Acta Metall Sin  2020, Vol. 56 Issue (6): 801-820    DOI: 10.11900/0412.1961.2019.00451
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Progress in Research on the Alloying of Binary Immiscible Metals
HUANG Yuan(), DU Jinlong, WANG Zumin
School of Materials Science and Engineering, Tianjin University, Tianjin 300354, China
Abstract

Materials based on binary immiscible metal systems are widely used in aerospace, nuclear fusion engineering, electronic packaging, anti-armor weapons and other fields. However, due to the positive formation heat and the large differences in the properties of the component, the direct alloying of binary immiscible metals and the preparation of the corresponding materials are very difficult. Varieties of methods have been developed for direct alloying of binary immiscible metals at home and abroad, and the thermodynamic and diffusion mechanism of these methods have been studied. In this review, firstly the principle and thermodynamic mechanism of mechanical alloying, physical vapor deposition and ion beam mixing, as well as their applications in binary immiscible metal powder alloys and nano-multilayer films are reviewed. Then the irradiation damage alloying (IDA) and high-temperature structure induced alloying (HTSIA) methods that are proposed and developed by our group are introduced. Besides, the principle, interfacial microstructure, thermodynamic mechanism, diffusion mechanism and application of these two methods were described in detail. Finally, the development trend of the research on alloying of binary immiscible metals is proposed.

 ZTFLH: TG131
Fund: National Key Research and Development Program of China(2018YFB0703904);National Key Research and Development Program of China(2017YFE0302600);National Natural Science Foundation of China(51471114);National Natural Science Foundation of China(51171128)
Corresponding Authors:  HUANG Yuan     E-mail:  yi_huangyuan@tju.edu.cn
 Fig.1  Schematic illustrations of severe plastic defor-mation process(a) high pressure torsion (P—pressure)(b) equal channel angular extrusion (R—outer angular radius, Φ—inner corner angle, ψ—outer corner angle)(c) accumulative roll bonding Fig.2  Schematic diagram of physical vapor deposition(a) vacuum evaporation (b) sputtering Fig.3  Schematic diagram of ion beam mixing Fig.4  Preparation process of the immiscible W/Ag, Mo/Ag and Mo/Cu laminated metal composites (LMCs) by irradiation damage alloying (IDA)[100]Color online Fig.5  EDX line-scanning results of the cross-section of the W/Ag LMCs[100]Color online(a) drift corrected spectrum profile (b) EDX line-scanning profile along the red-line in Fig.5a Fig.7  EDX line-scanning results of the cross-section of the Mo/Cu LMCs[100,102]Color online(a) drift corrected spectrum profile (b) EDX line-scanning profile along the red-line in Fig.7a Fig.8  Microscopic characterization for the interface of the W/Ag LMCs[100](a) HRTEM image (b) corresponding SAED pattern Fig.9  Microscopic characterization for the interface of the Mo/Ag LMCs[100,101](a) HRTEM image (b) corresponding SAED pattern Fig.10  Microscopic characterization for the interface of the Mo/Cu LMCs[100](a) HRTEM image (b) corresponding SAED pattern Fig.11  Variable energy positron annihilation spectroscopy (VEPAS) results of various samples[101] (S is the line shape parameter of Doppler broadening data, SB is the parameter that is normalized to the defect-free S value)(a) S parameter vs positron implantation energy for the pre-annealed pure Mo and the Ag+ implanted Mo(b) S parameter vs positron implantation energy for the pre-annealed pure Mo and the Mo/Ag laminated samples with a 100 nm thick Ag layer annealed at different temperatures Table 1  S parameter values and corresponding depth of the S peak for the Mo/Ag laminated samples annealed at different temperatures[101] Fig.6  EDX line-scanning results of the cross-section of the Mo/Ag LMCs[100,101]Color online(a) drift corrected spectrum profile (b) EDX line-scanning profile along the red-line in Fig.6a Fig.12  Cross-section TEM image for the Mo/Ag laminated sample annealed at 800 ℃ for 4 h (a) and the magnified image of the region marked with a white rectangular frame in Fig.12a (b)[101] Fig.13  Schematic view of the forming process of the Kirkendall voids in the Mo/Ag laminated sample[101] (IIPDs—irradiation-induced point defects )Color online Fig.14  Preparation process of the Nb/Cu joint by high-temperature structure induced alloying (HTSIA)[107] (F—force) Fig.15  HRTEM observation of the W/Cu interface of W/Cu joint prepared through the direct diffusion bonding[109]Color online(a) EDX line-scanning compositional profile(b) HRTEM image at W/Cu interface(c) filtered image of the region marked with blue rectangle in Fig.15b Fig.16  HRTEM images of microstructures of theW50Cu50 sintered powder metallurgy materials prepared by milling for 30 h (a) and 40 h (c) and subsequent sintering at 980 ℃ for 3 h, and the corresponding SAED patterns of Figs.16a and c (b, d)[109] (Insets in Figs.16a and c show the EDX results of W50Cu50 sintered powders) Fig.17  DSC curves of the original and annealed W and Cu rods[109] Fig.18  DSC curves of the 40 h milled W50Cu50 powder mixture before and after being annealed[109] Fig.19  Calculated curves of Gibbs free energy change for the alloying in W-Cu system[109](Einitial—total initial energy of W-Cu system, ΔGalloying—Gibbs energy for the alloying between W and Cu, $ΔGalloyingc$—Gibbs energy for the formation of W/Cu crystalline phases, $ΔGalloyinga$—Gibbs energy for the formation of W/Cu amorphous phases)