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.     

Crystal and magnetic structures of Laves phase compound NdCo2 in the temperature range between 9 and 300 K

The crystal and magnetic structures of the Laves phase compound NdCo₂ in the temperature range from 9 to 300 K are determined by Rietveld refinement technique, using high-resolution neutron powder diffraction data. The compound crystallizes in space group above the magnetic ordering temperature T_C (≈100 K), in space group I4₁/amd below T_C and in space group Imma below the tetragonal–orthorhombic structural/magnetic transitions at T_M ≈ 42 K. The assignment of the space groups to the crystal structures of NdCo₂ in different temperature ranges complies with the reported Mössbauer studies. Detailed information of the crystal and magnetic structures of NdCo₂ at different temperatures are reported.     

Magnetic structures of Zr6CoAs2-type Ho6−xErxMnBi2 solid solutions

Investigations were made by neutron diffraction on Zr₆CoAs₂-type (space group no. 189) Ho_6−xEr_xMnBi₂ solid solutions. The ferromagnetic ordering temperature decreases from Ho₆MnBi₂ (T_C = 200(6) K) to Er₆MnBi₂ (T_C = 100(4) K), whereas temperatures of ferrimagnetic (or antiferrimagnetic) ordering (T_Ferri and T_AFerri) are found to have non-monotonic dependences on the content of Er: T_Ferri = 58(4) K for Ho₆MnBi₂, T_Ferri = 162(4) K for Ho_4.5Er_1.5MnBi₂, T_Ferri = 150(4) K for Ho₃Er₃MnBi₂, T_AFerri = 78(4) K for Ho_1.5Er_4.5MnBi₂ and T_AFerri = 52(4) K for Er₆MnBi₂.

In these compounds, no local moment was detected on the manganese ion site, except for Ho_1.5Er_4.5MnBi₂ and Er₆MnBi₂ compounds. The manganese magnetic moments (μ_Mn) is 1.5μ_B and these are antiferromagnetically coupled with that of rare earth moments.     

Crystal structure and magnetic properties of the binary uranium–nickel alloy U11Ni16

The crystal structure of the U–Ni binary compound previously designated U₅Ni₇ was studied by X-ray single crystal diffraction showing that the exact formula is U₁₁Ni₁₆. Uranium and nickel atoms are distributed respectively on 5 and 6 Wyckoff positions of the trigonal space group R (n° 148), and the unit-cell dimensions in the hexagonal setting are: a=11.7786(4) Å, c=20.7485(8) Å. Magnetisation measurements indicate itinerant ferromagnetism below T_c=33 K for U₁₁Ni₁₆.     

The ternary system Al–Ni–Ti Part II: thermodynamic assessment and experimental investigation of polythermal phase equilibria

The Al–Ni–Ti phase diagram has been thermodynamically assessed and a consistent set of thermodynamic functions has been developed. The thermodynamic modeling is based on an experimental investigation of the phase equilibria in the composition range of 0.1x_Al0.7. Alloys were prepared by argon-arc or vacuum-electron beam melting of elemental powder blends. X-ray powder diffraction, metallography, SEM and EMPA-techniques were employed to analyze the samples in the as-cast state as well as after annealing at 800, 900 and 1000°C. The existence of the four ternary compounds, τ₁ to τ₄, has been confirmed, although homogeneity regions differ significantly from reports in the literature. The homogeneous phase, previously claimed at “Al₂₃Ni₂₆Ti₅₁”, is shown by high resolution microprobe and X-ray diffraction measurements to be an extremely fine-grained eutectic structure. The congruent melting behavior of τ₄=AlNi₂Ti is confirmed, but, in contrast to earlier reports, primary crystallization and congruent melting have been observed for τ₁=Al₁₃Ni₂Ti₅ and τ₃=Al₃NiTi₂. In contrast to earlier assessments, τ₁,τ₂ and τ₃ are experimentally found to be stable at 800, 900 and 1000°C. The thermodynamic modeling of the ternary phases τ₂ and τ₃ is done with simplified sublattice models, considering their crystal structure and homogeneity ranges. The sublattice model for τ₄ is taken from an earlier asessment of the nickel-rich ternary phase equilibria. The present assessment covers the entire composition range. An application to the solidification behavior of ternary alloys is also exemplified.     

