najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2023-14-1-107-111najo-199Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХInfluence of high energy milling on titanium oxide Ti3O5 crystal structureВлияние высокоэнергетического размола на кристаллическую структуру оксида титана Ti3O5https://orcid.org/0000-0003-1656-732XВалееваА. А.ValeevaA. A.

Альбина Ахметовна Валеева,

620108, Екатеринбург.

Albina A. Valeeva,

620108, Ekaterinburg.

anibla_v@mail.ruhttps://orcid.org/0000-0001-9229-6758ДорошеваИ. Б.DoroshevaI. B.

Ирина Борисовна Дорошева,

620002, Екатеринбург.

Irina B. Dorosheva, 

620002, Ekaterinburg.

dorosheva1993@mail.ruhttps://orcid.org/0000-0002-7604-5673СушниковаА. А.SushnikovaA. A.

Анна Алексеевна Сушникова,

620016 Екатеринбург.

Anna A. Sushnikova,

620016 Ekaterinburg.

sushnikova.ann@gmail.comИнститут химии твердого тела Уральского отделения Российской академии наукInstitute of Solid State Chemistry, Ural Branch of the Russian Academy of SciencesУральский Федеральный Университет; Институт металлургии Уральского отделения Российской академии наукUral Federal University; Institute of Metallurgy, Ural Branch of the Russian Academy of SciencesИнститут металлургии Уральского отделения Российской академии наукInstitute of Metallurgy, Ural Branch of the Russian Academy of Sciences202305062025141107111Copyright © Valeeva A.A., Dorosheva I.B., Sushnikova A.A., 20252025Валеева А.А., Дорошева И.Б., Сушникова А.А.Valeeva A.A., Dorosheva I.B., Sushnikova A.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/199

The titanium oxide (Ti3O5) microcrystals were synthesized by using solid-phase sintering from a mixture of titanium Ti and titanium dioxide TiO2 powders. Subsequently, Ti3O5 nanocrystals were produced by using high-energy ball milling for 15 – 480 minutes. A full-profile analysis of the X-ray diffraction spectra of milled Ti3O5 powders showed that high-energy milling does not lead to disordering or changing of the structure and stoichiometry, the structure remains monoclinic (sp. gr. C2/m), and XRD reflections are broadened due to the small particle size and microdeformations. Experimental data show that increasing of the milling time leads to decreasing of the coherent scattering regions up to 26 nm, increasing of the powder volume fraction of the nanophase up to 81 %, and increasing of microdeformations value. The morphology and the surface area of milled nanopowders were examined by SEM, HRTEM and BET techniques.

Микрокристаллы оксида титана (Ti3O5) были синтезированы методом  твердофазного спекания из смеси порошков титана Ti и диоксида титана TiO2. Далее, были получены нанокристаллы Ti3O5 методом высокоэнергетического размола в течение 15-480 минут. Полнопрофильный анализ рентгеновских спектров размолотых порошков Ti3O5 показал, что высокоэнергетический размол не приводит к разупорядочению или изменению кристаллической структуры и стехиометрии, структура остаётся моноклинной (пр.гр. C2/m), а рефлексы на рентгенограмме уширяются за счёт малого размера частиц и микродеформациям. Экспериментальные данные показывают, что увеличение времени размола приводит к уменьшению областей когерентного рассеяния до 26 нм, увеличению объемной доли порошка нанофазы до 81% и увеличению величины микродеформации в размолотом порошке. Кроме того, исследована морфология и удельная площадь поверхности размолотоых нанопорошков методами РЭМ, ПЭМ, и БЭТ.

