Mostafa, Ahmad ORCID: https://orcid.org/0000-0001-5625-1106 (2014) Experimental Investigation of the Phase Equilibria in the Mg-Mn-{Ce, Nd} and Ce-Mg-Zn Ternary Systems and Diffusivity Measurements of the Mg-{Ce, Nd, Zn} and Zn-{Ce, Nd} Binary Systems. PhD thesis, Concordia University.
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Abstract
In this work, the 450°C Mg-Mn-{Ce, Nd} and 300°C Ce-Mg-Zn isothermal sections were established using diffusion couples and key alloys. The phase relationships were determined using XDR, EDS/WDS and metallography. Diffusion couples were also used to measure the interdiffusion coefficients of the Mg-{Ce, Nd, Zn} and Zn-{Ce, Nd} binary systems based on the experimental composition profiles and Boltzmann-Matano method.
No ternary compounds were found in the Mg-Mn-{Ce, Nd} isothermal sections at 450°C. Microstructures of the ternary diffusion couples showed stationary Mn grain morphology in most of the diffusion zones. This was attributed to the affinity of Ce and Nd to Mg atoms, which forming several Mg-{Ce, Nd} binary compounds during the diffusion process. However, some of these binary compounds dissolved Mn. The ternary solubility of (γ-Ce)Mg,Mn, (CeMg), (CeMg3), (CeMg12), (α-Nd)Mg,Mn, (MgNd) and (Mg3Nd) was measured at 450°C to be 3.0, 5.1, 3.2, 1.8, 3.0, 13.0 and 3.7 at.% Mn, respectively. In both systems, the phase boundary lines were pointing towards the Mn-rich corner, except for the (α-Nd)Mg,Mn+Mn17Nd2+(MgNd) phase field.
Eight ternary compounds were observed in the Ce-Mg-Zn isothermal section at 300°C. These are: τ1 (Ce6Mg3Zn19), τ2 (CeMg29Zn25), τ3 (Ce2Mg3Zn3), τ4 (CeMg3Zn5), τ5
iv
(CeMg7Zn12), τ6 (CeMg2.3-xZn12.8+x; 0≤x≤1.1), τ7 (CeMgZn4) and τ8 (Ce(Mg1-yZny)11); 0.096≤y≤0.43). The ternary solubility of Zn in Ce-Mg compounds was found to increase with the decrease in Mg concentration. Accordingly, the ternary solid solubility of Zn in (CeMg12) and (CeMg3) was measured as 5.6 and 28.4 at.% Zn, respectively.
Diffusion couples with Boltzmann-Matano analysis were used to calculate the interdiffusion coefficients of the Mg-{Ce, Nd, Zn} and Zn-{Ce, Nd} systems. A systematic annealing procedure was followed to obtain all expected phases in the studied systems. For the available literature data for some of the compounds in the Mg-{Ce, Nd, Zn} systems, the calculated interdiffusion coefficients are in good agreement. The activation energy and the pre-exponential factor for the growth of the Mg-{Ce, Nd, Zn} compounds were determined using Arrhenius equation. The activation energies of the growth of the Mg-Ce compounds showed relatively higher values than those of Mg-Nd and Mg-Zn compounds.
Divisions: | Concordia University > Gina Cody School of Engineering and Computer Science > Mechanical and Industrial Engineering |
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Item Type: | Thesis (PhD) |
Authors: | Mostafa, Ahmad |
Institution: | Concordia University |
Degree Name: | Ph. D. |
Program: | Mechanical Engineering |
Date: | 20 May 2014 |
Thesis Supervisor(s): | Medraj, Mamoun |
Keywords: | Ternary phase diagrams, Magnesium alloys, Diffusion couples, Interdiffusion coefficients, Diffusivity, EDS/WDS, Key alloys, Equilibrium |
ID Code: | 978654 |
Deposited By: | AHMAD MOSTAFA |
Deposited On: | 26 Nov 2014 14:27 |
Last Modified: | 18 Jan 2018 17:47 |
References:
[1] D. Eliezer, E. Aghion, F. Froes, Magnesium science, technology and applications, Advanced Performance Materials, 5 (1998) 201-212.[2] M. Bamberger, G. Dehm, Trends in the Development of New Mg Alloys, Annu. Rev. Mater. Res., 38 (2008) 505-533.
