Synthesis and dielectric properties of pyrochlore solid solutions in the Bi2O3-ZnO-Nb2O5-TiO2 system

Phase studies of solid solutions based on (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ revealed extended regions of pyrochlore formation in the Bi₂O₃-ZnO-TiO₂-Nb₂O₅ system. At room temperature and 1 MHz (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ has a high permittivity ( = 200), low dielectric loss (tan<1·10^–4) and a temperature coefficient of the permittivity, , = –1300ppm/K. Pyrochlore solid solutions based on (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ can be formed with (Bi_2–xZn_x)(Ti_{2– x} Nb_x)O₇ (0.35x1.0) and with (Bi_1.5 Zn_0.5–y/3Ti_1.5+yNb_0.5–2y/3) O₇ (–1.5y0.75). Investigations of the dielectric characteristics showed that the high temperature dependence of the permittivity of (Bi_1.5 Zn_0.5)(Ti_1.5Nb_0.5)O₇ can be significantly modified by changing the composition of the pyrochlore within these regions of solid solubility. Below room temperature several of these compositions also exhibit a diffuse frequency dependent maximum in their permittivity characteristic of a transition to a relaxor type ferroelectric state. A third region of high permittivity pyrochlores with (Bi_1.5+2zZn_0.25–z Ti_2.25–z)O₇ (0.0z<0.15) was also identified in the Bi₂O₃-ZnO-TiO₂ sub system.     

The effect of Bi2O3 on the microstructure and electrical conductivity of ZrO2-Y2O3 ceramics

ZrO₂-Y₂O₃ ceramics with varying Bi₂O₃ contents were prepared and their microstructures and electrical conductivities investigated. The phase stability of cubic fluorite zirconia was disturbed by the introduction of Bi₂O₃ and tetragonal or monoclinic second phases appeared. The effect of the second phases on the intragrain and the grain boundary conductivities was investigated in the 300–550 C range using complex plane analysis in the frequency range of 5 Hz to 13 MHz. It showed that conductivity data could readily be interpreted in terms of possible physical models and electrical equivalent circuits. Tetragonal phases had a small positive influence on the intragrain conductivity. The grain 9boundary resistivity could be diminished by discrete monoclinic second phases which offered more conductive intergranular contacts.     

High oxygen ion conduction in some Bi2O3-Y2O3 (Er2O3) solid solutions

Highly densified bodies (~ 98 % theoretical density) of the Bi₂O₃-Y₂O₃(Er₂O₃) systems containing 30 moles % Y₂O₃ and 20 moles % Er₂O₃ respectively were prepared from both mixed oxides and coprecipitated oxalates. DC ionic conductivity and impedance complex plane analysis on sintered samples were performed. Under oxygen partial pressure ranging from 1 to 10 Pa was found that, samples containing 30 moles % yttria showed a pure ionic conductivity up to an oxygen partial pressure of 10⁻²⁰ Pa. Samples containing 20 moles % erbia, extended its ionic conductivity up to an oxygen partial pressure of 10⁻²² Pa. The impedance analysis shows the presence of only one semicircle at low tempertures and it is attributed to bulk conductivity contribution. The conductivity was higher for the Bi₂O₃-Er₂O₃ sintered solid electrolytes, in such a case, a conductivity as high as 1.38 ohm cm at 700ºC was obtained. The activation enthalpy for the conduction process was calculated in the temperature range from 200º to 700ºC in all the cases. Microstructural development in the sintered sample was also studied.     

DC electrical conductivity of Na2O-ZnO-B2O3 glass system

The d.c. electrical conductivity of Na₂O-ZnO-B₂O₃ glass system has been measured as a function of temperature in the range of 350–600°K. The conductivity data show that the activation energy of Na⁺ ions is dependent on ZnO concentration. The results have been discussed in the light of the cluster model of glasses.     

