Investigation of the Phase Transition in ZrTiO4 and ZrTiO4-SnO2 Solid Solutions

Continuous phase transitions were found to occur in ZrTiO₄ above and below a major discontinuity at 1125°±10°C. The space group of both forms of ZrTiO₄ is Pcnb. For specimens quenched from high temperatures, the volume of the unit cell decreases linearly from ∼1450°C to the discontinuity, with the major change occurring in the c axis. The volume decreases considerably at this temperature and continues to decrease with lower-temperature annealing. Substitutional tin in solid solution stabilizes the high-temperature structure type.     

Electrical Properties of ZnO-Bi2O3 Ceramics

The nonlinear volt-ampere characteristics and small-signal ac capacitance and resistance of sintered ZnO containing 0.5 mol% Bi₂O₃ were measured. Many of the electrical properties are related directly to the microstructure, which consists of conductive ZnO grains separated by a continuous amorphous Bl₂O₃, phase. The origin of the nonlinear conduction in the intergranular phase was confirmed by experiments with evaporated thin films. The proposed conduction mechanism in varistors containing ZnO and Bi₂O₃ is a combination of hopping and tunneling in the amorphous phase.     

Microstructure and Electrical Properties of Chemically Prepared Nb2O5-Doped SrTiO3 Ceramics

Chemically homogeneous SrTiO₃ powders of submicrometer size were obtained by alcohol dehydration and subsequent calcination of citrate/format solutions. Nb₂O₅-doped SrTiO₃ was prepared with various Sr:Ti ratios resulting in an anomalous increase in the dielectric constant ( K 'up to ∼8000) for donor-doped SrO-excess SrTiO₃. No semiconducting behavior was observed for donor-doped TiO₂-excess SrTiO₃ when fired in air. Therefore, a "brick-wall" type of microstructure was formed as a result of the excess SrO, giving rise to anomalously high dielectric constants.     

Fabrication, Mechanical Properties, and Electrical Conductivity of Co3O4 Ceramics

Well-densified Co₃O₄ ceramics (98.3% of theoretical) have been fabricated by the combined use of hot pressing (800°C/I h/30 MPa) and hot isostatic pressing (880°C/2 h/196 MPa). Their Vickers hardness and fracture toughness are 10.3 GPa and 4.2 MPa·m^1/2, respectively. They exhibit a high electrical conductivity of 3.35 × 10' S·cm⁻¹ at 800°C.     

Electrical Transport Properties of La2CuO4 Ceramics Processed by the Spark Plasma Sintering

Highly dense La₂CuO₄ ceramics have been prepared by the spark plasma sintering technique. Temperature dependence of electrical conductivity indicates that La₂CuO₄ ceramics sintered at over 875°C exhibit a metal-like behavior, which should be ascribed to the special La₂CuO₄ crystal structure and its correlation splitting of the half-filled d _{x 2− y 2} band. Our experimental data indicate that all of the La₂CuO₄ samples exhibit positive thermoelectric power in the whole measuring temperature range, indicating that the majority of charge carriers are holes. It is desirable to obtain good thermoelectric performance for this system by optimizing the electrical properties and reducing the thermal conductivity.     

Effect of Microstructure on the Properties of TiB2 Ceramics

Samples of a TiB₂ ceramic containing 0 to 10 wt% Ni were fabricated by hot-pressing. Several properties, including fracture strength, indentation fracture toughness, and thermal expansion (between 25° and 1000°C) were measured. Resulting data were correlated with sample microstructure and composition.     