[3] C. Blawert, N. Hort, K.U. Kainer, Automotive applications of magnesium and its alloys, Transactions- Indian Institute of Metals, 57 (2004) 397-408.
[4] B. Mordike, T. Ebert, Magnesium: Properties - Applications - Potential, Materials Science and Engineering 302 (2001) 37-45.
[5] H. Friedrich, B. Mordike, Magnesium Technology, Springer-Verlag, Berlin, 2006.
[6] J.J. Kim, D.S. Han, Recent development and applications of magnesium alloys in the Hyundai and Kia Motors Corporation, Materials Transactions, 49 (2008) 894 to 897.
[7] M. Mezbahul-Islam, A. Mostafa, M. Medraj, Essential magnesium alloys binary phase diagrams and their thermochemical data, Journal of Materials, (2014) Article ID: 704283, (In press).
[8] J. Bohlen, S. Yi, D. Letzig, K.U. Kainer, Effect of rare earth elements on the microstructure and texture development in magnesium–manganese alloys during extrusion, Materials Science and Engineering: A, 527 (2010) 7092-7098.
[9] H.-Y. Qi, G.-X. Huang, H. Bo, G.-L. Xu, L.-B. Liu, Z.-P. Jin, Thermodynamic description of the Mg–Nd–Zn ternary system, Journal of Alloys and Compounds, (2011) 3274–3281.
[10] A. K. Meshinchi, Improving the properties of magnesium alloys for high temperature applications, in: F. Czerwinski (Ed.) Magnesium Alloys – Design, Processing and Properties, InTech, 2011.
[11] B. Mordike, K. Kainer, Magnesium alloys and their applications, Willey-VCH, Weinheim, 2000.
[12] J. Cai, G. Ma, Z. Liu, H. Zhang, A. Wang, Z. Hu, Influence of rapid solidification on the mechanical properties of Mg-Zn-Ce-Ag magnesium alloy, Materials Science and Engineering: A, 456 (2007) 364-367.
[13] J.S. Kirkaldy, Diffusion in multi component metallic systems: II. Solutions for two-phase systems with applications to transformations in steel, Canadian Journal of Physics, 36 (1958) 907-916.
[14] J.S. Kirkaldy, L.C. Brown, Diffusion behaviour in ternary, multiphase systems, Canadian Metallurgical Qarterly, 2 (1963) 89-115.
[15] J.-C. Zhao, Methods for phase diagram determination, Elsevier Science, Amsterdam, 2007.
[16] M. Mezbahul-Islam, M. Medraj, Experimental study of the Cu–Ni–Y system at 700°C using diffusion couples and key alloys, Journal of Alloys and Compounds, 561 (2013) 161-173.
[17] H. Xu, Y. Du, Z. Zhou, Z. Jin, Determination of phase diagrams using the diffusion couple technique, Rare Metals, 25 (2006) 427-430.
[18] J.C. Zhao, M.R. Jackson, L.A. Peluso, Mapping of the Nb–Ti–Si phase diagram using diffusion multiples, Materials Science and Engineering: A, 372 (2004) 21-27.
[19] B. Predel, Si-Ti (Silicon-Titanium), in: O. Madelung (Ed.) Pu-Re – Zn-Zr, Springer Berlin Heidelberg, 1998, pp. 1-3.
[20] A. Kodentsov, G. Bastin, F. Loo, The diffusion couple technique in phase diagram determination, Journal of Alloys and Compounds, 320 (2001) 207-217.
[21] F.C. Campbell, Phase diagrams: Understanding the basics, in, ASM International, Ohio, 2012.
[22] H. Mehrer, Diffusion in solids (Fundamentals, methods, materials, diffusion-controlled processes), Springer-Verlag Berlin Heidelberg, Heidelberg, 2007.
[23] P. Shewmon, Diffusion in solids, Second ed., McGraw-Hill, New york, 1963.
[24] C. Matano, On the relation between the diffusion-coefficients and concentrations of solid Metals, Japanese Journal of Physics, 8 (1933) 109-113.
