Influence of zirconium addition on the microstructure,thermodynamic stability,thermal stability and mechanical properties of mechanical alloyed spark plasma sintered (MA-SPS) FeCoCrNi high entropy alloy

ABSTRACT

Equiatomic FeCoCrNi (Zr₀) and non-equiatomic FeCoCrNiZr_0.4 (Zr_0.4) high-entropy alloys (HEAs) were synthesised by mechanical alloying and spark plasma sintering. XRD analysis verified the formation of FCC and BCC solid solution phases in both alloys after 30?h of ball milling. While the SPS FeCoCrNi alloy contains both FCC and BCC solid solution phases, the FeCoCrNiZr_0.4 presents an FCC solid solution. The thermodynamic analysis showed that FeCoCrNiZr_0.4 is more stable with respect to the FeCoCrNi alloy. The phase stability of FeCoCrNiZr_0.4 was revealed up to ～800°C. The shear strength and hardness of the FeCoCrNi HEA improved with Zr addition. Failure analysis of the shear punch tested samples revealed a ductile fracture with dimple structure for FeCoCrNi and a brittle fracture with a smooth featureless surface for FeCoCrNiZr_0.4.     

Effect of vanadium addition on the microstructure, hardness, and wear resistance of Al0.5CoCrCuFeNi high-entropy alloy

The authors studied the effect of vanadium addition on the microstructure and properties of Al_0.5CoCrCuFeNi high-entropy alloy. The microstructure of Al_0.5CoCrCuFeNiV _x (x=0 to 2.0 in molar ratio) alloys was investigated by scanning electron microscopy, energy dispersive spectrometry, and X-ray diffraction. With little vanadium addition, the alloys are composed of a simple fcc solid-solution structure. As the vanadium content reaches 0.4, a BCC structure appears with spinodal decomposition and envelops the FCC dendrites. From x=0.4 to 1.0, the volume fraction of bcc structure phase increases with the vanadium content increase. When x=1.0, fcc dendrites become completely replaced by bcc dendrites. Needle-like σ-phase forms in bcc spinodal structure and increases from x=0.6 to 1.0 but disappears from x=1.2 to 2.0. The hardness and wear resistance of the alloys were measured and explained with the evolution of the microstructure. The hardness values of the alloys increase when the vanadium content increases from 0.4 to 1.0 and peak (640 HV) at a vanadium content of 1.0. The wear resistance increases by around 20 pct as the content of vanadium increases from x=0.6 to 1.2 and levels off beyond x=1.2. The optimal vanadium addition is between x=1.0 and 1.2. Compared with the previous investigation of Al_0.5CoCrCuFeNi alloy, the vanadium addition to the alloy promotes the alloy properties.     

Influence of Cr removal on the microstructure and mechanical behaviour of a high-entropy Al0.8Ti0.2CoNiFeCr alloy fabricated by powder metallurgy

We report a systematic study on the influence of Cr removal on the microstructure and mechanical behaviour of an ultra-fine grained (UFG) high-entropy alloy (HEA), Al_0.8Ti_0.2CoNiFeCr, fabricated via spark plasma sintering (SPS) of mechanically alloyed (MA’ed) powders from constituent elemental powders. The MA’ed Al_0.8Ti_0.2CoNiFeCr powders consist principally of a BCC phase (～85 vol.-%) with a small amount of FCC phase (～15 vol.-%), whereas the MA’ed Al_0.8Ti_0.2CoNiFe powders present similar phases to those in the MA’ed Al_0.8Ti_0.2CoNiFeCr powders. Interestingly, the SPS processed UFG Al_0.8Ti_0.2CoNiFeCr alloy contains mostly an FCC phase (～78 vol.-%) and some BCC phase (～22 vol.-%); in contrast, the SPS processed UFG Al_0.8Ti_0.2CoNiFe alloy consists of a slightly enriched BCC phase (～53 vol.-%) and an FCC phase (～47 vol.-%). In addition, the SPS processed Al_0.8Ti_0.2CoNiFe alloy exhibits slightly higher yield strength, compressive strength and hardness but lower plasticity than those of the SPS processed Al_0.8Ti_0.2CoNiFeCr alloy.

