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.     

添加Si/Ti对粉末冶金FiNiCrCo高熵合金物理力学和化学性能的影响（英文）

用粉末冶金法制备FiNiCrCoSi_x和FiNiCrCoTi_x高熵合金(HEAs)。其中x为0、0.3%、0.6%和0.9%(质量分数)。所有合金中均形成均匀分布的固溶体。与FiNiCrCo高熵合金相比,加入Si和Ti后,合金的密度和硬度提高,研究合金在不同载荷下的磨损率。结果表明,含0.3%Si和0.9%Ti的高熵合金磨损率最低。用XRD、SEM和EDX研究HEAs的相组或、晶粒尺寸和显微组织。通过H₂SO₄、HNO₃和HCl溶液浸泡实验,研究Si和Ti含量对烧结态FiNiCrCoSi_x和FiNiCrCoTi_x HEAs腐蚀行为和表面形貌的影响。在样品表面观察到不同尺寸的均匀腐蚀和局部点烛,且FiNiCrCoSi_0.3合金具有更小,更少的蚀坑,和优异的显微组织     

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.     

Effect of Cr on Microstructure and Properties of a Series of AlTiCr x FeCoNiCu High-Entropy Alloys

A series of AlTiCr _x FeCoNiCu (x: molar ratio, x = 0.5, 1.0, 1.5, 2.0, 2.5) high-entropy alloys (HEAs) were prepared by vacuum arc furnace. These alloys consist of α-phase, β-phase, and γ-phase. These phases are solid solutions. The structure of α-phase and γ-phase is face-centered cubic structure and that of β-phase is body-centered cubic (BCC) structure. There are four typical cast organizations in these alloys such as petal organization (α-phase), chrysanthemum organization (α-phase + β-phase), dendrite (β-phase), and inter-dendrite (γ-phase). The solidification mode of these alloys is affected by Chromium. If γ-phase is not considered, AlTiCr_0.5FeCoNiCu and AlTiCrFeCoNiCu belong to hypoeutectic alloys; AlTiCr_1.5FeCoNiCu, AlTiCr_2.0FeCoNiCu, and AlTiCr_2.5FeCoNiCu belong to hypereutectic alloys. The cast organizations of these alloys consist of pro-eutectic phase and eutectic structure (α + β). Compact eutectic structure and a certain amount of fine β-phase with uniform distribution are useful to improve the microhardness of the HEAs. More γ-phase and the microstructure with similar volume ratio values of α-phase and β-phase improve the compressive strength and toughness of these alloys. The compressive fracture of the series of AlTiCr _x FeCoNiCu HEAs shows brittle characteristics, suggesting that these HEAs are brittle materials.     

Aluminum Alloying Effects on Lattice Types, Microstructures, and Mechanical Behavior of High-Entropy Alloys Systems

The crystal lattice type is one of the dominant factors for controlling the mechanical behavior of high-entropy alloys (HEAs). For example, the yield strength at room temperature varies from 300 MPa for the face-centered-cubic (fcc) structured alloys, such as the CoCrCuFeNiTi _x system, to about 3,000 MPa for the body-centered-cubic (bcc) structured alloys, such as the AlCoCrFeNiTi _x system. The values of Vickers hardness range from 100 to 900, depending on lattice types and microstructures. As in conventional alloys with one or two principal elements, the addition of minor alloying elements to HEAs can further alter their mechanical properties, such as strength, plasticity, hardness, etc. Excessive alloying may even result in the change of lattice types of HEAs. In this report, we first review alloying effects on lattice types and properties of HEAs in five Al-containing HEA systems: Al _x CoCrCuFeNi, Al _x CoCrFeNi, Al _x CrFe_1.5MnNi_0.5, Al _x CoCrFeNiTi, and Al _x CrCuFeNi₂. It is found that Al acts as a strong bcc stabilizer, and its addition enhances the strength of the alloy at the cost of reduced ductility. The origins of such effects are then qualitatively discussed from the viewpoints of lattice-strain energies and electronic bonds. Quantification of the interaction between Al and 3d transition metals in fcc, bcc, and intermetallic compounds is illustrated in the thermodynamic modeling using the CALculation of PHAse Diagram method.     

