4 phase was discussed controversially by several authors. Microstructures of a quenched 55 . 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. experimental This work. 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.497 0.523 0. experimental Johnson and Muan experimental Degterov and Pelton calculated Kowalski and Spencer calculated Taylor and Dinsdale calculated Toker et al.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. 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.496 0. This value significantly deviates from the result of Bunting.52 0. Mc Nally measured a melting temperature of 2603 K in air using an induction furnace. whereas Toker 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. The data are in close agreement with the gas-solid equilibrium measurements by Jeannin et al. 1273 K. days for T < 1100 K. causing transfer of oxygen through the cell. that is. This indicates that the first phase to crystallize on solidification is Cr3O4 giving strong evidence for the stability of this phase. 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. Pugliese and Fitterer. and Tretjakow and Schmalzried were assigned to possible electronic conduction in the zirconia electrolyte used by the latter authors. Disagreement between the emf results from Pehlke et al.. and 1373 K. Davies and Smeltzer determined log( pO2 ) values of Cr2O3 at T=1173 K. and Lam. Pehlke et al.. Novokhatskii and Lenev studied the equilibrium of the reduction of Cr2O3 to Cr with hydrogen from T=1493 K to 1893 K. The independent results of corrected cell potentials of the two measurement series are excellent.. These authors used a flow method where thermal diffusion problems were suppressed by inserting corundum bushes into the reaction tube. Toker et al. Thus in this study the authors accept the findings of Toker et al. 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. Applying the same technique as Pehlke et al. 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. At T ≥ 1573 K they were confronted with the loss of a quarter of Cr in the case of oxidation. as well as transport of oxygen ions from the cathode to the Cr/Cr2O3 anode. The obtained 56 . Appreciable sublimation of metallic chromium was not observed. 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. used two separate series of emf measurements employing the solid oxide electrolyte galvanic cell technique from T = 1148 K to 1548 K. using an electrochemical cell with a calcia-zirconia electrolyte and a Fe/FeO reference electrode. thus at these temperatures log( pO2 ) values were determined solely from the reduction of Cr2O3.
53T + 1.1.3) For ° S298K (Cr2O3) Chase et al.68 ≤ T ≤ 323..53 + 2. and fitted the data to the heat of diffusion equation that considers some material properties employing a least-mean-squares fit.43 K.736 ×105 T −1 − 9759 (4.1) yielding ° H T − ° H 298K = 28.5 K to 340 K with mean increments of 0. The latter authors measured a consistent data set of heat capacities of synthetic eskolaite from T = 1.1. Heat Capacities. Uncertainties of 0.736 ×105 T −2 (4.. Bruce and Cannell applied a two-dimensional temperature wave method using a single crystal of Cr2O3 to calculate specific heat in the temperature range 290.56 K. The accuracy of this study is evident from excellent data reproduction by performing two runs in the entire temperature range.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 .7 % for Cp (T < 20 K) were estimated. who calculated ° S298K (Cr2O3) = 81. heat Contents.15 K Chase et al. and fitting procedure are worked out very carefully.4 % for Cp (20 K < T < 200 K) and 0.. and entropies: Anderson’s calorimetric data set of Cp-values lacks detailed documentation of the experimental procedure. Resulting Cp data correspond nicely to the most recent calorimetric results from Klemme et al. relied on the calculated results from heat content measurements performed by Kelley et al.37 J mol-1 K-1 at T = 298. Documentation of the experiments. The latter authors fitted their data measured from T = 400 K to 1800 K by H T − ° H 298K = aT + b T 2 + cT −1 + d 2 ° (4. 4.1.2) Temperature derivation of Eq.20 ×10−3 T − 3. relied on the results from Anderson. For Cp(Cr2O3) = 120.10 ×10−3 T 2 + 3. data presentation.2 results in C p = 28.17 ± 0.1.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.
Klemme et al.el° H 298K (Cr2O3) = –1128. This was circumvented by heating the combustion products to T = 1323 K.86 J K-1 mol-1.4 kJ mol-1 from several earlier studies.el° H 298K (Cr2O3) = –1139.el° H 298K (Cr2O3) =–1140. thermodynamic data for Cr-Cr2O3 from Fromm and Gebhardt. For the calculation of Δ f.el° H 298K (Cr2O3) = –1134. Degterov and Pelton reassessed the CrO-Cr2O3 subsystem for the molten slag database using a modified quasi-chemical model for the liquid phase.1 J K-1mol-1 by reevaluating emf data from Holzheid and O’Neill.98 ± 1. evaluated Δ f.42 kJ mol-1. Shirokov estimated Δ f. for example. who calculated ° S298K (Cr2O3) = 85.16 K. while Dellien et al. Dellien et al. Enthalpies of Formation: Roth and Wolf found Δ f. The latter authors proposed a 58 .74 ± 1. 4.2 ± 0.el° H 298K (Cr2O3) = –1122.el° H 298K (CrO) = –305. This procedure was critically documented by other authors.el° H 298K (Cr2O3) = –1125. Klemme et al. Klemme et al. Kowalski and Spencer used the associated solution model for the liquid phase based on the experimental data used by Taylor and Dinsdale. which is in good agreement with an early finding by Bunting who measured T = 2543 ± 25 K.5 kJ mol-1 (el=elements) by applying a calorimetric technique. adopted their ° S298K (Cr2O3) value from Wagman et al.72 kJ mol-1 from Wagman et al... Ramsey et al.3 Previous assessments of the Cr-O system Banik et al.4 kJ mol-1 by evaluating emf data from Holzheid and O’Neill. calculated Δ f..el° H 298K (Cr2O3) the heat content data given by Kelley et al. using a bomb calorimetric combustion technique at 1323 K and 30 atm oxygen pressure. were used. Shirokov estimated ° S298K of a metastable CrO phase to be 46. recommended Δ f. adopted Δ f.el° H 298K (Cr2O3) = –1128. used heat capacity and entropy data from tabulations of Coughlin to obtain Δ f. Navrotsky cited Garrels and Christ for Δ f.3 J K-1 mol-1 from their measurements. 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.4 kJ mol-1 for metastable CrO. Some difficulty caused by moisture adsorption was encountered in weighing the combustion products.Thermodynamic assessments functions.7 kJ mol-1. and thermodynamic estimates for CrO from Shirokov. Mah.1. recommend ° S298K (Cr2O3) = 83.7 ± 8.06 kJ mol-1. Chase et al.8 ± 2. Their calculated liquidus temperature of Cr2O3 in air is T = 2571.
Their optimization of one of the charged endpoints in their compound energy model for eskolaite and the use of six interaction parameters to describe the liquid may lead to problems on extrapolation to higher-order systems. and the temperature of the monotectic reaction of Cr(bcc) and liquid between the assessments of the Cr-O system.4 Thermodynamic modeling Solid phases: The crystal structure of eskolaite is α-Al2O3 type. space group R3c .1. Kelley et al. The magnetic properties of eskolaite can be described using a magnetic ordering model proposed by Inden. using the same thermodynamic models as the authors use in this work. Experimental information on phase relations for their assessment was taken from Ol’shanskii and Shlepov. and only few thermodynamic data of the Cr3O4 phase and the liquid phase exist. 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. Their calculated values for the enthalpy of formation and the entropy of Cr3O4 are in agreement with an estimate done by Chipman. Toker. The use of six parameters for the description of the Cr3O4 phase is somewhat incommensurate with the scanty experimental information of this phase. This is reflected by significant variations of the position of the eutectics. which are the two-sublattice ionic model for the liquid and the compound energy model for the Cr2+xO3 phase.4) 59 . Eskolaite shows an antiferromagnetic to paramagnetic transition at T = 305. 4. and Grube and Knabe.Thermodynamic assessments phase diagram in good agreement with the experimental data obtained by Toker. and simplified by Hillert and Jarl. Taylor and Dinsdale fitted Cp data from Anderson close to the antiferromagnetic to paramagnetic transition and data from Chase et al. the stability field of Cr3O4. especially as their miscibility gap does not close on increasing temperature. at elevated temperatures as a sum of magnetic and nonmagnetic contributions. There is a large uncertainty concerning the exact melting point of Cr2O3.5 K. In this model. The heat capacity of Cr3O4 was taken as 7/5 times the nonmagnetic value for Cr2O3 according to Neumann and Kopp’s rule.1..
The magnetic parameter p equals 0. their equation violates the fundamentals of defect chemistry and must be rejected in favor of the defect reaction given above (Eqs. This means that reduction is accomplished by the formation of interstitial Cr3+ and not by the formation of oxygen vacancies.1.28. which is in agreement with Young et al. The following other interstitial defects could be assumed: Cri•• giving a slope of pO2 −1 4 .Thermodynamic assessments where β is a parameter related to the total magnetic entropy. 4.Cr3+)2 (Cr3+.1.. however.1.5) 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. Inserting this ' into Eq. Assuming the defect reaction that describes the formation of oxygen vacancies: x x ' CrCr + 1 2OO → CrCr + 1 2 Va •• + 1 4O2(g) O (4.6 gives the proportionalities [Cri••• ] ∝ pO2 −3 16 and [CrCr ] ∝ pO2 −3 16 . it is important to submit the experimental data to a defect-chemistry analysis. Tc is the critical temperature for magnetic ordering. The defect chemistry of Cr2+xO3 with the sublattice occupation (Cr2+. Tc and β are both dependent on the composition.5 and 4.1. To explain their experimental results Matsui and Naito proposed a defect reaction that leads to the same proportionality. In the case of Cr2+xO3 modeled with interstitial Cr3+ the defect reaction reads x x ' x 2CrCr + Va ix + 3OO → 3 2CrCr + 1 2Cri••• + 1 4 Va ix + 9 4OO + 3 8O 2(g) (4.6) ' Assuming small defect concentrations all concentrations except [CrCr ] and [Cri••• ] are ~ 1 and ' can be ignored. Due to charge neutrality the relation [Cri••• ] = 3[CrCr ] must hold.1. 4.Va)1 (O2-)3 can be modeled using experimental data from Matsui and Naito.6). the latter because of the large size of Cr2+.7) 60 . and Cri•••• giving a slope of pO −3 20 2 . When modeling nonstoichiometry in an oxide phase. Both are unlikely: the former because it is unlikely to get Cr4+ on reduction.1. and τ = T/Tc.
1. for example charge disproportionation.. This slope does not correspond O to the experimental findings of Matsui and Naito. Fig. 4. the present authors believe that the different slopes are caused by a competing defect reaction. Cr3+ → Cr2+ + Cr4+. similar to the case of LaMnO3 perovskites.1 is a graphic representation of the model the authors use to describe the oxygen nonstoichiometry of eskolaite. 4.Thermodynamic assessments ' leads to a proportionality of [Va •• ] ∝ PO2 −1 6 and [CrCr ] ∝ PO2 −1 6 . The low nonstoichiometry data from Matsui and Naito show a different slope than their higher nonstoichiometry data. In contrast to Matsui and Naito who explain this assuming that neutral Cr forms interstitially. where each corner of the composition square represents a °G parameter. Only compounds along the neutral line can exist on their own. Also the defects cannot explain the electrical properties measured by Young et al. as it would make the description quite complex. The present authors didn’t consider this by their defect chemistry model.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.1. The corner Cr3+:Va:O2corresponds to stoichiometric Cr2O3. 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 .
This is done by using the two equations for the stoichiometric and the reduced endpoints.8) The last term describes the configurational entropy due to mixing of Cr3+ and Va on the interstitial site.1. The function to model the reduction then reads ° GCr2+ 3+ 2− 2 (Cr 2 3Va1 3 )(O )3 = °GCr O + 2 3 °GCrSER + A + BT + RT ( 2 3ln 2 3+1 3ln1 3) 2 3 (4. °G of the 3+ charged endmember (Cr3+)2 (Cr3+)1 (O2-)3 is chosen as reference and given the value °GCr3+ :Cr3+ . 4.63-188.8.131.52 to 4.1.9) In order to avoid the inevitable formation of miscibility gaps if the energy of the reciprocal relation is large we set this energy zero. 62 . The expressions for all °Gs at the corners resulting from Eq. Then the reciprocal relation reads ° G Cr3+ :Cr3+ + °G Cr 2+ :Va = °G Cr3+ :Va + °G Cr 2+ :Cr3+ = ΔGr (4.Thermodynamic assessments (Cr2+)2 (Cr3+2/3Va1/3)1 (O2-)3.10) This means that without introducing interaction parameters one gets an ideal description between Cr2O3 and Cr2+xO3. and by defining a reciprocal reaction giving four equations with which all °Gs at the corners can be expressed. one has to find functions of °G of three charged corners expressed solely in terms of the neutral compositions.10 are listed in Table 4.1. pp.2. 4.1. by choosing an arbitrary reference.1. which leads to ° G Cr3+ :Cr3+ + °G Cr 2+ :Va − °G Cr3+ :Va − °G Cr 2+ :Cr3+ =0 (4.1. labeled A in Fig.
− 3H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.543 102.Va L = −709542 Tc = −311.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.− 2 H Cr -3H O = GCR2O3 3+ Cr 3 SER SER GCr 2O:Cr3+ :O 2.Va q.Va)1 (O 2.= 121000 Solid Cr (bcc_A2) (Cr)1 (O.)3 ° ° ° ° Cr 3 SER SER GCr 2O:Va:O 2.52 mol O2 0 LCr 2+ :O2. Cr 3+ ) 2 (Cr 3+ .0 4341.0 S298 23.1.999 H298 ..− 3H Cr − 3H O = GCR2O3 + GHSERCR  3+ Cr O3 SER SER GCr 22+ :Cr3+ :O 2.Thermodynamic assessments Table 4.4 β = −0.28 Tc = 308. q = 2 yCr 2+ + 3 yCr3+ ° ° ° ° L SER GCr 2+ :Va q..6 β = 3.− H Cr = GCR_L L SER GCr3+ :Va q.2923T 3 Cr O3 SER SER GCr 22+ :Va:O 2.2923T 3 p = 0.996 15.008 CrO ° Cr1O SER SER GCr:O1 − H Cr − H O = GCR1O1 Cr2O3 (Cr 2+ .H0 4050.− 2 H Cr − 2H O = 2GCR1O1_L Reference Cr (bcc_A2) 1 2 Mass 51.= 0 LCr3+ :O2.+ qyVa .5 p = 0..Va q.− 2 H Cr − 3H O = GCR2O3_L L SER SER GCr 2+ :O2.0 Cr3O4 ° Cr3O SER SER GCr:O 4 − 3H Cr − 4 H O = GCR3O4 Functions 63 .)q p = 2 yO2.− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L L SER SER GCr3+ :O2.2 Thermodynamic description of the Cr-O System Element Element Cr O Liquid (Cr 2+ .Cr 3+ ) p (O 2.Va q.− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.
97 × 10-3T 2 + 1050000T -1 GCR1O1 = 0. With this expression one is able to obtain reasonable results for the liquid phase using the positive interaction parameters. Its heat capacity is given by Neumann and Kopp’s rule.Va and 0 LCr3+ :O2. It was not possible to model the oxygen solubility using the endmember °GCr:O as this endmember turned out to be too stable and CrO3 appeared in the stability diagram at high oxygen partial pressures.31451 J mol-1 K-1.5GHSEROO + 339673 − 121.8T ln T −4. who needed 4 parameters to model the Cr2O3 phase and had to arbitrarily equate the °G of (Cr2+)2 (Va)1 (O2-)3 to stoichiometric Cr2O3. 64 .Vaq-)q is chosen. 4. The descriptions for solid and liquid chromium metal and gaseous O2 are from Dinsdale. mol. the latter constraint is not needed in the model. 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.Cr2+)p(O2-.5GCR2O3 − 0. 0 LCr2+ :O2.2 (next page) is a graphic expression of the model.Thermodynamic assessments GCR2O3 = −1164542 + 728. As the experimental data on the liquid phase are scarce. and gaseous O are from Dinsdale In contrast to Taylor and Dinsdale.5GCR2O3 − 0. liquid Cr.56T − 119. The sublattice occupation (Cr3+.4T Note: All parameters are in SI units: J. and one can reduce the number of parameters to only two.Va that must of course be negative. K.51] is selected to describe the ionic liquid. Metastable CrO is described in the same way.. literature data from Caplan and Fraser are used. Fig. the number of parameters is kept as low as possible. Parameters for solid Cr.Va that are required to give the miscibility gap.1.5GHSEROO + 255269 − 53. The oxygen solubility in solid Cr(bcc) can be described by an interstitial solution model of the form (Cr)1(O.Va)3.5GCR2O3 − 0.. where each corner of the composition square represents a °G parameter of the liquid phase.5GHSEROO + 280045 − 93. Ionic liquid: The two-sublattice ionic liquid model[50. For the optimization of model parameters.82T GCR3O4 = 1.76T GCRO0 = 108305 + GCR2O3 + 2 GHSERCR  3 GCR2O3_L = GCR2O3 + 439078 − 169T GCR1O1_L = 0. Pa: R = 8. The Cr3O4 phase is based on the eskolaite phase.
In this model description of the liquid phase metallic Cr-liquid can be described by both the corners Cr2+:Va and Cr3+:Va.1. Cr3+:Va must be metastable compared to Cr2+:Va. 4.2. Hallstedt and Gauckler recently reoptimized the Cu-O liquid. The eutectic temperature is mainly determined by the value of the corner Cr2+:O2-. One derives the °GL functions of the oxide compositions (Cr3+:O2-) and (Cr2+:O2-) from the eskolaite phase. 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.Thermodynamic assessments Fig.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. One way of doing this would be to simply say that Cr3+:Va equals Cr2+:Va plus a large positive term. A special feature of the Cr-O system is the occurrence of a eutectic very close to the composition of CrO. This considerably improved the description of the Cu-O liquid and removed the inverted 65 . The °GL of liquid Cr is taken from Dinsdale. This is however problematic for reciprocal systems. in his original assessment of the Cu-O system. The liquid composition changes along the hyperbolic curves in Fig. for example +600000 as given to °GCu2+ :Va by Hallstedt et al. obtaining the parameter °GCu2+ :Va from the reciprocal relation and giving it a reciprocal energy of 0.1.
2 (pp. In principle.el° H 298. at T = 290 K and from T = 335 K to 338 K with a low relative weight. The first parameters to be optimized were the Cp-parameters of Cr2O3. and Toker et al. 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. The optimization of the thermodynamic parameters was performed using the PARROT module of the Thermo Calc database system.16 and ° S298. In the next step the authors optimized the nonstoichiometry of Cr2+xO3 using data from Matsui and Naito. The program minimizes the sum of squared errors between the calculated and experimentally determined phase diagram and thermodynamic data. These parameters were then kept fixed during the rest of the optimization.Thermodynamic assessments miscibility gap found at high temperatures in the original assessment.1.1. high temperature emf data from Holzheid and O’Neill  . Δ f. ΔGr = 0 (4. close to the antiferromagnetic to paramagnetic transition temperature.11) 4. To determine the parameters describing the enthalpy and entropy of Cr2O3 log( pO2 ) data from Jeannin et al.5 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Cr-O system is given in Table 4. experimental data on the liquidus at the oxygen poor side from Toker et al. and. They assessed Cr3O4 and the liquid simultaneously. Thus metallic liquid is given by the corner L parameter °GCr3+ :Va is obtained by the reciprocal reaction given as ° G LCr2+ :Va . The authors optimized Tc and β using Cp data from Klemme et al... Finally the solubility of O in solid Cr was optimized using data 66 . The data used were heat content data from Kelley et al. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence. and Cp data from Klemme et al. with low relative weight. using experimental phase equilibria data from Toker et al.16 data from Holzheid and O’Neill were used.The ° G L 3+ Cr :Va = 2 °G L 2+ Cr :Va + °G L 3+ Cr :O2- − 3 °G L 2+ Cr :O2- + ΔGr . The melting temperature of eskolaite in air was taken from Bunting. and experimental data on the liquidus at the oxygen rich side of the miscibility gap from Ol’shanskii and Shlepov.1. 63-64). An identical strategy is employed here.
1 (p. The gas phase was not included in the calculation An enlargement of the phase diagram close to the CrO composition is presented in Fig. In Table 4.1.6 Results and discussion Phase diagram: The calculated phase diagram with oxygen isobars is shown in Fig.1. 4.3 Calculated Cr-O phase diagram with oxygen isobars (Pa.1.3. 4.4 (next page). Fig. 4. 4. logarithmic) given. 54-55) values that were used for our optimization are written in italic letters. 67 .1.Thermodynamic assessments from Caplan and Fraser.1.
The calculated liquidus temperature of eskolaite in air is T = 2539 K.5 (next page) shows the calculated oxygen potential phase diagram of the Cr-O system with experimental log( pO ) data included. Fig. with experimental data and oxygen isobars (Pa. Cr3O4 is formed at T = 1918 K by the eutectoid reaction Cr2 O3 + Cr + 1 2O2 → Cr3O4 . in good agreement with the measurement from Bunting. 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.4 Enlargement of the calculated Cr-O phase diagram close to the CrO composition.Thermodynamic assessments Fig. At a mole fraction of oxygen > 0.1. and an earlier experiment from Ol’shanskii and Shlepov is slightly deviating from former optimizations. 2 68 . For the monotectic temperature of the reaction of Cr (bcc) and liquid the present authors calculate T = 2117 K.497 it decomposes in a peritectic reaction at T = 1973 K forming Cr2O3 and liquid. 4.1. 4.497. and for the eutectic one gets T=1938 K at a mole fraction of oxygen of 0.
Thermodynamic assessments Fig. Fig.1. 4.1. 4. 4.6. are particularly well reproduced by the authors’ optimization.6 Stability of Cr3O4 in the log( pO2 ) versus temperature diagram 69 . The stability of Cr3O4 is shown in the log( pO2 ) versus temperature diagram in Fig.5 Calculated oxygen potential phase diagram of the Cr-O system. with experimental log( pO2 ) data as a function of temperature from different studies The experimentally determined phase stabilities from Toker et al. The shape and size of the miscibility gap is speculative due to the lack of experimental data.1.
The comparison of the calculated nonstoichiometry in Cr2+xO3 with the experimental data by Matsui and Naito is given in Fig.098 at T = 1918 K.4. The cation overstoichiometry resulting from the presented optimization might seem somewhat high. 4. 4. Fig.Thermodynamic assessments The solubility of oxygen in Cr(bcc) is shown in Fig.1. The maximum calculated δ = 0.% at T=1938 K.08 at. 70 . If the commonly used – however grubby – notation “Cr2O3-δ” is applied.8 (next page).1. the total charge of Cr is given by 6+2δ.7 Calculated oxygen solubility in Cr(bcc) with experimental data and oxygen isobars (Pa.7. 4. logarithmic) included For the maximum solubility of oxygen in Cr(bcc) one calculates 0.1. but it results simply from the extrapolation of experimental data from Matsui and Naito on excess Cr as a function of pO down to the oxygen partial pressure at the Cr-Cr2O3 2 equilibrium following the proportionality given by the defect chemistry analysis in section 4.1.
4. as the introduction of an additional defect species would be required to reproduce these. 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. The solid lines correspond to the optimization that is accepted in this work. 4. The data at low oxygen nonstoichiometries were not used. Solid lines result from our accepted optimization without considering temperature dependence. 71 .8 Optimized nonstoichiometry of Cr2+xO3 with the only available experimental data from Matsui and Naito included.1. Therefore.Thermodynamic assessments 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 . Obviously the calculated results show a temperature dependence that is significantly stronger compared to the experiments. The low nonstoichiometry data show a different slope than the higher nonstoichiometry data. Optimization of a temperature dependence is represented by dotted lines.8) and leads to the reduced neutral endpoint being too stable at low temperatures.1.
el° H 298K = −306 kJ mol-1 . 4. 72 . and for ° S298K (Cr3O4) we get 175 J K-1mol-1. For Δ f.1.9 Comparison of calculated heat capacities of Cr2O3 with experimental data For the magnetic parameter β we calculate 3. and for Tc we get 308. For a metastable CrO phase we calculate Δ f.685 kJ mol-1. These values for Cr3O4 deviate significantly from the results of Taylor and Dinsdale who calculated Δ f ° H 298K (Cr3O4) = –1447. Fig. and for ° S298K (Cr2O3) we get 85 J K-1mol-1.1.. and ° S298K (Cr3O4) = 150. and ° S298K = −79 J K -1 mol-1 based on the estimates of Shirokov. Cp.555 J K-1 mol-1. which is in particularly good agreement with the data from Ramsey et al.6.el° H 298K (Cr2O3) we calculate –1123 kJ mol-1. which is very close to the results from Holzheid and O’Neill.0.el° H 298K (Cr3O4) we calculate –1402 kJ mol-1. 4. For Δ f.9) are well represented by our assessment.Thermodynamic assessments Thermodynamic Data: The heat capacities. of the solid Cr2O3 phase (Fig.
5.J. Wilde. 3. 1943.. D. Y. 42(7). Laboratory furnace for studies in controlled atmospheres. 2000.N.. 1931.I.Y.Thermodynamic assessments 4. pp. pp. Zhang. Folkman. C. R. Dokl. Grube. 1913.I. Acad.P. Peters. Hilty. E.1. Res. Ramprakash. Equilibrium phase relations and thermodynamics for the systems Cr-O and Fe-Cr-O in the temperature range 1500 to 1825 °C. P. 3. 44(10). Shlepov. J. J. Foger. Oxygen solubility and oxide phases in the FeCr-O system. R. 6(6). Ol’shanskii. J. W.P.H. pp. Z. 1955. 99. Ceram.F. Y.K. 1997. Deller. References 1. The ternary system MgO-Al2O3-Cr2O3. Eng.K.. 315-18. K. J.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. 1953. Bunting. Soc. Solid State Ionics. pp.S. Brit. Rees. Bur. G.N. F. 6. 91(3). 42(11). 73 . Toker.C. and that a large variation of the measured melting points of eskolaite exists. S. Wash.T. United States Patent 6039788. 297-310. pp. Sistema Cr-Cr2O3. 1978. Phase equilibria in the system Cr2O3-Al2O3. McNally. Knabe. W. Metall. Nat. 4. pp. W. 1961. R. Pennsylvania State University. 253-68. Melting and casting of high purity chromium with controlled oxygen content. The system palladium–chromium. T. I. J. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. R. 561-64. 947-49. 2. R. Nauk. it must be kept in mind that experimental data on the liquid miscibility gap are largely missing. 7. Badwal. 9. V. Elektrochem. Am. 10. Ceram. 203(2). 1936. pp.. Stand. Lam.L.. 793-804 (in German). Trans. 491-93. 8. pp.D. Melting points of some refractory oxides. 123-55. SSSR. Thesis. Akad.. However. Sci. melting points of MgO in a N2 atmosphere and of Cr2O3 in N2 and in air atmospheres. Kanolt. N. Ribbe.W. Forgeng. Min.
475-79. Trans. T. Rev. 22(2). Johnson. 1966.E. Phys.D. 430-33. Activities and phase boundaries in the Cr–Ni system using a solid electrolyte technique. The formation and dissolution of chromium oxides in chromium. The Cr-Cr2O3 oxygen buffer and the free energy of formation of Cr2O3 from high-temperature electrochemical measurements. R.. 13. 20. 59(3). W. Radzilowski. 1977. Phase diagrams for the systems Si-O and Cr-O. C. K. L.N. pp. pp.. 1942.. W. 48(7).R. Electrochem. pp. 21. Bruce. pp. 11(9). Electrochem. 19. 69(5). H. pp.H. F. 25. 22. pp. 230(6). Ceram. L. 1964. J.. chromic oxide. Muan. Hook. 17. Activities in iron–chromium alloys. pp. 1965. 1997-2002. The heat capacity of MgCr2O4. Lenev. pp. R. 1968. 15. H. 24. The thermodynamics of spinel phases (chromite.S. Ac.S. D. J. 4451-59.S. S. A. Affinity and enthalpy of the solid solution in the system Cr-Ni. The heat capacities of chromium. Soc. Berich. Metall. 1(7). Am. N.M. Soc. A.. Muan. 14. 39. Ac. 1686-93. Thermodynamic properties of Cr2O3 and FeCr2O4 at high temperatures. B. Grube. Z. O’Neill. Pehlke. H. Chem. 1991. Cannell. Am. Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites. Soc. R. Ceram. 51(8). Soc. Inorg.E.. L. 833-45. G. F. R. 121(4). 74 . Russ. Metall. G.Y. Richardson. 1078-80. Klemme.Thermodynamic assessments 11. 15(9). 227(2). Jeannin. C. Anderson. 1974. Schmalzried. 124. 1975. Soc. Toker. 2000.. J. B. M. 1970. 300-5. 543-49. ferrite. Adair. Geochim.. 85. 1963. Soc. Aime. Mineral.. chromous chloride and chromic chloride at low temperatures. pp. Smeltzer. 18. Metall. Geochim. E. 377-89 (in German). Darken. 12. Y. FeCr2O4. 23. T. 1278-83. 59. 1827-31. Gmelin.H.M. pp. Schnelle. Solid oxide electrolyte emf cell determination of the standard free energy of Cr2O3 and applications to chromium–bearing mineral systems. Equilibrium phase relations and thermodynamics of the Cr-O system in the temperature range of 1500 °C to 1825 °C. pp. Tretjakow. 396-402 (in German). Davies. Pugliese.D. pp. O’Neill. 488-91. J. pp. Oxygen and metal activities of the chromium–nickel–oxygen system between 900° and 1100°C. aluminate). pp. Jacob.A.. A. Flad. Fitterer.D. Am. Novokhatskii. Mannerskantz. Mazandarany. Cosmochim. 225-32. J. Elektrochem. H. J. R. 1977. 16.S. A. Specific heat of Cr2O3 near the Neel temperature. Trans. Aime. and Cr2O3 at low temperatures and derived thermodynamic properties. A. pp. Cosmochim. Holzheid. 1937. 1995.W..T. Metall. Bunsen Gesell.T.
Elektrochem. 1944. Minerals and Equilibria. 32. D. 76(13). P.G. Thermodynamics of the oxidation of chromium. 1954. E.K. Thermodynamic consideration on the system Cr-Cr2O3. A. 1985. Ref. Cosmochim.W.3rd ed. 1965. pp. 940-42. The heat of formation of chromium oxide.J. Selected values of chemical thermodynamic properties. 2.D. W.B.I. A. Heidelberg. 35. p. 30. Evans. Downey. Geochim. R. T. 45-46 (in German). Bangert. Schumm. J. N.A. 80 pp.H. K. D. p. 1975.. M. 43 pp. Soc. Tables for elements 35 through 53 in the standard order of arrangement. 1976. W... pp. and standard potentials. 662. Heats of formation of chromium oxide and cadmium oxide from combustion calorimetry. Schmitt. Garrels and C. Chem.M. 31. V. 17(6). 46. chemical equilibria. Mines Tech. Springer Verlag. R. NBS Tech. Electrochem. J. 37. SSSR. Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3. 270(4). Shirokov. 28. Ramsey. 135-38. E. 103(2). 3363-65. J. Dellien. N.. Hall. pp. Bur. Dokl. Thermodynamic properties of carbides of chromium.N.A. Lux. A. Metallkd. F. and tungsten: thermodynamic properties. 1): pp. Thermodynamic properties of chromous oxide. and CrO-Cr2O3-CaO systems. E. CrO-Cr2O3-Al2O3. Chromium. Caplan.H. 542. Soc. Banik. Phys.Thermodynamic assessments 26. Davies. 1996. U. Berlin. Nauk. A. New York. Huffman.H. Chem.A. R. Z. Janaf thermochemical tables .M. J. 476-87.M. Metal. Thermochemistry of chromium compounds. pp. Coughlin. Flurip. Burr. Fromm. Akad. pp. Chem. 34. Z. 1954. Ac.M. L. G. 410.. J. C. pp. Pelton. 1976. 39. Gebhardt: Gases and Carbon in Metals. Bur. Wagman. especially oxides at high temperature. Boericke. 29. 76(3). Jr. Mah. Christ: Solutions. Contributions to the data on theoretical metallurgy. Chase. Roth.L.S. Syverud. F. S. Parker.D. Ettmayer... 521-34 (in German). 1980. 1969. W. 39. molybdenum. Halow. McDonald. pp. 27. Hepler. Phase Equilib. 102. D. 33.. 75 . Rev. Am. 71(10): pp. 14(Suppl.A. Bailey. I. Mines Bull. Kelley. 1956. B.. Navrotsky. D. 1973.P. Notes.. I. J. Harper & Row. 644-45. Degterov. Paper. 36.R. J. Data. 283-310. 1940. 819-32. Wolf. 38. S.
de Witt.. 1991. Existence of hypostoichiometric chromium sesquioxide at low oxygen partial pressures. 136. L. 1985.N. 53. 51.. 19(3). A.. 2(3). pp. Caplan. 1955. pp. A two-sublattice model of molten solutions with different tendency of ionization. J. B. The oxygen partial-pressure dependence of the defect structure of chromium(III)oxide. Gerretson..T. 66(10). I. A. Calphad.H. 15(4).A. Jansson. 1957. Hillert. Burr: in Ductile Chromium. Determination of chemical and magnetic interchange energies in bcc alloys. 134(9).T. Dinsdale. 1985. M. Phase Equilib. Chipman.. Sr-Cu-O. pp.. Inden. pp.Thermodynamic assessments 40. Gauckler. 177-91. Atomic interactions in molten alloy steels.J.J.J. Matsui. B. 2001. 49. Calphad. 33-41. 16A. Naito. Young. Calphad. M. Calphad. 2257-60.J. pp. A model of alloying effects in ferromagnetic metals. Metallkd. Hallstedt. Metall.R. pp. 354-66. Bi-Cu-O. 48. 1987. 317-425. 50. Calphad. Remodelling of the liquid. 2005. Modification of the two-sublattice model for liquids. pp. K. D. J. Bi-Sr-O. Soc. Revision of the thermodynamic descriptions of the Cu-O. 30. A. T. M. pp. Sundman. Electrochem. 25(4). Ivas. 599-605. L.W. Gauckler. Povoden. J. 483-99. 76 . 109-19. J. J. 196. D. 577-82. 78-82. 41. J. Z. pp. 54. Ågren. General treatment.A. 47. bcc and fcc phases. Trans. 2003. Spencer. 52. M. Metallkd. 97-106. E. Thermodynamic reevaluation of the Cr-O. AgO. 1975. P. Mater. Calphad. G. 43. A. 1990. Jarl. Calphad.H. 180. 1995. 227-38. 1978. Ca-Cu-O and Sr-Ca-Cu-O systems. ASM. Sundman. Taylor. pp. 1991. Z. M. Sundman. 45. Fe-O and Ni-O systems: 229-43. 1994. A. p. 261-66. Predicting miscibility gaps in reciprocal liquids. B. Calculation of defect chemistry using the Calphad approach. B. Grundy. B. pp.W. Nucl. 15(5). Ag-Cu-O. L. pp. M. 81(5). 1994. Hillert. 15. Cleveland. E. 44. Gauckler. 42. Iron Steel Inst. Thermodynamic assessment of the copper-oxygen system. Ohio. SGTE data for pure elements. pp. 46. Hallstedt. Hillert. J. B. pp. T. J. Fraser. Dinsdale. J.J. 27(2). Risold. Kowalski. A thermodynamic assessment of the Ni-O. Cr-O and Cr-Ni-O systems using the ionic liquid and compound energy models.
