Thermoelectric properties of Ca0.8Dy0.2MnO3 synthesized by solution combustion process
© Park and Lee; licensee Springer. 2011
Received: 25 May 2011
Accepted: 5 October 2011
Published: 5 October 2011
High-quality Ca0.8Dy0.2MnO3 nano-powders were synthesized by the solution combustion process. The size of the synthesized Ca0.8Dy0.2MnO3 powders was approximately 23 nm. The green pellets were sintered at 1150-1300°C at a step size of 50°C. Sintered Ca0.8Dy0.2MnO3 bodies crystallized in the perovskite structure with an orthorhombic symmetry. The sintering temperature did not affect the Seebeck coefficient, but significantly affected the electrical conductivity. The electrical conductivity of Ca0.8Dy0.2MnO3 increased with increasing temperature, indicating a semiconducting behavior. The absolute value of the Seebeck coefficient gradually increased with an increase in temperature. The highest power factor (3.7 × 10-5 Wm-1 K-2 at 800°C) was obtained for Ca0.8Dy0.2MnO3 sintered at 1,250°C. In this study, we investigated the microstructure and thermoelectric properties of Ca0.8Dy0.2MnO3, depending on sintering temperature.
Keywordselectrical conductivity solution combustion process Seebeck coefficient power factor Ca0.8Dy0.2MnO3
Solid-state thermoelectric power generation based on Seebeck effects has potential applications in waste-heat recovery. Thermoelectric generation is thermodynamically similar to conventional vapor power generation or heat pumping cycles . Thermoelectric devices are not complicate, have no moving parts, and use electrons as working fluid instead of physical gases or liquids [1, 2]. The efficiency of thermoelectric devices is determined by the materials' dimensionless figure-of-merit, defined as ZT = σα 2/κT, where σ, α, κ, and T are the electrical conductivity, Seebeck coefficient, thermal conductivity, and absolute temperature, respectively. To be a good thermoelectric material, it is required to have a large electrical conductivity and Seebeck coefficient as well as a low thermal conductivity. The three parameters depend on each other since they are closely related to the scattering of charge carriers and lattice vibrations. It is thus necessary to compromise among them for optimizing the thermoelectric properties .
Kobayashi et al.  proposed the possibility of (R1-x Ca x )MnO-δ (R: Tb, Ho, and Y) with the orthorhombic perovskite-type structure as n-type thermoelectric materials. Since then, the electrical transport properties of (Ca0.9M0.1)MnO3 (M = Y, La, Ce, Sm, In, Sn, Sb, Pb, and Bi) have been studied, and reported that partial substitution for the Ca led to a significant increase in the electrical conductivity, along with a moderate decrease in the absolute value of the Seebeck coefficient, thereby improving the dimensionless figure-of-merit .
It is well known that controlling the microstructure and processing, especially sintering, is a feasible route to improve the thermoelectric performance. Therefore, in this study, to improve the thermoelectric properties, nano-sized Ca0.8Dy0.2MnO3 powders were synthesized by the solution combustion process. The solution combustion process is favorable for synthesizing pure and nano-sized high-quality oxide powders in a short time and is cost-effective [5, 6]. Subsequently, we sintered the Ca0.8Dy0.2MnO3 green pellets at 1150-1300°C and then investigated the microstructure and thermoelectric properties, depending on sintering temperature.
Ca0.8Dy0.2MnO3 powders were synthesized by the solution combustion process. The process involved the exothermic reaction initiated by metal nitrates (oxidizer) and an organic fuel (reductant). Ca(NO3)2 · 6H2O, Mn(NO3)2 · 6H2O, Dy(NO3)3 · 5H2O were used as oxidizers and glutamic acid (C5H9NO4) as combustion fuel. The molar ratio of the metal nitrates to the fuel in the precursor solution was adjusted to be 1:1. The appropriate proportions of the metal nitrates were separately dissolved in distilled water to prepare homogeneous solutions. The glutamic acid was separately dissolved in the solutions. The resulting solution was heated slowly on a hot plate, boiled, and dehydrated, forming a highly viscous gel. Subsequently, the gel frothed and swelled with evolution of huge volume of gases. The reaction lasted for 3-4 min and produced a foam that readily crumbled into powder. The size and morphology of the resulting powders were characterized with a transmission electron microscope (TEM; JEOL JEM-2100F) operating at 200 kV. Subsequently, the synthesized powders were calcined at 900 and 1,000°C for 12 h with intermediate grinding. The calcined nanopowders were cold-pressed under 137 MPa to prepare green pellets. The pellets were sintered at 1150-1300°C at a step of 50°C in air.
