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Physicochemical processes and thermochemical parameters of GdFeO3 formation from amorphous hydroxides: decisive role of carbonate impurities

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Abstract

The mechanism of formation of nanocrystalline gadolinium orthoferrite (GdFeO3) during the heat treatment of gadolinium and iron(III) hydroxides synthesized by ultrasound-assisted co-precipitation was studied. The obtained samples were investigated by energy-dispersive X-ray spectroscopy, simultaneous thermal analysis via coupled differential scanning calorimetry and thermogravimetric analysis (DSC–TGA), powder X-ray diffraction (PXRD) and Fourier-transform infrared (FTIR) spectroscopy. The DSC–TGA results confirm that the formation of GdFeO3 occurs after the complete decomposition of gadolinium oxycarbonate derivatives. The PXRD results indicate that GdFeO3 is formed as a result of the reaction of amorphous iron(III) oxide (am-Fe2O3) at temperatures of 675–700 °C with amorphous gadolinium oxide (am-Gd2O3) (primary carbonate-independent pathway) and at temperatures of 725–775 °C with cubic gadolinium oxide (c-Gd2O3) transformed from the hexagonal gadolinium oxide (h-Gd2O3) which results from the decomposition of gadolinium oxycarbonate derivatives at temperatures of 675–725 °C (secondary carbonate-dependent pathway). The FTIR results are consistent with the assumption that gadolinium oxycarbonate derivatives decompose with the formation of h-Gd2O3 in the last-mentioned temperature range. The enthalpy of the reaction of formation of nanocrystalline GdFeO3 defined from the DSC–TGA data is equal to − 16.89 ± 0.36 kJ mol−1. The activation energy for the formation of nanocrystalline GdFeO3 obtained from the DSC data is equal to 1193.62 ± 112.05 kJ mol−1, 1202.27 ± 112.06 kJ mol−1 and 1151.08 ± 106.53 kJ mol−1 according to the Kissinger, Augis–Bennett/Boswell and Flynn–Wall–Ozawa methods, respectively. Also, based on the DSC data, the true onset temperature of the formation of nanocrystalline GdFeO3 was found to be ~ 756 °C.

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Acknowledgements

The study was partially performed using the equipment of the Engineering Center of Saint Petersburg State Institute of Technology.

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Authors and Affiliations

  1. Saint Petersburg State Institute of Technology, Saint Petersburg, Russian Federation, 190013

    Yamen Albadi

  2. Al-Baath University, Homs, Syrian Arab Republic, 77

    Yamen Albadi

  3. Ioffe Institute, Saint Petersburg, Russian Federation, 194021

    Anastasia K. Bachina & Vadim I. Popkov

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Contributions

Y. Albadi and V. I. Popkov contributed to conceptualization, methodology, validation and formal analysis; Y. Albadi and A. K. Bachina did investigation; A. K. Bachina and V. I. Popkov helped in resources; Y. Albadi did data curation, writing—original draft, visualization and writing—review & editing; V. I. Popkov contributed to writing—review & editing, supervision, project administration and funding acquisition.

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Correspondence to Yamen Albadi.

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Albadi, Y., Bachina, A.K. & Popkov, V.I. Physicochemical processes and thermochemical parameters of GdFeO3 formation from amorphous hydroxides: decisive role of carbonate impurities. J Therm Anal Calorim 148, 13281–13295 (2023). https://doi.org/10.1007/s10973-023-12647-7

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