45 wt.N. a consistent set of thermodynamic model parameters is optimized for the Cr-Mn-O system based on experimental data.. Jansson. and (Mn1-yCry)1-xO are considered. Res. 22. pp.8 wt. Calphad. Relevance for solid oxide fuel cells is discussed. Grundy.2. and Mn-Cr binaries from Grundy et al.2]. Mater. The Thermo-Calc databank system. We are contributing to the understanding of the underlying thermodynamics of these processes by assessing the MnCr-O system using the CALPHAD approach. Povoden et al. 4. observed that the formation of chromium manganese spinel layers on top of a Cr2O3 oxide scale on the surface of a Mn-containing ferritic stainless steel (Crofer22 APU) interconnect with 76.6 wt. and the liquid is described using the two-sublattice model for ionic liquids. B. Sundman. The thermodynamic data of the pure elements are taken from Dinsdale. J. Also solid solutions of the phases (Cr1-yMny)2+xO3. Chromium manganese spinel MnyCr3-yO4 and its tetragonally distorted polymorph are described using the compound energy model. and Lee  77 . 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. pp. 153-90.. J. and the data for the Mn-O. Simner et al. By application of the CALPHAD method.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[1.2 Thermodynamic assessment of the Mn-Cr-O system for SOFC materials E. 4. 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. Andersson. Mn2-yCryO3. Cr-O. and L.J. Povoden..O. 9(2).% Fe.Thermodynamic assessments 55. 569-78. A.% Mn resulted in an improvement of short-term SOFC operation. Gauckler Int.% Cr. B. 2006. 1985. thus substantially diminishing the triple phase boundary area for the normal oxygen reduction reaction at the cathode/electrolyte interface. and 0. 97. However.
2.3 (p.Thermodynamic assessments respectively. bxb for Mn2O3 (bixbyite) with dissolved Cr. MnO2. and 4. Normal spinel is given by the formula [A2+](B3+)2O4. however all the binary oxides except pyrolusite (prl).4 (p.2. bcc for chromium manganese alloy with bcc A2 structure.2. α-spl for tetragonally distorted polymorph spinel solid solution. show varying degrees of mutual solid solubility. The most prominent oxide phase in the Mn-Cr-O system is cubic chromium manganese spinel with the formula MnyCr3-yO4. 4. 79). 4. mgs for Mn1-xO (manganosite) with dissolved Cr. 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. and liq for the liquid phase.2 (p. No new ternary phases are found in the Mn-Cr-O system. Fig. esk for Cr2+xO3 (eskolaite) with dissolved Mn. 80).2. In this work we use the following abbreviations: β-spl for cubic chromium manganese spinel solid solution. 4.2. 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+. 78 . 4. β-hsm (βhausmannite) for the cubic and α-hsm (α-hausmannite) for the tetragonally distorted Mn3O4 endmember of the spinel solid solution. whereas spinel of the formula [B3+](A2+B3+)O4 with half of B on the tetrahedral sites – marked with angular brackets in the above formulas – is called inverse spinel.2 Experimental Phase diagram data: Our calculated phase diagram of the MnOx-Cr2O3 system in air is shown in Figs.1. 80) shows the calculated phase diagram at pO2 = 1×10-4 Pa .
Fig.1 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. 4.2 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air.2. with experimental data. 4. The gas phase was not included in the calculation. 79 .2.Thermodynamic assessments Fig. The gas phase was not included in the calculation.
2. showing the expanded stability field of β-spl + mgs. with experimental data.Thermodynamic assessments Fig.4 Calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 under strongly reducing conditions ( PO2 = 1×10-4 Pa ).3 Mn rich part of the calculated pseudo-binary phase diagram of the system MnOx-Cr2O3 in air. 4. 80 . 4.2. Fig.
2.5.[14.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.14 at T = 1105 K in air. but it is lower than the findings from Speidel and Muan.2.2.3. next page). p.. and β-spl + esk + liq in equilibrium at T = 2243 ± 20 K. 81 . This value is in agreement with the result from Geller and Espinosa.2. Their data are shown in Figs. They estimate a minimum temperature of T = 773 K for the stability of β-spl. They consider the solubility limit of Mn in (Cr1-yMny)2+xO3 to be negligible. p. Pollert et al. 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. 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-yCryO3.15] 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. 79 and 4. 4. Their resulting phase diagram is in considerable disagreement with the findings of Speidel and Muan. report a solubility limit of y = 1.42 at oxygen partial pressure >> 20000 Pa. 4. Golikov et al. 4. The Mn solubility in (Cr2-yMny)1+xO3 reported from Speidel and Muan is significantly higher than it is found by Golikov et al. Pollert et al.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. Tanahashi et al. 79). and Pollert et al. 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. p.2. The solubility limit of Cr in Mn2-yCryO3 is measured by these authors to be y = 0. 80. They find β-spl + α-spl + bxb coexisting in equilibrium at T = 1183 ± 5 K.
5 Cr contents of β-spl in equilibrium with mgs.Thermodynamic assessments Fig. As the compositions of mgs 2 solid solution are located on the line connecting Mn1-xO with CrO in the ternary phase 82 . The compositions of β-spl are located on a line connecting MnCr2O4 with β-hsm in the ternary plot. 4. and mgs in equilibrium with β-spl in the pseudo-binary MnOx-Cr2O3 system as a function of oxygen partial pressures at T = 1073 K. They report small solubility of Mn in (Cr1-yMny)2+xO3 at pO2 = 2×10-6 . which increases slightly with increasing oxygen partial pressure.2.5). each phase in the quenched specimens was subjected to electron probe microanalysis (EPMA). In order to identify the equilibrium compositions. conclude that Mn is dissolved in cubic MnyCr3-yO4 in the form of Mn3O4. esk in equilibrium with β-spl. and significantly increasing Cr solubility in cubic MnyCr3-yO4 with decreasing oxygen partial pressure (Fig.2. 1473 K. and 1873 K. From this result Tanahashi et al. Phase relations were verified using X-ray diffraction. 4. β-spl in equilibrium with esk. They found increasing Mn solubility in cubic MnyCr3-yO4 at oxygen partial pressure higher than 2 ×10-2 Pa . 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. Experimental data are included.
 investigated the composition changes of the two phase equilibrium β-spl + mgs at T = 1073 K. two-phase fields and three-phase fields. p. Also the experimental result on the three phase equilibrium MnO + MnCr2O4 + bcc from Ranganathan is plotted.% at T = 1323 K performing an isopiestic experiment (Fig.2 cat.5.2. 4.2.2.Thermodynamic assessments diagram. There are no data on oxygen nonstoichiometry of MnyCr3-yO4. 1173 K. 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. 4. Fig. 4.1 to 10-13 Pa (Fig. Dotted lines are tie lines.6 Ternary phase diagram of the system Cr-Mn-O with stoichiometric single phase equilibria (points). Three-phase field boundaries are denoted with thin solid lines. these authors conclude that chromium oxide dissolves in (Mn1-yCry)1-xO in the form of CrO. and 1273 ± 5 K in the oxygen partial pressure range from 0.6). 83 . single solid solution phase equilibria (heavy lines). 82).
Giving α-spl the formula [Mn2+](Mn3+.5CrO2 (4. investigated the martensitic α-spl → β-spl transition temperatures. 4. derive Δ f °GMnCr2O4 = –958 ± 8 kJ mol-1 from liquid Mn. 79). solid Cr and oxygen at T = 1873 K in the pO range from 2×10-6 to 1.Cr3+)2O4 this corresponds to a minimum concentration of [Mn3+] = 0. With decreasing Mn-content the temperature for the transition decreases (Fig.8 do not show Jahn–Teller distortion at room temperatures.5 + Mn0.4 for the formation of α-spl. enthalpies and entropies of MnyCr3-yO4 samples annealed at T = 1723 K using X-ray analysis and DTA measurement.5AlO2 = AlO1.2. Tsai and Muan experimentally determined compositions of coexisting MnyCr3-yO4 . 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.MnyAl3-yO4 solid solutions formed from Cr2O3-Al2O3 mixtures at T = 1873 K.5 in Mn0. Samples with y < 1.5 + Mn0.2.5×10-4 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. Tanahashi et al. From these data and the activities of CrO1.1) β-spl Using compiled Δf °GMnO and Δf °GCr2O3  they calculate Δ f °GMnCr2O4 from its oxides to be –59 ± 8 kJ mol-1.5 in Mn0.2) (4. which is equivalent to Δf G of 1 2(Δ f GMnCr2O4 − Δ f GMnAl2O4 ) . 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. p.Thermodynamic assessments Holba et al.2.2. and remain β-spl.5AlO2 and AlO1. This means that the Gibbs energy of formation of β-spl of the composition MnCr2O4 from its 84 .3) β-spl to be –10 kJ mol-1 at T = 1873 K.5CrO2 obtained from a previous study they derive ΔG of the reaction CrO1.2.
According to these authors the transition of pure α-hsm to β-hsm takes place at T=1445 K.Thermodynamic assessments oxides using this calculation technique depends on the value of Δf °GMnAl2O4 . with experimental data and error bars. Filled symbols correspond to originally reported literature data.4 ± 10 kJ mol-1. 4.2. Δ f °GMnAl2O4 = –32.0 kJ mol-1 at T=1523 K. unfilled symbols correspond to recalculated values.1 kJ mol-1. present thermodynamic data on the transition of α-spl to β-spl.  in the CoO- β-spl The spread of Δ f °GMnCr2O4 values resulting from different studies and our recalculations is shown in Fig. 4.6 kJ mol-1 at T = 1873 K. –46.7.6 kJ mol-1 β-spl giving Δ f °GMnCr2O4 = –52.1 kJ mol-1. Biggers by using the same technique as Tsai and Muan β-spl MnO-Cr2O3 system found Δ f °GMnCr2O4 = –59. Tsai and Muan chose the value determined by Lenev and Novokhatskiy. Tetragonally distorted spinel (α-spl): Pollert et al. and ΔS α β = 13 J K-1 mol-1. 85 .2. and –36. Fig. Using other values for Δ f °GMnAl2O4 reported β-spl in the literature[25-27] leads to deviating Δ f °GMnCr2O4 of –34.7 Calculated Gibbs energy of formation of β-spl of the composition MnCr2O4 as a function of temperature. ΔΗ α β = 18810 J mol-1.
As the degree of inversity of β-spl is very low.4) This endmember is considerably more stable than the endmember of the formula [Cr2+](Mn3+)2O4.Mn2+. Thus the endmember ° β-spl β-spl G[Cr 2+ ](Mn3+ ) O becomes less stable the more stable °G[Mn 2+ ](Cr3+ ) O becomes.Mn3+)2O4 using the compound energy model[31–33]. The Gibbs energies of the endmembers [Mn2+](Mn3+)2O4 that corresponds to β-hsm. 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 (4.2. This state is denoted SER (Stable Element Reference). so we stick to the less complex description without Mn2+ and Mn4+ on the octahedral sites. In our description we further go along with the presumption that the amount of oxygen vacancies may be neglected.30]. β-spl can therefore be described by the simple formula [Mn2+.8]. and [Cr2+](Cr3+)2O4 that corresponds to Cr3O4 are taken from the assessed binaries[7.2. However there is no experimental data quantifying the amount of Mn4+ in β-spl. 2 4 2 4 86 .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. All endmembers of our model β-spl are neutral. They propose small polaron hopping between Mn3+ and Mn4+ on the octahedral sites as mechanism for the electrical conductivity.Cr2+](Cr3+. In our CALPHAD assessment the °G values of all compounds are given relative to the enthalpy of selected reference states for the elements at T = 298. Considering these findings an alternative description of β-spl would read [Mn2+. measured the electrical conductivity of β-spl. Lu et al. To maintain electroneutrality Mn2+ is formed on the octahedral sites resulting in a charge disproportionation reaction.5) The Gibbs energy of the reciprocal reaction is taken to be zero. We define this last endmember using a reciprocal relation ° Cr O β-spl β-hsm β-spl G[Cr2+ ](Mn3+ ) O = °G[Cr32+ 4](Cr3+ ) O + 1 3 °G[Mn 2+ ](Mn3+ ) O − °G[Mn2+ ](Cr3+ ) O 2 4 2 4 2 4 2 4 (4.Mn4+)2O4.Cr2+](Cr3+.Thermodynamic assessments 4.15 K and p = 105 Pa.2.Mn3+.
Thermodynamic assessments Tetragonally distorted spinel (α-spl): The transformation of β-spl to α-spl is due to the Jahn-Teller distortion of the octahedral sites occupied by trivalent Mn ions leading to the tetragonal structure of α-spl[11.Cr3+. Experiments[11.Mn3+)2O4 to describe α-spl.Cr2+.14..Cr3+)2(O2-)3. The Gibbs energy of [Mn2+](Mn3+)2O4 is equal to α-hsm. as the degree of inversity is increasing with higher temperature.Mn3+. Thus we may describe bxb as (Mn3+.15].34] show that α-spl is stabilized at high Mn contents.) 3 + Abxb (4. whereas for ordering due to Jahn–Teller distortion the opposite holds.Va)(O2-). and the Cr solubility in tetragonally distorted MnyCr3-yO4 does not extend beyond MnCr2O4. Due to these considerations we may write [Mn2+](Cr3+. It is very unlikely that trivalent cations are incorporated into the tetrahedral sites of α-spl. The Gibbs energy of the endmember (Mn3+)2(O2-)3 is taken from Grundy et al.Mn3+. The incorporation of chromium of valencies other than three is mentioned nowhere in literature.15. 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 (4.7) The experimental data could be reproduced without the optimization of a temperature dependent parameter. and the Gibbs energy of (Cr3+)2(O2-)3 is given by ° bxb esk G(Cr3+ ) O = °G(Cr3+ ) 2 3 2 (Va)1 (O 2. This is a reasonable assumption as the radii of these ions are very similar. Hence.2. Using this description the solubility of Cr in function of oxygen partial pressure experimentally determined by Tanahashi could not be reproduced correctly.2. 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+.Va)(O2-) leads to far more satisfactory 87 . (Mn2+.6) Bixbyite (bxb): Geller and Espinosa postulate the incorporation of Cr into Mn2-yCryO3 by a simple substitution mechanism between Cr3+ and Mn3+. the two endmembers of α-spl read [Mn2+](Mn3+)2O4 and [Mn2+](Cr3+)2O4.
Cr2+.2. Fig. Agreeing with these authors we model the solubility of Mn by (Cr3+.2.2. The Gibbs energy of (Mn3+)2(Cr3+)1(O2-)3 is given by 88 . 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.Va)1(O2-)3. 4. The model description of mgs is shown in Fig.8 Geometrical representation of the mgs phase described using the compound energy model.8.Thermodynamic assessments reproduction of these data. postulate the incorporation of trivalent Mn ions into (Cr1-yMny)2+xO3. These experiments also provide evidence against Cr being incorporated interstitially. 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.8) The Gibbs energies of the three other endmembers are taken from Grundy et al.Mn3+)2(Cr3+.. Eskolaite (esk): Pollert et al.)3 Gas − 1 3 °GO − 3 2 RT (1 3ln1 3 + 2 3ln 2 3) + Amgs 2 (4. 4. 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.
Cr2+.Va)3.2.1 (pp. No data are reported for the oxygen solubility in pure bcc A2 manganese metal.Va)3.2.Mn)1(O..The binary interaction parameters are taken from Grundy et al.4 Optimization of parameters The complete set of optimized thermodynamic parameters describing the Mn-Cr-O system is given in Table 4. 4.2.)3 + °GCr SER + Aesk (4. 89 . Povoden et al. Liquid: We model the liquid phase as (Cr3+.2. The descriptions of further alloy phases are taken from.39] . and Lee. 90-92). Cr-Mn alloys: We describe the oxygen solubility in bcc by an interstitial solution model of the form (Cr..)3 + Aesk (4.Mn3+ :O2- [38.. Assuming low oxygen solubility in bcc bcc manganese metal we give a large value to the endmember °GMn:O . The liquidus temperature is optimized using the interaction . Mn3+.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 .Thermodynamic assessments ° G esk3+ (Mn )2 (Cr3+ )1O3 = °G bxb3+ (Mn )2 (O2. Experimental data on the oxygen solubility in pure bcc A2 chromium metal were used for the description of (Cr)1(O.Mn2+)p(O2-.9) and the Gibbs energy of (Mn3+)2(Va)1(O2-)3 by ° G esk3+ (Mn )2 (Va)1O3 = °G bxb3+ (Mn )2 (O2.
.1 Thermodynamic description of the Cr-Mn-O system a) Element Element Reference Mass H298 .− 2 H Cr − 3H O = GCR2O3_L liq SER SER GCr 2+ :O2.Mn 2+ :Va q1 liq Cr 2+ .Va q- L L 0 liq Cr 2+ .− H Mn = GMN_L liq SER GMn3+ :Va q.938 15.2.− 2 H Cr − 2H O = 2GCR1O1_L liq SER GMn 2+ :Va q.H0 S298 Cr Mn O Liquid (liq) BCC_A2 CBCC_A12 ½ mol O2 51.)q p = 2 yO2..Cr 3+ .Va q.6 0 liq Mn 2+ :O 2.543 32.008 102.0 23.Mn 2+ .Thermodynamic assessments Table 4.Mn 3+ ) p (O 2. q = 2 yCr 2+ + 2 yMn 2+ + 3 yCr3+ + 3 yMn3+ ° ° ° ° ° ° ° ° liq SER GCr 2+ :Va q.− H Cr = 2GCR_L + GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+ :O2.Va q- L L = 121000 = 129519 = −45459 = −33859  = −15009 + 13.996 54.999 4050.Mn 3+ :O 2- L Bcc A2 alloy (bcc) (Mn..9479T = −188487.52 (Cr 2+ .+ qyVa ..Va q1 liq Mn 2+ :O 2.− H Cr = GCR_L liq SER GCr3+ :Va q.− 2 H Mn − 3H O = GMN2O3_L liq SER SER GMn 2+ :O2.− H Mn = 2GMN_L + GMN2O3_L − 3GMN1O1_L liq SER SER GMn3+ :O2.O)3 90 .6587T = 504 + 0.Mn 2+ :Va q- L 0 liq Cr 3+ .Mn 3+ :O 2.Cr)1 (Va.0 4996.0 4341..− 2 H Mn − 2H O = 2GMN1O1_L 0 liq Cr 2+ :O2.Va q- L 0 liq Mn 2+ .
− H Cr − H O = 0.Mn 3+ :O 2- L Bixbyite (bxb) (Mn 3+ .− 2 H Cr − 3H O = GCR2O3 + 3459 ° Eskolaite (esk) (Cr 2+ .)3 ° bxb SER SER GMn 3+ :O2.1853365T 0 mgs Mn 2+ .7339T  = −9162 + 4.− H Mn − H O = GMN1O1 − 21883.Va)1 (O 2.6 yCr 2+ :Cr3+ :O2esk Tcesk = 308.4183T  1 bcc Cr.− 2 H Mn − H Cr − 3H O = GMN2O3 + GHSERCR  + 39503 esk SER SER GMn 3+ :Va:O 2. Cr 3+ .Mn:Va L 0 bcc Cr:O.− 2 H Mn − 3H O = GMN2O3 bxb SER SER GCr 3+ :O 2.− 2 H Cr − 3H O = GCRO0 − 2 GHSERCR  − 5.Va L = −709542 p = 0.27 yMn + yCr yMn [0.− 2 H Mn − 3H O = GMN2O3 + 39503 ° ° ° Magnetic contribution p = 0.)3 ° ° ° esk SER SER GCr 3+ :Va:O 2.2923T 3 esk SER SER GCr 2+ :Va:O 2.)1 ° ° ° mgs SER SER GMn 2+ :O 2.Mn 3+ :O 2- L = −42104.28 esk Tcesk = 308.− H Mn − H O = GMN1O1 mgs SER SER GCr 3+ :O 2.− 2 H Cr − 3H O = GCR2O3 esk SER SER GCr 3+ :Cr3+ :O 2.− 3H Cr − 3H O = GCRO0 + 1 GHSERCR  − 5.6 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.Mn 3+ .3 − 7.− 3H Cr − 3H O = GCR2O3 + GHSERCR  esk SER SER GCr 2+ :Cr3+ :O 2. Cr 3+ .93265( yCr − yMn ) 4 ] Manganosite (mgs) (Mn 2+ .93845T mgs SER SER GMn 3+ :O2.72035( yCr − yMn ) 2 − 1.5GCR2O3 + 71549.Cr 3+ ) 2 (O 2.48643 − 0.8766 = 46513.008 yCr − 0.Mn:Va L = −20328 + 18.5213 − 22.6 yCr3+ :Cr3+ :O2esk β esk = 3 yCr :Cr 3+ 3+ 3+ :O 22- T esk c = 308.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.Va)1 (O 2.2923T 3 esk SER SER SER GMn 3+ :Cr3+ :O2.6 yCr 2+ :Va:O2- :O 22- esk β esk = 3 yCr :Va:O Cubic spinel (β-spl) 91 .117( yCr − yMn )8 ] β bcc = −0.5 yCr − 580 yMn + yCr yMn [−1325 − 1133( yCr − yMn ) 2 − 10294( yCr − yMn ) 4 + 26706( yCr − yMn ) 6 − 28.1533 1 mgs Mn 2+ .4 Tcbcc = −311.Mn 3+ ) 2 (Cr 3+ .
9+75.− H Cr − 2 H Mn − 4H O = GCR3O4+GMN3O4B -GSPINEL Tetragonally distorted spinel (α-spl) (Mn 2+ )1 (Cr 3+ .Mn3+ :O2- . 4. As the use of all the experimental data in a simultaneous least square calculation often leads to divergence.31451 J mol-1 K-1. Pa: R = 8. 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. 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.− 3H Mn − 4H O = GMN3O4 ° Functions GSPINEL = 2 GCR3O4+ 1 GMN3O4B 3 3 −210795.Mn 3+ ) 2 (O 2. Further we use – with lower weights – the temperature of the two phase equilibrium β-spl + liq at X(Cr) = 0.1T a) Note: All parameters are in SI units: J.− 3H Cr − 4H O = GCR3O4 β-spl SER SER GMn 2+ :Mn 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 . PARROT takes into account all sorts of thermodynamic and phase diagram data simultaneously.4 and 0 liq L Cr3+ .69T GTSPINEL = 2 GCR3O4+ 1 GMN3O4 3 3 −200941.5+61. The optimization of the thermodynamic parameters is performed using the PARROT module of the Thermo Calc database system.Thermodynamic assessments (Mn 2+ . K.Mn 3+ ) 2 (O 2.%) and α-spl is used to optimize Aβ-spl and Bβ-spl in Eq.− H Mn − 2 H Cr − 4H O = GSPINEL β-spl SER SER GCr 2+ :Cr 3+ :O 2.4. mol.2.− H Mn − 2 H Cr − 4H O = GTSPINEL α-spl SER SER GMn 2+ :Mn 3+ :O 184.108.40.206 cat.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.2. The program minimizes the sum of squared errors between the experimentally determined phase diagram and thermodynamic data and the corresponding calculated data. 4. The temperature found from Speidel and Muan for Cr the two phase equilibrium of Mn rich β-spl (Mn = 94.Cr 2+ )1 (Cr 3+ . 4. β-spl To optimize the parameters Aβ-spl and Bβ-spl in Eq.105 from Speidel and Muan to optimize Aβ-spl and Bβ-spl in Eq.. 4.) 4 ° α-spl SER SER SER GMn 2+ :Cr 3+ :O 2. 4.2.) 4 ° ° ° ° β-spl SER SER SER GMn 2+ :Cr 3+ :O2.4 and 0 Lliq3+ .Mn3+ :O2. All these data are given a high weight.4 and Aα-spl and Bα-spl in Eq.
2.2. 4.2. 220.127.116.11 Results Phase diagram data: The calculated phase diagram of the pseudo-binary system MnOx-Cr2O3 in air is shown in Figs. 4. From T = 513 K to 668 K and maximum X(Cr) = 0.4. and data from Pollert et al.2 cat.8 data on the solubility of Cr in (Mn1-yCry)1-xO from Tanahashi et al.2. The dotted line in Fig. p. 82.2. prl + bxb is stable in a small area from T = 668 K to 694 K and X(Cr) = 0 to 0. 4. 4. are used (Fig. 4.5.2. and Aα-spl and Bα-spl in Eq.3. 80) to optimize Aβ-spl and Bβ-spl in Eq. 4.4. 4.2. shown in Fig. and Aα-spl and Bα-spl in Eq.2.4. Abxb in Eq. 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. The maximum Cr solubility in Mn2-yCryO3 is 23 cat. p.2.6. In Fig.10 data on the solubility of Mn in (Cr1-yMny)2+xO3 from Pollert et al. on the temperature dependence of the diffusionless transformation of α-spl to β-spl shown in Fig. 79 to optimize Aβ-spl and Bβ-spl in Eq. 80 the Mn rich part of the diagram is shown in detail.054 in air. The maximum Mn solubility in (Cr1-yMny)2+xO3 is 0. 4. and for Aesk in Eq. This two-phase field expands under more reducing conditions which can be seen in the calculated phase diagram of 93 . β-spl is stable in a large temperature range from T = 513 K to 2243 K and from X(Cr) = 0 to X(Cr) = 0.23 in air. shown in Fig. 4. for Amgs in Eq. 4. αspl coexists with β-spl from X(Cr) = 0 at T = 1441 K to X(Cr) = 0. prl coexists with esk at T < 513 K in air.2. p. 79 shows the temperature dependence of the diffusionless transformation of α-spl to β-spl. The two-phase field bxb + α-spl is only found in a very small area at about 1150 K.5. 4.175 at T = 1156 K. on the phase equilibria α-spl + β-spl and α-spl + β-spl + bxb are used to optimize Aβ-spl and Bβ-spl in Eq.2. mgs is not stable in air. p. p. β-spl and esk coexist from X(Cr) = 0. p. 4.9 and 4. At pO2 = 400 Pa it starts to form in equilibrium with β-spl in a small area at the Mn-rich side of the MnOx-Cr2O3 system around T = 1840 K.2.2.2. p.Thermodynamic assessments oxygen partial pressures from Tanahashi et al. 82).2. 79 and Fig.7 is optimized using data on the solubility of Cr in Mn2-yCryO3 from Pollert. 4.65 prl and β-spl coexist in air.67 in air. on the two phase equilibrium β-spl + bxb in air (Fig. 82 are used.1 and 4.% at T = 668 K in air.66 to 0.2. bxb is stable from T = 694 K to 1154 K in air.6. p. We use data from Holba et al.2. 79. 4. 4. 4. 18.104.22.1682 at 1203 K in air.2.% at 2243 K in air. p.2.2. Temperature data from Speidel and Muan and Pollert et al.3.2.
6.2. were not used for the optimization.2. on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl at T = 1073 K. 82 experimental and calculated solubility data of Cr in mgs + β-spl. 4. In Fig. on the solubility of Cr in the phases of the two phase equilibria mgs + β-spl and esk + β-spl at 1873 K. and 1273 K in function of log(pO2 ) are compared to the calculated results from this work.5.2. 4. and from Bobov et al. p. 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. 4. 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.2. 1173 K. 80. Experimental data from Tanahashi et al.9 (next page). p. 4. The data from Bobov et al. p. 94 . and Mn in esk + β-spl are presented. Isothermal sections of the Cr2O3-MnO-MnO2 system at different temperatures are plotted in Fig.4.
9 Isothermal sections of the ternary system Cr2O3-MnO-MnO2 showing oxide and liquid evolution as a function of temperature and composition. 95 . Stoichiometric single phase equilibria are points. Three-phase field boundaries are denoted with thin lines.2. and single solid solution phase equilibria are heavy lines. Dotted lines are tielines. 4.Thermodynamic assessments Fig.
2.6 (p. on the other hand cannot be reproduced. 4.15 K. 4. 4. 4. 4. 80).2. Fig.6 Discussion Phase diagram data: Our assessed phase diagram is in rough agreement with the findings from Speidel and Muan. and Δf °G α-spl = –1625681 J mol-1 at T = 298. 82 agrees well with the results from Tanahashi et al.21 %.2. p.2.338 T with an error of ± 0. p. 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. ° α-spl S = 98 J mol-1K-1.2.5. The oxygen nonstoichiometry of mgs is yet insignificant (Fig.7.2. At this temperature small oxygen nonstoichiometry of esk is apparent. °SMnCr2O4 = 116 J mol-1 K-1. (Fig.2. β-spl + bxb. 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. and the two-phase fields prl + bxb. In the β-spl temperature range from 1050 to 1800 K Δ f °GMnCr2O4 from the oxides is given by the term –89167 + 29. and β-spl Δ f °GMnCr2O4 = –1634017 J mol at T = 298. and mgs + β-spl dominate the system in a wide temperature range from T=1200 K to 1900 K (Figs. p. 85. Our calculated T0 line for the diffusionless transformation of α-spl → β-spl is in perfect agreement with experiments by Holba et al.9 b). Our assessed phase diagram is in excellent agreement with the findings of Pollert et al. 4. 95) represents the phase relations of the oxides and the evolution of liquid formation.15 K. 83).2. 79). At T = 1873 K we get Δ f °GMnCr2O4 = –34388 J mol-1.Thermodynamic assessments Thermodynamic data: The calculated enthalpy.15] and Ranganathan et al.9 a to c). 4. At T=1700 K α-spl is no longer stable and the three-phase regions mgs + α-spl + β-spl and bxb + α-spl + β-spl (Fig. The results from Bobov et al.9 (p. 4. 4. as shown in Figs.2 (p. 4.2. For both cases Speidel and Muan mention the speculative character of their phase diagram due to the lack of experimental data. 79).9 a) disappear. For α-spl of the composition MnCr2O4 we calculate Δ f °H α-spl = –1596517 J mol-1. The calculated temperature dependence of the -1 Gibbs energy of formation of of β-spl of the composition MnCr2O4 from the oxides MnO and β-spl Cr2O3 is shown in Fig..2.3 (p. but it increases at elevated 96 .[14.2. 4. and Fig. The three-phase regions prl + esk + bxb and bxb + esk + β-spl. The calculated dependence of β-spl solid solubility on oxygen partial pressures shown in Fig.2.