[25] W. Callister, D. Rethwisch, Materials science and engineering: An introduction, 7th ed., John Wiley & Sons, Inc., United States, 2007.
[26] P. Echlin, Handbook of Sample Preparation for Scanning Electron Microscopy and X-Ray Microanalysis, Springer Science and Business Media, LLC, Cambridge, 2009.
[27] J.I. Goldstein, D. Newbury, D. Joy, C. Lyman, P. Echlin, E. Lifshin, L. Sawyer, J.R. Michael, Scanning electron microscopy and X-ray microanalysis, 3 ed., 2003 Kluwer Academic/Plenum Publishers, New York, 2003.
[28] R. Egerton, Physical Principles of Electron Microscopy: An Introduction to TEM, SEM, and AEM, Springer Science and Business Media, Inc, New York, USA, 2005.
[29] Y. Leng, Materials Characterization: Introduction to Microscopic and Spectroscopic Methods, JohnWiley & Sons (Asia) Ltd., Hong Kong 2008.
[30] T. Takenaka, Y. Narazaki, N. Uesaka, M. Kawakami, Improvement of corrosion resistance of magnesium alloys by surface film with rare earth element, Materials Transactions, 49 (2008) 1071-1076.
[31] D. Petrov, M. Mirgalovskaya, I. Strelnikova, E. Komova, The state diagram for magnesium corner of the Mg-Mn-Ce system, Baikov Institute of Metallurgy and Materials Science, 1 (1957) 144-147.
[32] L. Rolla, A. Iandelli, Contributions to the Knowledge of Rare Earth Metals and Their Alloys. The Alloys of Lanthanum with Manganese, Berichte der deutschen chemischen Gesellschaft (A and B Series), 75 (1942) 2091-2095.
[33] A. Iandelli, The Ce-Mn alloys, Proceedings of the National Academy of Sciences, 13 (1952) 265-268.
[34] B. Thamer, The system cerium-manganese in the range of 0-20 atomic percent manganese, Journal of the Less Common Metals, 7 (1964) 341-346.
[35] A. Palenzona, S. Cirafici, The Ce-Mn (Cerium-Manganese) system, Journal of Phase Equilibria, 17 (1996) 53-56.
[36] C. Tang, Y. Du, H. Xu, S. Hao, L. Zhang, Study on the nonexistence of liquid miscibility gap in the Ce-Mn system Journal of Mining and Metallurgy, 43 (2007) 21-28.
[37] C. Tang, Y. Du, L. Zhang, H. Xu, Z. Zhu, Thermodynamic assessment of the Ce-Mn system, Journal of Alloys and Compounds, 437 (2007) 102-106.
[38] Y. Kang, A. Pelton, P. Chartrand, P. Spencer, C. Fuerst, Critical evaluation and thermodynamic optimization of the binary systems in the Mg-Ce-Mn-Y system, Journal of Phase Equilibria and Diffusion, 28 (2007) 342-354.
[39] D. Petrov, M. Mirgalovskaya, I. Strelnikova, E. Komova, The Constitution Diagram for the Magnesium-Manganese System, Institute of Materials Science, Academy of Sciences of the Ukrainian SSR, 1 (1958) 142-143.
[40] N. Tiner, The Solubility of Manganese in Liquid Magnesium, Metals Technology, (1945) 1-7.
[41] A. Nayeb-Hashemi, J. Clark, The Mg−Mn (Magnesium-Manganese) system, Journal of Phase Equilibria, 6 (1985) 160-164.
[42] J. Gröbner, D. Mirkovic, M. Ohno, R. Schmid-Fetzer, Experimental investigation and thermodynamic calculation of binary Mg-Mn phase equilibria, Journal of Phase Equilibria and Diffusion, 26 (2005) 234-239.
[43] M. Asgar-Khan, M. Medraj, Thermodynamic description of the Mg-Mn, Al-Mn and Mg-Al-Mn systems using the modified quasichemical model for the liquid phases, Materials Transactions, 50 (2009) 1113-1122.
[44] X. Zhang, D. Kevorkov, I.-H. Jung, M. Pekguleryuz, Phase equilibria on the ternary Mg-Mn-Ce system at the Mg-rich corner, Journal of Alloys and Compounds, 482 (2009) 420-428.