Effect of Gd content on microstructure and dynamic mechanical properties of solution-treated Mg−xGd−3Y−0.5Zr alloy

The effect of Gd content ranging from 6.5 wt.% to 8.5 wt.% on microstructure evolution and dynamic mechanical behavior of Mg?xGd?3Y?0.5Zr alloys was investigated by optical microscopy, X-ray diffraction, scanning electron microscopy and split Hopkinson pressure bar. The microstructure of as-cast Mg?xGd?3Y?0.5Zr alloys indicates that the addition of Gd can promote grain refinement in the casting. Due to the rapid cooling rate during solidification, a large amount of non-equilibrium eutectic phase Mg₂₄(Gd,Y)₅ appears at the grain boundary of as-cast Mg?xGd?3Y?0.5Zr alloys. After solution treatment at 520 °C for 6 h, the Mg₂₄(Gd,Y)₅ phase dissolves into the matrix, and the rare earth hydrides (REH) phase appears. The stress?strain curves validate that the solution-treated Mg?xGd?3Y?0.5Zr alloys with optimal Gd contents maintain excellent dynamic properties at different strain rates. It was concluded that the variation of Gd content and the agglomeration of residual REH particles and dynamically precipitated fine particles are key factors affecting dynamic mechanical properties of Mg?xGd?3Y?0.5Zr alloys.     

Effect of the aluminium content of AlxCrFe1.5MnNi0.5 high-entropy alloys on the corrosion behaviour in aqueous environments

High-entropy alloys (HEAs) are a newly developed family of multi-component alloys. The potentiodynamic polarization and electrochemical impedance spectroscopy of the Al_xCrFe_1.5MnNi_0.5 alloys, obtained in H₂SO₄ and NaCl solutions, clearly revealed that the corrosion resistance increases as the concentration of aluminium decreases. The Al_xCrFe_1.5MnNi_0.5 alloys exhibited a wide passive region, which extended >1000 mV in acidic environments. The Nyquist plots of the Al-containing alloys had two capacitive loops, which represented the electrical double layer and the adsorptive layer. SEM micrographs revealed that the general and pitting corrosion susceptibility of the HEAs increased as the amount of aluminium in the alloy increased.     

High-Entropy Alloys with a Hexagonal Close-Packed Structure Designed by Equi-Atomic Alloy Strategy and Binary Phase Diagrams

High-entropy alloys (HEAs) with an atomic arrangement of a hexagonal close-packed (hcp) structure were found in YGdTbDyLu and GdTbDyTmLu alloys as a nearly single hcp phase. The equi-atomic alloy design for HEAs assisted by binary phase diagrams started with selecting constituent elements with the hcp structure at room temperature by permitting allotropic transformation at a high temperature. The binary phase diagrams comprising the elements thus selected were carefully examined for the characteristics of miscibility in both liquid and solid phases as well as in both solids due to allotropic transformation. The miscibility in interest was considerably narrow enough to prevent segregation from taking place during casting around the equi-atomic composition. The alloy design eventually gave candidates of quinary equi-atomic alloys comprising heavy lanthanides principally. The XRD analysis revealed that YGdTbDyLu and GdTbDyTmLu alloys thus designed are formed into the hcp structure in a nearly single phase. It was found that these YGdTbDyLu and GdTbDyTmLu HEAs with an hcp structure have delta parameter (δ) values of 1.4 and 1.6, respectively, and mixing enthalpy (ΔH _mix) = 0 kJ/mol for both alloys. These alloys were consistently plotted in zone S for disordered HEAs in a δ-ΔH _mix diagram reported by Zhang et al. (Adv Eng Mater 10:534, 2008). The value of valence electron concentration of the alloys was evaluated to be 3 as the first report for HEAs with an hcp structure. The finding of HEAs with the hcp structure is significant in that HEAs have been extended to covering all three simple metallic crystalline structures ultimately followed by the body- and face-centered cubic (bcc and fcc) phases and to all four simple solid solutions that contain the glassy phase from high-entropy bulk metallic glasses.     

Reassessment of Ni-Al and Ni-Fe-Al solidus temperatures

Solidus temperatures of the B2 NiAl phase have been determined by high-temperature differential thermal analysis for binary melt compositions Ni_xAl_100?x (45<x<57) and for ternary alloys Fe_yNi_50?yAl₅₀ (0≤y≤50). It was shown that the melting temperature of the stoichiometric Ni₅₀Al₅₀ phase is 1681 °C, which is 43 K higher than some literature data. The solidus line at the Ni-rich side of the Ni-Al phase diagram exhibits a steeper slope than that reported previously. Substituting Fe for Ni, the decrease of solidus temperature along the isoplethal section with 50 at.% Al of the ternary Ni-Fe-Al phase diagram exhibits a steep initial slope of ?13 K/at.% Fe for small Fe-fractions, which changes into a nearly linear decrease with an average slope of ?8.5 K/at.% Fe.     

