Evaluation of pressure and temperature effect on the structure and properties of Ca2.93Sr0.07Co4O9 ceramic materials

In this work, the effect of hot-pressing conditions on the performances of Sr-doped Ca3Co4O9 materials has been investigated. The samples were prepared from attrition milled precursors, which reduced the processing time. Samples were hot-pressed at temperatures (T) between 800 and 900 °C and pressures (P) from 51 to 71 MPa. The out-of-plane X-ray diffraction (XRD) showed that all samples are formed by the thermoelectric phase, with a good grain orientation which is improved with T, and P, as demonstrated by their Lotgering factor. The observations through Scanning Electron Microscopy (SEM) have revealed that grain sizes and orientation are enhanced with T, and P, as well as density through Archimedes''s method. All these trends are reflected in the flexural strength and microhardness. The electrical resistivity is lower when the T, or P, is increased, reaching 6.4 mO cm for samples processed at 900 °C and 71 MPa, which is about the best reported values in the literature. On the other hand, contrarily to the expected results, they also showed the highest S values, 182 µV/K, which are similar to the best reported values for highly dense textured materials. Thermal conductivity values do not follow a regular evolution with the hot-pressing conditions, probably due to internal stresses, reaching the lowest values at 800 °C in samples processed at 800 °C and 51 MPa (1.51 W/(K*m)) or 900 °C and 61 MPa (1.53 W/(K*m)). Consequently, the highest ZT values have been determined in samples processed at 900 °C and 61 MPa (0.35) which is higher than the best reported values in literature for bulk textured samples, to the best of our knowledge. © 2021 The Author

Tuning Ca3Co4O9 thermal and transport properties by TiC nanoparticles addition

Ca3Co4O9 + xwt.% TiC (x = 0, 0.25, 0.5, 0.75, and 1.0) polycrystalline thermoelectric ceramics have been prepared through the classical ceramic route. XRD characterization has demonstrated that all samples are mainly composed by the Ca3Co4O9 phase, while microstructural observation has shown that no reaction between both components has been produced. Moreover, TiC particles are well distributed for small additions, and start to agglomerate from 0.75 wt.% content. Density measurements showed that nearly no changes have been produced by TiC addition and nearly the whole porosity appears as open one. Furthermore, electrical resistivity decreases up to 0.75 wt.% addition, increasing for higher content. On the other hand, Seebeck coefficient has been maintained unchanged in all samples. In spite of an irregular behaviour of thermal conductivity with temperature, it tends to decrease when the temperature is raised, displaying the lowest values for the 0.25 wt.% samples. These data led to an increase of about 40% in ZT values at 800 °C for samples with 0.25 wt.% addition, when compared with the pure ones. Finally, linear thermal expansion coefficient is decreased when TiC content is increased, which can be exploited to fit the thermal expansion coefficients of all the components used to build a power generation thermoelectric module

Influence of the orthorhombic phase content on the dielectric and magnetic properties of YMnO3

Here, we report on the dielectric and magnetic properties of polycrystalline samples of YMnO3 where the ratio between both orthorhombic (o-YMO) and hexagonal (h-YMO) phases has been controlled by means of appropriate sintering treatments. Interestingly, we observe that the dielectric behavior is dominated by the presence of the metastable o-YMO phase, even though its amount remains as a minority phase. However it also influences the magnetic behavior for sintering temperatures below 1000 °C, and in addition, a weak ferromagnetic contribution is always detected in our polycrystalline samples regardless of the o-YMO content

Tuning thermoelectric properties of Ca0.9Gd0.1MnO3 by laser processing

Donor-doped CaMnO3 is an n-type semiconductor with perovskite structure, being considered as a potential n-type leg in thermoelectric modules. This oxide presents stability at high temperatures and allows tuning the relevant electrical and thermal transport properties through doping. In this work, Ca0.9Gd0.1MnO3 precursors have been prepared to produce fibres through the laser floating zone technique using different pulling rates. However, as-grown fibres did not present thermoelectric properties due to the presence of high amounts of secondary phases, leading to very high electrical resistivity values. The results have highlighted the importance of annealing procedures to reduce electrical resistivity, due to the decrease of secondary phases amount, and producing promising thermoelectric performances. The annealed samples present higher ZT values when the growth rate is decreased, reaching around 0.22 for the lowest growth rate, which is very close to the best values reported in the literature for these materials. Moreover, this procedure possesses an additional advantage considering that these samples can be directly used as n-type legs in thermoelectric modules for high-temperature applications. However, further studies should be made to determine the optimal amount of dopant

Effect of laser wavelength on the thermoelectric properties of Bi1.6Pb0.4Sr2Co2O8 textured ceramics processed by LFZ