4. At T = 1900 K liquid is formed at the Mn-rich side of the system. 4.2.9 f). and the-three phase fields bxb + β-spl + liq and mgs + β-spl + liq emerge (Fig. The calculated ΔHα needed for the transformation to take place. The occurrence of other Cr-Mn phases in the protective scales formed during thermal exposure of Crofer 22 APU interconnects is not expected thermodynamically. The 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. 4.9 d).. 4. which is at point A in Fig. 4. In a thermodynamic view the formation of β-sp with the composition MnCr2O4 (Point A in Fig. p. Hence.6.9 d). 84) on Crofer22 APU alloy is expected under SOFC operating conditions.6.2. This is obvious from Fig. Recently Qu et al. 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.2. found that the electrical conductivity of chromium manganese spinel increases with increasing Mn-content. and ΔSα β values for the transformation of α-spl to β-spl are very small. 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. must be kinetically controlled.9 c). 4.6. 83 associated with decreasing 97 .7 Applications on SOFC Due to the large stability range of β-spl and esk in air it is not realistic to prevent the formation of these unwanted phases under oxidizing conditions at the cathode side of SOFC operated with high Cr alloy interconnects and LSM cathode.2.Thermodynamic assessments temperatures becoming apparent at T = 2000 K (Fig. p. Even more three phase regions due to increasing liquid formation start to exist at T = 2000 K (Fig. At T = 2400 K the only remaining stable solid phases are esk and prl (Fig. 4.2. 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. The composition of Crofer22 APU alloy is close to the Cr-corner of the Mn-Cr-O phase diagram. indicating that only very little energy is 4.9 c). 22.214.171.124. p. At T = 1900 K phase relations become more complex due to incipient melting (Fig.2. 4.
Fergus. and Δf°G data for β-spl and α-spl. W. Y. and the only available -1 β-spl Δ f °GMnCr2O4 values are spread over a range of 31 kJ mol . Quadakkers. Zhang. H. p. Vielstich. 98 . Hilpert. 1-15. Chichester. 3. J. D. A.). 4. Lamm. K. Recalculating old experiments using new thermodynamic data together with phase diagram data we achieved a description.).2. Foger. Solid State Ionics. Solid State Ionics. Lanthanum chromite-based materials for solid oxide fuel cell interconnects.P. Handbook of Fuel Cells – Fundamentals. pp. H.P. L. Ramprakash. 297-310. 703.A.W. K. Miller. 2. M. Technology and Applications. which is very close to the experimental findings of several authors. p. in: W. 99. Singheiser. Göttingen. 1997. 2. 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. First European Solid Oxide Fuel Cell Forum Proceedings. and we present well-founded Δf°H. There is a surprising lack of thermodynamic data on β-spl. All features of the system are well described with the optimization of only 8 additional optimization parameters. 171. 2004.S. Hilpert.Thermodynamic assessments electrical conductivity. Deller. 4. K. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. Badwal.J. 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. Nickel. R. in: U. pp. °S. Bossel (Ed. Das. 1037. 2003. Gasteiger (Eds. Our Thermo Calc dataset resulting from the presented CALPHAD modeling of the Mn-CrO system allows the calculation of phase stabilities. 1994. Vol. S. Druckerei J.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. John Wiley & Sons. J. Kinzel. References 1.
Trans.25Mn2. J. Espinosa.M. pp. B. 1984. Solid State Chem. Phase Equilib.F. pp. Holba. 27. 3763-69. E.I. Stevenson.. 353-62. SGTE Data for Pure Elements.. 1975.H.Thermodynamic assessments 5.V. J. 71. J.P. 99 . Rev. Calphad. pp. Grundy. Chufarov.P.-G. 1977. A. 46. S. Gauckler. Phase Equilib. Metall. Yamauchi. B-J. 2003. Novak. Simner. Z. 8. 317-425. M. Phase equilibrium diagram of the system Mn-Cr-O. Chem. 1309-1315. Novak. N. Furuta. J. Phase diagram of the Mn2O3-Cr2O3 system in air. ISIJ Int. A 24. 1963.M. pp. 1145-47. 15. E. J. 10. 6. 24. Tanahashi. B 1. Soc. 13. Magnetic structure of manganese chromite. D. 1987. A.. V. Hastings. Y. Hajra. 38. Electrochem. 2005. Nevriva. 2001. J. M.R. 9. E.D. L. A740-45. Xia. Grundy. 41. Magnetic and crystallographic transitions in Sc3+. Phys. 562-65. Miscibility gap of MnxCr3-xO4 spinels. Ranganathan. G. 15(4). Geller.. Fujisawa. T. 1970. 1453-56. Mater. C. Bull. 126.. J. pp. 1919-1933. L. Povoden. 149-58.P. P. T. M. Bull. Bull. A. 19.. M. Bobov. pp. 750-751 (in Russian). Khim. pp. Phys. Balakirev. 1991. Diff. Phys. Nevřiva.. Speidel. Cr3+. 152. Soc. A. Pollert. J. Balakirev. 2006. Pollert. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Nevriva.G. 18. Zh. Lee. SOFC performance with Fe-Cr-Mn alloy interconnect. L.N.. Fiz. Golikov. A. pp. Alloy oxide equilibria in the Cr-Mn-O system. 16. Sci. Mater. Zalazinsky. Muan. Rev. J. Mater.F. 556-65. J.. Pollert. Am. 1962.W. 10. A. M. Assessment of the Mn-O system. E. 12. Res. The system manganese oxide-Cr2O3 in air.. L. 853-60.. V. 577-78. Ceram. pp. S.75O4 solid-solutions. Peculiarities of phase-diagram in the reduction of Me0. Yang. 14. 9. Corliss. Solids. 17. pp. pp. Golikov.J.N. Res. 21-39. 11. Hallstedt. and Ga3+ substituted Mn2O3. Gauckler. 1993.V. S. pp. G. pp.P. Tetragonal distortion of spinel solid-solutions MnCr2O4Mn3O4. pp. Dinsdale. 15. Phase equilibria of the MnO-SiO2CrOx system at 1873 K under controlled oxygen partial pressure. 1987.. G. 58. A thermodynamic evaluation of the Cr-Mn and Fe-Cr-Mn systems. Pederson. pp.J. Anderson. Y.. J. 7. 1980.
Parts I and II. Metallkd. Toker. VCH Verlagsgesellschaft mbH. T. pp.A. 29. Activity composition relations in refractory oxide solid-solutions at high-temperatures – the system Cr2O3-Al2O3.S. Izv. 2nd Ed. Novokhatskiy. Am. 22. Thesis. pp. Yamauchi. Hillert.A. 437-445. pp. 1993. Cmpd. R. Jansson. J. 225-232. Lenev.Y. Soc. A. Sundman. 75. University Park. S. Darken. 3. Fujisawa. 88. Jansson. B. 20. Pennsylvania State University. 66. Z. 1966. Dimitrov. M. Kim. Activity composition relations in FeCr2O4-FeAl2O4 and MnCr2O4MnAl2O4 solid-solutions at 1500°C and 1600 °C. C. J. Furuta.(in Russian). Payzant. E. Lu.. 25. 1412-15. pp. Lam: United States Patent 6039788.V. 26. Muan. A. 43.F.K.F. 2005. Acta Crystallogr. Alloy. pp. Weinheim. Andersson. PA. 24. Metall. H.. 575-84. ISIJ Int. Hillert. Taniguchi. Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides. Weyl. 161-76. Soc. Acta Metall.Cr2O3 solid solution at 1873 K. 1986. J. N. pp. Metall.M. H. Equilibrium phase-relations and thermodynamics of the Cr-O system in the temperature-range of 1500°C to 1825°C. Trans. Muan. 1979. Metall. Electrical conductivity of the manganese chromite spinel solid solution. 28. M. Tanahashi..T. Muan. 1992. The Compound Energy Formalism. K. 75. Z.. A 32. Guillermet. Phase diagram of system MnO-Al2O3 and thermodynamic properties of MnAl2O4. J. 23. 1976. 1407-11. McLean. C. Barin: Thermochemical Data of Pure Substances. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. pp. B. 1992. pp. Steel Res. Ceram.T. 7-13. 2000.. 73. Can. 27. Nauk SSSR. 320. M. 1991. 100 . N. 2003.D.. 81-87. A. pp. 1981.T. Shannon. 1988. R. Am.. 22. Tsai.-O. Soc. 89-92. 87-92. Sundman. Janke. Standard Gibbs free energy of formation of MnO-saturated MnO. 1050-53. pp. B. 31.D. Q. 79(2).Thermodynamic assessments 20. L. Paranthaman. A. Trans. Revision of thermodynamic data on MnO-Al2O3 melts. 35. Met.K. 2001.. A. M. Zhu. 751-67. T. Control of the manganese-oxygen reaction in pure iron melts.. M.. pp.. B. B. J. L. 32. 21. Hillert. 33. 34. Ceram. Application of the Compound-Energy Model to Oxide Systems. pp. J. Am. 30. 1995. D. I. Akad. Ceram. Tsai.P. I. pp. Biggers: Ph.. J. A. B. Jacob. 10B. 1966. 34. Thermodynamics of iron-manganese aluminate spinel inclusions in steel.
Sundman. Phase equilibria of the La-Cr-O system are calculated at T = 1273 K as a function of oxygen partial pressure. M. Solids. 343-. J. The calculated La-Cr phase diagram as well as LaO1. pp. B. 42. O’Keefe.5 phase diagrams in pure oxygen. Jansson. air. A. Ohio.J. 39. In the La-Cr-O system the Gibbs energy functions of La2CrO6. 1985. p. Fraser. Hillert. Cleveland.M. 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. The Thermo-Calc Databank System. Phys. J. Grundy.G. J. ASM. 37. pp. 1970. 114-24. Burr. Sundman. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects.Thermodynamic assessments 36. B.M. The electrical properties and defect structure of pure and chromium-doped MnO. The following standard data of 101 . and under reducing conditions are presented. J. Diff. 41. In the La-Cr system reported solubility of lanthanum in bcc chromium is considered in the modeling. M. A. Eremenko. Chen . L. Lukashenko. Modification of the Two-sublattice Model for Liquids. G. Jansson.M. (accepted) The La-Cr and the La-Cr-O systems are assessed using the Calphad approach. 1985. 153-90. 261-66. Ivas. Andersson. Calphad. Ivey. 109-19. 9(2).N. 153. pp. Metall. 4.R.. 16A. 947-962.5-CrO1. Sundman. A. Calphad. Chem.3 Thermodynamic assessment of the La-Cr-O system E. B. B. 38. in: Ductile Chromium. 1968. J. 196. Caplan.J. and L.A. J. V. 1991. 1957. Thermodynamic properties of alloys of manganese with transition elements of fourth period (Cr Fe Co Ni) and with copper. pp. Sidorko. Valigi. Chem. Power sources. B. pp. Phys. M. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization.-O. V. Gauckler J. Russ. La2(CrO4)3. T. 15. Trans. Ågren. 40. M. Jian. M. 31. and oxygen solubilities in bcc and fcc metals are modeled. 42. pp. Phase Equilib. Qu. D. W. 2006. D. and perovskitestructured LaCrO3 are presented. Hill. Povoden.
The liquid phase is modeled using the two-sublattice model for ionic liquids. As the thermal expansions of LaCrO3-based interconnect and conventional perovskite cathode materials are similar. All available experimental phase diagram.7 kJ mol-1 . Gibbs energy of formation from the and ° S 298 K (LaCrO3 ) = 109. recently Sr-. and Crdiffusion into the cathode from LaCrO3-based interconnects is significantly lower than from Cr-containing metallic interconnects. 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. aiming on minimizing the squared errors between 102 .3. V-doped and Zn-doped La1-xCaxCrO3-δ have been considered as promising alternative interconnect materials for SOFC. Furthermore earth alkaline-containing LaCrO3 has been proposed as a cathode material in a recent study by Jiang et al.Mn)2O4 spinel and Cr2O3 along with a severe cell voltage decrease[1-4]. The assessment of the La-Cr-O system using the Calphad approach is based on the recently reassessed La-O and Cr-O subsystems.403–0. and structurechemical data are critically assessed. oxides. thermodynamic. Sr-doped lanthanum manganites (LSM) with the perovskite structure are used as cathode materials in SOFC.oxides° H 298 K (LaCrO3 ) = −73. pO2 (decomp) = 10-20. The lattice stabilities of elements are adopted from Dinsdale. Cation nonstoichiometry of La1-xCrO3 perovskite is described using the compound energy formalism (CEF).oxides G(LaCrO3 ) = –72.1 Introduction In SOFC. 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. Δf. 4. and the model is submitted to a defect chemistry analysis. 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.Thermodynamic assessments stoichiometric perovskite are The calculated: Δf. the thermodynamic stability of the cathode is particularly important for efficient long-term operation. Diffusion of chromium from the metallic interconnect with high chromium content into the cathode leads to the formation of Mn(Cr.2 J mol-1 K -1 .97 Pa.0034 T (kJ mol-1) (T = 1273 K to 2673 K) is calculated.
The melting temperature of lanthanum chromite in air.% 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). but in the graphic presentation of the phase diagram in the same paper Tm(argon) ≈ 2600 K. As small additions of rare-earth metals essentially increase the high-temperature corrosion resistance of chromium.14. The solubility of La in αCrss decreases towards lower temperatures.17] .26].13].% Cr.68 at. reported a La solubility of 0.04 at.% at T = 2103 K.% Cr and a monotectic at T = 1983 K or T = 2103 K and 96 at.CrO1.3 Literature review of the La-Cr-O system In the LaO1.5 at.5 quasibinary system reveal a considerable spread. and the exact value of the oxygen partial pressure was not specified. Small solubility of La in αCrss was reported [12. found La < 0. No intermetallic phases were found in the La-Cr system[12. Berezutskii et al.2 Literature review of the La-Cr system The La-Cr system has a eutectic at T = 1138 K[12.. and Epstein et al. from T = 1073 K up to the melting of Cr using metallographic and microhardness techniques to be 2.5-CrO1. ΔH Cr at T = 1700 K using high-temperature calorimetry.[22-24] The melting temperature was measured with optical pyrometers. Tm(argon) = 2703 K was reported by Tresvjatskiy et al.1 at. and Berjoan 103 . This is not surprising as experiments are complicated due to the high investigation temperatures and evaporation of predominantly Cr[25. 4.% Cr2O3 (T = 2323±20 K). The solubility of La in αCrss was determined in investigations by Savitskii et al.% at 1983 K. is of technological interest.3.% or 99.4 at. and at 84 at. whereas Cr is almost insoluble in La. modeling of the La-solubility in bcc-structured Cr.13] and 3.3.% Cr2O3 (T = 2243 K) or 12 at. denoted as αCrss . Experimentally determined special points in the LaO1. Furthermore deviations between the data from Tresvjatskiy et al. determined the partial enthalpy of mixing in La-Cr liquid with infinite dilution of Cr. as well as a large liquidliquid miscibility gap[12.13]. Tm(air) = 2773 K was determined by Foëx and by Coutures using a thermal analysis technique described in more detail in earlier publications.5. Svechnikov et al.% Cr2O3 (T = 2248 K) or 80 at.Thermodynamic assessments experiments and calculation during the optimization of model parameters using the PARROT module of the Thermocalc software.% in αCrss at T = 1533 K. 4.5 system two eutectics were found at 19 at.
which in both studies was not exactly specified. The perovskite phase: Existing experimental data of lanthanum chromite perovskite structure[33-45]. Stoichiometries and thermal stability ranges of lanthanum chromates with complex formulae were reported by Berjoan et al.7 kJ mol-1.1 (next page). Using differential scanning calorimetry (DSC) he determined the enthalpy change of the reaction 3 2La 2 O3 + Cr2 O3 + O2(g) → 2La 2 CrO6 2 (4.3..33-35. La2(CrO4)3 decomposes by 890 −1030 K La 2 (CrO4 )3 ⎯⎯⎯⎯⎯ 2LaCrO3 + 0.43.Thermodynamic assessments may partly originate from differences of the oxygen partial pressure.25O2(g) ↑ → (4.  . The enthalpy of formation of La2(CrO4)3 from the elements at T = 298 K was proposed by Tsyrenova et al. LaCrO4 has been interpreted as a mixed-valent intermediate decomposition product of La2(CrO4)3[30. However these were in significant disagreement with later results obtained by the same author.1) at T=1055 K and pO2 =83000 Pa to be −151±8 kJ mol-1. whereas experiments on oxygen Lanthanum chromates: The following lanthanum chromates were documented: Berjoan reported that orthorhombic La2CrO6 forms at T > 923 K.3.3. and nonstoichiometry[55-56] along with the investigation techniques used are listed in Table 4.2) An enthalpy change of 231 kJ mol-1 was determined for this reaction at the average temperature of T = 960 K.31]. phase stability.5Cr2 O3 + 2. thermodynamics[30. The peritectic phase diagram proposed by Cassedanne is in gross conflict with the phase diagram data from the other groups. solubilities in αCrss are missing. 104 .46-53]. and Grundy et al. to be −3961±11. Experimental oxygen solubilities in pure Cr and La were considered in thermodynamic assessments by Povoden et al.
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. calculated = −62. calculated Enthalpy of the formation reaction La 2 O3 +1. calculated La (CrO4 )3 La (CrO4 )3 La 2 (CrO 4 )3 2 Δ f.oxides ° H 298K aCr2O3 = 1.5Cr2 O3 +1.2673 K this work.5 kJmol −1 solid oxide electrolyte .oxides ° H 298K Δ f.elements ° H 298K = −3845 kJmol−1 this work. (kJmol−1 ) T = 1090 K 98.4(kJmol −1 ).2 Jmol-1K -1 this work.403 − 0.1× 10−5 Knudsen mass spectrometry La CrO6 = −73.45 + 0.79 kJmol-1 Drop solution calorimetry in 2PbO × B2 O3 LaCrO3 LaCrO3 Δ f.11 × 10−4 this work.elements ° H 298K Δ f.1 ± 1.7 kJmol−1 .25O 2(g) → La 2 (CrO 4 )3 2 Δ f.4 HT (high temperature) .5Cr2 O3 + 2.35 kJmol-1 this work. calculated 2 Δ f.calorimetry T = 1350 K 133.06 ± 2. calculated 139.3.19.oxides ° H 975K LaCrO3 = −1368.5Cr2 O3 + 2.1 Calculated and experimental thermodynamic data of La-Cr oxides Rhombohedral LaCrO3 Standard enthalpy Δ f.2 kJmol-1 this work. 700 . calculated aCr2O3 = 1.based emf Enthalpy increments H − H 298 K . calculated Δ °G = −44.08530T (kJmol−1 ).based emf Δ °G = −79.0 kJmol−1 this work.002115T ± 0.38 kJmol −1 CaF2 .758 + 0. calculated Gibbs energy of formation by 1 3 La 2 O3 + Cr2 O3 → LaCrO3 2 4 T = 1273 K Δ °G = −76.2 HT . calculated ° 2 S 298K La CrO6 = 330 Jmol-1K -1 this work.1 × 10−4 ± 1. calculated = −73. calculated T = 1273 K T = 1273 K T = 2100 K T = 2100 K ° Δ °G = −30. calculated 94.52 kJmol −1 this work. calculated = −3961 ± 11.5O 2(g) → La 2 CrO6 2 Δ f.05 this work. fitted 105 .0034T (kJmol−1 ).oxides ° H 298K La (CrO4 )3 = −372 kJmol−1 this work.75 kJmol−1 this work.oxides ° H 1078K ° LaCrO3 Standard entropy S 298K LaCrO3 = 109.9 ± 1.Thermodynamic assessments Table 4. 855 -1073 K CaF2 .7 kJmol-1 this work.25O 2(g) 2 ΔH 298K La (CrO4 )3 = 231 kJmol−1 and this work. calculated Δ °G = −78. calculated Enthalpy of the dissociation reaction La 2 (CrO 4 )3 → 2LaCrO3 + 0.1 kJmol −1 Knudsen mass spectrometry Δ G = −72. this work.29 ± 0.emf Δ °G = −42.885 K CaF2 .elements ° H 298K ° 2 S 298K La (CrO4 )3 = 516 Jmol−1K −1 this work. calculated = −73.based emf Δ °G = −94. 1273 .
calculated 0.3. enthalpy and entropy changes of this first-order transition taken from the literature are listed in Table 4.x .75 a) calculated from adiabatic shield calorimetry a) used for optimization The reported transformation temperatures lie between T = 503 K and 583 K.25 at 536 K a) calculated from adiabatic shield calorimetry 340 ± (10 . The determined enthalpy and entropy changes vary from 277 J mol-1 to 502.63.84 at 503 − 583 K  calculated from adiabatic calorimetry 277 at 544 ± 1 K a) DSC 403. dilatometry 536  a) adiabatic shield calorimetry. this work.microscopy.2 Calculated and experimental data of the orthorhombic to rhombohedral transition of LaCrO3 Transition temperature (K) 540.XRD 533 estimated from neutron powder diffraction 509 DSC.2 along with the investigation techniques used.ray photography 550 HT .XRD 533 ± 3 a) DTA 543 XRD 533 HT . DSC 533 ± 5 a) HT . XRD Enthalpy change of transition (Jmol−1 ) 340.33-42].5 a) calculated from DSC 0. HT . HT .XRD. calculated 502. this work. thermogravimetry. The temperatures.XRD. Table 4.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.XRD 523 a) starting transition.40) at 533 ± 5 a) DSC 380 at 550 K DSC 310 at 509 K DSC Entropy change of transition (Jmol-1K −1 ) 0. HT . simultaneous DSC . calculated 503 − 583 adiabatic calorimetry 544 ± 1 a) DTA. HT .96 at 503 − 583K calculated from adiabatic calorimetry 0.XRD 541 a) completed transition.3. dilatometry.5 J mol-1 to 106 . DSC. DSC 535 cooling.XRD 540 ± 2 a) HT . DSC 550 HT .08 ± 41.08 J mol-1 and 0. this work. dilatometry 545 heating. simultaneous DSC .XRD 528 − 533 a) HT .XRD (air and vacuum) 563 ± 5 DTA.XRD.
in agreement with Berjoan (T = 1923 ± 20 K) using dilatometry. 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. reported no weight loss of lanthanum chromite at T=1273 K from pure oxygen to pO2 =10-16.Thermodynamic assessments 0. and Momin et al. (150 to 450 K) using DSC. 289 K. LaF3/CaF2/LaF3. Chemical stability: Nakamura et al. La2O3. A transformation from rhombohedral to cubic structure at a temperature close to T = 1300 K was reported by Ruiz et al. Azad et al. Cr2O3/O2. Peck et al. measured emf of Pt..% to 1. T = 700 to 885 K. Sakai et al.28 cat. and Dudek et al. Cr/Pt at 1273 K. Chen et al.. A magnetic order-disorder transition was documented to occur at T ≈ 287 K. and its oxgen nonstoichiometry is negligible. measured electromotive force (emf) of the solid oxide galvanic cell Pt/Cr. LaCrO3. Single phase lanthanum chromite with 0. This means that the perovskite phase does not decompose within this oxygen partial pressure range. reported T = 1923 K using high-temperature x-ray diffraction (HT-XRD). Enthalpy of formation: Cheng and Navrotsky determined the enthalpy of formation of LaCrO3 by oxide melt solution calorimetry at T = 1078 K. whereas Coutures et al. Cation nonstoichiometry and defect chemistry: Maximum excess Cr in single-phase La1-xCrO3 of 0. (T=100 K to 1000 K) using laser-flash calorimetry. 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. or 295 K. and T = 1273 K respectively. Enthalpy increments of LaCrO3 at T = 1090 K and 1350 K were measured by Suponitskii using a high-temperature heat-conducting calorimeter.% in furnace-cooled LaCrO3 annealed at T = 1773 K in air was reported from Khattak and Cox. Pt in pure oxygen from T = 855 K to 1073 K. Gibbs energy of formation: in order to obtain the Gibbs energy of formation of LaCrO3. O2/La2O3. and Sakai and Stølen (T = 272 K to 1000 K) using adiabatic shield calorimetry.38 cat. (T = 77 K to 280 K) using alternating current calorimetry.. 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). Höfer and Kock (480 to 610 K) and Satoh et al.96 J mol-1 K-1. Berjoan further reported prevailing of the cubic structure at T = 2173 K.% excess 107 . Chen et al.76 cat.1 Pa using thermogravimetry combined with X-ray diffraction (XRD). LaCrO3/MgO-stabilized ZrO2/Cr2O3.
affirming the lack of oxygen vacancies in the structure. the electrical conductivity being 2 proportional to pO2 −3 8 . 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.0 ×103 Pa to pO2 = 2. in line with the results from thermogravimetry.05 % up to T = 1250 K. Akashi et al. deduced n-type conductivity from measurements of transport number. ShvaikoShvaikovskii et al.1% in weight. measured the isothermal electrical conductivity of an equilibrated La1-xCrO3-Cr2O3 mixture with 5 vol. However n-type conductivity was not approved by any further study. thus the presence of interstitial Cr in reduced chromite was proposed. They observed an extraordinarily slow equilibration of the samples: More than four months were required to measure the electrical conductivity at equilibrium state. is inconsistent with the findings from Akashi et al. reported that concentrations of lanthanum vacancies and holes slightly increase from T = 1550 K to 1700 K.59] agree that the electrical neutrality is maintained by holes and lanthanum vacancies. reported that the ionic transport number in lanthanum chromite is less than 0. 108 . resistivity and thermo-emf at pO2 = 1Pa and pO = 102 Pa . 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. and Meadowcroft proposed the occurrence of chromium vacancies instead of lanthanum vacancies. 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. The transition from reduced to stoichiometric chromite was accompanied by a decrease of about 0.0 ×104 Pa . Several groups[58. Ruiz et al.57]. The conductivity was proportional to pO2 3 16 .Thermodynamic assessments Cr was prepared at T = 1773 K in a pure oxygen atmosphere.58-60]. and that the carrier is the hole in lanthanum chromite[25. Akashi et al. the same as reported in an earlier study. Iliev et al.% excess Cr2O3 from T = 1573 K to 1673 K from pO2 = 1. 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. In contrast to the other authors Shvaiko-Shvaikovskii et al.
3) SER H x is the standard enthalpy of the stable state of element x at 298. and O2 in proper stoichiometries and A + BT parameters that were fitted to the enthalpy of formation from the oxides. 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. and αCrss is then given by the two-sublattice description (La. For the reasons discussed recently. 5  A and B are adjustable parameters. we reassess the oxygen-solubility in Cr(bcc) using the model (Cr)(O. described the solubility of oxygen in Cr(bcc) using the model Cr(Va.O)1. Cr2O3.5 − H Cr − H O = °GCr(bcc) + (4.15 K and 10 Pa.3.Va were optimized with the same experimental data. mixedvalent chromates mentioned above. 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. and to optimize their model parameters with phase diagram data[19. The thermal stability of La2CrO6 is slightly influenced by the thermodynamics of the intermediate.Cr)(Va. These chromates can be interpreted as intermediate products in the 109 . The Gibbs energy of the end-member (Cr)(O)1. for its optimization. We chose the solubility values from Svechnikov et al.3. using the PARROT module of the Thermocalc software A was given the fix value 0 for the reasons discussed in an earlier paper. Eq.La:Va was given a positive value. 4.Va)1. as these data are more comparable to solubilities in other rare earths-transition elements systems. Solid oxides: Lanthanum chromates: The Gibbs energy function of La2CrO6 was based on the sum of the Gibbs energy functions of La2O3.O)3.4 Thermodynamic modeling and optimization Metal phases: In order to account for the solubility of La in αCrss . In order to refine the model parameters of La2CrO6.5. Povoden et al.1 as well as thermal stability data. and B and a regular interaction parameter 0 LCr:O.3.5.32]. the zeroth-order. The formation of chromates that contain mixed Cr valences may be explained by gradual reduction of Cr6+ in La2CrO6 as the temperature increases.Thermodynamic assessments 4. it was thus necessary to consider these mixed-valent chromates in a provisional version of the thermodynamic La-Cr-O database in spite of their arguable stoichiometries.
5 .4) Slight differences of the oxygen partial pressure during experiments may be reflected by a variable extent of Cr-reduction.32] (4. 4.(1. and enthalpy increment-data 110 . These lanthanum chromates with conflicting stoichiometries[19.32] are not included in the presented thermodynamic database. The model parameters were fitted to the experimental enthalpy and temperature of decomposition.Thermodynamic assessments scope of a sluggish decomposition of La2CrO6. The superscripts o-prv and r-prv stand for Gibbs energy expressions that have different values for orthorhombic and rhombohedral perovskite. which starts at T = 1153 K[19. GVCR4O and GLCR4O are set equal for orthorhombic and rhombohedral perovskite. and consequently ambiguous stoichiometries of mixed-valent intermediate chromates. 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.5) The parameters A.x CrO3 + O2 (g) ↑ 2 2 mixed-valent chromates → La 2 CrO6 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ [19.3. GRPRV denotes the Gibbs energy function for stoichiometric rhombohedral perovskite. The Gibbs energy function of La2(CrO4)3 was formulated using the same strategy as for La2CrO6. We go along with the interpretation of LaCrO4 being an intermediate reaction product during the decomposition of La2(CrO4)3 by Eq.3. activity-data of Cr2O3 in LaCrO3 from Peck et al. heat capacity-data obtained by adiabatic calorimetry from Sakai and Stølen. GVCR4O and GLCR4O stand for the Gibbs energy functions of the completely oxidized neutral endmember.3. °GLaCrO3 is given by ° r-prv SER SER SER GLaCrO3 − HLa − H Cr − 3H O = °GLa3+ :Cr3+ :O2− = GRPRV = 1° 1 GCr2O3  + °GLa2O3  + Gmag + A + BT + CT ln T 2 2 (4.32] and is completed at T = 1473 K or 1523 K. Stoichiometric perovskite: The Gibbs energy function of stoichiometric rhombohedral r-prv LaCrO3 with the sublattice formula (La3+)(Cr3+)(O2-).. The enthalpy of formation from the elements was not used as it is a calculated value.2 and do not include this phase in the modeling. and C are optimized using the enthalpy of formation from Cheng and Navrotsky. B. The simplified decomposition reaction reads 1+ x 1.5 x) La 2 O3 + La1.
Va)(Cr3+.Va)(Cr3+. B-site vacancies are energetically less favored than A-site vacancies in the perovskite structure[63.38.5-MnO1. 112-114) resulted in negligible concentrations of Va on the B-site and the anion sublattice.Va)3. A phase diagram with congruent melting of lanthanum chromite and two eutectics[18.40] and entropies[34. Thus the defects in n-type conducting lanthanum chromite are ambiguous and were not considered in the model. as there is no existing thermodynamic data for this transition. enthalpies[34. irreconcilable trouble is encountered at the extension to the LaO1. This means that the simplest sublattice model to describe cation nonstoichiometric La1-xCrO3 reads (La3+. The rhombohedral to cubic transformation at high temperatures is not considered in the model. 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+. 111 .5 system required for SOFC applications due to diversities between the model descriptions of lanthanum chromite and lanthanum manganite. While this model results in a satisfying reproduction of experimental data.64]. is unlikely due to the densely-packed perovskite structure.Thermodynamic assessments measured at high temperatures.Cr4+)(O2-)3.3 (pp.58] measurements.35] of transition having been obtained by combined investigation techniques and being internally most consistent. and oxygen nonstoichiometry can be excluded from thermogravimetry and electrical conductivity[37.Cr4+.3.19] cannot be reproduced by using the emf-experiments[49-52]. A+BT parameters of the low-temperature orthorhombic perovskite phase were optimized with those temperatures[34. Cation-nonstoichiometric perovskite: To choose a proper model for nonstoichiometric perovskite the following considerations are made: the formation of interstitial Cr in lanthanum chromite proposed by Shvaiko-Shvaikovskii et al.35.35.5-CrO1. Thus these data were excluded from the optimization.Va)(O2-. and the perovskite formula essentially remains La1-xCrO3. The optimization of selective model parameters listed in Table 4.42].40.
− 2 H Cr − 3H O = 5GCROLIQ − 179638 + 79.23T + (65393 − 23T )( yCr 2+ − yLa3+ ) Cr Lliq 2+ .Vaq.O = −355151.La3+ :O2.. Va q.422 ° Lbcc Cr.= 121000 Cr Cr Lliq 2+ . O)1.3.)q p = 2 yO2.− 2 H Cr − 2H O = 2GCR1O1_L Interaction terms Lliq 2+ :O2. Cr 3+ ) p (O 2.Vaq. q = 3 yLa3+ + 2 yCr 2+ + 3 yCr3+ ° ° ° ° ° ° liq SER GLa3+:Vaq.= 61397 − 5.008 yCr  112 .La3+ :Vaq.= −101850 − 39016( yCr 2+ − yLa3+ ) Cr Lliq 3+.4 Tcbcc = −311. Cr 2+ ..− H Cr = 2GCRLIQ − GCR2O3_L − 3GCR1O1_L liq SER SER GCr3+:O2.− HLa = GLALIQ liq SER SER GLa3+:O2.5T  2 4 Lbcc Cr:Va.= −101850 − 39016( yCr3+ − yLa3+ ) Cr Bcc A2 phase (La.923T  liq SER SER GCr 2+ :O2.+ qyVa .La3+:O2.− H Cr = GCRLIQ liq SER GCr3+:Vaq. Cr)(Va.La:Va = 83500 p = 0.5 yCr  β bcc = −0..3 Model descriptions and Gibbs energy functionsa) Liquid (liq) (La 3+ .5 ° ° bcc SER GCr:Va − HFe = GHSERCR  bcc SER GLa:Va − HLa = GLABCC 3 SER 3° bcc SER GCr:O − H Cr − H O = GHSERCR  + G (O 2(g) ) + 113.Thermodynamic assessments Table 4.= Lliq 3+ :O2.17755T 2 4 3 SER 3° SER ° bcc GLa:O − HLa − H O = GLABCC + G (O 2(g) ) − 855000 + 142.− 2 HLa − 3H O = GLA2O3LIQ liq SER GCr 2+ :Vaq.
