Superplastic behaviour of YBa2Cu3O7−x /Ag superconductors

High-temperature deformation characteristics of YBa₂Cu₃O_7–x oxide (YBCO) and YBa₂Cu₃O_7–x /Ag composite (YBCO/Ag) in uniaxial compression have been investigated. A compression test was carried out at temperatures from 780–930°C at initial strain rates between 10^–6 and 10^–4 s^–1. YBCO/Ag composites with fine, dense and equiaxed grains were compressed over 120% with no indication of failure at higher temperatures, and the strain-rate sensitivity exponent, m, was found to be about 0.42–0.46 between 890 and 930°C. They are considered to be one indication of superplasticity. The activation energy for deformation was 500–580 KJ mol^–1. The specimens suffered grain growth slightly during the deformation at 930°C and the majority of growth might be a function of exposure time, temperature and silver content, but each grain maintained the equiaxed shape after extensive superplastic deformation. This is consistent with a grain-boundary sliding mechanism. The silver at grain boundaries acts to decrease the activation energy for deformation and promote the grain-boundary sliding.     

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.     

Electrical properties of Li2O-La2O3-SiO2 electrode glasses after Ta2O5 doping and Ta implantation

Electrical conductivities, , of the Li₂O-La₂O₃-SiO₂ glasses were investigated as functions of Ta₂O₅ doping and Ta ion-implantation. A linear relationship between logarithm and the inverse of the sample temperature, T, was found in 2 to 4 mol% Ta₂O5 doped Li₂O-La₂O₃-SiO₂ glasses. The conductivity increases as Ta₂O₅ content increases at sample temperatures above 100°C. Fluences of 50 keV Ta ions per cm² from 5 × 10¹⁶ to 2 × 10¹⁷ were implanted into 0% and 2% Ta₂O₅ containing Li₂O-La₂O₃-SiO₂ glass samples. The activation energy of the conductivity was deduced from the relation between log and 1/T. It was found in implanted samples that the conductivity increased, but the activation energy and T _k–100 decreased, where T _k–100 is the sample temperature when the conductivity reaches 100 × 10^–1 S/cm. However, the Ta₂O₅ containing implanted samples show higher conductivities, lower activation energies and lower T _k–100. X-ray photoelectron spectroscopy (XPS) was used to study the structural modification introduced by implantation. Bridging oxygen (BO) and non-bridging oxygen (NBO), were observed in all samples. The changes in relative concentrations of BO and NBO before and after implantation clearly indicate the structure modification which results in the increase of the conductivity. It was clearly demonstrated in this study that both doping Ta₂O₅ and implanting Ta ions enhance the conductivity of Li₂O-La₂O₃-SiO₂ electrode glasses.     

Zr-Hf interdiffusion in polycrystalline Y2O3-(Zr+Hf)O2

Lattice and grain-boundary interdiffusion coefficients were calculated from the concentration distributions determined for Zr-Hf interdiffusion in polycrystalline 16Y₂O₃·84(Zr_1–x Hf _x )O₂ withx=0.020 and 0.100. The lattice interdiffusion coefficients were described byD=0.031 exp [–391 (kJ mol^–1)/RT] cm² sec^–1 and the grain-boundary diffusion parameters byD=1.5×10^–6exp [–309(kJ mol^–1)/RT] cm³ sec^–1 in the temperature range 1584–2116° C. Comparison of the results with those for the systems CaO-(Zr+Hf)O₂ and MgO-(Zr+Hf)O₂ indicated that the Zr self-diffusion coefficient was insensitive to the dopants in the fluorite-cubic ZrO₂ solid solutions.     

