激光熔覆高熵合金涂层组织结构及强化机理研究进展

激光熔覆作为一种绿色、高效的表面处理技术,能够快速制备组织致密、晶粒细小,与基体呈高强度冶金 结合的涂层,是近年来高熵合金领域的研究热点之一。概述了现有高熵合金涂层材料体系和制备方法,重点讨论 了激光熔覆CoCrFeNi-M 典型过渡族高熵合金涂层的组织结构,及其耐磨、耐蚀、抗高温氧化等性能,并归纳了 涂层的强化机制和方法。CoCrFeNi-M 系合金涂层主要呈现FCC 固溶体结构,综合力学性能普遍较好,通过合金 体系调控,在细晶强化、固溶强化、第二相强化等作用下,能够获得硬度、耐磨性、耐蚀性等性能的进一步提升。 同时,概述了激光熔覆难熔高熵合金涂层的组织结构,耐磨、耐蚀、抗高温氧化性能及性能强化机制,该体系合 金涂层主要呈现BCC 固溶体结构,硬度较高但室温韧性普遍不足,具有较好的高温强度,在高温领域具有较好 的应用前景,但抗高温氧化性能普遍不足,仍需通过合金体系优化进一步提升。此外,总结了基于激光熔覆技术 开展的高熵合金涂层制备及研究中存在的问题和不足,并展望了未来的发展方向。     

Y2O3对AlCoCrFeNi高熵合金涂层组织及力学性能的影响

利用激光熔覆技术在Q235钢基体表面分别制备出添加不同质量分数Y₂O₃的AlCoCrFeNi高熵合金涂层。采用X射线衍射仪、扫描电子显微镜、显微硬度计和摩擦磨损试验机对AlCoCrFeNi高熵合金涂层的微观组织、硬度及摩擦磨损性能进行了分析。结果表明:AlCoCrFeNi高熵合金涂层由面心立方结构（FCC）和体心立方结构（BCC）两相构成;随着Y₂O₃质量分数的提高,其体心立方结构相体积分数增加,而面心立方结构相的体积分数变化呈相反趋势。AlCoCrFeNi高熵合金涂层组织由等轴晶构成,加入Y₂O₃后,促进了熔池流动,使气孔逐渐消失,致密性提高,晶粒明显细化。添加质量分数5%Y₂O₃的涂层组织呈树枝晶状,形成弥散分布的YAl₂和Y₂O₃相;涂层的显微硬度可达HV 350,约为AlCoCrFeNi高熵合金涂层硬度的2倍,强化效果明显。Y₂O₃的添加有利于促进涂层中体心立方相的形成和YAl₂相的析出,能有效提高高熵合金涂层的硬度及耐磨性能。     

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...     

T10钢表面FeMoCoNiCrTix高熵合金熔覆层组织及性能

采用激光熔覆技术在T10A钢表面制备了FeMoCoNiCrTi_x（x分别为0.25,0.50,0.75,1.00）高熵合金熔覆层,分析了试样熔覆层及基体界面处的相结构及组织,并利用显微硬度计测试了试样处理前后的截面硬度变化。研究表明,经过激光熔覆在T10A钢表面得到的高熵合金层主要由NiCrFe、NiCrCoMo 2种固溶体为主,其结构分别为BCC结构和FCC结构,熔覆层的组织以柱状枝晶为主,界面处出现等轴晶;随着Ti含量增多,熔覆层由固溶强化变为固溶体与硬质相混合强化,熔覆层的HV硬度达到了792,热影响区的HV硬度达到了620,均高于基体硬度。同时耐磨损性能有了明显提高,磨损方式由粘着磨损逐渐变为磨粒磨损。      

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.     

