Abstract <p>The phase formation in the system of triple phosphates Sr–<i>M</i><sup>2+</sup>–<i>Ln</i><sup>3+</sup> (<i>M</i><sup>2+</sup> = Zn<sup>2+</sup>, Mg<sup>2+</sup>, Mn<sup>2+</sup>; <i>Ln</i><sup>3+</sup> = Eu<sup>3+</sup>, Tb<sup>3+</sup>) is considered. Specific features of the strontiowhitlockite phase formation and the isomorphism in the series of phosphates Sr<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11445_2025_8160_Article_IEq1.gif" Format="GIF" Height="11" Rendition="HTML" Resolution="72" Type="Linedraw" Width="25" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{9-x}}\)</EquationSource> <!--Cryst2460295Nikiforov-m1--> </InlineEquation>Mn<sub><i>x</i></sub>Tb(PO<sub>4</sub>)<sub>7</sub>, Sr<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11445_2025_8160_Article_IEq1.gif" Format="GIF" Height="11" Rendition="HTML" Resolution="72" Type="Linedraw" Width="25" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{9-x}}\)</EquationSource> <!--Cryst2460295Nikiforov-m2--> </InlineEquation>Mg<sub><i>x</i></sub>Eu(PO<sub>4</sub>)<sub>7</sub>, and Sr<InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11445_2025_8160_Article_IEq1.gif" Format="GIF" Height="11" Rendition="HTML" Resolution="72" Type="Linedraw" Width="25" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{9-x}}\)</EquationSource> <!--Cryst2460295Nikiforov-m3--> </InlineEquation>Zn<sub><i>x</i></sub>Eu(PO<sub>4</sub>)<sub>7</sub> (0 ≤ <i>x</i> ≤ 1.0), obtained by solid-phase synthesis, have been studied. It is shown that a continuous series of solid solutions of these compositions cannot be formed. Crystallization of phases with strontiowhitlockite-type structures is observed for only stoichiometric phosphates Sr<sub>8</sub>MgEu(PO<sub>4</sub>)<sub>7</sub> and Sr<sub>8</sub>ZnEu(PO<sub>4</sub>)<sub>7</sub>. Crystal chemical analysis of the possibility of strontiowhitlockite phase formation in the studied series is performed. It is shown that samples with the strontiowhitlockite structure crystallize in the centrosymmetric space group (sp. gr. <i>R</i><InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11445_2025_8160_Article_IEq4.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="10" /> </InlineMediaObject> <EquationSource Format="TEX">\(\bar {3}\)</EquationSource> <!--Cryst2460295Nikiforov-m4--> </InlineEquation><i>m</i>), in contrast to the mother structure of mineral whitlockite and its calcium-based synthetic analogues. The conditions for the formation of phosphates with the stronciowhitlockite structure are indicated. The photoluminescence properties have been investigated. It is shown that the samples exhibit stable photoluminescence in the red-orange region due to the emission of Eu<sup>3+</sup> cations, whereas a quenching effect is observed in the Sr<InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11445_2025_8160_Article_IEq1.gif" Format="GIF" Height="11" Rendition="HTML" Resolution="72" Type="Linedraw" Width="25" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{9-x}}\)</EquationSource> <!--Cryst2460295Nikiforov-m5--> </InlineEquation>Mn<sub><i>x</i></sub>Tb(PO<sub>4</sub>)<sub>7</sub> series.</p>

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Phase Formation in the System of Triple Phosphates Sr–M2+Ln3+ (M2+ = Zn2+, Mg2+, Mn2+; Ln3+ = Eu3+, Tb3+)

  • I. V. Nikiforov,
  • K. N. Yashina,
  • E. S. Zhukovskaya,
  • S. I. Gutnikov,
  • S. M. Aksenov,
  • D. V. Deyneko

摘要

Abstract

The phase formation in the system of triple phosphates Sr–M2+Ln3+ (M2+ = Zn2+, Mg2+, Mn2+; Ln3+ = Eu3+, Tb3+) is considered. Specific features of the strontiowhitlockite phase formation and the isomorphism in the series of phosphates Sr \(_{{9-x}}\) MnxTb(PO4)7, Sr \(_{{9-x}}\) MgxEu(PO4)7, and Sr \(_{{9-x}}\) ZnxEu(PO4)7 (0 ≤ x ≤ 1.0), obtained by solid-phase synthesis, have been studied. It is shown that a continuous series of solid solutions of these compositions cannot be formed. Crystallization of phases with strontiowhitlockite-type structures is observed for only stoichiometric phosphates Sr8MgEu(PO4)7 and Sr8ZnEu(PO4)7. Crystal chemical analysis of the possibility of strontiowhitlockite phase formation in the studied series is performed. It is shown that samples with the strontiowhitlockite structure crystallize in the centrosymmetric space group (sp. gr. R \(\bar {3}\) m), in contrast to the mother structure of mineral whitlockite and its calcium-based synthetic analogues. The conditions for the formation of phosphates with the stronciowhitlockite structure are indicated. The photoluminescence properties have been investigated. It is shown that the samples exhibit stable photoluminescence in the red-orange region due to the emission of Eu3+ cations, whereas a quenching effect is observed in the Sr \(_{{9-x}}\) MnxTb(PO4)7 series.