Tetrahedrites as thermoelectric materials: an overview

Tetrahedrites are natural earth-abundant minerals consisting of environmentally-friendly elements of copper and sulphur. Recently, research has been focused on the natural and synthetic minerals of tetrahedrite materials for thermoelectric applications. The thermoelectric figure of merit zT of around unity at similar to 723 K for many doped and natural tetrahedrite materials in the past 2-3 years was determined and this value is comparable to conventional p-type TE materials. In this review, a brief history of tetrahedrite materials is followed by information about its crystal structure and chemical bonding, electronic band structure and transport properties. Different synthesis approaches have been summarized. Also, this review outlines the effect of different doping elements on the thermoelectric properties of tetrahedrite materials, and the natural mineral tetrahedrite that can be used as thermoelectric materials.

High pressure states in condensed matter: I. High pressure behavior of the iron-sulphur system with applications to the earth's core. II. Empirical equation of state for organic compounds at high pressures

Part I:

The earth's core is generally accepted to be composed primarily of iron, with an admixture of other elements. Because the outer core is observed not to transmit shear waves at seismic frequencies, it is known to be liquid or primarily liquid. A new equation of state is presented for liquid iron, in the form of parameters for the 4th order Birch-Murnaghan and Mie-Grüneisen equations of state. The parameters were constrained by a set of values for numerous properties compiled from the literature. A detailed theoretical model is used to constrain the P-T behavior of the heat capacity, based on recent advances in the understanding of the interatomic potentials for transition metals. At the reference pressure of 10⁵ Pa and temperature of 1811 K (the normal melting point of Fe), the parameters are: ρ = 7037 kg/m³, K_S0 = 110 GPa, K_S' = 4.53, K_S" = -.0337 GPa-1, and γ = 2.8, with γ α ρ^-1.17. Comparison of the properties predicted by this model with the earth model PREM indicates that the outer core is 8 to 10 % less dense than pure liquid Fe at the same conditions. The inner core is also found to be 3 to 5% less dense than pure liquid Fe, supporting the idea of a partially molten inner core. The density deficit of the outer core implies that the elements dissolved in the liquid Fe are predominantly of lower atomic weight than Fe. Of the candidate light elements favored by researchers, only sulfur readily dissolves into Fe at low pressure, which means that this element was almost certainly concentrated in the core at early times. New melting data are presented for FeS and FeS₂ which indicate that the FeS₂ is the S-hearing liquidus solid phase at inner core pressures. Consideration of the requirement that the inner core boundary be observable by seismological means and the freezing behavior of solutions leads to the possibility that the outer core may contain a significant fraction of solid material. It is found that convection in the outer core is not hindered if the solid particles are entrained in the fluid flow. This model for a core of Fe and S admits temperatures in the range 3450K to 4200K at the top of the core. An all liquid Fe-S outer core would require a temperature of about 4900 K at the top of the core.

Part II.

The abundance of uses for organic compounds in the modern world results in many applications in which these materials are subjected to high pressures. This leads to the desire to be able to describe the behavior of these materials under such conditions. Unfortunately, the number of compounds is much greater than the number of experimental data available for many of the important properties. In the past, one approach that has worked well is the calculation of appropriate properties by summing the contributions from the organic functional groups making up molecules of the compounds in question. A new set of group contributions for the molar volume, volume thermal expansivity, heat capacity, and the Rao function is presented for functional groups containing C, H, and O. This set is, in most cases, limited in application to low molecular liquids. A new technique for the calculation of the pressure derivative of the bulk modulus is also presented. Comparison with data indicates that the presented technique works very well for most low molecular hydrocarbon liquids and somewhat less well for oxygen-bearing compounds. A similar comparison of previous results for polymers indicates that the existing tabulations of group contributions for this class of materials is in need of revision. There is also evidence that the Rao function contributions for polymers and low molecular compounds are somewhat different.

Zn-VI/Cu2O Heterojunctions for Earth-Abundant Photovoltaics

The need for sustainable energy production motivates the study of photovoltaic materials, which convert energy from sunlight directly into electricity. This work has focused on the development of Cu₂O as an earth-abundant solar absorber due to the abundance of its constituent elements in the earth's crust, its suitable band gap, and its potential for low cost processing. Crystalline wafers of Cu₂O with minority carrier diffusion lengths on the order of microns can be manufactured in a uniquely simple fashion — directly from copper foils by thermal oxidation. Furthermore, Cu₂O has an optical band gap of 1.9 eV, which gives it a detailed balance energy conversion efficiency of 24.7% and the possibility for an independently connected Si/Cu₂O dual junction with a detailed balance efficiency of 44.3%.

