Effects of Zr impurity on microscopic behavior of Hf metal

Hf metal with ∼ 3 wt% Zr impurity has been reinvestigated by perturbed angular correlation (PAC) spectroscopy using a LaBr₃(Ce)–BaF₂ detector set up to understand the microscopic behavior of this metal with temperature. From present measurements, five quadrupole interaction frequencies have been found at room temperature where both pure hcp fraction (∼33%) with 12 nearest neighbor Hf surrounding the probe ¹⁸¹Hf atom and the probe–impurity fraction (∼33%) corresponding to 11 nearest neighbor Hf plus one dissimilar Zr atom are clearly distinguished. At room temperature, the results for quadrupole frequency and asymmetry parameter are found to be ω_Q=51.6(4) Mrad/s, η=0.20(4) for the impurity fraction and ω_Q=46.8(2) Mrad/s, η=0 for the pure fraction with values of frequency distribution width δ=0 for both components. At 77 K, only 1 NN Zr impurity (∼93%) and pure hcp (∼7%) components have been found with a value of δ ∼ 10% for the impurity fraction. A drastic change in microstructural configuration of Hf metal is observed at 473 K where the impurity fraction increases to ∼ 50% and the pure hcp fraction reduces to ∼ 15% with abrupt changes in quadrupole frequencies for both components. The pure fraction then increases with temperature and enhances to ∼50% at 973 K. In the temperature range 473–973 K, quadrupole frequencies for both components are found to decrease slowly with temperature. Using the Arrhenius relation, binding energy (B) for the probe–impurity pair and the entropy of formation are measured from temperature dependent fractions of probe–impurity and pure hcp in the temperature range 473–773 K. The three other minor components found at different temperatures are attributed to crystalline defects.     

The nuclear quadrupole interaction at 111Cd and 181Ta sites in anatase and rutile TiO2: A TDPAC study

The nuclear quadrupole interaction of the I=5/2 state of the nuclear probes ¹¹¹Cd and ¹⁸¹Ta in the anatase and rutile polymorphs of bulk TiO₂ was studied using the time differential perturbed angular correlation (TDPAC) method. The fast–slow coincidence setup is based on CAMAC electronics. For anatase, the asymmetry parameter of the electric field gradient was η=0.22(1) and a quadrupole interaction frequency of ω_Q=44.01(3) Mrad/s was obtained for ¹⁸¹Ta. For rutile, the respective values are η=0.56(1) and ω_Q=130.07(9) Mrad/s. The values for rutile match closely with the literature values. In case of the ¹¹¹Cd probe produced from the beta decay of ¹¹¹Ag, the quadrupole interaction frequency for anatase was negligibly small as indicated by an unperturbed angular correlation in anatase. On the other hand for rutile the quadrupole frequency is ω_Q=61.74(2) Mrad/s and the asymmetry parameter η=0.23(1) for the ¹¹¹Cd probe. The results are interpreted in terms of the surrounding atom positions in the lattice and the charge state of the probe nucleus.     

Electric field gradients at 181Ta probe in ZrNi: Results from perturbed angular correlation and first-principles calculations

Results of temperature dependent perturbed angular correlation (PAC) measurements in the equiatomic ZrNi alloy have been reported for the first time using ¹⁸¹Hf probe. At room temperature, values of quadrupole frequency and asymmetry parameter for the major component (~80%) are found to be ω_Q=26.8(4) Mrad/s, and η=0.413(7). The resulting electric field gradient comes out to be V_zz=2.99 ×10¹⁷ V/cm² and this corresponds to the probe nuclei occupying the regular substitutional Zr sites. In ZrNi system, no magnetic interaction is observed down to 77 K indicating absence of any magnetism in this material. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) studies on an inactive but similarly prepared sample confirm the dominant presence of the orthorhombic ZrNi phase in the sample. A complementary density functional theory (DFT) calculation results in V_zz=−2.35×10¹⁷ V/cm², η=0.46 at the ¹⁸¹Ta probe impurity site and zero magnetic moment on each atomic site, in close agreement with the experimental results. Furthermore, it is found that electric field gradient for the regular component follows a T^3/2 temperature dependence between 77 and 353 K, beyond which it varies linearly with temperature.     

