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Polymorphism is observed in the Y3+xRh4Ge13−x series. The decrease of Y-content leads to the transformation of the primitive cubic Y3.6Rh4Ge12.4 [x = 0.6, space group Pm3¯n, a = 8.96095(9) Å], revealing a strongly disordered structure of the Yb3Rh4Sn13 Remeika prototype, into a body-centred cubic structure [La3Rh4Sn13 structure type, space group I4132, a = 17.90876(6) Å] for x = 0.4 and further into a tetragonal arrangement (Lu3Ir4Ge13 structure type, space group I41/amd, a = 17.86453(4) Å, a = 17.91076(6) Å) for the stoichiometric (i.e. x =0)Y3Rh4Ge13. Analogous symmetry lowering is found within the Y3+xIr4Ge13−x series, where the compound with Y-content x = 0.6 is crystallizing with La3Rh4Sn13 structure type [a = 17.90833(8) Å] and the stoichiometric Y3Ir4Ge13 is isostructural with the Rh-analogue [a = 17.89411(9) Å, a = 17.9353(1) Å]. The structural relationships of these derivatives of the Remeika prototype are discussed. Compounds from the Y3+xRh4Ge13−x series are found to be weakly-coupled BCS-like superconductors with Tc = 1.25, 0.43 and 0.6, for x = 0.6, 0.4 and 0, respectively. They also reveal low thermal conductivity (

Electron-rich [Fe(CN)4]6− features a π-backbonding scheme with non-innocent CN-ligands exhibiting weak C–N bonds and a d10 configuration on iron.

Lead chalcogenides are known for their thermoelectric properties since the first work of Thomas Seebeck on the discovery of this phenomenon. Yet, the electronic properties of lead telluride are still of interest due to the incomplete understanding of the metal-to-semiconductor transition at temperatures around 230 °C. Here, a temperature-dependent atomic-resolution transmission electron microscopy study performed on a single crystal of lead telluride reveals structural reasons for this electronic transition. Below the transition temperature, the formation of a dislocation network due to shifts of the NaCl-like atomic slabs perpendicular to {100} was observed. The local structure modification leads to the appearance of in-gap electronic states and causes metal-like electronic transport behavior. The dislocation network disappears with increasing temperature, yielding semiconductor-like electrical conductivity, and re-appears after cooling to room temperature restoring the metal-like behavior. The structural defects coupled to the ordering of stereochemically active lone pairs of lead atoms are discussed in the context of dislocations' formation. Lead telluride is an important thermoelectric material but its metal-to-semiconductor transition above 230 °C is not fully understood. Here, atomic-resolution transmission electron microscopy provides structural insights into this transition, explaining the metallic behavior by a dislocation network within the rock salt structure.

The metastable type-II clathrate Na24-δ Ge136 was obtained from Na12 Ge17 by applying a two-step procedure. At first, Na12 Ge17 was reacted at 70 °C with a solution of benzophenone in the ionic liquid (IL) 1,3-dibutyl-2-methylimidazolium-bis(trifluoromethylsulfonyl) azanide. The IL was inert towards Na12 Ge17 , but capable of dissolving the sodium salts formed in the redox reaction. By annealing at 340 °C under an argon atmosphere, the X-ray amorphous intermediate product was transformed to crystalline Na24-δ Ge136 (δ≈2) and α-Ge in an about 1 : 1 mass ratio. The product was characterized by X-ray powder diffraction, chemical analysis, and 23 Na solid-state NMR spectroscopy. Metallic properties of Na24-δ Ge136 were revealed by a significant Knight shift of the 23 Na NMR signals and by a Pauli-paramagnetic contribution to the magnetic susceptibility. At room temperature, Na24-δ Ge136 slowly ages, with a tendency to volume decrease and sodium loss.

