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.

     

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。     

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.     

Design of quaternary Ir-Nb-Ni-Al refractory superalloys

We propose a method for developing new quaternary Ir-Nb-Ni-Al refractory superalloys for ultra-high-temperature uses, by mixing two types of binary alloys, Ir-20 at. pct Nb and Ni-16.8 at. pct Al, which contain fcc/L1₂ two-phase coherent structures. For alloys of various Ir-Nb/Ni-Al compositions, we analyzed the microstructure and measured the compressive strengths. Phase analysis indicated that three-phase equilibria—fcc, Ir₃Nb-L1₂, and Ni₃Al-L1₂—existed in Ir-5Nb-62.4Ni-12.6Al (at. pct) (alloy A), Ir-10Nb-41.6Ni-8.4Al (at. pct) (alloy B), and Ir-15Nb-20.8Ni-4.2Al (at. pct) (alloy C) at 1400 °C; at 1300 °C, three phase equilibria—fcc, Ir₃Nb, and Ni₃Al—existed in alloys A and C and four-phase equilibria—fcc, Ir₃Nb, Ni₃Al, and IrAl-B2—existed in alloy B. The fcc/L1₂ coherent structure was examined by using transmission electron microscopy (TEM). At a temperature of 1200 °C, the compressive strength of these quaternary alloys was between 130 and 350 MPa, which was higher than that of commercial Ni-based superalloys, such as MarM247 (50 MPa), and lower than that of Ir-based binary alloys (500 MPa). Compared to Ir-based alloys, the compressive strain of these quaternary alloys was greatly improved. The potential of the quaternary alloys for ultra-high-temperature use is also discussed.     

Solidification of undercooled Fe-Cr-Ni alloys: Part I. Thermal behavior

Solidification of undercooled Fe-Cr-Ni alloys was studied by high-speed pyrometry during and after recalescence of levitated, gas-cooled droplets. Alloys were of 70 wt pct Fe, with Cr varying from 15 to 19.7 wt pct, balance was Ni. Undercoolings were up to about 300 K. Alloys of Cr content less than that of the eutectic (18.1 wt pct) have face-centered cubic (fee) (austenite) as their equilibrium primary phase, and alloys of higher Cr content have body-centered cubic (bcc) (ferrite) as their equilibrium primary phase. However, except at low undercoolings in the hypoeutectic alloys, all samples solidified with bcc as the primary phase; the bcc then transformed to fcc during initial recalescence for the lower Cr contents or during subsequent cooling for the higher Cr contents. The bcc-to-fcc transformation, whether in the semisolid or solid state, was detected by a second recalescence. In the hypoeutectic alloys, the growth of primary metastable bcc apparently results from preferred nucleation of bcc. The subsequent nucleation of fcc may occur at bcc/bcc grain boundaries. Formerly Graduate Student, Department of Materials Science and Engineering, Massachusetts Institute of Technology     

Magnetic contribution to the interdiffusion coefficients in bcc (<Emphasis Type="Italic">α</Emphasis>) and fcc (<Emphasis Type="Italic">γ</Emphasis>) Fe-Ni alloys

The interdiffusion coefficients in bcc (α) and fcc (γ) Fe-Ni alloys below their Curie temperatures have been calculated based on the magnetic contribution to the free energy for interdiffusion. The free energy for interdiffusion due to magnetic ordering in bcc Fe-Ni alloys is positive. The calculated interdiffusion coefficients in bcc Fe-Ni alloys fit the experimental data quite well. In fcc Fe-Ni alloys, the magnetic contribution to interdiffusion depends on both temperature and composition and is abnormal for Ni compositions in the Invar region. The free energy of vacancy formation is positive and the free energy of vacancy migration is negative, due to the effect of magnetic ordering. The interdiffusion coefficient in the ferromagnetic phase is lower than that extrapolated from the paramagnetic phase for Ni compositions of 50 at. pct and greater and is higher than that extrapolated from the paramagnetic phase for Ni compositions of 40 at. pct and lower.     

