Vacuum diffusion bonding of TC4 titanium alloy to T2 copper with VCrAl1.21Ni0.93Co1.85 high entropy alloy interlayer
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摘要:
根据伪二元合金设计策略和共晶高熵合金设计理念，设计并制备了VCrAl1.21Ni0.93Co1.85共晶高熵合金中间层用于真空扩散连接TC4钛合金和T2铜，研究了不同连接温度对TC4/T2扩散连接接头微观组织和力学性能的影响规律. 结果表明，所有接头界面结合良好无缺陷产生，在TC4侧的连接界面附近发生了部分相变，由α-Ti向β-Ti进行转变，并且形成了部分魏氏体组织. Ti2(Co, Ni)，Ti2(V, Cr, Al)，Ti(V, Cr, Co)和(V, Cr)(Al, Ni, Co)相形成在TC4/VCrAl1.21Ni0.93Co1.85界面上，而VCrAl1.21Ni0.93Co1.85/T2界面上形成了(V, Cr)(Al, Ni, Co)和(V, Cr)(Cu, Ni, Co)3相. 界面上形成高熵微观组织结构起到高熵固溶强化作用，扩散层I和II对应的生长激活能分别为229 kJ/mol和191 kJ/mol，接头抗剪强度在880 ℃时达到最大为194 MPa，接头主要沿着BCC基体相和B2相交替位置断裂，断口表面出现河流花样特征，属于一种典型的解理断裂模式.
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关键词:
- TC4钛合金/T2铜异种金属 /
- 真空扩散连接 /
- VCrAl1.21Ni0.93Co1.85中间层 /
- 微观组织 /
- 抗剪强度
Abstract:VCrAl1.21Ni0.93Co1.85 eutectic high entropy alloy interlayer was designed based on the pseudo-binary strategy and design concept of eutectic high entropy alloy, which was used to join TC4 titanium alloy and T2 copper via vacuum diffusion bonding. The influence of bonding temperature on the microstructure and mechanical property of TC4/T2 diffusion bonded joint was investigated. The results showed that all the joint were well combined without defects. TC4 titanium alloy adjacent to the diffusion layer underwent a phase transition from α-Ti to β-Ti, forming part of the Widmanstatten structure. Ti2(Co, Ni), Ti2(V, Cr, Al), Ti(V, Cr, Co) and (V, Cr)(Al, Ni, Co) phases appeared in the TC4/VCrAl1.21Ni0.93Co1.85 interface while (V, Cr)(Al, Ni, Co) and (V, Cr)(Cu, Ni, Co)3 phases formed in the VCrAl1.21Ni0.93Co1.85/T2 interface. The high entropy microstructure formed in the interface, which played the role of high entropy solution strengthening. The growth activation energy of diffusion layer I and II was 229 kJ/mol and 191 kJ/mol, respectively. The maximum shear strength of joint at 880 ℃ reached 194 MPa. The joint fracture was mainly along the BCC matrix phase and B2 phase alternately, and the fracture surface had the feature of river pattern, which belonged to a typical cleavage fracture mode.
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图 1 试验设计和准备
Figure 1. Experimental design and preparation. (a) sample assembly; (b) sample size; (c) welding process curve; (d) shear testing apparatus
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图 2 VCrAl1.21Ni0.93Co1.85多组元合金
Figure 2. VCrAl1.21Ni0.93Co1.85 multi-component alloy. (a) microstructure; (b) XRD pattern
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图 3 VCrAl1.21Ni0.93Co1.85中间层元素面扫描
Figure 3. Elemental map scanning results of VCrAl1.21Ni0.93Co1.85 interlayer. (a) BEI; (b) Al; (c) Cr; (d) V; (e) Ni; (f) Co
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图 4 不同连接温度保温60 min参数下TC4/VCrAl1.21Ni0.93Co1.85/T2接头的微观组织形貌
Figure 4. Microstructure morphology of TC4/VCrAl1.21Ni0.93Co1.85/T2 joints for 60 min under various bonding temperature. (a) 840 ℃; (b) 860 ℃; (c) 880 ℃; (d) 900 ℃
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图 5 不同连接温度下TC4/VCrAl1.21Ni0.93Co1.85和VCrAl1.21Ni0.93Co1.85/T2两侧的界面微观组织
Figure 5. Interfacial microstructure on TC4/VCrAl1.21Ni0.93Co1.85 and VCrAl1.21Ni0.93Co1.85/T2 sides under various bonding temperature. (a) TC4 840 ℃; (b) T2 840 ℃; (c) TC4 860 ℃; (d) T2 860 ℃; (e) TC4 880 ℃; (f) T2 880 ℃; (g) TC4 900 ℃; (h) T2 900 ℃
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图 6 880 ℃/60 min参数下TC4/VCrAl1.21Ni0.93Co1.85侧的元素分布
Figure 6. Distribution of elements on TC4/VCrAl1.21Ni0.93Co1.85 side at 880 ℃ for 60 min. (a) BEI; (b) Ti; (c) Co; (d) V; (e) Al; (f) Ni; (g) Cr
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图 7 880 ℃/60 min参数下VCrAl1.21Ni0.93Co1.85/T2侧的元素分布
Figure 7. Distribution of elements on the VCrAl1.21Ni0.93Co1.85/T2 side at 880 ℃ for 60 min. (a) BEI; (b) Co; (c) Cu; (d) V; (e) Al; (f) Ni; (g) Cr
