Электрофизические свойства оксидной бронзы NAxWO3

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Аннотация

Экспериментально определены закономерности формирования электрофизических свойств наночастиц путем измерения удельной проводимости образцов при нагреве и термостимулированной деинтеркаляцией ионов щелочных металлов. Разработан и собран экспериментальный стенд программно-управляемого нагрева и термоциклирования со специальной измерительной ячейкой для порошковых материалов. С его помощью была проведена сравнительная оценка эффективной энергии активации процессов деинтеркаляции ионов щелочных металлов в синтезированных образцах оксидных бронз и порошках, подвергавшихся дроблению в условиях интенсивного механического помола.

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Introduction

A large number of publications today dedicated to the materials after grinding to the nano range has acquired new optical and electrical properties [1, 2]. They can therefore be used as functional materials [3]. Nanoparticles of noble metals have found wide application in Biomedicine [4]. Open questions remain of conductivity [5] nanoscale layered and tunnel structures by their doping with alkali and alkaline earth metals. The paper presents first results of determination of the electrophysical properties of synthesized oxide bronzes.

The aim of this study was comparative examination of electrical conductivity of oxide bronzes for determine the activation energy in the processes of deintercalation.

Experimental techniques

The basis of measuring stand for measuring the conductivity of oxide bronze powders when heated inside a tube furnace is shown in Figure 1 (a).

 

Fig. 1 – a) Experimental setup; b) Measuring cell: 1-tungsten electrodes inserted into the cylindrical channels; 2-the studied material; 3-a tube of dielectric material with cylindrical hollow channels; 4 – capacity of the dielectric; 5 – thermocouple; 6 – hole for thermocouple; 7-ceramic washer; 8-a hollow bolt

 

The measuring cell is an iron U – shaped steel frame with curved inside edges. Inside the bolt is a tube of dielectric material (porcelain) with a cylindrical hollow channels. In the tube channels are inserted two tungsten electrodes. In a small thin-walled ceramic container is filled and compacted the investigated powder (or placed a small solid sample of the test material). Between the tube with electrodes and the hollow bolt is placed a thin dielectric washer. She has a hole diameter smaller than the diameter of the tube. The design is fixed hollow bolt. A chromel – alumel thermocouple is placed in a volume of powder through an additional hole in a ceramic container. Measuring cell with powder mounted on a tripod and placed in a high temperature furnace «UDIAN». Tungsten electrodes and a thermocouple connected to a digital multimeter «True RMS» via RS-232 output. Connecting to a computer using environment «MatLab» allows you to record the resistance and temperature of the test material at specified intervals of time. Measurement of temperature and resistance were conducted simultaneously, which allowed to analyze the temperature dependence of the electrical conductivity of oxide bronzes.

Mathematical model

As is well known [6, 7], at low temperatures the concentration of electrons in the conduction band of one type of impurity is determined from the equation:

                                                                                                                        σ=AT3/2exp(EakT),(1)

where Eа is the activation energy of the impurity semiconductor, k=1,38·10-23 J/K=8,625·10-5 eV is the Boltzmann's constant. As the mobility μ and the factor T3/2 сhange slowly compared to the exponential member in the region of low temperatures the conductivity of doped semiconductor is changed by the exponential law:

σ=σ0exp(EakT),(2)

where the coefficient σ0 depends on the kind of semiconductor.

One of the main characteristics of a semiconductor is its energy of activation. By measuring the resistance R at different temperatures T and build a graph of 1/T in a semilog scale, it is possible to find the activation energy. This is a straight line, i.e., the model: y=a+bx, y =lnσ, x=T-1, a=lnσ0, b=-Ea·k-1. The angular coefficient of this straight line we find the activation energy of impurity semiconductor.

Experimental results and discussion

Taking into account the methods of temperature analysis of SHS materials [8] and the introduction of corrections [9], with a limited number of distinguishable signal gradations against a noise background [10], activation energies were determined from the temperature dependence of the specific electric conductivity, as shown in Fig. 2.

