Grain Boundary Defect Chemistry of Acceptor-Doped Titanates: Space Charge Layer Width

The grain boundary space charge depletion layers in acceptor-doped SrTiO₃ and BaTiO₃ ceramics were investigated by impedance spectroscopy in the time and frequency domain. Based on the layer width and its dependence on the acceptor concentration, the temperature, and the oxygen partial pressure during annealing, a suggestion for a refined Schottky model is proposed. The local distribution of the donor-type grain boundary states causing the depletion layer and the resulting band bending are discussed.     

High-Temperature/Field Alternating-Current Behavior of ZnO-Based Varistors

The ac electrical response of the grain boundary in the ZnO–Bi₂O₃-based varistor system (in the frequency range 10⁻²≤f≤10⁷ Hz) has been analyzed using complex plane analysis techniques as a function of temperature (90°≤T≤150°C) and electric field (E_60%lmA/cm2≤E≤E_lmA/cm2). The high-temperature/field data were best represented in the impedance plane. The lumped parameter equivalent circuit representation, containing a voltage variable resistive element associated with the grain boundary, was in agreement with a model previously reported in the literature. The resulting equivalent circuit representation of the grain-boundary response consisting of a resistance and a capacitance are interpreted in terms of various phenomena occurring at the electrical thickness of the grain boundary.     

Polymorphic Behavior of Thin Evaporated Films of Zirconium and Hafnium Oxides

Polymorphism in thin evaporated films of zirconium and hafnium oxides was investigated from 100° to 1500°C by electron diffraction and transmission electron microscopy. The films have metastable cubic structures at room temperature and at moderate temperatures. Zirconium oxide, depending on temperature, exists in cubic, tetragonal, and monoclinic forms, whereas hafnium oxide transforms directly from the cubic to the monoclinic structure. The transformation temperatures depend on the oxygen partial pressure. Air annealing of thin films of ZrO₂ and HfO₂ lowered the temperature of transformation of the tetragonal and the cubic structure into the monoclinic structure by about 150° and 100°C, respectively. The cubic/tetragonal transformation of ZrO₂ is monotropic, whereas the tetragonal monoclinic transformation occurs by the typical nucleation and growth mechanism. Determination of grain size in ZrO₂ at the tetragonal/monoclinic transformation temperature showed that the transformation occurs when a constant grain size of about 800 Å is reached. The oxygen partial pressure, grain size, and temperatures at which the metastable phases exist were correlated. The rate of grain growth is enhanced by increase in oxygen partial pressure. The accelerated transformation in air is attributed to rapid attainment of the critical size; grain boundary energy is an important controlling factor in transformation.     

Effect of PO2 on Bulk and Grain Boundary Resistance of n-Type BaTiO3 at Cryogenic Temperatures

Complex impedance analysis at cryogenic temperatures has revealed that the bulk and grain boundary properties of BaTiO₃ polycrystals are very sensitive to the oxygen partial pressure during sintering. Polycrystals sintered at P _O2 as low as 10⁻¹⁵ atm were already electrically heterogeneous. The activation energy of the bulk conductivity in the rhombohedral phase was found to be close to that of the reduced undoped single crystal (i.e., 0.093 eV). The activation energy of the grain boundary conductivity increases with the temperature of the postsinter oxidation treatment from 0.064 to 0.113 eV. Analysis of polycrystalline BaTiO₃ sintered in reducing atmosphere and then annealed at P _O2= 0.2 atm has shown that the onset of the PTCR effect occurs at much higher temperatures than expected in the framework of the oxygen chemisorption model. The EPR intensity of barium and titanium vacancies increases after oxidation at T > 1000°C. A substantial PTCR effect is achieved only after prolonged annealing of the ceramic in air at temperatures as high as 1200–1250°C. This result suggests that the PTCR effect in polycrystalline BaTiO₃ is associated with interfacial segregation of cation vacancies during oxidation of the grain boundaries.     

