Double Helix of Icosahedra Structure and Spin Glass Magnetism of the δ-Co2.5Zn17.5-xMnx (x = 0.4-3.5) Pseudo-Binary Alloys.

We have synthesized δ-Co2.5Zn17.5-xMnx (x = 0.4-3.5) pseudo-binary alloys of 10 different compositions by a high-temperature solid-state synthetic route, determined their crystal structures and the Mn substitution pattern, and estimated the existence range of the δ-phase. The alloys crystallize in two chiral enantiomorphic space groups P62 and P64, where the basic atomic polyhedron of the chiral structure is an icosahedron and the neighboring icosahedra share vertices to form an infinitely long double helix along the hexagonal axis (like in the δ-Co2.5Zn17.5 parent binary phase). The alloys are pure δ-phase up to the Mn content x ≈ 3.5. The Mn atoms partially substitute Zn atoms at particular crystallographic sites located on the icosahedra. The study of magnetism was performed on the Co2.5Zn17.1Mn0.4 alloy with the lowest Mn content. Contrary to the expectation that structural chirality may induce the formation of a nontrivial magnetic state, a spin glass state with no relation to the structural chirality was found. The magnetic sublattice contains all of the necessary ingredients (randomness and frustration) for the formation of a spin glass state. Typical out-of-equilibrium dynamic phenomena of a spin system with broken ergodicity were detected below the spin freezing temperature Tf ≈ 8 K.

The Kondo Effect in CexLaLuScY (x = 0.05-1.0) High-Entropy Alloys.

In the search for electronic phenomena in high-entropy alloys (HEAs) that go beyond the independent-electron description, we have synthesized a series of hexagonal rare earth (RE)-based HEAs: CexLaLuScY (x = 0.05-1.0). The measurements of electrical resistivity, magnetic susceptibility and specific heat have shown that the CexLaLuScY HEAs exhibit the Kondo effect, which is of a single impurity type in the entire range of employed Ce concentrations despite the alloys being classified as dense (concentrated) Kondo systems. A comparison to other known dense Kondo systems has revealed that the Kondo effect in the CexLaLuScY HEAs behaves quite differently from the chemically ordered Kondo lattices but quite similar to the RE-containing magnetic metallic glasses and randomly chemically disordered Kondo lattices of the chemical formula RE1xRE21-xM (with RE1 being magnetic and RE2 being nonmagnetic). The main reason for the similarity between HEAs and the metallic glasses and chemically disordered Kondo lattices appears to be the absence of a periodic 4f sublattice in these systems, which prevents the formation of a coherent state between the 4f-scattering sites in the T→ 0 limit. The crystal-glass duality of HEAs does not bring conceptually new features to the Kondo effect that would not be already present in other disordered dense Kondo systems. This study broadens the classification of HEAs to correlated electron systems.

Complex magnetism of single-crystalline AlCoCrFeNi nanostructured high-entropy alloy.

We have investigated magnetism of the Al28Co20Cr11Fe15Ni26 single-crystalline high-entropy alloy. The material is nanostructured, composed of a B2 matrix with dispersed spherical-like A2 nanoparticles of average diameter 64 nm. The magnetism was studied from 2 to 400 K via direct-current magnetization, hysteresis curves, alternating-current magnetic susceptibility, and thermoremanent magnetization time decay, to determine the magnetic state that develops in this highly structurally and chemically inhomogeneous material. The results reveal that the Cr-free B2 matrix of composition Al28Co25Fe15Ni32 forms a disordered ferromagnetic (FM) state that undergoes an FM transition at TC≈ 390 K. The Al- and Ni-free A2 nanoparticles of average composition Co19Cr56Fe25 adopt a core-shell structure, where the shells of about 2 nm thickness are CoFe enriched. While the shells are FM, the nanoparticle cores are asperomagnetic, classifying into the broad class of spin glasses. Asperomagnetism develops below 15 K and exhibits broken-ergodicity phenomena, typical of magnetically frustrated systems.

Crystal Structure and Ferromagnetism of the CeFe9Si4 Intermetallic Compound.