A study of the oxidation kinetics of CuFeO2 in the Cu-Fe-O system

The oxidation kinetics of CuFeO₂ in the Cu-Fe-O system have been studied between 500 and 900° C in an atmosphere containing 1 vol% oxygen in a nitrogen stream using thermogravimetric analysis (TGA). It was found that addition of Fe₂O₃ to the CuFeO₂ caused a decrease in the oxidation rate while addition of CuO caused an increase. On increasing the concentration of Fe₂O₃ the activation energy was found to increase from ~ 18 kcal mol^–1 to ~ 45 kcal mol^–1 and the exponent n in Avrami's equationf=1-exp (–kt ⁿ) was also observed to increase, from 1.3 to 2.3. On adding CuO to the CuFeO₂ in the Cu-Fe-O system the activation energy decreased from ~ 18 kcal mol^–1 to ~ 8 kcal mol^–1. The variation in both values indicates changes in the oxidation mechanisms. The microstructural changes associated with oxidation have been studied using optical microscopy. A model has been proposed to explain the results.     

Oxidation behaviour of the sintered Si3N4-Y2O3-Al2O3 system

The oxidation behaviour of silicon nitride composed of Si₃N₄, Y₂O₃, Al₂O₃, AlN and TiO₂ was investigated in dry and wet air at 1100–1400 °C. The oxidation rates were confirmed to obey the parabolic law. An activation energy of 255 kJ mol^–1 was calculated from the Arrhenius plots of the results of oxidation in an air flow. In still air the oxidation rate was larger than that in an air flow, but the oxidation rate in flowing air was not affected by the air flow rate. -cristobalite and Y₂O₃·2SiO₂ were formed in oxidized surface layers. These crystal phases increased with increasing oxidation temperature. In particular, a higher content of -cristobalite was obtained in still air oxidation. The existence of water vapour in flowing air greatly promoted the oxidation.Concurrent with Kanagawa Academy of Science and Technology.     

Crystallization kinetics of amorphous Pb (Fe2/3W1/3) O3

Kinetic data analyses on the crystallization behaviour of amorphous lead iron tungstate (PFW) were carried out. A low value of the glass transition/melting point ratio (0.52) and a high value of the frequency factor (2 × 10³⁷ s^–1) of the first crystallization exotherm may indicate a high degree of metastability of the prepared PFW in the amorphous state. The Avrami exponent was determined to be 3.0, which suggests a bulk nucleation. The activation energy for crystallization was averaged to be 520 kJ mol^–1 for the first exotherm. The validity of the estimated values of the Avrami exponent and the activation energy were confirmed by comparing with an independently obtained product of the two parameters.     

Seebeck coefficient of V2O5-R2O3-TeO2 (R = Sb or Bi) glasses

The thermoelectric power of glasses in the systems V₂O₅-Sb₂O₃-TeO₂ and V₂O₅-Bi₂O₃-TeO₂ was measured at temperatures in the range 373–473 K. The glasses in both systems were found to be n-type semiconductors. The Seebeck coefficient, Q, at 473 K was determined as –192 to –151 VK^–1 for V₂O₅-Sb₂O₃-TeO₂ glasses, and –391 to –202 VK^–1 for V₂O₅-Bi₂O₃-TeO₂ glasses. For these glasses in both systems, Heikes' formula was satisfied adequately for the relationship between Q and In [C _v/(1-C_v)] (C _v = V⁴⁺/V_total, C _v is the ratio of the concentration of reduced vanadium ions), and discussions confirmed small polaron hopping conduction of the glasses in both systems. Mackenzie's formula relating to Q and V⁵⁺/V⁴⁺ was also applicable to the glasses in both systems, and it was concluded that the dominant factor determining Q was C _v.     