Nuclear quadrupole interaction at 181Ta in hafnium dioxide fiber: Time differential perturbed angular correlation measurements and ab initio calculations

The thermal behavior of hafnium dioxide fiber has been investigated with the aid of time differential perturbed angular correlation (TDPAC) technique along with XRD and SEM measurements. This study has proved a good thermal stability of the fibrous material up to 1173 K and the fiber loses its crystallinity to a meager extent at 1673 K. No phase transition has been observed up to 1673 K in this fiber. TDPAC parameters for the HfO₂ fiber annealed at 1173 K are ω_Q=124.6 (3) Mrad/s and η=0.36 (1). These values remain unaltered for the HfO₂ fiber annealed even at 1673 K. Electronic structure calculations based on the density functional theory (DFT) for HfO₂ doped with tantalum impurity have been performed and the calculated EFG parameters are in reasonable agreement with the experimental values.     

A.c. conductivity and relaxation in LiCoVO4 ceramics

The LiCoVO₄ compound is synthesized by solution-based chemical method. X-ray diffraction analysis exhibits a single phase nature of the compound with cubic structure. The dielectric constant (ε_r), tangent loss (tanδ) and a.c. conductivity (σ_ac) have been studied as a function of frequency and temperature using complex impedance spectroscopy (CIS) technique. The variation of (ε_r and tanδ) with frequency at studied temperatures shows a dispersive behavior at low frequencies. Frequency dependence of σ_ac at different temperatures obeys Jonscher’s universal power law governed by the relation: σ_ac = σ_dc + Aωⁿ, where n is the frequency exponent in the range of 0 ⩽ n ⩽ 1 and A is a constant that depends upon temperature.     

Reel-to-reel fabrication of meter-long YBCO coated conductor

YBa₂Cu₃O_7?δ (YBCO) superconductors were coated on the CeO₂/YSZ/Y₂O₃ buffered Ni-5at%W tapes by a reel-to-reel pulsed laser deposition (PLD). The process of a multi-layer deposition of YBCO film was explored. X-ray diffraction texture measurements showed good both in-plane and out of plane crystalline orientations in YBCO films. The average values calculated at a full width at half maximum (FWHM) of the peaks from phi-scans (φ) and omega (ω) scans for one meter-long YBCO tape were 7.49° and 4.71°, respectively. The critical current (I_c) was over 200 A/cm-width at 77 K and under self-field for meter-long YBCO tape. The critical transition temperature of the YBCO tape was typically as 90.1 K with 0.5 K transition widths.     

Dielectric properties and study of AC electrical conduction mechanisms by non-overlapping small polaron tunneling model in Bis(4-acetylanilinium) tetrachlorocuprate(II) compound

In the present work, the synthesis and characterization of the Bis(4-acetylanilinium) tetrachlorocuprate(II) compound are presented. The structure of this compound is analyzed by X-ray diffraction which confirms the formation of single phase and is in good agreement the literature. Indeed, the Thermo gravimetric Analysis (TGA) shows that the decomposition of the compound is observed in the range of 420–520 K. However, the differential thermal analysis (DTA) indicates the presence of a phase transition at T=363 k. Furthermore, the dielectric properties and AC conductivity were studied over a temperature range (338–413 K) and frequency range (200 Hz–5 MHz) using complex impedance spectroscopy. Dielectric measurements confirmed such thermal analyses by exhibiting the presence of an anomaly in the temperature range of 358–373 K. The complex impedance plots are analyzed by an electrical equivalent circuit consisting of resistance, constant phase element (CPE) and capacitance. The activation energy values of two distinct regions are obtained from log σT vs 1000/T plot and are found to be E=1.27 eV (T<363 K) and E=1.09 eV (363 K<T).The frequency dependence of ac conductivity, σ_ac, has been analyzed by Jonscher's universal power law σ(ω)=σ_dc+Aω^s. The value of s is to be temperature-dependent, which has a tendency to increase with temperature and the non-overlapping small polaron tunneling (NSPT) model is the most applicable conduction mechanism in the title compound.     

