Effect of segregation on initiation of corrosion of aluminium sacrificial anode containing mischmetal

Abstract

The effects of rare earth (RE) elemental additions in the form of mischmetal, added into an Al–Zn–In sacrificial anode alloy, were studied in 3% NaCl solution. Scanning electron microscopy and energy dispersive X-ray analysis were employed to analyse the microstructure of all Al alloys. Potentiodynamic polarisation of the anode material and a model alloy that simulated the segregated grain boundary composition were also investigated. The results showed that the microstructure of Al–Zn–In–RE alloy exhibited a typical dentritic form with small precipitates in an Al matrix and eutectic in interdendritic regions. Preferential attack from anodic segregation produced the early pitting and minor element enrichment on the surface, thus activating the anodes. Thus, using a RE mischmetal, which is much cheaper than pure RE elements, Al–Zn–In–RE alloys obtained desirable electrochemical properties for Al sacrificial anodes.     

不同稀土含量的铝合金牺牲阳极的显微组织研究

浇铸了4种不同RE含量的Al-Zn-In-Sn-Mg合金牺牲阳极.利用金相显微镜、扫描电镜(SEM)和能谱分析,确定了4种合金的晶粒尺寸、偏析相数量及其成分.结果表明:随着RE含量的增加,铝合金的晶粒变小,偏析相的数量先增加后减少;偏析相主要为晶界析出物和弥散相;RE含量不同时,晶界析出物不同;细化阳极晶粒最佳RE含量0.5%,0.3%RE时阳极偏析相数量最多.     

Effect of rare earth and calcium treatments on the mechanical,physical, and electrochemical properties of a 16Mn steel

Two treatment methods, namely Ca-Si injection into the ladle and rare earth (RE) additions to the mold, were investigated for their effectiveness in controlling the microstructure, particularly sulfide inclusions, and hence the properties of a 16Mn plain-carbon steel. A combined Ca + RE treatment increased the critical crack opening displacement in the transverse direction of sheet material to that in the rolling direction. The combined treatment also improved the resistance to stress-corrosion cracking (SCC) in a boiling 20 wt.% NH₄NO₃ solution. Too large a RE addition, ultimately lowers SCC resistance. The RE additions retarded austenite grain growth, whereas the Ca-only addition accelerated grain growth. The changes in fracture behavior, SCC resistance, and austenite grain growth behavior are explained in terms of the segregation of the RE to the grain boundaries and the subsequent changes in the electrochemical and mechanical properties of the grain boundaries relative to the grain interiors. A combined treatment of injecting 3.4 kg Ca-Si per ton of steel into the molten steel and adding 0.03 wt.% RE to the mold yielded optimum properties.     

Investigation of the age hardening behaviour of 6063 aluminium alloys refined with Ti,RE and B

The purpose of this study is to obtain a better understanding on the effect of ageing on the hardness of 6063 aluminium alloys refined with Ti, cerium-rich mixtures of rare earth (RE) and B with the aids of SEM, EDS, TEM, DSC, etc. The following conclusions have been obtained: the 6063 alloy with the joint additions of Ti, B and RE (10 w(Ti)/w(B) mass ratio) has the finest grain, compared to alloys with Ti or Ti and RE additions. Artificial ageing must be performed more than 7 d after extrusion. The 6063 alloys refined with Ti, Ti + RE or Ti + RE + B all have better ageing behaviour. It takes shorter ageing time to obtain a hardness near peak ageing hardness and there is no obvious decrease of ageing hardness of the alloys until ageing for 6 h at 200 °C. The addition of RE forms Al–Si–Mg–RE intermetallic constituents, resulting in lower strength of alloys than that with Ti addition.     