Effect of the primary phase on grain coarsening in undercooled Fe-Co alloys

Fe-Co alloy melts with Co contents of 10, 30, and 60 at. pct were undercooled to investigate the dependence of the primary phase on grain coarsening. A pronounced characteristic is that the metastable fcc phase in the Fe-10 at. pct Co alloy and the metastable bcc phase in the Fe-30 at. pct Co alloy will primarily nucleate when undercoolings of the melts are larger than the critical undercoolings for the formation of metastable phases in both alloys. No metastable bcc phase can be observed in the Fe-60 at. pct Co alloy, even when solidified at the maximum undercooling of ΔT = 312 K. Microstructural investigation shows that the grain size in Fe-10 and Fe-30 at. pct Co alloys increases with undercoolings when the undercoolings of the melts exceed the critical undercoolings. The grain size of the Fe-60 at. pct Co alloy solidified in the undercooling range of 30 to 312 K, in which no metastable phase can be produced, is much finer than those of the Fe-10 and Fe-30 at. pct Co alloys after the formation of metastable phases. The model for breakage of the primary metastable dendrite at the solid-liquid interface during recalescence and remelting of dendrite cores is suggested on the basis of microstructures observed in the Fe-10 and Fe-30 at. pct Co alloys. The grain coarsening after the formation of metastable phases is analyzed, indicating that the different crystal structures present after the crystallization of the primary phase may play a significant role in determining the final grain size in the undercooled Fe-Co melts.     

Microstructure and mechanical properties of sputter-deposited Cu1−x Ta x alloys

The microstructures and mechanical properties of a family of sputter-deposited Cu_1−x Ta _x (0<x<0.18) alloys have been investigated. The as-deposited microstructures for all film compositions consisted of a polycrystalline, face-centered-cubic (fcc) Cu matrix, with varying levels of Ta in solid solution, plus a very high density of discrete, 1 to 3 nm, fcc Ta particles. Decreased deposition temperature (−120 °C vs 100 °C) increased the level of Ta in solid solution. After annealing (900 °C for 1 hour) the as-deposited 6 at. pct Ta films, the Cu matrix grains remained submicron and the Ta particles remained fcc with no apparent particle coarsening. Additionally, the fcc Ta particles were found before and after annealing to be oriented identically with the Cu matrix and aligned on {111} and {100} habit planes. Annealing 17 at. pct Ta films at 900 °C for 1 hour resulted in the formation of body-centered-cubic (bcc) Ta particles (>50-nm diameter) in addition to the much smaller fcc Ta particles. Annealing the low and high Ta composition films at 900 °C for as long as 100 hours produced no observed change in either the Cu matrix grain size or the size and distribution of the fcc and bcc Ta particles. Microhardness and nanoindentation mechanical property evaluations of bulk hot-pressed materials indicated that the high strengths of the composites were unchanged, even after annealing for 100 hours at 900 °C.     

Mechanical properties of Ir-Nb alloys containing Ni and Al

Two alloys made by adding 5 or 10 at. pct, respectively, of Ni-18.9 at. pct Al to an Ir-15 at. pct Nb alloy were investigated. The microstructure and compressive strength at temperatures between room temperature and 1800 °C were investigated to evaluate the potential of these alloys for ultra-high-temperature use. Their microstructural evolution indicated that the two alloys formed fcc and L1₂-Ir₃Nb two-phase structures. The fcc and L1₂ two-phase structures were examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The 0.2 pct flow stresses were above 1000 MPa at temperatures up to 1200 °C, about 150 MPa at 1500 °C, and over 100 MPa at 1800 °C. The strength of the quaternary Ir-base alloys at 1200 °C was even higher than that of Ir-base binary and ternary alloys. And the strength of quaternary Ir-Nb-Ni-Al was equivalent to that of the Ir-15 at. pct Nb binary alloy at 1800 °C. The compressive ductility of quaternary (around 20 pct) was improved drastically compared with that of the Ir-base binary alloy (lower than 10 pct) and the ternary Ir-base alloys (about 11 pct). An excellent balance of high-temperature strength and ductility was obtained in the alloy with 10 at. pct Ni-18.9 at. pct Al. The effect of Ni and Al on the strength of the Ir-Nb binary alloy is discussed.     

