过冷(Fe1 -x Co x)79.3B20.7 合金的凝固

doi:10.11900/0412.1961.2024.00291

金属学报

2025, Vol. 61

Issue (1): 99-108 DOI: 10.11900/0412.1961.2024.00291

研究论文

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过冷(Fe₁_-_x Co _x)_79.3B_20.7 合金的凝固

杨林¹, 马长松¹, 刘连杰¹^,², 李金富¹^,³(

)

1 上海交通大学材料科学与工程学院金属基复合材料国家重点实验室上海 200240
2 中国工程物理研究院材料研究所绵阳 621907
3 上海交通大学材料科学与工程学院上海市激光制造与材料改性重点实验室上海 200240

Solidification of Undercooled (Fe₁_-_x Co _x)_79.3B_20.7 Alloys

YANG Lin¹, MA Changsong¹, LIU Lianjie¹^,², LI Jinfu¹^,³(

)

1 State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
2 Institute of Materials, China Academy of Engineering Physics, Mianyang 621907, China
3 Shanghai Key Laboratory of Materials Laser Processing and Modification, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

引用本文:

杨林, 马长松, 刘连杰, 李金富. 过冷(Fe₁_-_x Co _x)_79.3B_20.7 合金的凝固[J]. 金属学报, 2025, 61(1): 99-108.
Lin YANG, Changsong MA, Lianjie LIU, Jinfu LI. Solidification of Undercooled (Fe₁_-_x Co _x)_79.3B_20.7 Alloys[J]. Acta Metall Sin, 2025, 61(1): 99-108.

全文: PDF(4629 KB) HTML

摘要:

M₂₃B₆金属硼化物是很多金属材料中的强化相。为揭示该化合物相在Fe-Co-B合金中的形成问题，本工作采用熔融玻璃净化法进行了名义成分合金(Fe_{1 -}_x Co _x)_79.3B_20.7 (x = 0~1)的深过冷凝固实验。研究发现：当x ≤0.6时，随着过冷度的增加，初生相依次从M₂B、M₂₃B₆转变为α-M/M₃B，并且0.4 < x ≤0.6成分的合金存在L + M₂B→M₃B的包晶转变；对于x >0.6的合金，小过冷度下凝固的初生相为M₃B，随着过冷度的增加，初生相进一步从M₂B、M₂₃B₆向α-M/M₃B变化。随着Co含量增加，M₂₃B₆相析出的临界过冷度减小，M₂₃B₆相的稳定性提高。

关键词 ： Fe-Co-B合金, 过冷, 非平衡凝固, 相选择

Abstract：

M-B (M = Fe, Co, Ni) alloys have garnered significant attention in the automotive, petrochemical, and power electronics industries owing to their excellent corrosion resistance, wear resistance, and high-temperature strength. The service performances of the M-B alloys are closely related to that of borides. Among them, M₂₃B₆ generally exists as a metastable phase. However, the understanding of its formation is limited compared to that of other borides. To reveal the effect of Fe/Co content ratio on the solidification behavior of the Fe-Co-B alloys, particularly the formation of M₂₃B₆ phase, alloys with nominal composition of (Fe_{1 -}_x Co _x)_79.3B_20.7 (x = 0-1) were undercooled using the melt fluxing technique. Consequently, the solidification behaviors were systematically investigated. With the increase in the Co content, the stable eutectic reaction changed from L→α-M + M₂B for x <0.4 to L→α-M + M₃B for x >0.4. Consequently, the two eutectic reactions occurred at the same temperature at x =0.4, and a peritectic reaction L + M₂B→M₃B was observed at x > 0.4. With the increase in the undercooling, the primary phase changes from M₂B and M₂₃B₆ to α-M/M₃B in the alloys with x ≤0.6, and from M₃B, M₂B, and M₂₃B₆ to α-M/M₃B in the alloys with x >0.6. The increase in Co content reduced the critical undercooling for the M₂₃B₆ phase to precipitate primarily and improved its stability, that is, the primary M₂₃B₆ phase decomposed into α-M/M₂B in the following cooling process when the Co content is not excessively high. However, it could sometimes be reserved to room temperature in case of a very large Co content.

Key words： Fe-Co-B alloy undercooling non-equilibrium solidification phase selection

收稿日期: 2024-08-20

ZTFLH:

TG111.4

基金资助:国家自然科学基金项目(52231002);国家自然科学基金项目(51821001)

通讯作者: 李金富，jfli@sjtu.edu.cn，主要从事非平衡凝固理论及先进金属材料方面的研究

Corresponding author: LI Jinfu, professor, Tel: (021)54748530, E-mail: jfli@sjtu.edu.cn

作者简介: 杨林，男，1994年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2024.00291 或 https://www.ams.org.cn/CN/Y2025/V61/I1/99

图1 Fe-B和Co-B二元相图、(Fe1 - x Co x)79.3B20.7母合金锭的XRD谱及(Fe1 - x Co x)79.3B20.7合金加热熔化差示扫描量热(DSC)曲线