Neutron scattering of iron-based superconductors

Low-energy spin excitations have been studied on polycrystalline LaFeAsO_1?xF_x samples by inelastic neutron scattering. The Q-integrated dynamical spin susceptibility χ″(ω) of the superconducting samples is found to be comparable to that of the magnetically ordered parent sample. On the other hand, χ″(ω) almost vanishes at x = 0.158, where the superconducting transition temperature T_c is suppressed to 7 K. In addition, χ″(ω) in optimally doped LaFeAsO_0.918F_0.082 with T_c = 29 K exhibits a spin resonance mode. The peak energy, E_res, when scaled by k_BT_c is similar to the value of about 4.7 reported in other high-T_c iron-based superconductors. This result suggests that there is intimate relationship between the dynamical spin susceptibility and high-T_c superconductivity in iron-based superconductors, and is consistent with a nesting condition between Fermi surfaces at the Γ and M points.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.     

The evolution of electromagnetic response at low frequencies with the development of superconducting condensation in Tl2Ba2CaCu2O8+δ

We report the in-plane temperature dependent ac impedance spectrum of Tl₂Ba₂CaCu₂O_8+δ (Tl-2212) single crystal film with thickness 3000 Å and T_c = 96 K. In process of the superconducting condensation, the impedance spectrum z(ω,T₀) changed considerably and was very similar with the evolution of the spectrum under various dc bias voltages in the shallow superconducting state. The spectrum weight transfers from high frequency regions to lower ones and eventually diverges towards the dc limit. From the analysis, it seems that the superconducting ‘islands’ form first and then grow larger, till the formation of a ‘continent’. The impedance spectrum z(ω,B_I) at various dc bias B_I have also been studied.     

Extinguishment of propane/air co-flowing diffusion flames by fine water droplets

In the present study, extinguishment of propane/air co-flowing diffusion flame by fine water droplets was investigated experimentally. Water droplets are generated by piezoelectric atomizers with the maximum droplets flow rate of 1500 ml/h. When the fuel injection velocity U_f is low, an attached laminar diffusion flame with a premixed flame at the base is stabilized. At some distance from the burner rim, a transition from laminar to turbulent diffusion flame occurs, and a turbulent diffusion flame is formed in the downstream region. When the fuel injector rim is thin (δ = 0.5 mm), the flame stability deteriorates with increase of the co-flowing air stream velocity U_a and the water droplets flow rate Q_m. The stability mechanism can be explained by the balance of the gas velocity and the burning velocity of premixed flame formed at the base. However, when the injector rim is thick (δ = 5 mm), a recirculation zone is produced downstream of the injector rim. The dependence of the quenching distance H_q on U_f and Q_m is relatively weak, and the stability diagram shows curious features. It was shown that U_a is crucially important since it determines flow residence time; if U_a < 0.4 m/s, water droplets can evaporate when they go by the recirculation zone, and the water vapor can diffuse into the recirculation zone. However, if U_a > 0.4 m/s, the water droplets should pass by the recirculation zone without sufficiently evaporated and are not so effective to extinguish the flame. The supply velocity of droplet-laden air should be low enough so that water droplets can evaporate and water vapor can diffuse into the premixed region at the base to obtain sufficient effectiveness of water droplets for fire suppression.     