Thermogravimetric Analysis and Defect Models of the Oxygen Nonstoichiometry in La2–xSrxCuO4–y

The oxygen nonstoichiometry, y, of La_{2– x} Sr _x CuO_{4– y} (0 ≤ x ≤ 1) was determined as a function of temperature (800–1050°C) and oxygen partial pressure (10^–4 to 1 atm) by a thermogravimetric technique. The results were interpreted in terms of a number of defect models. It was found that a model based on the defect reaction 4Cu^×_Cu+ 2 V ^¨_o+ O_2(g)= 4Cu^._Cu+ 2O^×_o described the results well when the x and y dependences of the partial molar enthalpy of oxygen in the solid were considered. The large defect concentrations observed in this system lead to defect interactions, possibly ordering on the oxygen sublattice.     

Influence of Microstructure on the Electrical Properties of Iron-Substituted Calcium Titanate Ceramics

CaTi_0.8Fe_0.2O_3–δ ceramics with grain sizes that varied from 2 to 10 μm were obtained and studied using SEM, TEM, Mössbauer spectroscopy, impedance spectroscopy, and electrochemical oxygen permeability measurements. Smaller grains developed a core–shell microstructure that consisted of a pure CaTiO₃ core and an iron-rich microdomain structure at the shell. The effect of grain size on electronic conductivity was negligible. The ionic conductivity was higher for the ceramics with core–shell grains, which suggested that fast oxygen transport along microdomain walls may have occurred. For the homogeneous ceramics, the ionic conductivity decreased with decreased grain size, in which case the grain boundary represented an additional resistance, probably because of the depletion of oxygen vacancies.     

Resistance Degradation in Y(Cr,Mn)O3–Y2O3 Composite NTC Ceramics in Hostile Environments

A series of composite, negative temperature coefficient (NTC) ceramics were carefully processed with compositions based on the Y(Cr,Mn)O₃+Y₂O₃ system and these were investigated for resistance stability in hostile environments. This specific system is of interest for high-temperature automobile thermistors, however either through the processing or in use of these, materials can be exposed to reducing atmospheres at temperatures around 900°–1000°C. The thermochemical processes at intermediate temperatures and low     <10⁻¹⁰atm can influence the resistance of the given ceramics. Through an impedance analysis it is determined that the resistance increase is associated primarily with a grain boundary resistance increase. The grain and grain boundary elements are modeled through parallel constant phase element and resistance equivalent circuits connected in series. Possible origins of the defect chemistry being controlled through high-temperature processes at the sintering are partial Schottky reactions that are compensated through a superoxidation reaction on cooling and aging. The reduction process reversed the superoxidation reaction and transited the grain boundary surfaces to ionically compensated B-site vacancies with oxygen vacancies.     

Formation of Al2O3/Metal Composites by the Directed Oxidation of Molten Aluminum-Magnesium-Silicon Alloys: Part II, Growth Kinetics

The growth kinetics of an Al₂O₃/metal composite by the directed oxidation of an aluminum alloy (10 wt% Si, 3 wt% Mg, balance Al) have been measured as a function of temperature (1398 to 1548 K) and oxygen partial pressure in O₂/Ar gas mixtures. The growth rate exhibited an activation energy of ∼370 kJ/mol and a dependence on oxygen partial pressure consistent with a P _o^1/4₂ relationship. A dissolution-precipitation growth mechanism is proposed in which the growth rate is controlled by the electronic conductivity of an external Al₂O₃-doped MgO surface layer in conjunction with grain boundary diffusion of magnesium.     

Oxygen Sensors Based on the Electrical Conductivity of the Solid Solutions (Mg1–xFex)O and(Mg1–xCox)O

Solid solutions of general compositions (Mg_{1- x}Fe_x)O and (Mg_1-xCo_x)O (0.05 ≤ x ≤ 0.25) were investigated with regard to the dependence of their specific electrical conductivity on the oxygen partial pressure (10⁻¹⁷≤ po₂≤ 10⁵ Pa) at 900^c and 800°C. The experimental results, especially the slopes of plots of log σ vs log po₂ and the stability of the solid solutions studied, indicate that some of these compositions could be used as oxygen sensors at high temperatures.     

