Effect of dissolved hydrogen on electron transport in nickel–chromium alloys

The thermoelectric power and electrical resistance of Ni_0.95Cr_0.05H_c alloys (0≤c≤0.96), obtained by high pressure hydrogenation, have been measured between 80 and 300 K. The electrical resistance of two other Ni_1−xCr_x–H alloys (x=0.025 and 0.11) has been measured in the range from 4 to 300 K. The absorbed hydrogen acting as electron donor induces qualitative changes in the behavior of both properties. The negative temperature coefficient of resistance over a wide T-range and the non-monotonic course of the thermoelectric power are attributed to a Kondo-like effect, i.e., spin-flip scattering of electrons on magnetic moments localized at the chromium atoms.     

Constitution, structural chemistry and magnetism in the ternary system Ce–Ag–Si

Phase relations were established for the Ce–Ag–Si system at 850°C by means of X-ray diffraction, light optical microscopy and quantitative electron probe microanalysis. Phase equilibria are characterised by the existence of extended solid solutions starting from the binaries: Ce(Ag_xSi_1−x)_2−y (ThSi₂-type), Ce(Ag_1−xSi_x)_1−y (unknown structure type) and Ce(Ag_1−xSi_x)_2−y (unknown structure type). Three ternary phases were found to exist, CeAg₂Si₂ (ThCr₂Si₂-type), Ce(Ag_xSi_1−x)_2−y (AlB₂-type) and the new ternary compound CeAgSi₂ with unknown structure type. Magnetic behaviour was studied from magnetic susceptibility and magnetisation measurements down to 1.7 K and employing magnetic fields up to 5 T. Soft ferromagnetism is observed for CeAg_xSi_2−x (AlB₂-type) below 5 K. Alloys Ce(Ag_xSi_1−x)_2−y with 0.08<x_Ag<0.30 (ThSi₂-type) encounter ferromagnetic order below 7 K. For x_Ag=0.31 the ferromagnetic interaction changes to antiferromagnetism with T_N=5.7 K. For CeAgSi₂ ferrimagnetic or canted antiferromagnetic order is indicated below 7 K.     

Characterization and hydrogenation of CeNi5−xCrx (x = 0, 1, 2) alloys

The effect of partial substitution of Ni by Cr in CeNi₅ intermetallic compound has been studied by pressure–composition isotherm measurements for different temperatures. The samples were prepared of high purity materials using the standard arc melting technique in argon atmosphere. The structure and the elemental composition of different alloys have been investigated by means of XRD, SEM and EDX techniques. The unit cell volume of the alloy was found to increase with increasing Cr content. In order to calculate the hydrogen storage capacity pressure–composition isotherm has been investigated for CeNi_5−xCr_x (x = 1, 2) alloys in the temperature and pressure ranges of 293 ≤ T ≤ 333 K and 0.5 ≤ P ≤ 35 bar, respectively. The P–C–T isotherm for different alloys clearly shows the presence of three regions ,  + β and β. The enthalpy and entropy for the systems has also been calculated using Van’t Hoff plot. The variation of enthalpy and entropy with hydrogen content has also been studied.     

The effect of Nd content on the electrochemical properties of low-Co La–Mg–Ni-based hydrogen storage alloys

The low-Co content La_0.80−xNd_xMg_0.20Ni_3.20Co_0.20Al_0.20 (x = 0.20, 0.30, 0.40, 0.50, 0.60) alloys were prepared by inductive melting and the effect of Nd content on the electrochemical properties was investigated. XRD shows that the alloys consist mainly of LaNi₅ phase, La₂Ni₇ phase and minor LaNi₃ phase. The electrochemical P–C–T test shows hydrogen storage capacity increases first and then decreases with increasing x, which is also testified by the electrochemical measurement that the maximum discharge capacity increases from 290 mAh/g (x = 0.20) to 374 mAh/g (x = 0.30), and then decreases to 338 mAh/g (x = 0.60). The electrochemical kinetics test shows exchange current density I₀ increases with x increasing from 0.20 to 0.50 followed by a decrease for x = 0.60, and hydrogen diffusion coefficient D increases with increasing x. Accordingly high rate dischargeability increases with a slight decrease at x = 0.60 and the low temperature dischargeability increases with increase in Nd content. When x is 0.50, the alloy exhibits a better cycling stability.     