We have determined the crystal structure and the magnetic state of the CeFe9Si4 intermetallic compound. Our revised structural model (fully ordered tetragonal unit cell, I4/mcm) agrees with the previous literature report, except for some minor quantitative differences. Magnetically, the CeFe9Si4 undergoes a ferromagnetic transition at the temperature TC ≈ 94 K. Ferromagnetism in the combined Ce-Fe spin system is a result of interplay between the localized magnetism of the Ce sublattice and the Fe band (itinerant) magnetism. Ferromagnetic ordering obeys the rather general rule that the exchange spin coupling between atoms possessing more than half-full d shells with atoms possessing less than half-full d shells is antiferromagnetic (where the Ce atoms are considered as light d elements). Since in rare-earth metals from the light half of the lanthanide series, the magnetic moment is directed opposite to the spin, this results in ferromagnetism. The magnetoresistance and the magnetic specific heat show an additional temperature-dependent feature (a shoulder) deep inside the ferromagnetic phase that is considered to originate from the influence of the magnetization on the electronic band structure via the magnetoelastic coupling, which alters the Fe band magnetism below TC. The ferromagnetic phase of CeFe9Si4 is magnetically soft.

Electronic transport properties of the Al0.5TiZrPdCuNi alloy in the high-entropy alloy and metallic glass forms.

High-entropy alloys (HEAs) are characterized by a simultaneous presence of a crystal lattice and an amorphous-type chemical (substitutional) disorder. In order to unravel the effect of crystal-glass duality on the electronic transport properties of HEAs, we performed a comparative study of the electronic transport coefficients of a 6-component alloy Al0.5TiZrPdCuNi that can be prepared either as a HEA or as a metallic glass (MG) at the same chemical composition. The HEA and the MG states of the Al0.5TiZrPdCuNi alloy both show large, negative-temperature-coefficient resistivity, positive thermopower, positive Hall coefficient and small thermal conductivity. The transport coefficients were reproduced analytically by the spectral conductivity model, using the Kubo-Greenwood formalism. For both modifications of the material (HEA and MG), contribution of phonons to the transport coefficients was found small, so that their temperature dependence originates predominantly from the temperature dependence of the Fermi-Dirac function and the variation of the spectral conductivity and the related electronic density of states with energy within the Fermi-level region. The very similar electronic transport coefficients of the HEA and the MG states point towards essential role of the immense chemical disorder.

The Effect of Scandium on the Structure, Microstructure and Superconductivity of Equimolar Sc-Hf-Nb-Ta-Ti-Zr Refractory High-Entropy Alloys.

In this study, we investigate the scandium-containing Sc-Hf-Nb-Ta-Ti-Zr system of refractory high-entropy alloys (HEAs). Using the arc-melting method, we synthesized nine equimolar alloys (five 4-, three 5- and one 6-component), with all of them containing Sc. The alloys were characterized by XRD, electron microscopy and EDS, while superconductivity was investigated via electrical resistivity, specific heat and the Meissner effect. The results were compared to the parent Hf-Nb-Ta-Ti-Zr refractory HEAs, forming a single-phase body-centered cubic (bcc) structure and quite homogeneous microstructure. The addition of Sc produces a two-phase structure in the Sc-Hf-Nb-Ta-Ti-Zr alloys, with one phase being bcc and the other hexagonal close-packed (hcp). The hcp phase absorbs practically all Sc, whereas the Sc-poor bcc phase is identical to the bcc phase in the Hf-Nb-Ta-Ti-Zr parent system. Upon the Sc addition, the microstructure becomes very inhomogeneous. Large bcc dendrites (10-100 µm) are homogeneous in the central parts, but become a fine dispersion of sub-micron precipitates of the bcc and hcp phases close to the edges. The interdendritic regions are also a fine dispersion of the two phases. Superconductivity of the Sc-Hf-Nb-Ta-Ti-Zr alloys originates from the bcc phase fraction, which demonstrates identical superconducting parameters as the bcc Hf-Nb-Ta-Ti-Zr parent alloys, while the Sc-containing hcp phase fraction is non-superconducting.

Structure and Spin-Glass Magnetism of the MnxNi2Zn11-x Pseudobinary γ-Brasses at Low Mn Contents.