Exceptionally electron‐rich, nearly trigonal‐planar tricyanidometalate anions [Fe(CN)3]7− and [Ru(CN)3]7− were stabilized in LiSr3[Fe(CN)3] and AE3.5[M(CN)3] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of −IV. Microcrystalline powders were obtained by a solid‐state route, single crystals from alkali metal flux. While LiSr3[Fe(CN)3] crystallizes in P63/m, the polar space group P63 with three‐fold cell volume for AE3.5[M(CN)3] is confirmed by second harmonic generation. X‐ray diffraction, IR and Raman spectroscopy reveal longer C−N distances (124–128 pm) and much lower stretching frequencies (1484–1634 cm−1) than in classical cyanidometalates. Weak C−N bonds in combination with strong M−C π‐bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe−IV(CN−)3]7−, quantum chemical calculations reveal non‐innocent intermediate‐valent CN1.67− ligands and a closed‐shell d10 configuration for Fe, that is, Fe2−., The electron‐rich cyanidometalates [Fe(CN)3]7− and [Ru(CN)3]7− represent the first examples of group 8 elements with an oxidation state of −IV. DFT calculations reveal a nominal d10s0 configuration, which corresponds to an effective charge of 2−. The high negative charge also weakens the C−N bonds by the population of antibonding states.

Yb3Co4Ge13 is the first example of a Remeika phase with a 3D + 3 [space group P3n(α,0,0)000(0,α,0)000(0,0,α)000; a = 8.72328(1) A, α = 0.4974(2)] modulated crystal structure. A slight shift of the composition towards higher Yb-content (i.e. Yb3.2Co4Ge12.8) leads to the disappearance of the satellite reflections and stabilization of the disordered primitive cubic [space group Pmn, a = 8.74072(2) A] Remeika prototype structure. The stoichiometric structurally modulated germanide is a metal with hole-like charge carriers, where Yb-ions are in a temperature-dependent intermediate valence state varying from +2.60 to +2.66 for the temperature range 85–293 K. The valence fluctuations have been investigated by means of temperature dependent X-ray absorption spectroscopy, magnetic susceptibility and thermopower measurements.

The clathrate-I borosilicide K8−xBySi46−y (0.8 ≤ x ≤ 1.2 and 6.4 ≤ y ≤ 7.2; space group Pmn) was prepared in sealed tantalum ampoules between 900 °C and 1000 °C. By high-pressure preparation at 8 GPa and 1000 °C, a higher boron content is achieved (x = 0.2, y = 7.8). Crystal structure and composition were established from X-ray diffraction data, chemical analysis, WDX spectroscopy, and confirmed by 11B and 29Si NMR, and magnetic susceptibility measurements. The compositions are electron-balanced according to the Zintl rule within one estimated standard deviation. The lattice parameter varies with composition from a = 9.905 A for K7.85(2)B7.8(1)Si38.2(1) to a = 9.968(1) A for K6.80(2)B6.4(5)Si39.6(5).

Rb8B8Si38 forms under high-pressure, high-temperature conditions at p = 8 GPa and T = 1273 K. The new compound (space group Pm3n, a = 9.9583(1) A) is the second example for a clathrate-I borosilicide. The phase is inert against strong acids and bases and thermally stable up to 1300 K at ambient pressure. (Rb+)8(B-)8(Si0)38 is electronically balanced, diamagnetic, and shows semiconducting behavior with moderate Seebeck coefficient below 300 K. Chemical bonding analysis by the electron localizability approach confirms the description of Rb8B8Si38 as Zintl phase.

An efficient application of a material is only possible if we know its physical and chemical properties, which is frequently obstructed by the presence of micro‐ or macroscopic inclusions of secondary phases. While sometimes a sophisticated synthesis route can address this issue, often obtaining pure material is not possible. One example is TaGeIr, which has highly sample‐dependent properties resulting from the presence of several impurity phases, which influence electronic transport in the material. The effect of these minority phases was avoided by manufacturing, with the help of focused‐ion‐beam, a μm‐scale device containing only one phase—TaGeIr. This work provides evidence for intrinsic semiconducting behavior of TaGeIr and serves as an example of selective single‐domain device manufacturing. This approach gives a unique access to the properties of compounds that cannot be synthesized in single‐phase form, sparing costly and time‐consuming synthesis efforts., Perfection not required: In a study of intrinsic properties of intermetallic compounds, the synthesis of either single‐crystal or single‐phase material is the fundamental step. However, some materials cannot be prepared in single‐phase form. A new approach using a micro‐scale amount of material to study its intrinsic properties can significantly shorten this procedure and make the quest for “perfect” samples unnecessary.

