+ 210+ ACTA METALLURGICA SINICA (ENGLISH EDITION) Series B. Vol. 2 No. 3 pp 210-212 Jun 1989 LOCAL EQUILIBRIUM METHOD IN STUDYING PHASE DIAGRAM OF Mn-MnO SYSTEM CHEN Qiyuan Central South University of Technology. Changsha, China (Originally published in ACTA METALL SIN (CHINESE EDN) 24(6) 1988 pp B440—B442, received 15 June 1987: in revised form 28 November 1987] A special method based on the local equilibrium principle has been introduced in the research of the phase diagram of Min-MnO system, With this method, the problems of volatilization of Mn and the corrosion of Min and MnO 10 refractory materials were prevented efficiently. The solubility of oxygen in Ma and the composition of the interface between MnO and Mn were derermined. Partial phase diagram of Mn~MnO system were constructed according to pres- end experimental results KEY WORDS local equilibrium method, Mn~Mn0 system, phase diagram Mn-O system is an important basic system in metallurgical industry. Therefore the study of thermodynamic properties of this system is important in both theoretical and practical respects. However, there seems no complete phase diagram of Mn—O system so far. Especially, the phase diagram of Mn—MnO does not be experimentally studied due to the special experimental diffi- culties. They came from the very low equilibrium pressure of oxygen, high pressure of manganess vapour together with strong corrosion of Mn and MnO to the refractory materials, ete Asa part of the thermodynamic study of Mn-O system, a special local equilibrium method has been introduced to overcome the difficulties mentioned above and satisfactory results have been obtained 1, Experiments Using general static method, very long processing period is necessary to obtain the equilibrium composition at a certain temperature. But vast amount of Mn would volatilize during a long heating period. This problem makes the following method adoptable: two pieces of specimen of different phasse were brought into close contact at a certain temperature, and the unequilibrated components would mutually diffuse between the two phases. As a result, composition gradient in each phase woutd be set up. Not very long after, although the compositions far away from the interface remain unchanged, the concentrations by the interface would be approximately equal to the equilibrium concentrations of the two phases. Thus a local equilibrium at the interface migth be considered to have been set up. To decrease the volatilization of Mn and to avoid the difficulty resulting from its corrosiveness to refractory materials, a piece of metal Mn was compacted in MnO powder and pressed into a shape of cylinder. The sample was sintered and then kept at a given constant tem- perature for an appropriate period. After quenching at ~30 , the quenched sample was ana- lysed with the method of electron probe microunalysis. This method is similar to diffusion coup- te method used in the study oFalloy’s phase diagram. Based on the compositions of both phases at the interface. the tie lines in phase diagram were determined. There are some difficulties in the quantitative analysis of oxygen using electron probé method. Two standard samples simulating the two phases studied were prepared beforehand to obtain results as accurate as possible. A sample of metal Mn with known oxygen content was used as the standard of Mn phase. and a sample of stoichiometric MnO was used as the stand-2u- ard of MnO phase. The tests were made on an electron probe (model CAMEBAX-MICRO). ‘Fhe probe was calibrated frequently with standard samples to avoid the errors coming from any drift of the apparatus, 4—5 points within 10 em of the interface at 3—4 places with clear limits of intermediate layers were determined for each phase of each sample. Average values were used as the compositions of each phase. ‘The phases were contirmed by X-ray diffraction. 2. Results The results of electron probe microanalysis are shown in Table I. The solubility of oxygen in Table 1 Results of electron probe micreanal ysis ‘Specimen Temperature %O mol Ne °c MnO Mn B 1317 a9 (0.19 c 1365 478 0.146 D 1417 49.6 = E 1464 2.6 0.150 F 1515 499 0157 6 1256 74 0.180 1 1567 50.t 0,163 3 1243 478 = Mn could be expressed as In(%O mol)=~717.8/ T-1.454 (1) From the combination of Eq.(1) and the model of dilute solution, the eutectic tem- perature of Mn—Mn0 system was calculated to be 1242 and the eutectic composition to be 0.146%0 mole. The contents of Mn in solid solution of MnO could be expressed as In(%Mn mole)= 29660 / T-16.89 (2) Extrapolating Eq.) to eutectic temperature, the equilibrium content of Mn at eutectic temperature would be 14.70%Mn mole, or 46.0%O mole. Partial phase diagrams of this composition range are shown in Fig.1 and 2 12001 — grins meta) —| M65 nhoo|_7jMnemnofe ° oi _—o7 Mn %Omet Fig. 1 Part of the phase diagram of Mn-MnO system (0—0.3% O mol) Fig. 2. Part of phase diagram of Mn-MnO system (44-80% O mol)212- }. Discussion Schenck and co—workers [2] determined the oxygen content in molten Mn contained in an MnO crucible. Their results were much lower than those of present work and eutectic composition was only 0.033%0 mole. However, their eutectic temperature, 1242'C, was the same as that of present work. Thus, the results of present work should be more reliable than theirs. Several works [3—6] discovered that there is n—conductivity of MnO in extremely low pres- sure of oxygen and there are interstitial Mn ions with two effective charges. Picard and Gerdanian [3] and Bocquet and co—workers [6] assumed that there are slight solubility (substoichiometry) of Mn in MnO at the phase boundary toward Mn. At extremely low pressure of oxygen, the concentration of interstitial Mn ions is higher than other defects. But they did not experimentally estimate the composition range of this oxide. Present work has determined the composition. This experimental results are consistent with their assumption. According to present work, it can be seen that the local equilibrium method is a useful tool for studying the phase diagrams of metal oxides, especially for the system which can not be pro- cessed in a long-term heating. Acknowledgments — Thanks for the advices of Prof. Chen Xinmin, as well as the advices and helps of Prof. Jin Zhanpeng of the author’ s university and Associate Research Professor Xu Leying of Institute of Metal Re- search, Academia Sinica, Shenyang. ‘This work is a part of a project supported by the Science Fund of the Academia Sinica. REFERENCES. 1 Chen Qiyuan. Phase Diagram of Manganese-Oxvgen System and Kinetics of Decomposition of Manganese Dioxide, Doctoral dissertation, Central South University of Technology, Changsha, 1986 (in Chinese) 2 Schenck H, Frohberg M G, Nunninghoif R. Arch Eisemhiittenwes, 1964: 35 : 269 3 Picard C, Gerdanian P. J Solid State Chem, 1974: 11 : 190 4 Klingsberg C, Roy R. J Ant Ceram Soc, 1960: 43 : 620 5 Erot NG, Wagner J BJr..J Electrochem Soc, 971; 118 + 1665 6 Bocquet J-P. Kawahara M, Lacombe P. C R Hebd Seances Aead Sci{Paris), 1967: 265 : 1338 Correspondent : CHEN Qiyuan, Associate Professor,Department of Chemistry, Central South University of ‘Technology, Changsha, China