Trapping Amorphous Intermediates of Carbonates – A Combined Total Scattering and NMR Study

Crystallization via metastable phases plays an important role in chemical manufacturing, biomineralization, and protein crystallization, but the kinetic pathways leading from metastable phases to the stable crystalline modifications are not well understood. In particular, the fast crystallization of amorphous intermediates makes a detailed characterization challenging. To circumvent this problem, we devised a system that allows trapping and stabilizing the amorphous intermediates of representative carbonates (calcium, strontium, barium, manganese, and cadmium). The long-term stabilization of these transient species enabled a detailed investigation of their composition, structure, and morpho…

Solution synthesis of nanoparticular binary transition metal antimonides

The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were …

Mechanochemical Access to Defect-Stabilized Amorphous Calcium Carbonate

Amorphous calcium carbonate (ACC) is an important precursor in the biomineralization of crystalline CaCO3. The lifetime of transient ACC in nature is regulated by an organic matrix, to use it as an intermediate storage buffer or as a permanent structural element. The relevance of ACC in material science is related to our understanding of CaCO3 crystallization pathways. ACC can be obtained by liquid–liquid phase separation, and it is typically stabilized with the help of macromolecules. We have prepared ACC by milling calcite in a planetary ball mill. The ball-milled amorphous calcium carbonate (BM-ACC) was stabilized with small amounts of Na2CO3. The addition of foreign ions in form of Na2C…

Enhanced Debye level in nano Zn1+xSb, FeSb2, and NiSb: Nuclear inelastic spectroscopy on121Sb (Phys. Status Solidi B 5/2014)

Enhanced Debye level in nano Zn1+xSb, FeSb2, and NiSb: Nuclear inelastic spectroscopy on121Sb

The121 Sb partial density of phonon states (DPS) in nanopowder antimonides were obtained with nuclear inelastic scattering on , , and NiSb prepared by a wet chemistry route. The DPS is compared with the bulk counterpart. An increase of the Debye level indicative of a decrease of the isothermal speed of sound is systematically observed. This observation reveals that the decrease in speed of sound observed in nanostructured thermoelectric materials is not restricted to sintered nanocomposites.

SPS-assisted preparation of the Magnéli phase WO2.90 for thermoelectric applications

We describe the preparation and simultaneous consolidation of WO2.90 by spark plasma sintering (SPS). SPS allows for the direct manufacturing of large amounts of consolidated material. Synchrotron powder X-ray diffraction indicates that the material is single phase. Microstructure analysis indicates that the pellet is fully dense, allowing high-temperature thermoelectric properties to be reliably measured. The as-prepared samples of WO2.90 reach a ZT of 0.1 at 1100 K.

Wet Chemical Synthesis and a Combined X-ray and Mössbauer Study of the Formation of FeSb2 Nanoparticles

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder dif…

ChemInform Abstract: Solution Synthesis of Nanoparticular Binary Transition Metal Antimonides.

The transition metal antimonides MSb with M: Co, Ni, and Zn and Cu2Sb with particle sizes ranging from 20 to 60 nm are prepared using presynthesized antimony nanoparticles and activated metal nanoparticles as precursors.

Magnéli oxides as promising <em>n</em>-type thermoelectrics

The discovery of a large thermopower in cobalt oxides in 1997 lead to a surge of interest in oxides for thermoelectric application. Whereas conversion efficiencies of p-type oxides can compete with non-oxide materials, n-type oxides show significantly lower thermoelectric performances. In this context so-called Magneli oxides have recently gained attention as promising n-type thermoelectrics. A combination of crystallographic shear and intrinsic disorder lead to relatively low thermal conductivities and metallic-like electrical conductivities in Magneli oxides. Current peak-zT values of 0.3 around 1100 K for titanium and tungsten Magneli oxides are encouraging for future research. Here, we …

Thermoelectric properties of spark-plasma sintered nanoparticular FeSb2prepared via a solution chemistry approach

Nanoparticular FeSb2 was prepared in solution from cyclopentadienyl iron(ii) dicarbonyl dimer [Fe(Cp(CO)2)]2 and antimony nanoparticles. Spark plasma sintering was used as consolidation method to maintain the particle size. The thermoelectric performance of FeSb2 is limited by its high thermal conductivity. In this work, the thermal conductivity was suppressed by nearly 80% compared to the bulk value by introducing grain boundary scattering of phonons on the nanoscale. The thermoelectric properties of the consolidated FeSb2 emphasize the possibility of altering thermal transport of promising thermoelectric compounds by phonon scattering by engineering the interfaces at the nanoscale.