A combined structural, magnetic and thermoelectric study of polycrystalline ternary MIn2S4 (M = Mn, Fe, Co, Ni) thiospinels is presented. All compounds crystallize with MgAl2O4-type structure. Rietveld refinement analysis confirmed that the preferred crystallographic position of transition metal element changes from mainly tetrahedral 8a for Mn to exclusively octahedral 16d for Ni (i.e. increase of the inversion parameter). Magnetic susceptibility measurements revealed M-elements to possess 2+ oxidation state in MIn2S4. All these compounds order antiferromagnetically with Neel temperatures T-N ranging from 5-13 K. The studied thiospinels are n-type semiconductors with large values of electrical resistivity rho > 0.6 omega center dot m at room temperature. An increase of the inversion parameter leads to a reduction of the determined activation energies, as well as to a more disorder-like behavior of thermal conductivity. The highest thermoelectric Figure of merit ZT was observed for MIn2S4 with M = Fe, Ni, which adopt inverse spinel structure.

The binary strontium germanide SrGe6 was synthesized at high-pressure high-temperature conditions of approximately 10 GPa and typically 1400 K before quenching to ambient conditions. At ambient pressure, SrGe6 decomposes in a monotropic fashion at T = 680(10) K into SrGe2 and Ge, indicating its metastable character. Single-crystal X-ray diffraction data indicate that the compound SrGe6 adopts a new monoclinic structure type comprising a unique three-dimensional framework of germanium atoms with unusual cages hosting the strontium cations. Quantum chemical analysis of the chemical bonding shows that the framework consists of three- and four- bonded germanium atoms yielding the precise electron count Sr[(4bGe0]4[(3b)Ge−]2 in accordance with the 8 − N rule and the Zintl concept. Conflicting with that, a pseudo-gap in the electronic density of states appears clearly below the Fermi level, and elaborate bonding analysis reveals additional Sr–Ge interactions in the concave coordination polyhedron of the strontium atoms.

The clathrate I superconductor Sr8 Si46 is obtained under high-pressure high-temperature conditions, at 5 GPa and temperatures in the range of 1273 to 1373 K. At ambient pressure, the compound decomposes upon heating at T=796(5) K into Si and SrSi2 . The crystal structure of the clathrate is isotypic to that of Na8 Si46 . Chemical bonding analysis reveals conventional covalent bonding within the silicon network as well as additional multi-atomic interactions between Sr and Si within the framework cages. Physical measurements indicate a bulk BCS type II superconducting state below Tc =3.8(3) K.

A new approach for in-situ synthesis of crystalline Co–Fe–B nanoparticles was presented in which low temperature methods were developed by using metal chlorides and NaBH4 in an inorganic molten salt environment. Effects of different reaction systems/conditions on the phase formation, thermal behavior and microstructure were investigated. The melting point of reactants and impurities in final powders were reduced by the use of molten salt technique. After a reaction of CoCl2, FeCl3 and NaBH4 at 850 °C in sealed tubes, CoB and Fe3B phases formed separately. After a reaction under Ar flow; however, CoFeB2 solid solution nano powders were obtained in one step at 850 °C with an average size of 60 nm. After annealing at 1100 °C, stable and highly crystalline (CoFe)B2 solid solution phase with a Co:Fe molar ratio of 1:1 was achieved. As-synthesized particles exhibited ferromagnetic property, and possessed a narrow hysteresis curve characteristic of soft magnetic materials. Extended reaction temperature from 650 to 850 °C is seen to produce coercivity enhancement up to 500 Oe without significant reduction in saturation magnetization. On the other hand, after an annealing process and subsequent phase and chemical change, crystalline (CoFe)B2 particles exhibited superparamagnetic property.

