Hydrogenation of CaLi2−xMgx (0 ≤ x ≤ 2) with C14 Laves phase structure

CaLi_2−xMg_x (0 ≤ x ≤ 2) which has the C14-type Laves phase structure has been successfully synthesized and hydrogenated. The C14-type Laves phase structure was kept after hydrogenation of CaLi_2−xMg_x (x = 0.2, 0.5, 1). After hydrogenation of CaLi₂ and CaMg₂, the Laves phase disappeared. The CaH₂ and LiH phases were formed from CaLi₂ and the CaH₂ and Mg phases from CaMg₂, respectively. CaLi_2−xMg_x (0 < x < 2) ternary alloys formed stable hydride phases with the C14-type Laves phase structure in contrast to CaLi₂ and CaMg₂ binary alloys.     

Synthesis process of Mg–Ti BCC alloys by means of ball milling

The synthesis process of Mg–Ti alloys with a BCC (body centered cubic) structure by means of ball milling was studied by X-ray diffraction and various microscopic techniques. The morphology and crystal structure of Mg–Ti alloys changed with increase of milling time. During ball milling of Mg and Ti powders in molar ratio of 1:1, firstly, plate-like particles stuck on the surface of the milling pot and balls. After these plate-like particles fell off from the surface of the milling pot and balls, spherical particles with the mean diameter of 1 mm, in which concentric layers of Mg and Ti were disposed, were formed. These spherical particles were crushed into spherical particles with the diameter of around 10 μm by introduction of cracks along the boundaries between Mg and Ti layers. Finally, the Mg₅₀Ti₅₀ BCC phase with the lattice parameter of a = 0.342(1) nm and the grain size of 3 nm was formed. During milling of Mg and Ti to synthesize the BCC alloy, Mg and Ti were deformed mainly by the basal plane slip and the twinning deformation, respectively. Ti acted as abrasives for Mg which had stuck on the surface of the milling pot and balls. The BCC phase was found after Mg dissolved in Ti.     

Hydrogen sorption properties of Ti–Cr alloys synthesized by ball milling and cold rolling

Three Ti–Cr alloys with nominal compositions of TiCr_x (x = 2, 1.8 and 1.5) were synthesized by cold rolling and ball milling of as-cast ingots, and their microstructures and hydrogenation properties were studied. X-ray diffraction showed that TiCr_x transformed from a mixture of C14 and C15 Laves phases to a metastable BCC phase after 5 h of ball milling under argon. Cold rolling did not lead to the formation of a metastable BCC phase but only to the reduction of TiCr_x size particles under 20 nm. Surprisingly, the hydrogen absorption/desorption curves of cold rolled and ball milled samples at 323 K were quite similar. This result proves that hydrogen storage properties do not depend only on microstructure and that cold rolling could be an interesting method to synthesize hydrogen storage materials.     

Compositional dependence of phase formation and mechanical properties in three CoCrFeNi-(Mn/Al/Cu) high entropy alloys

Starting from three typical equiatomic CoCrFeNiMn, CoCrFeNiAl and CoCrFeNiCu high entropy alloys (HEAs), we systematically investigated the compositional dependence of phase formation and mechanical properties of 78 alloys by varying the atomic ratio of the constituent elements. It was found that the simple phase structures, including a single face-centered cubic (FCC) or body-centered cubic (BCC) phase, duplex FCC phases, duplex BCC phases, instead of intermetallics, could form within a broad compositional landscape in 68 out of the 78 alloys not limited to the equiatomic composition where the configurational mixing entropy is maximum. This fact indicates that it may be the nature of the constituent elements that leads to simple phase structure formation. With compositional variation, the microstructure and mechanical properties including hardness and tensile properties show corresponding changes. It was found that the hardness variation of samples within the same structure is smaller for the FCC than that of the BCC. Tensile results indicated that the tensile elongation of (CoCrFeMn)_(100−x)Ni_x (x = 0, 10 and 20) alloys increases with Ni addition due to the decreasing volume fraction of sigma phase. For the (CoCrFeAl)_(100−x)Ni_x (x = 27.3, 33.3, 38.5, 42.9 and 50) alloys, the yield strength decreases and tensile elongation increases with Ni addition due to decreasing volume fraction of BCC phase which is hard yet brittle. The present results are important to understand the phase formation and relationship between microstructure and mechanical properties in HEAs.     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Sn effect on microstructure and mechanical properties of ultrafine eutectic Ti–Fe–Sn alloys

Microstructural investigations on ultrafine eutectic (Ti₆₅Fe₃₅)_100−xSn_x alloys with x = 0, 1 and 3 at.% reveal that additional Sn is effective to control formation of the micron-scale dendrites and to decrease the length-scale of lamellar spacing with enhancing macroscopic plasticity at room temperature compression. Hence, it is possible to understand the influence of the microstructural change on the plasticity of the ultrafine eutectic Ti–Fe–Sn alloys.     