Bi1.6Pb0.4Sr2Co2O8 samples have been textured by the Laser Floating Zone (LFZ) process using Nd:YAG, and CO2 laser radiation. Using different wavelengths resulted in significant structural and microstructural modifications. Powder XRD patterns showed that the thermoelectric phase is the major one in both cases. Microstructural studies revealed that all samples presented the same phases but with much lower content of secondary ones in those processed with the CO2 laser. Electrical resistivity showed different behavior for the two types of samples, being in general, lower for the CO2 grown rods. Seebeck coefficient is lower for the CO2 grown samples up to 300 °C, and higher in the high-temperature range, reaching 240 μV/K at 650 °C, which is one of the highest values obtained so far in these compounds. Moreover, thermal conductivity at 600 °C for these samples (0.93 W/K m) is among the lowest reported in the literature. As a consequence, ZT values at 600 °C reached 0.42 in CO2 textured materials, about two times higher than the obtained in Nd:YAG ones. This value is among the highest reported so far in the literature, and is comparable to the performance attained for the same composition containing nanoparticles addition. All these properties, combined with the fact that the processed materials can be directly integrated into thermoelectric modules, render them highly attractive for industrial production

Effect of B-site doping on the thermoelectric performances of Ca0.97Y0.01 La0.01 Yb0.01Mn1-2xNbxMoxO3 thermoelectric ceramics

A-, and B-site multiple-doped Ca0.97Y0.01La0.01Yb0.01Mn1–2xNbxMoxO3 was studied for improving its thermoelectric thermoelectric performance. Samples were prepared from planetary milled precursors and sintered at 1310ºC for 12 h. XRD showed that sintered samples are nearly single phase, with small amounts of CaMn2O4. SEM analysis revealed that grain size decreases with Nb and Mo content, leading to lowered electrical resistivity, reaching 6.1 mΩ cm at 800ºC in x = 0.03 samples, 60% lower than that of pristine samples. The highest Seebeck coefficient for doped samples has been obtained for x = 0.005, 210μV/K at 800ºC. A high power factor (0.46 mW/K2 m at 800ºC) has been reached for x = 0.01 samples. However, thermal conductivity did not significantly vary with composition, leading to ZT∼0.27 at 800ºC for x = 0.005 samples, among the best reported in the literature. These results suggest that multi-doping approach opens new paths for integrating calcium manganite-based materials in thermoelectric modules for power generation at high temperatures

Significant reduction in processing time for Ca0.95Ce0.05MnO3 thermoelectric ceramics

Attrition-milling process has been applied to Ce-doped CaMnO3 precursors to obtain small grain-size powders. The use of Ce4+ as dopant instead a Rare Earth3+ has allowed decreasing by 50% the atomic proportion of dopant, to obtain equivalent charge carrier concentration, which is required for attaining promising properties for thermoelectric applications. An impressive decrease in thermal processing time was achieved, together with an increase in thermoelectric performances, when compared to classically prepared materials. XRD and SEM analysis have confirmed that the final material is nearly single phase. Moreover, grain sizes and density increase with the sintering duration. These microstructural differences are reflected in a significant decrease in electrical resistivity, when compared to the samples prepared from ball-milled precursors (used as reference), without drastically modifying the Seebeck coefficient values. On the other hand, despite of their high electrical conductivity, thermal conductivity is decreased for short time sintered materials, leading to the highest ZT values at 800 °C (∼0.27) in samples sintered for 1 h at 1310 °C. These values are among the best reported in the literature, but they have been obtained in very short time using a simple, and easily scalable process. The suggested approach presented in this work appears particularly promising for large-scale production of oxide-based thermoelectric modules for power generation

Substantial thermal conductivity reduction in mischmetal skutterudites Mm_xCo_4Sb_12 prepared under high-pressure conditions, due to uneven distribution of the rare-earth elements

Juan de la Cierva fellowshipThermoelectric mischmetal-filled Mm(x)Co(4)Sb(12) (Mm: natural cocktail of rare-earth elements, mostly Ce and La) skutterudites have been synthesized and sintered in one step under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. Synchrotron X-ray diffraction patterns display a splitting of the diffraction peaks ascribed to purely Ce-, and Mm-filled skutterudite phases, which have been analyzed and confirmed by high-resolution TEM and EELS. A total thermal conductivity () of 1.51 W m(-1) K-1 is measured at 773 K for Mm(0.5)Co(4)Sb(12), below that of other filled skutterudites, which is promoted by the enhanced phonon scattering over a broad range of the phonon spectrum due to the inhomogeneous and nanoscale mischmetal inclusion. Compared to undoped CoSb3 skutterudite synthesized by conventional methods, is reduced by a factor of 3, while the power factor is also substantially enhanced.Ministerio de Economia y Competitividad (España)Ministerio de Ciencia e Innovación (España)Agencia Estatal deInvestigación (España)Comunidad de MadridEuropean CommissionDepto. de Física de MaterialesDepto. de Química InorgánicaFac. de Ciencias FísicasFac. de Ciencias QuímicasInstituto Pluridisciplinar (IP)TRUEpubPagado por el auto