Oxide ionic conductivity and crystallographic properties of tetragonal type Bi2O3-based solid electrolyte doped with Ho2O3

Abstract

In the present work, the authors have investigated the binary system of (Bi₂O₃)_1–x(Ho₂O₃)_x. For the stabilisation of the tetragonal type solid solution, small amounts of Ho₂O₃ were doped into the monoclinic Bi₂O₃ via solid state reactions in the stoichiometric range 0·01≤x≤0·1. The crystal formula of the formed solid solution was determined as Bi(III)_4–4xHo(II)_4xO_6–2xVo_(2+2x) (where Vo is the oxide ion vacancy) according to the XRD and SEM microprobe results. In the crystal formula, stoichiometric values of x were 0·04≤x≤0·08, 0·03≤x≤0·09, 0·02≤x≤0·09 and 0·04≤x≤0·09 for annealing temperatures at 750, 800, 805 (quench) and 760°C (quench) respectively. The four probe electrical conductivity measurements showed that the studied system had an oxide ionic type electrical conductivity behaviour, which is increased with increasing dopant concentration and temperature. The obtained solid electrolyte system has an oxygen non-stoichiometry characteristic, and it contains O^2– vacancies, which have disordered arrangements in its tetragonal crystal structure. The increase in the amount of Ho₂O₃ doping and temperature causes an increasing degree of the disordering of oxygen vacancies and a decrease in the activation energy E_a.     

Synthesis and characterization of β type solid solution in the binary system of Bi2O3-Eu2O3

We have investigated Bi₂O₃-Eu₂O₃ binary system by doping with Eu₂O₃ in the composition range from 1 to 10 mole% via solid state reactions and succeeded to stabilize β-Bi₂O₃ phase which is metastable when pure. Stability of β-Bi₂O₃ polymorph was influenced by heat treatment temperature. Tetragonal type solid solution was obtained in 3–6 mole% addition range when annealed at 750°C and the range was 2–7 mole% when annealed at 800°C. We have also carried out investigations on lattice parameters, microstructural properties and elemental compositions of this β type solid solution for each doping ratio. Lattice parameters increased with amount of Eu₂O₃ addition. Our experimental observations strongly suggested that oxygen deficiency type non-stoichiometry is present in doped β type solid solutions.     

Effect of dopant concentration on electrical conductivity in the Sc2O3-ZrO2 system

Electrical conductivity measurements have been made as a function of dopant concentration (4 to 8 mol% Sc₂O₃) in the scandia-zirconia system, All the compositions studied had a tetragonal structure. The hombohedral phase was present only in samples prepared from mechanical mixtures of Sc₂O₃ and ZrO₂. In specimens prepared by coprecipitation, no phase lines were observed and the monoclinic zirconia (m-ZrO₂) phase was present for only Sc₂O₃ contents 5 mol %. The conductivity of Sc₂O₃-ZrO₂ decreased continuously with time up to 300 h anneal time between 700 and 1000° C. X-ray diffraction of coprecipated specimens of 7.8 mol % Sc₂O₃-ZrO₂ composition annealed at 1000° C (28 days), 750° C (42 days) or 460° C (189 days) did not reveal any changes to account for this. However, transmission electron microscopy showed that changes associated with the formation of very fine precipitates had occurred. The activation energy for conduction in the low-temperature region decreased monotonically with decrease in the scandia content. Jumps in the conductivity curves and hysterisis effects were observed in specimens containing m-ZrO₂.     

Optical,infrared and electrical conductivity of glasses in the TeO2-B2O3 system

Infrared (IR) and optical absorption spectra were measured in order to study the structure of some tellurite glasses containing boric oxide. The compositions (mol%) were (100-X) TeO₂,XB₂O₃ whereX=5, 10, 20, 25, 30. The optical spectra were measured at room temperature in the wavelength range 350–450 nm, and the results show that the fundamental absorption edge is a function of composition, with the optical absorption due to indirect transitions. The optical band gap increases with increasing B₂O₃ content. The validity of the Urbach rule was investigated. The IR results prove the distribution of the TeO₄ polyhedra which determines the network and the basic oscillations of the building units in the tellurite glasses. The IR results also prove the distribution of the boroxal group. The electrical conductivity was measured as a function of temperature in the temperature range (300–573 K). Both the conductivity and activation energy were found to be a function of added oxide type.     