The silicon-rich cage compound MgSi5 was obtained by high-pressure high-temperature synthesis. Initial crystal structure determination by electron diffraction tomography provided the basis for phase analyses in the process of synthesis optimization, finally facilitating the growth of single crystals suitable for X-ray diffraction experiments. The crystal structure of MgSi5 (space group Cmme, Pearson notation oS24, a=4.4868(2) A, b=10.1066(5) A, and c=9.0753(4) A) constitutes a new type of framework of four-bonded silicon atoms forming Si15 cages enclosing the Mg atoms. Two types of smaller Si8 cages remain empty. The atomic interactions are characterized by two-center two-electron bonds within the silicon framework. In addition, there is evidence for multi-center Mg-Si bonding in the large cavities of the framework and for lone-pair-like interactions in the smaller empty voids.

The crystal structure of the (Cr,Ni)4Si phase with and without Co was refined from X-ray powder diffraction data. The compound crystallises with an Au4Al-type structure (Pearson symbol cP20, space group P213): unit-cell parameter a = 0.611959(6) nm for the composition (Cr0.312Ni0.688)4Si, a = 0.612094(6) nm for (Cr0.375Ni0.625)4Si, and a = 0.612316(6) nm for (Cr0.337Co0.063Ni0.600)4Si. The magnetic susceptibility was measured in external fields up to 7 T at temperatures between 1.8 and 400 K. The three investigated samples exhibited paramagnetic behaviour described by the modified Curie-Weiss law: χ0 = 146∙10-6 emu g-at.-1, μeff = 0.21 μB/atom, θP = -13 K for (Cr0.312Ni0.688)4Si; χ0 = 158∙10-6 emu g-at.-1, μeff = 0.20 μB/atom, θP = -15 K for (Cr0.375Ni0.625)4Si; χ0 = 169∙10-6 emu g-at.-1, μeff = 0.18 μB/atom, θP = -52 K for (Cr0.337Co0.063Ni0.600)4Si.

Yb

Thermomechanically active shape-programmable elastomer microparticles are very promising for development of particulate composites with unique operational properties, which could be attractive for various applications, e.g., in 3D printing. Liquid crystal elastomers are one of the suitable candidate materials due to their remarkable spontaneous shape change response. Performed rheological and thermomechanical tests demonstrate that shear stress can be used to efficiently manipulate the nematic order-driven morphology of liquid crystal elastomer microparticles (μLCEs). Specifically, by exploiting the soft-elasticity character of the material through manipulation of shear amplitude time profile, the nematic director can be oriented along the flow, which results in alignment of microparticles. Using this method, a suspension of well-aligned, thermomechanically elongated monodomain μLCEs can be created by shear stress-assisted cooling. Although the alignment can be lost in absence of persistent flow, it is restored instantaneously on re-application of the flow. The reason for this is the preservation of particle elongation at room temperature in zero flow. This shape memory can be erased by heating the system to the isotropic phase. Our work represents an important step forward in the development of a new generation of shape-programmable materials, which are potentially suitable for additive manufacturing of artefacts with anisotropic physical properties.