Effects of annealing at 800 and 1000 °C on phase precipitates and hardness of Al7Cr20FexNi73−x alloys

The effects of Fe content on the microstructure, phase constituents and microhardness of the as-cast, 800 °C- or 1000 °C-annealed Al₇Cr₂₀Fe_xNi_73?x (x=13?66) alloys were investigated. Not all these alloys are composed of the single FCC phase. The BCC and B2 phases are found. It is confirmed that the BCC phase in the Al₇Cr₂₀Fe₆₆Ni₇ alloy is transformed from the FCC phase at about 900 °C during cooling. While in the 800 °C-annealed Al₇Cr₂₀Fe₆₀Ni₁₃ alloy, the FCC phase is stable and the hardness decreases. After annealing at 1000 °C, for the precipitation of the B2 particles, the Al content in the FCC phase decreases, which results in decreasing of the alloy hardness. Moreover, after annealing at 800 °C, a small amount of Al-rich B2 particles precipitate at the phase boundary and some nanocrystal BCC phase precipitates in the FCC matrix, which increases the hardness of the Al₇Cr₂₀Fe_xNi_73?x (x=41?49) alloys. These results will help to the composition design and processing design of the Al?Cr?Fe?Ni based high-entropy alloys.     

Structure and properties of titanium-free maraging alloys

The changes in the structure, phase composition, and physicomechanical properties of titanium-free maraging alloys based on the Fe-15–23% Ni-(Co, Mo, V) system after heating to the single-phase α field and two-phase α + γ field have been studied. It has been established that the strengthening of N15K10M5F5-type maraging alloys is caused by the precipitation of fine particles (20–50 nm) of intermetallic phases such as the fcc Ni₃(Mo, V) phase and the Fe₂(Mo, V) Laves phase (in the N23K9M6 alloys, with the formation of the Ni₃Mo and Fe₂Mo phases). It has been shown that the two-step aging of the N15K10M5F5 alloy leads to an additional strengthening by 200–250 MPa and provides the achievement of the ultimate tensile strength σ_u=2400?2500 MPa. The high-strength N15K10M5F5 maraging alloys are obtained with two levels of the coercive force H _c: (a) semihard maraging alloys with H _c=20?50 Oe and σ_u=2100?2400 MPa; and (b) hard magnetic maraging alloys with H _c=180?230 Oe and σ_u=1500?1800 MPa. The high-strength titanium-free N15K10M5F5 and N23K9M6 maraging alloys possess many properties characteristic of structural, elastic, and magnetic alloys and are thus multifunctional materials. These alloys can be used for advanced high-tech articles and as high-strength magnetic materials.     

Effect of deviations of composition from the quasi-binary section TiNi-TiCu on structural and phase transformations in rapidly quenched alloys

Methods of X-ray diffraction, transmission and scanning electron microscopy, and selected-area electron diffraction (SAED) have been used to study the phase and elemental composition and structure of alloys close to the stoichiometric Ti₅0Ni₂₅Cu₂₅ alloy. Based on the method of rapid quenching of the melt (free-jet melt spinning), alloys of the quasi-binary TiNi-TiCu section have been prepared, which in the initial as-cast state exhibited the thermoelastic martensitic transformations B ₂ ? B ₁₉ and related shape-memory effects. The chemical composition of the Ti_{50 + x} Ni₂₅Cu_{25 ? x} alloys was varied by changing titanium and copper concentrations within x ≤ ±1 at % (from Ti₄₉Ni₂₅Cu₂₆ to Ti₅₁Ni₂₅Cu₂₄). It has been established that quenching at a cooling rate equal to 10⁶ K/s leads to the amorphization of all the alloys under consideration. Heating to 723 K and higher leads to the devitrification of the alloy with the formation of a nanocrystalline or submicrocrystalline structure of the B2 austenite. The mechanical properties of these alloys have been measured in the initial amorphous state and in the polycrystalline martensitic state. It has been shown that, depending on the extent of the deviations of the alloy composition from the stoichiometry, which cause the decomposition of the alloys in the process of nanocrystallization, regular changes are observed in their mechanical properties and in the shape-memory effects. The kinetics of the processes of the devitrification of the alloys, as well of the forward and reverse martensitic transformations, have been studied, their characteristic temperatures have been determined, and a diagram of the dependence of the characteristic temperatures on the chemical composition of the alloys has been constructed.     