высокоэнергетический размолTi3O5РФАБЭТРЭМПЭМhigh-energy ball millingTi3O5XRDBETSEMHRTEMThe work was carried out in accordance with the state assignment for the Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Science (No. 0397-2019-0001). Authors thanks to Gerasimov E. Yu. for HRTEM experiments.ReferencesWang Y., Qin Y., et al. One-step synthesis and optical properties of blue titanium suboxide nanoparticles. J. of Crystal Growth, 2005, 282 (3–4), P. 402–406.Wang Y., Qin Y., et al. One-step synthesis and optical properties of blue titanium suboxide nanoparticles. J. of Crystal Growth, 2005, 282 (3–4), P. 402–406.Valeeva A.A., Kostenko M.G. Stable Ti9O10 nanophase grown from nonstoichiometric titanium monoxide TiOy nanopowder. Nanosystems: Phys. Chem. Math., 2017, 8 (6), P. 816–822.Valeeva A.A., Kostenko M.G. Stable Ti9O10 nanophase grown from nonstoichiometric titanium monoxide TiOy nanopowder. Nanosystems: Phys. Chem. Math., 2017, 8 (6), P. 816–822.Hauf C., Kniep R., Pfaff, G. Preparation of various titanium suboxide powders by reduction of TiO2 with silicon. J. of Materials Science, 1999, 34 (6), P. 1287–1292.Hauf C., Kniep R., Pfaff, G. Preparation of various titanium suboxide powders by reduction of TiO2 with silicon. J. of Materials Science, 1999, 34 (6), P. 1287–1292.Valeeva A.A., Nazarova S.Z., Rempel A.A. Influence of particle size, stoichiometry, and degree of long-range order on magnetic susceptibility of titanium monoxide. Physics of the Solid State, 2016, 58 (4), P. 771–778.Valeeva A.A., Nazarova S.Z., Rempel A.A. Influence of particle size, stoichiometry, and degree of long-range order on magnetic susceptibility of titanium monoxide. Physics of the Solid State, 2016, 58 (4), P. 771–778.Kostenko M.G., Valeeva A.A., Rempel A.A. Octahedral Clusters in Various Phases of Nonstoichiometric Titanium Monoxide. Mendeleev Communications, 2012, 22 (5), P. 245–247.Kostenko M.G., Valeeva A.A., Rempel A.A. Octahedral Clusters in Various Phases of Nonstoichiometric Titanium Monoxide. Mendeleev Communications, 2012, 22 (5), P. 245–247.Rempel A.A., Valeeva A.A. Thermodynamics of atomic ordering in nonstoichiometric transition metal monoxides. Mendeleev Communications, 2010, 20 (2), P. 101–103.Rempel A.A., Valeeva A.A. Thermodynamics of atomic ordering in nonstoichiometric transition metal monoxides. Mendeleev Communications, 2010, 20 (2), P. 101–103.Bachina A.K., Popkov V.I., et al. Synthesis, Characterization and Photocatalytic Activity of Spherulite-like r-TiO2 in Hydrogen Evolution Reaction and Methyl Violet Photodegradation. Catalysts, 2022, 12 (12), 1546.Bachina A.K., Popkov V.I., et al. Synthesis, Characterization and Photocatalytic Activity of Spherulite-like r-TiO2 in Hydrogen Evolution Reaction and Methyl Violet Photodegradation. Catalysts, 2022, 12 (12), 1546.Dorosheva I.B., Valeeva A.A., et al. Synthesis and Physicochemical Properties of Nanostructured TiO2 with Enhanced Photocatalytic Activity. Inorganic Materials, 2021, 57 (5), P. 503–510.Dorosheva I.B., Valeeva A.A., et al. Synthesis and Physicochemical Properties of Nanostructured TiO2 with Enhanced Photocatalytic Activity. Inorganic Materials, 2021, 57 (5), P. 503–510.Valeeva A.A., Dorosheva I.B., et al. Solar photocatalysts based on titanium dioxide nanotubes for hydrogen evolution from aqueous solutions of ethanol. Int. J. of Hydrogen Energy, 2021, 46 (32), P. 16917–16924.Valeeva A.A., Dorosheva I.B., et al. Solar photocatalysts based on titanium dioxide nanotubes for hydrogen