Thermal stability and magnetic properties of Gd–Fe–Al bulk amorphous alloys

Gd₆₅Fe₂₀Al₁₅, Gd₆₅Fe₁₅Al₂₀ and Gd₇₀Fe₁₅Al₁₅ bulk amorphous alloys were produced by copper mold casting method with the maximum diameters of 2, 1 and 1 mm, respectively. The crystallization temperature (T_x) and melting temperature (T_m) of the Gd₆₅Fe₂₀Al₁₅ bulk amorphous alloy are 808 and 943 K, respectively. Accordingly, the temperature interval of T_m and T_x, ΔT_m (=T_m − T_x), is as small as 135 K and the reduced crystallization temperature (T_x/T_m) is as high as 0.86. The small ΔT_m and high T_x/T_m values are presumed to be the origin for the achievement of the high amorphous-forming ability of the Gd–Fe–Al bulk amorphous alloy. The Gd₆₅Fe₂₀Al₁₅, Gd₆₅Fe₁₅Al₂₀ and Gd₇₀Fe₁₅Al₁₅ bulk amorphous cylinders with a diameter of 1 mm exhibit superparamagnetism at room temperature, while the amorphous ribbon shows the paramagnetism at room temperature. Finally, the mechanical properties of Gd₆₅Fe₂₀Al₁₅ bulk amorphous alloys are investigated.     

The 773 K isothermal section of the Nd–Ni–V ternary system

The 773 K isothermal section of the phase diagram of Nd–Ni–V ternary system was investigated by X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS) techniques. There are in total 14 single-phase regions, 25 two-phase regions and 12 three-phase regions in the 773 K isothermal section. The maximum solid solubilities of V in Ni, NdNi₅, Nd₂Ni₇ and NdNi₂, is about 16.5 at.% V, 2.0 at.% V, 1.0 at.% V and 3.0 at.% V at 773 K, respectively, and that of Nd in Ni, Ni₃V, Ni₂V, Ni₂V₃, NiV₃ and V does not exceed 1 at.% Nd. No ternary compounds have been observed in this work.     

The ternary system Al–Ni–Ti Part I: Isothermal section at 900°C; Experimental investigation and thermodynamic calculation

Phase relations in the ternary system Al–Ni–Ti have been experimentally established for the isothermal section at 900°C for concentrations 0.1x_Al0.7. The investigation is based on X-ray powder diffraction, metallography, SEM and EMPA-techniques on about 40 ternary alloys, prepared by argon-arc or vacuum-electron beam melting of proper elemental powder blends. The existence of four ternary compounds, τ₁ to τ₄, is confirmed, however, in contrast to earlier investigations at significantly different compositions and with different shape of the homogeneity regions. This is particularly true for the phase regions of τ₃-Al₃NiTi₂ with the MgZn₂-type structure ranging from Al₃₀Ni₂₈Ti₄₂ (composition lowest in Al) to Al₅₀Ni₁₆Ti₃₄ (composition richest in Al) and for τ₂-Al₂NiTi. The complex atom site substitution mechanism in τ₃ changing from Ti/Al exchange at Al-poor compositions towards Ni/Al replacement for the Al-rich part was monitored in detail by quantitative X-ray powder diffraction techniques (Rietveld analyses). In contrast to earlier reports, claiming a two-phase region Ni{Al_xTi_1-x}₂+τ₃, we observed two closely adjoining three-phase equilibria: ₂-AlTi₃+Ni{Al_xTi_1-x}₂+ τ₄-AlNi₂Ti and ₂-AlTi₃+τ₃-Al₂NiTi₂+τ₄-AlNi₂Ti. The earlier reported “homogeneous phase at Al₂₃Ni₂₆Ti₅₁′” was shown by high resolution microprobe and X-ray diffraction measurements to be an extremely fine-grained eutectic. The experimental results are in fine agreement with the thermodynamic calculation.     