The crystal structure of HfZrP

The crystal structure of HfZrP has been determined using single crystal X-ray diffraction data. This compound crystallizes in the orthorhombic space group Cmmm (No.65), with a=19.004(3), b=29.372(4), c=3.565(1) Å and the Zr₂P structure type. The Hf and Zr atoms are disordered on one site with total occupancy of 1.0. X-ray powder patterns indicate that (Hf_xZr_1−x)₂P alloys consist of single phase (Zr₂P-type),two phases and single phase (Hf₂P-type) corresponding to 0≤x≤0.5, 0.5<x<0.8 and 0.8≤x≤1.0, respectively.     

Phase stability,mechanical property,and electronic structure of Mg–Li system

First principle calculation reveals that the HCP, BCC, and FCC Mg_100?xLi_x phases are energetically favorable with negative heats of formation, and are predicted to be the most stable structures at 0 K when 0 ≤ x < 18, 18 ≤ x < 73, and 73 ≤ x ≤ 100, respectively. Calculation also shows that for Mg–Li phases there is an almost linear variation of bulk moduli with composition, and crystal structure has only a little effect on bulk moduli. In addition, it is found that Mg₃Li and MgLi have phase sequences of BCC → HCP → FCC and BCC → FCC under high pressure, respectively, and that the anomalous mechanical instability of the HCP MgLi phase would be attributed to its weak bonding and step-like electronic structure of valence bands.     

Phase formation in mechanically alloyed AlxCoCrCuFeNi (x = 0.45, 1, 2.5, 5 mol) high entropy alloys

Alloying behavior and phase transformations in Al_xCoCrCuFeNi (x = 0.45, 1, 2.5, 5 mol) multi-component high entropy alloys that are synthesized by mechanical alloying were studied. Two FCC phases along with a BCC phase were formed in Al_0.45CoCrCuFeNi and AlCoCrCuFeNi, while a single B2 phase was observed in higher Al containing alloys Al_2.5CoCrCuFeNi and Al₅CoCrCuFeNi. DSC analysis indicates that BCC phase present in the alloys could be Fe–Cr type solid solution. A detailed analysis suggests that two melting peaks observed during DSC in lower Al containing alloys can be attributed to that of Cu–Ni and Fe–Ni FCC solid solutions. The BCC phase disappears in Al_0.45CoCrCuFeNi and AlCoCrCuFeNi at high temperatures during DSC. However, Al₅CoCrCuFeNi retains its B2 structure despite of heating in DSC. Further, phases present in these alloys retain nanocrystallinity even after exposure to high temperatures. A critical analysis is presented to illustrate that solid solution formation criteria proposed for high entropy alloys in the literature are unable to explain the phase formation in the present study of alloys. Besides, these criteria seem to be applicable to high entropy alloys only under very specific conditions.     

Investigation on the structures and electrochemical performances of La0.75−xZrxMg0.25Ni3.2Co0.2Al0.1 (x = 0–0.2) electrode alloys prepared by melt spinning

In order to improve the electrochemical cycle stability of the La–Mg–Ni system A₂B₇-type electrode alloys, La in the alloy was partially substituted by Zr and the melt-spinning technology was used for preparing La_0.75−xZr_xMg_0.25Ni_3.2Co_0.2Al_0.1 (x = 0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The microstructures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results obtained by XRD, SEM and TEM showed that the as-cast and quenched alloys have a multiphase structure which is composed of two main phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Zr for La leads to an obvious increase of the LaNi₅ phase in the alloys, and it also helps the formation of a like amorphous structure in the as-quenched alloy. The results of the electrochemical measurement indicated that the substitution of Zr for La obviously decreased the discharge capacity of the as-cast and quenched alloys, but it significantly improved their cycle stability. The discharge capacity of the alloys (x ≤ 0.1) first increased and then decreased with the variety of the quenching rate. The cycle stability of the alloys monotonously rose with increasing quenching rate.     

