Characterization of Synthetic Non-Metallic Inclusions Consisting of TiN, Ti2O3, and Oxides of Al2O3 and MgO·Al2O3 Spinel Using Raman Spectroscopy
Abstract
:1. Introduction
2. Materials and Methods
2.1. Raman Spectroscopy
2.2. Calibration Model
3. Results
3.1. Raman Spectra Analysis Based on Phase Content
3.2. Qualitative Analysis of Phase Content Based on Raman Spectra
3.2.1. TiN–Al2O3 and TiN– MgO·Al2O3 (MA)
3.2.2. Ti2O3–Al2O3, Ti2O3–MgO·Al2O3 (MA)
3.3. Quantitative Estimation of the Phase Fractions in the Samples
3.4. Further Phase Estimation Assessment
4. Discussion
4.1. Observation of Specific Raman Peaks Relative to the Change in Phase Content
4.2. Further Phase Identification Evaluation
4.3. Potential Limitations in the Measurements and Prospect for Future Application
5. Conclusions
- The most suitable Raman peaks (bands) identified for estimating the phases content present in the samples were:
- For Ti2O3–MA and Ti2O3–Al2O3 samples: at 247 cm−1 for Ti2O3, at 416 and 773 cm−1 for MgO·Al2O3, and 383, 422, and 760 cm−1 for Al2O3.
- For TiN–Al2O3 and TiN–MA samples: Raman peaks at 157 cm−1 for TiN, at 773 cm−1 for MgO·Al2O3, and 383 cm−1 for Al2O3.
- The Raman spectra data pre-processed by using the SNV had improved statistical performance, such as R2, RMSECV, and RMSEP, in the evaluation of the phase contents compared to the analysis made using the raw Raman spectra data.
- This work and previous studies combined present the prospect of using Raman spectroscopy to characterize a complex multiphase system that may contain oxide- and nitride-based inclusions in steel samples.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Initial Phase Composition (wt%) | Phases Calculated Based on XRF Analysis (wt%) | Initial Phase Composition (wt%) | Phases Calculated Based on XRF Analysis (wt%) | ||||
---|---|---|---|---|---|---|---|
Ti2O3 | Al2O3 | Ti2O3 | Al2O3 | MgO·Al2O3 | Ti2O3 | MgO·Al2O3 | Ti2O3 |
90 | 10 | 90.3 | 9.7 | 10 | 90 | 9.0 | 91.0 |
80 | 20 | 81.6 | 18.4 | 20 | 80 | 18.0 | 82.0 |
70 | 30 | 74.5 | 25.5 | 30 | 70 | 32.1 | 67.9 |
60 | 40 | 58.0 | 42.0 | 40 | 60 | 39.0 | 61.0 |
55 | 45 | 52.0 | 48.0 | 45 | 55 | 47.5 | 52.5 |
50 | 50 | 48.5 | 51.5 | 50 | 50 | 51.0 | 49.0 |
40 | 60 | 35.9 | 64.1 | 60 | 40 | 73.7 | 26.3 |
30 | 70 | 28.0 | 72.0 | 70 | 30 | 65.5 | 34.5 |
20 | 80 | 21.0 | 79.0 | 80 | 20 | 82.3 | 17.7 |
10 | 90 | 7.0 | 93.0 | 90 | 10 | 91.0 | 9.0 |
Initial Phase Composition (wt%) | Phases Calculated Based on XRF Analysis (wt%) | Initial Phase Composition (wt%) | Phases Calculated Based on XRF Analysis (wt%) | ||||
---|---|---|---|---|---|---|---|
TiN | Al2O3 | TiN | Al2O3 | MgO·Al2O3 | TiN | MgO·Al2O3 | TiN |
10 | 90 | 9.0 | 91.0 | 10 | 90 | 8.0 | 92.0 |
20 | 80 | 16.0 | 84.0 | 20 | 80 | 22.0 | 78.0 |
30 | 70 | 28.8 | 71.2 | 30 | 70 | 28.8 | 71.2 |
40 | 60 | 36.8 | 63.2 | 40 | 60 | 36.8 | 63.2 |
50 | 50 | 46.7 | 53.3 | 45 | 55 | 46.7 | 53.3 |
60 | 40 | 53.0 | 47.0 | 50 | 50 | 52.0 | 48.0 |
70 | 30 | 56.7 | 43.3 | 60 | 40 | 56.7 | 43.3 |
80 | 20 | 75.3 | 24.7 | 70 | 30 | 75.3 | 24.7 |
90 | 10 | 83.9 | 16.1 | 80 | 20 | 83.9 | 16.1 |
90 | 10 | 91.2 | 8.8 |
Phase | Measured Peaks [Raman Shift, cm−1] | Reference Peaks [Raman Shift, cm−1] | Reference |