硼含量对Ni-Cr-Mo合金热腐蚀性能的影响

采用真空液相烧结法制备了4种掺加不同B含量的Ni-Cr-Mo合金,研究了B对其组织与性能的影响。研究结果表明,B与Mo、Cr、Ni等合金元素在烧结时可以形成共晶液相,通过原位化学反应,生成Mo2NiB2、(Mo,Cr)2NiB2陶瓷相。热腐蚀性试验表明,形成的硼化物相具有较好的耐腐蚀性,能够有效提高Ni-Cr-Mo合金的耐热腐蚀性能。     

Microstructures and properties of CoCrCuFeNiMox high-entropy alloys fabricated by mechanical alloying and spark plasma sintering

CoCrCuFeNiMox (x values in molar ratio, x?=?0, 0.2, 0.4 and 0.8) high-entropy alloys were prepared by mechanical alloying and spark plasma sintering method. The effects of Mo addition on microstructure and mechanical properties were investigated. The X-ray diffraction (XRD) result showed that the addition of Mo into CoCrCuFeNi high-entropy alloy (HEA) changed the original phase constitution from FCC to FCC?+?σ?+?μ and the peak intensity of (1 1 1) shifted to the left and decreased steadily. The field emission scanning electron microscope confirmed that the Cu-rich second FCC phase disappeared and the σ phase with a tetragonal structure expanded as the Mo content was increased. Additionally, a high density of dimple-like features were seen in CoCrCuFeNi HEA while typical quasi-cleavage facets could be observed from the fracture surfaces of the HEAs with the addition of Mo. The Mo0.8 alloy showed a good wear resistant and appropriate strength with fracture strain 22.70%, fraction coefficient 0.65, hardness 530?HV and compressive strength 1448?MPa.

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.     

Mn元素对过流冷却过共晶Al-22Si-2Fe-xMn合金显微组织及耐磨性的影响

采用常规铸造和分段式倾斜板过流冷却铸造工艺制备Al-22Si-2Fe-xMn合金，研究表明:过流冷却制备工艺能够改善初生Si形貌及尺寸，但对针状富Fe相作用有限.利用扫描电镜、X射线衍射及透射电镜等手段分析过流冷却条件下Mn元素添加对富Fe相晶体结构的影响，通过摩擦磨损实验研究不同Mn/Fe质量比的过共晶Al-Si合金的硬度及耐磨损性能.结果表明:随着过流冷却铸造过共晶Al-Si合金中Mn/Fe质量比增加，合金中四方结构的长针状富Fe相逐渐减少直至基本消失，当Mn/Fe质量比为0.7时，富Fe相主要为六方结构的块状或鱼骨状α-Al₁₅（Fe，Mn）₃Si₂相，此时，合金耐磨性较未添加Mn元素时有所提升，磨损机制以磨料磨损方式为主.      

Deposition of Amorphous Hardening Coatings by Electrospark Treatment in a Mixture of Crystalline Granules

This article is devoted to the formation of amorphous coatings on the steel 35 surface by electrospark treatment in a mixture of crystalline granules. It is revealed by the energy dispersive X-ray spectroscopy (EDS) that formed coatings contain W, Mo, Co, and Ni in various ratios. The weight of granules of various compositions decreases by 11–16 wt % for 6-h treatment due to electric erosion. The mass transfer coefficient varies in a range from 33 to 54%. X-ray structural analysis showed the prevalence of an amorphous phase (81–99%) in the structure of deposited layers. Annealing of coatings at a temperature above 1150°C leads to the crystallization of the amorphous phase into boron carbide of the M23(C, B)6 type, as well as into α-Fe. The coatings have an increased hardness of 10–15 GPa, while their wear resistance in the dry sliding wear mode under loads of 10 and 50 N is higher than for steel 35 by a factor of 3.3 and 1.6. The coating friction coefficient is lower than for steel 35 by 13–30% and was 0.27–0.31. The wear resistance of coatings in a dry abrasive wear mode is higher by a factor of 3–5 when compared with uncoated steel 35. The best characteristics are inherent without nickel and worst are inherent without cobalt. Thus, it is established that tungsten and cobalt increase the wear resistance of iron-based amorphous alloys, while nickel and molybdenum tend to worsen their tribotechnical behavior.     

Wear resistance of binary chromium alloys with Ti, Zr, Hf, Nb, and Ta

The sliding wear resistance was determined for chromium alloys with titanium, zirconium, hafnium, niobium, or tantalum. Those additives increased the wear resistance when present up to their maximum contents, which were 19% for Ti and 30–35% for the others (eutectic compositions). Comparative analysis of the data and the phase diagrams showed that the alloying had a larger effect in the one-phase regions of chromium-based solid solutions than for two-phase alloys containing Laves phases. In regard to improving the wear resistance of two-phase alloys the metal rank in the order Ti, Nb, Ta, Hf, and Zr.     