Bond strength dependent superionic phase transformation in the solid solution series Cu2ZnGeSe4−xSx

Recently, copper selenides have shown to be promising thermoelectric materials due to their possible superionic character resulting from mobile copper cations. Inspired by this recent development in the class of quaternary copper selenides we have focused on the structure-to-property relationships in the solid solution series Cu2ZnGeSe4−xSx. The material exhibits an insulator-to-metal transition at higher temperatures, with a transition temperature dependent on the sulfur content. However, the lattice parameters show linear thermal expansion at elevated temperatures only and therefore no indication of a structural phase transformation. 63Cu nuclear magnetic resonance shows clear indications…

Using crystallographic shear to reduce lattice thermal conductivity: high temperature thermoelectric characterization of the spark plasma sintered Magnéli phases WO2.90 and WO2.722.

Engineering of nanoscale structures is a requisite for controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require a conflicting combination of low thermal conductivity and low electrical resistivity. We report the thermoelectric properties of spark plasma sintered Magnéli phases WO2.90 and WO2.722. The crystallographic shear planes, which are a typical feature of the crystal structures of Magnéli-type metal oxides, lead to a remarkably low thermal conductivity for WO2.90. The figures of merit (ZT = 0.13 at 1100 K for WO2.90 and 0.07 at 1100 K for WO2.722) are relatively high for tungsten-oxygen compounds and metal oxides in general…

Enhanced thermoelectric properties of the n-type Magnéli phase WO2.90: reduced thermal conductivity through microstructure engineering

The thermoelectric properties of the Magneli phase WO2.90 were investigated, with special attention to how the thermoelectric performance can be altered by changing its microstructure. Spark plasma sintering (SPS) allowed the direct preparation of large amounts of consolidated material. Adding Ta2O5 to the reaction mixture lead to the formation of solid solutions W1−xTaxO2.90via a concurrent reaction between WO3 and Ta2O5 during the SPS treatment. In addition, micron-sized inclusions containing tungsten surrounded by WOx embedded in a WO2.90 matrix were formed, which act as additional scattering centers. As a result, the thermal conductivity of the Ta-containing samples was reduced by ≈30% …

Towards higher zT in early transition metal oxides: optimizing the charge carrier concentration of the WO3-x compounds

Abstract Thermoelectric devices are believed to play an important role in the energy research for the next decades. Thanks to their low costs coupled with high stability and sustainability, metal oxides are very promising materials even if their efficiencies still need improvements to ensure a wide applicability. Slightly reduced early transition metal oxides show intrinsic defects in the crystal structure which guarantee very low values of the thermal conductivity. The challenge to fulfil the “phonon-glass electron-crystal” concept is to decouple the optimization of the electronic properties from the thermal transport properties. In this contribution we report the optimization of the charg…

Properties of spark plasma sintered nanostructured Zn1+xSb

Engineering materials with specific physical properties has recently focused on the effect of nanoscopic inhomogeneities at the 10 nm scale. Such features are expected to scatter medium and long-wavelength phonons lowering thereby the thermal conductivity of the system without simultaneously decreasing the charge transport (phonon–glass electron–crystal concept). A new Zn1+xSb nanophase obtained by a wet chemical approach was densified by spark plasma sintering (SPS). Investigations on compounds subsumed as “Zn4Sb3” always suffer from its low thermal stability and the contamination of the nanoparticles with solvents and additives used in the synthesis. In order to gain insight into this com…