Effects of Ce and Mm additions on the glass forming ability of Al–Ni–Si metallic glass alloys

The effects of Ce and Mm contents on the glass forming ability (GFA) of melt-quenched Al_89−xNi₈Ce_xSi₃ and Al_89−xNi₈Mm_xSi₃ (x = 0, 1, 3, 5, 7 at.%) alloys have been systematically investigated by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). According to the XRD and DSC results, both Ce and Mm elements can enhance the GFA and thermal stability of the Al–Ni–Si alloys. Moreover, only the x = 5 and x = 7 alloys are totally amorphous in both systems quenched at the wheel speed of 36.6 m/s. Compared with amorphous Al₈₄Ni₈Ce₅Si₃ alloy at different cooling rates, amorphous Al₈₄Ni₈Mm₅Si₃ alloy has higher GFA which is considered to have relation to the different atomic structure of the amorphous alloy.     

Tailoring of misfit along interfaces between ZnxMn3−xO4 and Ag

This work is aimed at examining how the tetragonality of Zn_xMn_3−xO₄ spinel structures depends on the chemical composition when Zn_xMn_3−xO₄ is embedded in a metal matrix. The paper focuses on a wide range of Zn_xMn_3−xO₄ precipitates in a Ag matrix with x varying between 0 and 1.5. This variation of x has been obtained by internal oxidation of Ag–2at.%Mn–4at.%Zn in air followed by annealing in vacuo at different temperatures. It will be demonstrated that the Zn concentration x in Zn_xMn_3−xO₄ has a major influence on the interfacial misfit and orientation relation between Ag/Zn_xMn_3−xO₄. The degree of mismatch of 10.4% of 1 1 1 Ag–Mn₃O₄ and 2.4% of Ag–Zn_1.5Mn_1.5O₄ was visualized using the Bragg filtering technique on HRTEM micrographs of those interfaces. It was possible to identify misfit dislocations qualitatively with this technique at 1 1 1 Ag–Zn_xMn_3−xO₄ interfaces with different degree of mismatch.     

Microstructure evolution in CoNiGa shape memory alloys

Magnetic shape memory CoNiGa alloys hold great promise as new smart materials due to the good ductility and a wide range of martensitic transformation (MT) temperatures as well as magnetic transition points. This paper reports the results of investigations on the equilibrium phase constitution and microstructure evolution in quenched or aged CoNiGa alloys using the optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) methods. The dendritic γ phase decreases as lowering of Ga content in studied two series of samples (Co₅₀Ni_50 − xGa_x, x = 0–50 and Co_100 − 2yNi_yGa_y, y = 15–35). Some γ′ precipitates with different morphologies were found in given alloys conducted with water quenching (WQ) at 800 °C or long-time ageing at 300 °C. After 800 °C quenching, the γ′ phase has a rod-like shape for the Co₅₀Ni₃₀Ga₂₀ alloy but shows a Widmanstätten morphology as Ga increases to 25 at%, and trends to be block structure in further high Ga content alloy. In the case of 300 °C aged alloys, the γ′ particles prefer to nucleate in interior of γ phase or at the interface of β–γ. We also presented an illustrative vertical section phase diagram keeping 50 at% Co, and isothermal section phase diagram at 1150 and 800 °C of the CoNiGa system. Based on the schematic ternary phase diagram, the composition scope which potentially holds over the magnetic pure martensite phase structure at room temperature (RT) was pointed out. It is believed that this optimized range alloys would play an important role in the functional materials design for application.     