The metastable type‐II clathrate Na24‐δ Ge136 was obtained from Na12Ge17 by applying a two‐step procedure. At first, Na12Ge17 was reacted at 70 °C with a solution of benzophenone in the ionic liquid (IL) 1,3‐dibutyl‐2‐methylimidazolium‐bis(trifluoromethylsulfonyl) azanide. The IL was inert towards Na12Ge17, but capable of dissolving the sodium salts formed in the redox reaction. By annealing at 340 °C under an argon atmosphere, the X‐ray amorphous intermediate product was transformed to crystalline Na24‐δ Ge136 (δ≈2) and α‐Ge in an about 1 : 1 mass ratio. The product was characterized by X‐ray powder diffraction, chemical analysis, and 23Na solid‐state NMR spectroscopy. Metallic properties of Na24‐δ Ge136 were revealed by a significant Knight shift of the 23Na NMR signals and by a Pauli‐paramagnetic contribution to the magnetic susceptibility. At room temperature, Na24‐δ Ge136 slowly ages, with a tendency to volume decrease and sodium loss., The so far hardly accessible type‐II clathrate Na24‐δ Ge136 (δ≈2) was obtained in an about 1 : 1 mass ratio with α‐Ge from Na12Ge17 by redox reaction with benzophenone and subsequent heat treatment of the widely X‐ray amorphous intermediate. The phase is room‐temperature transient, diamagnetic and shows metallic properties as revealed by Knight‐shifted 23Na NMR signals and a Pauli‐paramagnetic contribution to the magnetic susceptibility.

Boron-rich materials combine chemical stability with refractory properties and, consequently, are interesting for high-temperature thermoelectric applications. Therefore, the magnetic, electrical, and thermal transport properties of the ${\mathrm{Y}}_{1\ensuremath{-}x}{\mathrm{Ce}}_{x}{\mathrm{CrB}}_{4}$ series have been investigated here to employ the concept of correlation-enhanced thermoelectric properties. Combining x-ray diffraction and energy- or wavelength-dispersive spectrometry, we find a rather narrow stability range of ${\mathrm{Y}}_{1\ensuremath{-}x}{\mathrm{Ce}}_{x}{\mathrm{CrB}}_{4}$, only samples on the Y- and Ce-rich substitution limits $(x=0,\phantom{\rule{0.28em}{0ex}}0.05,\phantom{\rule{0.28em}{0ex}}0.95,\phantom{\rule{0.28em}{0ex}}\mathrm{and}\phantom{\rule{0.28em}{0ex}}1)$ were obtained. Electrical resistivity data show a change from semiconducting $(x=0)$ to metallic behavior upon Ce substitution $(x\ensuremath{\ge}0.95)$. From magnetic susceptibility measurements and x-ray absorption spectroscopy, we find a temperature-dependent intermediate valence state of Ce of about $+3.5$. However, a fit of the magnetic susceptibility data to the Coqblin-Schrieffer model yields a surprisingly high Kondo temperature of about 1100 K. Together with the good thermal conductivity for the studied substitution series this impedes a suitable thermoelectric performance. Electronic structure calculations for ${\mathrm{YCrB}}_{4}$ support its narrow gap semiconducting nature in contrast to previous studies. Surprisingly, its electronic structure is characterized by pronounced van Hove singularities very close to the Fermi-level ${E}_{\mathrm{F}}$. They originate from nearly dispersionless Cr $3{d}_{{z}^{2}\ensuremath{-}{r}^{2}}$-derived bands in a large part of the Brillouin zone, suggesting the appearance of electronic instabilities upon rather small electron doping into these states.

The clathrate-I borosilicide K

Chemical synthesis of crystalline and nanoscale cobalt-iron metal boride powders was studied using hydrous metal chlorides and NaBH4. The effects of precursor concentration and optimized synthesis conditions on the phase formation, microstructure, and magnetic properties were investigated. After applying a reaction of CoCl2·6H2O-FeCl3·6H2O-NaBH4 at 850 °C, (CoFe)B2, (CoFe)B, Co2B, Fe3B, and Fe0.71Co0.29 boride phases were obtained from different synthesis conditions applied under autogenic pressure or Ar flow atmosphere. Oxychloride impurities were the reason for the reduced magnetization values. The highest saturation magnetization of 183 emu/g belongs to obtained nanoparticles containing (CoFe)B2 and (CoFe)B pure phases. High temperature magnetic measurements marked synthesized powders as soft magnetic materials up to 795 K while no Tc was reached for the obtained phases., Scientific and Technological Research Council of Turkey (TÜBİTAK); Novel Low Temperature Synthesis of Cobalt–Metal–Boron (Metal = Ni, Fe, Ti) Based Ternary Metal Borides from Metal Chlorides: Characterization and Application Oriented Investigations on Catalyzer/Magnet/Hybrid Composite Fabrication Project