复合稀土银合金组织与性能的研究

试验制备了8种稀土银合金，研究了复合稀土银合金的组织与性能，提出了复合稀土对银合金组织与性能的影响有互补性，复合稀土元素在铸态下偏聚且共生在枝晶边界上，形成了Ag5RE金属间化合物及氧化物，对银合金有显著的强化作用和细化晶粒作用，提高了银合金的再结晶温度，增强了银合金的耐热性。这种合金经冷变形后退火，可以消除枝晶偏析，含稀土的第2相化合物呈团絮状分布在结晶组织上，有利于改善银合金的组织与性能。     

Phase Characteristics of a U-22Pu-4Am-2Np-40Zr Metallic Alloy Containing Rare Earths

Metallic fuel alloys consisting of uranium (U), plutonium (Pu), and zirconium (Zr) with minor additions of americium (Am) and neptunium (Np) are under evaluation for potential use to transmute long-lived transuranic actinide isotopes in fast reactors. The current irradiation test series design, designated Advanced Fuel Cycle-2 (AFC2), includes minor additions of rare earth (RE) elements to simulate expected fission product carryover from the electrochemical molten salt reprocessing technique. The as-cast fuel alloys have been investigated for phase and thermal properties; specifically, enthalpies of transition, transition temperatures, and room temperature phase characteristics. Results and observations related to these characteristics for the “fresh” fuel alloys are provided. The alloy compositions are based on a U-22Pu-4Am-2Np-40Zr alloy, along with additions of 1.3 and 1.9 at.% RE (at the expense of uranium where RE denotes rare earth alloy of cerium, lanthanum, praseodymium, and neodymium). Phase behavior and associated transitions have been compared to available U-Pu-Zr ternary diagrams with acceptable agreement. Enthalpies of transition were deconvoluted from heating and cooling thermal traces for relatively reliable values. The RE additions to the base alloy have a minimal influence on the room temperature phases present and phase transition temperatures, but the room temperature phases present did impact the enthalpies of transition.     

铜基仿金合金

为了寻找金的代用品,长期以来研究者竞相研制铜基仿金合金以满足制造较大的金色艺术品。文中阐述了研制铜基仿金合金的原理及其金色度和抗变色性的测试方法,分别叙述了铝、锌、锡、铟、硅、镍、稀土等元素对合金金色度和抗变色性的影响。鉴于各研究者得出的合金化学成分相差极大,最后提供了较为合理的铜基仿金合金的化学成分。     

Influence of gd addition on the structure and properties of Au-Ni and Au?Ni?Cr alloys

The influence of Gd additions on the microstructure and properties of Au-Ni and Au-Ni-Cr alloys are reported. The alloys remain single phase solid solution at Gd contents of −0.1wt%, but at contents τ 0.1%, two phases structures are formed, consisting of (Au) and a low melting point intermetallic compound containing Gd. Trace additions of Gd refine the grain size, increase strength and the recrystallization temperature, but without detriment to the good electric conductivity of these alloys. The wear life of potentiometer windings made of gold alloys containing Gd are at least one order of magnitude higher than those made in the Gd-free gold alloys. The design of gold alloys for precise electrical contact and resistance materials by conventional and microalloying is discussed.     

Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

In memory of John Stringer (1934–2014), one of the leaders in studying the reactive element (RE) effects, this paper reviews the current status of understanding of the effect of RE dopants on high-temperature oxidation behavior, with an emphasis on recent research related to deploying alumina-forming alloys and coatings with optimal performance in commercial systems. In addition to the well-known interaction between indigenous sulfur and RE additions, effects have been observed with C, N, and O found in commercial alloys and coatings. While there are many similarities between alumina-forming alloys and coatings, the latter bring additional complicating factors such as the effects of O incorporation during thermal spraying MCrAlY coatings, coating roughness, and heat treatments that must be considered in optimizing the beneficial dopant addition. Analogies can be seen between RE effects in alloys and in the substrates beneath diffusion M–Al coatings. Recently, there has been more interest in the influence of mixed oxidant environments, since these may modify the manifestation of the RE effect. Finally, some thoughts are provided on optimizing the RE benefit and modeling oxidation of RE-doped alloys.     