Composition dependence of young’s modulus in Ti-V, Ti-Nb, and Ti-V-Sn alloys

The Young’s modulus of Ti-V and Ti-V-Sn alloys quenched from the β-phase region after solution treatment and cold rolling was investigated in relation to alloy compositions, microstructures, and constituent phases. The composition dependence of the Young’s modulus for quenched Ti-V binary alloys shows two minima of 69 GPa at Ti-10 mass pct V and 72 GPa at Ti-26 mass pct V. Between the two compositions, athermalω or stress-induced ω is introduced in retainedβ phase and increases Young’s modulus. That is, a low Young’s modulus is attained unless alloys undergoω transformation. In Ti-5 and -8 mass pct V, which under goα′ (hcp) martensitic transformation on quenching, the Young’s modulus further decreases by cold rolling, which can be reasonably explained by the formation ofα′ rolling texture. Comparing Young’s modulus in Ti-V binary alloy with that in Ti-Nb binary alloy, it is found that Young’s modulus is remarkably increased by athermal- or stress inducedω phase, and it shows a minimum when both martensitic andω transformation are suppressed during quenching in metastableβ alloys. The Sn addition to Ti-V binary alloy retards or suppresses athermal and stress-inducedω transformation, thereby decreasing Young’s modulus. Young’s modulus exhibits minimum values of 51 GPa in quenched (Ti-12 pct V)-2 pct Sn and of 57 GPa in cold-rolled (Ti-12 pct V)-6 pct Sn.     

Spark Plasma Sintering of Nanocrystalline Cu and Cu-10?Wt?Pct Pb Alloy

For the first time, we report here that high purity nanocrystalline Cu and Cu-10 wt pct Pb alloys can be densified with more than 90 pct theoretical density at a low temperature of 623 K (350 °C) using spark plasma sintering (SPS) in argon atmosphere at a pressure of 100 MPa. Scanning electron microscopy (SEM) analysis indicates that molten Pb particles travel through Cu grain boundaries, delineating a “flowlike” pattern in the microstructure. An extensive transmission electron microscopy (TEM) analysis of the ultrafine scale microstructure reveals partial wetting of Cu by liquid Pb as well as entrapment of Pb particles within the Cu matrix. The sintering kinetics and microstructural evolution are discussed in reference to the intrinsic characteristics of SPS as well as phase equilibria in the Cu-Pb system. An important result is that high hardness of around 2 GPa is measured in the Cu-10 wt pct Pb nanostructured alloy, SPS at 573 K to 623 K (300 °C to 350 °C).     

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.     

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.

     

Structure, Properties, and Glass Forming Ability of Melt-Spun Fe-Zr-B-Cu Alloys with Different Zr/B Ratios

Melt-spun ribbons of Fe_99–x–y Zr _x B _y Cu₁ alloys with x + y = 11 and x + y = 13 were prepared under similar experimental conditions and characterized for structure and soft magnetic properties. Substitution of Zr by B changes the structure of as-spun ribbons from completely amorphous to cellular bcc solid solution coexisting with the amorphous phase at intercellular regions and then to completely dendritic solid solution. The glass forming ability (GFA) of the Fe-Zr-B-Cu system, evaluated from thermodynamic properties such as enthalpy of mixing and mismatch entropy, is found to be in good agreement with the experimental observations. Annealing of all ribbons leads to the precipitation of nanocrystalline bcc α-Fe phase from both amorphous phase and already existing bcc solid solution. A window of alloy compositions that exhibit the best combination of soft magnetic properties (high saturation magnetization and low coercivity) was identified.     