Chemical and structural properties of the system Fe2O3-Cr2O3

Chemical and structural properties of the mixed metal oxides (1–x)Fe₂O₃+xCr₂O₃ were studied by different techniques. X-ray powder diffraction showed the existence of solid solutions, (Fe_1–x Cr _x )₂O₃, over the whole concentration region, 0x1. The gradual replacement of Fe³⁺ with Cr³⁺ ions in samples prepared at 900°C caused changes in unit-cell parameters; most of these changes took place in the region fromx0.3–0.9. The samples having the fraction of Cr₂O₃ in the region from 0.7–0.8, contained two closely related phases, with slightly different compositions. After an additional heat treatment at 1100°C, these samples contained only one phase.⁵⁷Fe Mössbauer spectroscopy showed a gradual decrease of hyperfine magnetic field with increasing Cr₂O₃ content. The sample having the fraction of Cr₂O₃ of 0.7, and prepared at 900°C, exhibited two separated sextets at room temperature, in comparison with other compositions showing one sextet. It was shown that Fourier transform infrared (FT-IR) spectroscopy is a powerful method for the investigation of structural changes in these solid solutions. The increase in the Cr₂O₃ content resulted in shifts of the corresponding infrared bands. In addition, a gradual transition of the spectrum typical for -Fe₂O₃ to the spectrum typical for Cr₂O₃ was shown. The transition effects observed in the FT-IR spectra were correlated with the X-ray powder diffraction and⁵⁷Fe Mössbauer spectroscopic results.     

Microstructure, electrical properties, and degradation behavior of praseodymium oxides-based zinc oxide varistors doped with Y2O3

The microstructure, electrical properties, and degradation behavior of Pr-based zinc oxide varistors, which are composed of Zn-Pr-Co-Cr-Y oxides were investigated according to Y₂O₃ additive content in the range 0.5–4.0 mol%. The majority of the Sadded Y₂O₃ were segregated at the multiple ZnO grain junctions and grain boundaries. The average grain size was markedly decreased in the range 27.3–8.6 m with increasing Y₂O₃ additive content. Y₂O₃ acted as an inhibitor of grain growth. Additions of Y₂O₃ increased the varistor voltage in the range 36.90–686.58 V/mm, increased the nonlinear exponent in the range 3.75–87.42, decreased the leakage current in the range 115.48–0.047A, increased the barrier height in the range 1.06–2.16 eV, and decreased the donor concentration in the rang 1.87 × 10¹⁸–0.19 × 10¹⁸ cm^–3. Y₂O₃ acted as an acceptor, as a result of the decrease of donor concentration. All Pr-based ZnO varistors doped with Y₂O₃ exhibited very predominant degradation characteristics, which show a nearly symmetric I-V after the stress. In particular, since 4.0 mol% Y₂O₃-added ZnO varistor has not only very excellent non-ohmicity, but also very stable degradation behavior, it is estimated to be sufficiently used to various application fields.     

The surface diffusion coefficients of MgO and Al2O3

From the measurement of neck size and neck curvature during the sintering of two spheres the surface diffusion coefficients of MgO and Al₂O₃ were determined. The spheres of both materials were machined from single crystals. The following values of surface diffusion coefficients were found: for MgO,D _{s s} = 3.7 × 10^–4 exp (407.8 kJ mol^–1/RT m³ sec^–1; for Al₂O₃,D _{s s} = 1.5 × 10^–2 exp (518.7 kJ mol^–1/RT) m³ sec^–1.     

High-temperature creep of yttrium-aluminium garnet single crystals

High-temperature creep in single crystals of Y₃Al₅O₁₂ (YAG) was studied by constant strainrate compression tests. The creep resistance of YAG is very high: a stress of ~ 300 MPa is needed to deform at a strain rate of 10^–6 (s^–1) at a temperature as high as 1900 K (~0.84 T _m, (melting temperature)). YAG deforms using the 111 {1¯10} slip systems following a power law with stress exponent n ~ 3 and activation energy E* ~ 720 kJ mol^–1. However, a small dependence of n on temperature and of E* on stress was observed. This stress-dependence of activation energy combined with the observed dislocation microstructures suggests that the high creep resistance of YAG is due to the difficulty of dislocation glide as opposed to the difficulty of climb. Present dislocation creep data are compared with diffusion creep data and a deformation mechanism map is constructed. Large transition stresses (2–3 GPa for 10 m grain size) are predicted, implying that deformation of most fine-grained YAG will occur by diffusion creep.     

