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NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2018, 9 (4), P. 544-548
Effect of high pressures and high temperatures on the structure of nanostructured
titanium monoxide
A. A. Valeeva1'2, M. G. Kostenko1, A. Pfitzner3, A. A. Rempel1'2
institute of Solid State Chemistry UB RAS, 91, Pervomaiskaya st., Ekaterinburg, 620990, Russia 2Ural Federal University named after the first President of Russia B. N. Eltsin,
91, Mira st., Ekaterinburg, 620002, Russia 3Institute of Inorganic Chemistry, Regensburg University, Regensburg, Germany
PACS 61.72.Dd, 61.72.Bb, 64.70.Nd, 71.20.Ps DOI 10.17586/2220-8054-2018-9-4-544-548
The structure of nanostructured titanium monoxide TiOo.98 containing structural vacancies in two sublattices simultaneously has been modified via thermobaric annealing. Analysis of the experimental data on thermobaric synthesis of nanostructured TiOo.98 with cubic B1 type structure at temperatures 573 - 2273 K and pressure 6 GPa revealed that a transition from the cubic B1 (sp. gr. Fm3m) phase to the trigonal H2O3 (sp. gr. R3c) phase takes place in the nanostructured monoxide as a result of high pressures and high temperatures. The first-principle calculations of the cohesive energy and electronic structure show that the trigonal phase with space group R3c is energetically favorable compared to the cubic phase of the same composition T1O3/2 and the orthorhombic ordered H2O3 (sp. gr. Immm) phase.
Keywords: nanostructured titanium monoxide, structural vacancy, nonstoichiometry, high pressure, high temperature, phase transition, electronic structure.
Received: 25 May 2018 Revised: 12 July 2018
1. Introduction
Oxides, carbides and nitrides of transition metals of IV - V groups of the periodic table having B1 type crystal structure feature wide homogeneity regions due to an anomalously high concentration of structural vacancies -crystal lattice sites which are not occupied by atoms [1,2]. Vacancies are associated not only with nonstoichiom-etry, but also with short- and long-range order effects allowing a great number of various phases and structural modifications of a compound to be obtained while retaining the type of its basis crystal structure [3-8]. This peculiarity is of importance in terms of the topical problem of designing materials with pre-defined properties.
Titianium monoxide is a unique compound with a wide homogeneity region (TiO0.7 - TiO1.3) and an anomalously high (to 30 at. %) concentration of vacancies simultaneously in the metal and nonmetal sublattices of B1 structure [8-13]. The experimental works performed earlier on samples of microcrystalline titanium monoxide showed that electron irradiation [14,15] and the treatment by pressure [16-19] or heat [8-12] lead to the modification of the structure and properties by changing the concentration of the vacancies or the way of their arrangement in the structure. In the nanostate, in addition to point defects (structural vacancies), two-dimensional defects (crystal surface) should also be taken into consideration. The interference of these two types of defects extends the variety of possible structural modifications and the range of controllable properties [20-23]. In particular, while high-temperature annealing of microcrystalline titanium monoxide gives rise to the monoclinic phase Ti5O5 [10-12], in the experiment on nanostructured samples a Ti9O10 phase was observed whose structure is not typical of micro-crystalline state [24]. The aim of this work is to study the behavior of the structure of nanostructured titanium monoxide under high pressure and high temperature.
2. Experimental
The microcrystals of titanium monoxide TiOy with the average size of ~ 25 ^m have been synthesized by the solid phase sintering from a mixture of titanium Ti and titanium dioxide TiO2 powders in vacuum 10-3 Pa at 1770 K. In order to achieve a disordered state of titanium dioxide, the evacuated (10-3 Pa) quartz ampoules with samples were annealed for 3 h at 1330 K, whereupon they were dropped into the water, the quenching rate was ~ 200 K/s. According to the XRD data, the microcrystalline powder contained reflections only of the cubic phase with B1 structure (sp. gr. Fm3m) with a disordered arrangement of vacancies in sublattices. A multi-parameter certification of the samples was carried out with the use of chemical, spectral, pycnometer, X-ray diffraction and
X-ray structure analysis methods. The heat treatment method for obtaining the disordered and ordered states and the results of attestation of the synthesized samples are described in detail in work [12].
