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Oxygen removal and subsequent morphology transformation of TiOx<1 powders in electrodeoxidation process

TiOx<1粉体在电脱氧过程中的氧移除和持续性形貌转变

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Abstract

In this study, TiOx<1 powders obtained from the combustion synthesis of TiO2 and Mg was used as cathode to prepare low-oxygen titanium powders by electrochemical deoxidation process. The mechanism of oxygen removal, composition and morphology change of TiOx<1 powders during electrode oxidation were investigated. The residual oxygen content in electrodeoxidized TiOx<1 powders is linearly related to the deoxidation time. An obvious sintering neck between titanium particles with less than 0.35wt% oxygen could be observed after electrodeoxidation for 2 h. The removal of oxygen from Ti lattice promotes the surface diffusion of titanium atoms and leads to subsequent sintering and growth of TiOx<1 powders in electrodeoxidation. The morphology of TiOx<1 powders was transformed into coral and porous flakes from agglomerated small particles with a decrease in residual oxygen content and an extension of deoxidation time.

摘要

在本研究中, 将二氧化钛和镁粉以自蔓延燃烧合成制备的TiOx<1粉末用作阴极, 通过电化学脱氧工艺制备低氧钛粉。利用电化学分析、XRD、SEM、XPS、TEM 等测试表征手段研究了电化学脱氧过程中TiOx<1粉末的脱氧过程、成分和形貌转变。结果表明: TiOx<1粉末电脱氧后的残余氧含量与还原时间呈线性关系。电脱氧2 h 后, 在氧含量低于0.35wt%的钛颗粒之间可观察到明显的烧结颈。钛晶格中的氧移除促进了钛原子的表面扩散, 从而导致TiOx<1粉末在电脱氧过程中的烧结和持续性长大。随着残余氧含量的降低和脱氧时间的延长, TiOx<1粉末形貌从团聚的小颗粒状转变为珊瑚状和多孔片状。

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References

  1. TAKEDA O, OUCHI T, OKABE T H. Recent progress in titanium extraction and recycling [J]. Metallurgical and Materials Transactions B, 2020, 51(4): 1315–1328. DOI: https://doi.org/10.1007/s11663-020-01898-6.

    Article  Google Scholar 

  2. REDDY R G, SHINDE P S, LIU Ai-min. Review—The emerging technologies for producing low-cost titanium [J]. Journal of the Electrochemical Society, 2021, 168(4): 042502. DOI: https://doi.org/10.1149/1945-7111/abe50d.

    Article  Google Scholar 

  3. QIU Guan-zhou, GUO Yu-feng. Current situation and development trend of titanium metal industry in China [J]. International Journal of Minerals, Metallurgy and Materials, 2022, 29(4): 599–610. DOI: https://doi.org/10.1007/s12613-022-2455-y.

    Article  MathSciNet  Google Scholar 

  4. FANG Z Z, PARAMORE J D, SUN Pei, et al. Powder metallurgy of titanium—Past, present, and future [J]. International Materials Reviews, 2018, 63(7): 407–459. DOI: https://doi.org/10.1080/09506608.2017.1366003.

    Article  Google Scholar 

  5. TAKEDA O, OKABE T H. Current status of titanium recycling and related technologies [J]. JOM, 2019, 71(6): 1981–1990. DOI: https://doi.org/10.1007/s11837-018-3278-1.

    Article  Google Scholar 

  6. DRING K, DASHWOOD R, INMAN D. Voltammetry of titanium dioxide in molten calcium chloride at 900 °C [J]. Journal of the Electrochemical Society, 2005, 152(3): E104. DOI: https://doi.org/10.1149/1.1860515.

    Article  Google Scholar 

  7. ZHANG Ying, LU Wei-liang, SUN Pei, et al. Deoxygenation of Ti metal: A review of processes in literature [J]. International Journal of Refractory Metals and Hard Materials, 2020, 91: 105270. DOI: https://doi.org/10.1016/j.ijrmhm.2020.105270.