Special theme block on high entropy alloys, guest edited by Paula Alvaredo Olmos, Universidad Carlos III de Madrid, Spain, and Sheng Guo, Chalmers University, Gothenburg, Sweden.     

Mechanical performance of the Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoCrCuFeNi high-entropy alloy system with multiprincipal elements

The Al _x CoCrCuFeNi alloys with multiprincipal elements (x=the aluminum content in molar ratio, from 0 to 3.0) were synthesized using a well-developed arc-melting and casting method, and their mechanical properties were investigated. These alloys exhibited promising mechanical properties, including excellent elevated-temperature strength and good wear resistance. With the addition of aluminum from x=0 to 3.0, the hardness of the alloys increased from HV 133 to 655, mainly attributed to the increased portion of strong bcc phase to ductile fcc phase, both of which were strengthened by the solid solution of aluminum atoms and the precipitation of nanophases. The alloys exhibited superior high-temperature strengths up to 800 °C, among which the Al_0.5CoCrCuFeNi alloy, especially, had enhanced plasticity and a large strain-hardening capacity. Moreover, the wear resistance of these alloys was similar to that of ferrous alloys at the same hardness level, while the alloys with lower hardness exhibited relatively higher resistance because of their large strain-hardening capacity.     

Processing and characterisation of nano crystalline AlCoCrCuFeTix high-entropy alloy

In this work multi-component equiatomic and non-equiatomic AlCoCrCuFeTi_x hexanary high-entropy alloys (HEA) was synthesised through mechanical alloying. The prepared powder was sintered via spark plasma sintering. Influence of alloying element variation in the multi-component system was studied in terms of phase formation and crystal structure by using Thermo-Calc and X-ray diffraction characterization technique (XRD). Particle morphology and chemical analysis studies were carried out through scanning electron microscopy along with Electron Dispersive X-ray Spectroscopy. The crystal structure and nano crystallinity of the hexanary system were recognised using transmission electron microscope (TEM and Selected Area Electron Diffraction [SAED]) while the formation of a solid solution was also studied and discussed. From the XRD and TEM characterisation of 20?h in, milled powders and sintered samples, it was confirmed that the developed HEA system forms a single solid solution BCC phase. The sintered alloy exhibits 97% relative density and an average hardness of 590?VHN.

Special theme block on high entropy alloys, guest edited by Paula Alvaredo Olmos, Universidad Carlos III de Madrid, Spain, and Sheng Guo, Chalmers University, Gothenburg, Sweden.     

Microstructure and properties of CrMnFeCoNi high-entropy alloy prepared by mechanical alloying and spark plasma sintering

The equiatomic ratio CrMnFeCoNi high entropy alloy (HEA) was prepared by mechanical alloying (MA) and spark plasma sintering. This paper reports the behaviour of MA, the phase formation, microstructure and mechanical properties of CrMnFeCoNi HEA. With the increase of milling time, solid solution with single FCC phase was gradually formed. The single FCC phase remained as matrix after SPS at 1373?K and 50?MPa. Ultrafine-grained microstructure and good mechanical properties were obtained: At room temperature, the as-sintered bulks exhibit an excellent combination of high compressive strength (2390?MPa) and high fracture strain (47%).     