The pseudobinary MnxNi2Zn11-x γ-brass-type phases at low Mn dopant levels (x = 0.1-0.5) were investigated. Crystal structures were determined for the two loading compositions of x = 0.3 and 0.5. The structures were solved in the cubic space group of I43m and are described in close analogy to the Ni2Zn11 parent γ-brass that is based on the 26-atom cluster, consisting of inner tetrahedron (IT), outer tetrahedron (OT), octahedron (OH), and cuboctahedron (CO). The refined site occupancies of the MnxNi2Zn11-x (x = 0.3, 0.5) reveal that the cluster center, which is empty in the Ni2Zn11, shows a partial occupation by Zn, with a partial depletion of Zn at the IT sites. The OH sites show a mixed Zn/Mn occupation. The OT and CO sites remain intact with respect to Ni2Zn11. Magnetic properties were studied for the Mn0.3Ni2Zn10.7 composition. The temperature-dependent zero-field-cooled and field-cooled magnetization, the ac susceptibility, the M(H) hysteresis curves, the thermoremanent magnetization, and the memory effect demonstrate typical broken-ergodicity phenomena of a magnetically frustrated spin system below the spin freezing temperature Tf ≈ 16 K. The Mn0.3Ni2Zn10.7 γ-brass phase classifies as a spin glass, originating predominantly from the random distribution of diluted Mn moments on the octahedral partial structure.

Structure and Superconductivity of Tin-Containing HfTiZrSnM (M = Cu, Fe, Nb, Ni) Medium-Entropy and High-Entropy Alloys.

In an attempt to incorporate tin (Sn) into high-entropy alloys composed of refractory metals Hf, Nb, Ti and Zr with the addition of 3d transition metals Cu, Fe, and Ni, we synthesized a series of alloys in the system HfTiZrSnM (M = Cu, Fe, Nb, Ni). The alloys were characterized crystallographically, microstructurally, and compositionally, and their physical properties were determined, with the emphasis on superconductivity. All Sn-containing alloys are multi-phase mixtures of intermetallic compounds (in most cases four). A common feature of the alloys is a microstructure of large crystalline grains of a hexagonal (Hf, Ti, Zr)5Sn3 partially ordered phase embedded in a matrix that also contains many small inclusions. In the HfTiZrSnCu alloy, some Cu is also incorporated into the grains. Based on the electrical resistivity, specific heat, and magnetization measurements, a superconducting (SC) state was observed in the HfTiZr, HfTiZrSn, HfTiZrSnNi, and HfTiZrSnNb alloys. The HfTiZrSnFe alloy shows a partial SC transition, whereas the HfTiZrSnCu alloy is non-superconducting. All SC alloys are type II superconductors and belong to the Anderson class of "dirty" superconductors.

Molecular dynamics of 1-ethyl-3-methylimidazolium triflate ionic liquid studied by 1H and 19F nuclear magnetic resonances.

The molecular dynamics of an ionic liquid (IL) composed of a 1-ethyl-3-methylimidazolium cation and a triflate (trifluoromethanesulfonate) anion, abbreviated as [Emim][TfO], were studied by NMR spectroscopy. By measuring the temperature-dependent high-field 1H and 19F spin-lattice relaxation (SLR) rates, the frequency-dependent 1H and 19F SLR dispersion curves using fast-field-cycling relaxometry, and the temperature-dependent 1H and 19F diffusion constants, and by utilizing the fact that the primary NMR-active nucleus on the Emim cation is 1H, whereas on the TfO anion it is 19F, the cationic and anionic dynamics were studied separately. A single theoretical relaxation model successfully reproduced all the experimental data of both types of resonant nuclei by fitting all the data simultaneously with the same set of fit parameters. Upon cooling, [Emim][TfO] exhibited a supercooled liquid phase between TSL = 256 K and the crystallization temperature TCr ≈ 227-222 K, as confirmed by differential scanning calorimetry (DSC) experiments. Theoretical analysis revealed that within the liquid and the supercooled liquid states of [Emim][TfO], the 1H and 19F relaxation rates are affected by both the rotational and translational diffusional processes with no discontinuous change at TSL. While the rotational diffusion is well described as an Arrhenius thermally activated process, the translational diffusion undergoes strong freezing dynamics that are well described by the Vogel-Fulcher model assuming a freezing temperature of T0 = 157 K. The existence of the supercooled liquid region in the [Emim][TfO] IL should be taken into account when using this IL for a specific application.