${\mathrm{TaSnS}}_{2}$ single crystal and polycrystalline samples are investigated in detail by magnetization, electrical resistivity, and specific heat as well as Raman spectroscopy and nuclear magnetic resonance (NMR). Studies are focused on the temperature and magnetic field dependence of the superconducting state. We determine the critical fields for both directions $B\ensuremath{\parallel}c$ and $B\ensuremath{\perp}\phantom{\rule{0.16em}{0ex}}c$. Additionally, we investigate the dependence of the resistivity, the critical temperature, and the structure through Raman spectroscopy under high pressure up to 10 GPa. At a pressure of $\ensuremath{\approx}3\phantom{\rule{0.28em}{0ex}}\mathrm{GPa}$ the superconductivity is suppressed below our minimum temperature. The Sn NMR powder spectrum shows a single line which is expected for the ${\mathrm{TaSnS}}_{2}$ phase and confirms the high sample quality. Pronounced de Haas-van Alphen oscillations in the ac susceptibility of polycrystalline sample reveal two pairs of frequencies indicating coexisting small and large Fermi surfaces. The effective mass of the smaller Fermi surface is $\ensuremath{\approx}0.5{m}_{\mathrm{e}}$. We compare these results with the band structures from DFT calculations. Our findings on ${\mathrm{TaSnS}}_{2}$ are discussed in terms of a quasi-two-dimensional BCS superconductivity.

Rb8B8Si38 forms under high-pressure, high-temperature conditions at p = 8 GPa and T = 1273 K. The new compound (space group Pm3̅n, a = 9.9583(1) Å) is the second example for a clathrate-I borosilicide. The phase is inert against strong acids and bases and thermally stable up to 1300 K at ambient pressure. (Rb+)8(B–)8(Si0)38 is electronically balanced, diamagnetic, and shows semiconducting behavior with moderate Seebeck coefficient below 300 K. Chemical bonding analysis by the electron localizability approach confirms the description of Rb8B8Si38 as Zintl phase., Rb8B8Si38 is obtained under high-pressure, high-temperature conditions and is the second example for a clathrate-I borosilicide (space group Pm3̅n; a = 9.9583(1) Å). The compound shows high thermal and chemical stability. The Zintl phase (Rb+)8(B−)8(Si0)38 is electronically balanced and diamagnetic and shows semiconducting behavior.

Hf2B2–2δIr5+δ crystallizes with a new type of structure: space group Pbam, a = 5.6300(3) Å, b = 11.2599(5) Å, and c = 3.8328(2) Å. Nearly 5% of the boron pairs are randomly replaced by single iridium atoms (Ir5+δB2–2δ). From an analysis of the chemical bonding, the crystal structure can be understood as a three-dimensional framework stabilized by covalent two-atom B–B and Ir–Ir as well as three-atom Ir–Ir–B and Ir–Ir–Ir interactions. The hafnium atoms center 14-atom cavities and transfer a significant amount of charge to the polyanionic boron–iridium framework. This refractory boride displays moderate hardness and is a Pauli paramagnet with metallic electrical resistivity, Seebeck coefficient, and thermal conductivity. The metallic character of this system is also confirmed by electronic structure calculations revealing 5.8 states eV–1 fu–1 at the Fermi level. Zr2B2–2δIr5+δ is found to be isotypic with Hf2B2–2δIr5+δ, and both form a continuous solid solution., Hf2Ir5+δB2−2δ is a cage compound with a three-dimensional anionic boron−iridium framework composed of [B2Ir8] units with cavities bearing the hafnium cations. Zr2Ir5+δB2−2δ is found to be isotypic with Hf2Ir5+δB2−2δ, and both form a continuous solid solution.