    Article  Google Scholar 

  8. TSUKIHASHI F, HATTA T, TAWARA E. Thermodynamics of calcium and oxygen in molten titanium and titanium-aluminum alloy [J]. Metallurgical and Materials Transactions B, 1996, 27(6): 967–972. DOI: https://doi.org/10.1007/s11663-996-0010-2.

    Article  Google Scholar 

  9. OKABE T H, ODA T, MITSUDA Y. Titanium powder production by preform reduction process (PRP) [J]. Journal of Alloys and Compounds, 2004, 364(1–2): 156–163. DOI: https://doi.org/10.1016/S0925-8388(03)00610-8.

    Article  Google Scholar 

  10. PARK I, ABIKO T, OKABE T H. Production of titanium powder directly from TiO2 in CaCl2 through an electronically mediated reaction (EMR) [J]. Journal of Physics and Chemistry of Solids, 2005, 66(2–4): 410–413. DOI: https://doi.org/10.1016/j.jpcs.2004.06.052.

    Article  Google Scholar 

  11. SUZUKI R O, AIZAWA M, ONO K. Calcium-deoxidation of niobium and titanium in Ca-saturated CaCl2 molten salt [J]. Journal of Alloys and Compounds, 1999, 288(1–2): 173–182. DOI: https://doi.org/10.1016/S0925-8388(99)00116-4.

    Article  Google Scholar 

  12. ZHANG Ying, FANG Z Z, SUN Pei, et al. Thermodynamic destabilization of Ti-O solid solution by H2 and deoxygenation of Ti using Mg [J]. Journal of the American Chemical Society, 2016, 138(22): 6916–6919. DOI: https://doi.org/10.1021/jacs.6b00845.

    Article  Google Scholar 

  13. ZHANG Ying, FANG Z Z, XIA Yang, et al. Hydrogen assisted magnesiothermic reduction of TiO2 [J]. Chemical Engineering Journal, 2017, 308: 299–310. DOI: https://doi.org/10.1016/j.cej.2016.09.066.

    Article  Google Scholar 

  14. SHIN H S, HUR J M, JEONG S M, et al. Direct electrochemical reduction of titanium dioxide in molten lithium chloride [J]. Journal of Industrial and Engineering Chemistry, 2012, 18(1): 438–442. DOI: https://doi.org/10.1016/j.jiec.2011.11.111.

    Article  Google Scholar 

  15. CHEN G. Interactions of molten salts with cathode products in the FFC Cambridge Process [J]. International Journal of Minerals, Metallurgy and Materials, 2020, 27(12): 1572–1587.

    Article  Google Scholar 

  16. SUZUKI R O, INOUE S. Calciothermic reduction of titanium oxide in molten CaCl2 [J]. Metallurgical and Materials Transactions B, 2003, 34(3): 277–285. DOI: https://doi.org/10.1007/s11663-003-0073-2.

    Article  Google Scholar 

  17. ZHANG Ying, FANG Z Z, SUN Pei, et al. A perspective on thermochemical and electrochemical processes for titanium metal production [J]. JOM, 2017, 69(10): 1861–1868. DOI: https://doi.org/10.1007/s11837-017-2481-9.

    Article  Google Scholar 

  18. ZHOU Xin-yu, DOU Zhi-he, ZHANG Ting-an, et al. Preparation of low-oxygen Ti powder from TiO2 through combining self-propagating high temperature synthesis and electrodeoxidation [J]. Transactions of Nonferrous Metals Society of China, 2022, 32(10): 3469–3477. DOI: https://doi.org/10.1016/S1003-6326(22)66033-3.

    Article  Google Scholar 

  19. NAKAMURA M, OISHI T, et al. Electrochemical deoxidation of titanium [J]. Metallurgical and Materials Transactions B, 1993, 24(3): 449–455. DOI: https://doi.org/10.1007/BF02666427.

    Article  Google Scholar 

  20. TANINOUCHI Y K, HAMANAKA Y, OKABE T H. Electrochemical deoxidation of titanium and its alloy using molten magnesium chloride [J]. Metallurgical and Materials Transactions B, 2016, 47(6): 3394–3404. DOI: https://doi.org/10.1007/s11663-016-0792-9.