Effect of La Doping on the Phase Conversion, Microstructure Change, and Electrical Properties of Bi2Fe4O9 Ceramics

Undoped and La-doped Bi₂Fe₄O₉ ceramics were synthesized using a soft chemical method. It is observed that in calcining La-doped Bi₂Fe₄O₉, Bi(La)FeO₃ phase rather than Bi_{2− x} La _x Fe₄O₉ gradually increases with increasing La doping content. The phase conversion from mullite-type structure of Bi₂Fe₄O₉ to rhombohedrally distorted perovskite one of Bi(La)FeO₃ with increasing La doping content indicates that La doping can stabilize the structure of BiFeO₃. This is further evidenced that Bi₂Fe₄O₉ can be directly converted to Bi(La)FeO₃ by heating the mixtures of nominal composition of Bi₂Fe₄O₉/ x La₂O₃. Furthermore, the microstructure changes and the room temperature hysteresis loops and leakage current for Bi_{2− x} La _x Fe₄O₉ with x =0 and 0.02 were characterized.     

Microstructure and Electrical Properties of MgAl2O4 Thin Films for Humidity Sensing

Active elements for humidity sensors based upon MgAl₂O₄ thin films or sintered pellets were investigated. Thin films were deposited on Si/SiO₂ substrates by radiofrequency (rf) sputtering. Sintered MgAl₂O₄ pellets were prepared by traditional ceramic processing. Scanning electron microscopy (SEM) analysis showed that the thin films were rather dense and homogeneous, made up of clustered particles of about 20–30 nm, while the pellets showed a wide pore-size distribution. X-ray photoelectron spectroscopy (XPS) demonstrated that the thin films have a stoichiometry close to that of MgAl₂O₄. Sintered MgAl₂O₄ is crystalline, while it is disordered in thin-film form. The presence of two different components of the Al 2 p peaks was correlated with the structural difference between pellets and thin films. The relationship between good film–substrate adhesive properties and the chemical composition at the interface was studied. The electrical properties of the sensing elements were studied at 40°C in environments at different relative humidity (RH) values between 2% and 95%, using ac impedance spectroscopy. MgAl₂O₄ thin films showed interesting characteristics in terms of their use in humidity-measurement devices. Resistance versus RH sensitivity values showed variations as high as 4 orders of magnitude in the RH range tested for thin films, and 5 orders of magnitude for pellets. The differences in the electrical behavior of MgAl₂O₄ pellets and thin films were correlated with their different microstructures.     

Influence of Processing Conditions on the Electrical Properties of CaCu3Ti4O12 Ceramics

The electrical properties of a series of CaCu₃Ti₄O₁₂ ceramics prepared by the mixed oxide route and sintered at 1115°C in air for 1–24 h to produce different ceramic microstructures have been studied by Impedance Spectroscopy. As-fired ceramics are electrically heterogeneous, consisting of semiconducting grains and insulating grain boundaries, and can be modelled to a first approximation on an equivalent circuit based on two parallel RC elements connected in series. The grain boundary resistance and capacitance values vary as a function of sintering time and correlate with the ceramic microstructure based on the brickwork layer model for electroceramics. The large range of apparent high permittivity values for CaCu₃Ti₄O₁₂ ceramics is therefore attributed to variations in ceramic microstructure. The grain-boundary resistance decreases by three to four orders of magnitude after heat treatment in N₂ at 800°–1000°C but can be recovered to the original value by heat treatment in O₂ at 1000°C. The bulk resistivity decreases from ∼80 to 30 Ω·cm with increasing sintering time but is independent of heat treatment in N₂ or O₂ at 800°–1000°C. The origin of the bulk semiconductivity is discussed and appears to be related to partial decomposition of CaCu₃Ti₄O₁₂ at the high sintering temperatures required to form dense ceramics, and not to oxygen loss.     

Electrical Properties of PrFeO3 and Pr2NiO4

The electrical conductivity of PrFeO₃ and Pr₂NiO₄ was investigated at 300° thd 1000°C and at oxygen partial pressures of 1 to 10⁻²⁰ atm and the phase relations and nonstoichiometry of these materials were studied. The results suggest that PrFeO₃ is a semiconductor exhibiting intrinsic behavior at T>300°C and P_o2 >10⁻⁵ atm. The conductivity of Pr₂NiO₄ depends on P_o2 and is thus related to deviations from stoichiometry. These results for Pr₂NiO₃ raise questions about the validity of the suggested semiconductor-to-metal transition model for explaining the electrical properties of La₂NiO₃ and Nd₂Ni0₄.     