Effect of Ba6Ti17O40/BaTiO3 Interface Structure on {111} Twin Formation and Abnormal Grain Growth in BaTiO3

A structural transition of Ba₆Ti₁₇O₄₀/BaTiO₃ interfaces from faceted to rough was induced by reducing oxygen partial pressure in the atmosphere. As the oxygen partial pressure decreased, the number densities of {111} twins and abnormal grain decreased. TEM observation showed that the twin formation was governed only by the faceting of the interface. Experimental evidence of {111} twin-assisted abnormal growth of faceted BaTiO₃ grains was also obtained.     

High-Temperature Stability of Lanthanum Orthophosphate (Monazite) on Silicon Carbide at Low Oxygen Partial Pressures

The stability of lanthanum orthophosphate (LaPO₄) on SiC was investigated using a LaPO₄-coated SiC fiber at 1200°–1400°C at low oxygen partial pressures. A critical oxygen partial pressure exists below which LaPO₄ is reduced in the presence of SiC and reacts to form La₂O₃ or La₂Si₂O₇ and SiO₂ as the solid reaction products. The critical oxygen partial pressure increases from ∼0.5 Pa at 1200°C to ∼50 Pa at 1400°C. Above the critical oxygen partial pressure, a thin SiO₂ film, which acts as a reaction barrier, exists between the SiC fiber and the LaPO₄ coating. Continuous LaPO₄ coatings and high strengths were obtained for coated fibers that were heated at or below 1300°C and just above the critical oxygen partial pressure for each temperature. At temperatures above 1300°C, the thin LaPO₄ coating becomes morphologically unstable due to free-energy minimization as the grain size reaches the coating thickness, which allows the SiO₂ oxidation product to penetrate the coating.     

Effect of Oxygen Partial Pressure on the Dielectric Properties and Microstructures of Cofired Base-Metal-Electrode Multilayer Ceramic Capacitors

The dielectric properties, dopant distributions, and microstructures of BaTiO₃-based multilayer ceramic capacitors (MLCCs) sintered in H₂–N₂–H₂O atmospheres with     =10^−7.5 Pa (BMX-7.5) and     =10^−9.5 Pa (BMX-9.5) were studied, and the effects of oxygen partial pressures were analyzed. Dielectric measurements showed that BMX-7.5 had a lower dielectric constant at temperatures above 20°C, but a higher dielectric constant at temperatures below 10°C when compared with BMX-9.5. The coexistence of core–shell and core grains was observed in bright field (BF) transmission electron microscopy images in both types of capacitors. Triple-point and grain boundary phases were observed more frequently in BMX-9.5 than in BMX-7.5, and energy-dispersive X-ray spectrometer point-by-point analysis revealed that these second phases contained high concentrations of dopants such as Si, Y, and Ca. The dopant concentration in the shell regions in BMX-7.5 was higher than that in similar regions in BMX-9.5. Smeared and twisted grain boundaries with fringes observed in both types of MLCCs indicated that the shell regions in both samples were formed either by diffusion of foreign ions into BaTiO₃ or by crystallization of grain boundary and triple-point liquid phases. It was deduced that the partial pressure of oxygen in the sintering atmosphere influenced the microstructures, dopant distributions, and core–shell ratios of the grains in these materials.     