Effect of Er2O3 addition on the microstructure, electrical properties, and stability of Pr6O11-based ZnO ceramic varistors

The microstructure, electrical properties, and stability of Pr₆O₁₁-based ZnO varistors, which are composed of ZnO-Pr₆O₁₁-CoO-Er₂O₃ systems, were investigated with Er₂O₃ additive content. The density of ceramics was in the range of 84–88% of TD at 1300 °C and 93–98% of TD at 1350 °C, and greatly affected the stability. Most of the added-Er₂O₃ were segregated at nodal points. The varistors with 0.5 mol% Er₂O₃ sintered at 1300 °C exhibited the best nonlinear current-voltage characteristics, which the nonlinear exponent is 52.8 and the leakage current is 9.8 A. All the varistors sintered at 1300 °C, even under relatively weak stress, exhibited the thermal runaway within short time in order of high leakage current. On the contrary, the stability of varistors sintered at 1350 °C exhibited far higher stability than that at 1300 °C. Particularly, the varistors with 0.5 mol% Er₂O₃ exhibited not only relatively good nonlinear current-voltage characteristics, which the nonlinear exponent is 34.8 and the leakage current is 7.4 A, but also excellent stability, which the variation rates of varistor voltage, nonlinear exponent, and leakage current are below 1%, 3%, and 3%, respectively, even under more severe stress such as (0.80 V _{1 mA}/90 °C/12 h) + (0.85 V _{1 mA}/115 °C/12 h) + (0.90 V _{1 mA}/120 °C/12 h).     

Nucleation and crystallization kinetics of CaO-Al2O3-2SiO2 in powdered anorthite glass

The nucleation and crystallization kinetics of CaO-Al₂O₃-2SiO₂ crystals in powdered anorthite glass with particle size <44 m in which CaO-Al₂O₃-2SiO₂ crystals were found to crystallize in the heating process of the glass, were studied by nonisothermal measurements using differential thermal analysis (DTA). The temperature of maximum nucleation rate was determined from the DTA curves of samples heat treated at different temperatures. The activation energy and kinetic parameters were simultaneously calculated from the DTA data using previously reported kinetic models. The crystallization process of a sample heat treated at the temperature of the maximum nucleation rate was fitted to kinetic equations with an Avrami constant, n2 and a dimensionality of crystal growth, m2, indicating that the constant number of nuclei of CaO-Al₂O₃-2SiO₂ precipitated in a glass matrix grew two-dimensionally with an activation energy taken as an average of the values calculated by the Kissinger and also the Augis and Bennett method of 679±4 kJ mol^–1.     

Kinetics and thermodynamics of intracrystalline Fe-Ga distribution in Y3(Fe,Ga)5O12

Garnets of composition Y₃Fe_5–x Ga _x O₁₂, withx=0–5, were synthesized from oxides. Samples with various Ga content were annealed at temperatures between 700–1290° C; the heating duration varied between 90 s and 1350 h. Cation distribution was measured by Mössbauer spectroscopy at room temperature. The standard free energy change for the exchange reaction Fe³⁺ (tet)+ Ga³⁺ (oct)Fe³⁺ (oct)+Ga³⁺ (tet) is about 20 kJ mol^–1, and decreases slightly with increasing Fe content. The specific rate constants for the ordering process were determined according to the Mueller model for order-disorder kinetics. The activation energies for the ordering process between 200–250 kJ mol^–1 were calculated from the temperature dependence of the specific rate constants.     