Formation and Stability of Equiatomic and Nonequiatomic Nanocrystalline CuNiCoZnAlTi High-Entropy Alloys by Mechanical Alloying

Nanocrystalline equiatomic high-entropy alloys (HEAs) have been synthesized by mechanical alloying in the Cu-Ni-Co-Zn-Al-Ti system from the binary CuNi alloy to the hexanary CuNiCoZnAlTi alloy. An attempt also has been made to find the influence of nonequiatomic compositions on the HEA formation by varying the Cu content up to 50 at. pct (Cu _x NiCoZnAlTi; x = 0, 8.33, 33.33, 49.98 at. pct). The phase formation and stability of mechanically alloyed powder at an elevated temperature (1073 K [800 °C] for 1 hour) were studied. The nanocrystalline equiatomic Cu-Ni-Co-Zn-Al-Ti alloys have a face-centered cubic (fcc) structure up to quinary compositions and have a body-centered cubic (bcc) structure in a hexanary alloy. In nonequiatomic alloys, bcc is the dominating phase in the alloys containing 0 and 8.33 at. pct of Cu, and the fcc phase was observed in alloys with 33.33 and 49.98 at. pct of Cu. The Vicker’s bulk hardness and compressive strength of the equiatomic nanocrystalline hexanary CuNiCoZnAlTi HEA after hot isostatic pressing is 8.79 GPa, and the compressive strength is 2.76 GPa. The hardness of these HEAs is higher than most commercial hard facing alloys (e.g., Stellite, which is 4.94 GPa).     

粉末冶金法制备CrFeNiCuMoCo高熵合金的组织与性能

利用粉末冶金法制备CrFeNiCuMoCo高熵合金,用带有能谱的扫描电子显微镜(SEM/EDS)、X射线衍射仪、显微/维氏硬度计、电化学工作站、材料试验机等对CrFeNiCuMoCo高熵合金组织结构进行分析并测试其硬度、耐蚀性和压缩性能.结果表明:CrFeNiCuMoCo高熵合金组织形貌简单;物相主要由FCC和BCC两相组成,Mo元素和Cu元素在合金中存在偏析现象;合金的耐蚀性能优异,与304不锈钢相比,自腐蚀电流密度减小1个数量级;组元间原子半径的差异导致较大的晶格畸变,阻碍位错的运动,使得固溶强化效应增强;Mo元素起到细化晶粒作用,使该合金具有较高的硬度和抗压强度,合金硬度为485 HV,抗压强度约为1 385MPa;断裂类型为脆性解理断裂.     

铸态共晶高熵合金的研究进展

铸态共晶高熵合金在室温下的力学性能受到其化学成分、相组成和微观组织形貌的影响,是选用恰当的共晶高熵合金以适应于复杂服役环境的重要判据.文中通过调研近年来共晶高熵合金的相关文献,概述了共晶高熵合金的研究现状,按化学元素和共晶组织的相组成特点对共晶高熵合金进行了分类,即主要由FCC相+B2/BCC相组成的AlCoCrFeN...     

Microstructure characterization of Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoCrCuFeNi high-entropy alloy system with multiprincipal elements

A new approach for the design of alloy systems with multiprincipal elements is presented in this research. The Al _x CoCrCuFeNi alloys with different aluminum contents (i.e., x values in molar ratio, x=0 to 3.0) were synthesized using a well-developed arc-melting and casting method. These alloys possessed simple fcc/bcc structures, and their phase diagram was predicted by microstructure characterization and differential thermal analyses. With little aluminum addition, the alloys were composed of a simple fcc solid-solution structure. As the aluminum content reached x=0.8, a bcc structure appeared and constructed with mixed fcc and bcc eutectic phases. Spinodal decomposition occurred further on when the aluminum contents were higher than x=1.0, leading to the formation of modulated plate structures. A single ordered bcc structure was obtained for aluminum contents larger than x=2.8. The effects of high mixing entropy and sluggish cooperative diffusion enhance the formation of simple solid-solution phases and submicronic structures with nanoprecipitates in the alloys with multiprincipal elements rather than intermetallic compounds.     

