Quantitative Determination of Iron Redox State in Copper–Iron–Silicate Slags by Electron Probe Microanalysis.
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| Title: | Quantitative Determination of Iron Redox State in Copper–Iron–Silicate Slags by Electron Probe Microanalysis. |
|---|---|
| Authors: | Starykh, Roman1 (AUTHOR) r.starykh@uq.edu.au, Sineva, Svetlana1 (AUTHOR), Shishin, Denis1 (AUTHOR), Jak, Evgueni1 (AUTHOR) |
| Source: | Journal of the American Ceramic Society. Jun2026, Vol. 109 Issue 6, p1-23. 23p. |
| Subjects: | Electron probe microanalysis, Iron oxidation, Oxidation states, Oxide ceramics, Analytical chemistry, Cations |
| Abstract: | Iron‐bearing silicate systems are fundamental components of oxide melts, glasses, and ceramic materials, where multivalent iron strongly influences structure, thermodynamic properties, and redox behavior. Accurate determination of iron oxidation state remains a central challenge in studies of high‐temperature silicate systems because ferric to ferrous ratio control oxygen activity, defect chemistry, and phase equilibria. In this study, a quantitative approach for estimating the Fe3+/(Fe3+ + Fe2+) ratio is presented based on direct measurement of oxygen concentration in oxide system by electron probe microanalysis (EPMA). Two sets of samples in the Cu─Si─Fe─O system were synthesized using equilibration and quenching techniques, producing phase assemblages involving slag/copper/tridymite or slag/copper/magnetite (or wüstite) phases. Equilibration experiments were conducted at 1250°C and 1300°C, over oxygen partial pressures ranging from 10−9 to 10−6.5 atm, followed by rapid quenching of the samples to preserve high‐temperature equilibrium states. Elemental phase compositions, including metal cations and oxygen, were analyzed by EPMA. The measured oxygen concentrations were used to calculate valence states of metal cations (Cu+, Si4+, Fe2+, and Fe3+, respectively), enabling direct determination of the ferric to ferrous ratio in the samples. The experimental results have been compared with calculated and literature data, demonstrating that accurate oxygen quantification by EPMA provides a reliable approach for oxidation state determination in complex oxide systems. Beyond metallurgical slags, the proposed methodology is applicable to silicate melts, glasses, and ceramic materials, where multivalent cations control structure, defect chemistry, and thermodynamic behavior, offering a robust experimental tool for studies redox‐dependent properties in high‐temperature oxide materials. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of the American Ceramic Society is the property of Wiley-Blackwell 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.) | |
| Database: | Engineering Source |
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| Header | DbId: egs DbLabel: Engineering Source An: 194810597 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Quantitative Determination of Iron Redox State in Copper–Iron–Silicate Slags by Electron Probe Microanalysis. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Starykh%2C+Roman%22">Starykh, Roman</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> r.starykh@uq.edu.au</i><br /><searchLink fieldCode="AR" term="%22Sineva%2C+Svetlana%22">Sineva, Svetlana</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Shishin%2C+Denis%22">Shishin, Denis</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Jak%2C+Evgueni%22">Jak, Evgueni</searchLink><relatesTo>1</relatesTo> (AUTHOR) – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Ceramic+Society%22">Journal of the American Ceramic Society</searchLink>. Jun2026, Vol. 109 Issue 6, p1-23. 23p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Electron+probe+microanalysis%22">Electron probe microanalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Iron+oxidation%22">Iron oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation+states%22">Oxidation states</searchLink><br /><searchLink fieldCode="DE" term="%22Oxide+ceramics%22">Oxide ceramics</searchLink><br /><searchLink fieldCode="DE" term="%22Analytical+chemistry%22">Analytical chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Cations%22">Cations</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Iron‐bearing silicate systems are fundamental components of oxide melts, glasses, and ceramic materials, where multivalent iron strongly influences structure, thermodynamic properties, and redox behavior. Accurate determination of iron oxidation state remains a central challenge in studies of high‐temperature silicate systems because ferric to ferrous ratio control oxygen activity, defect chemistry, and phase equilibria. In this study, a quantitative approach for estimating the Fe3+/(Fe3+ + Fe2+) ratio is presented based on direct measurement of oxygen concentration in oxide system by electron probe microanalysis (EPMA). Two sets of samples in the Cu─Si─Fe─O system were synthesized using equilibration and quenching techniques, producing phase assemblages involving slag/copper/tridymite or slag/copper/magnetite (or wüstite) phases. Equilibration experiments were conducted at 1250°C and 1300°C, over oxygen partial pressures ranging from 10−9 to 10−6.5 atm, followed by rapid quenching of the samples to preserve high‐temperature equilibrium states. Elemental phase compositions, including metal cations and oxygen, were analyzed by EPMA. The measured oxygen concentrations were used to calculate valence states of metal cations (Cu+, Si4+, Fe2+, and Fe3+, respectively), enabling direct determination of the ferric to ferrous ratio in the samples. The experimental results have been compared with calculated and literature data, demonstrating that accurate oxygen quantification by EPMA provides a reliable approach for oxidation state determination in complex oxide systems. Beyond metallurgical slags, the proposed methodology is applicable to silicate melts, glasses, and ceramic materials, where multivalent cations control structure, defect chemistry, and thermodynamic behavior, offering a robust experimental tool for studies redox‐dependent properties in high‐temperature oxide materials. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Ceramic Society is the property of Wiley-Blackwell 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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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1111/jace.70929 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 23 StartPage: 1 Subjects: – SubjectFull: Electron probe microanalysis Type: general – SubjectFull: Iron oxidation Type: general – SubjectFull: Oxidation states Type: general – SubjectFull: Oxide ceramics Type: general – SubjectFull: Analytical chemistry Type: general – SubjectFull: Cations Type: general Titles: – TitleFull: Quantitative Determination of Iron Redox State in Copper–Iron–Silicate Slags by Electron Probe Microanalysis. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Starykh, Roman – PersonEntity: Name: NameFull: Sineva, Svetlana – PersonEntity: Name: NameFull: Shishin, Denis – PersonEntity: Name: NameFull: Jak, Evgueni IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 06 Text: Jun2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 00027820 Numbering: – Type: volume Value: 109 – Type: issue Value: 6 Titles: – TitleFull: Journal of the American Ceramic Society Type: main |
| ResultId | 1 |