Interaction of hydrogen with the LaNi4.9In0.1, LaNi4.8In0.2 and LaNi4.8 alloys and their Nd analogues

The single phase nature of the alloys LaNi_4.9In_0.1, LaNi_4.8In_0.2, NdNi_4.9In_0.1, NdNi_4.8In_0.2 of the systems LaNi_5−xIn_x and NdNi_5−xIn_x was confirmed by means of X-ray powder diffractometry. Nonstoichiometric alloys LaNi_4.8 and NdNi_4.8 were prepared and were also found to be good single phase materials. All these alloys crystallize with the same hexagonal structure of the CaCu₅ type (space group P6/mmm) as do their prototypes LaNi₅ and NdNi₅. In order to determine the interaction with hydrogen the alloys were exposed to hydrogen gas and the pressure composition desorption isotherms were measured. It was found that all alloys react readily and reversibly absorb large amounts of up to 6.54 hydrogen atoms per alloy formula unit. Generally the equilibrium pressure and the hydrogen capacity decrease with the decreasing nickel content. Presence of indium in the alloy acts in favour of these trends. Furthermore, the increasing content of indium in the alloy system drastically alters the slope and the pressure of the plateau observed at higher pressure of the two isotherm plateaux of the NdNi₅–hydrogen system. The final result is a merge of both plateaux into a single one for the hydrogen desorption isotherms of NdNi_4.8In_0.2. However, the isotherms of nonstoichiometric NdNi_4.8 still exhibit two separated pressure plateau regions. The thermodynamic parameters of hydride formation, i.e., the entropy change, the enthalpy and the Gibbs free energy of formation have also been extracted for all alloy–hydrogen systems.     

Low-temperature synthesis and characterization of (Zn,Ni)TiO3 ceramics by a modified sol–gel route

Hexagonal ilmenite-type (Zn_1−xNi_x)TiO₃ (x = 0, 0.85–1.0) ceramic powders were successfully synthesized by a sol–gel route with low temperature (800 °C) sintering, which was modified by using the two-step heat treatment so as to obtain pure products. The thermal stability of the hexagonal (Zn,Ni)TiO₃ was enhanced with the increasing amount of nickel addition. FE-SEM observations demonstrated that the average crystallite sizes of (Zn_1−xNi_x)TiO₃ remarkably decreased from more than 200 nm to less than 100 nm with the increasing solubility x. The dielectric properties of (Zn_1−xNi_x)TiO₃ were measured at different frequencies and the results showed that there existed maximum values both for the dielectric constants and the loss tangents at x = 0.85.     

Solid state phase equilibria in the Fe–Ga–Sb ternary system at 600 °C

Solid state phase equilibria in the ternary Fe–Ga–Sb diagram were determined at 600 °C using experimental techniques such as X-ray diffraction, electron probe microanalysis and scanning electron microscopy. Very limited solid solutions were measured in the binary constituent Fe–Ga and Fe–Sb compounds except for the -phase (Fe_≈2.55Sb₂) which extends from 42 to 48 at.% Sb. In the Fe-rich part of the diagram, a ternary phase Fe_tGa_2−xSb_x (2.15≤t≤2.80) was evidenced which corresponds in fact to a solid solution into which Ga and Sb substitute one another on the same hexagonal sublattice. This phase, which can be truly considered as a pseudo-binary one since its origin results from the -phase, shows an extended homogeneity range with a Ga-rich limit corresponding to the formula Fe_tGa_0.8Sb_1.2. Moreover, it crystallizes in hexagonal symmetry with a disordered structure derivative from the NiAs-type (B8₁). This pseudo-binary phase is in thermodynamic equilibrium with all the binaries of the system except FeGa₃. The main result of the ternary Fe–Ga–Sb diagram remains the existence of a diphasic region between the Fe_tGa_2−xSb_x phase (1.2≤x≤1.6; 2.15≤t≤2.80) and the semiconductor GaSb. Nevertheless, at 600 °C, this pseudo-binary phase does not extend up to the Fe₃GaSb composition which is stoichiometric in Ga and Sb. Finally, a comparative study has been made with the three other ternary systems Fe–Ga–As, Ni–Ga–As and Ni–Ga–Sb previously reported, and the consequences for the solid state interdiffusions in Metal/III–V semiconductor heterostructures are discussed.     