Microstructure and Performance Characterization of a Novel Cobalt High-Entropy Alloy

In this research, a novel high-entropy alloy (HEA) having the equiatomic Co–Cr–Fe–Ni composition with high W (> 18 wt pct), low C (< 1 wt pct) and minor Mo contents is created by combining the features of HEA and Stellite alloy, which is designated as HE6. The bulk specimens of HE6 are fabricated from the alloy powder via spark plasma sintering (SPS) or plasma transferred arc (PTA) welding process. The microstructural analyses using SEM/EDX/XRD reveal that HE6 has a microstructure consisting of diverse carbides and intermetallics embedded in a solid solution matrix which is constituted with multiple element FCC structures. The hardness and dry-sliding wear tests show that HE6 does not perform as well as Stellite 6, which is the benchmark of Stellite alloys. Under the electrochemical and immersion corrosion tests in hydrochloric acid and sulfuric acid, HE6 displays passivation ability by forming protective Cr oxide films, but localized corrosion (pitting) can occur when the oxide films are broken. HE6 exhibits lower corrosion rates under the immersion test in hydrochloric acid and sulfuric acid for the longer testing duration (72 hours), compared to Stellite 6, and also shows a nearly stable corrosion rate with testing duration extended, indicating better repairing ability of the oxide films.

     

Effect of Ni on Microstructure and Mechanical Properties of CrMnFeCoNi High Entropy Alloy

The effect of Ni content on microstructure and mechanical properties of the CrMnFeCoNi high entropy alloy (HEA) has been studied. The Ni content varied from 0 to 20 at% in the composition (CrMnFeMn)_100?xNi_x, where x?=?0, 2.5, 5, 10, 15, and 20 at%. The alloys were synthesized by vacuum arc melting and the microstructure as well as hardness of the as-cast alloys were studied. Alloys with low Ni content (x?≤?2.5%) consists of a two-phase microstructure of dendritic and inter-dendritic regions with fcc (matrix) and tetragonal (sigma) crystal structure, respectively. When the Ni content is 5 at%, two-phase structure with fcc (matrix) and bcc (secondary phase) is observed, with the addition of Mn-rich inclusions that are present in the entire matrix. Alloys with higher Ni content (x?≥?10, at%) exhibit a single phase of fcc structure. Hardness of the HEAs decreases from 320 to 120 Hv with increase in Ni content, and the high hardness of these alloys with low Ni content is due to the mixture of both fcc and hard tetragonal (sigma) phases.

     

Comparison between ultrafine-grained WC–Co and WC–HEA-cemented carbides

The AlFeCoNiCrTi high-entropy alloy (HEA) powders were prepared by high-energy ball milling. The ultrafine-grained WC–HEA and WC–Co-cemented carbides were fabricated through planetary ball milling and heat-pressure sintering. The microstructures and properties of the sintered alloys were compared using scanning electron microscope, X-ray diffraction, mechanical property testing and electrochemical testing. It has been shown that the AlFeCoNiCrTi HEA can be used as a binder for the ultrafine-grained WC-based cemented carbide. The WC–HEA-cemented carbide has better performances than the WC–Co-cemented carbide. The suitable contents of HEA can inhibit the WC grain growth and improve the mechanical properties and corrosion resistance of cemented carbides.     

Influence of alloying elements and grain refiner on microstructure,mechanical and wear properties of Mg-Al-Zn alloys

In the present investigation, the effects of alloying elements (Sn, Pb) and grain refiner (Ag, Zr) on microstructure, mechanical and wear properties of as-cast Mg-Al-Zn alloys were studied. The alloys were prepared through melting-casting route under a protective atmosphere and cast into a permanent mould. The microstructure of the base alloy consisted of α-Mg, Mg₁₇Al₁₂ continuous eutectic phase at the grain boundary and Mg-Zn phase was distributed within the grains. Addition of Sn and Pb suppressed the formation of continuous Mg₁₇Al₁₂ eutectic phase and formed Pb enriched Mg₂Sn precipitates at the grain boundary as well as inside the grain. The Ag and Zr addition to Mg-Al-Zn-Sn-Pb alloy suppressed the Mg₁₇Al₁₂ phase formation and refined the grains leading to improve mechanical properties. Addition of Sn, Pb and grain refiner (Ag, Zr) significantly enhanced the tensile strength and elongation but reduced hardness. The Ag addition imparted best tensile properties, where ultimate tensile strength (UTS) and elongation are 205?MPa and 8.0%, respectively. The fracture surfaces were examined under SEM which revealed cleavage facets and dimple formation. Therefore, the cleavage fracture and dimple rupture were considered as the dominant fracture mechanisms for developed Mg alloys. The cumulative volume loss of Mg alloys increased with sliding distance and applied load. The coefficient of friction decreased with sliding distance. The microscopic observation, analysis of the wear surface and coefficient of friction revealed that the wear mechanism of developed Mg alloys changes from abrasion oxidation to delamination wear.     

