Structure and electrical properties of single-phase cobalt manganese oxide spinels Mn3xCoxO4 sintered classically and by spark plasma sintering(SPS)

Cobalt manganese oxide spinels Mn3�xCoxO4 (with 0.98pxp3) were prepared by the thermal decomposition in air of oxalate precursors. The influence of the thermal treatments on the structure of these materials is emphasized. Single-phase ceramics were obtained after optimization of the sintering parameters. A precise phase diagram for the Co–Mn–O system is proposed according to thermal stability and structure of oxide powders. The electrical measurements on single-phase ceramics show that low values of resistivity can be achieved. The conduction could take place through jumps of polarons between Mn3+ and Mn4+ on octahedral sites. These compounds present interesting electrical characteristics for negative temperature coefficient (NTC) thermistor application

Soft chemistry synthesis of the perovskite CaCu3Ti4O12

The perovskite CaCu3Ti4O12 (CCT) has been obtained after calcination of oxalate precursors at 900–1000 °C in air. Those precursors are prepared using a soft chemistry method, the coprecipitation. The oxalate powders consist of disk-like particles of 2–3 μm diameter and 300–400 nm thickness. By varying the ratio of the initial amounts of metal chlorides, additional phases (CaTiO3, TiO2 and CuO) could be obtained besides CCT. The corresponding multiphased ceramics present improved dielectric properties

Thermal Expansion of (Ba1-xLax))Ti1-x/4 O 3 Solid Solutions

Deformation and the thermal expansion coefficient of ceramic samples of (Ba1−xLax)Ti1−x /4 O 3 solid solutions (x= 0, 0.026, 0.036, 0.054) were studied in the temperature range 120–700 K. Based on an analysis of the data obtained, the temperature–composition phase diagram is refined, and the temperature dependence of the polarization is calculated. The results are discussed in combination with the dielectric measurement data

Dielectric properties of CaCu3Ti4O12 based multiphased ceramics

A “soft chemistry” method, the coprecipitation, has been used to synthesize the perovskite CaCu3Ti4O12 (CCT). Three main types of materials were obtained for both powders and sintered ceramics: a monophased consisting of the pure CCT phase, a biphased (CCT + CaTiO3), and a three-phased (CCT + CaTiO3 + copper oxide (CuO or Cu2O)). These ceramics, sintered at low temperature, 1050 °C, present original dielectric properties. The relative permittivity determined in the temperature range (−150 < T < 250 °C) is significantly higher than the one reported in the literature. Internal barrier layer capacitor is the probable mechanism to explain the particular behaviour. Moreover, the presence of a copper oxide phase beside the perovksite CCT plays an important role for enhancing the dielectric properties

Mixed manganese spinel oxides: optical properties in the infrared range

Spinel oxides in manganite family are studied in terms of optical properties in the infrared range (3–12 lm). The reflectivity is measured on sintered pellets. The complex refractive index is estimated by fitting hemispherical directional reflectance in both polarizations, perpendicular and parallel. The influence of different metallic cations (Ni, Co, Fe, Cu) is compared. In particular, in the case of manganese nickel copper oxides, the impact of variations in copper and nickel contents is evaluated. Cationic distribution is determined and correlated to the optical characteristics. These materials, usually used for NTC thermistor applications, are investigated for IR charges in coating

Magnetic properties of cobalt and manganese oxide spinel ceramics

Magnetic susceptibility measurements, magnetization and neutron diffraction results at low temperature for cobalt and manganese oxide spinel ceramics are presented. The Curie temperature varies similarly with the sample composition in ceramics and powders. The experimental molar Curie constant variation is explained by the presence of Co2+, CoIII, Mn3+ and Mn4+, and possibly Co3+ in the octahedral sites for the cobalt rich phases. The magnetic moments of the cations in tetrahedral and octahedral sites are not collinear and the global magnetization is oriented in a third direction

Microstructure of Ba1−xLaxTiO3−δ ceramics sintered by spark plasma sintering

Nano-sized Ba1−xLaxTiO3 (0.00 ≤ x ≤ 0.14) powders were prepared by a coprecipitation method and calcined at 850 °C in air. The corresponding ceramics were obtained by Spark Plasma Sintering (SPS) at 1050 °C. These ceramics are oxygen deficient and are marked as Ba1−xLaxTiO3−δ. Both powders and ceramics were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). The effect of lanthanum concentration on the densification behavior, on the structure and the microstructure of the oxides was investigated. Average grain sizes are comprised between 54 (3) nm and 27 (2) nm for powders, and 330 (11) nm and 36 (1) nm for ceramics according to the La-doping level. Powders crystallize in the cubic (or pseudo-cubic) perovskite phase. The structure of ceramics consists in a mixture of cubic (or pseudo-cubic) and tetragonal perovskite type phases. As the lanthanum content increases, the tetragonality of the samples decreases, as well as the grain size

Investigation of nucleation and crystal growth kinetics of nickel manganese oxalates

The nucleation and the crystal growth rates of mixed nickel manganese oxalates have been determined from the changes of the ionic concentration of the solution and the crystal size distribution during the precipitation process within a supersaturation range 0–0.1 M. Thermodynamic solubility calculations have been used to identify the different species contributing the precipitation reaction and for estimation of the thermodynamic constant. Experimental data show that the nucleation rate of mixed nickel manganese oxalate in this supersaturation range is consistent with a primary heterogeneous mechanism and was found to obey to an exponential law. The crystal growth rates indicate a surface-integration-controlled mechanism with a first-order law with respect to the supersaturation

Thermochemistry of iron manganese oxide spinels

Oxide melt solution calorimetry has been performed on iron manganese oxide spinels prepared at high temperature. The enthalpy of formation of (MnxFe1−x)3O4 at 298 K from the oxides, tetragonal Mn3O4 (hausmannite) and cubic Fe3O4 (magnetite), is negative from x=0 to x=0.67 and becomes slightly positive for 0.670.6) spinels of intermediate compositions. The enthalpies of formation are discussed in terms of three factors: oxidation–reduction relative to the end-members, cation distribution, and tetragonality. A combination of measured enthalpies and Gibbs free energies of formation in the literature provides entropies of mixing. ΔSmix, consistent with a cation distribution in which all trivalent manganese is octahedral and all other ions are randomly distributed for x>0.5, but the entropy of mixing appears to be smaller than these predicted values for x<0.4

Hydrothermal synthesis of nanosized BaTiO3 powders and dielectric properties of corresponding ceramics

BaTiO3 fine powders were synthesized by hydrothermal method at 150 °C or 250 °C for 7 h, starting from a mixture of TiCl3 + BaCl2 or TiO2 + BaCl2. The size of the crystallites is close to 20 nm whatever the starting mixture and the reaction temperature. These powders are well crystallized and constituted of a mixture of the metastable cubic and stable tetragonal phases. The ceramics obtained after uniaxial pressing and sintering at 1250 °C for 10 h or 20 h present high densification (up to 99.8%). The Curie temperature (Tc) and the electrical permittivity ( r) of the ceramics strongly depend on the type of titanium source that has been used for preparing the powder and on the sintering dwell time. Particularly, Tc is shifted towards lower temperature when TiCl3 is used. The permittivity value at Tc of BaTiO3 sintered at 1250 °C for 10 h reaches 7000 and 11,000 with respectively TiCl3 and TiO2 used as titanium source