Mechanism of ZrTiO4 Synthesis by Mechanochemical Processing of TiO2 and ZrO2

High-energy ball milling initiates a solid-state reaction in an equimolar mixture of TiO₂ and ZrO₂. The first stage of ball milling induced the transformation of anatase TiO₂ to high-pressure phase TiO₂ (II), isostructural with ZrTiO₄. The formation of solid solutions monoclinic ZrO₂/TiO₂ and TiO₂ (II)/ZrO₂ was observed in the intermediate stage. Afterward, a nanosized ZrTiO₄ phase was formed in the milled product from the TiO₂ (II)/ZrO₂ solid solution. The sintering of the milled product at a temperature <1100°C was examined in situ by Raman spectroscopy. The full solid-state reaction toward ZrTiO₄ ceramic is completed at a temperature considerably lower than reported in the literature.     

Effects of Niobium Doping on the Microstructure and Electrical Properties of 0.36BiScO3–0.64PbTiO3 Ceramics

Recently, a new family of piezoelectric perovskite materials based on the solid solution (1− x )BiScO₃– x PbTiO₃ was developed. This system was found to have a Curie temperature higher than 450°C and excellent piezoelectric properties near the MPB composition. Niobium, as a donor dopant in the piezoelectric system Pb(Zr,Ti)O₃ and other lead - based perovskite materials, has commonly been used to increase the electrical resistivity, dielectric, and piezoelectric properties. In the current work, the effect of niobium substitution in the BS–PT system has been reported. The results of niobium additions in the BS–PT system showed no large enhancement of the piezoelectric properties. Niobium doping also led to lower Curie temperatures and higher dielectric loss. Further grain size effects in niobium - doped BS–PT compositions provided experimental evidence of significant extrinsic contributions to the piezoelectric properties in this system.     

Synthesis and Electrical Properties of Dense Ce0.9Gd0.1O1.95 Ceramics

Uniform spherical powders of Ce_0.9Gd_0.1O_1.95 with an average diameter of 250 nm were obtained at 700°C from a sol-gel process of mixing nitrates and ethylene glycol. Broadening of the X-ray peaks of the fluorite structure reveals a small crystallite size within the powders. Sintering in air of pressed pellets of the powders at 1585°C gives ceramics of 99% theoretical density with grain sizes 1-10 µm and a cubic unit cell a = 5.422 ± 0.034 Å. The electrical conductivity σ=σ_o+σ_e has two components. In air or argon, the electronic component σ_e is negligible and the oxide-ion conductivity σ_o is not described by a classical Arrhenius equation; a pronounced curvature at T similar/congruent T * has been observed in the Arrhenius plot of the bulk conductivity. The system could be modeled by a condensation of mobile oxygen vacancies into ordered clusters below a temperature T * similar/congruent 583 ± 45°C and a motional enthalpy Δ H _m= 0.63 ± 0.01 eV for the vacancies. A measured trapping energy Δ H _t(1 - T/T *) has Δ H _t= 0.19 ± 0.01 eV = 2.57 kT *. In a reducing atmosphere, σ_e exhibits a small-polaron motional enthalpy Δ H _p= 0.40 ± 0.08 eV for transfer of a 4 f electron from a Ce³⁺ to a Ce⁴⁺ ion and a Δ H _p+Δ H _pt= 0.51 ± 0.04 eV at T < T *.     

Electrical Conduction Properties of LaP3O9 Glass and Glass–Ceramics

Electrical conduction properties of undoped and 1 mol% Sr-doped LaP₃O₉ glasses and glass–ceramics were investigated over the temperature range of 673–1123 K. Both the materials showed relatively low conductivities in the glassy state. However, the conductivity of the Sr-doped LaP₃O₉ glass significantly increased with a heat treatment above the crystallization temperature, while the conductivity of the undoped LaP₃O₉ glass did not improve even after the heat treatment. It was concluded that crystallization of the Sr-doped LaP₃O₉ glass induced protonic conduction and thus enhanced the conductivity. Electrical conduction properties of the Sr-doped LaP₃O₉ glass–ceramic fundamentally resembled those of the sintered crystalline Sr-doped LaP₃O₉.     