图2 (Fe1 - x Co x)79.3B20.7母合金锭组织的OM像

图3 (Fe0.8Co0.2)79.3B20.7合金的凝固冷却曲线、XRD谱及不同过冷度(ΔT)下合金组织的OM像

图4 (Fe0.6Co0.4)79.3B20.7合金的凝固冷却曲线、XRD谱及不同过冷度下合金组织的OM像

图5 ΔT = 44 K时(Fe0.6Co0.4)79.3B20.7合金的组织

图6 (Fe0.4Co0.6)79.3B20.7合金的凝固冷却曲线、XRD谱及不同过冷度下合金组织的OM像和EBSD像

图7 (Fe0.2Co0.8)79.3B20.7合金的凝固冷却曲线、XRD谱及不同过冷度下合金组织的OM像和EBSD像

图8 x = 0.4、0.6时(Fe1 - x Co x)-B伪二元系示意相图

图9 (Fe1 - x Co x)79.3B20.7合金各初生相析出的临界过冷度范围及其与Co含量的关系

图10 各成分合金的凝固路径示意图

1	Zhang J J, Liu J C, Liao H M, et al. A review on relationship between morphology of boride of Fe-B alloys and the wear/corrosion resistant properties and mechanisms[J]. J. Mater. Res. Technol., 2019, 8: 6308
2	Liu Z W, Zhou B, Liao X F, et al. Research status and future development of (Ce, La, Y)-F-B permanent magnets based on full high-abundance rare earth elements[J]. Acta Metall. Sin., 2024, 60: 585
2	刘仲武, 周帮, 廖雪峰等. 全高丰度稀土(Ce, La, Y)-Fe-B永磁的研究现状和未来发展[J]. 金属学报, 2024, 60: 585 doi: 10.11900/0412.1961.2023.00117
3	Ünal E, Yaşar A, Karahan İ H. A review of electrodeposited composite coatings with Ni-B alloy matrix[J]. Mater. Res. Express, 2019, 6: 092004
4	Liu Z W, He J Y. Several issues on the development of grain boundary diffusion process for Nd-Fe-B permanent magnets[J]. Acta Metall. Sin., 2021, 57: 1155
4	刘仲武, 何家毅. 钕铁硼永磁晶界扩散技术和理论发展的几个问题[J]. 金属学报, 2021, 57: 1155 doi: 10.11900/0412.1961.2020.00438
5	Barati Q, Hadavi S M M. Electroless Ni-B and composite coatings: A critical review on formation mechanism, properties, applications and future trends[J]. Surf. Interfaces, 2020, 21: 100702
6	Xu X L, Hao Y C, Wu Q, et al. Microstructure refinement mechanisms in undercooled solidification of binary and ternary nickel based alloys[J]. J. Mater. Res. Technol., 2023, 24: 737
7	Madah F, Amadeh A A, Dehghanian C. Investigation on the phase transformation of electroless Ni-B coating after dry sliding against alumina ball[J]. J. Alloys Compd., 2016, 658: 272
8	Pal S, Jayaram V. Effect of microstructure on the hardness and dry sliding behavior of electroless Ni-B coating[J]. Materialia, 2018, 4: 47
9	Safavi M S, Tanhaei M, Ahmadipour M F, et al. Electrodeposited Ni-Co alloy-particle composite coatings: A comprehensive review[J]. Surf. Coat. Technol., 2020, 382: 125153
10	Li J F, Zhou Y H. Remelting of primary solid in rapid solidification of deeply undercooled alloy melts[J]. Acta Metall. Sin., 2018, 54: 627 doi: 10.11900/0412.1961.2017.00537
10	李金富, 周尧和. 液态金属深过冷快速凝固过程中初生固相的重熔[J]. 金属学报, 2018, 54: 627 doi: 10.11900/0412.1961.2017.00537
11	Liang L, Xu X L, Zhao Y H, et al. Solidification microstructure evolution and grain refinement mechanism under high undercooling of undercooled Ni₉₀Cu₁₀ alloys[J]. Mater. Res. Express, 2019, 6(12): 1265k5
12	Li J F, Lü Y L, Yang G C, et al. Secondary arm spacing of undercooled Ni₅₀Cu₅₀ alloy[J]. Acta Metall. Sin., 1998, 34: 586
12	李金富, 吕衣礼, 杨根仓等. 过冷Ni₅₀Cu₅₀合金的二次枝晶间距[J]. 金属学报, 1998, 34: 586
13	Quirinale D G, Rustan G E, Kreyssig A, et al. Synergistic stabilization of metastable Fe₂₃B₆ and γ-Fe in undercooled Fe₈₃B₁₇ [J]. Appl. Phys. Lett., 2015, 106: 241906
14	Liu L J, Yang L, Li J F. Solidification pathways in highly undercooled Co_79.3B_20.7 alloy[J]. Metall. Mater. Trans., 2021, 52A: 4324
15	Wei X X, Xu W, Kang J L, et al. Metastable Co₂₃B₆ phase solidified from deeply undercooled Co_79.3B_20.7 alloy melt[J]. J. Mater. Sci., 2016, 51: 6436
16	Xu J F, Liu F, Dang B. Phase selection in undercooled Ni-3.3 wt pct B alloy melt[J]. Metall. Mater. Trans., 2013, 44A: 1401
