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.     

Electron microscopy and X-ray diffraction studies of rapidly quenched Zr---Ni and Hf---Ni ribbons with about 90 at.% Ni

The structure of melt-spun ribbons of the alloys Zr₉Ni₉₁, Zr₁₀Ni₉₀ and Hf₁₁Ni₈₉ was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ribbons of the Zr₉Ni₉₁ and Zr₁₀Ni₉₀ alloys prepared at a high cooling rate (ribbon thickness d=11 μm) were characterized by an amorphous matrix with a few per cent of quenched-in crystallites. The ribbon of the Hf₁₁Ni₈₉ alloy prepared with the same thickness (i.e. at the same cooling rate) exhibited a nanocrystalline grain structure of the HfNi₅ phase. Thicker ribbons of the Zr₉Ni₉₁ alloy (d=17–22 μm), for which the quench rate was correspondingly lower, were obtained as a b.c.c. Ni(Zr) solid solution phase with a grain size of nearly 1 μm. A high resolution (HR) TEM study of one of the Zr₉Ni₉₁ crystalline ribbons revealed a fine structure of the interior of the crystallites which can be attributed to an ordering on the Zr sublattice over distances of several nanometres within the b.c.c. grains.     

The effect of Hf substitution for Zr on glass forming ability and magnetic property of FeCoZrMoBAlY bulk metallic glasses

Bulk metallic glasses (BMGs) Fe₆₁Co₆Zr_8−xHf_xMo₇B₁₅Al₁Y₂ (x = 0–8) have been produced by copper mold casting technique using industrial raw materials. The effect of substitution of Hf for Zr on the glass forming ability (GFA) and the magnetic property has been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and superconducting quantum interference device (SQUID). It was found that the substitution of an appropriate amount of Hf for Zr can improve the GFA of the base alloy Fe₆₁Co₆Zr₈Mo₇B₁₅Al₁Y₂, as demonstrated by the increase in reduced glass transition temperature T_rg (=T_g/T_l) and GFA parameters of γ (=T_x/T_g + T_l) and δ (=T_x/T_l − T_g). The Fe₆₁Co₆Zr₅Hf₃Mo₇B₁₅Al₁Y₂ alloy exhibits the highest GFA with the largest T_rg (0.612) and δ (1.633), and can cast a fully amorphous rod in 3 mm diameter. The substitution of Hf for Zr also enhances the magnetic properties, as verified by the increase in saturation magnetization (M_s) in the alloy of Fe₆₁Co₆Zr₃Hf₅Mo₇B₁₅Al₁Y₂, whose M_s is approximately 1.5 times higher than that of the base alloy (x = 0) at room temperature. Finally, the effect of the substitution of Hf for Zr on glass forming ability and magnetic properties is discussed.     

Densification, mechanical properties and wear behavior of WC–VC–Co–Al hardmetals

The effect of VC and Al additions on the sintering behavior, hardness, toughness, elastic properties and wear characteristics of WC–10 wt% Co has been studied. The amount of VC in the compositions varied up to 18 wt% and the aluminum contents was fixed at 2 wt% with the purpose to promote the in situ formation of the CoAl intermetallic phase. The specimens were prepared by vacuum sintering in the 1350–1500 °C range during 1 h. The sintered samples densification improved both with the temperature and VC contents up to 13 wt%. The heterogeneous microstructure consisting of WC, (W, V)C_1−x and intermetallic Al₅Co₂ phase indicated that the expected reactive sintering induced by the Co and Al could not be properly controlled due to the large Al particle size used, resulting in isolated aluminum enriched pools. Vickers hardness and toughness followed an antagonistic behavior with values ranging from 12.8–17.5 GPa and 7.7–10.5 MPa m^1/2, respectively. The sliding wear performance evaluation showed that friction decreases with VC addition but it could not be established a tendency for the wear rate coefficient though values obtained allow to consider these experimental compositions as promising wear resistant materials.     

Deformation Behaviors of an Additive-Manufactured Ni32Co30Cr10Fe10Al18 Eutectic High Entropy Alloy at Ambient and Elevated Temperatures

Eutectic high-entropy alloys (EHEAs) that have superior formability are attractive for direct laser deposition technology. In this study, a regular-shaped bulk Ni₃₂Co₃₀Cr₁₀Fe₁₀Al₁₈ EHEA without apparent pores and micro-cracks was successfully fabricated by direct laser deposition. The as-deposited alloy showed a high tensile strength of 1.3 GPa with a ductility of 35% at ambient temperature and a tensile strength of 320 MPa at 760 °C. The deformation mechanisms of the as-deposited alloy at ambient and elevated temperatures were investigated by coupling the in-situ tensile test with a scanning electron microscope. It is revealed that the excellent combination of strength and ductility originated from the synergic effects of the FCC and B2 phases in eutectic lamellae. And the generation of cracks along phase boundaries restricted its high-temperature strength above 760 °C.     