[45] D. Wood, E. Cramer, Phase relations in the magnesium-rich portion of the cerium-magnesium system, Journal of the Less Common Metals, 9 (1965) 321-337.
[46] Q. Johnson, G. Smith, The crystal structure of Ce5Mg42, Acta Crystallographica, 22 (1967) 360-365.
[47] J. Pahlman, J. Smith, Thermodynamics of formation of compounds in the Ce-Mg, Nd-Mg, Gd-Mg, Dy-Mg, Er-Mg, and Lu-Mg binary systems in the temperature range 650to 930K, Metallurgical and Materials Transactions B, 3 (1972) 2423-2432.
[48] A. Nayeb-Hashemi, J. Clark, The Ce-Mg (Cerium-Magnesium) system, Journal of Phase Equilibria, 9 (1988) 162-172.
[49] A. Saccone, D. Macciò, S. Delfino, F. Hayes, F. Ferro, Mg-Ce alloys. Experimental investigation by Smith thermal analysis, Journal of Thermal Analysis and Calorimetry, 66 (2001) 47-57.
[50] ASM Handbook, Volume 03 - Alloy Phase Diagrams, ASM International, Ohio, 1992.
[51] X. Zhang, D. Kevorkov, M. Pekguleryuz, Stoichiometry Study on the Binary Compounds in the Mg-Ce System: Part I, Journal of Alloys and Compounds, 475 (2009) 361-367.
[52] H. Okamoto, Ce-Mg (Cerium-Magnesium), Journal of Phase Equilibria and Diffusion, 32 (2011) 265–266.
[53] X. Zhang, D. Kevorkov, M. Pekguleryuz, Study on the binary Intermetallic compounds in the Mg-Ce system, Intermetallics, 17 (2009) 496-503.
[54] X. Zhang, D. Kevorkov, M. Pekguleryuz, Study on the intermetallic phases in the Mg-Ce system: Part II. Diffusion couple investigation, Journal of Alloys and Compounds, 501 (2010) 366-370.
[55] P. Villars, L. Calvert, Pearson’s Crystal Data, Crystal Structure Database for Inorganic Compounds, CD-ROM software version 1.3, (2009).
[56] G. Raynor, Constitution of Ternary and Some Complex Alloys of Magnesium, International metals reviews, 22 (1977) 65-96.
[57] M. Pezat, A. Hbika, B. Darriet, Study of alloy composition CeMg11M (M = V, Cr, Mn, Fe, Co) and their application in hydrogen storage, Materials Research Bulletin, 15 (1980) 139-146.
[58] PANalytical, Ver2.2b (2.2.2), in, Almelo, The Netherlands, 01-11-2006.
[59] Y.-N. Zhang, D. Kevorkov, F. Bridier, M. Medraj, Experimental study of the Ca–Mg–Zn system using diffusion couples and key alloys, Science and Technology of Advanced Materials, 12 (2011) 1-13.
[60] J.A. Gann, A.W. Winston, Magnesium and its alloys, Industrial and Engineering Chemistry, 19 (1927) 1193-1201.
[61] Y. Xu, L.S. Chumbley, F.C. Laabs Liquid metal extraction of Nd from NdFeB magnet scrap, Journal of Materials Research, 15 (2000) 2296-2304.
[62] D. Wellbeloved, P. Craven, J. Waudby, Manganese and Manganese Alloys, in: Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co., 2000.
[63] V.T. Witusiewicz, F. Sommer, E.J. Mittemeijer, Reevaluation of the Fe-Mn phase diagram, Journal of Phase Equilibria and Diffusion, 25 (2004) 346-354.
[64] A. Saccone, S. Delfino, R. Ferro, Systematics of rare earth-manganese alloys: Nd-Mn phase diagram, International Journal of Materials Research, 84 (1993) 563-568.
[65] Y. Kang, A. Pelton, P. Chartrand, P. Spencer, C. Fuerst, Thermodynamic database development of the Mg-Ce-Mn-Y system for Mg alloy design, Metallurgical and Materials Transactions A, 38 (2007) 1231-1243.