Crystallographic and magnetic properties of HfFe6Ge6-type REFe6Sn4Ge2 compounds (RE = Y, Gd–Er)

The REFe₆Sn₄Ge₂ (RE = Y, Gd–Er) compounds have been synthesized and studied by powder X-ray diffraction and magnetisation measurements. These compounds crystallize in the hexagonal HfFe₆Ge₆ structure although the parent ternary compounds REFe₆X₆ (X = Ge, Sn) display more complicated orthorhombic crystal structure. This evolution is discussed and interpreted on the basis of the relaxation of some RE–X contacts in the quaternary compounds. The iron sublattice order antiferromagnetically above room temperature (554 ≤ T_N ≤ 560 K) while the paramagnetic RE compounds display a second transition at low temperature (7.3 ≤ T_t ≤ 42.7 K). The magnetisation versus field curves display a metamagnetic behaviour at 4.2 K. The corresponding value of the magnetisation suggests a non-collinear ordering of the RE sublattice.     

Electrical transport in UNi0.5Sb2 single crystals

Single crystals of UNi₀.₅Sb₂ were investigated by means of Seebeck coefficient and Hall effect measurements in the temperature range 5–300 K. The results corroborated the occurrence of two magnetic phase transitions: from para- to antiferromagnetic state at T_N = 161.5 K and a spin-reorientation near T_t = 64 K. The first-order character of the latter feature was proved by studying in detail the electrical resistivity and the magnetic susceptibility of single-crystalline UNi₀.₅Sb₂ in the vicinity of T_t.     

Magnetic structure of the CeScSi-type RScGe compounds (R = Pr, Nd, Tb)

Subsequent magnetic transitions were recently reported for the CeScSi-type RScGe (R = rare earth) equiatomic intermetallic compounds. The compounds TbScGe and NdScGe order ferromagnetically at T_C = 216 K and T_C = 200 K, respectively whereas PrScGe orders antiferromagnetically at T_N = 140 K. In addition, PrScGe demonstrates two other magnetic transitions at T_C1 = 88 K and T_C2 = 80 K in an applied field of 5 kOe. An investigation by neutron diffraction has been now carried out on these phases in an attempt to solve the magnetic structures corresponding to each ordering, and in this article the results obtained are reported. Below the Curie point, the magnetic structure of TbScGe and NdScGe is collinear ferromagnetic. The magnetic moment of Tb atoms coincides with the Z-axis of CeScSi-type unit cell (M_Tb = 8.63μ_B at 2 K), whereas the magnetic moment of Nd atoms has the θ = 52(2)° angle with Z-axis (M_Nd = 3.53(2)μ_B at 2 K). Below the Néel temperature, T_N = 140 K the magnetic structure of PrScGe consists of antiferromagnetic (0 0 2) rare-earth double layers with magnetic moments of the rare earth atoms collinearly ordered. The magnetic moments of Pr atoms (M_Pr = 1.72(3)μ_B at 100 K) have the θ = 62(2)° angle with the Z-axis. Between T_C1 = 82 K and T_C2 = 62 K the conversion of the commensurate antiferromagnetic collinear type structure to the ferrimagnetic collinear type structure with propagation vector K = [0, 0, 1/2] was observed: the magnetic moments of Pr double layers became sine modulated along the Z-axis. Below T_C2 = 62 K the magnetic structure of PrScGe compound consists of ferrimagnetic (0 0 1/2) layers (amplitude of Pr magnetic moment M_Pr = 3.31(9)μ_B at 5 K).     