evolution from aqueous solutions of ethanol. Int. J. of Hydrogen Energy, 2021, 46 (32), P. 16917–16924.Rempel A.A., Valeeva A.A. Nanostructured titanium dioxide for medicinal chemistry. Russian Chemical Bulletin, 2019, 68 (12), P. 2163–2171.Rempel A.A., Valeeva A.A. Nanostructured titanium dioxide for medicinal chemistry. Russian Chemical Bulletin, 2019, 68 (12), P. 2163–2171.Dorosheva I.B., Valeeva A.A., Rempel A.A. Sol-gel synthesis of nanosized titanium dioxide at various pH of the initial solution. AIP Conference Proceedings, 2017, 1886, 020006.Dorosheva I.B., Valeeva A.A., Rempel A.A. Sol-gel synthesis of nanosized titanium dioxide at various pH of the initial solution. AIP Conference Proceedings, 2017, 1886, 020006.Rempel A.A., Kuznetsova Y.V., et al. High Photocatalytic Activity Under Visible Light of Sandwich Structures Based on Anodic TiO2/CdS Nanoparticles/Sol–Gel TiO2. Topics in Catalysis, 2020, 63 (1–2), P. 130–138.Rempel A.A., Kuznetsova Y.V., et al. High Photocatalytic Activity Under Visible Light of Sandwich Structures Based on Anodic TiO2/CdS Nanoparticles/Sol–Gel TiO2. Topics in Catalysis, 2020, 63 (1–2), P. 130–138.Popkov V.I., Bachina A.K., et al. Synthesis, morphology and electrochemical properties of spherulite titania nanocrystals. Ceramics Int., 2020, 46 (14), P. 24483–24487.Popkov V.I., Bachina A.K., et al. Synthesis, morphology and electrochemical properties of spherulite titania nanocrystals. Ceramics Int., 2020, 46 (14), P. 24483–24487.Vasilevskaia A.K., Popkov V.I., Valeeva A.A., Rempel A.A. Formation of nonstoichiometric titanium oxides nanoparticles TinO2n−1 upon heattreatments of titanium hydroxide and anatase nanoparticles in a hydrogen flow. Russian J. of Applied Chemistry, 2016, 89 (8), P. 1211–1220.Vasilevskaia A.K., Popkov V.I., Valeeva A.A., Rempel A.A. Formation of nonstoichiometric titanium oxides nanoparticles TinO2n−1 upon heattreatments of titanium hydroxide and anatase nanoparticles in a hydrogen flow. Russian J. of Applied Chemistry, 2016, 89 (8), P. 1211–1220.Yoshimatsu K., Sakata O., Ohtomo A. Superconductivity in Ti4O7 and γ-Ti3O5 films. Scientific Reports, 2017, 7 (1), P. 1–7.Yoshimatsu K., Sakata O., Ohtomo A. Superconductivity in Ti4O7 and γ-Ti3O5 films. Scientific Reports, 2017, 7 (1), P. 1–7.Yang S., Zhang L., et al. A novel carbon thermal reduction approach to prepare recorded purity β-Ti3O5 compacts from titanium dioxide and phenolic resin, J. of Alloys and Compounds, 2021, 853, 157360.Yang S., Zhang L., et al. A novel carbon thermal reduction approach to prepare recorded purity β-Ti3O5 compacts from titanium dioxide and phenolic resin, J. of Alloys and Compounds, 2021, 853, 157360.Tanaka K., Nasu T., et al. Structural Phase Transition between γ-Ti3O5 and δ-Ti3O5 by Breaking of a One-Dimensionally Conducting Pathway. Crystal Growth & Design, 2014, 15 (2), P. 653–657.Tanaka K., Nasu T., et al. Structural Phase Transition between γ-Ti3O5 and δ-Ti3O5 by Breaking of a One-Dimensionally Conducting Pathway. Crystal Growth & Design, 2014, 15 (2), P. 653–657.Rempel A.A., Valeeva A.A., Vokhmintsev A.S., Weinstein I.A. Titanium dioxide nanotubes: Synthesis, structure, properties and applications. Russian Chemical Reviews, 2021, 90 (11), P. 1397–1414.Rempel A.A., Valeeva A.A., Vokhmintsev A.S., Weinstein I.A. Titanium dioxide nanotubes: Synthesis, structure, properties and applications. Russian Chemical Reviews, 2021, 90 (11), P. 1397–1414.Valeeva A.A., Rempel A.A., et al. Nonstoichiometry, structure and