Al 27 NMR local study of the Al0.5TiZrPdCuNi alloy in high-entropy alloy and metallic glass forms

We report a Al27 nuclear magnetic resonance (NMR) local spectroscopic study of the NMR lineshape and Knight shift of a six-component Al0.5TiZrPdCuNi metallic alloy that can be prepared either as a crystalline high-entropy alloy (HEA) or as an amorphous metallic glass (MG) at the same chemical composition. For both structural modifications of the material (HEA and MG), we have determined the distribution of electric-field-gradient (EFG) tensors and the local electronic density of states (DOS) g(ϵF) at the Fermi level at the position of Al27 nuclei. A theoretical I=52 quadrupole-perturbed NMR spectrum, pertinent to both cubic HEAs and amorphous MGs, has been derived using the Gaussian isotropic model of the EFG tensor distribution, and excellent fits of the experimental spectra were obtained. The EFG distribution function of the MG state is about twice broader than that of the HEA state, reflecting the existence of a (distorted) crystal lattice in the latter and its absence in the former. The T2 dependence of the Knight shift indicates that the DOS is changing rapidly with energy within the Fermi level region for both structural modifications. The local DOS at the Al27 sites of the HEA sample is ∼10% larger than that of the MG state, indicating comparable degrees of disorder

Polymer-dispersed liquid crystal elastomers as moldable shape-programmable material

The current development of soft shape-memory materials often results in materials that are typically limited to the synthesis of thin-walled specimens and usually rely on complex, low-yield manufacturing techniques to fabricate macro-sized, solid three-dimensional objects. However, such geometrical limitations and slow production rates can significantly hinder their practical implementation. In this work, we demonstrate a shape-memory composite material that can be effortlessly molded into arbitrary shapes or sizes. The composite material is made from main-chain liquid crystal elastomer (MC-LCE) microparticles dispersed in a silicone polymer matrix. Shape-programmability is achieved via low-temperature induced glassiness and hardening of MC-LCE inclusions, which effectively freezes-in any mechanically instilled deformations. Once thermally reset, the composite returns to its initial shape and can be shape-programmed again. Magnetically aligning MC-LCE microparticles prior to curing allows the shape-programmed artefacts to be additionally thermomechanically functionalized. Therefore, our material enables efficient morphing among the virgin, thermally-programmed, and thermomechanically-controlled shapes

Li16Sr6Ge6N, Li16Sr6Ge6.5 and related lithium alkaline‐earth metal tetrelides : alternative filling of voids by nitride or tetrelide ions

Large black single crystals with a metallic luster of Li16Sr6Ge6N and several other representatives of the series Li16Ae6Tt6N and Li16Ae6Tt6.5 (Ae=Ca, Sr; Tt=Si, Ge, Sn, Pb) were grown from mixtures of the respective elements with addition of binary alkaline‐earth metal nitrides or lithium nitride in the case of the nitrides. For the synthesis a modified high‐temperature centrifugation‐aided filtration (HTCAF) technique using reactive lithium melts was employed. These metallic phases crystallize in an ordered defect‐variant of the Sc11Ir4 type with selective occupation of the smaller octahedral voids in the origin (000) with N and the larger rhombic dodecahedral voids in (00 1/2) with Tt. Charge balance assuming the presence of exclusively closed shell ions for all examples accounts for an electronic excess. Diamagnetism despite metallic properties is consistent with results from electronic structure calculations.Projekt DEA

Tricyanidoferrates(−IV) and ruthenates(−IV) with non‐innocent cyanido ligands

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 AE(3.5)[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 P6(3)/m, the polar space group P6(3) with three-fold cell volume for AE(3.5)[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 pi-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 d(10) configuration for Fe, that is, Fe2-

Anisotropic superconductivity and quantum oscillations in the layered dichalcogenide TaSnS2

TaSnS2 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∥c and B⊥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 ≈3GPa the superconductivity is suppressed below our minimum temperature. The Sn NMR powder spectrum shows a single line which is expected for the TaSnS2 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 ≈0.5me. We compare these results with the band structures from DFT calculations. Our findings on TaSnS2 are discussed in terms of a quasi-two-dimensional BCS superconductivity