− HCr − 3HO = °GVa:Cr4+:O2.− 2HLa − 3HCr − 12HO = GLA2CR3O12 La (CrO ) 113 .− HLa − HCr − 3HO = 5 6 GS4O +GOPRV − GS3V + 1 6GS4V + Gmag ° r-prv SER SER SER GLa3+ :Cr4+:O2.5GVVV − 2GLCR4O − 0.Va:O2.− HLa − HCr − 3HO = GRPRV + Gmag o-prv SER SER SER GLa3+ :Cr4+:O2.− HCr − 3HO = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O + 0.5GVVV − 2GLCR4O + 0.5GVVV − 2GLCR4O − 0.5GVVV − 2GLCR4O + 0.5 °G(O2(g) ) + Gmag ° r-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GRPRV − 1.75 °G(O2(g) ) − 1..− HLa − HCr − 3HO = 5 6GS4O +GRPRV − GS3V + 1 6GS4V + Gmag ° ° ° o-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GOPRV − 1.= 250000 La La Magnetic contribution Tco-prv = Tcr-prv = 291.894 yi:j:k SER SER SER 2 GLa3+ :Cr6 :O2.− 2HLa − HCr − 6HO = GLA2CRO6 6+ La CrO La 2 (CrO4 )3 (La 3+ )2 (Cr 6+ )3 (O2.− HLa − HCr − 3HO = GOPRV + Gmag r-prv SER SER SER GLa3+ :Cr3+:O2.Va:O2. Va)(O2.− HCr − 3HO = GRPRV + 1.41263T + Gmag ° o-prv SER SER r-prv SER SER GVa:Cr4+:O2. Va)3 ° ° ° o-prv SER SER SER GLa3+ :Cr3+:O2.= Lprv3+:Cr4+.5GVCR4O +0.Cr3+ k = O-2.35 yi:j:k i = La 3+ .5GVCR4O +0.5 °G(O2(g) ) + Gmag o-prv SER SER GLa3+:Cr4+ :Va − HLa − HCr = 5 6GS4O − GS3V +1 6GS4V +GOPRV − 1.75 °G(O2(g) ) − 1.Cr3+ . Va La .5 °G(O2(g) ) + Gmag r-prv SER SER GLa3+:Cr3+ :Va − HLa − HCr = GRPRV − 1.− HCr − 3HO = GOPRV + 1.5 °G(O2(g) ) + Gmag ° o-prv SER SER GVa:Cr3+:O2.5GVCR4O +0.Va)(Cr 4+ .Thermodynamic assessments La1-xCrO3 perovskite (La 3+ .)6 ° prv β o-prv = β r-prv = 0.35056T + Gmag Interaction term Lprv3+:Cr3+.5GVCR4O +0.Chromates La 2CrO6 (La 3+ )2 (Cr 6+ )(O2.Va j = Cr 4+ .35056T + Gmag ° o-prv SER r-prv SER GVa:Cr4+:Va − HCr = °GVa:Cr4+:Va − HCr = = 2GVCR4O + 1 3GVVV − 4 3GLCR4O − °G(O2(g) ) + 4.5 °G(O2(g) ) + 4.41263T + Gmag ° o-prv SER GVa:Cr3+:Va − HCr = GOPRV + 1.)12 ° SER SER SER 4 3 2 GLa3+ :Cr6+:O2.41263T + Gmag ° r-prv SER SER GVa:Cr3+:O2.75 °G(O2(g) ) − 1.75 °G(O2(g) ) − 1.41263T + Gmag ° r-prv SER GVa:Cr3+:Va − HCr = GRPRV + 1.
00307T 2 + 190000T −1 +0.5GCR2O3 + 0.5GCR2O3 + 2.5GCR2O3 − 73591 + 2.75 °G(O2(g) ) − 72615 − 4.68T ln T Stoichiometric rhombohedral perovskite GRPRV = 0.5GCR2O3 − 73931 + 3.3.5GCR2O3 GVCR4O = 0.31451 J mol-1 K-1. The second-last term describes the excess Gibbs energy of mixing due to interactions of ions in the mixture.9T − 47. R = 8.25 °G(O2(g) ) − 200000 Perovskite reference GS4V = −607870 + 268. mol.Thermodynamic assessments Functions Perovskite Stoichiometric orthorhombic perovskite GOPRV = 0.6) i j k i j k where yi is the site fraction of Va and La3+ on the A-sublattice.68T ln T Neutral nonstoichiometric perovskite endmembers GS4O = −597648 + 213.56T ln(T ) − 0. R = 8.5GLA2O3A + 0.5GCR2O3 − 1.00307T 2 + 190000T −1 +0.25 °G(O2(g) ) La 2CrO6 GLA2CRO6 = GLA2O3A + 0. K.5GCR2O3 + 0.25 °G(O2(g) ) − 371557 + 205T a) All parameters are in SI units : J.25 °G(O2(g) ) GS3O = −472704 + 191.25 °G(O2(g) ) − 291802 − 250T GLCR4O =1 3GLA2O3A + 0.5GCR2O3 + 0.01T − 0. yj is the site fraction of Cr3+.00307T 2 + 190000T −1 +0.5GLA2O3A + 0.5GCR2O3 + 0.31451 Jmol K −1 −1 Using the compound energy formalism (CEF)[66-68] the molar Gibbs energy of La1-xCrO3 reads ⎛ ⎜ ⎝ ⎞ ⎟ ⎠ ° prv prv Gm = ∑∑∑ yi y j yk °Gi: j:k + RT ⎜ ∑ yi ln yi + ∑ y j ln y j + ∑ yk ln yk ⎟ + EGm + Gmag (4.38T − 0. and yk is the site fraction of O2.38T − 47.5T La 2 (CrO4 )3 GLA2CR3O12 = GLA2O3A + 1. Cr4+ and Va on the B-sublattice.7186T − 47.and Va on the anion sublattice of the perovskite A1-xBO3.56T ln(T ) − 0. These are accounted for by the 114 .56T ln(T ) − 0. The third-last term accounts for the configurational entropy of mixing.
1 is a visualization of the Cr-containing part of the model the authors use to describe the cation nonstoichiometry of lanthanum chromite. Only compounds inside the neutral plane can exist on their own. These endmembers of 3 3 nonstoichiometric perovskite have been fixed firmly by a sufficient number of consistent experiments in 3 the LaO1. with the 8 Cr-containing compounds being the corners of the cube. A short summary of this model can be found in Chen et al. 4. The parameters of the compound energy formalism are the Gibbs energies of the not necessarily neutral 12 end-member compounds °Gi: j:k . The thin lines margin the neutral plane.) and °G(La3+ )(Cr 4+ )(Va) from Povoden et al. 115 . Fig. 112-114).5-SrO-CrO1.. Thus the authors prv prv adopted °G(La3+ )(Cr 4+ )(O2.) and °G(La3+ )(Cr 4+ )(Va) are given in Table 4. The neutral compounds used for the optimization are marked by the black spots.5 3 system  .3 (pp.3.3. ° prv prv G(La3+ )(Cr 4+ )(O2. The magnetic parameters Tc and β were fitted to the C p data around the magnetic transition temperature from Sakai and Stølen.Thermodynamic assessments optimization of interaction parameters. Fig.3.1 Representation of the Cr-containing part of the model for nonstoichiometric lanthanum chromite. For the magnetic part of the Gibbs energy a magnetic ordering-model proposed by Inden and simplified by Hillert and Jarl was used. The last term designates the magnetic contribution to the Gibbs energy. 4.
9) Using Eqs. ° prv G(La3+ )(Cr3+ )(Va) results from a reciprocal relation which was set zero in analogy to Grundy et 3 al.3.8 and adopting the Gibbs energies of the remaining endmembers ° prv prv prv prv G(La3+ )(Va)(O2.with Va on the anion sublattice.7 and A of Eq.3.) . 3 3 3  .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. was considered in the optimization.) .) .8 it describes random mixing of La3+ and Va on the A-site. 4.5 to 4. °G(Va)(Va)(O2.3.7 describes random mixing of O2. °G(Va)(Cr 4+ )(O2. the 12 endmembers of the compound energy formalism of the perovskite phase are defined.8 are optimized using experimental data of excess Cr in perovskite.) . were used to obtain ° prv prv prv prv G(Va)(Cr3+ )(O2. 4.3.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 = ° (4.3. °G(Va)(Cr3+ )(Va) . The 116 .r-prv SER SER o-prv.  : 3° G (O2(g) ) 2 ° o-prv. 4. Furthermore the temperature dependence of lanthanum vancancy and hole concentrations from Akashi et al. °G(La3+ )(Va)(Va) . and °G(Va)(Cr 4+ )(Va) . As cation diffusion in La1-xCrO3 is extremely slow even at high temperatures. The parameters A and B of Eq. 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. and °G(Va)(Va)(Va)3 from Grundy et al.r-prv GLaCrVa3 − HLa − H Cr = °GLa3+ :Cr3+ :Va = GLaCrO3 − (4. In Eq.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. 4.3.3. 4. The configurational entropy3 3 3 3 term in Eq.3.3.
2 (next page). as were the two sub-regular interaction parameters. Higher oxidation states are unlikely to exist in the liquid at normal oxygen partial pressures. Furthermore the two regular interaction parameters 0 Lliq 3+ . 4.Va:Cr4+ :O2.and 0Lprv3+ .La3+ :Va Cr Cr interaction parameters to account for interactions between La and Cr.Cr2+. the temperature of the eutectic at the Cr-rich side from Berjoan. It was based on the liquid descriptions of the binary subsystems.La3+ :O2.= Cr Cr Cr 1 liq Cr 2+ .that were given La La the same values circumvents too high Cr4+ contents at low temperatures that would be in conflict with the experiments. we defined pO2 = 1 Pa. The liquid is thus given by the model description (La3+.La3+ :Va and subregular 1Lliq 2+ .5 system from Tresvjatskiy et al. together with experimental phase diagram data[12.Cr3+)p(O2-.La3+ :O2- L were optimized.Thermodynamic assessments introduction of positive interaction parameters 0Lprv3+ . The liquid phase: The two-sublattice model for ionic liquids[73. did not specify the value of the prevailing oxygen partial pressure during their phase diagram experiments conducted in an argon atmosphere.14] at the eutectic and monotectic in the metallic La-Cr system and the partial enthalpy of mixing of Cr.74] was used for the description of the liquid phase of the La-Cr-O system.14. ΔH Cr  in La-Cr liquid were used to optimize the temperature-dependent regular 0 Lliq 2+ .3.La3+ :O2.Vaq-)q. Using the following data for their optimization led to the lowest error between experiments and calculation: the composition and temperature of the eutectic at the La-rich side and the composition of the eutectic at the Cr-rich side in the oxide LaO1. As a value of the oxygen partial pressure is required for the optimization.La3+ :O2.= 0 Lliq 2+ .17]. The experimentally determined temperatures and liquid compositions[13. thus the two regular interaction parameters were set equal to each other.5 Results and Discussion The La-Cr system: The calculated phase diagram of the La-Cr system is presented in Fig..3.13. Berjoan and Tresvjatskiy et al. The chromium species considered in the liquid are Cr2+ and Cr3+.Va:Cr3+ :O2. 4. 117 .5. and the congruent melting temperature of the perovskite phase from Coutures et al.CrO1. and Foëx. It was assumed that the interactions between Cr2+-La3+ and Cr3+-La3+ are of the same order of magnitude in the oxide melt.and the two subregular 1Lliq 3+ .
4. which is tantamount to a small solubility of La in αCrss in agreement with the experiments [14. The calculated enthalpies of mixing are shown in Fig.La:Va used to model the bcc phase results in a large miscibility gap between the La-rich and Cr-rich metals. The positive value of 0Lbcc Cr. 4.17] .Thermodynamic assessments Fig. denoted as γ La ss .2 Calculated phase diagram of the La-Cr system with data from the literature included (symbols).3. 118 . the lowest temperature of stable γ La ss . of 2 ×10-3 at.3.3 (next page) together with the experimentally determined value that is well reproduced by the calculation. which further decreases as a function of increasing temperature.% at 1134 K. The model description of the bcc phase results in a tiny solubility of Cr in La(bcc).
CrO1. The higher value was favored by Dinsdale and is adopted in this study.5 phase diagrams in pure oxygen at pO2 =105 Pa. 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. which are T = 2180 K and 2130 K. A satisfying reproduction of the experimental data was obtained by considering a moderate temperature dependence of 0 liq Cr 2+ . in air at 119 . 4. at T = 1700 K included (symbol with error-bar). with the experiment from Berezutskii et al.3.25 and T ≈ 5000 K that is of course unphysical. This is unfortunately associated with Cr an inverse liquid-liquid miscibility gap with a minimum at X(Cr) = 0.La3+ :Va L and 1Lliq 2+ .Thermodynamic assessments Fig.3 Calculated partial enthalpies of mixing of La and Cr in La-Cr liquid.La3+ :Va .. The La-Cr-O system: Phase equilibria: Calculated LaO1. and integral enthalpies of mixing as a function of composition. and Svechnikov et al. whereas the lower melting temperature was chosen by Savitskii et al.5.
Excess Cr in lanthanum chromite is favored at high oxygen partial pressures.3.5-CrO1. 4. and under reducing conditions representing argon atmosphere at pO2 = 1 Pa with experimental data included (symbols). La2CrO6 is stable within a wide temperature-range in pure oxygen. Fig.3. whereas it does not form in air and argon atmosphere. 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. air atmosphere. Due to the ambiguous oxygen partial pressure of phase diagram experiments[18. Be it that the reported thermodynamic data of La2CrO6 and La2(CrO4)3 are correct.4 together with experimental data[18-21].4 Calculated phase diagrams of the LaO1. This is in line with the interpretations of Raman spectra from Iliev et al. On the other hand a significant amount of Cr3+ in the ionic liquid is reduced to Cr2+ under reducing conditions. Under oxidizing conditions Cr3+ is favored over Cr2+ in the liquid. reflected by the disappearance of Cr overstoichiometry. and under reducing conditions at pO2 = 1 Pa representing the typical oxygen partial pressure in argon atmosphere are shown in Fig.5 system in pure oxygen. A decrease of Cr4+ during annealing of an originally lanthanum-deficient perovskite phase under reducing conditions is predicted by the model. and orthorhombic perovskite is stable only at pO2 ≤102 Pa. 4.Thermodynamic assessments pO2 = 21278 Pa. lanthanum chromite is expected to be metastable at room temperature.19] and the conflicting data on the melting temperature of lanthanum chromite in argon atmosphere the presented liquid description is rather tentative. and the liquid stability increases considerably at the Cr-rich part of the system 120 .
2 (p. was obtained using the new model description (Cr)(O. The liquid description using the twosublattice model for ionic liquids also resulted in a significantly larger decrease of the melting temperature of lanthanum chromite at pO2 ≈ 1 Pa than the given values in argon atmosphere.1 (p. Despite this discrepancy we did not go for an alternative liquid model for the sake of consistency with our previously assessed systems.3.3. 4.04 Pa metallic liquid forms at the lanthanum-rich side of the phase diagram.3. Thermodynamic data: Calculated thermodynamic data of solid oxides are listed together with experimental data from the literature in Table 4. 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. 4.5 Calculated phase equilibria of the La-Cr-O system at T = 1273 K as a function of oxygen partial pressure. It is obvious that no mutual solubilities of La and Cr in bcc metal in equilibrium with oxides are expected.3. The same oxygen solubility in Cr as in the assessment by Povoden et al.Thermodynamic assessments leading to a considerably lowered eutectic temperature. In Fig.5.3 (pp. Table 4.5 calculated phase equilibria of the La-Cr-O system at T = 1273 K are shown as a function of oxygen partial pressure. At pO2 = 10-34. 121 . Calculated and experimental data on the orthorhombic to rhombohedral transition of LaCrO3 are listed in Table 4.Va)1. 105).3. 106).
Anyway the model parameters were fitted to the experimental data. 4.Thermodynamic assessments Lanthanum chromates: Testing an optimization of model parameters of La2(CrO4)3 by using all available thermodynamic data[29. whereas the calculated standard enthalpy of formation from the elements was rejected.6 Calculated heat capacities of LaCrO3 (solid curve) as a function of T with experimental data included (symbols). 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]. bearing in mind the high degree of uncertainty of the resulting description. Fig. The perovskite phase: the calculated heat capacities of LaCrO3 are compared with experiments from the literature in Fig.3. 4.3.6. The use of C p -data from Sakai and Stølen along with enthalpy increment-data from Suponitskii to optimize the 122 .31] resulted in gross disagreement between optimized and reported values. The calculated C p -curve extrapolates well to high temperatures. The considerable error might be explained by experimental difficulties to reach equilibrium at the low investigation temperatures. The dashed line marks the temperature of the o-prv ↔ r-prv transition.
For the sake of compatibility with the recent assessment of the La-Fe-O system we chose p = 0.3. 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 (4.3. Two values for the magnetic parameter p are possible depending on the crystal structure. Only the use of the latter data for the optimization resulted in the proper phase diagram with congruent melting of the perovskite phase and two eutectics.28 or p = 0.6. p.4. As CTlnT was set equal for o-prv and r-prv. 105. 4.4. Experimental enthalpy increments are well reproduced by the calculation (see Table 4. 105). and hcp is not available in the literature. as it unavoidably leads to emf that are too low.Thermodynamic assessments parameter CTlnT of the Gibbs energy of stoichiometric perovskite resulted in the lowest error between experiments and calculation. It needs to be clarified why all of the emf-measurements are problematic: Azad et al. In this case the emf depends on the activity 123 . 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.1.or oxygen-containing atmosphere. whereby the proper p-value for structures other than bcc.3. 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. The resulting Gibbs energies of formation from emf-measurements are remarkably less negative than the Gibbs energies of formation derived from Knudsen mass spectrometry. The calculated C p -peak at T = 290 K reflects the temperature of the magnetic order-disorder transition. p. 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. p=0.70] using p = 0.35] the term CTlnT is fixed firmly.28 and p=0.10) are listed as a function of temperature together with data from the literature [49-53] in Table 4. Yet it is obvious that the CaF2based emf-technique is neither suitable for the determination of thermodynamic data of lanthanum chromite.3. Due to the consistency between both groups of calorimetric experiments[30. the transition temperature being in agreement with the experiments. A small peak which was found around 855 K can be explained most likely by the decomposition of an undetected impurity phase. The C p -anomaly is equally well reproduced by the model[69. The calculated transition temperature of T = 540 K is shown by the broken line in Fig. their C p is the same.28.1. fcc.
3. Chemical stability of the perovskite phase: The calculated oxygen partial pressure for the decomposition of lanthanum chromite by the reaction 1 3 LaCrO3 → La 2 O3 + αCr + O2 (g) ↑ 2 4 (4. Fig. and changing activity of CaO at the electrode/electrolyte interface can alter the chemical potential of fluorine at this electrode and thus the emf across the electrolyte.3.11 is plotted as a function of temperature and oxygen partial pressure in Fig.97 at 1273 K.11) is pO2 = 10-20.3.7. 4. 4.Thermodynamic assessments of CaO at the electrode/electrolyte interface. The calculated decomposition of the perovskite phase by Eq.3. 4.7 Calculated decomposition of lanthanum chromite as a function of temperature and oxygen partial pressure. Defect chemistry of the perovskite phase: 124 .
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. [CrCr ] ∝ PO2 16 . A La A Va B Cr B Cr A La A Va B Cr y prv 4+ and the tiny fractions y prv and y prv are plotted logarithmically as a function of B Cr B Va O Va log pO2 at T = 1073 K and 1673 K in Fig. yprv 3+ . CrCr . and yprv 4+ in the compound energy formalism. 4.)3 + O2(g) → (La 3+3 Va1 3 )(Cr 4+ )(O2.: 1 (La 3+ )(Cr 3+ )(O2. yprv . yprv 3+ .3.Thermodynamic assessments Applying a defect chemistry analysis of La1-xCrO3 in equilibrium with Cr2O3 the following defect reaction for its oxidation can be written in the sublattice form.3. [CrCr ] . A La 125 . 4.3. Va La .14) x x x For small oxidation extent [La La ] .15) • Substituting this into Eq. if [Va ′′′ ] and [Va •• ] are O Cr assumed to be negligible according to Akashi et al. The line for yprv 3+ at 1073 K cannot be seen as it is very close to 1.3.8 (next page) for lanthanum chromite in equilibrium with Cr2O3. La x x • ′′′ The concentrations of the defects LaLa . and CrCr in La1-xCrO3 correspond to the site 3 fractions yprv 3+ .3. yprv .)3 2 4 (4.14 gives the proportionalities [Va ′′′ ].12) Using Kröger-Vink notation this defect reaction reads 1 2 x 1 x x x • x La La +CrCr +3OO + O2(g) → La La + Va ′′′ + CrCr +3OO 4 3 3 La (4.3. and [OO ] can be considered to be ~ 1. yprv 3+ . and charge neutrality is maintained by 1 • [Va ′′′ ]= [CrCr ] La 3 (4.
4.0 ×103 Pa and pO2 = 2.3. 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.9 (next page) the calculated slopes of VaLa and CrCr are 126 . is calculated from very high to very low oxygen partial pressures. hence oxidation of LaCrO3 to La1-xCrO3 governs the electrical conductivity of perovskite with fixed activity of Cr2O3 at unity between pO2 = 105 Pa and 10-8 Pa at this • temperature.8 Calculated site fractions of species in La1-xCrO3 in thermodynamic equilibrium with Cr2O3 logarithmically plotted at T = 1073 K and 1673 K as a function of of 3/16 of the calculated defect concentrations is indicated in the triangle. 4.0 ×104 Pa determined by Akashi et al. This slope is • fixed by the defect reaction Eq. 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.. may be explained by problems of reaching equilibrium due to extraordinarily slow cation diffusion in • ′′′ lanthanum chromite. In Fig.12. The conflicting data from Shvaiko-Shvaikovskii et al.3. The slope • At T=1073 K a constant slope of 3/16 of the defect concentrations [Va ′′′ ] and [CrCr ] shown in La the triangle. 4.3.Thermodynamic assessments Fig. pO 2 .
The calculated concentrations agree well with the data derived from electrical conductivity • measurements. The presented defect chemistry calculations are still rather tentative. broken lines).3.9 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. as calculated [Va ′′′ ] and [Va •• ] are very small.Thermodynamic assessments • compared with slopes of [Va ′′′ ] and [CrCr ] determined by Akashi et al. 4. Fig. derived from electrical conductivity measurements (symbols with error-bars.3. The calculated O Cr relative defect concentrations are in line with those proposed by Akashi et al. as a function of La reciprocal temperatures. as the temperature and oxygen partial pressure dependence of excess Cr in La1-xCrO3 has not been investigated systematically so far. 4. The calculated amount of [Va ′′′ ] relative to [CrCr ] is fixed by the criterion for La charge neutrality. Eq.15. 127 ..
4. The thermodynamic descriptions of lanthanum chromates and the liquid phase are rather tentative due to humble or sketchy experimental information.G. 2. 1997. Carlsson. Druckerei J. S. 4013-22. P. Y. pp.). 2000. 703. Soc. Deller. M. Jiang. The thermodynamic modeling of lanthanum chromite was based on experimental thermodynamic data reported by Peck et al. Hilpert. Using the new database the stability limits of lanthanum chromite in function of temperature and oxygen partial pressure can be quantified.H. S. Solid State Ionics. The proposed existence of lanthanum vacancies and holes to maintain charge neutrality in lanthanum chromite with excess Cr is reproduced by the model. 2. A. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. P. 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.3. and K. p. Zhang. 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. Nickel. 297-310. pp. Larsen. First European Solid Oxide Fuel Cell Forum Proceedings. Kjaer and J. J. Miller. Electrochem. 1994.. Kinzel. J. Das. 3. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells. Vol. Badwal. 147(11). The orthorhombic to rhombohedral transition in lanthanum chromite and the magnetic order-disorder transformation are well reproduced by the model. A. H. and Cheng and Navrotsky.6 Conclusions Model parameters of the presented thermodynamic La-Cr-O database were optimized with assessed thermodynamic and phase diagram data. Zhang. Ramprakash and J. R. D. U.P. References 1.Thermodynamic assessments 4. Mechanism and kinetics. as the use of these data for the optimization of model parameters resulted in a proper reproduction of the phase equilibria derived from experiments. Foger. Cr-Mn deposition at the three-phase boundary observed by TEM.-M. K. 99. However the amounts of excess Cr in La1-xCrO3 used for the optimization of the cation nonstoichiometry are preliminary. S. I. Foger.P. K. Bossel (Ed. Proceedings of the 26th Risoe International Syposium on 128 . Göttingen.
J. Kobzenko. Chem. Solids. Oxid. and V doped-LaCrO3 interconnect materials prepared by Pechini. pp. p. Zhao.-H. 2008. P. E. Peck. Met. A. Shin. A. pp. M. 27(4).. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. 2. Phys. Smith et al.K.G. 1985. O. M. 1973.. K. Tavadze. J. Geupel. 2006. Grundy. Akad. O. Properties of Cu. 25(5-6). Electrical conductivity and performance of doped LaCrO3 perovskite oxides for solid oxide fuel cells. A. Jiang. Bulia. pp. 266271. 9. 1901-07. Yttrium and lanthanum solubility in chromium. 167-71 (in Ukrainian). L.-R. Shul. N. Meng. pp. Thermochemistry of binary alloys of lanthanum with 3d-transition metals. 7. A. 153-90. 1986. F. Lee. L. Russian J. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. S. 2006. Kim. M. Yang.-Y. 1986. 12.M. Wu.. pp. 45(5-6).-G. J. D. Liu. D. Sundman. Chem.V. A. Kireev. Crystal structures of metals and alloys. 16. 5.P. S. Pu. L. pp. X. B.V. Terekhova. Gauckler. Dinsdale. J. Powder Metall Met. S. Kobal. Lim. G. 335-350. 176. 82-89.. 14. Phase Equilib. Liu. 155-62. V. J. Power Sources. Risø National Laboratory. N. 1991. Aldinger. pp. B. Barabash and Y.V. pp.T. 2008. R. J.P. A. B.I. 264 (in Russian). 6. Kiev. Savitskii. 723-27. Berezutskii. Jansson. Song. 15. 353-362.. 13. 10. 2006. Durygin. High-temperature corrosion of dilute chromium-lanthanum alloys.M. 362-63. Mikadze. Liu. ultrasonic spray pyrolysis and glycine nitrate processes for SOFC. Zinkevich.F. J.P. Wang. Diff. 451-56. Y. The Thermo-Calc databank system. Povoden. 8.F. 1960.). SGTE data for pure elements. Keshelava.J. Linderoth. 11. Ivancenko. pp. Naukova Dumka. 2006. Saxena. J. F. 17. S. Liu.M.-O. pp. pp. 9(2). Ceram. S. J.Thermodynamic assessments Materials Science: Solid State Electrochemistry. T. Andersson. Li.N. Phase diagram for alloys in the chromium-lanthanum system. Calphad.P.N. Power Sources. 15(4).I. Svechnikov.-H. Calphad. (Eds. Kholopov. V. G.I. pp. and D.-H. Electroceram. 5(3). Nauk.-H. Ivanov. Dong. 129 . M. Dopov. V. 2005. Ong. J. 67. E. Roskilde. 317-425. High sintering ability and electrical conductivity of Zn doped La(Ca)CrO3 based interconnect ceramics for SOFCs. Inorg. M. Usenko. V. Diwu. Z.N. Denmark. 177. G.-K. Ni.
8. Bauer. Y. 13. Lopato. Temp.P. 25. pp. Appl. L. pp. Allg.A. Khim. Hautes. Cienc. Berjoan. Ceram. Epstein. Gauckler. Stability and thermodynamic properties of rare earth perovskites. 2004. M. Contribution to the study of interactions between oxygen and mixed lanthanum oxide and chromium oxide(III). 2(2). A. 22. A. 2. Coutures. 94-99. Anorg. Suponitskii. 1965.L. 27. Int. Sci. 1980. U. or lanthanum chromite. 3. A. Cassedanne. 2005. Refract. 260. Gr. O.L.. Karapetyants. pp. Examination of freezing points of rare earth oxides and chromites. Acad. 1969. Thermal properties and thermochemistry of lanthanide chromates. Hautes. Measurement of the freezing points of refractory oxides. 313-24 (in German). Coutures.S. Energy Comm. 24. M. 1963. Sc.B. Foёx. pp. Zh. A. pp. Thermochemical properties of lanthanum chromates(VI). Acad. 130 . Z. J. 1225-33. Hallstedt. Tresvjatskiy. pp. Tsyrenova. 26. 337. V. Phase Equilib. S. An. 309-26 (in French). S. 1968. 13. R. pp. Measurement of the solidification points of several refractory oxides. 61-67.A. 294-99. 28. Chem. Rouanet. Hautes. 30. Phase correlation in the systems formed by oxides of rare earths and by oxide of chromium.M. 45-50. Berjoan. Badie. pp. Dickerson. Int. 40(1). R. Comments on the allotropic transformations of the rare earth sesquioxides.G.R. 5. At. 105-13. 19.K. 45(2). M. Suvorov.M. J.B. Int... BMI-1376. 9(1). Paris. 1965.Thermodynamic assessments 17.. 2001. Meadowcroft. Foёx. pp. Temp. M. Rev.. J. 22(2). M. 1966. 1968. Energy. Rev. D.F.V. 1974. Comparison of thermal properties of oxygen-containing compounds of rare-earth elements.. pp. R. Suponitskii. 18.. L. Brit. C. Yu. Chemical equilibria involving lanthanum chromite. Phys. Shevchik. Fiz.G. pp. 33136. 57-60 (in French). Int. High Temp. Foёx. J. Grundy. Rev. Russ.. Pavlivov. 6389-92 (in French). Chem.J. R. pp. 54(2). Foёx. S. 20. Sol. B.-P. S. Thermodynamic assessment of the lanthanumoxygen system.. 21. Ed. Flamand.. 29. 1976.. 119-35 (in French). 2705-07. Bras.. Solubility limits of yttrium and the lanthanide rare-earth elements in chromium and chromium-iron alloys. J. Temp. 48(11). pp. Some properties of strontium-doped lanthanum chromite.N. 23. scandium and yttrium. Shevchenco. J. 1959. A.. Ind. Examination of the equilibrium diagram La2O3-Cr2O3. B.N.
Y. Izv. Reznitskii. Izv. 1991. 2000. Kishi. J. Sc. J. Ni)O3 Perovskite System. Miner. Ruiz.. A. at Temperatures from 298. 1976. Crystal Chemistry and Thermal Behavior in the La(Cr. pp. 524-29. pp. T. High Temp. Kamiyama. Anthony. Tsuda. Phase Transitions in Solid Solutions Based on Lanthanum Chromite. Mirza.Thermodynamic assessments 31. N. Shimojyo. 39. A. A. pp. pp. A. K. 1993. 132. 27(5). Tagawa. Lopato. and Entropy of Lanthanum Chromite between 298 and 900 °K. Nauk SSSR.P. Hashimoto. Tanaka. 42. H. 1973. High-Temperature X-ray Diffractometric Studies of LaCrO3. Rev.. N. Phys. 322(1-2). 140(10). Anorg.G.R. 1963. Yu. 183-90. 1271-74 (in French). Y. 35.F. S. Tresvyatskii. Sci. S. Pavlikov. Electrochem. Lett. M. Raccah. Sakai K. Mater. Allg. 5-8 (in French)..P. 1970. J. Neorg. N. Nauk SSSR. 679-82 (in Russian). Soc. Kamiyama. Lyutsko. 1995. 33. K. 1-14 (in German). N. 32. 1246-48. Chem. D. 131 . Momin. B.. P. S. C. E. Neorg.. Tolochko. V. H. LaCrO4. Analysis of Crystal Structure and Phase Transition of LaCrO3 by Various Diffraction Measurements. Sakai. Acad. 23(9).G. 154. 38. Chem. Terao. 36. 1966. T. A. On the Semiconducting Properties of Lanthanum Chromite.B. pp. 1985. Stølen. 309-16 (in French). Paris B. 2(4). Foëx. I lanthanum chromate(V). Mater. 41. pp. Akad.-M. 37. pp. Zonov. S. T. Specific Heat. 43.E. 2889-94. Kock. pp.M. J. M. 1967. J. W. Z.P. pp. R. K. C.R. Korobeinikova. Höfer. Rev. 40. 10.S. Solid State Ionics. Takagi.. Acad. Morii. 2000. J.C.N.A. K. On the chromates(V) of the rare earths.M. Geller. LaCrO3 at Room Temperature. H. Chim. I. J. Berjoan.V.. pp. Tsuzuki. L. 1520-24 (in Russian). pp.. Some Observations on the Formation and Structure of Lanthanum Chromite. Heat Capacity and Thermodynamic Properties of Lanthanum(III) Chromate(III): LaCrO3. Sc. pp. 34. Solid State Chem. Dokiya. 14(4). 1973. Yoshida. V. Phase Transformations of Certain Chromites of the Rare Earth Elements. Structural study and thermal decomposition of lanthanum based chromate. 264. 805-06. Kononyuk. 10. Evaluation of the Thermal Conductivity. Oikawa. 2(4). Paris C. Mater. Hashimoto. Schwarz. 493-506. Mathews.F. Akad. 276. Enthalpy. M. Coutures.. pp. Structural Phase Transition of Orthorhombic LaCrO3 Studied by Neutron Powder Diffraction. 1167-72. Phase Transitions in Perovskitelike Compounds of the Rare Earths. Thermodyn.15 K. T. Traverse. Oikawa.