However, the highest energy conversion efficiency achieved in a photovoltaic device with a Cu₂O absorber layer is currently only 5.38% despite the favorable optical and electronic properties listed above. There are several challenges to making a Cu₂O photovoltaic device, including an inability to dope the material, its relatively low chemical stability compared to other oxides, and a lack of suitable heterojunction partners due to an unusually small electron affinity. We have addressed the low chemical stability, namely the fact that Cu₂O is an especially reactive oxide due to its low enthalpy of formation (ΔH_f⁰ = -168.7 kJ/mol), by developing a novel surface preparation technique. We have addressed the lack of suitable heterojunction partners by investigating the heterojunction band alignment of several Zn-VI materials with Cu₂O. Finally, We have addressed the typically high series resistance of Cu₂O wafers by developing methods to make very thin, bulk Cu₂O, including devices on Cu₂O wafers as thin as 20 microns. Using these methods we have been able to achieve photovoltages over 1 V, and have demonstrated the potential of a new heterojunction material, Zn(O,S).

Effect of alkaline-earth metal composition on spectroscopic properties of Er3+ in fluorophosphate glasses

Optical spectroscopic properties of Er3+-doped alkaline-earth metal modified fluoropho sphate glasses have been investigated experimentally for developing broadband fiber and planar amplifiers. The results show a strong correlation between the alkaline-earth metal content and the spectroscopic parameters such as absorption and emission cross sections, full widths at half-maximum and Judd-Ofelt intensity parameters. It is found that strontium ions could have more influences on the Judd-Ofelt intensity parameters and the absorption and emission cross sections than other alkaline-earth metal ions such as Mg2+, Ca2+, Ba2+. The sample containing 23 mol% strontium fluoride exhibits the maximum emission cross section of 7.58 x 10(-21) cm(2), the broadest full width at half-maximum of 65 nm and the longer lifetime of 8.6 ms among the alkaline-earth metal modified fluorophosphates glasses studied. The Judd-Ofelt intensity parameter Omega(6)s, the emission cross sections and the full widths at half-maximum in the Er3+-doped fluorophosphate glasses studied are larger than in the silicate and phosphate glasses.

Ultrabroad infrared luminescences from Bi-doped alkaline earth metal germanate glasses

We report on ultrabroad infrared (IR) luminescences covering the 1000-1700-nm wavelength region, from Bi-doped 75GeO(2) 20RO-5Al(2)O(3) 1B(2)O(3) (R = Sr, Ca, and Mg) glasses. The full width at half-maximum of the IR luminescences excited at 980 nm increases (315 -> 440 -> 510 nm) with the change of alkaline earth metal (Mg2+ -> Ca2+ -> Sr2+). The fluorescence lifetime of the glass samples is 1725, 157, and 264 mu s when R is Sr, Ca, and Mg, respectively. These materials may be promising candidates for broad-band fiber amplifiers and tunable laser resources.

Rare-earth-doped silica microchip laser fabricated by sintering nanoporous glass

We report a new method for fabricating rare-earth-doped silica glasses for laser materials obtained by sintering nanoporous silica glasses impregnated with rare-earth-doped ions. The fabricated materials have no residual pores and show good optical and mechanical properties. Good performance from a Nd3+-doped silica microchip laser operating at 1.064 mum is successfully demonstrated, suggesting that the fabricated silica glasses have potential for use as active materials for high-power solid-state lasers. (C) 2005 Optical Society of America.

CALCULATED ELECTRONIC AND MAGNETIC-STRUCTURES OF THE NEW TERNARY RARE-EARTH IRON NITRIDE ND2FE17N3

The electronic and magnetic structures of Nd2Fe17 and Nd2Fe17N3 have been calculated using the first-principle, spin-polarized orthogonalized linear combination of atomic orbitals method. Comparative studies of the two materials reveal important effects of the nitrogen atoms (at 9e site) on the electronic and magnetic structures. Results are presented for the total density of states, site-projected partial density of states and the spin magnetic moments on four nonequivalent Fe sites. The highest magnetic moments are found to be located on the 6c site for Nd2Fe17 and on the 9d site for Nd2Fe17N3, in agreement with the neutron and Mossbauer experiments. The variation trends of the magnetic moments on different Fe sites are discussed in terms of the separation between Fe and N atoms. Compared with Nd2Fe17, an increase in the exchange splitting of the Fe d band is found in Nd2Fe17N3, which accounts for its higher Curie temperature as observed in experiments. The calculated results show that the nitrogen atoms are charge acceptors in these compounds.

