Calculation of interaction of AlCl, AlCl₂ and AlCl₃ on Al₄C₃ (001) Al₄CO₄ (001) and Al₂CO (001) planes

Abstract

To make sure the intermediate products of the carbothermic reduction of Al₂O₃ process, such as Al₄CO₄, Al₂CO and Al₄C₃, and the interaction of AlCl, AlCl₂, AlCl₃ with Al₄CO₄, Al₂CO and Al₄C₃, respectively, thermodynamic analyses were used to study the chloride reaction production of them under the vacuum situation. The stable structures and electronic properties of AlCl, AlCl₂ and AlCl₃ adsorbed on Al₄CO₄, Al₂CO and Al₄C₃ were calculated by first-principles calculations by the CASTEP module in the Materials Studio program. The results show that the AlCl₃ and AlCl₂ molecules have decomposed on the plane of Al₄C₃ (001), while there are no obvious decomposition of AlCl₃ and AlCl₂ on Al₄CO₄ (001) and Al₂CO (001) planes. The adsorption of AlCl on the Al₄CO₄ (001) and Al₂CO (001) planes is stronger than that on the Al₄C₃(001) plane. The interaction strength of AlCl₃, as well as AlCl₂, with Al₄CO₄, Al₂CO and Al₄C₃ is in the sequence of Al₄CO₄<Al₂CO<Al₄C₃, while the interaction strength of AlCl with Al₄CO₄, Al₂CO and Al₄C₃ is in the sequence of Al₄CO₄>Al₂CO>Al₄C₃.

Keywords

Ab initio / chloride reaction / carbothermic reduction / Al₄C₃ / Al₄CO₄ / Al₂CO

References

[1] YuQ-c, YuanH-b, ZhuF-long. Carbothermic reduction of alumina with carbon in vacuum [J]. Journal of Central South University, 2012, 19(7): 1813-1816

[2] FengY-b, YangB, DaiY-nian. Thermodynamics of carbothermal reduction of alumina in vacuum [J]. The Chinese Journal of Nonferrous Metals, 2011, 21(7): 1748-1755

[3] HalmannM, FreiA, SteinfeldA. Vacuum carbothermic reduction of Al₂O₃, BeO, MgO-CaO, TiO₂, ZrO₂, HfO₂+ZrO₂, SiO₂, SiO₂+Fe₂O₃, and GeO₂ to the metals: A thermodynamic study [J]. Mineral Processing and Extractive Metallurgy Review, 2011, 32(4): 247-266

[4] RhamdhaniM A, DewanM A, BrooksG A, MitchellJ B, PrenticeL. Alternative Al production methods [J]. Mineral Processing and Extractive Metallurgy, 2013, 122(2): 87-104

[5] YuQ-c, YuanH-b, ZhuF-long. Carbothermic reduction of alumina with carbon in vacuum [J]. Journal of Central South University, 2012, 19(7): 1813-1816

[6] KruesiM, GalvezM E, HalmannM, SteinfeldA. Solar aluminum production by vacuum carbothermal reduction of alumina: Thermodynamic and experimental analyses [J]. Metallurgical and Materials Transactions B, 2011, 42(1): 254-260

[7] YuanH-b, ZhuF-l, YangB, YuQ-c, XuB-q, DaiY-nian. Aluminum production by alumina carbothermic reduction-chlorination in vacuum [J]. Chinese Journal of Vacuum Science and Technology, 2010, 30(6): 582-587

[8] FengY-b, YuQ-c, YangB, DaiY-nian. Extraction of aluminum from alumina by disproportionation process of AlCl in vacuum [J]. Transactions of Nonferrous Metals Society of China, 2013, 23(9): 2781-2785

[9] ZhuF-l, YangB, YuanH-b, YuQ-c, XuB-q, DaiY-nian. Behavior analysis of silica in aluminum production by alumina carbothermic reduction-chlorination process in vacuum [J]. Vacuum, 2011, 85(10): 968-971

[10] LiQ-x, ShenH-l, YangB, DaiY-nian. Thermodynamic study of aluminum sub-oxide formation and decomposition in vacuum condition [J]. Nonferrous Metals Engineering, 2009, 61(3): 58-61

[11] YuanH-b, YangB, XuB-q, YuQ-c, FengY-b, DaiY-nian. Aluminum production by carbothermo-chlorination reduction of alumina in vacuum [J]. Transactions of Nonferrous Metals Society of China, 2010, 20(8): 1505-1510

[12] ZhuF-l, YangB, YuQ-c, XuB-q, DaiY-nian. Study on mechanism of aluminum production by alumina carbothermic reduction-chlorination process in vacuum [C]. EPD Congress, 2011, San Diego, John Wiley & Sons, Inc.: 613-620

[13] YeD-lunPractical Handbook of the thermodynamic data for inorganic compounds [M], 2002, Beijing, Metallurgical Industry Press

[14] BarinI, KnackeO, KubaschewskiO, HesselmanKThermochemical properties of inorganic substances [M], 1991, Berlin, Springer Verlag

[15] LandoltBThermodynamic properties of inorganic material [M], 1999, Berlin, Springer-Verlag

[16] BarinI, PlatzkiGThermochemical data of pure substances, Part I [M], 1993, Weinheim, VCH Verlags Gesellschaft

[17] BonnieJ MThermodynamic data for fifty reference elements [M], 1993, Cleveland, National Aeronautics and Space Administration

[18] GesingT M, JeitschkoW. The crystal structures of Zr₃Al₃C₅, ScAl₃C₃, and UAl₃C₃ and their relation to the structures of U₂Al₃C₄ and Al₄C₃ [J]. Journal of solid state chemistry, 1998, 140(2): 396-401

[19] CoxJ H, PidgeonL M. The X-ray diffraction patterns of aluminum carbide Al₄C₃ and aluminum oxycarbide Al₄O₄C [J]. Canadian Journal of Chemistry, 1963, 41(6): 1414-1416

[20] HeyrmanM, ChatillonC. Thermodynamics of the Al-C-O ternary system I. Second and third law critical analysis of oxycarbide enthalpies from vapor pressure determinations [J]. Journal of the Electrochemical Society, 2006, 153(7): E119-E130

[21] DluzewskiP A, GóreckaJ, KozlowskiM, PaszkowiczW, YamaguchiA. Transmission electron microscopy and X-ray diffraction studies of Al₂CO microcrystals [J]. Materials Chemistry and Physics, 2003, 81(2): 383-386

[22] YuanH-b, FengY-b, YangB, YuQ-c, XuB-q, WangP-yan. Thermal behavior of alumina in process of carbothermic reduction and chloride to produce aluminum [J]. The Chinese Journal of Nonferrous Metals, 2010, 20(4): 777-783

[23] BernasconiL, MaddenP A, WilsonM. Ionic to molecular transition in AlCl3: An examination of the electronic structure [J]. Phys Chem Comm, 2002, 5(1): 1-11

[24] YuW-z, YangB, ZhuF-l, JiangW-l, YuQ-c, XuB-qiang. Investigation of chlorination process in aluminum production by carbothermic-chlorination reduction of Al₂O₃ under vacuum [J]. Vacuum, 2012, 86(8): 1113-1117