[66] A. Nayeb-Hashemi, J. Clark, The Mg−Nd system (Magnesium-Neodymium), Bulletin of Alloy Phase Diagrams, 9 (1988) 618-623.
[67] S. Delfino, A. Saccone, F. Ferro, Phase relationships in the neodymium-magnesium alloy system, Metallurgical and Materials Transactions A, 21 (1990) 2109-2114.
[68] R. Joseph, K. Gschneidner, Solid solubility of magnesium in some lanthanide metals, Transactions of the American Institute of Mining and Metallurgical Engineers, 233 (1965) 2063-2069.
[69] J.J. Park, L.L. Wyman, Phase Relationships in Magnesium Alloys., in, WADC Technical report: Astia Document No. AD142110, 1957, pp. 1-27.
[70] M. Drits, E. Padezhnova, N. Miklina, The combined solubility of noedymium and zinc in solid magnesium, Russian Metallurgy (Metally), 3 (1974) 143-146.
[71] L.L. Rokhlin, Magnesium alloyscontaining rare earth metals: Structure and properties, Taylor and Francis, New York, 2003.
[72] H. Kirchmayr, W. Lugscheider, Die Zustandsbilder Neodym-Samarium- und Terbium-Mangan, Zeitschrift für Metallkunde, 61 (1970) 22-23.
[73] S. Makhalenko, Y. Kuz'ma, X-ray diffraction investigations of the Nd-Mn system, Izvestiya Akademii Nauk SSSR, Neorganicheskie Materialy (Inorganic Materials (USSR)), 26 (1990) 2432-2433.
[74] A.O. Mostafa, A.E. Gheribi, D. Kevorkov, M. Mezbahul-Islam, M. Medraj, Experimental investigation and first-principle calculations coupled with thermodynamic modeling of the Mn–Nd phase diagram, Calphad, 42 (2013) 27-37.
[75] M. Drits, Z. Sviderskaya, L. Rokhlin, Alloys of the Mg-Mn-Nd system adjacent to the magnesium corner, Zhurnal neorganjoheskoi Khimii (Journal of Inorganic Chemistry), 7 (1963) 2771-2777.
[76] M. Drits, N. Bochvar, Phase equilibria in the Mg-Nd-Mn-Ni system, Doklady Akademii Nauk SSSR 178, No. 2 (1968) 403-405.
[77] V.I. Dybkov, Growth Kinetics of Chemical Compound Layers, Cambridge Int Science Publishing, Cambridge, UK, 2004.
[78] A.A. Kodentsov, G.F. Bastin, F.J.J. Van Loo, The diffusion couple technique in phase diagram determination, Journal of Alloys and Compounds, 320 (2001) 207-217.
[79] S. Gorsse, C. Hutchinson, B. Chevalier, J. Nie, A thermodynamic assessment of the Mg-Nd binary system using random solution and associate models for the liquid phase, Journal of Alloys and Compounds, 392 (2005) 253-262.
[80] M. Huang, H. Li, H. Ding, Y. Ren, G. Qin, S. Hao, Partial phase relationships of Mg-Zn-Ce system at 350°C, Transactions of Nonferrous Metals Society of China, 19 (2009) 681-685.
[81] P. Ghosh, M. Mezbahul-Islam, M. Medraj, Critical assessment and thermodynamic modeling of Mg–Zn, Mg–Sn, Sn–Zn and Mg–Sn–Zn systems, Calphad, 36 (2012) 28-43.
[82] Y.M. Zhu, A.J. Morton, J.F. Nie, Improvement in the age-hardening response of Mg–Y–Zn alloys by Ag additions, Scripta Materialia, 58 (2008) 525-528.
[83] G. Omori, S. Matsuo, H. Asada, Precipitation process in a Mg-Ce alloy, Transactions of the Japan Institute of Metals, 16 (1975) 247-256.
[84] M.-l. Huang, H.-x. Li, H. Ding, L. Bao, X.-b. Ma, S.-m. Hao, Intermetallics and phase relations of Mg-Zn-Ce alloys at 400 °C, Transactions of Nonferrous Metals Society of China, 22 (2012) 539-545.