Temporal evolution of the nanostructure of Al(Sc,Zr) alloys: Part II-coarsening of Al3(Sc1−xZrx) precipitates

The coarsening behavior of four Al(Sc,Zr) alloys containing small volume fractions (<0.01) of Al₃(Sc_1−xZr_x) (L1₂) precipitates was investigated employing conventional transmission electron microscopy (CTEM) and high-resolution electron microscopy (HREM). The activation energies for diffusion-limited coarsening were obtained employing the Umantsev–Olson–Kuehmann–Voorhees (UOKV) model for multi-component alloys. The addition of Zr is shown to retard significantly the coarsening rate and stabilize precipitate morphologies. HREM of Al(Sc,Zr) alloys aged at 300 °C reveals Al₃(Sc_1−xZr_x) precipitates with sharp facets parallel to {1 0 0} and {1 1 0} planes. Coarsening of Al-0.07 Sc-0.019 Zr at.%, Al-0.06 Sc-0.005 Zr at.% and Al-0.09 Sc-0.047 Zr at.% alloys is shown to be controlled by volume diffusion of Zr atoms, while coarsening of Al-0.14 Sc-0.012 Zr at.% is controlled by volume diffusion of Sc atoms.     

Temporal evolution of the nanostructure of Al(Sc,Zr) alloys: Part I – Chemical compositions of Al3(Sc1−xZrx) precipitates

Atom-probe tomography (APT) and high-resolution transmission electron microscopy are used to study the chemical composition and nanostructural temporal evolution of Al₃(Sc_1−xZr_x) precipitates in an Al–0.09 Sc–0.047 Zr at.% alloy aged at 300 °C. Concentration profiles, via APT, reveal that Sc and Zr partition to Al₃(Sc_1−xZr_x) precipitates and Zr segregates concomitantly to the -Al/Al₃(Sc_1−xZr_x) interface. The Zr concentration in the precipitates increases with increasing aging time, reaching a maximum value of 1.5 at.% at 576 h. The relative Gibbsian interfacial excess of Zr, with respect to Al and Sc, reaches a maximum value of 1.24 ± 0.62 atoms nm⁻² after 2412 h. The temporal evolution of Al₃(Sc_1−xZr_x) precipitates is determined by measuring the time dependence of the depletion of the matrix supersaturation of Sc and Zr. The time dependency of the supersaturation of Zr does not follow the asymptotic t^−1/3 law while that of Sc does, indicating that a quasi-stationary state is not achieved for both Sc and Zr.     

Thermal and conductometric studies of the CeBr3–MBr binary systems (M = Li, Na)

DSC was used to investigate phase equilibrium in the CeBr₃–MBr (M = Li, Na) systems. They represent typical examples of simple eutectic systems. The eutectic composition and eutectic temperature, x(CeBr₃) = 0.249, T_eut = 709 K and x(CeBr₃) = 0.372, T_eut = 692 K, were found for CeBr₃–LiBr and CeBr₃–NaBr systems, respectively.

The electrical conductivity of CeBr₃–MBr liquid mixtures, together with that of pure components was measured down to temperatures below solidification. Results obtained are discussed in term of possible complex formation.     

Magnetocrystalline anisotropy of Nd3(Fe1−xCox)27.7Ti1.3Ny compounds

The effect of Co substitution for Fe in Nd₃(Fe_1−xCo_x)_27.7Ti_1.3N_y (0 ≤ x ≤ 0.4) compounds on the magnetocrystalline anisotropy has been investigated. The anisotropy constants K's and the anisotropy field H_A have been deduced from the magnetization curves measured on magnetically aligned powder (4–7 μm) samples. The obtained results show that at RT the anisotropy is uniaxial and H_A (about 10 T) does not change substantially upon the substitution. At 5 K the results for K's give evidence for the presence of easy-cone-type anisotropy. The cone angle as well as the anisotropy field decrease upon the substitution from 21.6° to 11.8° and from 22.8 to 18.6 T, respectively.     

Phase diagram and electrical conductivity of the CeBr3–RbBr binary system

Phase equilibrium in the CeBr₃–RbBr binary system was established from differential scanning calorimetry (DSC). This system has three compounds Rb₃CeBr₆, Rb₂CeBr₅ and RbCe₂Br₇ and two eutectics located at (x = 0.141; 858 K) and (x = 0.528; 762 K), respectively. Rb₃CeBr₆ forms at 614 K, undergoes a solid–solid phase transition at 695 K and melts congruently at 966 K. Rb₂CeBr₅ melts incongruently at 830 K and RbCe₂Br₇ at 741 K. The electrical conductivity of CeBr₃–RbBr liquid mixtures was measured down to temperatures below solidification over the whole composition range. Results obtained are discussed in term of possible complex formation.     