17	Liu F, Xu J F, Zhang D, et al. Solidification of highly undercooled hypereutectic Ni-Ni₃B alloy melt[J]. Metall. Mater. Trans., 2014, 45A: 4810
18	Battezzati L, Antonione C, Baricco M. Undercooling of Ni-B and Fe-B alloys and their metastable phase diagrams[J]. J. Alloys Compd., 1997, 247: 164
19	Ohodnicki Jr P R, Cates N C, Laughlin D E, et al. Ab initio theoretical study of magnetization and phase stability of the (Fe, Co, Ni)₂₃B₆ and (Fe, Co, Ni)₂₃Zr₆ structures of Cr₂₃C₆ and Mn₂₃Th₆ prototypes[J]. Phys. Rev., 2008, 78B: 144414
20	Li J F, Li W. Structure and glass-forming ability of Al-based amorphous alloys[J]. Acta Metall. Sin., 2022, 58: 457 doi: 10.11900/0412.1961.2021.00561
20	李金富, 李伟. 铝基非晶合金的结构与非晶形成能力[J]. 金属学报, 2022, 58: 457 doi: 10.11900/0412.1961.2021.00561
21	Yang G, Liu W G, Han X B, et al. Effects of alloying substitutions on the anti-disproportionation behavior of ZrCo alloy[J]. Int. J. Hydrogen Energy, 2017, 42: 15782
22	Zhang Q S, Zhang W, Louzguine-Luzgin D V, et al. Effect of substituting elements on glass-forming ability of the new Zr₄₈Cu₃₆Al₈Ag₈ bulk metallic glass-forming alloy[J]. J. Alloys Compd., 2010, 504: S18
23	Wu M D, Wang J C, Li P L, et al. Research progress on the anti-disproportionation of the ZrCo alloy by element substitution[J]. Materials, 2020, 13: 3977
24	Xu T, Li R, Xiao R J, et al. Tuning glass formation and brittle behaviors by similar solvent element substitution in (Mn, Fe)-based bulk metallic glasses[J]. Mater. Sci. Eng., 2015, A626: 16
25	Mitrica D, Badea I C, Serban B A, et al. Complex concentrated alloys for substitution of critical raw materials in applications for extreme conditions[J]. Materials, 2021, 14: 1197
26	Yang T, Yuan Z M, Bu W G, et al. Effect of elemental substitution on the structure and hydrogen storage properties of LaMgNi₄ alloy[J]. Mater. Des., 2016, 93: 46
27	Palumbo M, Cacciamani G, Bosco E, et al. Driving forces for crystal nucleation in Fe-B liquid and amorphous alloys[J]. Intermetallics, 2003, 11: 1293
28	Okamoto H. B-Fe (Boron-Iron)[J]. J. Phase Equilib. Diffus., 2004, 25: 297
29	Massalski T B, Okamoto H, Subramanian P R, et al. Binary Alloy Phase Diagrams[M]. 2nd Ed., Materials Park: ASM International, 1990: 482
30	Raghavan V. B-Co-Fe (Boron-Cobalt-Iron)[J]. J. Phase Equilib. Diffus., 2012, 33: 392
31	Liu Y Q, Zhao X S, Yang J, et al. Thermodynamic optimization of the boron-cobalt-iron system[J]. J. Alloys Compd., 2011, 509: 4805
32	Jackson K A, Uhlmann D R, Hunt J D. On the nature of crystal growth from the melt[J]. J. Cryst. Growth, 1967, 1: 1
33	Li M J, Kuribayashi K. Nucleation-controlled microstructures and anomalous eutectic formation in undercooled Co-Sn and Ni-Si eutectic melts[J]. Metall. Mater. Trans., 2003, 34A: 2999
34	Herlach D M. Non-equilibrium solidification of undercooled metallic metals[J]. Mater. Sci. Eng., 1994, R12: 177
35	Li M J, Ozawa S, Kuribayashi K. On determining the phase-selection principle in solidification from undercooled melts-competitive nucleation or competitive growth?[J]. Philos. Mag. Lett., 2004, 84: 483
36	Turnbull D. Kinetics of solidification of supercooled liquid mercury droplets[J]. J. Chem. Phys., 1952, 20: 411
37	Turnbull D. Formation of crystal nuclei in liquid metals[J]. J. Appl. Phys., 1950, 21: 1022
38	Wei X X, Xu W, Kang J L, et al. Phase selection in solidification of undercooled Co-B alloys[J]. J. Mater. Sci. Technol., 2017, 33: 352 doi: 10.1016/j.jmst.2016.09.012

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