Effects of rare earth on the structure and properties of Mg–6Zn–5Al–4Gd–1RE (RE = Ce or Y) alloys

The microstructures and mechanical properties of Mg-6Zn-5Al-4Gd-1RE (RE = Ce or Y) alloys were investigated. The addition of Ce or Y obviously refines the grain size for the Mg-6Zn-5Al-4Gd-based alloy, while the Y element has a better refining effect. The Ce and Y show different grain-refining mechanisms: Ce addition mostly promotes the growth of secondary dendrite, while Y addition mainly increases the heterogeneous nucleation sites.

Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

Synthesis of Tributylphosphate Capped Luminescent Rare Earth Phosphate Nanocrystals in an Ionic Liquid Microemulsion

Uniform rare earth phosphate (REPO4, RE = La-Tb) nanocrystals were successfully synthesized in a properly designed TBP/[Omim]Cl/H2O (tributylphosphate/1-octyl-3-methyl-imidazolium chloride/water) microemulsion system. The phosphoryl groups anchored the TBP molecules oil the surfaces of the nanocrystals, and this made the nanocrystals easily dispersed in some imidazolium-based ILs. LaPO4:Eu3+ and CePO4:Tb3+ nanocrystals capped with TBP showed bright red and green emission under UV excitation, with enhanced emission intensity and lifetimes compared with the uncapped ones.

Novel Near-Infrared Luminescent Hybrid Materials Covalently Linking with Lanthanide [Nd(III), Er(III), Yb(III), and Sm(III)] Complexes via a Primary beta-Diketone Ligand: Synthesis and Photophysical Studies

A series of novel, colorless, and transparent sot-gel derived hybrid materials Ln-DBM-Si covalently grafted with Ln(DBM-OH)(3)center dot 2H(2)O (where DBM-OH = o-hydroxydibenzoylmethane, Ln = Nd, Er, Yb, and Sin) were prepared through the primary beta-diketone ligand DBM-OH. The structures and optical properties of Ln-DBM-Si were studied in detail. The investigation results revealed that the lanthanide complexes were successfully in situ grafted into the corresponding hybrids Ln-DBM-Si. Upon excitation at the maximum absorption of ligands, the resultant materials displayed excellent near-infrared luminescence.

Adhesive strength of new thermal barrier coatings of rare earth zirconates

La2Zr2O7 (LZ) and La-2(Zr0.7Ce0.3)(2)O-7 (LZ7C3) as novel candidate materials for thermal barrier coatings (TBCs) were prepared by electron beam-physical vapor deposition (EB-PVD). The adhesive strength of the as-deposited LZ and LZ7C3 coatings were evaluated by transverse scratch test. Meanwhile, the factors affecting the critical load value were also investigated. The critical load value of LZ7C3 coating is larger than that of LZ coating, whereas both values of these two coatings are lower than that of the traditional coating material, i.e. 8 wt% yttria stabilized zirconia (8YSZ). The micro-cracks formed in the scratch channel can partially release the stress in the coating and then enhance the adhesive strength of the coating. The width of the scratch channel and the surface spallation after transverse scratch test are effective factors to evaluate the adhesive strength of LZ and LZ7C3 coatings.

Effect of silver nanoparticles on luminescent properties of europium complex in di-ureasil hybrid materials

Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.

Ceramic materials for thermal barrier coatings

This paper summarizes the basic properties of ceramic materials for thermal barrier coatings. Ceramics, in contrast to metals, are often more resistant to oxidation, corrosion and wear, as well as being better thermal insulators. Except yttria stabilized zirconia, other materials such as lanthanum zirconate and rare earth oxides are also promising materials for thermal barrier coatings.

Crystal structure and electrochemical properties of rare earth non-stoichiometric AB(5)-type alloy as negative electrode material in Ni-MH battery

The La0.85MgxNi4.5Co0.35Al0.15 (0.05less than or equal toxless than or equal to0.35) system compounds have been prepared by are melting method under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes. The electrochemical properties of these alloys have been studied through the charge-discharge recycle testing at different temperatures and discharge currents. It is found that the La0.85Mg0.25Ni4.5Co0.35Al0.(15) alloy electrode is capable of performing high-rate discharge. Moreover, it has very excellent electrochemical properties as negative electrode materials in Ni-MH battery at low temperature, even at -40degreesC.