Nanocrystals of titanium monoxide were produced by high-energy milling in a Retsch PM 200 planetary ball mill using Y2O3-stabilized ZrO2 grinding media and vials. The ball-to-powder weight ratio in our experiments was 10:1. The milling liquid used was isopropanol. The high-energy milling conditions were as follows: milling time of 15, 30, 60, 120, 240, and 480 min; rotation direction reversed every 15 min; interval between direction reversals, 5 s; rotation speed of the disk supporting the grinding vials, 500 rpm [22].
The XRD studies of TiOy were carried out with a STOE STADI P transmission diffractometer equipped with a linear PSD, a Ge-monochromator, and a Mythen 1 K detector at 293 K. The measurements were performed using CuKa1 radiation, the 26 range was 10-116 ° with a step-width of 0.015 Polycrystalline silicon (a = 543.07 pm) was used as external standard. The XRD patterns were measured both in a short run and a longer run with better statistics. Four XRD powder patterns were summed up for better statistics and were used for a full profile analysis. The error of the lattice constant determination was about 1 pm. The phase analysis of the XRD pattern was performed using the Powder Cell 2.4 program. For phase identification the powder standards database ICDD PDF2 (ICDD, USA, Release 2009) was used. There are small crystalline peaks around 26 = 36.7, 41.5 and 54.2 degree in the initial sample. According to phase analysis, the impurity lines on the XRD pattern are from an unidentified compound.
In addition to reducing particle size, that is, comminuting, milling produces internal lattice strain in the resulting nanoparticles. The diameter of nanocrystals D was determined from the broadening of X-ray diffraction reflections by the Williamson-Hall method [25,26]. Owing to the fragmentation of ordered titanium monoxides with near-stoichiometric compositions, we obtained nanoparticles 20 ± 10 nm in size, with the lowest lattice strain at a level of 0.3 %. The fragmentation of disordered titanium monoxides with both substoichiometric and superstoichiometric compositions resulted in roughly the same particle size, about 40 ± 10 nm, but the lattice strain was three times higher. Analysis of X-ray diffraction patterns showed that high-energy milling led to disordering and reduced the degree of long-range order. The techniques used to prepare nanocrystals by high-energy milling, analysis of X-ray diffraction patterns, SEM and TEM pictures, calculation of the coherent scattering region sizes were described elsewhere [22,24].
High-pressure experiments were performed on a modified high-pressure plant (Sack & KiesselBach 1041, Germany). The nanostructured titanium monoxide powder was placed into a cylindrical boron nitride capsule; then the capsule was covered with pyrophyllite Al2(OH)2(Si2O5 )2 serving as a medium for pressure transfer. After that, the upper and lower parts of the capsule were covered with graphite lids. Initially, the pressure was increased to 6 GPa over 60 sec, and then the temperature was raised, also over 60 sec. In this study, the experiments were carried out at 573, 773, 1273, 1773 and 2273 K. The pressure and temperature were held constant for 60 min, then the temperature in the cell was rapidly decreased to ambient temperature at the rate of ~ 200 K/sec at approximately constant pressure, and after that, the pressure was released to atmospheric pressure during several seconds. The experiments were repeated 2-3 times under the same conditions, and according to the XRD data, the reproducibility of the results was observed.
3. Results and discussion
The results of X-ray diffraction experiments on samples subjected to thermobaric annealing are presented in Table 1 and Fig. 1. The microcrystalline state, according to [16-19], is characterized by large lattice period values, 418 - 421 pm. The temperature dependence of the lattice period for the nanostructured state is not monotonic: in the temperature interval from 298 to 773 K the lattice period increases from 417.6 to 417.82 pm. At 1273 K, the lattice period decreases to 417.5 pm and at 1773 K it reaches the value of 416.07 pm. At 2273 K, the lattice period increases to 417.54 pm, which is somewhat smaller than that observed at 298 K. The temperature range, over which the lattice period of the basis structure increases monotonously, corresponds to the sole initial disordered cubic phase. At temperatures above 1273 K, the system becomes two-phase. A trigonal phase Ti2O3 (sp. gr. R3c) is formed, whose structure is not a B1 derivative and contains no vacancies.
