低价氯化钛浆料直接电化学还原制备钛铝合金新工艺研究

朱福兴; 马占山; 邓斌; 穆天柱; 邱克辉

doi:10.7513/j.issn.1004-7638.2024.01.002

低价氯化钛浆料直接电化学还原制备钛铝合金新工艺研究

doi: 10.7513/j.issn.1004-7638.2024.01.002

朱福兴^{1, 2,},
马占山^{1, 3},
邓斌¹,
穆天柱¹,
邱克辉^2, ,

1.
钒钛资源综合利用国家重点实验室, 攀钢集团研究院有限公司，四川攀枝花 617000
2.
成都理工大学材料与化学化工学院，四川成都 610059
3.
上海大学材料科学与工程学院，上海 200444

基金项目: 国家重点基础研究发展计划（亚熔盐体系钒钛铬盐结晶相分离及电化学还原新过程基础研究,2013CB632600）。

详细信息

作者简介:
朱福兴，1986年出生，男，云南泸水人，硕士研究生，高级工程师，主要研究方向为钛冶金和镁冶金，E-mail：pzhzfx@sina.com

通讯作者:
邱克辉，1956年出生，男，四川资阳人，教授，主要研究方向为钒钛稀土新材料，E-mail：qkh2188@163.com

中图分类号: TF823
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出版历程
- 收稿日期: 2023-08-07
- 刊出日期: 2024-02-01

A new process for preparing Ti-Al alloys from low-valance titanium chlorides slurry by direct electrochemical reduction

Zhu Fuxing^{1, 2
,},
Ma Zhanshan^{1, 3},
Deng Bin¹,
Mu Tianzhu¹,
Qiu Kehui^{2
, ,}

1.
State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization, Pangang Group Research Institute Co., Ltd., Panzhihua 617000, Sichuan, China
2.
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, China
3.
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

摘要

摘要: 针对低价氯化钛（LTC）浆料熔盐电解制备钛铝合金存在的电化学行为研究不系统、合金产品的高温抗氧化特性不明晰等问题，采用电化学工作站、示差热重分析仪等手段对LTC浆料在熔盐体系中电化学行为及合金产品的高温抗氧化特性进行研究。结果表明，LTC浆料在熔盐体系中可直接电化学还原制备Ti-Al合金，且为逐级还原的历程：Ti³⁺→Ti²⁺，Al³⁺→Al，Ti³⁺/Al³⁺→Ti-Al合金和Ti²⁺→Ti；随着熔盐体系中Ti³⁺离子浓度的增加，钛铝合金的组成变化规律为:Al/Al₃Ti→Al₃Ti₂/Al₅Ti₂→AlTi/Al_0.64Ti_0.36→Al_0.64Ti_0.36/AlTi₃→AlTi₃→AlTi₃/Ti→Ti，产品形貌变化规律为：粗枝晶→细枝晶→细球状结构→粗球状团聚体→细球状团聚体→细球多孔状→多孔状结构。钛铝合金中随着铝含量和产品致密性的增加，合金的抗高温氧化性能逐渐增强，Al_0.64Ti_0.36/AlTi₃合金经高温熔炼后呈Al含量更高的α₂/γ和γ组织，使其高温抗氧化性能优于商用Ti48Al2Cr2Nb。钛铝合金产品高温氧化历程为：Ti-Al合金→铝酸钛→金红石/氧化铝，并且形成的氧化物层可有效防止钛铝合金的进一步氧化。
- 钛铝合金 /
- 低价氯化钛浆料 /
- 电化学还原 /
- 高温抗氧化性
Abstract: Owing to the lack of systematic research on electrochemical behaviors and unclear high-temperature oxidation resistance characteristics of Ti-Al alloys prepared from low-valence titanium chlorides slurry by the electrochemical reduction in molten salt, the electrochemical workstation and differential thermal gravimetric analyzer were used to study the electrochemical behavior of LTC slurry in the molten salt system and the high-temperature oxidation resistance characteristics of alloy products. The results show that LTC slurry can be directly electrochemically reduced to Ti-Al alloys, following a step-by-step reduction process: Ti³⁺→Ti²⁺, Al³⁺→Al, Ti³⁺/Al³⁺→Ti-Al alloys, and Ti²⁺→Ti. As the concentration of Ti³⁺ ions in molten salts increases, the composition of Ti-Al alloys changes as follows: Al/Al₃Ti→Al₃Ti₂/Al₅Ti₂→AlTi/Al_0.64Ti_0.36→Al_0.64Ti_0.36/AlTi₃→AlTi₃→AlTi₃/Ti→Ti. The variation law of product morphology is as follows: coarse dendrite→fine dendrite→fine spherical structure→coarse spherical aggregate→fine spherical aggregate→fine spherical porous structure→porous structure. With the increase of aluminum content and product density in Ti-Al alloys, the high-temperature oxidation resistance gradually enhances. After high-temperature melting, Al_0.64Ti_0.36/AlTi₃ alloy shows α₂ and γ phase structures with a higher Al content, and its high-temperature oxidation resistance is superior to commercial Ti48Al2Cr2Nb. The high-temperature oxidation process of Ti-Al alloys is as follows: Ti-Al alloys→titanium aluminate→rutile/alumina, and the formed oxide layer can effectively prevent further oxidation.
- Ti-Al alloys /
- low-valance titanium chlorides slurry /
- electrochemical reduction /
- high temperature oxidation resistance