Synthesis and characterization of LiGaxMn2−xO4 (0 ≤ x ≤ 0.05) by triethanolamine-assisted sol–gel method

Spinel LiGa_xMn_2−xO₄ (0 ≤ x ≤ 0.05) cathode materials with phase-pure particles and nano-sized distribution were synthesized by sol–gel method using triethanolamine as the chelating agent. The effects of heat treatment on the physicochemical properties of the spinel LiGa_xMn_2−xO₄ powders were examined with thermogravimetric and differential thermal analysis (TG/DTA), powder X-ray diffraction (XRD) and scanning electron micrograph (SEM). The LiGa_xMn_2−xO₄ (0 ≤ x ≤ 0.05) electrodes were characterized electrochemically by charge/discharge experiments under a current rate of 0.5C at 55 °C. Although the Ga-doped spinel electrode showed smaller initial discharge capacity, it exhibited better cycling performance than the undoped-LiMn₂O₄ electrode. The dQ/dV versus potential plots at 55 °C revealed that the improvement in cycling performance of the Ga-doped spinel electrode is attributed to stabilization of the spinel structure by the presence of gallium ion.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

The ternary system: silicon–titanium–uranium

Phase equilibria in the system Si–Ti–U were established at 1000 °C by optical microscopy, EMPA and X-ray diffraction. Two ternary compounds were observed and were characterised by X-ray powder data refinement: (1) stoichiometric U₂Ti₃Si₄ (U₂Mo₃Si₄-type) with a small homogeneity region of about 3 at.% exchange U/Ti and (2) U_2−xTi_3+xSi₄ (Zr₅Si₄-type) extending at 1000 °C for 0.7<x<1.3. Mutual solubility of U-silicides and Ti-silicides was found to be below about 1 at.%. The Ti,U-rich part of the diagram was also investigated at 850 °C establishing the tie-lines to the low temperature compounds U₂Ti and U₃Si. U₂Ti₃Si₄ is weakly paramagnetic following a Curie–Weiss law above 50 K with μ_eff.=2.67 μ_B/U, Θ_P=−150 K and χ₀=1.45×10⁻³ emu/mol (18.2×10⁻⁹ m³/mol).     

Small-angle neutron scattering and differential scanning calorimetry studies on the copper clustering stage of Fe–Si–B–Nb–Cu nanocrystalline alloys

The kinetics of copper clustering and primary crystallization of FINEMET type alloys with the compositions Fe_74.5−xSi_13.5B₉Nb₃Cu_x and Fe₇₇Si₁₁B₉Nb_3−xCu_x have been studied by small-angle neutron scattering (SANS) and high-sensitivity differential scanning calorimetry (DSC) in order to explain the different optimized Cu contents, x, for obtaining the highest permeability in these two alloys. SANS results have shown that the alloys with the optimized Cu contents have the finest nanocrystalline microstructures. Kinetic analyses of Cu clustering prior to primary crystallization have shown that the number density of Cu clusters becomes highest at the crystallization stage of -Fe primary crystals in the alloy containing an optimized amount of Cu.     

Cycle stabilities of the La0.7Mg0.3Ni2.55−xCo0.45Mx (M = Fe, Mn, Al; x = 0, 0.1) electrode alloys prepared by casting and rapid quenching

In order to improve the cycle stability of La–Mg–Ni system (PuNi₃-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe, Mn and Al, and the electrode alloys La_0.7Mg_0.3Ni_2.55−xCo_0.45M_x (M = Fe, Mn, Al; x = 0, 0.1) were prepared by casting and rapid quenching. The effects of the substitution of Fe, Mn and Al for Ni and rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Mn obviously raises the amount of the LaNi₂ phase. The substitution of Al and Fe leads to a significant refinement of the as-quenched alloy's grains. The substitution of Al strongly restrains the formation of an amorphous in the as-quenched alloy, but the substitution of Fe is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Mn and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive influence of the substitution elements on the cycle stabilities of the as-cast alloys is in proper order Al > Fe > Mn, and for as-quenched alloys, the order is Fe > Al > Mn. Rapid quenching engenders an inappreciable influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.