properties of nanocrystalline oxides, carbides and sulfides. Russian Chemical Reviews, 2021, 90 (51), P. 601–626.Valeeva A.A., Rempel A.A., et al. Nonstoichiometry, structure and properties of nanocrystalline oxides, carbides and sulfides. Russian Chemical Reviews, 2021, 90 (51), P. 601–626.Valeeva A.A., Nazarova S.Z., Rempel A.A. Nanosize effect on phase transformations of titanium oxide Ti2O3. J. of Alloys and Compounds, 2019, 817, 153215.Valeeva A.A., Nazarova S.Z., Rempel A.A. Nanosize effect on phase transformations of titanium oxide Ti2O3. J. of Alloys and Compounds, 2019, 817, 153215.Valeeva A.A., Nazarova S.Z., et al. Effects of high mechanical treatment and long-term annealing on crystal structure and thermal stability of Ti2O3 nanocrystals. RSC Advances, 2020, 10 (43), P. 25717–25720.Valeeva A.A., Nazarova S.Z., et al. Effects of high mechanical treatment and long-term annealing on crystal structure and thermal stability of Ti2O3 nanocrystals. RSC Advances, 2020, 10 (43), P. 25717–25720.Indris S., Amade R., et al. Preparation by High-Energy Milling, Characterization, and Catalytic Properties of Nanocrystalline TiO2. The J. of Physical Chemistry B, 2005, 109 (49), P. 23274–23278.Indris S., Amade R., et al. Preparation by High-Energy Milling, Characterization, and Catalytic Properties of Nanocrystalline TiO2. The J. of Physical Chemistry B, 2005, 109 (49), P. 23274–23278.Melchakova O.V., Pechishcheva N.V., Korobitsyna A.D. Mechanically activated rutile and its sorption properties with regard to gallium and germanium. Tsvetnye Metally, 2019, 1, P. 32–39.Melchakova O.V., Pechishcheva N.V., Korobitsyna A.D. Mechanically activated rutile and its sorption properties with regard to gallium and germanium. Tsvetnye Metally, 2019, 1, P. 32–39.Valeeva A A., Schrottner H., Rempel A.A. Fragmentation of disordered titanium monoxide of stoichiometric composition TiO.¨ Russian Chemical Bulletin, 2014, 63 (12), P. 2729–2732.Valeeva A A., Schrottner H., Rempel A.A. Fragmentation of disordered titanium monoxide of stoichiometric composition TiO.¨ Russian Chemical Bulletin, 2014, 63 (12), P. 2729–2732.Valeeva A.A., Nazarova S.Z., Rempel A.A. Size effect on magnetic susceptibility of titanium monoxide nanocrystals. Physica Status Solidi B, 2016, 253 (2), P. 392–396.Valeeva A.A., Nazarova S.Z., Rempel A.A. Size effect on magnetic susceptibility of titanium monoxide nanocrystals. Physica Status Solidi B, 2016, 253 (2), P. 392–396.Uzunova-Bujnova M., Dimitrov D., et al. Effect of the mechanoactivation on the structure, sorption and photocatalytic properties of titanium dioxide. Materials Chemistry and Physics, 2008, 110 (2–3), P. 291–298.Uzunova-Bujnova M., Dimitrov D., et al. Effect of the mechanoactivation on the structure, sorption and photocatalytic properties of titanium dioxide. Materials Chemistry and Physics, 2008, 110 (2–3), P. 291–298.Ordinartsev D.P., Pechishcheva N.V., et al. Nanosized Titania for Removing Cr(VI) and As(III) from Aqueous Solutions. Russian J. of Physical Chemistry A, 2022, 96 (11), P. 2408–2416.Ordinartsev D.P., Pechishcheva N.V., et al. Nanosized Titania for Removing Cr(VI) and As(III) from Aqueous Solutions. Russian J. of Physical Chemistry A, 2022, 96 (11), P. 2408–2416.Hall W.H. X-Ray Line Broadening in Metals. Proceedings of the Physical Society, 1949, 62, P. 741–743Hall W.H. X-Ray Line Broadening in Metals. Proceedings of the Physical Society, 1949, 62, P. 741–743

The authors declare that there are no conflicts of interest present.