ABSTRACT
Novel filled skutterudites BayNi4Sb12-xSnx (ymax = 0.93) have been prepared by arc melting followed by annealing at 250, 350 and 450 °C up to 30 days in vacuum-sealed quartz vials. Extension of the homogeneity region, solidus temperatures and structural investigations were performed for the skutterudite phase in the ternary Ni-Sn-Sb and in the quaternary Ba-Ni-Sb-Sn systems. Phase equilibria in the Ni-Sn-Sb system at 450 °C were established by means of Electron Probe Microanalysis (EPMA) and X-ray Powder Diffraction (XPD). With rather small cages Ni4(Sb,Sn)12, the Ba-Ni-Sn-Sb skutterudite system is perfectly suited to study the influence of filler atoms on the phonon thermal conductivity. Single-phase samples with the composition Ni4Sb8.2Sn3.8, Ba0.42Ni4Sb8.2Sn3.8 and Ba0.92Ni4Sb6.7Sn5.3 were used to measure their physical properties, i.e. temperature dependent electrical resistivity, Seebeck coefficient and thermal conductivity. The resistivity data demonstrate a crossover from metallic to semiconducting behaviour. The corresponding gap width was extracted from the maxima in the Seebeck coefficient data as a function of temperature. Single crystal X-ray structure analyses at 100, 200 and 300 K revealed the thermal expansion coefficients as well as Einstein and Debye temperatures for Ba0.73Ni4Sb8.1Sn3.9 and Ba0.95Ni4Sb6.1Sn5.9. These data were in accordance with the Debye temperatures obtained from the specific heat (4.4 K < T < 140 K) and Mössbauer spectroscopy (10 K < T < 290 K). Rather small atom displacement parameters for the Ba filler atoms indicate a severe reduction in the "rattling behaviour" consistent with the high levels of lattice thermal conductivity. The elastic moduli, collected from Resonant Ultrasonic Spectroscopy ranged from 100 GPa for Ni4Sb8.2Sn3.8 to 116 GPa for Ba0.92Ni4Sb6.7Sn5.3. The thermal expansion coefficients were 11.8 × 10(-6) K(-1) for Ni4Sb8.2Sn3.8 and 13.8 × 10(-6) K(-1) for Ba0.92Ni4Sb6.7Sn5.3. The room temperature Vickers hardness values vary within the range from 2.6 GPa to 4.7 GPa. Severe plastic deformation via high-pressure torsion was used to introduce nanostructuring; however, the physical properties before and after HPT showed no significant effect on the materials thermoelectric behaviour.
ABSTRACT
X-ray single crystal (XSC) and powder diffraction data (XPD) were used to elucidate the crystal structure of a new refractory silicon boride Ta7Si2(Si(x)B(1-x))2 (x = 0.12). Tetragonal Ta7Si2(Si(x)B(1-x))2 (space group P4/mbm; a = 0.62219(2) nm, c = 0.83283(3) nm) with B atoms randomly sharing the 4g site with Si atoms is isotypic with the boride structure of (Re,Co)7B4. The architecture of the structure of Ta7Si2(Si(x)B(1-x))2 combines layers of three-capped triangular metal prisms (Si,B)[Ta(6+2)(Si,B)] alternating with double layers of two-capped Si[Ta(8+1)Si] Archimedian metal antiprisms. Consequently, the metal framework contains (B/Si) pairs and Si-Si dumbbells. These two types of coordination figures around the nonmetal atoms are typical for the system-inherent structures of Ta2B (or Ta2Si) and Ta3B2. DFT calculations showed strong B(Si)-B(Si) and Si-Si bonding and represent Ta7Si2(Si(x)B(1-x))2 as a covalent-ionic compound. This bonding behavior is reflected in the high hardness value of 1750 HV. The Sommerfeld constant, γ = 7.58 mJ/mol K(2), as derived from the electronic density of states, calculated at the Fermi level, suggests typical metallic behavior.