Big-data analysis of phase-formation rules in high-entropy alloys

Big-data analysis of phase-formation rules of high-entropy alloys (HEAs) was conducted and a phase for-mation rule from a dynamic view was deduced.It was indicated in literatures that cooling rate has a strong influence on the phase formation of HEAs.Higher cooling rate may promote the generation of amorphous phase, and accordingly suppress the formation of intermetallics.Meanwhile, it was also shown that cool-ing rate had little impact on the formation of solid-solution phase.To demonstrate this rule, a series of Fe-CoNi(AlSiB)x HEAs ribbons were fabricated by a melt-spinning technique, and the microstructure, me-chanical, and magnetic properties were also investigated.The results show that all ribbons exhibit disor-dered solid-solution structure.The addition of boron changes the alloy from ductility to brittleness, but without evident change of magnetic properties.The alloy in the nominal composition of FeCoNi(AlSi)0.2 has the best combination of mechanical and magnetic properties.A distinct feature of HEAs in magnetiza-tion was noticed and explained.     

载荷对Fe-Cr-C-Nb堆焊合金松散磨粒磨损行为的影响

采用熔化极气体保护焊技术（gas metal arc welding,GMAW）制备了Fe-Cr-C-Nb堆焊合金,对合金在不同法向载荷（70~190 N）下进行干砂/橡胶轮松散三体磨粒磨损实验。通过X射线衍射分析、扫描电子显微镜观察、能谱分析、磨损失重测试、体视显微镜观察、激光扫描共焦显微镜观察和维氏硬度测量等手段表征了合金显微组织与磨痕特征,研究了合金在不同法向载荷作用下磨损行为的变化。结果表明:堆焊合金显微组织主要由初生奥氏体基体、网状共晶组织及分布于基体上的NbC硬质相组成;合金磨损损失、磨痕深度随法向载荷增大而增大,磨损机制主要为奥氏体基体的微切削及NbC、M₇C₃的脆性剥落;法向载荷的提高加剧了磨痕亚表面的加工硬化,从而提高了奥氏体基体耐磨性,这导致磨损损失及磨痕深度增长幅度缓慢。     

Microstructure and Properties of Fe-Cr-C Hardfacing Alloys Reinforced with TiC-NbC

The hypereutectic Fe-Cr-C hardfacing alloys with different contents of TiB2 and Nb were prepared by selfshielded flux cored arc welding.The microstructure of a series of hypereutectic Fe-Cr-C hardfacing alloys added with various TiB2 and Nb contents was investigated by using optical microscopy(OM),scanning electron microscopy(SEM)and X-ray diffraction(XRD).In addition,their Rockwell hardness,microhardness and resistance to abrasive wear were tested.The results showed that the microstructure of a series of hypereutectic Fe-Cr-C hardfacing alloys consisted mainly of martensite,austenite,primary M7C3 carbides and eutectic M7C3 carbides.With the addition of TiB2,a new hard-phase TiC was produced in the hardfacing alloys.And in the alloys added with TiB2 and Nb,a new hard composite phase TiC-NbC was formed.The microhardness of the matrix was improved by adding TiB2 and Nb,but the effect on the Rockwell hardness of Fe-Cr-C hardfacing alloys was insignificant.The addition of TiB2 and Nb can also decrease the size of the primary M7C3 carbides and make the primary M7C3 homogeneous.As a result,the reinforced matrix,the more homogeneous primary M7C3 carbides,and the new hard-phase TiC-NbC all improved the wear resistance of Fe-Cr-C hardfacing alloys.     

医用钛合金及其表面改性技术的研究现状

介绍了新型医用钛合金的研究开发现状，分析了医用钛合金存在的主要问题，即耐磨性、耐腐蚀性和生物活性有待进一步提高。阐述了表面改性对提高钛合金的耐磨性能、耐腐蚀性能和生物活性的作用。指出应当重视钛合金表面生物活性陶瓷涂层的稳定性问题。认为通过研究开发综合性能更优的新型医用钛合金，寻求更为理想的表面改性工艺以及运用复合涂层制备技术，有望逐步解决钛合金在临床应用中存在的问题。     

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.     