Mater.M. pp. November 1991. A. W. N. 53.. Res. pp. Mn. T. 1990. Polish J. Nakamura. K. Yuan. G. M. 20(1). 2006. V. Structural Studies of the (La. Kozlowska-Róg. R. 52. Meng.-Q. Cr. Kawada. Peck. 49. Res. Tagawa. H. Raman Spectroscopy of Low-Temperature (Pnma) and High-Temperature (R 3 c) Phases of LaCrO3. Róg. Hashimoto.-L. Weinberg.. Yokokawa. M. Heat Capacity Measurement of Lanthanum Chromite by Laser Flash Method. T. T. Sudha. Japan.M. J. 56. M. J. 55. 81.-Y. pp. S. Rev. Matsushita. 1997. 45. B. Kolev. Chen. J. 1977. 2006. 108(9). Soc. Dokiya. 54. Z. Alloys Compt. Gauckler. 463-72. Kikegawa. Mat. 3266-72. M. 5(3). Kobertz. Ceram. Experimental Results. Kojima. Thermodynamic Stability of LaCrO3 and CaZrO3 Using a Solid-State Galvanic Cell Method. 1961. Method. 23-29. 1987. Dudek. 192(4). 51. A. M. K.Thermodynamic assessments 44. H. Y.. Miller. 50. H. Co. Y.J. pp. Thermodynamic Stability of LaCrO3 by a CaF2Based E. Abrashev. 14. pp. F. 19-24 (in Chinese). 191-200. G. Rare Metals. D. Y. Cox. X. 649-59. Sun. M. 46. Heat Capacities of LnCrO3 (Ln=Rare Earth). D. Kyoto. A. Bull.P. Ni) in Reducing Atmosphere I. 445-46. J. Res. Cmaidalka. Phys. 1998. 25(5).. Koseki. 74. 2007. Yoshida. 176-82. 1979. Stability of the Perovskite Phase LaBO3 (B=V. N. Satoh. Huang. pp. I.G. 562-66. Y. Larssen. Mater. 214301-1214301-7. Wang. 259. G.P. W. Abstracts of the 27th Symposium on Thermal Analysis and Calorimetry. Sakai.Sr)CrO3 System. Xing. pp.. Pressure-Induced Structural Phase Transition of LaCrO3. Hadjiev. P. N. N. Chen. Less-Common Met. Chem. S. Takahashi. 47. 691-94. Takagi. 7677 (in Japanese). M.. A. T. Bull. Cheng. Thermodynamic Properties of LaCrO3. Petzow. 2005.E. H. Nickel. L. Sreedharan. Hilpert. M. Z. pp. J. and Ni). Fe. 79(12). Zhongguo Xitu Xuebao. Li. Chung. Kamegashira. X. pp. Murakami. R. 48. Azad. 12.N.Y. 132 . 166(1). Am. Navrotsky. Khattack and D. 57-62. Electron Paramagnetic Resonance and Antiferromagnetism in LaCrO3. C.F. Zhou. pp. Determination of the Standard Free Energy of Formation of LaCrO3 at 1273 K. O.. Nature. Hao. Li. Solid State Commun. Dokiya.. N. pp. pp. Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties. Iliev. J. Co. Enthalpies of Formation of LaMO3 Perovskites (M=Cr.-H. Litvinchuk. 1996. Fe.V. pp. H.
The Compound Energy Formalism. 2003.. E. Calphad. Chen. 1. Shvaiko-Shvaikovskii. 36. Chem.. Miodownik. Alloy. B. Determination of Chemical and Magnetic Interchange Energies in BCC Alloys. Hillert. Goto. 64. Application of the Compound-Energy Model to Oxide Systems. 1989. 30. 1998. Calphad. 1595-1609. 2(3). Inden. Nauk SSSR. Phase Equilib. L.F. Ordered Defects & Nonstoichiometry in Metal Oxides of Perovskite & Related Structures. Indian J. Metallkd. accepted 63. M. T. Chen. p 161-76. pp. 66. Hillert. 61. 164. 320. T..V. p 227-38. V. Advances in Catalysis. N.J. Electrical Transport in Light Rare-Earth Orthochromites. 32. Hillert.. Sundman.N. J. G. 1441-45 (in Russian). 70. 1988. Z. B.S. 68. pp.P.. Thermodynamic Assessment of the La-Fe-O System.L. Gauckler. Electrical Transport in Rare Earth OrthoChromites.. T. -Manganites and -Ferrites. 66(10). Povoden. Andersson. 1971. 133 . 79(2). V.J. A CompoundEnergy Model of Ordering in a Phase with Sites of Different Coordination Numbers. Lal. E.G.. B. 59. Calculation of Defect Chemistry Using the CALPHAD Approach. Phase Equilib. 71. Gauckler. J. M. A. pp. Rao. Rao. 1984. Rao.. B. Diff. Solid State Ionics. Neorg.-O. Akashi. pp. G. pp. 577-82. 23A. Hillert. Wanklyn. T.G. M. Grundy. 437-45. 265-84.K. Calphad Calculation of Phase Diagrams. Fierro.N. 65. Gauckler. 345-58.B.J.N. Ivas. Thermodynamic Assessment of the Co-O System.G. Influence of the Synthesis Conditions on the Electrical Properties of LaCrO3. pp.R. A. M. J. 1979. A. L. 81-87. Hallstedt.Thermodynamic assessments 57. J. pp. B. 1986. M. Ivas. Metallkd. 67. Sci. H. 2006. Izv. Mater. Povoden-Karadeniz. 1978. Acta Metall. 2001. I. 58. J. A. Z. Grundy. L. V.M. Gordon. Superstructures. Elsevier Science Ltd..P. Mater. A Model of Alloying Effects in Ferromagnetic Metals. A. M. 69. 94-96. 1982. pp. Maruyama. Vol. C. J. 17.E. 60.. Solids. 62. C. Cmpd. Jarl. Saunders. Transport of Lanthanum Ion and Hole in LaCrO3 Determined by Electrical Conductivity Measurements. Vidyasagar. 2003. 243-. Popov. pp.N. Akad. Chem.R. 15(8). Phys. Jansson. 177-83. General Treatment. Structure and Reactivity of Perovskite-Type Oxides. 24(3). Jansson. T. Tripathi. pp. B. 1975. pp. M. 34. Guillermet. Pergamon Materials Series. L. J. K. 212-27. Tejuca. J. pp. 33-41. Sundman. Gopalakrishnan.
Appl. 1990. 73. B. 1985. 1991. 109-19. Chen. Hillert. K. Gibbs energy functions of SrCrO4. A. A Two-Sublattice Model of Molten Solutions with Different Tendency of Ionization. Sr2. 15. B.4.1 Introduction Sr-doped lanthanum manganite (LSM) with the perovskite structure ABO3-δ is used as cathode materials in SOFC. 74. 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. submitted to Scripta Mater. R. Chen.67Cr2O8. Trans.N. 261-66. 4. Akila. M. 4.2].J. Electrochem. M. For the construction of the 134 .T. The Mobility of Oxygen Ions in CaF2. J. Povoden. and SrCr2O4 are presented. Grundy. Experimental solid solubilities and nonstoichiometries in La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ are reproduced by the model. as well as defect concentrations of the cathode contaminated by Cr at different temperatures and oxygen partial pressures. 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. Jansson. Sundman. 20. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. L.Thermodynamic assessments 72. Grundy. B. thermodynamic driving forces and activities. 294-300. and L. Jacob. E. 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. A. A. Povoden. J. Metall. pp. Ågren.N. pp. Calphad. pp.. 16A. Modification of the Two-sublattice Model for Liquids. Sundman. Sr2CrO4. The database should meet the demand to calculate stable and metastable phase equilibria.4 Thermodynamic La-Sr-Mn-Cr-O oxide database for SOFC applications E. M. These requirements are conformed by using the CALPHAD approach.J. Gauckler. 75.
Phase equilibria in the La-Sr-Cr-O oxide system in air at 1223 K and under vacuum at 1873 K were determined by using solid state technique. Due to large differences between the ionic radii of La3+ and Mn3+ and possible coordination numbers (1.785 Å for at maximum 6-fold coordinated Mn3+) we omit Mn3+ on the A-site.67Cr2O8 by using microprobe analysis. and La-Cr-O databases are adopted[3-5]. On the other hand the conflicting phase equilibria presented by Kisil lack experimental details. Cr-O. Calculation of the oxygen nonstoichiometry of perovskite + MnO instead of metastable single phase perovskite leads to a good agreement between experimental and calculated nonstoichiometries. and the LaSr-Mn-O oxide database is taken from Grundy et al.5 Å for 12-fold coordinated La3+. The stoichiometry of a phase defined as Sr3Cr2O8 was later corrected to be essentially Sr2.Thermodynamic assessments La-Sr-Mn-Cr-O oxide database La-Mn-Cr-O oxide and La-Sr-Cr-O oxide systems are assessed. allowed Mn3+ on the A-site of LSM to reproduce experimental oxygen nonstoichiometries under low oxygen partial pressures. 0. 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-Cr-O oxide: Thermodynamic functions for Sr-Cr-oxides in the SSUB database are based on estimates. No quaternary phases or solid solutions were found in the Sr-Mn-Cr-O oxide system. whereas emf measurements using CaF2-based emftechnique led to conflicting results likely caused by competing reactions.15-19]: for the stabilities of SrCr2O4 and Sr2CrO4 we trust the accurate study of Jacob. Limited solution of Sr in La1-xSrxCrO3-δ perovskite was confirmed by a later investigation. which is in agreement with Negas and Roth. The 135 .2 Assessment of data from the literature Previous assessments of the La-O. with a slight modification: Grundy et al. 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. Differences concern the reported stabilities of further compounds[11. Sr-Mn-Cr-O oxide is treated as ideal extension from the subsystems.4.12. 4. Sr3Cr2O7 was approved as high pressure phase only.12]. in agreement with Hartl and Braungart.
Peck et al. Positive δ in the perovskite formula reflects oxygen deficiency.3 at T = 1173 K that Cr4+ were absent in the latter.2.3. Sr(La. 0.3 using Knudsen mass spectrometry. 0.25. and 0. Cr4+ and oxygen vacancies are regarded as the major defects[23.1. concluded from the similarity between X-ray absorbtion spectra of Cr K of LaCrO3 and La1-xSrxMn0. 136 . 1373 K. −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.Sr)CrO4 showed reproducible stoichiometry.8Sr0. and the solubility of Cr is unknown. whereas negative δ essentially stands for cation nonstoichiometriy.Sr)CrO4 is ambiguous. thermodynamic data are missing. In contrast to Peck et al.2MnO3 and Cr2O3 at 1073 K was reported after 1000 h of heat treatment in air. The exact temperature and oxygen partial pressure range of Sr(La.24].5O3-δ with x = 0.Thermodynamic assessments existence of several Ruddlesden-Popper phases is restricted to reducing conditions. Thus its extension to the quinary database would not be reliable.Sr)CrO4 were stable in air. Complete solid solution between the LaMnO3 and the LaCrO3 perovskites was affirmed. and δ = 0. it was proposed earlier that Sr(La. and 1573 K. As Ruddlesden-Popper phases have not been reported to form during SOFC operation with LSM cathodes.2.Sr)CrO4 is omitted in the modeling. and 0.2. and La0. and 0.09. 1473K.5Cr0.1O3-δ was measured using thermogravimetry.2CrO3-δ at 1273 K were measured as a function of oxygen partial pressure using thermogravimetry. Myoshi et al.3 at T = 1273K.1. and 0. and 0. Nonstoichiometry data for La1-xSrxCrO3-δ with x=0. Perovskite+MnCr2O4 spinel equilibrium of a powdered mixture of La0.1. solely Sr(La. Plint et al. Cheng and Navrotsky measured enthalpies of formation of La1-xSrxCrO3-δ with x = 0. La-Mn-Cr-O oxide: In the La-Mn-Cr-O oxide system no quaternary stoichiometric compounds were reported.9Cr0. 0.3 as a function of temperature and oxygen partial pressure using XRD analysis. −0.04. investigated the single phase region of La1-xSrxCrO3 with x = 0. 0.8Sr0. determined the Gibbs energy of formation of La1-xSrxCrO3 with x = 0.1. and −0. La-Sr-Mn-Cr-O oxide: In the La-Sr-Mn-Cr-O oxide system complete solid solubility of Mn and Cr is reported for La1-xSrxMn1-yCryO3-δ perovskite. 0. δ of LaMn0.2.11 using drop calorimetry at T = 1080 K.2.
H a is the standard enthalpy of the stable state of element a at 298. 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. Sr2. A and B are adjustable parameters.36−40].4. and La1-xSrxMn1-yCryO3-δ [8. Thus. most likely due to interactions that cannot be reproduced by the model. LaMn1-xCrxO3-δ [26. Transitions of LaMn1-xCrxO3-δ are complex as they depend on temperature. All 137 .15 K and 105 Pa. whereas diversities exist regarding the transitions in La1-xSrxMn1-yCryO3-δ .67Cr2O8+SrCrO4+Cr2O3 as a function of temperature and oxygen partial pressure[11.12]. 7/6.1) SER v = 0.41] were reported.12] and phase stabilities of SrCr2O4 and Sr2CrO4 investigated by equilibration experiments of different mixed oxide compositions under controlled atmospheres.67Cr2O8 following the proposed formula and for the Ruddlesden-Popper phase Sr2CrO4.75. However we did not obtain satisfying results in higher-order perovskites. 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[11.43] for LaCrO3. Magnetic transitions have been well reproduced by an ordering-model[42. and Sr2CrO4 respectively. Consistency among transition data for La1-xSrxCrO3-δ and LaMn1-xCrxO3-δ prevails. their modeling was omitted without consequences for the applicability of the database for SOFC. 4. (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. 0.and perovskite layers of the latter.67Cr2O8.3 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 SrCr2O4.4.Thermodynamic assessments The perovskite phase: Magnetic and structural transitions of La1-xSrxCrO3-δ [29−35]. SrCr2O4. accounting for the structural feature of alternating rocksalt.25 for SrCrO4. in terms of the applicability of the new database for SOFC the authors omit structural transitions in the modeling. and 0. As the magnetic transitions are low temperature features. composition and oxygen partial pressure. and the equilibrium Sr2.
Δ ° H = −55. Δ ° H = −20.0 kJmol-1 this work. T = 2000 K. Table 4. Δ °G = −93.= GS3V + 1 6GS4O − 1 6GS4V GSr 2+ :Cr 3+ :Va = GS3V − 5 6GS4O + 5 6GS4V Table 4.3 kJmol-1 this work. Δ °G = −93. ° Δ ° H = −36.67 Cr2 O8 + SrCrO 4 + Cr2 O3 Δμ O 2 = −265. T = 298 K.1. calc.6 kJmol-1 this work.1080 − 1380 K (1 − x) 2 La 2 O3 + xSrO + 1 2 Cr2 O3 + x 4 O 2 − δ 2 O2 = La1− xSrx CrO3−δ x = 0. Δ °G = −102.2 + 0. δ = 0.2.67Cr2O8 = −508507 J.4 kJmol-1 this work.88 kJmol-1 x = 0.6 J ASr2CrO4 = −145000 J.3.4. T = 298 K. Δ °G = −85. BSrCr2O4 = −95. calc.106904T kJmol-1 .5 kJmol-1 x = 0.1 Optimized model parameters Sr .3.2.1 kJmol-1 this work.950 − 1280 K Sr2.54 kJmol-1 x = 0.4.7 kJmol-1 x = 0.11. calc. Δ ° H = −34.1073 − 1473 K Δμ O 2 = −276. calc. BSr2. δ = 0. T = 298 K. T = 298 K.04.15553T kJmol-1 . δ = 0. calc.Thermodynamic assessments reported phase equilibria are correctly reproduced by the model.340 + 0.4. δ = 0.8 kJmol-1 this work.5 °GO2  ° ° ° GLa3+ :Cr 4+ :O2. δ = 0.825 ± 0.15832T kJmol-1 this work.851 − 1116 K Δ °G = −273.2 Calculated and experimental thermodynamic data SrO +1 2 Cr2 O3 + 3 4 O 2 = SrCrO 4 Δ °G = −273. Δ ° H = −59.7 kJmol-1 x = 0. T = 2000 K. T = 2000 K. calc. Δ ° H = −20.767 + 0.67Cr2O8 = 219 J La1 − xSrxCrO3 − δ ° gas GLa3+ :Cr 4+ :Va = 5 6GS4O − GS3V + 1 6GS4V + GRPRV − 1. Δ H = −65.5 J ASr2. calc. δ = 0. calc. ° Δ ° H = −67. T = 298 K.3 kJmol-1 this work. T = 298 K. Δ ° H = −34.76 kJmol -1 x = 0. Δ °G = −88. Δ ° H = −50.1. calc.4.859 + 0. calc.09.48 kJmol -1 138 .4 kJmol-1 this work. δ = 0.2 kJmol-1 this work.2. BSrCrO4 = 131.= 5 6GS4O − GS3V + 1 6GS4V + GRPRV GSr 2+ :Cr 3+ :O2. Δ ° H = −56. Δ H = −48.1 and 4. Δ °G = −109. Δ °G = −213.13152T kJmol-1 this work.2. Optimized parameters and calculated and experimental thermodynamic data are listed in Table 4. calc.Cr oxides ASrCrO4 = −273771 J. δ = 0.72 kJmol-1 x = 0.15 kJmol-1 x = 0.3.050 + 0.166T kJmol-1 . BSr2CrO4 = 50 J ASrCr2O4 = 98000 J.1. δ = 0. Δμ O 2 = −262.13157T kJmol-1 .774 + 0.
Va)(Cr3+. R = 8. and (Va)(Va)(Va)3 and ternary interaction parameters are adopted[5.48].Va)(O-2.g. 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 (4.4. We adopt the description (A.2) where yi is the site fraction of each cation and Va on the A-sublattice.Va)(B.Va)(O2-. The molar Gibbs energy °G of La1-xSrxCrO3-δ is uniquely defined as follows: °Gs of the endmembers (La3+)(Cr3+)(O2-)3.and Va on the anion sublattice. The second-last term accounts for the configurational entropy of mixing. Using the above model and the proposed defect chemistry[22-24] the sublattice formula for La1-xSrxCrO3-δ reads (La3+. and yk is the site fraction of O2. (La3+)(Va)(Va)3. e. yj is the site fraction of each cation and Va on the B-sublattice.Cr4+.Thermodynamic assessments The perovskite phase: It is essential for a consistent description of the perovskite phase that defects that occur in the structure in low-order systems remain on the same sites at the extension to higher order. The last term describes the excess Gibbs energy of mixing.Va)3 with A.Va)3. Typical compositions of Sr-doped lanthanum manganites used for SOFC cathodes. (La3+)(Cr3+)(Va)3.8Sr0.4. It can be accounted for by introducing interaction parameters. °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. and A and B parameters of °G of two neutral compounds 139 . The parameters of the compound energy formalism are the Gibbs energies of the end-member compounds °Gi: j:k .Sr2+. B = cations and Va = vacancies using the compound energy formalism.31451 J mol-1 K-1.2MnO3-δ are rhombohedral at SOFC operating temperatures (T=1073 K to 1273 K). Thus it is reliable to take the Gibbs energies of the compounds of rhombohedral perovskite from  for the model. (Va)(Va)(O2-)3. (La3+)(Va)(O2-)3. La0. this is achieved by using the same model. and small amounts of Cr brought into the cathode unlikely lead to a change of the structure. (Sr2+)(Va)(Va)3. (Sr2+)(Va)(O2-)3.3) is chosen as reference.6.
Mn3+:O2-) accounting for interactions between Cr and Mn cations is fitted to experimental nonstoichiometries.24] of La1-xSrxCrO3-δ. 4. 4. °Gs of the remaining endmembers (La )(Cr )(Va)3.Mn . and nonstoichiometries[23.5 − H Sr − H Cr − 2.4 Results and discussion The reproduction of experimentally determined Gibbs energies and enthalpies of formation. Thus for LaMn1-xCrxO3-δ we propose the sublattice formula (La3+.4.Va)3. it is expected that it is not removed from the structure if the phase is doped.5Va0. 138). and in Figs. it is reliable to allow Cr4+ on the B-site: as Cr4+ exists in nonstoichiometric lanthanum chromite perovskite.6.Cr .4. The 3+ 2+ sublattice 2+ 3+ formula 4+ 3+ of 4+ the 2- quinary perovskite reads (La .4.Va)(O2-.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. 0L(La3+:Cr3+. All endmember compounds have been defined in the assessed subsystems.5 in Eq.4) ° SER SER SER GSrCrO2.20].Mn4+. Though structure-chemical information of site occupancies in LaMn1-xCrxO3-δ perovskite is missing.Thermodynamic assessments ° SER SER SER GSrCrO3 − H Sr − H Cr − 3H O = °GSr2+ :Cr 4+ :O2− = GS4O = °GSrO + 1° 1 gas  G + °GO2  + A + BT 2 Cr2O3 4 (4.Mn3+.Mn .Va)(O . solid solubilities[18. and (Sr2+)(Cr3+)(Va)3 are obtained by conversions of reciprocal equations that are set zero and are listed in Table 4. (Sr2+)(Cr3+)(O2-)3. 138).2 for ° GSrCrO2.4.Cr4+. A = 136453 and B = −91. The regular interaction parameter 0L(La3+:Cr3+.1 (p. All endmembers have been defined in the assessed subsystems.4. 4.Sr . 140 .Cr3+. Eq.4. with A = 27027 and B = −69.Mn3+:O2-) = +9421 J.4.2 (p.4. 4.5Va0.4 denotes °G (Sr2+)(Cr4+)(O2-)3.5.2 (next page).Va)(Mn .4.5) are optimized with all available experimental data of the perovskite phase. and phase equilibria in the La-Sr-Cr-O oxide system by the modeling is satisfying as shown in Table 4.Cr .1 and 4. 3+ 4+ (La3+)(Cr4+)(O2-)3.Va)(Mn2+.Va)3.
two phase. Filled circles. and circles with crosses denote single phase.Thermodynamic assessments Fig.5 system calculated at T = 1223 K in air atmosphere (solid lines) with experimental data included (symbols). and three phase equilibria. 4. 141 . blank circles.4. prv = La1-xSrxCrO3-δ. Calculated phase equilibria are the same as in.5-SrO-CrO1.1 LaO1.
2. 4.3 as a function of oxygen partial pressure. The calculated isothermal section of the La-Mn-Cr-O oxide system at T = 1273 K in air is presented in Fig.2. β-spl = cubic Cr-Mn-spinel. and 0.4. The calculated nonstoichiometries of La1-xSrxCrO3-δ are in good agreement with the experimental values at higher temperatures. 4. p. 142 .1.5-MnOx-CrO1.3 LaO1.4 (next page).4. 141 Calculated (lines) and experimental (symbols)[22.4. 0. 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.Thermodynamic assessments Fig.23] nonstoichiometries of La1-xSrxCrO3-δ at different temperatures for x = 0. Fig. prv = LaMn1-xCrxO3-δ.25.5 system calculated at T = 1273 K in air atmosphere.3. 0.4. α-spl = tetragonally distorted Cr-Mn-spinel. as shown in Fig. 4. However it was not possible to reproduce the nonstoichiometries at T = 1073 K and 973 K. possibly caused by equilibration difficulties due to slow diffusion. 4.
and the conclusion of missing Cr4+ is not based on a direct chemical analysis of Cr valencies. it would be necessary to give large positive values to the regular interaction parameters 0 0 L(Sr2+:Cr3+. and oxygen partial pressure.Thermodynamic assessments Fig. temperature. The new database is adapted for quantitative calculations of 143 .Sr2+. Experimental findings[8.Cr3+. Thus we stick to a model without interaction parameters. this model allows the quantitative calculation of defects as a function of composition.9Cr0.Va)(Mn2+. 4.Va)(O2-.28] are in line with our calculations. To approximate the absence of Cr4+ in quinary perovskite.5 Conclusions The thermodynamic La-Sr-Mn-Cr-O oxide database has been obtained by combining thermodynamic assessments of oxide subsystems.1O3-δ at different temperatures as a function of oxygen partial pressure.4.Mn3+. We believe that complete removal of Cr4+ from the perovskite structure is unlikely.Mn4+. Optimized by experiments in pseudoternary and pseudoquaternary oxide subsystems. 4. Experimentally determined nonstoichiometry of LaCrO3 indicates the existence of some Cr4+. We propose the model (La3+.Mn3+:O2-).4.Mn3+:O2-) and L(Sr2+:Cr4+.Cr4+.4 Calculated (lines) and experimental (symbols) nonstoichiometries of LaMn0.Va)3 for the quinary perovskite phase.
7. P. J. Hack (ed. 5. B.T. 147. 99. 353-62. Jacob. Prewitt. H. Deposition of chromium species at Sr-doped LaMnO3 electrodes in solid oxide fuel cells I.P. Grundy. Foger. Mechanism and kinetics. Diff. 4013-4022. A. The SGTE casebook: thermodynamics at work. 771-774. pp. 4.. Foger. S. J. Chemical thermodynamic considerations in sintering of LaCrO3-based perovskites. Liu. B- Stru. La1-xMn1-yO3-z perovskites modelled with and without antisite defects using the Calphad approach.J.-K. Inorg. J. K. pp.P. Shannon.N. A. accepted 6. 2000.. J. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. pp. Zhang. Phys. 2000. S. Durygin. Demina. Geupel. 2006. Solids. 138. pp. Z. R. K. Saxena. Grundy. Thermodynamic assessment of the La-Cr-O system. London. 1969.J. Aldinger. Filonova. L.. 67. A. J. Russ. S.N. pp. 1996. Electrochem.N. 2007. 21. K. Jiang. Gauckler. M. Hallstedt. 1991. Chem. A. 9. 925-. N.P. J. Electrochem Soc.. Yokokawa. Diff. J. Ramprakash and J. S. E. B25.D. Effective ionic radii in oxides and fluorides. Solid State Ionics.N. E. Yang. Sakai. Phase Equilib.J. and L. Zinkevich. Phase diagram and thermodynamics of the La2O3-Ga2O3 system revisited. Abraham. T. M. L. K. Chen. 1997. Soc.K.Thermodynamic assessments phase equilibria and defect chemistry in a Sr-doped lanthanum manganite SOFC cathode poisoned by chromium. 2004. C.. Solid State Ionics. J. 52. Phase relations in the system Sr-Cr-O and thermodynamic properties of SrCrO4 and Sr3Cr2O8. Dokiya. pp.). Gauckler. 1721. R. 297-310. A. Zhang. 10.A. Grundy. 1018-27. Ivas. 27(4). Povoden. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells. P. Petrov. 173. Deller.. F. Phase Equilib.N. T. A. Y. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Acta Crystall. M. Phase Equilib. 46-53. pp.. K. Badwal. Institute of Materials. 2. pp.T. 144 . Kawada. M. 11. 1901-07. Chem. Povoden. 2006. pp. Gauckler. 3. E. 8. References 1. S.
Nonstoichiometry of the perovskitetype oxide La1-xSrxCrO3-δ. pp. Kaimai. Kisil. Electrochem.K.M. Hilpert.67Va0. 18.. K. 1490-91. Standard Gibbs energies of formation of SrCrO4 and Sr3Cr2O8. Sr2. Inorg. System SrO-chromium oxide in air and oxygen. Solid State Chem. 1158-61. Peck. pp. 2003.. pp. Ch. Fueki. A. H.. Mizusaki. Defect formation and mechanical stability of perovskites based on LaCrO3 for solid oxide fuel cells (SOFC).G. J. 23. Thermochim. 4112-. Mizusaki. Akashi. B. Miller. Wessel. Z. O..M. J. B. 33. Energetics of La1-xAxCrO3-δ perovskites (A = Ca or Sr). D. Steinbrech. M. pp. 119-24. Yamauchi. S. pp..-H. A. Nickel. Slobodin. 9. J. T. Sreedharan. Kawada. 20. Yashiro. M. Meschke. J. Strontiumchromate(V. pp. 234-44. 143. 24. R. F. S. O. Negas. K. Braungart. T. Roth. Inoue. Solid State Ionics.W. pp. Cheng. 2007. Sudha. pp. 145 . Vaporization and thermodynamics of La1-xSrxCrO3-δ investigated by Knudsen effusion mass spectrometry. A. 21. E. 1969.V.H. Miller. Jim. T. 294-300. R. K. D. Boroomand. 17. 22. R. S. H. 178. Solid State Sci. 1984. 952-953 (in German). K. T. Revisiting the Sr-Cr(IV)-O system at high pressure and temperature with special reference to Sr3Cr2O7. Solid State Ionics. A. 16. pp. K. 23. J. 177. 1989. a hightemperature compound with defect-bariumphosphate-structure. Y. pp. 1990. The standard Gibbs energies of formation of ACrO4 (A=Ca. F. Solid State Ionics. Ceram.67. T. Onuma. Acta.33(CrO4)0. Mater. 1992. Alario-Franco. Ishikawa. 1978. Mater. The mobility of oxygen ions in CaF2. pp.33(CrO4)1. 564-73. 129-36. Navrotsky. Europ. 20. 59-65. Azad. M. 2004. J... Phase formation in the system SrO-CrO3-Cr2O3. Pt. R. VI). pp. 15. pp.T. Zuev.. Appl. Peck. Res. Sharova. 2005. Myoshi. Solid State Chem. Teller. R. 401-12. Jacob. 25. H. A. 123. 1998.S. 19. Hilpert. Maruyama.A. E. L. Yokokawa. Castillo-Martínez. 73A. Soc. Sr or Ba) from emf-measurements. Matsumoto. 39. T. 2001. K. 1999. 431-42. NBS A Phys. Singheiser. 12. J. Akila and K. N. 300920. 194. Phase diagram studies in the SrO-Cr2O3-La2O3 system in air and under low oxygen pressure. Hilpert.Thermodynamic assessments 12. J. 13. Naturforsch. 14. Hartl.
Morii. Hashimoto. 1998. J. V. H. Hinatsu. Matsunaga. Magnetic and neutron diffraction study on perovskites La1-xSrxCrO3. T.G. Oikawa. T. 2003. Francesconi. T. pp. 2006. Nakamura. 463-71. T. 12.95Sr0. 141.K. Sakai.75Sr0. Bari. J. Mat. Res. pp. 222-29. Hashimoto. Hinatsu. Kishimoto. C. Y. Y.R. Matsubara. 35. K.. F. R. Matter. pp. 2006. pp. xSrxCrO3 Analysis of magnetic and structural phase transition behaviors of La1- for preparation of phase diagram. J.25CrO3 at high temperatures. Horita. C.Sr)CrO3 system. 170. Power Sources. Muirhead.5Mn0. Tyagi.: Condens. Tao. M. 2000. Takahashi. Morales.9Cr0. Thermochim. Nakamura. K. 2008. Long. M. Y. 177. Hashimoto. Magnetization and resistivity in chromium doped manganites. 0. Structural study of La0. Solid State Ionics. Matsunaga. T.15). Yusuf. 1999. 18. pp. Irvine.E. Ramanadham.85Sr0. Nakamura. J.: Condens. Chiba.M.S. Electronic transport in the novel SOFC anode material La1-xSrxCr0. Analysis of relationship between magnetic property and crystal structure of La1-xSrxCrO3 (x=0. 1977. 2008. 176. H. C. Solid State Comm. 502-06. 11. Inami. 404-10. Caneiro.1O3+δ (3. Shimojo. 2005.. Solid State Chem. 8661-72. Takahashi. M. T. Ohba. Kawaji. Y. Acta.R. 2006. Solid State Ionics. J. Xiong. P. Matsunaga. 34. N.. Cabeza.. 177. A. Thermodynamic considerations on Cr poisoning in SOFC cathodes. Sato.P. Chakraborty.M. 2008. 12.: Condens. 146 . 132-. H. Cox. Thermochim. 474. 26. Tezuka. pp. 31.12) compound. Solid State Chem.E. K. 32. M. J. 145. pp. K. J. Y. Phys. T. Y. Atake. 36. Y. S. Pomjakushin. Tezuka.15CrO3 by means of powder neutron diffraction. Y. P. N.05CrO3 and La0. 4151-60. pp. Morii. K.A. Matter. A. Bull.13.A. 404-10. Takahashi. Arai.-P. 33. K. H. 28. L. M. 3193-98. Khattak. Yokokawa. Structural studies of (La. Matter. Krishna. Yamaji. H.00 ≤ 3+δ ≤ 3. H. F. Phys.5O3±δ. Connor. 2005-08. Y. D. Komatsu. 27. 29. O. S.S. Shimojo. 435. 57-. 30. A. K. Evolution of crystal structure with the oxygen content in the LaMn0. Greaves. S. Y. Studies on magnetic properties of La0. Brito.M.T. Arai. H. Plint. H. 2569-78.Thermodynamic assessments 25. Acta. Phys.