Effect of cooling rate on crystallization of metallic Zr–Cu–Ni glass

X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were employed to investigate the effect of cooling rate on crystallization behavior of metallic Zr₇₀Cu₂₀Ni₁₀ glass. It is found that all DSC traces of the metallic Zr₇₀Cu₂₀Ni₁₀ glasses under different cooling rates exhibit two exothermic peaks, indicating that the crystallization of metallic Zr₇₀Cu₂₀Ni₁₀ glass proceeds through a double-stage mode. In our previous studies, we have concluded that the first exothermic reaction mainly corresponds to the precipitation of the Zr₂Cu phase, and the second one is mainly due to the formation of nanoscale Zr₂Ni particles. It is observed that there exists a close relationship between the cooling rate and thermodynamic parameters of metallic Zr₇₀Cu₂₀Ni₁₀ glass, such as the onset crystallization temperature T_x, the first peak temperature T_p1 and the second one T_p2. The above three thermodynamic parameters reach a maximum when the surface velocity is 30 m/s. This effect is just similar to that of the Ni concentration, which has been discussed in our previous works. The activation energy for crystallization and the local Avrami exponent of metallic Zr–Cu–Ni glass under isothermal annealing conditions also exhibit a similar tendency with the cooling rate.     

Oxidation behavior of ceramic coatings on Ti–6Al–4V by micro-plasma oxidation

Compound ceramic coatings prepared on Ti–6Al–4V alloy by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO₂ solution were oxidized under different temperature in air. The phase composition and surface morphology of the coatings before and after oxidation were investigated by X-ray diffractometry and scanning electron microscopy, respectively. Meantime, the weight gains and the high temperature oxidation characteristics of the coated samples were investigated. The results show that the coatings prepared by MPO were composed of a large amount of Al₂TiO₅ and a little -Al₂O₃ and rutile TiO₂. And the oxidation process of the coated samples included the decomposition of the Al₂TiO₅ in the coating, the oxidation of the substrate and the changes of the coating structure. After high temperature oxidation, the increase of -Al₂O₃ in the coating was due to the decomposition of Al₂TiO₅, whereas the increase of rutile TiO₂ in the coating was attributable to both the decomposition of Al₂TiO₅ and the oxidation of the Ti substrate. The main crystalline of the coatings became rutile TiO₂ after the oxidation of 1000 °C for 1 h. The decomposition of Al₂TiO₅ in the coating occurred at 900 and 1000 °C, and its half decomposition time was less than 1 h at 1000 °C. Increasing oxidation temperature or extending oxidation time, the weight gains of coated samples was increased to different extent. However, the weigh gains of the coated samples was much lower than that of the substrate, so the ceramic coatings improved the oxidation resistance of Ti alloy greatly under the experimental conditions.     

Magnetic phase transition in Ti-doped ErCo2 alloys

The homogeneity range of U₂Co_17−xSi_x system with the hexagonal Th₂Ni₁₇-type crystal structure extends from x = 1 to 3.4. The variation of the magnetic properties within the homogeneity range was studied on single crystals. All the compounds are ferromagnetic, M_s and T_C decrease monotonously with increasing Si content. The strongly modified magnetic anisotropy of U₂Co_17−xSi_x, as compared to isostructural Lu₂Co_17−xSi_x with the non-magnetic Lu, points to a magnetic state of U up to x = 3.0. The U contribution to K₁ decreases with increasing Si content and vanishes at x = 3.4 that can be treated as a transition from magnetic to non-magnetic state of U. Spin reorientation was observed with varying temperature in compounds with x ≤ 3 due to a competition of the U and Co sublattices anisotropies which occurs as two second-order phase transitions of the “plane–cone” and the “cone–axis” type.     

Effects of replacing Ni by Co on the crystallization behaviors of Al–Ni–La amorphous alloys

Effects of replacing Ni by Co on the crystallization behaviors of three Al–Ni–La amorphous alloys, i.e. Al₈₅Ni₉La₆, Al₈₆Ni₉La₅ and Al₈₇Ni₈La₅ were investigated by X-ray diffraction and differential scanning calorimeter. The results show that the glass-forming ability decreases when Ni is replaced by excessive Co. Meanwhile replacing Ni by Co improves the thermal stability, enlarges the supercooled liquid region ΔT_x and promotes the precipitation of the metastable phase(s) as the primary phase. The apparent activation energy E_a1 of the first reaction changes complicatedly during the replacement and is strongly dependent on the type of the primary phase, i.e. diffusion of atoms.     