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图 1 添加LTC前后Mo和Al工作电极（WE）上的CV曲线

Figure 1. CV curves obtained on Mo and Al working electrodes (WE) before and after LTC addition

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图 2 不同温度下KCl-LiCl-MgCl₂-LTC体系的CP曲线

Figure 2. CP curves of KCl-LiCl-MgCl₂-LTC system at different temperatures

(a)450 ℃；(b)500 ℃；(c)550 ℃；(d)600 ℃；(e)650 ℃；(f)700 ℃

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图 3 不同温度下Jτ^1/2-J曲线和其计算的扩散系数与温度关系

(a)Jτ^1/2-J曲线；(b)扩散系数与温度关系

Figure 3. Jτ^1/2-J curves and the diffusion coefficient of Ti³⁺/Ti²⁺ at different temperatures

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图 4 不同钛铝比（[Ti]/[Ti]+[Al])）合金产品氧化的TG-DSC曲线

Figure 4. TG-DSC curves of Ti-Al alloy products with the change of [Ti]/([Ti]+[Al])

（a）Ti；（b）AlTi₃/Ti；（c）AlTi₃；（d）Al_0.64Ti_0.36/AlTi₃

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图 5 烧结（a）和熔锭（b）钛铝合金的金相组织形貌

Figure 5. Metallographic morphology of sintered and ingot Ti-Al alloys

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图 6 钛铝合金锭的外观（a）、金相组织（b）和SEM-EDS（c）结果

Figure 6. Appearance (a), metallographic structure (b) and SEM-EDS (c) of Ti-Al alloy ingot

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图 7 烧结钛铝（a）、熔锭钛铝（b）和Ti48 Al2 Cr2 Nb（c）合金的TG-DSC曲线

Figure 7. TG-DSC curves of the sintered Ti-Al (a), ingot Ti-Al (b) and Ti48 Al2 Cr2 Nb alloys (c)

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图 8 氧化后熔锭钛铝（a）和Ti48Al2Cr2Nb（b）合金的SEM形貌

Figure 8. SEM images of the Ti-Al ingot (a)and Ti48Al2Cr2Nb alloys (b) after oxidation

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图 9 熔锭钛铝（a）和Ti48Al2Cr2Nb（b）合金表面氧化层厚度检测结果

Figure 9. Results of surface oxide layer thickness of Ti-Al ingot and Ti48Al2Cr2Nb alloys

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图 10 钛铝合金氧化产物的MLA色差图（a）和SEM-EDS结果（b）

Figure 10. MLA color difference diagram (a) and SEM-EDS of Ti-Al alloys (b) after oxidized

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表 1 电解质中[Ti]/([Ti]+[Al])比例对阴极产物组成及形貌的影响

Table 1. The effect of molar ratios of [Ti]/([Ti]+[Al]) in electrolytes on the compositions and morphology of cathodic products

电解质[Ti]/([Ti]+[Al])	阴极产物[Ti]/([Ti]+[Al])	物相组成	形貌特征
0.15	0.182	Al、Al₃Ti	粗大枝晶
0.38	0.394	Al₃Ti₂，Al₅Ti₂	细枝晶
0.50	0.485	AlTi、Al_0.64Ti_0.36	细球状结构
0.69	0.725	Al_0.64Ti_0.36、AlTi₃	粗状况团聚体
0.77	0.764	AlTi₃	细球状团聚体
0.83	0.880	AlTi₃、Ti	细球多孔状
1.00	1.000	Ti	多孔状

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表 2 钛铝合金锭高温氧化后重量变化情况

Table 2. Weight changes of Ti-Al alloy ingot after high-temperature oxidation

合金类别	氧化前/g	氧化后/g	增重率/%
钛铝合金锭	3.018	3.059	1.36
Ti48Al2Cr2Nb	1.222	1.229	0.57

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