Andrè. 42. 46. R. pp. Yau. Synthesis. H. M. S. Bourèe. Rundlöf. (a). B. Kallel. 45. Sundman. G. Anderson. Ghedira.3).V. Gauckler.1. Phase Equilib.2. Dinsdale. J. 15(4).. J. 437-43. J. Folgado. pp. A. 153-90. nuclear structure. Grundy. A.A. Calphad. 1997. Calphad. Sci. 2001. Mater. The thermo-calc databank system. Determination of chemical and magnetic interchange energies in bcc alloys. 320. Effect of Cr doping in La0.. M. M. 1991. Structural effects of Co and Cr substitution in LaMnO3+δ. S. Tseggai. 16. 184. pp. Tellgren. Metallkd. SGTE data for pure elements. D. Nordblad. 2005. S. Kuscer.5. and magnetic properties of LaCr1-yMnyO3 (y=0. 161-76.R. Z. pp. Assessment of the La-Mn-O system. Risold. 0. Hrovat. M. X-ray-powder diffraction structural phasetransition study of La(Cr1-xMnx)O3 (x=0 to 0. Hallstedt. 2008. Calphad. 317-425.. 66(10). 26. H. 1975. Chen. J. Dhahri. Zemni. Ceram. Hillert and M.-O. J. Jansson. 20. D. Howard. Bernik. General treatment. 39. 532-40. Mater. Alloy Compd. Inden. L. M. Gauckler. J.. 41. B. 319-25. 2(3). 457. J. 227-38. 1992. Alloy. pp. 1985.. 131-51 147 . 2001. Andersson. J. M. pp. Cmpd. B. The strontium-oxygen system. 0. 1996.-K. P. 75. Metni. Am. M. Hillert. Hallstedt. Vincent. L. 577-82. 1685-87. Soc. pp. The compound energy formalism. J. Stat. E. pp. Martinez. Oumezzine. M. 38. Jarl. Holc. Beltrán.3Mn1-xCrxO3 with 0 ≤ x ≤ 0. El-Fadli. A model of alloying effects in ferromagnetic metals. 1978. D. B. 9. H. F.N. Z. Chem.. N. E. J. F.7Sr0. 47. Dhahri. pp. Diff.Thermodynamic assessments 37. 48. Kolar.U. Beltrán. Sol. Lett. and 0. A.J. 353-61.J. 44. 143-46. 2000.25) using the Rietveld method of analysis. 10. G. I. J. 43. Calphad.T. Preliminary data on solid solubility between LaCrO3 and LaFeO3 or LaMnO3. 40. D.. Phys. Sapiña.
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. From the thermodynamic calculations structural chemical changes in the cathode perovskite caused by the interaction with chromium can be predicted: it is shown that the interaction of chromium with the LSM cathode leads to a change of the defect chemistry of the perovskite phase. This has consequences for the electrochemical properties of the cell: the electronic conductivity of the cathode will decrease. Chen. whereas Cr2O3 is metastable. T.J. and L. 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. 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. Even though the chromium problem cannot be solved satisfactorily by varying the cathode composition or the SOFC operating conditions. From the results of these calculations it is concluded that the processes of chromium poisoning of solid oxide fuel cells (SOFC) are partly explicable by thermodynamics. The spinel formation goes along with increasing Mn2+ in LSM under decreasing oxygen partial pressures. Gauckler. M. 148 . In particular the concentrations of cation and oxygen vacancies are smaller than in an LSM without chromium under decreased oxygen partial pressure at 1273 K. Proper strategies to prevent the problem of chromium “poisoning” are proposed. Povoden. the deterioration of the cell performance is expected to be less pronounced when the cell is operated at lower temperatures and current loads.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. Ivas.
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. Both groups of researchers agree that without polarization Cr is randomly deposited inside the cathode. 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. mechanical strength.Thermodynamic calculations of impacts of Cr on LSM cathodes 5. The chemical dissociation approach is coherently based on the interpretation of a large number of impedance spectra. This reduction reaction would compete with the oxygen reduction and lead to blocking of the active sites at the triple phase boundary (TPB). -reduction. associated to these nuclei. and -diffusion process. electron-donating LSM and oxygen-accepting yttrium-stabilized zirconia (YSZ) are available. 149 . where they cause the degradation of the cell by detrimentally affecting the O2adsorbtion.1 Introduction Chromium-containing metallic interconnects are commonly used in planar-design solid oxide fuel cells (SOFC) due to their high oxidation resistance. as well as low fabrication costs. and no Cr2O3(s) is formed. where the reaction partners for the reduction. Consequences of Cr poisoning have been investigated specifically in (La1-xSrx)MnO3-δ (LSM) perovskite-structured cathodes. Consequently Cr-Mn spinel and Cr2O3(s) would form. 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. 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]. 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. In the last decade a lot of efforts were made to elucidate the degradation mechanisms. Ad 1) In an LSM cathode the reduction of CrO3(g) is expected to be localized at the triple phase boundary. On the other hand the electrochemical reduction of CrO3(g) was rejected by the authors favoring the chemical dissociation approach. good electronic and negligible ionic conductivity. thermal stability. though partly with conflicting results.
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.
1 phase fractions in Cr-“poisoned” La0. B.1MnO3-δ and defect concentrations of La0.2 Phase equilibria in Cr-“poisoned” La0. 126.96.36.199MnO3-δ as a function of oxygen partial pressure at T=1273 K and 1073 K at μ(CrO3) = −300000 J mol-1 Fig. 5.9Sr0. 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. A.1(Mn. Vertical lines indicate boundaries between different phase equilibria 153 .Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.9Sr0.9Sr0. with A and B standing for the cation sublattices and C standing for the oxygen sublattice.
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.
tetragonally distorted Mn3O4 (t-sp) is expected to form.2 Thermodynamic calculations of (La0. 5.7 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 as a function of oxygen partial pressure at T = 1273 K and 1073 K and μ(CrO3) = −300000 J mol-1 157 .Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.3.8Sr0.3.3. At T = 1073 K Mn2O3 is stable in a Cr-contaminated LSM cathode with excess Mn in air.8Sr0. 5. Fig. 5.2)0.3.9MnO3-δ contaminated by chromium From Fig.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 5.2)0.7 phase fractions in Cr-“poisoned” (La0.
Thermodynamic calculations of impacts of Cr on LSM cathodes In Fig.3.8Sr0.8 Calculated site fractions of ions in cubic spinel formed during chromium “poisoning” at T = 1273 K It is interesting whether the consequences of chromium for the concentrations of defects in LSM(Cr) with excess Mn are more or less pronounced than in cation-stoichiometric LSM(Cr): Phase equilibria and defect concentrations in a (La0.8 the compositional changes of cubic spinel are plotted as a function of oxygen partial pressure at T = 1273 K.9 (next page). Fig.3.2)0. 5. 158 . In general. the compositions of the spinel phases formed during chromium “poisoning” become richer in Cr under more reducing conditions.9MnO3-δ cathode are shown in Fig. as in the case of cation-stoichiometric LSM. 5. 5.3.
9(Mn.8Sr0.Cr)O3-δ and defect concentrations in (La0. 5.3. 5.9 Phase equilibria in Cr-“poisoned” (La0. and the concentration of oxygen vacancies is lower in LSM(Cr) than in LSM at relatively high and low pO2 . In LSM(Cr) the concentrations of these cation vacancies drop strongly at low pO2 .3.Cr)O3-δ as a function of oxygen partial pressure at T = 1273 and μ(CrO3) = −300000 J mol-1. 5. 5.8Sr0. 159 .8Sr0.3.2)0. Mn2+ is higher in LSM(Cr) than in LSM at higher pO2 .3.9MnO3-δ with Cr (broken lines in Fig.2)0.9(Mn.10) and without Cr (solid lines in Fig.10) at 1273 K.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.10 (next page) is a comparison of defect concentrations of (La0. 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. The vertical line indicates the boundary between different phase equilibria Fig.2)0.
1.148Mn0.1 Compositions of LSM(Cr) and spinel in equilibrium at different T at pO2=1 Pa with and without Cr.9MnO3-δ (solid lines) as a function of oxygen partial pressure at T = 1273. next page.8Sr0.11.947O3-δ spinel formation becomes important only at pO2 < 0.2)0.3. Calculated concentrations of all species in LSM(Cr) and tetragonally distorted spinel in equilibrium are listed in Table 5.3.871Sr0.9(Mn.2)0. 160 .3. 5.3. 5.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. 5.3 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 La0.10 Defect concentrations in (La0.Cr)O3-δ (dashed lines) and (La0.1 Pa.3. as it is illustrated in Fig. Table 5.8Sr0.
and the concentration of oxygen vacancies is almost an order of magnitude lower then in (La0.871Sr0. 5.8Sr0.9MnO3-δ at high oxygen partial pressures. The influence of chromium on defect concentrations in La0.11 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. 5.947O3-δ is half of an order of magnitude higher than in (La0.8Sr0.Cr)0. 161 .947O3-δ is illustrated in Fig.Cr)0.2)0.148(Mn.3.2)0.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig. after reaching a plateau at pO2 = 103 Pa. y(Va)C even decrease slightly towards lower pO2 .148(Mn. next page: The concentration of oxygen vacancies in La0.12.3. However.871Sr0.9MnO3-δ at pO2 = 10-1 Pa.
9MnO3 without chromium. The more negative the driving force. 5.4 Formation of Cr2O3 This phase was not found in the thermodynamic calculations. and thus its formation is kinetically controlled. the more energy is needed to stabilize the phase.2)0. 5. If the driving force is 0. One can get an idea about the degree of metastability of a phase by calculating its thermodynamic driving force. In Fig.871Sr0. and the driving force for the formation of the phase is low.Thermodynamic calculations of impacts of Cr on LSM cathodes Fig.148(Mn.12 Phase equilibria in Cr-“poisoned” Mn-deficient LSM and defect concentrations in La0. 162 .8Sr0. Vertical lines indicate boundaries between different phase equilibria 5.Cr)0.3. This is the amount of energy that is needed to bring the phase to its stable state.3. Dashed lines indicate the defect concentrations in (La0.3. the phase is thermodynamically stable.947O3-δ as a function of oxygen partial pressure at T = 1273 K and μ(CrO3) = −300000 J mol-1 (solid lines).13 (next page) the driving force of Cr2O3 is plotted as a function of temperature at two different pO2 in a LSM cathode with excess Mn under Cr-“poisoning”.
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.
Ramprakash. Taniguchi. Advances.I. Matsuzaki. 6. Dependence of SOFC cathode degradation by chromiumcontaining alloy on compositions of electrodes and electrolytes. S.S. 297-310. Y. 2004. Zhang. K. Y. pp. S. I. J. 1995. Foger. 151(11). Solid State Ionics. Soc. interaction between Mn from LSM with Cr may be cumbered by proper doping of the perovskite with further B-site cations. 271-278. Y.. J. Electrochem. Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator. Zhang. Badwal. pp. 166 . 2000. 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. A1961-68. Apateanu. L. Y. 2004. 132. Soc. Matsuzaki. J. U. 284-93. Stimming. R. H. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells I. 3195-3205. Thus it is expected that in this case the consequences of Crpoisoning will persist particularly at high current loads.C. Akiyama. H.P. References 1. Saitoh. M. Furthermore. pp.P.P. 3. Kawamura. Foger. pp. Electrochem.. 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. Yasuda. Miyake. pp. 73-9. J. Electrochem. pp. Mechanisms and kinetics. Yasuo. J. Soc. S. V. 147(9). T. 2001. 2. 55. 5. K.Thermodynamic calculations of impacts of Cr on LSM cathodes By lowering the operation temperature of SOFC additional phases are expected to form at lower oxygen partial pressures. Power Sources. 1997. 148. 2000. Jiang.P. I. J. Birss. S. Tu.. A126-31. Solid State Ionics. 4. 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. 127. Chromium poisoning of LSM-YSZ SOFC cathodes. Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator. Deller. 99. aging mechanisms and lifetime in solid-oxide fuel cells. Kadowaki. 7. Power Sources. Paulson. J. Y. Yasuda. pp. T. Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells.
Y. J. Povoden.Sr)(Co. 4013-22. 1-22. pp. Chem. 27. Filonova. Zhen. 2000. 97. M. Zhen.. S. 18.W. Soc. Sundman. B (119) (2005) 80-86.N. pp. E..G. Power Sources. 9. Hallstedt. Fergus. J. 11. L. 2006. Y. K.P. 147. Zhang. pp.J. Sci. 167 . I. Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells. 15. 1961. 10. pp.Fe)O3 cathode for solid oxide fuel cells with iron-chromium metallic interconnect.P. Cohen. 2007. J. S.Sr)MnO3 and (La. Jiang. J. Demina. Power Sources. The volatilization of chromium oxide. Europ. Electrochem. pp. J. Ceam. Electrochem. 17. 32.P. J. Mater. Jansson. Russ. J. pp. 153-190. S.N. J. pp. Deposition of chromium species at Srdoped LaMnO3 electrodes in solid oxide fuel cells. Grundy. Oxygen reduction on strontium-doped LaMnO3 cathodes in the absence and presence of an iron-chromium alloy interconnect. E. 31. 180. 108. 1043-1052. S. L. 9. 361-73. Grundy. Characterization and performance of (La. Caplan and M. Mechanisms and kinetics. 16. The Thermo-Calc databank system. S. 2002.. D. Zhang. 771-774. A.Ba)(Co. 13. 2006. pp. Gauckler. A comparison of O2 reduction reactions on porous (La. S.P.A. Eng. 22. A. Andersson. L. Y.P. Zhen. Povoden. 20. Krumpelt et al. Soc. Soc. A.J. 2006. J. Wu. J. 438-442. J. Hydrogen Energy. 3664-71.P. 2008. 2001. Foger. comm. Jiang. J. 12.. Gauckler. 23. Zheng. 2007. J.. A comparative investigation of chromium deposition at air electrodes of solid oxide fuel cells. Phase Equilib. 1985. 22.N. 21. S. J. 353-62. Calphad. Jiang. Use of gaseous Cr species to diagnose surface and bulk process for O2reduction in solid oxide fuel cells. 19. Applied Electrochem. pp. L. J.N. B.D.D. 2004. Int. J. B.P. Jiang.Fe)O3 electrodes. 4th international symposium on solid oxide fuel cells and pers. Zhang. Mater. 162. Apateanu. Zheng and P.-O. Gauckler. 146. Grundy. Int. Assessment of the La-Sr-Mn-O system. Res.. Petrov.. Li. pp. FY Annual report. 28. Jiang. A. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. Solid State Ionics. X. Jiang. 39-43. Calphad. 2004. 14. E. A. 52. S. B. Diff. Jiang.N.J.P. 695-703. 191-201. Phase equilibria in the system LaMnO3SrMnO3-SrCrO4-LaCrO3. 181-192. pp. pp. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. 56978.Thermodynamic calculations of impacts of Cr on LSM cathodes 8. Inorg. pp.P.. 2002. pp.
T. Hilpert. 26. Maruyama. p. O. 2006. L. 168 . Yamamoto. NJ (1989). PV 89-11. M.A. p. The Electrochemical Society Proceedings Series. Power sources. pp.U.M. Phillips. Sakai. H. Singheiser. A. Mertens. K.. N.M. Structure and transport property of manganese-chromium-iron oxide as main compound in oxide scales of alloy interconnects for SOFCs. 176. Kishimoto. A. Howard.. Caneiro. Ed. N. J. B1252-B64. in SOFC-IV. H. S. Soc. 27. Qu.G. Koc. Pennington. Horita. L.B. S. pp. in SOFC-1. Electrical and microstructural characterization of spinel phases as potential coatings for SOFC metallic interconnects.C.E. Brito. D. 472. 681-686. Dokiya. J.Thermodynamic calculations of impacts of Cr on LSM cathodes 24. 220. Pennington. pp. Xiong. W. K. E. Chromium poisoning of the porous composite cathode. H. pp. Yamaji. Kleitz. 154 (12). Hill. Eds. Effect of cathode thickness and current density.. Sammes. 28. 25. Siebert. E. 114-24. Yokokawa. Electrocatalytic properties and nonstoichiometry of the high-temperature air electrode La1-xSrxMnO3. Soc. Tagawa. 1991. Ivey. The Electrochemical Society Proceedings Series. A. Konysheva. Anderson. J. NJ (1995). Jian. M. M. J. Hammou. 2007. T. PV 95-01. Y. H. J. R. 153. Penkalla. Electrochem. Electrochem. 138. M.. Singhal. Singhal. 29. H. 2005. S. Solid State Ionics. Hammouche.C. 1212-16.P.
1659411*T*LN(T)-.34*T*LN(T)-.988+174.5388*T*LN(T).0*T*LN(T)-2. 1193 Y -136609. STATE ATOMIC MASS AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1. Dinsdale 1991 @@ La.836315*T-34.053968535*T**2 -4.34397*T-163.284604*T-26.6651E+03 4.6902E+01. 550 Y -3381. fcc ENTER-SYMBO FUNCTION GLAFCC 298.3088*T*LN(T). 4000 N @@ La. bcc ENTER-SYMBO FUNCTION GLABCC 298.Appendix Appendix La-Cr databasea) @@ Database La-Cr.072353*T-21.344+344.001295165*T**2. AMEND-ELEMENT CR BCC_A2 5. 2000 Y -8205. Dinsdale 1991 @@ La.004045175*T**2 -5..403+120. 1134 Y -16377.008371705*T**2 +6. 800 Y +321682.492988*T-39.908*t*LN(T)+0.94+157.413+59.1996E+01 2.440708*T*LN(T)-0.35429E+01.00189435*T**2 -1.3088*T*LN(T).08252*T+513. AMEND-ELEMENT VA VACUUM 0 H0 6.91+1123.25865E-07*T**3.06113*T-17.7919*T*LN(T)-0.9547989E-05*T**3-36581228*T**(-1).0500E+03 0 S0 0.15 -3952. 6000 N @@------------------------------------------------------------------@@ Solid metals.15 169 .88526E+32*T**(-9).882+181.387295093*T**2 +4.894+218. bcc ENTER-SYMBO FUNCTION GHSERCR 298.673-3565.47721E-06*T**3+139250*T**(-1). 4000 N @@ Cr..8932E-07*T**3-399448*T**(-1).18*T-50. double hcp ENTER-SYMBO FUNCTION GHSERLA 298. Povoden-Karadeniz 2008 @@ GO G ENTER-ELEMENT LA CR VA @@ELEMENT NAME REF.48*T-26.413074*T*LN(T)+0.15 -8856..390071*T-34.3891E+02 5. 2000 Y -15608.056395E-06*T**3+21167204*T**(-1).161+88. @@ ---------------------------------------------------------@@ Functions @@ ---------------------------------------------------------@@ Standard data for elements.15 -7968. 2180 Y -34869.
28626*T+17. 1100 Y +393886.207991*T-19.015+146. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.93775E-06*T**3-133541*T**(-1).56798*T*LN(T)+. 2000 Y -12599.066199E-06*T**3+20994153*T**(-1). 6000 N @@ Cr2 gas.7643*T*LN(T)-. 600 Y +426628.005444405*T**2 +4. 8200 Y -92343.616317*T-50*T*LN(T).403+41. 4000 N @@ ---------------------------------------------------------------------@@ Liquid metal functions.908*T*LN(T)+.5*T**(-1).06299*T*LN(T)-0.37615E-21*T**7.653+18.018431*T-34.15*T**(-1). 4000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.23012*T-11.984+335. from SGTE ENTER-SYMBOL FUNCTION F7763T 298.15 +422273.15 +390765.001513089*T**2 -4.02767321*T**2 170 .004045175*T**2 -5.747-246.253215E-04*T**2 -1. 1400 Y +642608.23648333E-07*T**3-722515*T**(-1).020171603*T**2 +2.15 +15483.70261E-07*T**3+2891891*T**(-1).232-104.7919*T*LN(T)-0.25865E-07*T**3.47721E-06*T**3+139250*T**(-1)+2.042032405*T**2 -3.54399*T-34.004961847*T**2 -1.33826017E-06*T**3-312130.843-369. 1134 Y -124598.016725*T-42.011938995*T**2 +1.00189435*T**2 -1.71447833E-07*T**3+102710.085237*T+2.1*T**(-1).96003*T*LN(T)+.64743*T*LN(T)-.006002155*T**2 +1.1074654*T-19.928-44.3347881*T-22.0188*T*LN(T)+0.0441+773.386+178.0188191*T*LN(T)-0.004+171.00406*T*LN(T)+0. 10000 N @@ Cr gas.4786162*T-13.82257667E-08*T**3+5.007085085*T**2 -4. 800 Y +613345.61216717E-06*T**3+154422.346741*T*LN(T)+0.418475E+08*T**(-1).791973*T*LN(T)-0. 1300 Y +404460.36083*T*LN(T)+7.878375*T-139.15 +5332.955-30.30043383E-07*T**3-34158815*T**(-1).5192158*T-21. 2180 Y -16459.331-31.3088*T*LN(T).5353212*T-40.0037094435*T**2 -2. from SGTE ENTER-SYMBO FUNCTION F7491T 298.17+114.15 +598511. 1134 Y -3942.905-85. from SGTE @@ La(g) ENTER-SYMBO FUNCTION F12026T 298.588679E-07*T**3+10285.85*T**(-1).059775*T-26.83676*T*LN(T)-0.976+955.797+89.0037862445*T**2 -2.878761*T-21.3088*T*LN(T). 3200 Y +497751.338363*T-111. 6000 N @@-----------------------------------------------------------@@ Gas functions @@ La gas.2*T**(-1).69883E-07*T**3-1738066.Appendix -6109.
137623*T-105. @@-----------------------------------------------------------@@ Gas ENTER-PHASE GAS G 1 LA CR CR2.. @@ GO PAR SET-OUT-LEVEL.4843765E+08*T**(-1). set-interactive a) databases scripts can be used in Thermocalc with the extension .CR:VA.. 5800 Y -484185..5939925E-07*T**3+14793625*T**(-1).97520167E-07*T**3+7. ENTER-PAR G(LIQ. 2 1 0...CR:VA..15 +GHSERCR. VA.15 -0.34+623.1) 298....... ENTER-PAR G(GAS...15 +F7763T+RTLNP.0) 298.LA. fcc ENTER-PHASE LAFCC..0) 298. N..tcm 171 .CR:VA.. ENTER-PAR G(LADHCP.0) 298.. 6000 N @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Metals @@ La. VA.LA... ENTER-PAR L(BCC. @@ La.. ENTER-PAR G(GAS.CR:VA..... ENTER-PAR G(GAS....CR:VA.CR:VA.0) 298...4 ENTER-PAR TC(BCC.CR:VA.135805E+08*T**(-1). ENTER-PAR L(LIQ.. ENTER-PAR G(LAFCC.15 +GLABCC. ENTER-PAR BMAGN(BCC.LA:VA.07969*T*LN(T)-.055+2598....15 +GCR_L.. ideal extension from lower-order systems ENTER-PHASE LIQ. @@ Interaction parameters from binaries ENTER-PAR L(LIQ. 2 1 3 LA CR.0) 298..0) 298. 2300 Y +553119... AMEND-PHASE-DESC BCC MAGN -1 0.15 -311..CR2...LA:VA...15 +GHSERLA. AMEND-PHASE LIQ COMP 2.CR..15 64573-23*t......0) 298.15 +GLALIQ.188555*T-52.Appendix +1.0) 298.5 LA .49*t.15 83500.0) 298. ENTER-PAR G(LIQ.004229401*T**2 +1..0) 298.. ENTER-PAR G(BCC.895+159.028597625*T**2 -4. @@ ----------------------------------------------------------------@@ Alloys @@ BCC_A2 ALLOY ENTER-PHASE BCC..0) 298..605906E-06*T**3-5831655*T**(-1). 2 1 1 LA.15 +F7491T+RTLNP. 3900 Y +347492.15 60713-5.....LA:VA.LA..0) 298....7145*T*LN(T)+.LA:VA.0) 298. @@ ------------------------------------------------------------------------@@ Liquid.9699545E-04*T**2 +1.15 +GLAFCC.. ENTER-PAR G(BCC... VA.LA... VA.51783483E-07*T**3+1.008..15 +F12026T+RTLNP...25559*T-334.... 2 1 1 LA CR.. dhcp ENTER-PHASE LADHCP.5.0428*T*LN(T)+3..
6902E+01..4938E+01 4.6651E+03 5.2008E+01. AMEND-ELEMENT MN CBCC_A12 5.3891E+02 6.. @@ Actual version: Dec2008 by Povoden-Karadeniz @@ @@ COMMENTS @@ @@ Sr-Cr-O liquid: simple description.0252E+02.5694E+01.5680E+03 5. AMEND-ELEMENT O 1/2_MOLE_O2(G) 1..7620E+01 6. AMEND-ELEMENT H 1/2_MOLE_H2(G) 0. first version: Feb2006 by Povoden. STATE ATOMIC MASS H0 S0 AMEND-ELEMENT LA DOUBLE_HCP(ABAC) 1. AMEND-ELEMENT VA VACUUM 0 0 0. AMEND-ELEMENT SR SR_FCC_A1 8.5999E+01 4. associate at composition SrCrO4 can @@ help for better fit to experiments – future work @@ @@ No data exist for Sr-Mn-Cr-O. Solubility of Cr in SrMnO3 not known @@ --> Subsystem Sr-Mn-Cr-O is a purely ideal extention @@ @@ no oxygen solubility in La-oxide description (taken from Zinkevich et @@ al.1008E+01 0 0. as only few phase @@ diagram data exist! @@ -------------------------------------------------------------------GO G ENTER-ELEMENT LA SR MN CR O VA H @@ELEMENT NAME REF..1996E+01 4.35429E+01.9960E+03 3...Appendix La-Sr-Mn-Cr-O-(H) oxide database @@ LA-SR-Mn-CR-O-(H) oxide. AMEND-ELEMENT CR BCC_A2 5..65340E+02.3410E+03 1. @@ @@ -------------------------------------------------------------------@@ 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 .) considered @@ @@ Quinary Ruddlesden popper phase is very tentative. Povoden-Karadeniz @@ @@ Database La-Sr-Mn-Cr-O-(H).0500E+03 2.
2000 N @@ Cr.005098873*T**2 +6.6184604E-07*T**3-38364.908*t*LN(T)+0.00734768*T**2 +69827. 1519 Y -28733. cbcca12 ENTER-SYMBO FUNCTION GHSERMN 298.4582*T*LN(T)-0.47721E-06*T**3+139250*T**(-1).8932E-07*T**3-399448*T**(-1).1659411*T*LN(T)-.882+181.27966+130.34*T*LN(T)-.059572*T-23.284604*T-26. 820 Y -13380.656847E30*T**(-9). bcc ENTER-SYMBO FUNCTION GHSERCR 298.84189E-07*T**3+850134*T**(-1).905*T*LN(T)-4.41+312.001295165*T**2. 550 Y -3381. 3000 N @@ Mn.344+344. 2000 Y -15608.872255-25.0905432*T*LN(T)-3.390071*T-34.15 -3480.1355068*T*LN(T)-0.94+157. 1000 Y 173 .5028601*T-11.18*T-50.251266E-3*T**2 +1.15 -8856.413+59. 2180 Y -34869.3088*T*LN(T).8742*T**(-1).48*T-26. 4000 N @@ Sr.00189435*T**2 -1.67477E-07*T**3-2055*T**(-1).15 -7532.0*T*LN(T)-2.88526E+32*T**(-9).196104*T-30.15 -8115.15 -7968.183879*T-23.61225E-3*T**2 -1.403+120. (1/2 O2) ENTER-SYMBO FUNCTION GHSEROO 298.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. fcc ENTER-SYMBO FUNCTION GHSERSR 298.008371705*T**2 +6.102+153.367+107. Dinsdale 1991 @@ La. 6000 N @@ O1.2648*T-48*T*LN(T)+1. double hcp ENTER-SYMBO FUNCTION GHSERLA 298.06113*T-17.1*T**(-1).
78055555E-09*T**3+262904. optimized @@ La-oxides. Povoden 2005 @@ METASTABLE CRO ENTER-SYMBO FUNCTION GCR1O1 298.15 -9.006854*T**2 +808000*T**(-1)-1E7*T**(-2).15 +GSROSOL+GHSEROO-43740+70*T..8*T*LN(T)-4....12922234E+05*T**(-1)...15 -1.. ALPHA-MN3O4 (DISTORTED) ENTER-SYMBO FUNCTION GTMN3O4 298. @@ SrO2 ENTER-SYMBO FUNCTION GSRO2SOL 298...15 +108305+GCR2O3+0.64955386E+05*T**(-1).056E-02*T**2 +6.54747566E+02*T*LN(T) -1. MNO ENTER-SYMBO FUNCTION GMN1O1 298.778*T**(-1). @@ BETA-HAUSMANNITE. @@ @@ MN2O3-FUNCTION. BETA-MN3O4 (CUBIC) ENTER-SYMBO FUNCTION GCMN3O4 298..76*T.9*T-47.. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3D 298.15 -1. ENTER-SYMBO FUNCTION GLA2O3H 298...85001409E-03*T**2+2.. @@ Mn-oxides..96393E+05+5.629*T*LN(T)-0.911E+01*T*LN(T)-2..15 -5... @@ ESKOLAITE..728+31... 3300 Y -13986. MODIFIED.05E+06*T**(-1).74079033E-02*T**2+9. @@ -------------------------------------------------------------- 174 .97E-03*T**2 +1.9536*T*LN(T)-4. 6000 N @@-----------------------------------------------------------@@ Binary oxides.15 +0.02477557E+05+2.. Grundy 2006 ENTER-SYMBO FUNCTION GMN2O3 298. @@ ALPHA-HAUSMANNITE..25243E-04*T**2 +1.15 -607870+268.0721E-08*T**3+4383200*T**(-1).9579637E-04*T**2 +6.15 +1..76015+12.95379396E+02*T-6. Risold 1996 @@ SrO ENTER-SYMBO FUNCTION GSROSOL 298.15 -4.5*GHSEROO+280045-93. @@ CR-SPINEL CR3O4 ENTER-SYMBO FUNCTION GCR3O4 298..986*T+GLA2O3D. Cr2O3 ENTER-SYMBO FUNCTION GCR2O3 298..52766201E+01*T*LN(T) -7.8138015*T*LN(T)-5. MN1O2 ENTER-SYMBO FUNCTION GMN1O2 298.54747566E+02*T*LN(T) -1. @@ reduced neutral endmember of CR2O3 ENTER-SYMBO FUNCTION GCRO0 298..75120338E+02*T-1.15 -1.66000166*T-16.68352649E+01*T*LN(T) -3.74079033E-02*T**2+9. ENTER-SYMBO FUNCTION GLA2O3X 298.9664*T-120.82*T..0822E+05*T**(-1)...555*T+GLA2O3D... @@ Sr-oxides..5*GCR2O3-0. @@ Cr-O oxides.259625*T-18.00307*T**2 +190000*T**(-1)..86138663E+05*T**(-1).41618912E+06+8.6846E+02*T-9.45091278E+05+3.89567858E+02*T-1.66666666667*GHSERCR. Grundy 2003 @@ MANGANOSITE.15 -1833257+692..56*T*LN(T)-0..5*GHSEROO+255269-53.59355626E+02*T-4..15 32350-13.5*GCR2O3-0.15 43192-18.86138663E+05*T**(-1).. @@ PYROLYSITE.164542E+06+7....2856E+02*T-119..Appendix -6568.43703676E+06+8.80284521E-03*T**2+6.