Structure–Property Relationships of BaTi1−2yGayNbyO3 (0≤y≤0.35) Ceramics

BaTi_{1−2 y} Ga _y Nb _y O₃ (BTGN) (0≤ y ≤0.35) powders were synthesized at 1300°C by the conventional solid-state method. Room temperature x-ray diffraction patterns for y ≤0.025 and 0.05≤ y ≤0.30 can be indexed as the tetragonal ( P 4 mm ) and cubic ( Pm     m ) polymorphs of BaTiO₃, respectively, whereas y =0.35 consists of a mixture of the cubic polymorph of BaTiO₃ and an 8H hexagonal-type perovskite ( P 6₃/ mcm ) isostructural with Ba₈Ti₃Nb₄O₂₄. Scanning electron microscopy shows the microstructures of BTGN ceramics ( y ≤0.30) sintered at 1500°C to consist of fine grains (1–3 μm) within a narrow grain size and shape distribution. Room temperature transmission electron microscopy for y ≤0.08 reveals core–shell structures and (111) twins in some grains; however, their relative volume decreases with y . Energy dispersive spectroscopy reveals the cores to be Ga and Nb deficient with respect to y . For y >0.08 there is no evidence of core–shell structures, however, some grains have a high density of dislocations, consistent with chemical inhomogeneity. BTGN ceramics exhibit a diverse range of dielectric behavior in the temperature range 120–450 K and can be subdivided into two groups. 0.025≤ y ≤0.15 display modest ferroelectric relaxor-type behavior, with high room temperature permittivity, ɛ₂₅', (>300 at 10 kHz), whereas 0.25≤ y ≤0.30 are temperature and frequency stable dielectrics with ɛ₂₅'<100 that resonate at microwave frequencies with modest quality factors, Q × f , ∼3720 GHz (at ∼5 GHz) for y =0.30.     

Blocking Grain Boundaries in Yttria-Doped and Undoped Ceria Ceramics of High Purity

CeO₂ samples doped with 10, 1.0, and 0.1 mol% Y₂O₃ and undoped CeO₂ samples of high purity were studied by impedance spectroscopy at temperatures <800°C and under various oxygen partial pressures. According to microstructural investigations by SEM and analytical STEM (equipped with EDXS), the grain boundaries were free of any second phase, providing direct grain-to-grain contacts. An amorphous siliceous phase was detected at only a few triple junctions, if at all; as a result, its contribution to the grain-boundary resistance was negligible. Nevertheless, the specific grain-boundary conductivities were still 2–7 orders of magnitude lower than the bulk conductivities, depending on dopant concentration, temperature, and oxygen partial pressure. The charge carrier transport across the grain boundaries occurred only through the grain-to-grain contacts, whose properties were then determined by the space-charge layer. The space-charge potential in acceptor-doped CeO₂ was positive, causing the simultaneous depletion of oxygen vacancies and accumulation of electrons in the space-charge layer. The very low grain-boundary conductivities can be accounted for by the oxygen-vacancy depletion; the accumulation of electrons became evident in weakly doped and undoped CeO₂ at high temperatures and under low oxygen partial pressures.     

Structure and Dielectric Properties of the Ba(Mg1/3Nb2/3)O3-La(Mg2/3Nb1/3)O3 System

A complete range of perovskite solid solutions can be formed in the (1 − x )Ba(Mg_1/3Nb_2/3)O₃- x La(Mg_2/3Nb_1/3)O₃ (BMN-LMN) pseudobinary system. While pure BMN adopts a 1:2 cation ordered structure, 1:1 ordered phases are stabilized for 0.05 ≤ x ≤ 1.0. Dark-field TEM images indicate that the La-doped solid solutions are comprised of large 1:1 ordered domains and no evidence was found for a phase-separated structure. This observation coupled with the systematic variations in the intensities of the supercell reflections supports a charge-balanced "random-site" model for the 1:1 ordering. The substitution of La also induces a transformation from a negative to positive temperature coefficient of capacitance in the region 0.25 ≤ x ≤ 0.5.     

Bulk Conductivity and Defect Chemistry of Acceptor-Doped Strontium Titanate in the Quenched State

The grain bulk conductivity of acceptor-doped SrTiO₃ ceramics was investigated by the impedance analysis method after quenching from high-temperature equilibria. The influence of the oxygen partial pressure during equilibration, P ^Eq_O2, is described in terms of a defect model for titanates. From a comparison between the experimental results and the predictions of this model, a predominant ionic conductivity is concluded for a wide P ^Eq_O2 range (approximately 10⁻¹¹ to 10⁵ Pa). The influence of the ionization energy of the acceptors and of possible defect association is discussed.     