Effect of microstructure on the strength,toughness, and stress-corrosion cracking susceptibility of a metastable beta titanium alloy (Ti−11.5Mo−6Zr−4.5Sn)

This paper describes the influence of mictrostructure on the mechanical properties of the alloy Ti?11.5Mo?6Zr?4.5Sn. The phase transformations are similar to those that occur in binary Ti?Mo alloys containing 10 to 12 pct Mo. Thus, the β phase can be retained by quenching from above 1400°F. The β phase deforms in a complex manner, including mechanical twinning, and is characterized by low strength, high ductility, and high toughness. The ω phase, which also forms on quenching, is stable at temperatures up to 800°F. Yield strengths of up to 220 ksi have been measured in (β+ω) structures, the strength level being dependent on the size and volume fraction of the ω phase. In contrast, fracture toughness reaches a minimum value of }20 ksi \(\sqrt {in} \) when the ω particle size ≥100Å. (β+α) structures show good combinations of yield strength and fracture toughness. Unfortunately, the best combinations are susceptible to stress-corrosion cracking in aqueous solutions containing halide ions.     

Crystallographic and electrochemical characteristics of La0.7Mg0.3Ni5.5? x (Al0.5Mo0.5) x ( x =0 to 0.8) hydrogen storage alloys

The structure, hydrogen storage property, and electrochemical characteristics of the La_0.7Mg_0.3Ni_5.5−x (Al_0.5Mo_0.5) _x (x=0, 0.2, 0.4, 0.6, 0.8) hydrogen storage alloys have been investigated systematically. It has been found by X-ray powder diffraction and Rietveld analysis that the alloys are multiphase and consist of impurity Ni phase and two main crystallographic phases, namely, the La(La, Mg)₂Ni₉ phase and the LaNi₅ phase, and the lattice parameters and the cell volumes of both the La(La, Mg)₂Ni₉ phase and the LaNi₅ phase increase with increasing Al and Mo content in the alloys. The P-C isotherm curves indicated that the hydrogen storage capacity of the alloy first increases and then decreases with increasing x, and the equilibrium pressure decreases with increasing x. The electrochemical measurements show that the maximum discharge capacity first increases from 298.5 (x=0) to 328.3 mAh/g (x=0.6) and then decreases to 304.7 mAh/g (x=0.8). The high rate dischargeability (HRD) of the alloy electrodes increases lineally from 65.4 pct (x=0) to 86.6 pct (x=0.8) at the discharge current density of 1200 mA/g. Moreover, the exchange current density of the alloy electrodes also increases monotonously with increasing x by the linear polarization curves. The hydrogen diffusion coefficient in the alloy bulk, D, increases with increasing Al and Mo content and thus enhances the low-temperature dischargeability (LTD) of the alloy electrodes.     

Effect of Cobalt on Phase Formation, Microstructure, and Mechanical Properties of Cu50?xCoxZr50 (x?=?2, 5, 10, 20?at.?pct) Alloys

In this work, the effect of cobalt on the phase formation and mechanical properties of rapidly solidified Cu_50?xCo_xZr₅₀ (x?=?2, 5, 10, and 20?at.?pct) alloys was investigated. CuZr martensite forms in the case of low Co contents (x?=?2 and 5?at.?pct), while in the alloys with 10 and 20?at.?pct Co, the B2 phase is stable even at room temperature. The deformation behavior of the rods under compressive loading depends strongly on the microstructure and, thus, on the alloy composition. Cobalt affects the fracture strength of the as-cast samples, and deformation is accompanied by two yield stresses for high Co-content alloys, which undergo deformation-induced martensitic transformation.     