Incipient chemical instabilities of nanophase Fe-Cu alloys prepared by mechanical alloying

We used Mössbauer spectrometry, X-ray diffractometry, a novel imaging method of electron energy loss spectrometry, and small-angle neutron scattering (SANS) to study early stage thermal instabilities of nanophase Fe-Cu alloys prepared by mechanical attrition. Mössbauer spectrometry confirmed previous reports of an extended Cu solubility in the body-centered cubic (bcc) phase of the as-milled material. Mössbauer spectrometry also provided evidence that in the compositional range of bcc-face-centered-cubic (fcc) two-phase coexistence, the bcc phase had a Cu concentration nearly the same as the overall composition of the alloy. After the as-milled powders were annealed at temperatures as low as 200 °C, however, Mössbauer spectrometry showed significant chemical unmixing of the Cu and Fe atoms. In annealed bcc Fe-20 pet Cu alloys, SANS measurements indicated that Cu segregated to grain boundaries. This segregation of Cu atoms to bcc grain boundaries did not alter significantly the tendency for grain growth, however. X-ray diffractometry showed that grain growth during thermal annealing was similar for all alloys, although grain growth was small at temperatures below 300 °C. The two-phase (bcc plus fcc) alloy of Fe-30 pc Cu was more unstable against chemical segregation than were the single-phase (bcc or fcc) alloys. Energy-filtered imaging indicated that the Cu atoms segregated to regions around the bcc grains, perhaps to the adjacent fcc crystallites.     

Thermal Stability in Nanocrystalline Fe-30?Wt?Pct Ni Alloy Induced by Surface Mechanical Attrition Treatment

By means of surface mechanical attrition treatment (SMAT), a nanocrystalline surface layer is produced in Fe-30 wt pct Ni alloy, accompanying the formation of the strain-induced martensite. The thermal stability of nanocrystalline martensite and parent phase austenite in Fe-30 wt pct Ni alloy is studied by X-ray diffraction (XRD) and transmission electron microscope (TEM). The grain growth kinetics parameters, time exponent, n, and activation energy, Q, for both martensite and austenite, are determined, respectively. The TEM observations indicate that abnormal grain growth occurs during annealing at high temperatures.     

Theoretical treatment of the solidification of undercooled Fe-Cr-Ni melts

The solidification behavior of undercooled Fe-Cr-Ni melts is analyzed with respect to the competitive formation of body-centered cubic (bcc) phase (ferrite) and face-centered cubic (fcc) phase (austenite). The activation energies of homogeneous nucleation and growth velocities for both phases as functions of undercooling of the melt are calculated on the basis of current theories of nucleation and dendrite growth using data of thermodynamic properties available in the literature. As model systems for numerical calculations, the alloys Fe-18.5Cr-11Ni forming primary ferrite and Fe-18.5Cr-12.5Ni forming primary austenite under near-equilibrium solid-ification conditions are considered. Nucleation of the bcc phase is always promoted in the under-cooled primary ferrite alloy, whereas the barrier for bcc nucleation falls below that for fcc nucleation for large undercooling in primary austenite alloys. With rising undercooling, tran-sitions of the fastest growth mode were found from bcc to fcc and subsequently from fcc to bcc for the primary ferrite forming alloy and from fcc to bcc for the primary austenite forming alloy. The results of the calculations provide a basis for understanding contradictory experi-mental findings reported in the literature concerning phase selection in rapidly solidified stainless steel melts for different process conditions. Formerly Visiting Scientist at the Institut fur Raumsimulation     

Cu-Containing Fe-Ni Corrosion-Resistant Alloys Designed by a Cluster-Based Stable Solid Solution Model

Copper is a good corrosion resisting element, but due to its immiscibility with Fe, it is only used as a minor-alloying element in stainless steels. In this work, we introduced a double-cluster structure model [CuNi₁₂][NiFe₁₂] _m for stable solid solutions in Cu-containing Fe-Ni corrosion-resistant invar alloys. Our model takes into account all of the enthalpies between the element pairs by assuming Fe-Ni and Ni-Cu nearest neighbors and by avoiding Fe-Cu ones, so that the ideally stabilized structures are described by mixing two cuboctahedral clusters in the fcc lattice, NiFe₁₂ and CuNi₁₂. Two alloy series were designed by varying the relative proportions of the two clusters and the Cu contents. It was proved that the alloys with Cu contents below those prescribed by this model could easily be solutionized and water-quenched to a monolithic fcc solid solution, and resultant alloys possessed good corrosion-resisting properties in 3.5 wt pct NaCl solution.