A multicaloric material as a link between electrocaloric and magnetocaloric refrigeration.

The existence and feasibility of the multicaloric, polycrystalline material 0.8Pb(Fe1/2Nb1/2)O3-0.2Pb(Mg1/2W1/2)O3, exhibiting magnetocaloric and electrocaloric properties, are demonstrated. Both the electrocaloric and magnetocaloric effects are observed over a broad temperature range below room temperature. The maximum magnetocaloric temperature change of ~0.26 K is obtained with a magnetic-field amplitude of 70 kOe at a temperature of 5 K, while the maximum electrocaloric temperature change of ~0.25 K is obtained with an electric-field amplitude of 60 kV/cm at a temperature of 180 K. The material allows a multicaloric cooling mode or a separate caloric-modes operation depending on the origin of the external field and the temperature at which the field is applied.

The perfect soft mode: giant phonon instability in a ferroelectric.

Previous studies of unstable ('soft') optical modes in ferroelectrics have reported minimum frequencies of 1 cm(-1) (30 GHz) for underdamped phonons. In this work we fabricate a cylindrical coaxial specimen and rectangular plate waveguide specimens of tris-sarcosine calcium chloride (TSCC) and follow its soft mode several orders of magnitude lower to 1 GHz. Below 30 GHz the relaxation time is probably characteristic of domain wall motion; the new theory of Pakhomov et al (2013 Ferroelectrics at press) predicts 0.5 THz far from TC and a (T - T(C))/T(C) dependence, in agreement with our experimental values. This discovery has implications for GHz electronics such as phased array radar or other voltage-tunable low-loss components. The mean-field frequency description of the soft mode response f(T) is supported via precision calorimetry on TSCC with and without Br-doping. The ferroelectric-antiferroelectric phase transition, previously suggested from high-pressure data, is confirmed at 45 K at 1 atm.

Quantitative determination of magnetic force on a coronary stent in MRI.

PURPOSE: To introduce an analytical method for a quantitative determination of magnetic force on a coronary stent in the magnetic resonance imaging (MRI) magnet that is generally applicable to metallic implants. Magnetic forces on metallic implants in the MRI magnets are traditionally determined empirically by measuring deflection from the vertical plane at the central axis of the magnet and at the point of the largest force along the longitudinal axis of the magnet. MATERIALS AND METHODS: Magnetic and chemical characterization of the stents was performed by a commercial magnetometer and energy-dispersive X-ray spectroscopy. Magnetic force on the stents fabricated of paramagnetic alloys (surgical stainless steel and cobalt-chromium) was determined by measuring the stent's magnetic dipole moment and employing the on-axis magnetic field profile of an MRI magnet. RESULTS: The maximum force on the stainless steel stent was found to be F(S,max) = 0.18 mN, whereas on the cobalt-chromium stent it was F(C,max) = 0.06 mN. CONCLUSION: The magnetic force on the investigated paramagnetic stents is even smaller than the gravitational force acting on the stents in the Earth's gravity field, so that it has no physiological impact on the stented vessels.

High-resolution calorimetric study of Pb(Mg(1/3)Nb(2/3))O3 single crystal.

Motivated by the long-standing unresolved enigma of the relaxor ferroelectric ground state, we performed a high-resolution heat capacity and polarization study of the field-induced phase transition in the relaxor ferroelectric single crystal Pb(Mg(1/3)Nb(2/3))O3 (PMN) oriented along the [110] direction. We show that the discontinuous evolution of polarization as a function of the electric field or temperature is a consequence of a true first order transition from a glassy to ferroelectric state, which is accompanied by an excess heat capacity anomaly and released latent heat. We also find that in a zero field there is no ferroelectric phase transition in bulk PMN at any temperature, indicating that the nonergodic dipolar glass phase persists down to the lowest temperatures.