稀土、钛变质对贝氏体铸钢成分偏析及强韧性的影响

研究了稀土、钛和稀土 /钛复合变质对贝氏体铸钢成分偏析和强韧性的影响。结果表明 :采用稀土 /钛复合变质剂能基本上消除碳和其它元素 (Si、Cr)的枝晶偏析。复合变质后铸钢的硬度和冲击韧度同时提高。冲击韧度提高来源于晶粒细化、残余块状奥氏体较少、夹杂物改性等。硬度提高主要是由于成份偏析较小 ,使枝干碳和合金元素含量提高 ,从而使马氏体中的碳含量提高所致。     

On the corrosion of binary magnesium-rare earth alloys

The corrosion properties of high-pressure die cast (HPDC) magnesium-rare earth (RE) based alloys have been studied. Binary additions of La, Ce and Nd to commercially pure Mg were made up to a nominal 6 wt.%. It was found that the intermetallic phases formed in the eutectic were Mg₁₂La, Mg₁₂Ce and Mg₃Nd, respectively. Results indicated that increasing RE alloying additions systematically increased corrosion rates. This was also described in the context of the electrochemical response of Mg-RE intermetallics - which were independently assessed by the electrochemical microcapillary technique.This study is a discrete effort towards revealing the electrochemical effect of carefully controlled binary alloying additions to magnesium in order to elucidate the microstructure-corrosion relationship more generally for HPDC Mg alloys. Such fundamental information is seen to not only be useful in understanding the corrosion of alloys which presently contain RE additions, but may be exploited in the design of magnesium alloys with more predictable corrosion behaviour. There is a special need to understand this relationship - particularly for magnesium that commonly displays poor corrosion resistance.     

Effects of RE on microstructure and properties of AZ91 magnesium alloy

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合金元素Mg对含RE铝阳极组织与性能的影响

采用恒电流方法,测定了Al-5Zn-0.05In-0.1Sn-0.3RE和Al-5Zn-0.05In-0.1Sn-Mg-0.3RE两种铝合金牺牲阳极材料电流效率、利用金相显微镜、扫描电镜和能谱分析,研究了它们的金相组织。结果表明：镁对含RE铝阳极性能有较大改善,镁的添加改变了铝合金晶界偏析相的组成;晶界析出物Mg相减轻了铝阳极的晶界腐蚀和晶粒脱落。     

活性元素对合金高温氧化的作用机制

合金内添加微量活性元素可以显著改善合金的抗高温 氧化性能.活性元素效应已在高温合金和抗高温氧化的防护涂层上得到大量应用,而其微观 作用机制尚未完全明了.本文综述了已有的活性元素微观作用模型,并分析了各种模型存在 的缺点,对国内的研究成果也作了总结.同时指出未来着重解决的问题.     

The segregation of elements in high-refractory-content single-crystal nickel-based superalloys

Nickel-based superalloys are complex alloys that contain ten to 15 elements that are widely used in industries where high-temperature strength and corrosion resistance are required. Alloy additions commonly include Cr, Co, W, Ta, Al, Ti, Re, Mo, and, in some alloys, Ru. Each of these additions can affect the as-cast microstructure due to differences in elemental segregation. A better understanding of the effects of typical additions to nickel-based superalloys on the segregation of the elements in the alloy can help identify potential improvements in the processing of current alloys and the development of new alloys. Therefore, the effects of several common alloying additions on solidification segregation and defects were evaluated. In general, an increase in the degree of elemental segregation was observed with increases in each of the elements listed except cobalt and molybdenum. Increased levels of cobalt and molybdenum resulted in reductions in the segregation of most of the elements in the alloy. For more information, contact G.E. Fuchs, University of Florida, Department of Materials Science and Engineering, 116 Rhines Hall, Gainesville, FL 82611, USA; (352) 846-3317; fax (352) 392-7219; e-mail gfuch@mse.ufl.edu.     

Influences of complex modification of P and RE on microstructure and mechanical properties of hypereutectic Al-20Si alloy

P and RE complex modification of hypereutectic A1-Si alloys was conducted. The influences of P, RE content on the microstructure and mechanical properties of alloys were investigated. The complex modifications of P and RE make the coarse block primary silicon obviously refined and the large needle eutectic silicon modified to the fine fibrous or lamella ones. P mainly refines the primary silicon, but excess P is unfavorable to the refinement of primary silicon. RE can well refine the primary and eutectic silicon, but its modification effect on the eutectic silicon is more obvious. P can repress the modification of RE on the eutectic silicon The alloys with the additions of 0.08% P and 0.60% RE have the optimal microstructure and the highest mechanical properties. Compared with the unmodified alloy, the primary silicon of alloys can be refined from 66.4 μm to 23.3μm and the eutectic silicon can be refined from 8.3 μm to 5.2μm. The tensile strength is improved from 256 MPa to 306 MPa and the elongation is improved from 0.35% to 0.48%.     