Solid State Interaction in Ni-Mo-B System During Mechanical Alloying and Annealing

This work presents the results of a study of Ni_87?x Mo _x B₁₃ alloys (x?=?7, 10 and 14?at.%), which were obtained by mechanical alloying (MA) of elemental powder mixtures in a MAPF-2M high-energy planetary ball mill. The x-ray diffraction analysis and differential scanning calorimetry measurements were used. The single-phase fcc solid solutions of Mo and B in Ni were formed by MA of Ni-Mo-B mixtures of various compositions for 6-8?h. The coherent domain sizes of solid solutions calculated from the x-ray peak widths were 12-14?nm. The exothermic effects on the DSC curves, which corresponded to the phase transformations of supersaturated Ni(Mo,B) solid solutions, were observed during heating of the synthesized alloys. After heating to 700?°C, the alloys contained a fcc Ni(Mo) phase and a metastable hexagonal MoB₄ phase. Thermodynamically stable phase composition of Ni₈₀Mo₇B₁₃ and Ni₇₇Mo₁₀B₁₃ alloys, containing three phases: fcc Ni (Mo), Ni₂₁Mo₂B₆ with cubic lattice and Ni₃B with orthorhombic lattice, was reached after the isothermal annealing at 1000?°C. The ratio between the amounts of these phases in the alloys corresponds to their location in a three-phase area of the Ni-Mo-B equilibrium phase diagram.     

In-situ layered double hydroxides on Mg−Ca alloy: Role of calcium in magnesium alloy

Mg?Al layered double hydroxides (LDHs), produced on cast Mg?xCa (x=0.5, 0.8, 2.0, wt.%) alloys by an in-situ growth method, showed good corrosion resistance compared to the bare magnesium substrate. The influence mechanism of the second phase (Mg₂Ca) on LDHs production was investigated. Increasing Ca content increased the amount of Mg₂Ca, decreasing the grain size and the corrosion rate of the alloys. The increased amount of the second phase particles and the grain refinement promoted the growth of LDHs, and thus led to the decreasing of corrosion rate of the Mg?xCa alloys with LDHs. A higher Mg₂Ca amount resulted in forming fluffy LDHs. Due to the dual effects of the second phase (Mg₂Ca) for LDHs growth and microgalvanic corrosion, LDHs/Mg?0.8Ca showed the lowest corrosion rate.     

Magnetic structure and phase composition of microinhomogeneous PdMn x Fe1 − x alloys

Mössbauer analysis of ternary PdMn _x Fe_{1 ? x} alloys in the range of concentrational transition from a ferromagnetic PdFe (F ₁) (T _C = 725 K) to an antiferromagnetic PdMn (A) (T _N = 815 K) phase has been carried out at temperatures T ～ 80 and 295 K. An estimation of the relative volumes of the ferromagnetic and antiferromagnetic ordered phases in the molecular-field approximation was performed via calculation of the magnetic susceptibility of the alloy with x = 0.5; an analysis of the microstructure of the alloy with x = 0.45 was performed using the Bitter-figures technique. For the alloys with extreme concentrations, Mössbauer spectra have been obtained in two different forms, i.e., a doublet with H _hf < 50 kOe for the antiferromagnetic alloys with x > 0.8 and a sextet with H _hf ～ 350 kOe for the ferromagnetic alloys with x < 0.2. In the intermediate concentration range, a wide spectrum of hyperfine fields 0 < H _hf < 350 kOe has been observed, which is due to a microinhomogeneous multiphase state.     