The obtained values of effective activation energy for the processes of intercalation in oxide bronzes:

                               Еа=8,625·10-5eV×10317=88984×10-5eV=0,898eV (Na0,1WO3);                           (3)

                                Еа=8,625·10-5eV×2772 =81954×10-5eV=0,820eV (Na0,2TiO2);                           (4)

                               Еа=8,625·10-5eV×18091=35681×10-5eV=0,357eV (K0,12TiO2).                           (5)

 

Fig. 2 – The inverse temperature dependence of electrical conductivity: а) Na0,1WO3; b) Na0,2TiO2; c) K0,12TiO2

 

Biofunctional material based Na0.1WO3 illuminated by Er-laser radiation with a wavelength of 1.3-1.5 μm [11], which corresponds to:

                                         λ=hc/Eа; hc =4,1×10-15 ×3× 108=12,3×10-7 eV×m;                                     (6)

                                             Еa(λ=1,5μm)=0,82eV; Еa(λ=1,3μm)=0,9eV.                                        (7)

Given the above, the thermal effect is observed due to the educated «intercalation» levels.

Conclusions

Chemical methods, laser-chemical and SHS received a new biofunctional synthesis of nanoparticles of complex metal oxides and oxide bronzes. Nanoparticles of oxide bronzes of transition metals possess high photothermal effect of the absorption of quanta of light by nanocrystals [12]. Such nano-sized crystals of complex oxides and oxide bronzes having the properties of semiconductors with low activation energy of conductivity have a high absorption in the IR region of the spectrum. The special role of the surface in semiconductors is that it has a surface energy levels located in the bandgap (surface States); electrons and holes within those levels localized near the surface. Therefore, along with deep "intercalation" levels, should be formed near surface levels. The levels of both types detected in all samples. The energies corresponding to them can differ in 2 times.

Acknowledgement: Authors thanks Russian Foundation for Basic Research for financial aid in this work. Grant RFBR- 15-42-00106.

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Об авторах

Наркиза Ямалетдиновна Бикбердина

Югорский государственный университет

Автор, ответственный за переписку.
Email: bikberdina.narkiza@mail.ru

Cтудент кафедры физики и общетехнических дисциплин Института (НОЦ) технических систем и информационных технологий

Россия, 628012, г. Ханты-Мансийск, ул. Чехова, 16

Марина Петровна Бороненко

Югорский государственный университет

Email: m_boronenko@ugrasu.ru

Кандидат технических наук, доцент кафедры физики и общетехнических дисциплин Института (НОЦ) технических систем и информационных технологий 

Россия, 628012, г. Ханты-Мансийск, ул. Чехова, 16

Павел Юрьевич Гуляев

Югорский государственный университет

Email: p_gulyaev@ugrasu.ru

Доктор технических наук, профессор кафедры физики и общетехнических дисциплин Института (НОЦ) технических систем и информационных технологий 

Россия, 628012, г. Ханты-Мансийск, ул. Чехова, 16

Руслан Данилович Юнусов

Югорский государственный университет

Email: yunusov5251@gmail.com

Студент кафедры физики и общетехнических дисциплин Института (НОЦ) технических систем и информационных технологий