Synthetic bulk and natural pyrite from the hydrothermal mine in Schonbrunn (Saxony, Germany) are confirmed to be stoichiometric FeS2 compounds and stable (for thermoelectric applications) up to ∼600 K by combined thermal, chemical, spectroscopic and X-ray diffraction analyses. Natural pyrite with a small amount (

A detailed study of polycrystalline indium-based In1-x□xIn2S4 (x = 0.16, 0.22, 0.28, and 0.33) thiospinel is presented (□- vacancy). Comprehensive investigation of synthesis conditions, phase composition and thermoelectric properties was performed by means of various diffraction, microscopic and spectroscopic methods. Single-phase α- and β-In1-x□xIn2S4 were found in samples with 0.16 ≤x≤ 0.22 and x = 0.33 (In2S3), respectively. In contrast, it is shown that In0.72□0.28In2S4 contains both α- and β-polymorphic modifications. Consequently, the thermoelectric characterization of well-defined α- and β-In1-x□xIn2S4 is conducted for the first time. α-In1-x□xIn2S4 (x = 0.16 and 0.22) revealed n-type semiconducting behavior, a large Seebeck coefficient (>|200|μV K-1) and moderate charge carrier mobility on the level of ∼20 cm2 V-1 s-1 at room temperature (RT). Decreases in charge carrier concentration (increase of electrical resistivity) and thermal conductivity (even below 0.6 W m-1 K-1 at 760 K) for larger In-content are observed. Although β-In0.67□0.33In2S4 (β-In2S3) is a distinct polymorphic modification, it followed the abovementioned trend in thermal conductivity and displayed significantly higher charge carrier mobility (∼104 cm2 V-1 s-1 at RT). These findings indicate that structural disorder in the α-modification affects both electronic and thermal properties in this thiospinel. The reduction of thermal conductivity counterbalances a lowered power factor and, thus, the thermoelectric figure of merit ZTmax = 0.2 at 760 K is nearly the same for both α- and β-In1-x□xIn2S4.

This work presents the heat capacity of four lithium stannides Li17Sn4, Li7Sn2, Li13Sn5 and Li7Sn3 covering a temperature range from (2 to 865) K. Two different calorimeters depending on their specification were used. A calorimetric method based on a relaxation technique was applied in the low temperature region from (2 to 300) K and data between (300 to 865) K were measured with a DSC utilising the Cp-by-step method. The accuracy of the experimental data is better than ± 2% above 20 K and rises up to 20% below 20 K. The obtained data were split into appropriate temperature intervals and fitted to common heat capacity functions. The low temperature measurement permits the calculation of the standard entropy and entropy of formation as well as temperature coefficients of electronic and lattice contributions to the heat capacity. This study represents a significant improvement of the data basis for thermodynamic calculations (e.g. CALPHAD) and to the understanding of electrochemical equilibria in the Li-Sn-System.

The structural properties of modulated SrGe6− x (x≈0.45) were investigated by means of single-crystal and powder X-ray diffraction combined with quantum chemical calculations. The framework compound SrGe6− x adopts a defect variant of the EuGa2Ge4-type crystal structure. Samples of the binary compound with nominal compositions 0≤x≤0.5 were synthesized at pressures from 5 to 6 GPa and a temperature of typically 1400 K. The product reveals diffraction peaks of the EuGa2Ge4-type subcell plus additional reflections indicating an ordered superstructure. Detailed crystal structure analysis evidences the incommensurate nature of the superstructure and a modulation of the vacancy ordering in the germanium network. The computations have shown that the non-stoichiometric composition of the framework with its local defect organization affects the calculated charge of the strontium anions. Although the chemical composition is close to a charge-balanced situation, temperature-dependent resistivity measurements showed metal-type conductivity. At ambient pressure SrGe6− x decomposes exothermally and irreversibly at T=680(10) K into SrGe2 and germanium, indicating its metastable nature at ambient pressure.

