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Mechanism of Oxygen–Chlorine Potential Interaction During the Ca/Y-Mediated Solid-State Deoxidation of Zirconium.

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Title: Mechanism of Oxygen–Chlorine Potential Interaction During the Ca/Y-Mediated Solid-State Deoxidation of Zirconium.
Authors: Ma, Zhaohui1,2,3 (AUTHOR), Yan, Guoqing2,3 (AUTHOR) yanguoqing@grinm.com, Yan, Xiao2,3 (AUTHOR), Ding, Haiyang4 (AUTHOR), Wu, Gang2,3 (AUTHOR), Zhang, Shunli2,3 (AUTHOR), Zhang, Jiandong2,3 (AUTHOR), Chen, Weidong1 (AUTHOR), Wang, Lijun1 (AUTHOR)
Source: Materials (1996-1944). Jun2026, Vol. 19 Issue 12, p2515. 23p.
Subjects: Phase equilibrium, Chlorination, Zirconium oxide, Reduction potential
Abstract: Highlights: Dynamic shift of oxygen mediator from Ca to metallic Y by increasing chlorine potential, explaining non-monotonic O variation in Zr. Establishment of three-phase equilibrium (Y–YOCl–YCl3) enabling in-depth deoxidation of Zr down to 20 ppm at 1173 K. Synergistic mechanism of O and Cl potentials clarified, providing a novel framework for designing efficient gettering systems. Zirconium (Zr) is a strategic metal resource whose performance is significantly degraded by high oxygen content. The external gettering process is an effective approach for in-depth deoxidation of Zr. In this study, the deoxidation behavior of Zr in the Ca-Y-CaCl2 external gettering system was investigated by adjusting the chlorine potential through YCl3 addition. The change of oxygen potential and its synergistic control mechanism during the variation of chlorine potential were systematically examined. The results demonstrated that with increasing chlorine potential, the system undergoes a sequence of reactions: chlorination of Ca, formation of metallic Y, formation of YOCl, dissolution of Y2O3, and formation of YCl3, ultimately reaching a three-phase equilibrium of Y-YOCl-YCl3. During this process, the oxygen content of Zr fluctuates notably, which is primarily attributed to the shift in the oxygen-transfer medium from Ca to Y. This transition changes the oxygen potential control mechanism from indirect Y-Ca control to direct Y control. After reaching equilibrium at 1173 K for 72 h, the equilibrium oxygen content of Zr initially remains stable with increasing chlorine potential, then gradually decreases, eventually reaching 20 ppmw. This trend is consistent with the mutual interaction of oxygen potential and chlorine potential. The findings provide important theoretical insights into the interaction between oxygen and chlorine potentials in deoxidation systems, elucidate the multi-element synergistic mechanism for oxygen control, and contribute to the design of efficient deoxidation systems. [ABSTRACT FROM AUTHOR]
Copyright of Materials (1996-1944) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Label: Title
  Group: Ti
  Data: Mechanism of Oxygen–Chlorine Potential Interaction During the Ca/Y-Mediated Solid-State Deoxidation of Zirconium.
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  Data: <searchLink fieldCode="JN" term="%22Materials+%281996-1944%29%22">Materials (1996-1944)</searchLink>. Jun2026, Vol. 19 Issue 12, p2515. 23p.
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  Data: <searchLink fieldCode="DE" term="%22Phase+equilibrium%22">Phase equilibrium</searchLink><br /><searchLink fieldCode="DE" term="%22Chlorination%22">Chlorination</searchLink><br /><searchLink fieldCode="DE" term="%22Zirconium+oxide%22">Zirconium oxide</searchLink><br /><searchLink fieldCode="DE" term="%22Reduction+potential%22">Reduction potential</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Highlights: Dynamic shift of oxygen mediator from Ca to metallic Y by increasing chlorine potential, explaining non-monotonic O variation in Zr. Establishment of three-phase equilibrium (Y–YOCl–YCl3) enabling in-depth deoxidation of Zr down to 20 ppm at 1173 K. Synergistic mechanism of O and Cl potentials clarified, providing a novel framework for designing efficient gettering systems. Zirconium (Zr) is a strategic metal resource whose performance is significantly degraded by high oxygen content. The external gettering process is an effective approach for in-depth deoxidation of Zr. In this study, the deoxidation behavior of Zr in the Ca-Y-CaCl2 external gettering system was investigated by adjusting the chlorine potential through YCl3 addition. The change of oxygen potential and its synergistic control mechanism during the variation of chlorine potential were systematically examined. The results demonstrated that with increasing chlorine potential, the system undergoes a sequence of reactions: chlorination of Ca, formation of metallic Y, formation of YOCl, dissolution of Y2O3, and formation of YCl3, ultimately reaching a three-phase equilibrium of Y-YOCl-YCl3. During this process, the oxygen content of Zr fluctuates notably, which is primarily attributed to the shift in the oxygen-transfer medium from Ca to Y. This transition changes the oxygen potential control mechanism from indirect Y-Ca control to direct Y control. After reaching equilibrium at 1173 K for 72 h, the equilibrium oxygen content of Zr initially remains stable with increasing chlorine potential, then gradually decreases, eventually reaching 20 ppmw. This trend is consistent with the mutual interaction of oxygen potential and chlorine potential. The findings provide important theoretical insights into the interaction between oxygen and chlorine potentials in deoxidation systems, elucidate the multi-element synergistic mechanism for oxygen control, and contribute to the design of efficient deoxidation systems. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Materials (1996-1944) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Type: general
      – SubjectFull: Chlorination
        Type: general
      – SubjectFull: Zirconium oxide
        Type: general
      – SubjectFull: Reduction potential
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      – TitleFull: Mechanism of Oxygen–Chlorine Potential Interaction During the Ca/Y-Mediated Solid-State Deoxidation of Zirconium.
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              Text: Jun2026
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