Effect of copper on magnetostriction and mechanical properties of TbDyFe alloys

The intrinsic brittleness of the TbDyFe alloy significantly decreases its mach inability and applications.This paper aims to improve the toughness of TbDyFe alloy by adding Cu. Various alloys of the type(Tb_(0.3)Dy_(0.7))_(0.37)Fe_(0.63-χ)Cu_χ(χ=0, 0,01.0.03, 0.05, 0.08, 0.1) were fabricated by an arc melting furnace under a high purity argon atmosphere. The microstructure, magnetostrictive properties and mechanical performance were studied systematically. The results show that the (Tb,Dy)Cu phase forms in these alloys upon the addition of Cu. Correspondingly, their toughness improves, attributed to the formation of a (Tb,Dy)Cu phase. Compared to the Cu-free alloy, the fracture toughness (Kic) increases 2-3 times with increasing Cu content. However, the magnetostriction performance of these alloys declines with Cu addition, due to the low-magnetic performance of the (Tb,Dy)Cu phase at room temperature. Compared with other alloys, the alloy with the addition of 1at%Cu shows the best compromise between the saturation magnetostriction and fracture toughness.     

含Cu高熵合金的组织结构和力学性能分析

高熵合金（HEAs）是一种由5种或5种以上元素以接近等原子比的方式混合而成的一种新型合金。HEAs的概念为开发具有独特性能的先进材料提供了新的途径,这是传统的基于单一主导元素的微合金化方法无法实现的。由于Cu元素与HEAs中其他元素的混合焓均为正值,因而更容易偏聚形成富Cu的面心立方（fcc）结构。本文主要总结了合金成分、制备方法对含Cu HEAs组织结构的影响规律以及含Cu HEAs的热稳定性。例如Al的添加会使CoCrCuFeNi合金从fcc单相转变为fcc+bcc的双相结构,而Ni含量的增加则会将AlCoCrCuNi的多相组织转变为单相fcc结构。与传统铸造工艺相比,选区激光熔化和喷溅急冷等具有极高的冷却速度,限制了元素的扩散,因而制备而成的AlCoCuFeNi和AlCoCrCuFeNi合金均是bcc结构。组织结构的改变会进一步影响含Cu HEAs力学性能,因而本文也探讨了合金成分、制备工艺和服役温度与力学性能的关系。例如,V的添加可以提高合金的强度,以先进制备方法如选区激光熔化或激光粉末熔融得到的合金具有优于铸造合金的力学性能。     

The effect of deformation-induced transformation on the fracture toughness of commercial titanium alloys

The effect of deformation-induced transformation of metastableβ phase on the ductility and toughness of four commercial titanium alloys was investigated. Tensile tests, Charpy impact tests, and both static and dynamic fracture toughness tests were carried out at temperatures between 77 and 473 K on four titanium alloys containing metastableβ phase. Deformation-inducedα″ (orthorhombic martensite) was observed in an (α + β)-type Ti-6Al-2Sn-4Zr-6Mo alloy. The dynamic fracture toughness of this alloy increased considerably at 223 K compared to those at other temperatures. In another (α + β)-type Ti-6A1-4V alloy, the static fracture toughness at 123 K and the dynamic fracture toughness at 223 K were increased considerably by the presence of deformation-induced martensite compared to those at other temperatures. The strength increased as the temperature decreased in this alloy. An abnormal elongation of aβ-type alloy, Ti-15V-3Al-3Sn-3Cr, at 123 K was attributed to the mechanical twinning of theβ phase. However, the effect of deformation-induced transformation on the fracture toughness of Ti-3Al-8V-6Cr-4Mo-4Zr alloy was not observed. Formerly Visiting Associate Professor, Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University, Pittsburgh, PA. Formerly with the Department of Production Systems Engineering, Toyohashi University of Technology.