    Article  Google Scholar 

  21. OH J M, LEE B K, SUH C Y, et al. Deoxidation of Ti powder and preparation of Ti ingot with low oxygen concentration [J]. Materials Transactions, 2012, 53(6): 1075–1077. DOI: https://doi.org/10.2320/matertrans.m2012004.

    Article  Google Scholar 

  22. OH J M, KWON H, KIM W, et al. Oxygen behavior during non-contact deoxidation of titanium powder using calcium vapor [J]. Thin Solid Films, 2014, 551: 98–101. DOI: https://doi.org/10.1016/j.tsf.2013.11.076.

    Article  Google Scholar 

  23. LEFEBVRE L P, BARIL E. Effect of oxygen concentration and distribution on the compression properties on titanium foams [J]. Advanced Engineering Materials, 2008, 10(9): 868–876. DOI: https://doi.org/10.1002/adem.200800122.

    Article  Google Scholar 

  24. LI Dong-yang, HE Hao, LOU Jia, et al. Effect of oxygen contents on predominant sintering mechanism during initial stage of pure titanium powder [J]. Powder Technology, 2020, 361: 617–623. DOI: https://doi.org/10.1016/j.powtec.2019.11.070.

    Article  Google Scholar 

  25. YANG Y F, QIAN M. Fundamental understanding of the dissolution of oxide film on Ti powder and the unique scavenging feature by LaB6 [J]. Metallurgical and Materials Transactions A, 2018, 49(1): 1–6. DOI: https://doi.org/10.1007/s11661-017-4366-5.

    Article  Google Scholar 

  26. LI Dong-yang, HE Hao, LOU Jia, et al. Effect of oxygen contents on predominant sintering mechanism during initial stage of pure titanium powder [J]. Powder Technology, 2020, 361: 617–623. DOI: https://doi.org/10.1016/j.powtec.2019.11.070.

    Article  Google Scholar 

  27. PANIGRAHI B B, GODKHINDI M M, DAS K, et al. Sintering kinetics of micrometric titanium powder [J]. Materials Science and Engineering A, 2005, 396(1–2): 255–262. DOI: https://doi.org/10.1016/j.msea.2005.01.016.

    Article  Google Scholar 

  28. SONG M, HAN S, MIN D, et al. Diffusion of oxygen in β-titanium [J]. Scripta Materialia, 2008, 59(6): 623–626. DOI: https://doi.org/10.1016/j.scriptamat.2008.05.037.

    Article  Google Scholar 

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Authors and Affiliations

  1. Key Laboratory of Ecological Metallurgy of Multi-metal Intergrown Ores of Ministry of Education, Shenyang, 110819, China

    Xin-yu Zhou  (周新宇) & Zhi-he Dou  (豆志河)

  2. School of Metallurgy, Northeastern University, Shenyang, 110819, China

    Ting-an Zhang  (张廷安), Chen Zhang  (张晨) & Dao-guang Du  (杜道光)

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  1. Xin-yu Zhou  (周新宇)
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  2. Zhi-he Dou  (豆志河)
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  4. Chen Zhang  (张晨)
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  5. Dao-guang Du  (杜道光)
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Contributions

ZHOU Xin-yu, ZHANG Chen and DU Daoguang handled the text of this paper and the formatting of this paper. DOU Zhi-he and ZHANG Ting-an prepared the concept for the paper. ZHOU Xin-yu did the experimental work for the paper. All authors have read and agreed to the published version of the manuscript. Finally, this whole paper submission was handled by ZHOU Xin-yu.

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Correspondence to Zhi-he Dou  (豆志河) or Ting-an Zhang  (张廷安).

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Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper.

Foundation item: Projects((N2225012, N2224001-9) supported by the Fundamental Research Funds for Central Universities, China; Projects(U1908225, 52174333) supported by the National Natural Science Foundation of China

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Zhou, Xy., Dou, Zh., Zhang, Ta. et al. Oxygen removal and subsequent morphology transformation of TiOx<1 powders in electrodeoxidation process. J. Cent. South Univ. 30, 1435–1446 (2023). https://doi.org/10.1007/s11771-023-5332-6

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  • DOI: https://doi.org/10.1007/s11771-023-5332-6

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