Crystallization behavior of amorphous solid solutions and phase sepration in the Cr2O3-Fe2O3 system

Fine particles of the amorphous Cr₂O₃-Fe₂O₂ solid solutions were prepared by dehydration of coprecipitated hydroxides and their crystallization behavior was studied by differential thermal analysis and X-ray diffraction. The peak temperature for crystallization attained a maximum at a composition near Fe₂O₃ content of about 60 mol % and the activation energy for crystallization attained a minimum at a composition near Fe₂O₃ content of about 50 mol % in this quasibinary system. Phase separation occurred in a range of Fe₂O₃ content from about 35 to 80 mol % in the corundum-type solid solutions heat treated at 600 °C for 2 h. Crystallization behavior was discussed briefly related with phase separation and diffusion in fine particles.     

Influence of eutectic addition on the electrical conductivity of Li2O:B2O3 system

Addition of three eutectics, Li₂SO₄:Li₂CO₃, 3Li₂O·Nb₂O₅:LiNbO₃ and AgI:Ag₂SO₄ has been tried in the Li₂O:B₂O₃ glass system. The electrical conductivity increases with the addition of eutectic. The amount of lithium fraction and the melting point of the eutectic govern the conductivity.     

Glass formation region and electrical conductivity in the system B2O3-Li2O-Li3PO4

Glass formation region was determined for the B₂O₃-Li₂O-Li₃PO₄ system. Under the present experimental conditions, binary lithium borate glasses could be formed containing a maximum of 27 mol% Li₂O. However, this could be increased to 36 mol% in the ternary system. Electrical conductivity was measured at temperatures ranging from room temperature to 350°C. The temperature dependence of the electrical conductivity of these glasses follows Arrhenius equation. The conductivity increased with increasingly alkali content. Maximum conductivity of the order of 10⁻⁴ ohm⁻¹ cm⁻¹ was obtained with the glass containing about 36 mol% Li₂O at 250°C. Activation energy for conduction also varied with total Li₂O content.     

Effect of heat treatment and irradiation on electrical conductivity and crystallization in the BaO-B2O3-Fe2O3 glass system

A glass system was prepared according to the formula 75 mol % B₂O₃-(25 –x) mol % BaO –x mol % Fe₂O₃, wherex = 0, 1, 2.5, 5, 7.5 and 10. The glasses were subjected to heat treatment at 550° C for 2, 6, 12, 18 and 24 h. The glasses were also irradiated using-rays at a dose of 4.805 × 10⁴ rad h^–1 for 12, 18 and 24 h. An X-ray diffraction technique was used to identify the separated crystalline phases. The electrical conductivity and activation energy of untreated, heat-treated and irradiated samples were measured and calculated. The rate and the dimensions of crystallization were also calculated by using the Avrami equation. It was found that-Fe₂O₃ is the separated phase when a sample containing 7.5 mol% Fe₂O₃ is heat treated for 24h;-Fe₂O₃ and Fe₂O₃ are the separated phases when the sample containing 10 mol% Fe₂O₃ is heat treated for 6, 12 and 18 h, with the addition of BaO when the sample is heat treated for 24 h. A miminum value for the electrical conductivity of glass samples was found to occur around an Fe₂O₃/BaO ratio of 0.425. The rate of crystallization in the sample containing 10 mol% Fe₂O₃ is 1.30607 × 10^–3 and the geometry of crystallizationn is 1.2238, which indicates that the crystallization was in one dimension.     