Two new calcium nitridomanganates, Ca12 [Mn19 N23 ] (P3, a=11.81341(3) A, c=5.58975(2) A, Z=1) and Ca133 [Mn216 N260 ] (P3‾ , a=39.477(1) A, c=5.5974(2) A, Z=1), were obtained by a gas-solid reaction of Ca3 N2 and Mn with N2 at 1273 K and 1223 K, respectively. The crystal structure of Ca12 [Mn19 N23 ] was determined from high-resolution X-ray synchrotron powder diffraction data, whereas single-crystal X-ray diffraction was employed to establish the crystal structure of the Ca133 [Mn216 N260 ] phase, which classifies as a complex metallic alloy (CMA). Both crystal structures have 2D nitridomanganate layers containing similar building blocks but of different levels of structural complexity. Bonding analysis as well as magnetic susceptibility and electron spin resonance measurements revealed that only a fraction of the Mn atoms in both structures carries a localized magnetic moment, while for most Mn species the magnetism is quenched as a result of metal-metal bond formation.

LuGe3 was obtained under high-pressure and high-temperature conditions at pressures between 8(1) and 14(2) GPa and at temperatures in the range from 1100(150) to 1500(150) K. The high-pressure phase is isotypic to DyGe3 and decomposes at ambient pressure and T = 690 K mainly into ( cF8)Ge and LuGe2- x. Chemical bonding analysis of LuGe3 reveals two-center electron-deficient Ge-Ge bonds, multicenter polar Lu-Ge interactions, and lone pairs on germanium. Magnetic susceptibility, specific heat, and electrical conductivity measurements indicate transition into a superconducting state below Tc = 3.3(3) K.

Several Mn-based compounds have been identified as promising materials to replace permanent magnetic alloys based on rare earth elements. Amongst them is the compound BiMn, in particular the low temperature modification α-BiMn (hP4, AsNi-type, B81), which has been shown to exhibit interesting magnetic properties. In the present study, it was attempted to synthesize phase-pure α-BiMn by annealing samples at 320 °C and centrifuging them at this temperature. In this way, it was possible to obtain a distinct phase separation with the intermetallic compound on top and the liquid Bi, which is always present after the high-temperature syntheses, at the bottom. After solidification, α-BiMn with a purity of up to 87%, though not phase-pure, could be recovered. Thermal analyses as well as the temperature dependence of the magnetization indicated a peritectic decomposition at 355 ± 2 °C whereas the phase re-formed on cooling at 341 ± 2 °C. High-temperature X-ray diffraction led to a complete oxidation of the sample even in a rather pure He atmosphere. Magnetic measurements showed an increase of the coercivity of α-BiMn with increasing temperature, in general agreement with earlier literature reports. The Curie temperature could not be determined experimentally as it is apparently higher than the temperature of the peritectic decomposition.

Sodium is widely used as a substituting element in p-type PbTe-based thermoelectric materials. In this work, two series of polycrystalline samples Pb1–yNayTe1–y/2 (total charge balance) and Pb1–xNaxTe (total charge nonbalance) were examined. Na has limited solubility for both of the series. The MAS 23Na NMR analysis of Pb1–xNaxTe series (for Pb0.98Na0.02Te sample after spark-plasma sintering, SPS) reveals only one Na signal, corresponding to Na atoms coordinated by six Te atoms, indicating substitution of Pb by Na without defects in the Te sublattice. In the Pb1–yNayTe1–y/2 series, clustering of Na atoms with reduced coordination by Te was observed. Additional heat treatment of these samples leads to the reorganization of the Na clusters in PbTe and their equilibration with the homogenized distribution of Na in the whole volume. The maximum ZT values of 1.4–1.6 at 760 K are established for both Pb1–xNaxTe and Pb1–yNayTe1–y/2 series. Upon long-time annealing at 873 K, reorganization and redistribution of N...