Effect of Ge4+ and Mg2+ doping on superconductivity,fluctuation induced conductivity and interplanar coupling of TlSr2CaCu2O7−δ superconductors

Substitution of Ge⁴⁺ in place of Cu in Tl_0.85Cr_0.15Sr₂CaCu_2?xGe_xO_7?δ (x = 0–0.6) showed initial increase in zero critical temperature value, T_{c zero} from 98 K (x = 0) to 100 K (x = 0.1) and in the range of 85–86 K for x = 0.2–0.3. The slow decrease in T_{c zero} is unexpected as tetravalent Ge⁴⁺ substitution is expected to strongly reduce hole concentration in the samples and suppress T_{c zero}. Excess conductivity analyses of resistance versus temperature data based on Asmalazov–Larkin (AL) theory revealed that the substitution induced 2D-to-3D transition of fluctuation induced conductivity with the highest transition temperature, T_2D–3D observed at x = 0.1. FTIR spectroscopy analysis indicates Ge⁴⁺ substitution cause reduction in CuO₂/GeO₂ interplanar distance while our calculation based on Lawrence–Doniach model revealed highest superconducting coherence length, ξ_c(0) and interplanar coupling, J at x = 0.3. On the other hand, substitution of divalent Mg²⁺ for Ca²⁺ in (Tl_0.5Pb_0.5)(Sr_1.8Yb_0.2)(Ca_1?yMg_y)Cu₂O₇ (y = 0–1.0), which is not expected to directly vary hole concentration, surprisingly caused T_{c zero} to increase from 89.6 K (y = 0) to an optimum value of 95.9 K (y = 0.6) before decreasing with further increase in y. Excess conductivity analyses showed 2D-to-3D transition of fluctuation induced conductivity for all samples where the highest T_2D–3D was at y = 0.4. Similar calculation revealed highest values of ξ_c(0) and J also at y = 0.4. FTIR analysis of the samples indicates inequivalent Cu(1)O(2)Pb/Tl lengths and possible tilting of CuO₂ plane as a result of Mg²⁺ substitution. The increased ξ_c(0) and J as a result of the Ge⁴⁺ and Mg²⁺ substitutions are suggested to contributed to sustenance of superconductivity above 80 K in the samples.     

Numerical and perturbative computations of solitary waves of the Benjamin–Ono equation with higher order nonlinearity using Christov rational basis functions

Computation of solitons of the cubically-nonlinear Benjamin–Ono equation is challenging. First, the equation contains the Hilbert transform, a nonlocal integral operator. Second, its solitary waves decay only as O(1/∣x∣²). To solve the integro-differential equation for waves traveling at a phase speed c, we introduced the artificial homotopy H(u_XX) ? c u + (1 ? δ)u² + δu³ = 0, δ ∈ [0, 1] and solved it in two ways. The first was continuation in the homotopy parameter δ, marching from the known Benjamin–Ono soliton for δ = 0 to the cubically-nonlinear soliton at δ = 1. The second strategy was to bypass continuation by numerically computing perturbation series in δ and forming Padé approximants to obtain a very accurate approximation at δ = 1. To further minimize computations, we derived an elementary theorem to reduce the two-parameter soliton family to a parameter-free function, the soliton symmetric about the origin with unit phase speed. Solitons for higher order Benjamin–Ono equations are also computed and compared to their Korteweg–deVries counterparts. All computations applied the pseudospectral method with a basis of rational orthogonal functions invented by Christov, which are eigenfunctions of the Hilbert transform.     

High temperature properties of the n = 2 Ruddlesden–Popper phases (La,Sr)3(Fe,Ni)2O7−δ

The crystal chemistry and mixed conductor properties of the n = 2 member of the Ruddlesden–Popper (R–P) phases Sr_3−xLa_xFe_2−yNi_yO_7−δ with 0 ≤ x ≤ 0.3 and 0 ≤ y ≤ 1.0 have been studied at high temperature. High-temperature X-ray diffraction and thermogravimetric measurements of the equilibrium pO₂ (10^− 5 ≤ pO₂ ≤ 1 atm) in the temperature range 400 ≤ T ≤ 1000 °C indicate that the Sr₃FeNiO_7−δ phase is able to accommodate a large oxygen non-stoichiometry (δ ∼ 1.5) without structural transformations. The electrical conductivity and oxygen permeability increase with the substitution of Ni for Fe in the range 550 ≤ T ≤ 1000 °C. The electrical transport of the Sr₃FeNiO_7−δ phase is thermally activated and the activation energy decreases with the substitution of Ni for Fe for a given oxygen content. The increase in the oxygen permeation flux with increasing Ni content is due to an increasing oxygen non-stoichiometry and a lower activation energy for permeation.     