Россия, 628012, г. Ханты-Мансийск, ул. Чехова, 16

Список литературы

  1. Development Prospects of SHS Technologies in Altai State Technical University [Text] / V. V. Evstigneev, I. V. Miljukova, V. D. Goncharov [et al.] // International Journal of Self-Propagating High-Temperature Synthesis. – 2006. – Vol. 15. – № 1. – Pp. 99–104.
  2. Gulyaev, P. Yu. Plasma spraying of protective coatings from ferromagnetic SHS-materials [Text] / P. Yu. Gulyaev // International Research Journal. – 2013. – № 12-1 (19). – Pp. 74–77.
  3. Microstructure and evolution of (TiB2+Al2O3)/NiAl composites prepared by self-propagation high-temperature synthesis [Text] / X. J. Song, H. Z. Cui, L. L.Cao [et al.] // Transactions of Nonferrous Metals Society of China. – Vol. 26, Issue 7. – Pp. 1878–1884.
  4. Photothermal effects of laser heating of iron oxide and oxide bronze nanoparticles in cartilaginous tissues [Text] / E. N. Sobol, A. I. Omelchenko, S. S. Pavlova [et al.] // Nanotechnologies in Russia. – 2012. – Vol. 7, № 3–4. – Pp. 127–131.
  5. Gulyaev, P. Abnormal photo-thermal effect of laser radiation on highly defect oxide bronze nanoparticles at the sub-threshold [Text] / P. Yu. Gulyaev, M. K. Kotvanova, A. I. Omelchenko // IOP Conf. Series: Journal of Physics : Conf. Series. – 2017. – Vol. 830(1).
  6. Gulyaev, P. Yu.Trace-Analysis of Images of the Differential Chronogram of the Combustion Wave for Recognition of Transitional Modes of SHS [Text] / P. Yu. Gulyaev, V. Jordan // CEUR Workshop Proceedings. – 2017. – Vol. 1940. – Pp. 37–44.
  7. Gulyaev, P. Yu. Nanotechnologies of the treatment and preparation of transition metals complex oxides with a high photo-thermal effect [Text] / P. Yu. Gulyaev, M. K. Kotvanova, A. I. Omelchenko // Fizika i Khimiya Obrabotki Materialov. – 2017. – № 4. – Pp. 74–82.
  8. In-situ selfpropagating-hightemperature-synthesis controlled by plasma [Text] / P. Yu. Gulyaev, I. P. Gulyaev, Cui Hongzhi, I. V. Milyukova // Yugra state university bulletin. – 2012. – № 2 (25). – Pp. 28–33.
  9. Temperature measurements for Ni-Al and Ti-Al phase control in SHS Synthesis and plasma spray processes [Text] / P. Yu. Gulyaev, I. P. Gulyaev, I. V. Milyukova, H.-Z. Cui // High Temperatures – High Pressures. – 2015. – Vol. 44. – № 2. – Pp. 83–92.
  10. Increasing accuracy of high temperature and speed processes micropy-rometry [Text] / M. P. Boronenko, P. Yu. Gulyaev, A. E. Seregin, A. G. Bebiya // IOP Conference Series: Materials Science and Engineering. – 2015. – Vol. 93. – № 1.
  11. Gulyaev, P. Yu. Laser activation of repair processes in viscously elastic biological tissues after impregnation by nanoparticles with abnormal high photothermal effect [Text] / P. Yu. Gulyaev, A. I. Omelchenko // International Research Journal. – 2016. – № 11-4 (53). – Pp. 146–152.
  12. Thermal analysis of reaction producing KXTiO2 [Text] / K. Borodina, S. Sorokina, N. Blinova [et al.] // Journal of Thermal Analysis and Calorimetry. – 2017. – Vol. 21. – Pp. 1–6.

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2. Рисунок 1 - а) Экспериментальная установка. б) Измерительная ячейка: 1-вольфрамовые электроды, вставленные в цилиндрические каналы; 2 - изученный материал; 3 - трубка из диэлектрического материала с цилиндрическими полыми каналами; 4 - емкость диэлектрика; 5 - термопары; 6 - отверстие для термопары; 7-керамическая шайба; 8 - полый болт

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3. Рисунок 2 - Обратная зависимость электропроводности от температуры: а) Na0,1WO3; б) Na0,2TiO2; c) K0,12TiO2

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© Бикбердина Н.Я., Бороненко М.П., Гуляев П.Ю., Юнусов Р.Д., 2017

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