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图 8 在TC4/EHEA侧界面扩散层透射表征
Figure 8. TEM characterization of interfacial diffusion layer on the TC4/EHEA side. (a) bright field image; (b) 1; (c) 2; (d) 3; (e) 4; (f) 5
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图 9 在EHEA/T2侧界面扩散层透射表征
Figure 9. TEM characterization of interfacial diffusion layer on the EHEA/T2 side. (a) bright field image; (b) 1; (c) 2; (d) 3
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图 10 TC4/VCrAl1.21Ni0.93Co1.85和VCrAl1.21Ni0.93Co1.85/T2两侧界面层动力学分析
Figure 10. Kinetics of interfacial layers on TC4/VCrAl1.21Ni0.93Co1.85 and VCrAl1.21Ni0.93Co1.85/T2 sides. (a) thickness of diffusion layers for 60 min under different temperature; (b) growth activation energy of diffusion layers I and II
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图 11 60 min不同连接温度下接头的力学性能
Figure 11. Mechanical properties of joints at different connection temperatures for 60 min. (a) shear strength; (b) load-displacement curve
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图 12 不同连接温度下TC4/VCrAl1.21Ni0.93Co1.85/T2接头的断裂路径
Figure 12. Fracture paths of TC4/VCrAl1.21Ni0.93Co1.85/T2 joints under various bonding temperature. (a) 840 ℃; (b) 860 ℃; (c) 880 ℃; (d) 900 ℃
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图 13 880 ℃/60 min参数下TC4/VCrAl1.21Ni0.93Co1.85/T2接头的断口形貌
Figure 13. Fracture morphologies of TC4/VCrAl1.21Ni0.93Co1.85/T2 joint at 880 ℃ for 60 min. (a) on TC4 side; (b) enlarged morphology in Fig. 13(a); (c) on T2 side; (d) enlarged morphology in Fig. 13(c)
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图 14 60 min不同温度下TC4/VCrAl1.21Ni0.93Co1.85/T2接头断口表面的XRD
Figure 14. XRD of fracture surface for TC4/VCrAl1.21Ni0.93Co1.85/T2 joints under different temperatures for 60 min. (a) TC4 side at 880 ℃; (b) T2 side at 880 ℃; (c) TC4 side at 900 ℃; (d) T2 side at 900 ℃
表 1 母材和中间层的化学成分(质量分数，%)
Table 1 Chemical component of base materials and interlayer
材料 Al V Co Cr Ni Si P S Ti Cu TC4 6.03 3.97 — — — — — — 余量 — T2 — — — — — ≤0.03 ≤0.02 ≤0.01 — 余量 中间层 10.91 17.01 36.41 17.36 18.31 — — — — — 
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表 2 扩散连接工艺参数
Table 2 Parameters of the diffusion bonding
组 连接温度
T/℃保温时间
t/min连接压力
P/MPa中间层厚度
l/μm1 840 60 8 160 2 860 60 8 160 3 880 60 8 160 4 900 60 8 160
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表 3 图2(a)中标记位置的EPMA定量点分析结果(原子分数，%)
Table 3 EPMA quantitative analysis results of the marked locations in Fig. 2(a)
位置 Al V Co Cr Ni 可能的相 A 19.1 15.8 35.5 15.8 13.8 B2 B 13.2 17.6 35.4 21.7 12.1 BCC
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表 4 图5(e)和图5(f)中标记点处的元素分析结果(原子分数，%)
Table 4 Elemental analysis results of the marked points in Fig. 5(e) and Fig. 5(f)
位置 Ti Cu Co Al V Cr Ni 可能的相 1 75.7 — 0.4 21.2 2.2 0.2 0.4 Ti3Al 2 70.0 — 4.8 10.8 8.0 4.7 1.7 β-Ti 3 58.8 — 19.0 6.8 3.4 3.1 8.9 Ti2(Co, Ni) 4 61.3 — 6.0 11.7 11.1 8.2 1.8 Ti2(V, Cr, Al) 5 39.4 — 15.5 9.5 14.1 16.4 5.1 Ti(V, Cr, Co) 6 7.5 — 25.7 16.4 19.1 23.3 8.0 (V, Cr)(Al, Ni, Co) 7 — 10.3 41.7 3.2 17.1 16.2 11.5 (V, Cr)(Cu, Ni, Co)2 8 — 43.5 24.4 2.1 11.5 12.5 6.0 (V, Cr)(Cu, Ni, Co)3
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表 5 图13(b)和图13(d)中标记点的元素分析结果(原子分数，%)
Table 5 Elemental analysis results of the marked points in Fig. 13(b) and Fig. 13(d)
位置 Ti Al V Cr Co Ni 可能的相 1 56.9 9.2 5.9 6.2 15.4 6.4 Ti3(Co, Ni) 2 48.4 17.7 5.3 5.3 18.0 5.5 Ti3AlCo 3 21.2 23.3 11.3 10.2 24.5 9.5 TiAl(V, Cr, Co, Ni) 4 58.0 9.4 5.8 5.4 14.9 6.5 Ti2(V, Cr, Co) 5 5.5 17.1 20.1 25.1 25.1 7.1 BCC 6 0.2 19.1 15.8 14.5 35.7 14.7 BCC 7 17.3 16.8 21.6 17.8 20.6 5.9 TiAl(V, Cr, Co)2 8 50.7 16.8 10.1 8.0 10.8 3.6 Ti3Al(V, Co) 9 0.6 24.2 15.4 12.3 32.9 14.6 B2 10 60.0 8.2 3.7 3.9 16.4 7.8 Ti2(Co, Ni) 11 0.1 12.4 18.8 21.8 34.7 12.2 BCC 12 19.2 20.6 12.7 10.1 27.2 10.2 TiAl(V, Cr)(Co, Ni) 13 0.3 22.5 15.5 14.7 33.6 13.4 B2
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