[85] A.M. Korolkov, Y.P. Saldau, Solubility of Zn and Ce in Mg in the Solid State, Izvestiia Sektora fiziko-khimicheskogo analiza, 16 (1946) 295-306.
[86] E.V. Melnik, M.F. Kostina, Ya.P. Yarmlyuk, O.F. Zmii, Study of the Magnesium-Zinc-Cerium and Magnesium-Zinc-Calcium Ternary Systems, Magnievye Splavy, Mater.Vses. Soveshch. Issled., Razrab. Primen. Magnievyhk Splavov, (1978) 95-99.
[87] M.E. Drits, E.I. Drozdova, I.G. Korolkova, V.V. Kinzhibalo, A.T. Tyvanchuk, Investigation of Polythermal Sections of the Mg-Zn-Ce System in the Mg-Rich Region, Russian Metallurgy (Metally), 2 (1989) 195-197.
[88] U. Kolitsch, P. Bellen, S. Kaesche, D. Maccio, N. Bochvar, Y. Liberov, P. Rogl, Cerium-Magnesium-Zinc, in: G. Effenberg, G. Petzow (Eds.) Ternary Alloys –A Comprehensive Compendium of Evaluated Constitutional Data and Phase Diagrams, VCH Verlagsgesellscahft, MSI GmbH,Weinheim, Stuttgart, Germany, 2000, pp. 168–176.
[89] R. Agarwal, S. G. Fries, H. L. Lukas, G. Petzow, F. Sommer, T. G. Chart, G. Effenberg, Assessment of the Mg-Zn system, Zeitschrift für Metallkunde, 83 (1992) 216-223.
[90] D. Kevorkov, M. Pekguleryuz, Experimental study of the Ce-Mg-Zn phase diagram at 350°C via diffusion couple techniques, Journal of Alloys and Compounds, 478 (2009) 427-436.
[91] C.-n. Chiu, J. Gröbner, A. Kozlov, R. Schmid-Fetzer, Experimental study and thermodynamic assessment of ternary Mg–Zn–Ce phase relations focused on Mg-rich alloys, Intermetallics, 18 (2010) 399-405.
[92] V. Pavlyuk, B. Marciniak, E. Różycka-Sokołowska, The isothermal section of the phase diagram of Ce–Mg–Zn ternary system at 470 K, Intermetallics, 20 (2012) 8-15.
[93] H. Okamoto, Supplemental literature review of binary phase diagrams: Cs-In, Cs-K, Cs-Rb, Eu-In, Ho-Mn, K-Rb, Li-Mg, Mg-Nd, Mg-Zn, Mn-Sm, O-Sb, and Si-Sr, Journal of Phase Equilibria and Diffusion, 34 (2013) 251-263.
[94] Available online: www.MagNET.ubc.ca, (accessed on May 22, 2014).
[95] R. Ferro, A. Saccone, G. Borzone, Rare earth metals in light alloys, Journal of Rare Earths, 15 (1997) 45-61.
[96] X. Tao, Y. Ouyang, H. Liu, Y. Feng, Y. Du, Y. He, Z. Jin, Phase Stability of Magnesium-Rare Earth Binary Systems From First-Principles Calculations, Journal of Alloys and Compounds, 509 (2011) 6899-6907.
[97] X.K. Zhu, R.K. O'Nions, Monazite chemical composition: some implications for monazite geochronology, Contrib Mineral Petrol, 137 (1999) 351-363.
[98] N. Stanford, D. Phelan, The formation of randomly textured magnesium alloy sheet through rapid solidification, Acta Materialia, 58 (2010) 3642-3654.
[99] K. Lal, V. Levy, Study of the diffusion of cerium and lanthanum in magnesium, Comptes rendus hebdomadaires des séances. Série C: Sciences chimiques, 262 (1966) 107-109.
[100] Y. Xu, L. Chumbley, G. Weigelt, F. Laabs Analysis of interdiffusion of Dy, Nd, and Pr in Mg, Journal of Materials Research, 16 (2001) 3287-3292
[101] S. Brennan, K. Bermudez, Y. Sohn, Intermetallic growth and interdiffusion in the Mg-Nd system, in: W. Pool, K. Kainer (Eds.) 9th International Conference on Magnesium Alloys and th
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