Sintering process of Y2O3-added Si3N4

The sintering process of Y₂O₃-added Si₃N₄ has been investigated by dilatometry and microstructural observations. Densification was promoted above 1440 ° C by the formation of eutectic melts in the Y₂O₃-SiO₂-Si₃N₄ triangle. However, the dilatometric curves indicated no shrinkage corresponding to the rearrangement process, despite liquid-phase sintering. The kinetic order for The Initial-stage sintering was 0.47 to 0.49. These values indicated that the phase-boundary reaction was rate controlling. The apparent activation energy (323 kJ mol^–1) was smaller than the dissociation energy for the Si-N bond (435 kJ mol^–1). ESR data and lattice strain indicated that the disordered crystalline structure of the Si₃N₄ starting powder promoted the reaction of Si₃N₄ with eutectic melts. After a period of initial-stage sintering, the formation of fibrous -Si₃N₄ grains resulted in interlocked structures to interrupt the densification.     

Preparation and characterization of two new dielectric ceramics Ba4NdTiNb3O15 and Ba3Nd2Ti2Nb2O15

Two new cation-deficient hexagonal perovskites Ba₄NdTiNb₃O₁₅ and Ba₃Nd₂Ti₂Nb₂O₁₅ were prepared in the BaO–Nd₂O₃–TiO₂–Nb₂O₅ system by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction and scanning electron microscope (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. Ba₄NdTiNb₃O₁₅ has a dielectric constant of 38.15, a high-quality factors (Q _u ×f >18 700 at 5.4422 GHz), and a small temperature coefficient of resonant frequency ( _f )+12 ppm °C^–1 at room temperature; Ba₃Nd₂Ti₂Nb₂O₁₅ has a higher dielectric constant of 46.83 with high-quality factors Q _u ×f >19 500 at 5.0980 GHz, and _f +28 ppm °C^–1.     

Sintering process of Y2O3 and Al2O3-doped Si3N4

The sintering process of Y₂O₃- and Al₂O₃-doped Si₃N₄ has been investigated by dilatometry and microstructural observations. The densification progressed through three processes. The bulk density increased to 85% theoretical without the formation of -Si₃N₄ in the initial process. The densification once terminated after the second process. The / transformation of Si₃N₄ and the related formation of prismatic grains reduced the densification rate in the second process, although the grain size and the aspect ratio were very small. The final process was the densification of -Si₃N₄, where the fibrous grains grew remarkably. The kinetic order for the densification of -Si₃N₄ indicated a diffusion-rate controlling mechanism with the activation energy of 244 kJ mol^–1 (<1450 ° C) and 193 kJ mol^–1 (>1450 ° C). The influence of heating rate on the grain growth was characterized by a parameter derived from kinetic parameters. The relationships between grain growth and densification behaviour have also been discussed.     

Electronic Conduction in the Na2O ·nAl2O3–Y2O3 System

The electronic conductivity of Na₂O · nAl₂O₃–Y₂O₃ materials is found to vary from 10^–5 to 10^–1 S/m between room temperature and 800°C and to increase from 10^–5 to 10^–4 S/m as the frequency increases from 100 Hz to 200 kHz. The temperature variation of conductivity is interpreted in terms of the energy band structure.     

Sinterability improvement of Ba(Mg1/3Ta2/3)O3 dielectric ceramics

The sinterability of Ba(Mg_1/3Ta_2/3)O₃ ceramics synthesized by solid-state-reaction methods was investigated. The poor sinterability of the present ceramics was found to be primarily due to the presence of satellite secondary phases of Ba₅Ta₄O₁₅ and Ba₄Ta₂O₉, and the nearly complete densification of Ba(Mg_1/3Ta_2/3)O₃ ceramics was accomplished successfully by controlling the phase constitution of the calcined powders. For this purpose, enhanced ball-milling processes were found to be extremely effective. Moreover, excellent microwave dielectric characteristics (_r = 24.5–24.7, Q = 26 000 at 9.8 GHz, and _f = 1.7 p.p.m. C^–1) were attained in the dense Ba(Mg_1/3Ta_2/3)O₃ ceramics without additives.