Affordable FeCrNiMnCu high entropy alloys with excellent comprehensive tensile properties

Fe_0.4Cr_0.4NiMn_xCu (0 ≤ x ≤ 1.4) high entropy alloys (HEAs) were prepared by copper-mold casting. The phase selection, microstructure, tensile properties and fracture morphologies were investigated. The microstructure with dual FCC phases was formed in the as-cast HEAs with x ≤ 1, and BCC phase was crystallized from the central FCC dendrites of HEAs with x = 1.2 and 1.4. In homogenized Fe_0.4Cr_0.4NiMnCu HEA, needle-like shaped BCC phase was formed resulting in a slight enhancement of yield strength. Compositional heterogeneity was detected in both FCC and BCC dendrites. These HEAs exhibit excellent comprehensive tensile properties, e.g. the yield strength, ultimate strength and elongation of the HEA with x = 1 reaches 439 MPa, 884 MPa and 23.4%, respectively. High density of dislocations in FCC matrix was formed after tensile deformation. FCC type of fine polyhedra, which is mainly composed of Cr, Mn and O, is formed in dendrites. In this work, the phase selection and strengthening mechanism were evaluated based on atomic size factor. It was found that two criteria can be employed to predict the phase regions of current alloys. The solid solution strengthening for this HEA system is the most important among the four kinds of strengthening mechanisms.     

Investigations of mechanically alloyed Ni–Zr–Ti–Si amorphous alloys with significant supercooled regions

This study examined the amorphization behavior of Ni₅₇Zr₂₀Ti_23−xSi_x (x=0, 1, 3) alloy powders synthesized by mechanical alloying technique. According to the results, after 5 h of milling, the mechanically alloyed powders were amorphous at compositions of Ni₅₇Zr₂₀Ti_23−xSi_x (x=0, 1, 3). The amorphization behavior of Ni₅₇Zr₂₀Ti₂₀Si₃ was examined in details. The conventional X-ray diffraction and synchrotron EXAFS results confirm that the fully amorphous powders formed after 5 h of milling. The thermal stability of the Ni₅₇Zr₂₀Ti_23−xSi_x amorphous powders was investigated by differential scanning calorimeter (DSC). As the results demonstrated, the amorphous powders were found to exhibit a large supercooled liquid region before crystallization. The supercooled liquid regions, defined by the difference between T_g and T_x, (i.e. ΔT=T_g−T_x), are 95 K, 66 K, and 88 K, for Ni₅₇Zr₂₀Ti₂₃, Ni₅₇Zr₂₀Ti₂₂Si₁, and Ni₅₇Zr₂₀Ti₂₀Si₃, respectively.     

New dielectric material system of La(Mg1/2Ti1/2)O3–Ca0.6La0.8/3TiO3 for microwave applications

The microstructure and microwave dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics system with ZnO additions (0.5 wt.%) investigated by the conventional solid-state route have been studied. Doping with ZnO (0.5 wt.%) can effectively promote the densification and the dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. 0.6La(Mg_1/2Ti_1/2)O₃–0.4Ca_0.6La_0.8/3TiO₃ ceramics with 0.5 wt.% ZnO addition possess a dielectric constant (_r) of 43.6, a Q × f value of 48,000 (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −1 ppm/°C sintering at 1475 °C. As the content of La(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 62,900 (GHz) for x = 0.8 is achieved at the sintering temperature 1475 °C. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Magnetic study of Ti-substituted NiFe2O4 ferrite

The Ni_1+xTi_xFe_2−2xO₄ (0 ≤ x ≤ 0.1) ferrite systems prepared by a semi-chemical route, have been studied by electron paramagnetic resonance (EPR) at X-band, Mössbauer spectroscopy and magnetization measurements at various temperatures. EPR spectra of these samples comprise generally a broad and asymmetric EPR signal. The variation of g_eff and peak-to-peak line width ΔH_pp, with Ti concentration and temperature are attributed to the variation of dipole–dipole interaction and the superexchange interaction. Mössbauer spectra comprise two sets of sextet attributed to Fe³⁺ at two distinct sites-A and -B. Ti⁴⁺ ions are concluded to occupy the octahedral B-sites. Magnetic moment is found to decrease with the increase of Ti⁴⁺ concentration. The effective magnetic field H_eff at the A-sites also follows a similar trend. The reason is attributed to the canted structure of spins in the Ti-doped samples. An anomalous behavior at x = 0.015 is observed in the properties studied here and some sort of phase change is believed to occur at 473 K in these ferrites.     

Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

On Synthesis and Magnetic Properties of Nd(Fe, Mo, Ti)12Zx (Z=N, H)

NdFe_10+xMo_2−2xTi_x compounds with 0≤x≤1.0 have been prepared by using the reduction–diffusion process with superfine precursors as starting materials. With increasing Ti-content, the intrinsic magnetic properties, such as the Curie temperature, saturation magnetization and magnetocrystalline field, are improved. The interstitial compounds NdFe_10+xMo_2−2xTi_xZ_y (Z=N, H) were obtained and exhibit significant enhancement of the intrinsic magnetic properties upon nitrogenation.     