Lanthanum Oxyfluoride: Structure, Stability, and Ionic Conductivity

Structure and phase transition of LaO_{1− x} F_{1+2 x} , prepared by solid-state reaction of La₂O₃ and LaF₃, was investigated by X-ray powder diffraction and differential scanning calorimetry for both positive and negative values of the nonstoichiometric parameter x . The electrical conductivity was investigated as a function of temperature and oxygen partial pressure using AC impedance spectroscopy. Fluoride ion was identified as the migrating species in LaOF by coulometric titration and transport number determined by Tubandt technique and EMF measurements. Activation energy for conduction in LaOF was 58.5 (±0.8) kJ/mol. Conductivity increased with increasing fluorine concentration in the oxyfluoride phase, suggesting that interstitial fluoride ions are more mobile than vacancies. Although the values of ionic conductivity of cubic LaOF are lower, the oxygen partial pressure range for predominantly ionic conduction is larger than that for the commonly used stabilized-zirconia electrolytes. Thermodynamic analysis shows that the oxyfluoride is stable in atmospheres containing diatomic oxygen. However, the oxyfluoride phase can degrade with time at high temperatures in atmospheres containing water vapor, because of the higher stability of HF compared with H₂O.     

Degradation of Multilayer Ceramic Capacitors with Nickel Electrodes

The mechanism of degradation, or IR drop, of BaTiO₃-based Ni-electrode chip capacitors has been studied, with special attention to the microstructure. Degradation occurred mainly at the center of the capacitors. Longer-life capacitors were obtained under conditions of low oxygen partial pressure, 10⁻¹² atm, during sintering, and had larger grain sizes and smaller quantities of grain boundary phase. The existence of oxygen vacancies in the grain boundary phase was confirmed by cathode luminescence measurement. Double layers along the surfaces of the Ni electrodes were also related to the life of the capacitors.     

Microstructure and Creep Behavior of a Si3N4–SiC Micronanocomposite

The microstructure and its influence on the creep behaviour of carbon derived Si₃N₄-SiC micro/nanocomposite tested in bending at temperatures from 1200° to 1400°C in air has been studied. No phase and microstructure change after creep test implied that material is stable at tested temperature range. After creep test only partial crystallization of glassy intergranular phase has been observed. Creep parameters n close to 1, apparent activation energy around 350 kJ/mol together with TEM observation indicated that the main creep mechanisms is solution precipitation controlled by interface reaction in combination with grain boundary sliding caused by the amorphous intergranular phases present in microstructure. However, the grain boundary sliding is hindered by local SiC particles interlocking neighboring Si₃N₄ grains.     

Impedance Spectroscopy of Undoped BaTiO3 Ceramics

The electrical properties of ceramic BaTiO₃ were investigated by ac impedance spectroscopy over the ranges 25°-330°C and 0.03 Hz-1 MHz. Results are compared with those obtained from fixed-frequency measurements, at 1 kHz and 100 kHz. Fixed-frequency Curie-Weiss plots show deviations from linearity at temperatures well above t _c. The ac measurements show that grain boundary impedances influence Curie-Weiss plots in two ways: at high temperatures, they increasingly dominate the fixed-frequency permittivities; at lower temperatures, closer to T ^c, the high-frequency permittivity contains a contribution from grain boundary effects. Methods for extraction of bulk and grain boundary capacitances from permittivity and electric modulus complex plane plots are discussed. The importance of selecting the appropriate equivalent circuit to model the impedance response is stressed. A constriction impedance model for the grain boundary in BaTiO₃ ceramics is proposed: the grain boundary capacitance is neither temperature-independent, nor shows Curie-Weiss behavior. The grain boundary is ferroelectric, similar to the grains, but its impedance is modified by either air gaps or high-impedance electrical inhomogeneity in the region of the necks between grains; the activation energy of the constriction grain boundary impedance differs from that of the bulk, suggesting differences in defect states or impurity levels.