Impure zirconia electrical conductivity enhancement by rare-earth minority ions in the Y2O3 RE2O3 ZrO2 system

Impure zirconia stabilized by 12 wt% yttria concentrate (85 wt% Y₂O₃ + 15 wt% rare-earth (RE)) was found to have high grain and grain-boundary electrical conductivities. The influence of the RE on the segregation of impurities was studied for four different compositions. Microstructure features are evidence for the enhanced segregation of impurities due to RE ions. The increased grain and grain-boundary conductivities are a consequence of the segregation of impurities.     

Conductivity of reduced solid solutions in the system Na2OAl2O3TiO2

Solid solutions of the “titanium bronze” phase found in the system Na₂OAl₂O₃TiO₂ were made conductive either by H₂ reduction or the use of metallic Ti. Conductivity measurements by pulse and D.C. methods (blocking electrodes) show semiconducting behavior with activation energies decreasing with the extent of reduction, from 101 kJ/mole in “unreduced” samples to 39.8 kJ/mole in samples reduced with Ti metal. At about 600°C, all samples have conductivities about 7×10^?3 ohm^?1cm^?1, indicating that reduction occurs by oxygen loss in the Ar atmosphere. The occurrence of semiconductivity rather than metallic conductivity is explained by the blocking of conduction paths by the Al ions. Absorption spectra show no discrete spectrum for Ti³⁺, but a broad absorption band indicates the presence of delocalized electrons.     

D.c. conductivity and hopping mechanism in Bi2O3-B2O3 glasses

The physical and transport properties of semiconducting glasses are highly interesting, providing useful information regarding the structure and conduction mechanism, respectively. The physical and transport properties such as density, number of ions per unit volume, hopping distance, polaron radius, d,c. conductivity and activation energy are reported. Similarly the hopping conduction mechanism is examined. The physical property (density) is used to determine the probable structure of the glass sample. The small polaron hopping model is applied to the glass system. The methods of examining the hopping conduction mechanism are discussed in the light of the small polaron model. The methods suggested by Holstein and by Sayer and Mansingh are applied to the determination of adiabatic or non-adiabatic hopping conduction. It was observed that in this system adiabatic hopping conduction is present.     

Influence of Ag2SO4 addition on the electrical conductivity of the Li2O:B2O3 system

Glasses in the Li₂O:B₂O₃:Ag₂SO₄ system were prepared with varying silver sulphate contents. From the present results it can be said that the amorphous matrix accepts Ag₂SO₄ up to 5 mol% without any devitrification. The enhancement in conductivity with change in the structure of metaborate glass is due to Ag₂SO₄.     

Investigation of the main structural units in Bi2O3-TiO2solutions

To investigate a possible correlation between observed crystal growth phenomena and the structure in the liquid phase of Bi₂O₃-TiO₂ solutions, densities and viscosities have been measured and interpreted by the hard sphere model for liquids. The main flow units are probably BiO ₂ ^? and BiO⁺ with some Ti complex formation which increases with increasing TiO₂. A change in the complex formation occurs at 12 mol % TiO₂.     

Pseudo-binary system Bi2O3-TeO2 in air

The phase equilibria in the pseudo-binary system Bi₂O₃-TeO₂ at 600° 950° C in air were examined by solid-state reaction techniques and X-ray powder diffraction method. Four pseudo-binary compounds appeared, i.e., -Bi₂O₃ type solid solution having a compositional range of (1-x)Bi₂O₃·xTeO₂ wherex=0 0.4 a new compound Bi₆Te₂O₁₅ which has an orthorhombic cell of a=2.27(4) nm, b=1.06(1) nm and c = 0.539(8) nm, 2Bi₂O₃ · 3TeO₂, and an unidentified phase Bi₂O₃·2TeO₂. The formation of the phase Bi₆Te₂O₁₅, in which all the Te ions are hexavalent, was confirmed by the thermogravimetry and by the Mössbauer spectra. The liquidus curves for whole system were determined by DTA method.