Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12
Ceramic CaCu3Ti4O12 (ССТО), Ca0.98Cu3Ti4O11.96F0.04 (CΔCTOF), and CaCu3Ti4O11.92F0.08 (CCTOF) were synthesized by the solid-state reaction technique. Fluorine stimulates the formation of Cu-depleted grains, Cu3+ ions, and Cu-rich composites CuO-xCCTO-yTiO2-zSiO2-wСaF2 (w < z < y < x < 1)...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2024-06-01
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| Series: | Open Ceramics |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666539524000452 |
| _version_ | 1797237982625792000 |
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| author | O.Z. Yanchevskii O.I. V'yunov T.O. Plutenko A.G. Belous V.V. Trachevskii Yu.O. Zagorodniy I. Matolínová K. Veltruská V. Kalinovych |
| author_facet | O.Z. Yanchevskii O.I. V'yunov T.O. Plutenko A.G. Belous V.V. Trachevskii Yu.O. Zagorodniy I. Matolínová K. Veltruská V. Kalinovych |
| author_sort | O.Z. Yanchevskii |
| collection | DOAJ |
| description | Ceramic CaCu3Ti4O12 (ССТО), Ca0.98Cu3Ti4O11.96F0.04 (CΔCTOF), and CaCu3Ti4O11.92F0.08 (CCTOF) were synthesized by the solid-state reaction technique. Fluorine stimulates the formation of Cu-depleted grains, Cu3+ ions, and Cu-rich composites CuO-xCCTO-yTiO2-zSiO2-wСaF2 (w < z < y < x < 1), which include parts of grinding bodies. The observed structures are distinct from simple grain boundaries of the perovskite phase. They exhibit a terrace-ledge-kink (TLK) morphology and, in some cases, the presence of twinning planes, both independent of fluorine content. They are responsible for the nanoscale barrier layer capacitance (NBLC) component of the dielectric response of both CCTO and CuO ceramics. Changes in the unit cell parameter a, and titanium and copper valences indicate that Ca2+ ions occupy part of Cu vacancies in the grains of CCTO and CCTOF. In CΔCTOF, Ti3+ ions in the copper sublattice were found for the first time using NMR. The maximum ε′1kHz = 6.9 × 104 demonstrates CΔCTOF and the minimum tan δ = 0.045 is characteristic of CCTOF. |
| first_indexed | 2024-04-24T17:28:24Z |
| format | Article |
| id | doaj.art-9d1609dbc15844e5abe351954c989443 |
| institution | Directory Open Access Journal |
| issn | 2666-5395 |
| language | English |
| last_indexed | 2024-04-24T17:28:24Z |
| publishDate | 2024-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Open Ceramics |
| spelling | doaj.art-9d1609dbc15844e5abe351954c9894432024-03-28T06:38:46ZengElsevierOpen Ceramics2666-53952024-06-0118100581Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12O.Z. Yanchevskii0O.I. V'yunov1T.O. Plutenko2A.G. Belous3V.V. Trachevskii4Yu.O. Zagorodniy5I. Matolínová6K. Veltruská7V. Kalinovych8Department of Solid State Chemistry, V. I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, 03142, Kyiv, UkraineDepartment of Solid State Chemistry, V. I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, 03142, Kyiv, Ukraine; Technical Center of the National Academy of Sciences of Ukraine, Pokrovska str. 13, 04070, Kyiv, Ukraine; Corresponding author. Department of Solid State Chemistry, V. I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, 03142, Kyiv, Ukraine.Department of Solid State Chemistry, V. I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, 03142, Kyiv, UkraineDepartment of Solid State Chemistry, V. I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, 03142, Kyiv, UkraineTechnical Center of the National Academy of Sciences of Ukraine, Pokrovska str. 13, 04070, Kyiv, UkraineI.M. Frantsevich Institute for Problems of Material Sciences NAS of Ukraine, Omelyan Pritsak str. 3, 03142, Kyiv, UkraineDept. Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, 180 00, Prague, Czech RepublicDept. Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, 180 00, Prague, Czech RepublicDept. Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, 180 00, Prague, Czech RepublicCeramic CaCu3Ti4O12 (ССТО), Ca0.98Cu3Ti4O11.96F0.04 (CΔCTOF), and CaCu3Ti4O11.92F0.08 (CCTOF) were synthesized by the solid-state reaction technique. Fluorine stimulates the formation of Cu-depleted grains, Cu3+ ions, and Cu-rich composites CuO-xCCTO-yTiO2-zSiO2-wСaF2 (w < z < y < x < 1), which include parts of grinding bodies. The observed structures are distinct from simple grain boundaries of the perovskite phase. They exhibit a terrace-ledge-kink (TLK) morphology and, in some cases, the presence of twinning planes, both independent of fluorine content. They are responsible for the nanoscale barrier layer capacitance (NBLC) component of the dielectric response of both CCTO and CuO ceramics. Changes in the unit cell parameter a, and titanium and copper valences indicate that Ca2+ ions occupy part of Cu vacancies in the grains of CCTO and CCTOF. In CΔCTOF, Ti3+ ions in the copper sublattice were found for the first time using NMR. The maximum ε′1kHz = 6.9 × 104 demonstrates CΔCTOF and the minimum tan δ = 0.045 is characteristic of CCTOF.http://www.sciencedirect.com/science/article/pii/S2666539524000452 |
| spellingShingle | O.Z. Yanchevskii O.I. V'yunov T.O. Plutenko A.G. Belous V.V. Trachevskii Yu.O. Zagorodniy I. Matolínová K. Veltruská V. Kalinovych Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12 Open Ceramics |
| title | Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12 |
| title_full | Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12 |
| title_fullStr | Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12 |
| title_full_unstemmed | Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12 |
| title_short | Effect of fluorine on terrace-ledge-kink morphology and valence state of copper and titanium ions in CaCu3Ti4O12 |
| title_sort | effect of fluorine on terrace ledge kink morphology and valence state of copper and titanium ions in cacu3ti4o12 |
| url | http://www.sciencedirect.com/science/article/pii/S2666539524000452 |
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