The Er–Ni–B system

The phase diagram of the ternary Er–Ni–B system at 1070 K has been built using the results of X-ray diffraction. As a result of our research the existence of twelve ternary borides has been confirmed, the composition of the boride ErNi₇B₃ (space group I4₁/amd, own structure type) has been refined and three new compounds have been found, namely: ErNi_6.5B₃ (cubic structure), Er_0.917Ni_4.09B (space group P6/mmm, own structure type), ErNi₈B₂ (unknown structure). The two latter borides exist only in as-cast samples.     

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).     

Magnetic entropy change in polycrystalline La1−xKxMnO3 perovskites

Polycrystalline samples of potassium doped lanthanum manganites having nanometric crystallite size have been synthesized by pyrophoric method. The Curie temperature (T_C) of the prepared samples is found to be strongly dependent on K content and spans between 260 and 309 K. Close to T_C, large change in magnetic entropy has been observed in all the samples. The maximum magnetic entropy change observed for samples with different concentration of K, exhibits a linear dependence with the applied magnetic field. Adiabatic temperature change at T_C at 1 T also increases with K doping and attains a maximum of 2.1 K for La_0.85K_0.15MnO₃. Estimated relative cooling power of La_1−xK_xMnO₃ compounds is nearly one-third of pure Gd. In addition to the tuneability of T_C between 260 and 310 K, higher chemical stability, lower eddy current heating and inexpensive preparation technique; the magnetic entropy change in La_0.85K_0.15MnO₃ compound at 1 T magnetic field is found to be 3.00 J/kg K and is 89% to that known for the prototype magnetic refrigerant (pure Gd). Our result on magnetocaloric properties suggests that La_1−xK_xMnO₃ compounds are attractive as a possible refrigerant for near room temperature magnetic refrigeration.     

Effect of Pr and Co substitution on magnetic properties and magnetic entropy changes in LaFe13−xSix compounds

Effect of Pr and Co substitution on magnetic properties and magnetic entropy changes in the cubic NaZn₁₃-type compound LaFe_11.2Si_1.8 has been experimentally investigated. Replacing 30 at.% La with Pr leads to a decrease of Curie temperature from 216 to 203 K, and drives the magnetic transition from second-order to first-order. As a result, magnetic entropy change, under a field change of 0–5 T, increases from 13.7 to 19.4 J/kg K. Substitution of Co for Fe in La₀₇Pr_0.3Fe_11.2Si_1.8 can adjust T_C to around room temperature. A magnetic entropy change of 9.3 J/kg K at T_C = 290 K for a field change from 0 to 5 T is obtained in La₀₇Pr_0.3Fe_10.4Co_0.8Si_1.8. A reversible variation of magnetization with temperature and magnetic field is observed in the present compound, which is highly desired by the magnetic refrigeration application.     

Microstructure and mechanical properties of mechanically alloyed and spark plasma sintered amorphous–nanocrystalline Al65Cu20Ti15 intermetallic matrix composite reinforced with TiO2 nanoparticles

Multiphase Al₆₅Cu₂₀Ti₁₅ intermetallic alloy matrix composite, dispersed with 10 wt.% of TiO₂ nanoparticles, has been processed by mechanical alloying, followed by spark plasma sintering under pressure in the temperature range of 623–873 K. Differential scanning calorimetry and X-ray diffraction suggest that equilibrium crystalline phases evolve from the amorphous or intermediate crystalline phases. Transmission electron microscopy shows that the composite sintered at 873 K has partially amorphous microstructure, with dispersion of equilibrium, crystalline, intermetallic precipitates of Al₅CuTi₂, Al₃Ti, and Al₂Cu of 25–50 nm size, besides the TiO₂. The composite sintered at 873 K exhibits little porosity, hardness of 5.6 GPa, indentation fracture toughness in the range of 3.1–4.2 MPa√m, and compressive strength of 1.1 GPa. Indentation crack deflection by TiO₂ particle aggregates causes increase in fracture resistance with crack length, and suggests R-curve type behaviour. The study provides guidelines for processing high strength amorphous–nanocrystalline intermetallic composites based on the Al–Cu–Ti ternary system.