Al-Zn-Mg-Cu系铝合金中不同区域电子结构及应力腐蚀机理分析

利用计算机编程建立了Al--Zn--Mg--Cu合金 (7175铝合金) 中α--Al, η相及α--Al大角度晶界原子集团模型, 采用递归法计算 合金中Zn, Mg, Cu和H的环境敏感镶嵌能、原子间相互作用能、Fermi能级和态密度等电子结构参数, 分析了合金的应力腐蚀机理. 计算 结果表明: Mg, Cu和H容易在晶界偏析. Mg对H具有吸引作用, 促进H在晶界偏析, 引起晶界氢脆; Zn增大晶界与晶内的电位差, 降低合 金抗腐蚀性; Cu能减小晶界与晶内Fermi能级差, 降低晶界与晶内的电位差, 具有减缓合金腐蚀的作用. 计算结果还表明: η相的Fermi能 级最高, 腐蚀过程中作为阳极优先溶解. 由于η相俘获H, 当晶界析出断续η相时可减弱晶界H的偏析, 提高抗腐蚀性; 但晶界连续分布η相则形成腐蚀通道, 加速腐蚀进程.     

细化变质处理对铸造Al-7.5Si-4Cu合金力学性能和组织的影响(英文)

研究了单一和复合Al-5Ti-B、RE和Al-10Sr细化变质剂对砂型铸造Al-7.5Si-4Cu合金力学性能、显微组织、细化变质效果及其金属间化合物变化的影响。结果表明:与单一细化变质处理以及铸态相比,经过添加质量分数为0.8%的Al-5Ti-B、0.1%的RE和0.1%的Al-10Sr细化变质剂复合细化变质处理后铸造Al-7.5Si-4Cu合金的力学性能和显微组织都得到了显著改善。对于单一细化变质处理,加入0.8%的Al-5Ti-B中间合金后,合金的抗拉强度和布氏硬度得到大幅度提高,并且细化了α(Al)相。加入0.1%的RE中间合金后,合金的伸长率得到了最大程度的提高。这是因为RE的加入使铝合金熔液而得到净化,同时改变了金属间化合物的形状。而加入0.1%的Al-10Sr变质剂后,合金的屈服强度得到改善,但其他性能的改善有限。Al-10Sr变质剂对共晶硅具有较强的变质作用,但使得铝合金熔体含气量增加并形成严重的柱状晶组织。利用硅相的平均面积和长宽比描述细化变质效果得到的结论与力学性能和组织分析的结果相同。     

稀土银合金铸态及再结晶组织的观察与分析

制备了不同稀土含量的银合金,用电子探针扫描仪观察了几种银合金的铸态组织和再结晶退火组织。研究合金的铸态组织时发现,含微量稀土(0.016％La)的银合金为固溶态,显示大晶粒组织;含0．12％RE的银合金有少量分散的球状第二相稀土化合物分布在大晶粒组织上;含1．2％RE的银合金中的稀土化合物枝晶形成连续的网状分布。稀土元素的加入,细化了冷变形再结晶组织的晶粒,经过破碎、再聚集所形成的分散的银稀土化合物第二相有效地强化了银合金,并提高合金的热稳定性。     

Optimal modifying and refining processes for A356 aluminium alloys

M illions of alum inium alloy com ponents are produced using A356 alum inium alloys, which provide high fluidity, good 'castability'and m echanical properties. A356 alloys are widely used to fabricate structural castings for autom otive and other industrial applications. For α (Al) refining,A356 alum inium alloys usually apply Al-Tim aster alloys in the range 0.08-0.20% Ti, resulting in high consum ption of Al-Ti m aster alloys and higher production cost.M odification ofthe Al-Sieutectic …