Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state
Electron Probe X-ray Microanalysis (EPMA) is a key method for studying phase equilibria in oxide materials, offering an effective balance of precision, accuracy, cost, speed and spatial resolution. It provides valuable compositional data for single phase and multiphase materials, particularly those...
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| Language: | English |
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Elsevier
2025-07-01
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| Series: | Materials & Design |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S0264127525006008 |
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| author | Roman Starykh Svetlana Sineva Denis Shishin Evgueni Jak |
| author_facet | Roman Starykh Svetlana Sineva Denis Shishin Evgueni Jak |
| author_sort | Roman Starykh |
| collection | DOAJ |
| description | Electron Probe X-ray Microanalysis (EPMA) is a key method for studying phase equilibria in oxide materials, offering an effective balance of precision, accuracy, cost, speed and spatial resolution. It provides valuable compositional data for single phase and multiphase materials, particularly those with complex microstructures. Historically, high absorption of characteristic X-rays has limited the accuracy of oxygen quantification, leading to reliance on metal cation measurements and assumed oxidation states, often resulting in inaccuracies. This study highlights recent advancements in EPMA sample preparation and measurement techniques that significantly enhance oxygen quantification. To validate the method, Fe-O system samples were synthesized at 1300 °C (1573 K) under controlled oxygen partial pressures. A wide range of P(O2) was employed to cover the Fe3+/(Fe2+ + Fe3+) ratios from 0.1 to 1.0 in wüstite, spinel, and hematite phases. The results were compared with existing thermodynamic models and experimental data, demonstrating excellent agreement. The enhanced EPMA methodology offers potential for direct quantitative measurement of oxygen, which in turn, opens an opportunity to estimate Fe3+/(Fe2+ + Fe3+) ratios in complex chemical systems, including quenched slags. The approach is applicable to other metals with variable oxidation states, provided a single element primarily drives oxidation state changes. |
| format | Article |
| id | doaj-art-d16d72783e4e4911948badf8860523bc |
| institution | DOAJ |
| issn | 0264-1275 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Materials & Design |
| spelling | doaj-art-d16d72783e4e4911948badf8860523bc2025-08-20T03:22:04ZengElsevierMaterials & Design0264-12752025-07-0125511418010.1016/j.matdes.2025.114180Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation stateRoman Starykh0Svetlana Sineva1Denis Shishin2Evgueni Jak3Corresponding author.; PYROSEARCH, The University of Queensland, Brisbane, QLD 4072, AustraliaPYROSEARCH, The University of Queensland, Brisbane, QLD 4072, AustraliaPYROSEARCH, The University of Queensland, Brisbane, QLD 4072, AustraliaPYROSEARCH, The University of Queensland, Brisbane, QLD 4072, AustraliaElectron Probe X-ray Microanalysis (EPMA) is a key method for studying phase equilibria in oxide materials, offering an effective balance of precision, accuracy, cost, speed and spatial resolution. It provides valuable compositional data for single phase and multiphase materials, particularly those with complex microstructures. Historically, high absorption of characteristic X-rays has limited the accuracy of oxygen quantification, leading to reliance on metal cation measurements and assumed oxidation states, often resulting in inaccuracies. This study highlights recent advancements in EPMA sample preparation and measurement techniques that significantly enhance oxygen quantification. To validate the method, Fe-O system samples were synthesized at 1300 °C (1573 K) under controlled oxygen partial pressures. A wide range of P(O2) was employed to cover the Fe3+/(Fe2+ + Fe3+) ratios from 0.1 to 1.0 in wüstite, spinel, and hematite phases. The results were compared with existing thermodynamic models and experimental data, demonstrating excellent agreement. The enhanced EPMA methodology offers potential for direct quantitative measurement of oxygen, which in turn, opens an opportunity to estimate Fe3+/(Fe2+ + Fe3+) ratios in complex chemical systems, including quenched slags. The approach is applicable to other metals with variable oxidation states, provided a single element primarily drives oxidation state changes.http://www.sciencedirect.com/science/article/pii/S0264127525006008Fe-O systemFerric to ferrous ratioOxygen measurementEPMA |
| spellingShingle | Roman Starykh Svetlana Sineva Denis Shishin Evgueni Jak Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state Materials & Design Fe-O system Ferric to ferrous ratio Oxygen measurement EPMA |
| title | Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state |
| title_full | Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state |
| title_fullStr | Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state |
| title_full_unstemmed | Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state |
| title_short | Quantitative measurement of oxygen by Electron Probe X-ray Microanalysis for estimation of iron oxidation state |
| title_sort | quantitative measurement of oxygen by electron probe x ray microanalysis for estimation of iron oxidation state |
| topic | Fe-O system Ferric to ferrous ratio Oxygen measurement EPMA |
| url | http://www.sciencedirect.com/science/article/pii/S0264127525006008 |
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