The first-principle calculations of the cohesion energy and electronic structure, performed by the technique described in [24] with the use of code [27], reveal that the trigonal phase with the R3c space group is energetically advantageous compared with the disordered cubic phase of the same TiO3/2 composition and with the orthorhombic ordered phase Ti2O3 (sp. gr. Immm) [28] having a 51-derived structure. The calculated cohesive energy of the phase with R3c space group is -17.76 eV vs. -16.21 ±0.04 eV for the disordered cubic phase and -17.25 eV for the orthorhombic ordered phase with space group Immm. Fig. 2 displays the density of electronic states calculated for three alternative structures of the TiO3/2 composition. All of them possess metallic conduction; the largest density of states at the Fermi level was observed for the orthorhombic model [28]. The trigonal phase observed
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A. A. Valeeva, M. G. Kostenko, A. Pfitzner, A. A. Rempel
Table 1. The conditions of thermobaric treatment of nanostructured titanium monoxide TiOo.98 and the XPD results after treatment
T, P TiOy(sp. gr. Fm3m) Ti2O3 (sp.gr. R3c)
Lattice period a si, pm CTiOy, mass.% Crystal size D, nm Lattice period as 1, pm CTi2O3, mass. % Crystal size D, nm
298 K 417.60 100 40 - - -
573 K, 6 GPa 417.63 100 42 - - -
773 K, 6 GPa 417.82 100 50 - - -
1273 K, 6 GPa 417.05 70 50 511.4, 1379.0 30 75
1773 K, 6 GPa 416.07 60 50 511.7, 1379.9 40 80
2273 K, 6 GPa 417.54 30 50 512.3, 1378.7 70 80
2273 k
1773 k
1273 k
773 k 573 k initial
II I '
_i_1_i_1_i_1_1_1_i_1_i_1_1_i_1_i_i_i_1_1_i_i_i_
30 40 50 60 70
2 0, degree
Fig. 1. The experimental X-ray diffraction patterns of TiO0.98 powders: initial nanostructured powder; after thermobaric treatment at 6 GPa and 573, 773, 1273, 1773, 2273 K (phases: I -TiOy (sp. gr. Fm3m), II - Ti2O3 (sp. gr. R3c))
in the experiment was characterized by a much wider p-d gap between the valence band and the conduction band compared with the p-d gap of B1 derived structures.
The nonmonotonic character of the temperature dependence of the lattice period observed in the experiment is likely to be due to the isolation of the trigonal phase Ti2O3, whose composition (TiO3/2) differs from the composition of the initial disordered cubic phase TiO0 98. In order to retain the initial ratio of components in the two-phase system, the composition of the disordered cubic phase should be shifted into the substoichiometric region. However, for the microcrystalline phase under atmospheric pressure this would mean a lattice period enhancement [29], whereas in our case the lattice period decreases. This suggests a different mechanism of variation in the composition and vacancy concentration compared with the microcrystalline state under atmospheric pressure. Note also that the nanostate features smaller lattice period values compared with the microcrystalline state, which agrees with the predictions of theoretical calculations [30].
E-Ef, eV
Fig. 2. The density of O 2p (red lines) and Ti 3d (blue lines) electronic states calculated for the disordered cubic phase TiO3/2 (sp. gr. Fm3m), the orthorhombic ordered phase Ti2O3 (sp. gr. Immm), as well as for the trigonal phase Ti2O3 (sp. gr. R3c) observed in the experiment
4. Conclusion
In the present work, the nanostructured TiOo.98 powder, which contained structural vacancies in two sublattices simultaneously, was subjected to high pressures up to 60 kbar and high temperatures up to 2273 K. The X-ray powder diffraction revealed a change of the structure from cubic TiOy phase (sp. gr. Fm3m) to the trigonal phase Ti2O3 (sp. gr. R3c) after applying the high pressure in combination with the high temperature. According to first-principle calculations, the trigonal Ti2O3 (sp. gr. R3c) phase observed in the experiment is energetically favorable compared to the cubic phase of the same TiO3/2 composition and the orthorhombic-ordered Ti2O3 (sp. gr. Immm) phase and is characterized by a much wider p-d gap between the valence band and the conduction band compared with the p-d gap of structures derived from B1 structure. The purposeful synthesis of materials based on particles of various stoichiometry, crystal size and dimension with pre-defined properties and structure gives enhanced functionality and provides comprehensive control of the settings.
Acknowledgements
We are grateful to Dr. M. Andratschke, F. Rau, and U. Schiessl (Institute of Inorganic Chemistry, Regensburg University) for their help during the experiments.
The work was carried out at the Institute of Solid State Chemistry UB RAS with financial support from the Russian Science Foundation (project 14-23-00025). The electronic structure calculations were performed on "Uran" supercomputer at the IMM UB RAS.
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