Humidity-Sensitive Electrical Conduction of MgCr2O4-TiO2 Porous Ceramics

The crystalline phase, microstructure, semiconduction, and humidity-sensitive electrical conduction of MgCr₂O₄-TiO₂ ceramics were studied. A solid solution with TiO₂ up to 30 mol% occurs as a single phase with a pure MgCr₂O₄-type spinel structure. The humidity-sensitive electrical conduction of the MgCr₂O₄-TiO₂ porous ceramics is the most promising for humidity-sensing devices.     

Sintering and Electrical Properties of Lead-Free Na0.5K0.5NbO3 Piezoelectric Ceramics

Lead-free Na_0.5K_0.5NbO₃ (NKN) piezoelectric ceramics were fairly well densified at a relatively low temperature under atmospheric conditions. A relative density of 96%–99% can be achieved by either using high-energy attrition milling or adding 1 mol% oxide additives. It is suggested that ultra-fine starting powders by active milling or oxygen vacancies and even liquid phases from B-site oxide additives mainly lead to improved sintering. Not only were dielectric properties influenced by oxide additives, such as the Curie temperature ( T _c) and dielectric loss ( D ), but also the ferroelectricity was modified. A relatively large remanent polarization was produced, ranging from 16 μC/cm² for pure NKN to 23 μC/cm² for ZnO-added NKN samples. The following dielectric and piezoelectric properties were obtained: relative permittivity ɛ ^T ₃₃/ɛ ₀ =570–650, planar mode electromechanical coupling factor, k _p=32%–44%, and piezoelectric strain constant, d ₃₃=92–117 pC/N.     

Microstructure and Electrical Properties of [(K0.50Na0.50)0.95−xLi0.05Agx](Nb0.95Ta0.05)O3 Lead-Free Ceramics

[(K_0.50Na_0.50)_{0.95− x} Li_0.05Ag _x ](Nb_0.95Ta_0.05)O₃ (KNLNANT- x ) lead-free piezoelectric ceramics were prepared by normal sintering. Effects of the Ag content on the microstructure and electrical properties of KNLNANT- x ceramics were systematically investigated. It is found that the ceramics with x =0.03 exhibit relatively good electrical properties along with high Curie temperature: ( d ₃₃∼252 pC/N, T _c∼438°C, k _p∼45.4%, P _r∼30.1 μC/cm², E _c∼13.8 kV/cm, ɛ_r∼1030, and tan δ∼2.6%). The related mechanism for enhanced electrical properties of the ceramics was also discussed. These results show that KNLNANT-0.03 ceramic is a promising candidate material for high temperature lead-free piezoelectric ceramics.     

Effect of Ionic Substitution on the Thermal Expansion of ZrTiO4

New oxide compounds with α-PbO₂ structure have been synthesized by solid-state reactions. These are derived from ZrTiO₄ and HfTiO₄ by a different kind of ionic substitution. The thermal expansion behavior of these phases was investigated by means of a dilatometer and an X-ray heating diffractometer. These measurements revealed rather low expansion for some of the Zr(Me³⁺/Me⁵⁺)O₄, solid solutions. This behavior is attributed to their high expansion anisotropy, which leads to extended formation of microcracks.     

Electrical Properties and Cation Valencies in Mn3O4

The electrical conductivity and thermopower of Mn₃O₄ were measured in the temperature range 920° to 1530°C. Electrical conduction in cubic Mn₃O₄ is explained by the small polaron hopping of electron holes between Mn⁴⁺ and Mn³⁺ on octahedral sites. The concentrations of Mn⁴⁺ and Mn³⁺ are governed by the disproportionation equilibrium 2Mn _oct ³⁺⇄Mn _oct ⁴⁺+ Mn _oct ²⁺. This model also explains the electrical behavior of NiMn₂O₄ and CuMn₂O₄.