ENTER-SYMBO FUNCTION GSM3OZ 298.. ENTER-SYMBO FUNCTION RE_ALPHA 298. @@ LA7 @@ ENTER-SYMBO FUNCTION GLA7 298.5*GLA2O3D+GCR2O3+2..5*GMN2O3-7..14*T. @@ LA2CR3O12 ENTER-SYMBO FUNCTION GLA2CR3 298.5*GCR2O3+9..15 0. @@ SrMn3Oz as SrMnO3_Mn2O3 ENTER-SYMBO FUNCTION GSM4OZ 298..15 GLA2O3D+1....5*GCR2O3+4. @@ @@ Functions of the Sr-Mn-O system.99100000E+04-90*T.. @@ @@ Functions of the La-Mn-O system.. @@ Sr7Mn4O1 175 .5*GHSEROO-154101-2. ENTER-SYMBO FUNCTION SRH_ALPH 298..15 +GSROSOL+0.... @@ RP1 ENTER-SYMBO FUNCTION GS4O_RP1 298.799*T..15 +3*GSROSOL+2*GMN1O2-8.15 +GSROSOL+0..15 +2*GSROSOL+2.. @@ RP3 ENTER-SYMBO FUNCTION GSM4_RP3 298.. ENTER-SYMBO FUNCTION GSM3_HEX 298.. 2005 ENTER-SYMBO FUNCTION GL2MNO4 298.15 +2*GSROSOL+2....5*GLA2O3D+0...15 +2*GSROSOL+2...... ENTER-SYMBO FUNCTION SRX_ALPH 298..15 +GLA2O3D+2.5*GHSEROO-73045-4...71704891E+01*T.70000000E+01*T..15 +GSROSOL+GLA2O3D+GMN2O3-137400.15 +GMN2O3+GSM3_HEX-2.... Grundy 2004 ENTER-SYMBO FUNCTION SR_ALPHA 298....5*GMN2O3-68300. Grundy et al..32830000E+05.5*GHSEROO-371557+205*T.79100000E+03.15 GLA2O3D+0.78500000E+05.5*GHSEROO-540404-9.55*T.26029731E+04-3.. ENTER-SYMBO FUNCTION GL3O_RP2 298.15 +GSROSOL+GMN1O2-1.Appendix @@ Ternary oxides.15 +4*GSROSOL+3*GMN1O2-3.15 +GLA2O3D+GMN1O1+6. Grundy 2004 @@ HEX Phase ENTER-SYMBO FUNCTION GSM4_HEX 298..15 +2*GSROSOL+GMN1O2-1... ENTER-SYMBO FUNCTION RE_BETA 298...19200000E+04.11300000E+05.5E+04... ENTER-SYMBO FUNCTION GL3O_RP1 298.158E+04....5E+04.15 @@ 3.. @@ RP2 ENTER-SYMBO FUNCTION GS4O_RP2 298. optimized (except perovskite functions) @@ @@ Functions of the La-Sr-O system....15 0. ENTER-SYMBO FUNCTION LA_BETA 298.15 +GMN2O3+GSM4_HEX-8.73000000E+03 -1. @@ @@ Functions of the La-Cr-O system...5E+04..5*GCR2O3+1. @@ intermediate La-chromates @@ LA16 @@ ENTER-SYMBO FUNCTION GLA16 298. Povoden 2008 @@ LA2CRO6 ENTER-SYMBO FUNCTION GLA2CRO6 298.15 @@ 8*GLA2O3D+3...
19*T*LN(T) +232934*T**(-1).44550000E+04 176 . ENTER-SYMBO FUNCTION GVVV 298..6*T..5*GMN2O3-63367+51. Povoden 2008 @@ Ruddlesden Popper phase ENTER-SYMBO FUNCTION GREFRP 298.5*GLA2O3D+0.15 0. ENTER-SYMBO FUNCTION GL4O 298.33333333334*GTMN3O4-200942+75...5*GCR2O3+1....15 +2. @@ @@ Functions of the Sr-Cr-O system.5*GLA2O3D+0..15 2*GSROSOL+0..75*GMN1O2-91857+20.... @@ ENTER-SYMBO FUNCTION GL3OL 298. ENTER-SYMBO FUNCTION GMS3O 298...77*T-7.5*GLA2O3D+GMN1O1+27672.19*T*LN(T) +232934*T**(-1)-3429+4. @@ SR2CRO4 ENTER-SYMBO FUNCTION GS2CO4 298...15 +0. Povoden 2008 @@ SRCR2O4 ENTER-SYMBO FUNCTION GSC2O4 298...666666667*GCR3O4+.73000000E+03-1.15 +0.5*GHSEROO-145000+50*T.666666667*GCR3O4+. @@ TETRAGONALLY DISTORTED SPINEL ENTER-SYMBO FUNCTION GTSPINEL 298.15 +GSROSOL+GCR2O3+98000-95.5*GLA2O3D+0.15 +0.72*t......5*GHSEROO.333333333333*GHSEROO -508507+219*T.....5*GCR2O3+0.5*GHSEROO-273771 +131...77*T-7..15 0.5*GMN2O3-7. @@ SR3CR2O8 ENTER-SYMBO FUNCTION GS3C2O8 298.5*GMN2O3-63367+51.333333*GLA2O3D+GMN1O2-53760..5*T.15 +2*GSROSOL+0. @@ @@ Functions of the La-Sr-Cr-O oxide system.5*GMN2O3-63367+51.15 +7*GSROSOL+4*GMN1O2-6..5*GCR2O3+0.15 +GLACRO3+GSROSOL+7000-25*t.15 +GSROSOL+0. Povoden 2005 @@ CUBIC SPINEL ENTER-SYMBO FUNCTION GSPINEL 298. ENTER-SYMBO FUNCTION GV4O 298.4*t.15 +GSROSOL+GCR2O3+3*GHSEROO-325047+196*T...15 +6*GL2O+4*GL4O+3*GV4O-12*GL3O-254212..15 +0.. @@ ---------------------------------------------------------------@@ Perovskite functions @@ Grundy 2005 @@ Charge compensated by Mn+4 (correct) ENTER-SYMBO FUNCTION GL3O 298.12450000E+05+50*T..19*T*LN(T) +232934*T**(-1)+400-0. @@ ENTER-SYMBO FUNCTION GL3OR 298. @@ SRCRO4 ENTER-SYMBO FUNCTION GSCO4 298. ENTER-SYMBO FUNCTION GL2O 298..5*GLA2O3D+0...31*T. ENTER-SYMBO FUNCTION GLCR3O_RP1 298. @@ @@ Functions of the Mn-Cr-O system.15 +0.15 +GSROSOL+0...77*T-7..1*T..66666667*GSROSOL+GCR2O3+2... @@ SRCR2O7 ENTER-SYMBO FUNCTION GSC2O7 298.Appendix ENTER-SYMBO FUNCTION GS7M4 298.69*T.15 +0...3+61...33333333334*GCMN3O4-210795..
2180 Y -16459. ENTER-SYMBO FUNCTION GMS4O 298.981237E-06*T**3-265559*T**(-1).5*GCR2O3+0...69000000E+00*T...018431*T-34.2386*T+135166-88..37615E-21*T**7.653+18.656847E30*T**(-9)..00189435*T**2 -1....15 +5332..1840595E-2*T**2 +4.616317*T-50*T*LN(T)..93775E-06*T**3-133541*T**(-1).15 +15483. 1134 Y -3942. 1519 Y +GHSERMN+18739.41929E-21*T**7.984+335.5*GCR2O3-73591+2.. @@ Functions for defect chemistry ENTER-SYMBO FUNCTION GVCR4O 298.15 +GSROSOL+0.23012*T-11. 6000 N @@ --------------------------------------------------------------------- 177 .15 GSROSOL+0.15 GSROSOL+0..15 0..26500000E+04 -7.47721E-06*T**3+139250*T**(-1)+2.5*GCR2O3-2.63*t.997-10.51-13. ENTER-SYMBO FUNCTION ANTI 298.463*T*LN(T).004+171. 3000 N @@ Mn ENTER-SYMBO FUNCTION GMN_L 298.91-12. @@ (LaSr)CrO3+/-delta-Perovskite @@ Reference SrCrVa3 ENTER-SYMBO FUNCTION GS4V 298..118994*T-5.29+213.68*T* LN(T)..15 +547422.15 +GHSERMN+17859.5*GCR2O3+0.5*GCR2O3+0.5*GHSEROO-200000.5*GLA2O3D+0. ENTER-SYMBO FUNCTION GLACR4O 298.059775*T-26.38*T-0. Dinsdale 1991 @@ La ENTER-SYMBO FUNCTION GLALIQ 298.908*T*LN(T)+.. ENTER-SYMBO FUNCTION GALACRO3 298.15 +2194..VA)O3 ENTER-SYMBO FUNCTION GN 298.2288*T-1...5*GHSEROO.020171603*T**2 +2.. @@ Function for neutral endmember SrCrO3 ENTER-SYMBO FUNCTION GS4O 298.70000000E+01*T.15 0... 4000 N @@ Sr ENTER-SYMBO FUNCTION GSRLIQ 298.0188191*T*LN(T)-0.11300000E+05+2.0668978*T*LN(T)-3.52*t. @@ ---------------------------------------------------------------------@@ LIQUID FUNCTIONS @@ ---------------------------------------------------------------------@@ Liquid metal functions.6208*T-4.33333*GLA2O3D+.15 0.5*GCR2O3+11..5*GHSEROO+10222-55. 1050 Y -10855..015+146.406219*T-39. @@ Function for neutral endmember SR(CR+3.... @@ Reciprocals: all 0!!!!! @@ @@ Povoden 2008 @@ LaCrO3-PEROVSKITE ENTER-SYMBO FUNCTION GLACRO3 298. 3000 N @@ Cr ENTER-SYMBO FUNCTION GCR_L 298.5*GHSEROO-291802-250*t.15 +GSROSOL+GMN1O2-1.Appendix -1.3088*T*LN(T)..15 +GLACRO3-340+0..42*t.
097*T*LN(T)-0.63356E+08*T**(-1).008463125*T**2 +1.0 (1998).31437957E+01*T.5*GHSEROO+339673-121.96003*T*LN(T)+.R. 601 N @@ -----------------------------------------------------------------------@@ GAS FUNCTIONS @@ --------------------CHROMIUM GAS---------------------------------------@@ CR Gas: SGTE v 3..8788-3288. 1000 Y +167489.8669*T*LN(T) +. @@ liquid SrO.2320948*T**2-9.629*T*LN(T)-0.588679E-07*T**3+10285.9664*T-120...Appendix @@ Liquid oxide functions.555*T*LN(T)+0.253215E-04*T**2-1. @@ liquid Mn oxides.1684007*T-39.00631160667*T**3+5.36083*T* LN(T) +7.59563*T-186.06284295E+01*T.0063*T**2 +31300*T**(-1)+9.178604*T-117. Class: 4 @@ SGTE=scientific group thermodata Europe @@ ENTER-SYMBO FUNCTION F7491T 298.15 -332319. ENTER-SYMBO FUNCTION GCR2O3_L 298.R.18729*T+495.928-44.003139382*T**2 -1. 6000 N @@ CR1O1 Gas (SGTE 1998.A..001513089*T**2 -4.5329*T*LN(T)+.15 +2*GMN1O1+GHSEROO-6.48508*T**2-.A..S).15 -566346+449*T-73.00148*T**2 +873600*T**(-1)+1.23648333E-07*T**3-722515*T**(-1). 1100 Y +393886.36845867E-08*T**3+6.5192158*T-21..49525609E+04+4.C.9513659*T-30.C. ENTER-SYMBO FUNCTION GMN2O3_L 298.2897*T*LN(T)-..4-33.135*T**(-1). 500 Y -62418. REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCR1O1_G 298.15 +390765.62+32.15 0. Grundy ENTER-SYMBO FUNCTION GMN1O1_L 298. Risold ENTER-SYMBO FUNCTION GSROLIQ 298.4*T. @@------------------------------------------------------------------@@ LIQUID WATER. Class: 4 ENTER-SYMBO FUNCTION GH2O_L 298.A.. @@ liquid Cr oxides.15 +173449.R. Zinkevich 2006 ENTER-SYMBO FUNCTION GLA2O3LIQ 298.229905E-07*T**3+35263.15 GMN1O1+4.917665E-05*T**3-18523425*T**(-1).722975E-07*T**3-64209900*T**(-1)... 10000 N @@ CR1O1 Gas.52515733E-07*T**3+682877*T**(-1). from T.31*T-40.1304*T*LN(T) -.282+741.1074654*T-19.224944*T-121.5*GCR2O3-0.74749*T*LN(T)+.671+1078.15 +176483. from T. Povoden ENTER-SYMBO FUNCTION GCR1O1_L 298...48744*T*LN(T)-.237405*T+14. 178 .9+142414.S.504926*T**2+4. 900 Y +170853.. 540 Y -8528143. optimized @@ liquid La2O3.5567E-7*T**3.S Class: 5) ENTER-SYMBO FUNCTION F7705T 298.502-414. 8400 Y -403765.69E-7*T**3. source: Thermocenter of russian academy @@ of science (T.C..6220*T.869-31.15 GCR2O3+439078-169*T.39465890E+04-2.19*T*LN(T) +27..1*T*LN(T).15*T**(-1).15 -1833257+692.. 600 Y -331037..14296167E-05*T**3+978019*T**(-1).708+805.331-31.41*T*LN(T). 4000 Y +307209.35563E+08*T**(-1).00607059*T**2 +9.45*T-22596.00119977*T**2 -1.083*T-30..006854*T**2 +808000*T**(-1)-1E7*T**(-2)+141329-56.3+37.
383-1950.45*T**(-1). 6000 N @@ -------------O-H GAS----------------------------------@@ H2 Gas (JANAF THERMOCHEMICAL TABLES SGTE) ENTER-SYMBO FUNCTION H2GAS 298.A.Appendix 3000 N @@ CR1O2 Gas.97393+78.17486667E-07*T**3+1572175*T**(-1).15 -9522.15 +243206.569*T*LN(T)-0.0922361*T**2 +4. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION HGAS 298.09482*T-134.5*T**(-1).6+6101.44768833E-06*T**3-2.00623741*T**2-6.0847281*T-17.02763076*T**2 +4.43E-6*T**3.15 -109942.61*T-57. 3000 N @@-------------------OXYGEN GAS------------------------------------@@ O Gas (JANAF 1982.8435*T*LN(T)+.555105E-07*T**3-2. reassessment Chen 2006. 2100 Y +866367.1894682*T-31.696*T*LN(T)-0.89*T-82.0010728235*T**2 +1.05535833E-07*T**3+1246309.S Class: 4) ENTER-SYMBO FUNCTION F10963T 298.15 -250423.01667E-8*T**3.23131283E-08*T**3-42897.5273873*T-31.1304835E+08*T**(-1).13383*T-764.10457667E-06*T**3+12362250*T**(-1).C. 1000 Y +180.0155*T**2 +245800*T**(-1)+2.15 -341231. 4900 Y +97590. 1000 Y -118120+123.00016*T**2 +1814700*T**(-1)+7.21188*T*LN(T)-5.8612582*T-21.108664-15.4989821*T-20. from T. 700 Y +114760.2687055E-04*T**2 -1. 1100 Y -256145.R. 1300 Y +49468.423-52.879+30.798361*T-149.0216*T**2 +428900*T**(-1)+3.59*T-39.1284109*T**2 +5.494-20.6128262*T-17.64520667E-09*T**3-3973170.84857*T*LN(T)-0.46390667E-07*T**3+56582.C.15 +130696.621+24.039707355*T**2 -4.4437*T*LN(T)-.14281783E-08*T**3+3561002. 2950 Y +252301.01555*T*LN(T)+1.1663+92. from T.5*T**(-1).0027589925*T**2 -7.43044*T*LN(T) -.09*T**(-1). 3000 N @@ CR1O3 Gas.35707*T*LN(T)+0.413565E-04*T**2 +7.58118*T*LN(T)-.3*T**(-1).623+176.3696*T*LN(T)+.33E-9*T**3.9608*T*LN(T)+.10286*T*LN(T)+.01283575*T**2 -3.01526167E-08*T**3-64163. 2800 Y 179 .60539333E-06*T**3+99530.00012*T**2 +932050*T**(-1)-8.70834*T+223. 3500 Y -1866338.78+10.99+130.78611*T*LN(T).05082*T*LN(T)-0. 2100 Y -18840.626737*T-60.075-3566.R.944-37.2*T*LN(T)-. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O3_G 298.043+890.00206456*T**2 -5. reassessed by Ming Chen 2006.45*T**(-1).09852775*T**2 -2.15 +211801.2001*T*LN(T)-.610855E+08*T**(-1).A.59784667E-06*T**3+9. 1000 Y -354716.401E-6*T**3. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION GCR1O2_G 298.09+299.007055445*T**2+3. 6000 N @@ H Gas (JANAF 1982.14618667E-07*T**3-1280036*T**(-1).00584168*T**2 +3. 6000 N @@ O3 Gas (SGTE 1998.81*T-56.5*T**(-1).434+4.3956+710.80563*T+421. assessment dated 3/77 from SGTE) ENTER-SYMBO FUNCTION F13349T 298. 6000 N @@ H2O1 Gas (SGTE 1998.45470312*T-28.3120249*T-32. 2800 Y +409416.S Class: 4) ENTER-SYMBO FUNCTION F14021T 298.1699975E+08*T**(-1).9096643*T-27.40916*T*LN(T) -.526*T*LN(T)-0.306855E-06*T**3-21589870*T**(-1).
52+180.0016703495*T**2-1.1173*T*LN(T) +6.15 +68260+52.690197*T-42.0019361405*T**2-1.77*T-83.242048*T-24. 3000 N @@ CRO2(OH) Gas.96842*T*LN(T) -.94216*T*LN(T) -.9*T*LN(T) -.0018*T**2+2218000*T**(-1)-2.775*T*LN(T) -. 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 298.15 +1075.326117*T-69.0023107985*T**2+5.51E-7*T**3. 18000 Y -165728.34404917E-07*T**3+116618.S Class: 4) ENTER-SYMBO FUNCTION F10729T 298.82*T**(-1).94271*T*LN(T) -.97699*T*LN(T) +.87*T-46.259882*T-92.64106-55. 20000 N @@ H1O1 Gas (SGTE 1998.799205E-07*T**3-25503.002*T**2+185600*T**(-1)-1. 8600 Y +41016.05*T**(-1).0015*T**2+938850*T**(-1)+5. from T.573855E-09*T**3+26048030*T**(-1).0018*T**2+1338300*T**(-1)+9.036948065*T**2+6. 3000 N @@ CR(OH)2 Gas.0792741*T-24.4077*T*LN(T) +. from T.1931655E+08*T**(-1).765625E+08*T**(-1). 1000 Y -276268.927*T*LN(T) -0.659505E-06*T**3+65357.724*T*LN(T) -0.003149545*T**2+1.00501027*T**2+2.551*T*LN(T) +0.42186*T*LN(T) -.32333233E-08*T**3+1.91863E-08*T**3-6415210*T**(-1).99164+54.45435*T*LN(T) -.686636*T-25.10636*T*LN(T) -.A.6898+15.S Class: 1) ENTER-SYMBO FUNCTION F10666T 298.0007*T**2+243850*T**(-1)-9.0783-20. 3000 Y +31735.7*T-72.213599E-04*T**2-1.15 -497678+273. 1000 Y 56684+136.52*T-74.4391015E+08*T**(-1).971-37.5127-12.36297E-06*T**3-29469.97594167E-08*T**3+2458230.7343256*T-24. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O2_G 298.334E-8*T**3.191295*T-50.32+190.2768*T*LN(T) +6.12331E-04*T**2-6.47*T-96. 3000 N @@ CRO(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O2_G 298.277-65.257*T*LN(T) -0.42189E-05*T**2-1. 3600 Y -67875.406716*T-68.007931945*T**2+4.2E-7*T**3. 1000 Y 180 .122915E-07*T**3+925845*T**(-1).39E-6*T**3.R.Appendix -268423.75E-7*T**3.953+370.15 -274384.771+239.2016233*T-40.47539017E-08*T**3+1.001713168*T**2-6.C.003069987*T**2+6.1497212*T-26. 20000 N @@ H1O2 Gas (SGTE 1998.15 -351288.2921095E-09*T**3-4. 6000 N @@ H2O2 Gas (JANAF SECOND EDIT SGTE) ENTER-SYMBO FUNCTION F10983T 298.8961+275.15 -147258.0031*T**2+266750*T**(-1)-9.292415E+08*T**(-1).86*T-75.30298483E-10*T**3-8.5*T**(-1).65*T**(-1).645643*T-59.24542*T*LN(T) +.77872*T*LN(T) +2.29733833E-07*T**3+684985. 800 Y -7932. 8400 Y -489068.65*T**(-1).418+116. 700 Y -156470.175*T*LN(T) +0.018507875*T**2+2. assessment Chen 2006.R.15E-8*T**3.4+195.053*T*LN(T) -0.135E-7*T**3.505+120. 1000 Y -492562+351.5*T**(-1).53*T-57.882+553.C. +326722. 18000 Y -154907.A.15 +30698.0146*T**2+715900*T**(-1)+2.9096451*T-29. 1500 N @@-------------------CR-O-H GAS---------------------------------------@@ CR(OH)1 Gas REASSESSED BY MING CHEN (2006) BASED ON EBBINGHAUS (1993) ENTER-SYMBO FUNCTION GCRH1O1_G 298.
1000 Y -806262+567*T-131.0099*T**2+770750*T**(-1)+5. 1000 Y -582354+394.6*T-109.019*T**2+513600*T**(-1)+1.525*T*LN(T) -0. 3000 N @@ CRO(OH)4 Gas.05+820.098*T*LN(T) -0.014*T**2+1.91E-7*T**3.97*T-79.15 -978211.004*T**2+1.15 -1029121.15 -578683+391.3*T-121.049*T*LN(T) -0.0054*T**2+1023500*T**(-1)-1.67833E-07*T**3.004*T**2+2094950*T**(-1)+1. 1000 Y -1053466+1080.819*T*LN(T) -0.Appendix -359644+228.25*T*LN(T) -0. 1000 Y -861477. 1000 Y -997791.83+534. 3000 N @@ CR(OH)4 Gas. assessment Chen 2006.5*T*LN(T) +0. 1000 Y -991549.18913267E-06*T**3-77266.46-2142. 1000 Y +421602.15 -787712+400*T-107. 3000 N @@ CRH1 Gas (SGTE 1998. from T.65*T*LN(T) -0. assessment Chen 2006. assessment Chen 2006.77E-6*T**3.00994042*T**2+1.S Class: 4) ENTER-SYMBO FUNCTION F7586T 298.355E-6*T**3.15 -851590.0096*T**2+4.93E-7*T**3.35E-7*T**3.6022*T*LN(T) -.8+813.15 -650064.4+51. 3000 N @@ CR(OH)3 Gas. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH6O6_G 298.006*T**2+2525450*T**(-1)+2.15 -902751.16*T*LN(T) -0.014*T**2+6008850*T**(-1)+7.6+712.86*T*LN(T) -0. 5500 Y +1270342. 3000 N @@ CRO(OH)2 Gas.006*T**2+498450*T**(-1)-2.37019*T*LN(T) -.11767E-6*T**3.545E-7*T**3.874*T*LN(T) -0.9865812*T-37.01*T**2+4151100*T**(-1)+5.0049*T**2+3311450*T**(-1)+2.37*T-125. 3500 Y +587860.2*T-109. combined assessment Chen 2006 @@ based on Ebbinghaus 1995 @@ and from Povoden-Karadeniz based on Opila 2007 ENTER-SYMBO FUNCTION GCRH2O4_G 298.35E-07*T**3+665100*T**(-1).34E-7*T**3.99444833E-08*T**3-86705500*T**(-1).9391*T*LN(T) 181 .2*T*LN(T) -0.455*T*LN(T) -0. assessment Chen 2006.1+867.349852E-04*T**2-1.6*T-195.3*T-137.R.74*T-146.008*T**2+840600*T**(-1)-1.00056*T**2+663150*T**(-1)-5.15 +432449. 3000 N @@ CR(OH)6 Gas.7467E-7*T**3. 3000 N @@ CR(OH)5 Gas. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O4_G 298. 1000 Y -909897. based on Ebbinghaus 1993 ENTER-SYMBO FUNCTION G_CRH4O5 298.9958E-06*T**3.457*T*LN(T) -0.99681*T*LN(T) +3. 1000 Y -656538+448.8867E-7*T**3.41*T*LN(T) -0.524*T*LN(T) -0.002*T*LN(T) -0.004*T**2+785800*T**(-1)-2.378E-6*T**3.5*T-163*T*LN(T) +0. 3000 N @@ CRO2(OH)2 Gas. assessment Chen 2006.12+967. 3000 N @@ CRO(OH)3 Gas. assessment Chen 2006 based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH2O3_G 298.3E-7*T**3.A.0086*T**2+3058600*T**(-1)+4.945E-07*T**3+4671850*T**(-1).76+600.86+694.713-424.C.36214*T+18.026-56.8967E-07*T**3+1688150*T**(-1).9*T-190.05*T**(-1).45*T-229.97*T-180.15 -976204+672.60191*T+219. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH5O5_G 298. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH3O3_G 298.386334*T-22. assessment Chen 2006.973194012145*T-158.007723995*T**2+7. based on Ebbinghaus 1995 ENTER-SYMBO FUNCTION GCRH4O4_G 298.0065*T**2+2669300*T**(-1)+3.7+464.13133917E-07*T**3+1368173*T**(-1).89*T-216.6*T-162.
.LA+3:VA..LA+3..0) 298...0).MN:O.15 +GLA2O3D.. 2 2 3 LA+3 SR+2.. ENTER-PAR G(BETA.LA+3...SR+2:VA..15 +GLAO. +GLA2O3D-3*GHSEROO. O-2 VA. ENTER-PAR G(LA2O3SS..81E+01*T..0). +SRX_ALPH+GHSEROO+15. +SRH_ALPH-2*GHSEROO +15. ENTER-PAR L(LA2O3SS.15 +GSRO2SOL. ENTER-PAR G(LA2O3SS....0)..... ENTER-PAR G(BETA... ENTER-PAR L(LA2O3_CUBSS.0) 298....15 +2. +GLA2O3X.LA+3:O-2. +LA_BETA.LA+3:VA.. ENTER-PAR G(LA2O3_CUBSS.. ENTER-PAR G(LA2O3_HEXSS.SR+2:VA.15 -20000.. O-2 VA. ENTER-PAR G(LA2O3_HEXSS... Grundy. ENTER-PAR G(LA2O3_HEXSS. +GLA2O3H.15 +193600-78.....15 -20000.... @@ ENTER-PHASE LA2O3_HEXSS.. ENTER-PAR G(LA2O3SS...20451E+08*T**(-1).0)...LA+3:VA.LA+3.15 +193600-78.LA+3:VA.... ENTER-PAR G(LA2O3_CUBSS.. ENTER-PAR L(LA2O3_CUBSS.0). ENTER-PAR G(LA2O3_CUBSS.SR+2:O-2.....1) 298.0) 298.0) 298..87691*T..SR+2:O-2..LA+3:O-2..LA+2:VA....0).. +GLA2O3H-3*GHSEROO.1*T.SR+2:O-2. +GLA2O3X-3*GHSEROO.. ENTER-PAR L(LA2O3_HEXSS......SR+2:VA. ENTER-PAR G(LA2O3_HEXSS. +GLAO-GHSEROO...0)..SR+2:VA. O-2 VA..15 +168700-78. +SR_ALPHA+416100+GHSEROO -0...33333333*RE_BETA +15....87691*T. ENTER-PAR L(LA2O3SS.0).1*T..0).LA+3:O-2.....0). O-2 VA.0) 298.. @@ ENTER-PHASE LA2O3_CUBSS.034109635*T**2+7..SR+2:O-2. @@ @@ Mn oxides.. 6000 N @@ @@ @@ -------------------------------------------------------------------@@ Phases @@ ------------------------------------------------------------------@@ Binary oxides @@ @@ Sr oxides..LA+3.87691*T..149E+05-7.. ENTER-PAR L(LA2O3_HEXSS.0) 298.SR+2:VA.15 +2.1) 298..SR+2:O-2.0) 298..SR+2:O-2..LA+2:O-2.81E+01*T..0) 298. ENTER-PAR G(SRO2.. ENTER-PAR G(LA2O3SS.LA+3..87691*T...LA+3. 1 SRO2.277845E-07*T**3-5. Risold @@ ENTER-PHASE SRO2. ENTER-PAR G(LA2O3SS.. MN1O2 ENTER-PHASE MN1O2..0).SR+2:O-2..Appendix -.. @@ La4SrO7 as BETA phase ENTER-PHASE BETA. ENTER-PAR L(LA2O3_CUBSS.SRO2... Chen @@ ENTER-PHASE LA2O3SS. ENTER-PAR G(LA2O3_CUBSS.87691*T..0)... ENTER-PAR G(MN1O2.. 182 .LA+3:O-2.. +SR_ALPHA+GHSEROO +15.SR+2:O-2..1*T. Grundy @@ @@ STOICHIOMETRIC PYROLYSITE...149E+05-7. 2 2 3 LA+3 SR+2.LA+3..0)..15 +GMN1O2..87691*T. ENTER-PAR G(LA2O3SS. +SRH_ALPH+GHSEROO+15. +SRX_ALPH2*GHSEROO+15. 2 2 3 LA+2 LA+3 SR+2. ENTER-PAR L(LA2O3_CUBSS. +SR_ALPHA-2*GHSEROO +15....SR+2:VA. 2 1 2 MN...87691*T.0) 298.15 +168700-78...0).. @@ ---------------------------------------------------------------------@@ Ternary oxides @@ @@ LA-SR-O. +LA_BETA-3*GHSEROO.0) 298.LA+3.SR+2:VA... O..0). 2 2 3 LA+3 SR+2. ENTER-PAR G(BETA.1*T..
.. 2 1 1 LA+3 SR+2 VA.. ENTER-PAR G(SRO.... 4 1 1 1 5 LA+3..5*GHSEROO +11. 3 4 3 9 LA+3. +GSM4_RP3.SR+2:MN+3:O-2:MN+4:VA..SR+2:MN+3:O-2:MN+3:VA.0) 298.. +GSM3_HEX-2.0).......SR+2:MN+3:O-2. ENTER-PAR G(SRMN3O6..0) 298... O-2 VA..15 +GL2MNO4..SR+2:MN+4:O-2.... +GSM4OZ-3*GHSEROO. O.SR+2:O-2... 3 7 2 16 LA. MN+2..LA+3:CR+6:O-2... ENTER-PAR G(SRO... @@ @@ LA-MN-O.Appendix ENTER-PAR G(BETA. O-2. ENTER-PAR G(SRMNO3_HEX. @@ La4Sr3O9. +GSROSOL..15 +GLA7.. 0.......15 +GLA16... MN+3 MN+4..0). @@ ENTER-PHASE SRMN3O6.SR+2:O-2. +GSM3_HEX+0. MN+3 MN+4.. O-2. CR+6.. @@ intermediate La-chromates @@ STOICHIOMETRIC LA16 @@ ENTER-PHASE LA16. ENTER-PAR G(LA4SR3O9. +GSM3OZ+0.. O-2.87691*T. CR.75*T.. +GS7M4. 5 1 2 3 1 3 SR+2.. ENTER-PAR G(SRMN3O6. ENTER-PAR L(BETA. ENTER-PAR G(LA2CR3. @@ @@ LA-CR-O.... ENTER-PAR L(BETA. O-2... +2*GLA2O3D+3*GSROSOL+229800 -136.. ENTER-PAR G(L2MNO4...0)..LA+3....0).LA:CR:O....... 3 16 7 44 LA.. O.0). ENTER-PAR G(SRMN3O6.15 -121000-237. ENTER-PAR G(LA2CRO6. Povoden @@ @@ STOICHIOMETRIC LA2CRO6 ENTER-PHASE LA2CRO6. @@ ENTER-PAR G(LA16.... +0... +GSM3OZ-2. MN+3..15 +GLMN2O5. Grundy @@ ENTER-PHASE SR7MN4O15..5*GLA2O3D+113700...0). MN+4.. O-2 VA. ENTER-PAR G(LMN2O5..LA:CR:O.0)..15 +GLA2CR3. Grundy @@ ENTER-PHASE L2MNO4. ENTER-PAR G(SR7MN4O15. @@ ENTER-PHASE SR4MN3O10.. CR+6..0) 298..5*GHSEROO +11. ENTER-PAR G(SRO.. @@ ENTER-PHASE SRMNO3_HEX.0) 298. 3 2 3 12 LA+3. SR+2.66666667*RE_BETA+15.0) 298.SR+2:VA.15 +GLA2CRO6. 3 2 1 4 LA+3. +SR_ALPHA+416100-2*GHSEROO +0...LA+3:MN+3:MN+4:O-2.0) 298..SR+2:MN+3:O-2:MN+4:O-2......LA+3..0). 183 .. @@ SrO Solid Solution ENTER-PHASE SRO.LA+3:CR+6:O-2..0). MN+4.5*GHSEROO +11. ENTER-PAR G(SRMN3O6... @@ ENTER-PAR G(LA7. Stoichiometric ENTER-PHASE LA4SR3O9..... 3 7 4 15 SR+2. O-2. O-2. 3 4 3 10 SR+2. MN+4. @@ @@ SR-MN-O. @@ STOICHIOMETRIC LA7 @@ ENTER-PHASE LA7..0).. 3 2 1 6 LA+3...23859*T. ENTER-PAR G(SR4MN3O10...23859*T.5*GHSEROO +11. O-2.0).. O-2.SR+2:VA. MN+3.. O-2..LA+3:MN+2:O-2.23859*T.0).0) 298.SR+2:MN+4:O-2. @@ @@ STOICHIOMETRIC LA2CR3O12 ENTER-PHASE LA2CR3.LA+3:SR+2:O-2. ENTER-PAR G(SRMNO3_HEX..8*T..0).SR+2:MN+3:O-2:MN+3:O-2.SR+2:MN+3:VA.VA:O-2. @@ ENTER-PHASE LMN2O5. +GSM4OZ..0) 298.8*T..15 -121000-237. CR...23859*T........ 3 1 1 3 SR+2....LA+3:O-2..
