This paper focuses on the kinetics of Cr4+ formation in Cr,Ca:YAG ceramics prepared by solid-state reaction sintering. The kinetics of Cr4+ formation was studied by annealing of Cr,Ca:YAG ceramics in ambient air under different temperatures at different times, resulting in the transformation of Cr3+ to Cr4+. The activation energy (Ea) of Cr3+ oxidation determined by the Jander model was 2.7 ± 0.2 eV, which is in good correlation with the activation energy of innergrain oxygen diffusion in the YAG lattice. It is concluded that Cr3+ to Cr4+ transformation in YAG ceramics is limited by oxygen diffusion through the grain body. It was established that in Cr,Ca:YAG ceramics, the intralattice cation exchange, in which the Cr4+ ions exchange positions with the Al3+ ions, switching from "A" to "D" sites, is faster than Cr3+ to Cr4+ oxidation. In the temperature range of 900-1300 °C, the reaction enthalpy of Al3+/Cr4+ ion exchange between octahedral "A" and tetrahedral "D" lattice sites is close to zero, and this exchange ratio is thermodynamically driven by entropy.
Kinetics of Cr3+ to Cr4+ ion valence transformations and intra-lattice cation exchange of Cr4+ in Cr,Ca:YAG ceramics used as laser gain and passive Q-switching media / Chaika, M. A.; Tomala, R.; Strek, W.; Hreniak, D.; Dluzewski, P.; Morawiec, K.; Mateychenko, P. V.; Fedorov, A. G.; Doroshenko, A. G.; Parkhomenko, S. V.; Lesniewska-Matys, K.; Podniesinski, D.; Kozlowska, A.; Mancardi, G.; Vovk, O. M.. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 151:13(2019), pp. 134708-1-134708-10. [10.1063/1.5118321]
|Titolo:||Kinetics of Cr3+ to Cr4+ ion valence transformations and intra-lattice cation exchange of Cr4+ in Cr,Ca:YAG ceramics used as laser gain and passive Q-switching media|
|Data di pubblicazione:||2019|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1063/1.5118321|
|Appare nelle tipologie:||1.1 Articolo in rivista|