钛合金固相渗硼-稀土渗硼机理研究

表面强化处理可以大幅提升钛合金的耐磨性， 也有利于钛合金在高温环境中应用。 钛合金高温固相渗硼是 重要的表面强化方式， 添加稀土提高渗硼效率是重要技术手段。 为深入研究稀土的渗硼催化机制， 本文开展了 900~1050℃渗硼试验， 重点分析了渗硼剂在试验后的相组成变化。 结果表明， 稀土可通过与硼源、 氧发生化学反 应， 生成熔点较低的稀土硼酸盐。 本文对该硼酸盐发挥的作用进行了解释， 论述了稀土在渗硼反应过程中的作用。 经过渗硼的钛合金表面形成了 TiB/TiB2 双相渗层， 显微组织分析表明该渗层与基材结合紧密、 无孔洞缺陷。 本文 还对渗硼钛合金的拉伸性能、 表面摩擦系数、 维氏硬度、 高温洛氏硬度、 结合力等基础力学性能进行了测试， 结 果表明， 渗硼钛合金具有优良的综合力学性能。     

Wear resistance and high-temperature compression strength of Fcc CuCoNiCrAl<Subscript>0.5</Subscript>Fe alloy with boron addition

This study discusses the wear resistance and high-temperature compression strength of CuCoNiCrAl_0.5Fe alloy with various amounts of boron addition. Experiments show that within the atomic ratio of boron addition from x=0 to x=1.0 in CuCoNiCrAl_0.5FeB _x (referred to as B-0 to B-1.0 alloys), the alloys are of fcc structure with boride precipitation. The volume fraction of borides increases with increasing boron addition. The corresponding hardness increases from HV 232 to HV 736. Wear resistance and high-temperature compression strength are significantly enhanced by the formation of boride. The alloys with boride are less tough. The superior wear resistance of B-1.0 alloy, which is even better than SUJ2 wear-resistant steel, indicates that the CuCoNiCrAl_0.5FeB _x alloys have potential applications as ambient- and high-temperature mold, tool, and structural materials.     

Preparation and properties of Al-Mn alloy coatings in NaCl-KCl-AlCl3-CeCl3 molten salts

Al-Mn alloy coatings were electrodeposited on an iron substrate from AlCl3-NaCl-KCl molten salts with anhydrous MnCl2 enhanced by the addition of CeCl3. The microstructure and properties of the Al-Mn alloy coatings were investigated, and scanning electron microscopy, X-ray diffraction, and polarization curves were used to determine the composition, surface morphology, phase structure, and corrosion resistance of the obtained deposits. The results showed that the surface coatings were smooth, and that the crystallites were dense and uniform when 0.22 wt.% CeCl3 was added to the molten salt. An amorphous mixture of Al and Al6Mn was obtained. CeCl3 enhanced the corrosion resistance and increased the hardness of the single amorphous phase alloys. The pitting potential of the coating was approximately -1.1239 V, and its hardness was 390 kgf/mm2.     

Correlation of microstructure with the wear resistance and fracture toughness of duocast materials composed of high-chromium white cast iron and low-chromium steel

The objective of this study is to investigate the correlation of microstructure with wear resistance and fracture toughness in duocast materials that consisted of a high-chromium white cast iron and a low-chromium steel as the wear-resistant and ductile parts, respectively. Different shapes, sizes, volume fractions, and distributions of M₇C₃ carbides were employed in the wear-resistant part by changing the amount of chromium and molybdenum. In the alloys containing a large amount of chromium, a number of large hexagonal-shaped primary carbides and fine eutectic carbides were formed. These large primary carbides were so hard and brittle that they easily fractured or fell off from the matrix, thereby deteriorating the wear resistance and fracture toughness. In the alloys containing a smaller amount of chromium, however, a network structure of eutectic carbides having a lower hardness than the primary carbides was developed well along solidification cell boundaries and led to the improvement of both wear resistance and toughness. The addition of molybdenum also helped enhance the wear resistance by forming additional M₂C carbides without losing the fracture toughness. Under the duocasting conditions used in the present study, the appropriate compositions for wear resistance and fracture toughness were 17 to 18 pct chromium and 2 to 3 pct molybdenum.     

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.