---|---|---|---|
TiN | 157 s, 260 m, 620 m | 152 s, 340 m, 410 m, 620 m, | [23] |
Al2O3 | 422 s, 383 m, 760 m, | 413–420 s, 375–380 m, 758 m, | [24] |
MgO·Al2O3 | 416 s, 674 m, 773 m | 409–412 s, 666–674 m, 767–772 m | [25] |
Ti2O3 | 247 s, 335 m, | 247 s, 336 m, 423 w | [26] |
System | Relative Intensity | R2 | System | Relative Intensity | R2 |
---|---|---|---|---|---|
(i) TiN-Al2O3 | 382/157 | 0.99 | (iii) TiN-MgO·Al2O3 | 674/157 | 0.91 |
382/260 | 0.74 | 674/260 | 0.97 | ||
422/157 | 0.94 | 416/157 | 0.98 | ||
422/260 | 0.72 | 422/260 | 0.96 | ||
760/157 | 0.98 | 773/157 | 0.98 | ||
760/335 | 0.87 | 773/335 | 0.95 | ||
382/620 | 0.88 | 674/620 | 0.93 | ||
760/620 | 0.95 | 773/620 | 0.97 | ||
(ii) Ti2O3-Al2O3 | 382/247 | 0.86 | (iv) Ti2O3-MgO·Al2O3 | 416/247 | 0.98 |
382/335 | 0.95 | 416/335 | 0.95 | ||
422/247 | 0.97 | 674/247 | 0.81 | ||
422/335 | 0.93 | 674/335 | 0.89 | ||
760/247 | 0.90 | 774/247 | 0.79 | ||
760/335 | 0.95 | 774/335 | 0.87 |
System | Phase | Method | R2CAL | R2CV | R2PRED. | RMSEC, (wt%) | RMSECV, (wt%) | RMSEP, (wt%) |
---|---|---|---|---|---|---|---|---|
(i) TiN–Al2O3 | TiN | Raw Data | 0.86 | 0.79 | 0.58 | 11.56 | 15.14 | 15.01 |
SNV Data | 0.95 | 0.94 | 0.84 | 6.68 | 7.79 | 9.08 | ||
Al2O3 | Raw Data | 0.86 | 0.79 | 0.58 | 11.56 | 15.14 | 15.11 | |
SNV Data | 0.96 | 0.95 | 0.94 | 6.11 | 7.71 | 9.07 | ||
(ii) TiN–MgO·Al2O3 | TiN | Raw Data | 0.61 | 0.48 | 0.61 | 14.63 | 18.10 | 14.63 |
SNV Data | 0.99 | 0.99 | 0.98 | 2.60 | 3.10 | 3.01 | ||
MgO·Al2O3 | Raw Data | 0.86 | 0.79 | 0.81 | 11.83 | 13.99 | 14.14 | |
SNV Data | 0.98 | 0.99 | 0.98 | 2.94 | 2.97 | 3.12 |
System | Phase | Method | R2CAL | R2CV | R2PRED. | RMSEC, (wt%) | RMSECV, (wt%) | RMSEP, (wt%) |
---|---|---|---|---|---|---|---|---|
(i) Ti2O3–Al2O3 | Ti2O3 | Raw Data | 0.98 | 0.98 | 0.98 | 3.26 | 3.57 | 2.98 |
SNV Data | 0.99 | 0.98 | 0.98 | 3.26 | 3.64 | 2.98 | ||
Al2O3 | Raw Data | 0.99 | 0.99 | 0.98 | 3.11 | 3.68 | 2.94 | |
SNV Data | 0.98 | 0.99 | 0.98 | 3.35 | 3.70 | 2.95 | ||
(ii) Ti2O3–MgO·Al2O3 | Ti2O3 | Raw Data | 0.94 | 0.97 | 0.95 | 5.14 | 6.09 | 5.75 |
SNV Data | 0.98 | 0.98 | 0.97 | 4.81 | 3.22 | 3.02 | ||
MgO·Al2O3 | Raw Data | 0.93 | 0.96 | 0.94 | 5.23 | 6.46 | 7.17 | |
SNV Data | 0.98 | 0.97 | 0.97 | 4.81 | 5.28 | 4.79 |
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Gyakwaa, F.; Alatarvas, T.; Shu, Q.; Aula, M.; Fabritius, T. Characterization of Synthetic Non-Metallic Inclusions Consisting of TiN, Ti2O3, and Oxides of Al2O3 and MgO·Al2O3 Spinel Using Raman Spectroscopy. Metals 2021, 11, 1549. https://doi.org/10.3390/met11101549
Gyakwaa F, Alatarvas T, Shu Q, Aula M, Fabritius T. Characterization of Synthetic Non-Metallic Inclusions Consisting of TiN, Ti2O3, and Oxides of Al2O3 and MgO·Al2O3 Spinel Using Raman Spectroscopy. Metals. 2021; 11(10):1549. https://doi.org/10.3390/met11101549
Chicago/Turabian StyleGyakwaa, Francis, Tuomas Alatarvas, Qifeng Shu, Matti Aula, and Timo Fabritius. 2021. "Characterization of Synthetic Non-Metallic Inclusions Consisting of TiN, Ti2O3, and Oxides of Al2O3 and MgO·Al2O3 Spinel Using Raman Spectroscopy" Metals 11, no. 10: 1549. https://doi.org/10.3390/met11101549