Shear flow-controlled shape memory of polymer resin dispersed liquid crystal elastomer microparticles

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

Making and Breaking Bonds in Superconducting SrAl_4–<i>x</i>Si_<i>x</i> (0 ≤ <i>x</i> ≤ 2)

We explored the role of valence electron concentration in bond formation and superconductivity of mixed silicon–aluminum networks by using high-pressure synthesis to obtain the BaAl₄-type structural pattern in solid solution samples SrAl_4–<i>x</i>Si_<i>x</i> where 0 ≤ <i>x</i> ≤ 2. Local ordering of aluminum and silicon in SrAl_4–<i>x</i>Si_<i>x</i> was evidenced by nuclear magnetic resonance experiments. Subsequent bonding analysis by quantum chemical techniques in real space demonstrated that the strong deviation of the lattice parameters in SrAl_4–<i>x</i>Si_<i>x</i> from Vegard’s law can be attributed to the strengthening of interatomic Al–Al and Al–Si bonds within the layers (perpendicular to [001]) for 0 ≤ <i>x</i> ≤ 1.5, followed by the breaking of the interlayer bonds (parallel to [001]) for 1.5 < <i>x</i> ≤ 2 and leading to the structural transition from the BaAl₄ structure type with three-dimensional anionic framework at lower <i>x</i> values to the two-dimensional anion of the BaZn₂P₂ structure type with increasing <i>x</i> values. Low-temperature measurements of the resistivity and heat capacity reveal that SrAl_2.5Si_1.5 and SrAl₂Si₂ prepared at high pressures exhibit superconductivity with critical temperatures of 2.1 and 2.6 K, respectively

Composition dependent polymorphism and superconductivity in Y3+x{Rh,Ir}4Ge13−x

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 Pm3n, a = 8.96095(9) angstrom], revealing a strongly disordered structure of the Yb3Rh4Sn13 Remeika prototype, into a body-centred cubic structure [La3Rh4Sn13 structure type, space group I4(1)32, a = 17.90876(6) angstrom] for x = 0.4 and further into a tetragonal arrangement (Lu3Ir4Ge13 structure type, space group I4(1)/amd, a = 17.86453(4) angstrom, a = 17.91076(6) angstrom) 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) angstrom] and the stoichiometric Y3Ir4Ge13 is isostructural with the Rh-analogue [a = 17.89411(9) angstrom, a = 17.9353(1) angstrom]. 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 T-c = 1.25, 0.43 and 0.6, for x = 0.6, 0.4 and 0, respectively. They also reveal low thermal conductivity (<1.5 W K-1 m(-1) in the temperature range 1.8-350 K) and small Seebeck coefficients. The latter are common for metallic systems. Y3Rh4Ge13 undergoes a first-order phase transition at T-f = 177 K, with signatures compatible to a charge density wave scenario. The electronic structure calculations confirm the instability of the idealized Yb3Rh4Sn13-like structural arrangements for Y3Rh4Ge13 and Y3Ir4Ge13

Thermoelectric stability of Eu- and Na-substituted PbTe

As one family of the most investigated thermoelectrics (TE), PbTe-based materials have been developed into state-of-the-art p-type and n-type TE materials. However, there are quite a few studies focusing on the reproducibility of TE properties and microstructure evolution during different heat treatments. In this work, Pb0.98-xNa0.02EuxTe (x = 0-0.030) samples were systematically examined after three different kinds of heat treatments: spark plasma sintering (SPS), laser flash measurement (LFA), and long-term annealing. The maximal solubility of Eu (ca. 1.0 atom%) in Pb0.98-xNa0.02EuxTe was established at 873 K. The most inhomogeneous samples (samples after SPS) show highest values of figure-of-merit, ZTmax, of up to 2.1 at 760 K, due to a large number of micrometer-scale sodium- and europium-rich aggregations in them. After additional heat treatment (LFA measurement or long-term annealing), the ZTmax value reduces to 1.6. The distribution of Eu and Na in the samples becomes much more homogeneous, accompanied by increased lattice parameters and decreased carrier concentrations. The long-term annealed samples have the best stable TE properties and good mechanical stability in the cyclic measurements. Surface protection needs to be considered for the temperatures above 773 K in order to avoid material decomposition