Simulation on microstructure evolution and mechanical properties of Mg−Y alloys: Effect of trace Y

The influence of trace Y on the microstructure evolution and mechanical properties of Mg_100?xY_x (x=0.25, 0.75, 1.5, 3, 4, 5, at.%) alloys during solidification process was investigated via molecular dynamics (MD) simulations. The results show that the Mg_100?xY_x alloys are mainly characterized by a face-centered cubic (FCC) crystal structure; this is different from pure metal Mg, which exhibits a hexagonal close packed (HCP) structure at room temperature. Among these alloys, Mg_99.25Y_0.75 has a larger proportion of FCC cluster structures, with the highest fraction reaching 56.65%. As the content of the Y increases up to 5 at.% (Mg₉₅Y₅ alloy), the amount of amorphous structures increases. The mechanical properties of the Mg_100?xY_x alloys are closely related to their microstructures. The Mg_99.25Y_0.75 and Mg₉₇Y₃ alloys exhibit the highest yield strengths of 1.86 and 1.90 GPa, respectively. The deformation mechanism of the Mg?Y alloys is described at the atomic level, and it is found that a difference in the FCC proportion caused by different Y contents leads to distinct deformation mechanisms.     

Magnetic and structural properties of the chromium-based Mn1−xCdxCr2S4 thiospinel

The (Mn_1−xCd_x)Cr₂S₄ phases (0 ≤ x ≤ 0.6) have been synthesized from the corresponding elements at 1123 K. These samples were characterized by powder X-ray diffraction (XRD) and magnetic susceptibility. The (Mn_1−xCd_x)Cr₂S₄ compounds crystallize in the space group Fd-3m with cell parameters a = 10.101(6) Å, 10.139(3) Å, 10.165(2) Å, and 10.192(1) Å for x = 0, 0.2, 0.4 and 0.6, respectively. An overall ferrimagnetic behavior is observed for all samples. The ferromagnetic component increases rapidly when manganese is substituted by non-magnetic cadmium, as shown by ZFC/FC measurements. At the same time, the value of the magnetization M₅₀ at 50 kOe, deduced from M(H) loops, also increases with increasing cadmium content because the antiferromagnetic alignment between chromium and manganese spins is progressively lost, leading toward well aligned moments pointing into the same direction. These results are explained by a rearrangement of the chromium spins when Mn located at the tetrahedral sites, is substituted by Cd.     

Structural and magnetic susceptibility studies of samarium substituted magnesium–zinc ferrites

Polycrystalline soft ferrites Mg_1−x–Zn_x–Fe_2−y–Sm_y–O₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0; y = 0.0, 0.05 and 0.1) were prepared by usual ceramic method. The samples were characterized by X-ray diffraction and IR techniques. Magnetic properties have been studied from magnetization and (a)–(c) susceptibility measurements. The XRD patterns of all the samples reveal the formation of single-phase cubic spinel. The IR spectra show two strong absorption bands in the frequency range 300–800 cm⁻¹. The magnetization measurements exhibit the Neel's collinear ferrimagnetic behavior for x ≤ 0.2 and suggest non-collinear Y–K (Yaffet–Kittel) type magnetic ordering for x ≥ 0.4. The samples with x ≥ 0.8 are paramagnetic at and above the room temperature. Variation of ac susceptibility with temperature exhibit the single domain structure (SD) with x = 0.0 and multi-domain (MD) structure with x ≥ 0.2 on substitution of Zn²⁺ content. On substitution of Sm³⁺ content, the samples exhibit SD for x = 0.0, MD for x = 0.2 and MD to SP transition for x ≥ 0.4.     

Niobium–aluminum oxynitride prepared by ammonolysis of oxide precursor obtained through the citrate route

Oxynitrides in the (Nb_1−xAl_x)(O,N) quaternary system were prepared by ammonolysis of oxide precursor obtained through the citrate route. The products at 1000 °C were a mixture of Nb(N,O) and NbN_0.95 at the niobium end (x = 0) and amorphous Al(O,N) at the aluminum end (x = 1). A new cubic compound (A) appeared mixed with Nb(N,O) in the compositional range 0.1 ≤ x ≤ 0.4. Its almost pure product was obtained at x = 0.5. The X-ray diffraction pattern was rock salt type (Nb_0.56Al_0.44)(O_0.38N_0.37□₀₂₅) in F_m−3m with a = 0.43481(1) nm. The product showed superconductivity with T_c = 15 K. Its crystallinity was much improved and its superconducting volume fraction increased to 32% after its thermal annealing at 1100 °C in evacuated sealed tube. A second cubic compound (B), rock salt type Nb[(O,N)_0.85□_0.15] with a = 0.434 nm, was observed mixed with amorphous Al(O,N) in the as-prepared products of the range 0.6 ≤ x ≤ 0.9.