Effects of Mg content on microstructure and mechanical properties of low Zn-containing Al−xMg−3Zn−1Cu cast alloys

Effects of Mg content on the microstructure and mechanical properties of low Zn-containing Al?xMg? 3Zn?1Cu cast alloys (x=3?5, wt.%) were investigated. As Mg content increased in the as-cast alloys, the grains were refined due to enhanced growth restriction, and the formation of η-Mg(AlZnCu)₂ and S-Al₂CuMg phases was inhibited while the formation of T-Mg₃₂(AlZnCu)₄₉ phase was promoted when Mg content exceeded 4 wt.%. The increase of Mg content encumbered the solution kinetics by increasing the size of eutectic phase but accelerated and enhanced the age-hardening through expediting precipitation kinetics and elevating the number density of the precipitates. As Mg content increased, the yield strength and tensile strength of the as-cast, solution-treated and peak-aged alloys were severally improved, while the elongation of the alloys decreased. The tensile strength and elongation of the peak-aged Al?5Mg?3Zn?1Cu alloy exceed 500 MPa and 5%, respectively. Precipitation strengthening implemented by T′ precipitates is the predominant strengthening mechanism in the peak-aged alloys and is enhanced by increasing Mg content.     

A quinary Ti–Zr–Hf–Be–Cu high entropy bulk metallic glass with a critical size of 12 mm

A quinary Ti₂₀Zr₂₀Hf₂₀Be₂₀Cu₂₀ high entropy bulk metallic glass (HE-BMG), with a critical diameter (D_c) of 12 mm—the largest size in the reported quinary high entropy alloys (HEAs), has been successfully prepared by copper mold casing. This novel HE-BMG possesses a supercooled liquid region ΔT (=T_x − T_g) of 78 K, indicating a better thermal stability than those of other HE-BMGs. In addition, the HE-BMG exhibits a relatively good compressive plasticity (2.2 ± 0.1%) among the HE-BMGs. The newly developed HE-BMG may offer insights for the indepth understanding of the fundamental issues associated with the glass formation and the unique structure-property relationship when combining the features of HEAs and BMGs together.     

固溶态和挤压态Mg-xLi-3Al-2Zn-0.5Y(x=4,8,12)合金的显微组织和腐蚀行为

研究固溶态和挤压态Mg-xLi-3Al-2Zn-0.5Y(x=4,8,12,质量分数,%)合金的显微组织和腐蚀行为。结果表明,当锂含量从4%增加到12%,合金基体由α-Mg单相转变为α-Mg+β-Li双相,再转变为β-Li单相。Mg-4Li-3Al-2Zn-0.5Y和Mg-12Li-3Al-2Zn-0.5Y合金具有晶间腐蚀和点蚀的混合腐蚀特征,前者与沿晶界析出的AlLi相有关,后者与第二相与基体之间的高电位差有关。挤压态合金的耐蚀性优于固溶态合金。挤压态Mg-8Li-3Al-2Zn-0.5Y合金具有最低腐蚀速率(P_W=(0.63±0.26)mm/a),主要归因于该合金的第二相分布更均匀、通过牺牲β-Li相形成的保护性α-Mg相和相对完整的更均匀分布的氧化膜。     

Magnetic-field-induced martensitic transformations in Ni47 − x Mn42 + x In11 alloys (with 0 ≤ x ≤ 2)

Magnetic properties and martensitic transformations in the Ni_{47 ? x} Mn_{42 + x} In₁₁ alloys (with 0 ≤ x ≤ 2) have been studied. The magnetic-field-induced martensitic transformation was found to be observed for all the alloys. The critical temperatures of magnetic and structural phase transformations, temperature dependences of spontaneous magnetization of austenite and martensite, and the critical field, at which the martensitic transformation occurs, have been determined based on magnetic measurements performed for the alloys under study. The spontaneous magnetization of the alloys in the martensitic state has been shown to be lower than that in the magnetic-field-induced austenitic state by a factor of six.     

Phase transformations during deformation of Fe-Ni and Fe-Mn alloys produced by mechanical alloying

Compositions of Fe_{(100 ? x)}Mn _x (x = 10 and 12 at. %) and Fe_{(100 ? y)}Ni _y (y = 18 and 20 at. %) were produced by combined mechanical alloying of pure-metal powders and annealed in the austenitic field. After annealing and cooling to room temperature, the alloys had a single-phase austenitic structure. During deformation, the γ phase partially transforms into the α ₂ phase (and/or ? phase in Fe-Mn alloys). The phase composition of the alloys after deformation depends on the amount of alloying elements and the predeformation annealing regime. The amount of martensite in the structure of a bulk alloy obtained by powder compacting grows proportionally to the degree of deformation of the sample.