VA:O-2. ENTER-PAR BMAGN(MN2O3.. @@ @@ SR2.MN+3:O-2:VA.MN+2..87691*T... ENTER-PAR L(MNO_HALIT.MN+3:VA:VA..0) 298.0) 298.CR+3:O-2:VA. MN+3 MN+4.SR+2:MN+4:VA.CR+3:O-2:VA.15 0. O-2. ENTER-PAR G(MN2O3. ENTER-PAR G(SCO4. +GSM4_HEX-3*GHSEROO....0) 298.87691*T.15 +3*GSROSOL+GMN2O3+GHSEROO. ENTER-PAR G(MN2O3. ENTER-PAR G(MNO_HALIT... O-2.MN+2:O-2....15 +308.5*GCR2O3-7.CR+3:O-2.CR+3:O-2:O-2..MN+2..15 +GCR2O3+GHSEROO +100000+15...SR+2:SR+2:MN+4:O-2.. O-2..93845*T +71549. ENTER-PAR G(RP2...0) 298..15 +GCR2O3-3*GHSEROO.. ENTER-PAR G(MN2O3.87691*T. @@ @@ Mn2O3 (Compatible with C-Y2O3. +GSM4_HEX.0) 298..67CR2O8 ENTER-PHASE S3C2N. 4 1 2 2 7 SR+2..MN+3:O-2:VA. Grundy... ENTER-PAR G(SC2O4.. @@ @@ SR-CR-O.CR+3:VA:VA.59. 3 1 2 7 SR+2.15 +GCR2O3+3459... O.. 3 1 2 4 SR+2.. CR.0) 298. ENTER-PHASE MNO_HALIT. ENTER-PAR G(MN2O3...0) 298.... ENTER-PAR G(MNO_HALIT. Grundy modified it in LSM modeling ENTER-PHASE RP2.15 +GMN1O1.15 +GSC2O4. ENTER-PAR TC(MN2O3....15 +GS4O_RP2.15 +GS3C2O8. ENTER-PAR G(MNO_HALIT.65131533E+04.666667 2 8 SR.0) 298... ENTER-PAR L(MNO_HALIT. Chen.0) 298.Appendix ENTER-PAR G(SRMNO3_HEX.15 +GMN2O3+GHSEROO +100000+15.1) 298. CR+4.. O-2 VA.0) 298.15 +GMN2O3-2*GHSEROO +100000+15....0) 298. ENTER-PAR G(MNO_HALIT. 3 2 1 4 SR+2.0) 298.SR+2:CR+4:O-2. doubtful phase @@ ENTER-PHASE SC2O7......0) 298...15 +4... ..15 +GMN2O3.MN+3:O-2. @@ @@ RP2...15 +0.SR+2:MN+4:O-2.. 3 2 3 1 MN+3 CR+3. ENTER-PAR G(SRMNO3_HEX.87691*T..SR+2:CR+6:O-2. ENTER-PAR G(RP2.15 +3... O-2.15 +GMN2O3-3*GHSEROO.. @@ ENTER-PAR G(SC2O7..MN+3:VA:O-2.MN+3:O-2..15 +GCR2O3-2*GHSEROO +100000+15.CR+3:VA:O-2.CR+3:O-2:VA.0) 298.0) 298...28 ENTER-PAR TC(MN2O3..0) 298.15 +GSCO4.0)... Grundy. Povoden-Karadeniz ENTER-PHASE SCO4. CR+6. @@ SR2CRO4 ENTER-PHASE S2CO4.15 +GS2CO4.SR+2:CR+3:O-2..0) 298.0) 298.5213 -22. Povoden-Karadeniz 184 .0).MN+3:O-2:VA. Povoden-K. O-2. CR+6..15 +GMN1O1-21883... ENTER-PAR G(MN2O3.0) 298.... Povoden-Karadeniz) ENTER-PHASE MN2O3. @@ SRCRO4....0) 298...1853365*T.. @@ @@ CR-MN-O....SR:CR:O...15 -4.. O-2. @@ SRCR2O7. AMEND-PHASE MN2O3 MAGN.... ENTER-PAR G(MN2O3.0) 298.SR+2:SR+2:MN+3:O-2.. 3 2. Povoden @@ @@ SRCR2O4 ENTER-PHASE SC2O4..15 +GSC2O7... 3 1 1 4 SR+2.6.15 +309... 2 1 1 MN+2 MN+3 CR+3 VA.. ENTER-PAR G(S2CO4.....0) 298. NONSTOICHIOMETRIC CR2O3 SOLID SOLUTION.SR+2:CR+6:O-2.MN+3:O-2.... ENTER-PAR G(MN2O3. CR+3. @@ @@ ESKOLAITE. SR+2.15 +0.... ENTER-PAR G(MN2O3. Povoden @@ @@ NONSTOICHIOMETRIC MANGANOSITE (MNO) SOLID SOLUTION. ENTER-PAR G(S3C2N..0) 298.3..... O-2 VA..MN+3:O-2:O-2.21048766E+04. ENTER-PAR BMAGN(MN2O3..0) 298.
ENTER-PAR TC(CR2O3....0) 298..15 +GMN2O3+GSERCR+39503. 4 1 2 2 7 SR+2.0) 298.. ENTER-PAR BMAGN(CR2O3. CR+3 VA.0) 298.CR+2:CR+3:O-2. Grundy @@ ENTER-PHASE LS3MN2O7.CR+2:VA:O-2. 3 1 2 4 MN+2 CR+2...666666666667*GHSERCR -5..15 +GTMN3O4.0) 298. ENTER-PAR TC(CR2O3. ENTER-PAR G(CR2O3. ENTER-PAR BMAGN(CR2O3...0).0) 298.15 +GCRO0 -0.0) 298..15 +GCMN3O4...15 +GTSPINEL.23859*T.59..15 +0..15 +GCRO0 +. @@ @@ CUBIC SPINEL. ENTER-PAR G(CR2O3..15 +309. ENTER-PAR G(TMNCR2O4...MN+3:VA:O-2.MN+2:CR+3:O-2.... MN+3 MN+4...15 +GSPINEL..0) 298... ENTER-PAR TC(CR2O3.15 +3.15 +0. Grundy.33333333334*GHSERCR -5..0) 298.SR+2:LA+3:MN+4:O-2.0) 298. Grundy.15 +3.47717*T. ENTER-PAR G(CR2O3... ENTER-PAR TC(CR2O3..28 ENTER-PAR TC(CR2O3..0) 298. 3 1 1 3 LA+3 SR+2 VA....6. ENTER-PAR G(CMNCR2O4.0) 298. MN+3 CR+3..0) 298.0) 298. 3 1 2 4 MN+2.CR+3:CR+3:O-2.. ENTER-PAR G(TMNCR2O4...0) 298..2923*T.SR+2:MN+2:O-2.. +GMS3O+GL2O-GL3OR2*GHSEROO+22. ENTER-PAR G(LS3MN2O7.0) 298.. LA+3 SR+2. +GMS3O+GL2O-GL3OR+GHSEROO +22..MN+3:VA:O-2.15 +308..CR+3:VA:O-2. @@ -----------------------------------------------------------------------@@ Quaternary oxides @@ @@ La-Sr-Mn-O..15 +GCR3O4+GCMN3O4-GSPINEL..CR+2:CR+3:O-2..15 +308. Povoden-Karadeniz ENTER-PHASE CMNCR2O4. ENTER-PAR G(RPEROV. +GMS4O.....SR+2:MN+2:VA.0) 298.......47717*T....6....15 +308..CR+3:VA:O-2.15 +GS4O_RP2.0) 298.CR+2:CR+3:O-2.6.15 +3*GSROSOL+GMN2O3 +GHSEROO. ENTER-PAR G(CR2O3. ENTER-PAR BMAGN(CR2O3. ENTER-PAR G(LS3MN2O7.0). +GMS3O+0.0) 298. @@ -----------------------------------------------------------------------@@ Quinary phases. AMEND-PHASE CR2O3 MAGN.0) 298. ENTER-PAR G(LS3MN2O7.. O-2.MN+3:CR+3:O-2.15 +3... ENTER-PAR TC(CR2O3..0) 298.SR+2:SR+2:MN+4:O-2. @@ DISTORTED_SPINEL..Appendix ENTER-PHASE CR2O3... ideal extensions from lower-order systems @@ @@ high temperature rhombohedral perovskite.MN+3:VA:O-2. ENTER-PAR G(LS3MN2O7. ENTER-PAR G(CMNCR2O4.. ENTER-PAR BMAGN(CR2O3.0) 298.. O-2.... O-2.. Grundy. Povoden-Karadeniz ENTER-PHASE TMNCR2O4...0)...SR+2:LA+3:MN+3:O-2.MN+2:MN+3:O-2. O-2.15 +308..CR+3:VA:O-2.SR+2:MN+4:O-2. ENTER-PAR G(CMNCR2O4.CR+3:CR+3:O-2.15 +GCR2O3+GHSERCR. MN+3 CR+3...SR+2:SR+2:MN+3:O-2.5*GHSEROO+11..0) 298..0) 298.15 +3. ENTER-PAR G(CR2O3.. 3 2 1 3 MN+3 CR+2 CR+3. 185 .SR+2:MN+3:O-2.0) 298... ENTER-PAR G(CMNCR2O4. ....MN+2:MN+3:O-2.. ENTER-PAR BMAGN(CR2O3.. ENTER-PAR G(CR2O3. O-2 VA.15 +309. ENTER-PAR BMAGN(CR2O3...2923*T..MN+3:CR+3:O-2.. ENTER-PAR G(RPEROV.CR+2:CR+3:O-2.CR+2:MN+3:O-2....CR+2:VA:O-2.0) 298.15 +GL3O_RP2. @@ ENTER-PAR G(RPEROV..6.. Povoden-Karadeniz ENTER-PHASE RPEROV.....CR+2:VA:O-2......0).15 +GCR3O4.0) 298...15 +GMN2O3+39503.59.0) 298... MN+2 MN+3 MN+4 CR+3 CR+4 VA. ENTER-PAR G(RPEROV..0) 298...15 +GCR2O3.MN+3:CR+3:O-2.CR+3:CR+3:O-2....MN+2:CR+3:O-2.15 +GL3O_RP2+GS4O_RP2 -3*GSROSOL -GMN2O3-GHSEROO-R_RP2.
.82596*T. G(RPEROV..LA+3:CR+4:VA.. ENTER-PAR G(RPEROV....0).. +GLACRO3.0).. +GN-0.....0).. ENTER-PAR G(RPEROV.33333*GL4O +GHSEROO+4.66667*GL4O+0. G(RPEROV.....0).0). ENTER-PAR G(RPEROV. ENTER-PAR G(RPEROV. +GL2O-2.... +GN+0.5*GV4O+0. G(RPEROV.0). ENTER-PAR G(RPEROV..0).LA+3:MN+2:VA. +GL2O+0... +0.0).SR+2:VA:VA.. ENTER-PAR G(RPEROV.5*GHSEROO -1. ENTER-PAR G(RPEROV. +GLACRO3+1. +GL2O+1.. +GL3OR+1.VA:MN+3:O-2. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.41263*T.LA+3:MN+3:VA...5*GVCR4O+0..1666667*GS4O -0.35057*T.5*GHSEROO+11. ENTER-PAR G(RPEROV...0)...8333333*GS4V..35056*T..62121*T.5*GV4O+0. G(RPEROV..5*GVVV-2*GL4O -1.LA+3:CR+3:VA. GS4O+GLACRO3-GN-0.SR+2:VA:O-2.VA:MN+2:VA...5*GHSEROO+11. ENTER-PAR G(RPEROV. +0.0).333*GL4O -2*GHSEROO+4. +GS4V. ENTER-PAR G(RPEROV. +GL3OR-3*GHSEROO..VA:MN+4:VA.0). +2*GVCR4O+0..VA:VA:VA.41263*T.Appendix ENTER-PAR G(RPEROV...LA+3:MN+2:O-2.23859*T.SR+2:CR+4:VA... +2*GL4O+0.16666667*GS4V+GLACRO3 -3*GHSEROO.LA+3:MN+4:VA.VA:CR+3:VA.41263*T.5*GVVV -2*GLACR4O-1.0)... ENTER-PAR G(RPEROV.0).....5*GVCR4O+0. G(RPEROV. GS4O-GN-0..166667*GVVV -3.35057*T..0).... +GLACRO3-3*GHSEROO.3333*GVVV -1.5*GV4O -0.. ENTER-PAR G(RPEROV. +2*GV4O+0.3333*GVVV-1. +2*GV4O+0.....VA:CR+3:O-2.0).SR+2:MN+3:VA. +GLACRO3+1... ENTER-PAR G(RPEROV..5*GHSEROO -1.. +GMS3O-GL3OR+2*GL4O -1. +GL3OR....SR+2:CR+3:VA..0)..41263*T.16666667*GS4V.0).SR+2:CR+3:O-2.........VA:CR+4:O-2. +GMS3O-2.SR+2:CR+4:O-2.5*GHSEROO-1.8333333*GS4O +0. G(RPEROV.. +2*GVCR4O+0.0)...0). ENTER-PAR G(RPEROV.0).41263*T. G(RPEROV.5*GVVV-2*GL4O +1..0).VA:MN+4:O-2.166667*GVVV -0....VA:CR+4:VA.. ENTER-PAR G(RPEROV.33333*GVVV -1.76318*T..0).5*GV4O+0..5*GVVV -2*GLACR4O+1. ENTER-PAR G(RPEROV.LA+3:VA:O-2.1666667*GS4O +0.0).5*GHSEROO+5.... +GVVV..66667*GL4O+0..5*GHSEROO+1. ENTER-PAR G(RPEROV.0).5*GV4O -1..0)..41263*T.5*GV4O -0. +GL3OR+1.76318*T..2386*T..VA:VA:O-2..5*GHSEROO+5... G(RPEROV... +GS4O.5*GVVV +1.LA+3:CR+4:O-2..5*GVVV-2*GL4O -GHSEROO+9.333*GLACR4O -2*GHSEROO+4.0).VA:MN+3:VA....33333*GLACR4O +GHSEROO+4...0).0)...35056*T. +2*GL4O-1..5*GV4O+0...0)..0). ENTER-PAR G(RPEROV..... +GVVV+3*GHSEROO.LA+3:CR+3:O-2.33333*GVVV-1...LA+3:MN+4:O-2.5*GV4O+0.16666667*GS4V.5*GHSEROO +1. ENTER-PAR G(RPEROV..SR+2:MN+4:VA. +GMS4O-3*GHSEROO.5*GHSEROO+11.5*GHSEROO-1. +GMS3O+2*GL4O-1. @@ Optimized interactions 186 .1666667*GS4O +0..5*GVVV-1. ENTER-PAR G(RPEROV.2386*T..LA+3:MN+3:O-2.5*GVVV-GL3OR -GHSEROO+12.62121*T..0).LA+3:VA:VA.. ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR ENTER-PAR G(RPEROV.5*GVVV +2*GHSEROO+12..5*GV4O +0.
..1) 298. ENTER-PAR L(RPEROV. @@ ENTER-PAR G(RP...SR+2:SR+2:CR+4:O-2:O-2..MN+3:O-2. ENTER-PAR L(RPEROV. ENTER-PAR L(RPEROV.SR+2:SR+2. ENTER-PAR L(RPEROV.. 20.....1) 298. @@ ENTER-PAR L(RP. ENTER-PAR L(ION.. @@ ENTER-PAR G(RP.SR+2:CR+4.0) 298.15 +2*GSROSOL+0.LA+3:CR+3.. ENTER-PAR G(ION...0) 298...0) 298...0) 298. @@ ENTER-PAR G(RP..0).CR+2:O-2...LA+3:O-2..0) 298.1) 298...15 -1.15 +GLA2O3LIQ..15 +121000. ENTER-PAR G(ION.. ENTER-PAR L(ION..SR+2:MN+3:O-2..0) 298.5*GHSEROO..15 +GCR2O3_L. scarce experimental data @@ ENTER-PHASE RP.15 1.15 GS2CO4..15 +GMN2O3_L..SR+2:MN+2:O-2....0) 298. @@ ENTER-PAR G(RP..CR+2:VA..0) 298.5*GMN2O3 @@ -0.LA+3. ENTER-PAR G(ION.15 -11316.0) 298..LA+3. ENTER-PAR L(RPEROV....15 GS2CO4+GLCR3O_RP1 @@ -GREFRP.1).. ENTER-PAR G(ION.. ENTER-PAR L(RPEROV.MN+2:O-2.MN+2:VA.. @@ next two interaction parameters can be used to fit @@ Cr4+ amount in perovskite ENTER-PAR L(RPEROV..15 -119062..15 -1297.SR+2:MN+4:VA.LA+3:MN+4.15 +121000. 187 .0)...5*t. -117000. LA+3 SR+2.VA...SR+2:SR+2:MN+3:O-2:O-2.LA+3.1).LA+3:CR+3..MN+2:VA.. 250000.CR+3:VA.0) 298.0) 298. ENTER-PAR L(RPEROV..LA+3.LA+3. ENTER-PAR L(RPEROV. @@ ENTER-PAR L(RP...MN+2:VA.15 3766.LA+3....MN+3:VA.LA+3:VA....LA+3..... @@ ENTER-PAR G(RP.....MN+3:O-2..15 -4.1)..SR+2:LA+3:CR+4:O-2:O-2. @@ Interaction parameters from ternaries ENTER-PAR L(ION.0) 298..15 +2*GSROLIQ.38590000E+04.CR+3:O-2..SR+2:LA+3:CR+3:O-2:O-2.0) 298.15 +GL3O_RP1+GS4O_RP1 @@ -2*GSROSOL-0.MN+3:O-2. AMEND-PHASE IONIC_LIQUID COMP 2.Appendix ENTER-PAR L(RPEROV.....5*GMN2O3 @@ +0.LA+3..... ENTER-PAR L(RPEROV.6.LA+3:CR+4:O-2:O-2.SR+2:MN+4:O-2.. -2. ENTER-PAR G(ION. @@ @@ Ruddlesden-Popper phase.5*GHSEROO.15 0.SR+2:SR+2. ENTER-PAR L(ION.. O-2....LA+3:MN+4. ENTER-PAR G(ION....SR+2:SR+2:CR+3:O-2:O-2.MN+2:O-2..15 +GLCR3O_RP1.MN+2:O-2. ENTER-PAR G(ION.. O-2 VA. -136600.. @@ Interaction parameters from binaries ENTER-PAR L(ION.VA:O-2..0) 298.VA.LA+3:CR+3...15 -3..1) 298. ENTER-PAR L(ION.0) 298. @@ ENTER-PAR G(RP.VA. ENTER-PAR L(RPEROV.VA:O-2.. ideal extension from lower-order systems..... ENTER-PAR G(ION. @@ ENTER-PAR G(RP. MN+3 MN+4 CR+3 CR+4.0) 298....0) 298..15 +GS4O_RP1.0) 298.. ENTER-PAR L(RPEROV.15 100000...0) 298.CR+3:O-2..0).....15 100000. -117000.15 +2*GCR_L+GCR2O3_L-3*GCR1O1_L.0) 298..LA+3:CR+3:O-2:O-2..MN+3:O-2...15 GREFRP.0) 298. ENTER-PAR G(ION.SR+2:MN+2:VA.SR+2:CR+4.15 2*GCR1O1_L.SR+2:O-2..0) 298.MN+2:O-2. ENTER-PAR L(ION..VA:MN+4:O-2.15 +GLALIQ..SR+2:SR+2:MN+4:O-2:O-2.0) 298.. Povoden-Karadeniz ENTER-PHASE IONIC_LIQUID Y LA+3 SR+2 MN+2 MN+3 CR+2 CR+3. ENTER-PAR G(ION..4..15 +2*GMN_L+GMN2O3_L-3*GMN1O1_L..0)..0) 298.LA+3:CR+4. @@ ENTER-PAR G(RP.0) 298..29519000E+05. ENTER-PAR L(RPEROV.....15 +GMN_L...MN+4:O-2... @@ O-2.0) 298.0) 298.. 250000.SR+2:LA+3:MN+3:O-2:O-2.. ENTER-PAR L(ION.15 0....VA:O-2.15 +GL3O_RP1.54590000E+04.. ENTER-PAR G(ION. -136600...0).15 +2*GMN1O1_L.0) 298.MN+3:O-2. ENTER-PAR G(ION.MN+2..1)..VA.LA+3:CR+3.0) 298.15 185. preliminary..... 5 1 1 1 3 1 SR+2.MN+3:O-2... 9248.0) 298..15 +GCR_L..SR+2:VA.LA+3.15 +GSRLIQ...CR+2:O-2.SR+2:LA+3:MN+4:O-2:O-2.0) 298. ENTER-PAR L(RPEROV. @@ -----------------------------------------------------------------------@@ Liquid.0) 298....MN+3:O-2..15 +11368..
ENTER-PAR G(GAS...MN+2:VA..0) 298...... 20000 N ENTER-PAR G(GAS..0) 298. ENTER-PAR L(ION..15 -39016..... ENTER-PAR G(GAS.SR+2..0) 298....15 -101850..15 +F10666T+RTLNP..0) 298.15 +GCRH6O6_G+RTLNP...1) 298.15 -39016.CR+2:VA.15 +GCRH1O3_G+RTLNP. ENTER-PAR G(GAS..0) 298.0) 298.15 +F10729T+RTLNP.....CR+3:O-2....15 -101850.0) 298.15 -179575.SR+2.0) 298.0) 298.MN+2.... ENTER-PAR L(ION.15 -176300.15 200000.15 +GCRH2O4_G+RTLNP..15 -9111.0) 298. ENTER-PAR G(GAS..0) 298.0) 298..15 +GCRH5O5_G+RTLNP....0) 298. ENTER-PAR L(ION.0) 298.15 +46000. 6000 N ENTER-PAR G(GAS.SR+2. 20000 N @@ @@ O2 reference gas ENTER-PHASE O2GAS.CRH1O1.CR+2:VA.CRH2O3.0) 298.0) 298.CR+2:O-2. ENTER-PAR G(GAS.15 +GCR1O1_G+RTLNP.15 +GCR1O2_G+RTLNP. ENTER-PAR L(ION.0) 298..CR+2:VA.0) 298.CRH4O5. 1 O2...CR+3:O-2....LA+3..1) 298.H.0) 298...CRH1.H2O1...0) 298...CRH6O6.MN+3:O-2..Appendix ENTER-PAR L(ION. ENTER-PAR L(IONIC.... @@-----------------------------------------------------------@@ Cr-GAS. 6000 N ENTER-PAR G(GAS.15 +GCRH2O2_G+RTLNP. ENTER-PAR L(ION..LA+3.CRH4O4..0) 298....15 +GCRH4O5_G+RTLNP.15 +64573-23*T.H1O1.CR1O2..0) 298.0) 298..0) 298.O2. ENTER-PAR G(GAS...0) 298..0) 298. ENTER-PAR L(IONIC.. 20000 N ENTER-PAR G(GAS. ENTER-PAR L(ION. ENTER-PAR G(GAS.15 -188487.15 +F14021T+RTLNP. ENTER-PAR L(ION.SR+2.15 +GCRH1O2_G+RTLNP.1) 298.. 6000 N ENTER-PAR G(GAS.15 +H2GAS+RTLNP.LA+3. 1 H2O1. ENTER-PAR G(GAS.CR+3:O-2. ENTER-PAR G(GAS.15 -176300.H1O2.H2O1.15 +504+0. ENTER-PAR G(GAS.CRH1O2.15 -619869.CR+2:VA.0) 298..15 +HGAS+RTLNP....CR+2:O-2. 6000 N ENTER-PAR G(GAS.... ENTER-PAR G(GAS. ENTER-PAR L(IONIC.15 -179575..CRH2O2.1) 298.O3. 1 CR1O3.CRH3O3. 6000 N ENTER-PAR G(GAS.MN+3.0) 298...H2. 188 . @@ @@ H2O reference gas ENTER-PHASE STEAM.SR+2. ENTER-PAR G(GAS.CRH1O3.LA+3......SR+2..0) 298. 20000 N ENTER-PAR G(GAS. SGTE and reassessments by Chen.LA+3..15 -15009+13.15 +GCRH2O3_G+RTLNP. ENTER-PAR L(ION..0) 298.15 +F10983T+RTLNP.15 +GCRH4O4_G+RTLNP..MN+2:O-2.O.LA+3.CR1O3.SR+2.15 +F10963T+RTLNP...CR+2:VA..15 +GCRH1O1_G+RTLNP..CRH3O4...15 +F13704T+RTLNP.. ENTER-PAR G(CRGAS.0) 298.CR1O3.CR+2:O-2.15 +F7586T+RTLNP. ENTER-PAR G(STEAM...15 +F10963T+RTLNP.0) 298.0) 298.H2O2.0) 298.6587*T. ENTER-PAR G(GAS.....7..0) 298.. ENTER-PAR L(ION.15 +GCRH3O4_G+RTLNP.15 -119062.. 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.. ENTER-PAR G(GAS. ENTER-PAR L(ION. ENTER-PAR L(ION...1) 298.SR+2.15 +GCRH3O3_G+RTLNP.15 +60713-5..0) 298..15 +F13349T+RTLNP.MN+3:O-2...15 +GCR1O3_G+RTLNP.. @@ @@ CRO3 reference gas ENTER-PHASE CRGAS..CR+2:O-2.0) 298..0) 298.CRH5O5.LA+3. 1500 N ENTER-PAR G(GAS....CR1O1.49*T.9479*T. ENTER-PAR L(IONIC.CRH2O4. ENTER-PAR G(GAS..0) 298.MN+2..CR+3:O-2.15 -619869.CR+3:O-2.15 +GCR1O3_G+RTLNP.MN+2:VA.4) 298. 6000 N ENTER-PAR G(GAS...LA+3. ENTER-PAR L(IONIC. ENTER-PAR L(ION. ENTER-PAR L(IONIC.1) 298.
..O2.. N... set-interactive +2*GHSEROO+RTLNP.Appendix ENTER-PAR G(O2GAS. 189 ..0) 298..15 @@ GO PAR @@ SET-OUT-LEVEL..
1992-1999 Geoscience Studies. Dr. Badertscher. 1973. Ludwig J. carbon and strontium isotope systematics in two profiles across the Glarus thrust: implications for fluid flow. Nonmetallic Inorganic Materials. Povoden. Abart. Graz. Petrol. Erwin Date and place of birth: March 18. M. Rainer Abart 1983-1991 Realistisches Gymnasium. 143. Oxygen. Dr. Department of Materials. 192-208. thesis: „ Thermodynamic Database of the La-Sr-Mn-Cr-O Oxide System and Applications to Solid Oxide Fuel Cells“. ETH Zurich. Dr.Curriculum vitae Curriculum Vitae Personal data Povoden-Karadeniz. 2002. Graz Publications R. 190 . Prof. and E. Contr. Karl-Franzens University Graz Master thesis: „Kontaktmetamorphose und Fluid-Gestein-Interaktion in der östlichen Monzoni Kontaktaureole“. Georg Hoinkes and Prof. Switzerland. N. Gauckler. Pestalozzistrasse 5. Prof. Berliner Ring. pp. D. Burkhard.. Graz 1979-1983 Elementary School. Miner. Austria Education 01/2005 – 12/2008 Ph.
J.. M. A.J. Petrol. Povoden. and L. A. and L. Ivas. Gauckler. Int.J. 97. Phase Equilib. T.N.. Povoden. J.J.N. Grundy. T. Grundy. M. and L. 2006. 30.J. to be submitted. 27.N. 2006. Chen.Curriculum vitae E.J.N. Gauckler. A. pp. Res. Gauckler. Chen. 33-41. to be submitted. T.N. Miner. Gauckler. and L. pp. Diff. Thermodynamic assessment of the Mn-Cr-O system for solid oxide fuel cell (SOFC) materials. Povoden. 2009. M. A.J. 1. 2006.J. A. Chen. Grundy. Ivas. Degradation of planar solid oxide fuel cells with (La1-xSrx)1-yMnO3 cathodes and Cr-alloy interconnects. Grundy. Calculation of defect chemistry using the CALPHAD approach. Gauckler.. Povoden. E. A. Gauckler. and L. pp. Povoden. Povoden. 353-62. and L.J. Abart. Phase Equilib. and L. E.Diff. Diff.N. pp. Gauckler. 99-120. Thermodynamic assessment of the La-Fe-O system. to be submitted. A. E. 569-78.N. T. Grundy. Phase Equilib. Thermodynamic calculations of impacts of chromium on Sr-doped Lanthanum manganite (LSM) cathodes for solid oxide fuel cells (SOFC). Ivas. Calphad. Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole. J. 2002. Gauckler. and L. Povoden. E. Grundy. Horacek. M. 12-27. Thermodynamic reassessment of the Cr-O system in the framework of solid oxide fuel cell (SOFC) research. Povoden. Thermodynamic La-Sr-Mn-Cr-O oxide database for solid oxide fuel cell applications. Povoden.J.. Grundy. 76. Chen. (accepted) E. E. J. E. pp. Gauckler 191 . Presentations Assessment of the Cr-O system in the frame of SOFC research E. and R. E. M. Povoden-Karadeniz. Thermodynamic assessment of the La-Cr-O system. and L. Ivas. Mater.
and L. Gauckler Poster Presentation CALPHAD XXXVI.J. August 4th. Vienna. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fel cell (SOFC) materials E. and L. Colorado. A. 2006 The BiO3/2-SbO3/2-ZnO Phase Diagram at 1115°C in air E.J. EMPA Dübendorf. Pennsylvania State University. Switzerland. 2005 Thermodynamic Assessment of the Cr-Mn-O System for Solid Oxide Fuel Cell (SOFC) Materials E. Povoden. September 18th – 22nd. Netherlands. A. October 20th. Peng.J. May 06th -11th. Gauckler Oral Presentation HTMC XII. Z. Switzerland. A. 2006 Thermodynamic assessment of the La-Mn-Cr-O system for applications on solid oxide fuel cell (SOFC) materials using the CALPHAD approach E. and L. Povoden.N. Grundy. Povoden. Grundy. USA. 2005 Thermodynamic assessment of the Cr-Mn-O system for solid oxide fuel cell (SOFC) materials E. Maastricht. and L. 2007 Thermodynamic assessment of the La-Cr-O and LaO3/2-MnOx-CrO3/2 Systems 192 . Boulder.N. Gauckler Oral Presentation 3rd Fuel Cell Research Symposium. USA. Grundy. Povoden.D. students.N.Curriculum vitae Poster Presentation CALPHAD XXXIV.J. Austria. March 16th. EMPA Dübendorf. Povoden Oral Presentation 1st EMPA symposium for Ph. Pennsylvania. May 6th – 11th. Gauckler Oral Presentation Thermo 2006.
Lehrstuhl für physikalische Chemie.N. Povoden Oral Presentation Guest Talk. 2007 The thermodynamic LaO1. Gauckler Oral Presentation CALPHAD XXXVI.5-CrO1. Pennsylvania. and L. Finland.5-CrO1.5-SrO-FeO1. A. Monatnuniversität Leoben.J.N. A. Pennsylvania State University. 2007 Thermodynamic modeling for solid oxide fuel cell research . USA. May 6th – 11th. 2008 Thermodynamic LaO1. Povoden.5 and LaO1.J. Chen.The La-Sr-Mn-Cr-O system E. Grundy.Curriculum vitae E. and L. 2008 193 .5 databases for SOFC applications using the CALPHAD approach E. Saariselkä. June 16th – 21st. M.5-SrO-FeO1.5-CrO1.5-SrO-MnO1. ETH Zurich.5-SrO-MnO1.5 and LaO1. March 28th. June 27th. Gauckler Oral Presentation CALPHAD XXXVII.5 databases for solid oxide fuel cells (SOFC) applications E. Povoden. Povoden Oral Presentation 2nd MRC Graduate Symposium . Grundy.5-CrO1.
2007.5 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.X)3 is to be used…” Thus the model was also corrected in the thermodynamic assessment of the La-Fe-O system. The following argumentation for modeling of the oxygen solubility in bcc using (physically wrong!) Me(O. Hallstedt et al.Va)1. lines 7-14 and Table 4. Diff.Erratum.Cr)(O. J. 112 According to the latest discussion by B. otherwise the disordered model for interstitials in bcc. In previous papers the authors have proposed the model Me(Va. p.3. accepted.. Phase Equilib.” . 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.. p 2837 the correct model is (La.Cr)(O.O)1. 109.O)3 is undoubtedly a reasonable model description for the oxygen solubility in bcc.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. For these reasons. 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.Va)3 and not (La.Va)1.. 31(1). p. Povoden-Karadeniz et al.3.5 based on the argument.5…. 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. (Me)1(Va. Calphad.
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.