The porosity of as-sintered Ca0.8Dy0.2MnO3 was measured by the Archimedes' principle. The crystal structure of as-sintered samples was analyzed with an X-ray diffractometer (XRD; Rigaku DMAX-2500) using Cu K α radiation at 40 kV and 100 mA. The microstructure of as-sintered samples was investigated with a field emission scanning electron microscope (FESEM; Hitachi S4700). To measure the thermoelectric properties as a function of temperature, the electrical conductivity σ and the Seebeck coefficient α were simultaneously measured over a temperature range of 500-800°C.
Samples for the measurements of thermoelectric properties were cut out of the sintered bodies in the form of rectangular bars of 2 × 2 × 15 mm3 with a diamond saw and polished with SiC emery paper. The electrical conductivity σ was measured by the direct current (dc) four-probe method. For thermopower measurements, a temperature difference ΔT in the sample was generated by passing cool Ar gas over one end of the sample placed inside a quartz protection tube. The temperature difference ΔT between the two ends of each sample was controlled at 4-6°C by varying the flowing rate of Ar gas. The thermoelectric voltage ΔE measured as a function of the temperature difference ΔT gave a straight line. The Seebeck coefficient α was calculated from the relation α = ΔE/ΔT.
3. Results and discussion
In the polaron hopping conduction, an electron moves by a thermally activated hopping process from one localized state to another with the activation energy E h . The electrical conductivity σ is written as σ = (C/T)exp(-E h/k B T), where C, T, E h, and k B are the charge carrier concentration, the absolute temperature, the activation energy, and the Boltzmann constant, respectively . The electrical conductivity of the small polaron hopping conduction in the adiabatic case is given as σ = neμ = nea 2(A/T)exp(-E h/k B T), where n is the carrier concentration, e is the electrical charge of the carrier, μ is the carrier mobility, a is the intersite distance of hopping, E h is the activation energy for hopping, and A is the pre-exponential tern related to the carrier scattering mechanism, respectively [3, 13].
We synthesized Ca0.8Dy0.2MnO3 nanopowders (approximately 23 nm in size), which showed spherical and regular morphologies, and smooth surfaces, by the glutamic acid-assisted combustion method. The nano-sized powders led to dense and fine-grained pellets at low sintering temperature. The average grain sizes of the Ca0.8Dy0.2MnO3 sintered at 1150, 1200, 1250, and 1300°C were 399, 430, 545, and 590 nm, respectively. In addition, the densities of the Ca0.8Dy0.2MnO3 sintered at 1150, 1200, 1250, and 1300°C were 81.5, 87.2, 98.5, and 96.3% of the theoretical density, respectively. The Ca0.8Dy0.2MnO3 sintered had an orthorhombic perovskite-type structure, belonging to the Pnma space group. The electrical conductivity increased with increasing sintering temperature, reaching a maximum at 1250°C, and then decreased with further increasing sintering temperature. However, a noticeable change in the Seebeck coefficient of Ca0.8Dy0.2MnO3 sintered at various temperatures was not evident. The Ca0.8Dy0.2MnO3 sintered at 1250°C showed the highest power factor (3.7 × 10-5 Wm-1 K-2) at 800°C. It is necessary to control the sintering temperature of Ca0.8Dy0.2MnO3 for improving the thermoelectric properties.
This study is the outcome of a Manpower Development Program for Energy & Resources supported by the Ministry of Knowledge and Economy (MKE), Republic of Korea.
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