Si-delta doping and spacer thickness effects on the electronic properties in Si-delta-doped AlGaAs/GaAs HEMT structures

In this work, we investigate the effect of the δ-Si doping on the barrier and the spacer thickness on the electronic properties of AlGaAs/GaAs HEMTs structures grown by molecular beam epitaxy on (1 0 0) oriented GaAs substrates. Photoluminescence measurements as function of the temperature are used to determine the relaxation processes of the electron and the hole in the channel. The photoluminescence characterizations of Si-delta-doped AlGaAs/GaAs HEMTs structures have been studied in the 10–300 K temperature range. Low temperature PL spectra show the optical transition (E_e–h) that occurs between the fundamental states of electrons to holes in the GaAs channel. Increase of the Si-δ-doping density and decrease of the spacer width improve the two-dimensional electron gas confinement and decrease defects densities in the canal. The band structure of Si-delta-doped AlGaAs/GaAs HEMTs structures at T = 10 K has been studied theoretically using the finite differences method to self-consistently and simultaneously solve Schrödinger and Poisson equations written within the Hartree approximation.     

Oxygen nonstoichiometry and defect equilibrium in La2 − xSrxNiO4 + δ

Nonstoichiometric variation of oxygen content in La_2 ? xSr_xNiO_4 + δ (x = 0, 0.1, 0.2, 0.3, 0.4) and decomposition P(O₂) were determined by means of high temperature gravimetry and coulometric titration. The measurements were carried out in the temperature range between 873 and 1173 K and the P(O₂) range between 10^? 20 and 1 bar. La_2 ? xSr_xNiO_4 + δ showed the oxygen excess and the oxygen deficient compositions depending on P(O₂), temperature, and the Sr content. The value of partial molar enthalpy of oxygen approaches zero as δ increases in the oxygen excess region, which indicate that the interstitial oxygen formation reaction is suppressed as δ increase. The relationship between δ and logP(O₂) were analyzed by two types of defect equilibrium models. One is a localized electron model, and the other is a delocalized electron model. Both models can well explain the oxygen nonstoichiometry of La_2 ? xSr_xNiO_4 + δ with a regular solution approximation.     

High-temperature compressive creep behaviour of the perovskite-type oxide Ba0.5Sr0.5Co0.8Fe0.2O3 − δ

Compressive creep tests have been performed on perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ ceramics. The activation energy, stress exponent and inverse grain size exponent of the steady-state creep rates are evaluated at p(O₂) = 0.21 ? 10⁵ Pa and 0.01 ? 10⁵ Pa in the stress, temperature and grain size ranges 5–20 MPa, 1078–1208 K and 2.5–17.4 µm, respectively. The results indicate that the creep rate of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ is controlled by diffusion of cations via both the oxide lattice (bulk diffusion) and along grain boundaries. The creep rate of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ increases profoundly by more than one order of magnitude at 1153–1178 K, which is tentatively linked with the onset of the hexagonal-to-cubic phase transition in this compound.     

Missing superconductivity in BaAlSi with the AlB2 type structure

The solid solutions BaAl_1−xSi_1+x (0 ⩽ x ⩽ 0.5) were prepared. The compound with the stoichiometric composition (x = 0) did not show superconductivity as reported by other investigators, but the solid solutions with x > 0 became superconductors with a transition temperature T_c = 2.8 K. The comparison of the lattice parameters with those of the other isotypic ternary superconductors MAlSi (M = Ca, Sr) suggested that the superconductivity could be related to the lattice parameter within the (AlSi) plane rather than the interlayer spacing. The band structures near the Fermi level of MAlSi (M = Ca, Sr, Ba) were measured using soft X-ray photoelectron spectroscopy, which were in good agreement with the calculated ones, confirming that the contribution of the d orbitals of the alkaline-earth metals were predominant in the conduction bands.