表面毛化WC-Co硬质合金与铝的真空扩散连接

采用机械方法对WC-Co硬质合金表面进行焊前毛化加工,然后采用BNi2钎料对毛化后的硬质合金表面进行预涂覆处理,最终利用毛化凸台在铝中的压入及界面元素的扩散反应实现WC-Co硬质合金与铝的真空扩散连接. 结果表明,接头界面结构为:Al/Al₃Ni+Al₃Ni₂+Al₅Co₂/Co-Ni(s.s)/W-Co-Ni/WC-Co. 随着预涂覆温度的升高,W-Co-Ni化合物相的体积增大,界面由平齐向不规则演变;随着扩散温度的提高,Al₃Ni+Al₃Ni₂+Al₅Co₂层厚度增加. 当工艺参数增加时,接头抗剪强度呈现出先升高后降低的变化趋势,特别是当预涂覆温度为1 050 ℃,扩散连接温度为575 ℃,保温时间为90 min时,接头室温抗剪强度达到最大值51 MPa,明显高于未毛化接头的抗剪强度.     

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.     

Ta1/0Cr18Ni9薄板储能焊熔核高熵化机理

针对钽与钢之间物化性质差异大,焊接时易产生脆性金属间化合物而导致熔焊接头性能低下及裂纹等问题,按照熔核金属高熵化技术思路,利用基于密度泛函理论的热力学第一性原理设计出新型中间层合金Ta₂₀Fe₂₀Ni₂₀Cr₂₀Co₂₀,结合熔合比得到适用于钽/钢储能焊中间层合金成分为Ta₇Ni₃₂Cr₁₉Co₄₂. 采用真空电弧炉熔制纽扣合金锭,继而使用单辊急冷法制备出中间合金箔材,将其用于Ta1/0Cr18Ni9薄板的储能焊连接. 结果表明,在储能焊条件下,Ta1/Ta₇Ni₃₂Cr₁₉Co₄₂/0Cr18Ni9搭接接头形成形貌规则、完整,长径约0.8 mm的扁球形熔核,熔核整体向钢侧发生了偏移. 熔核组织由简单的FCC固溶体组成,无金属间化合物析出,具有典型的高熵合金特征,实现了熔核金属高熵化. 在焊接电压1 000 V,电容500 μF,电极压力30 N下,Ta1/Ta₇Ni₃₂Cr₁₉Co₄₂/0Cr18Ni9储能焊接头平均强度可达到395 MPa.     

La–Mg–Ni ternary hydrogen storage alloys with Ce2Ni7-type and Gd2Co7-type structure as negative electrodes for Ni/Mh batteries

Hydrogen strorage alloys with formula La_1.5Mg_0.5Ni₇ were prepared by induction melting followed by different annealing treatments (1073, 1123 and 1173 K) for 24 h. The alloy composition, alloy microstructure and electrochemical properties were investigated, respectively. The results showed that the multi-phase structure of as-cast alloy was converted into a double-phase structure (Gd₂Co₇-type phase and Ce₂Ni₇-type phase) through annealing treatments. Mg atoms were mainly located in Laves unit of Gd₂Co₇-type unit cell and Ce₂Ni₇-type unit cell. The electrochemical capacity of alloy electrodes after annealing treatment could be up to 390 mAh/g. The cyclic stability of alloy electrodes was significantly improved by annealing treatments; After 150 charge/discharge cycles, the capacity retention ratio of alloy annealed at 1173 K was the highest (81.9%). The high rate dischargeability of alloy electrodes was also improved due to annealing treatment.     

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.     

Influence of Sintering Temperature on Microstructure and Mechanical Properties of Al_2O_3 Ceramic via 3D Stereolithography

In this work,aluminum oxide(Al_2O_3) ceramic samples were fabricated by 3D stereolithography printing.Printing process was followed by debinding and sintering.In addition,the effect of sintering temperature on micro structure and properties was investigated.Flexure strength was observed to increase with increasing sintering temperature due to fewer pores,fewer defects and stronger grain boundary bonding of samples at higher sintering temperatures.Maximum flexure strength of 138.5 MPa was obtained when sintering temperature was 150℃.Furthermore,the shrinkage along length direction decreased with the decreasing sintering temperature until reaching minimum value of 1.02% after sintering at 1200℃.After sintering at 1280℃,flexure strength was 24.0 MPa and the shrinkage along length direction was 2.1%,which meets demands of ceramic core.     

Powder processing and densification behaviour of alumina–high zirconia nanocomposites using chloride precursors

Al₂O₃–ZrO₂ composites having nominal equal volume fraction of Al₂O₃ and ZrO₂ were prepared from gel-precipitated powder, precipitated powder and washed precipitated powder. These different processing routes affected the crystallization temperature of the amorphous powder as well as the phase evolution of Al₂O₃ and ZrO₂ during calcination. The agglomerate size was largest for gel-precipitated powder (30 μm) and it was smallest for washed precipitated powder (19 μm). While gel-precipitated powder produce hard agglomerated powder (P_j = 110 MPa), washed precipitated powder produce soft agglomerates with low agglomeration strength (P_j = 70 MPa). Thus, washed precipitated powder could sinter to a high density at lower sintering temperature. The bending strength exhibits a semi logarithmic relationship with porosity. The hardness shows an increasing trend with sintering temperature.     

