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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

Chen Yuyong, Zhang Shuzhi, Kong Fantao, et al. Progress in β-solidifying γ-TiAl based alloys[J]. Chinese Journal of Rare Metals, 2012, 36(1): 154−160. doi: 10.7513/j.issn.1004-7638.2024.01.002
引用本文: Chen Yuyong, Zhang Shuzhi, Kong Fantao, et al. Progress in β-solidifying γ-TiAl based alloys[J]. Chinese Journal of Rare Metals, 2012, 361): 154160. doi: 10.7513/j.issn.1004-7638.2024.01.002
Zhu Fuxing, Ma Zhanshan, Deng Bin, Mu Tianzhu, Qiu Kehui. A new process for preparing Ti-Al alloys from low-valance titanium chlorides slurry by direct electrochemical reduction[J]. IRON STEEL VANADIUM TITANIUM, 2024, 45(1): 4-11. doi: 10.7513/j.issn.1004-7638.2024.01.002
Citation: Zhu Fuxing, Ma Zhanshan, Deng Bin, Mu Tianzhu, Qiu Kehui. A new process for preparing Ti-Al alloys from low-valance titanium chlorides slurry by direct electrochemical reduction[J]. IRON STEEL VANADIUM TITANIUM, 2024, 45(1): 4-11. 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
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

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

  • 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/Al0.64Ti0.36→Al0.64Ti0.36/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,Al0.64Ti0.36/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。
  • 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

    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 ℃

    图  3  不同温度下1/2-J曲线和其计算的扩散系数与温度关系

    (a)1/2-J曲线;(b)扩散系数与温度关系

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

    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)Al0.64Ti0.36/AlTi3

    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

    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

    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)

    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

    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

    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

    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
    0.150.182Al、Al3Ti粗大枝晶
    0.380.394Al3Ti2,Al5Ti2细枝晶
    0.500.485AlTi、Al0.64Ti0.36细球状结构
    0.690.725Al0.64Ti0.36、AlTi3粗状况团聚体
    0.770.764AlTi3细球状团聚体
    0.830.880AlTi3、Ti细球多孔状
    1.001.000Ti多孔状
    下载: 导出CSV

    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
    下载: 导出CSV
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  • 收稿日期:  2023-08-07
  • 刊出日期:  2024-02-01

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