Effect of overall composition on thermally induced solid-state transformations in thick EB PVD Al/Ni multilayers

Multilayered Ni/Al samples 20–70 μm thick of different average stoichiometries were prepared by electron-beam physical vapour deposition technique. The periodicity in the multilayers varied between 0.2 μm and 0.8 μm. The course of the solid-state transformations initiated by heating the samples at a constant rate has been studied. Intermetallic Al₃Ni was found to be the first phase to form upon heating of all samples studied. Further reactions were dependent on the average composition of the sample so that Al–Ni compounds increasingly richer in Ni formed as the nickel content increased. In general, the phases Al₃Ni, Al₃Ni₂, AlNi, and AlNi₃ have been observed upon heating the samples to 600 °C. The phases were more likely to form in succession rather than to grow simultaneously.     

Two-phase microstructure in Pr-(Fe, Co, Ni)-B sintered magnets

A search was carried out for a two-phase sintered magnet comprising Pr₂TM₁₄B and PrTM, where TM stands for Fe, Co and Ni. Specimens were prepared by a powder metallurgical method using alloys with compositions Pr₁₇(Fe_0.6Co_0.3Ni_0.1)₈₃−_χB_χ (x = 4, 5 and 6). X-Ray diffraction and scanning electron microscopy—energy-dispersive X-ray studies have revealed that two-phase magnets are realized for Pr₁₇(Fe_0.6Co_0.3Ni_0.1)₇₈B₅. The microstructures of these sintered magnets are characterized by Pr₂TM₁₄B grains surrounded by an intergranular Ni-rich PrTM phase whose thickness is less than about 3 μ.     

Formation of Al–Y oxide during processing of γ-TiAl

While processing Y₂O₃ dispersed γ-TiAl, Y₂O₃ particles which dissolved during hot isostatic pressing (HIP’ing) were found to precipitate during the heat treatment in the form of a mixed Al–Y oxide. To understand the chemical reaction that occurs between Y₂O₃ and γ-TiAl during the heat treatment cycle, a powder mixture comprising of γ-TiAl and 10 wt.% Y₂O₃ was mechanically alloyed (MA’d) for 8 h and the milled powder was subjected to differential thermal analysis (DTA) at 1150 °C prior to analyzing it using X-ray diffraction technique. The present study clearly demonstrates that aluminum in the combined form either as γ-TiAl or Al₂O₃ reacts in a similar manner with Y₂O₃ when milled and heat treated at 1150 °C. In either case there is formation of Al₂Y₄O₉ (2Y₂O₃.Al₂O₃).     

Synthesis and characterization of doped LaCrO3 perovskite prepared by EDTA–citrate complexing method

The La_0.85Sr_0.15Cr_0.95Ni_0.02Co_0.02O₃ (LSC) interconnect materials for solid oxide fuel cells (SOFCs) were synthesized by EDTA–citrate complexing method. Thermal decomposition behavior of the gel, phase formation and morphology of LSC powders were characterized by thermogravimetry/differential thermal (DSC/TG) analysis, X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. It appeared that lower pH value (pH 4.9) of the precursor solution resulted in a transient liquid phase, SrCrO₄, in the calcined LSC powder. The sintering characteristics, electrical conductivity and thermal expansion properties of sintered bars were investigated. La_0.85Sr_0.15Cr_0.95Ni_0.02Co_0.02O₃ prepared in the condition of pH 4.9 showed an electrical conductivity of 15.6 S cm⁻¹ at 800 °C and a thermal expansion coefficient (TEC) of 10.8 × 10⁻⁶ K⁻¹ (20–900 °C), which is suitable for use as interconnect materials for SOFCs.     

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.     

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.     

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.     

Metastable bcc Ni produced by rod milling and chemical leaching

Nanocrystalline Al₆₀Ni₄₀ and Ni have been obtained by rod milling Al and Ni powder mixtures and chemical leaching Al atoms from the rod-milled Al₆₀Ni₄₀, respectively. The rod-milled alloy powders retained their bcc structure after being treated at room temperature and at 85 °C with a 25–30 wt.% KOH solution. The leached powders are very active and easily explode when they come into contact with air. The leached powders were transformed to a ferromagnetic fcc phase at high temperature. On cooling of the specimen from 600 °C, spontaneous magnetization M sharply increased at about 350 °C, indicating that the bcc phase was transformed to an fcc phase. It has been confirmed that the leaching temperature and annealing temperature and KOH concentration have a considerable effect on structural and magnetic properties.