Development of single-phased copper alloy for seawater applications: As a cost-effective substitute for Cu-10Ni alloy

Cu-10Ni alloy is a standard material for seawater application. Under Indian scenario, where half of copper and whole of Ni (and Cu-Ni) requirement is met by imports, search for a cheaper substitute is obvious. An attempt has been made to develop a single-phased copper alloy containing 10 wt% Ni, 29 wt% Zn, up to 5 wt% Mn and 1 wt% Fe as a substitute to Cu-10wt% Ni-1wt% Fe alloy. Studies on Corrosion resistance of test alloys were carried out in synthetic seawater (ASTM D 114-75) by electro-chemical methods (cathodic and anodic polarization). Corrosion product film formed on alloy containing 5wt% Mn was characterized by SEM and XRD. A film of Cu₂O was found to form on the surface of the alloy, which accords corrosion protection. The test alloys containing 29 wt% Zn and 3 or 5 wt% Mn have exhibited better corrosion resistance in synthetic seawater than Cu-10Ni alloy. The role of Mn and Zn addition has been discussed.     

晶粒细化对Cu-40Ni合金在酸性含Cl-介质中耐蚀性能的影响

采用电弧熔炼（CA）和机械合金化（MA）通过热压烧结工艺制备了晶粒尺寸差别较大的Cu-40Ni合金，借助于PARM273A和M5210电化学综合测量仪，利用动电位扫描法和交流阻抗技术对比研究了上述合金在酸性含Cl^-介质中的腐蚀电化学性能以及腐蚀机制。结果表明：两种合金的腐蚀电位随时间逐渐稳定，在中性Na2SO4溶液中加入H2SO4和NaCl后，两种合金的自腐蚀电位负移；晶粒细化后，两种合金的自腐蚀电位则正移。两种合金在中性及酸性含Cl^-介质中均存在钝化现象，但在酸性含Cl^-介质中钝化区间很短，钝化能力较弱。两种合金的交流阻抗谱均由单容抗弧组成，反应由电化学过程控制。晶粒细化后，合金中存在大量晶界，参与腐蚀反应的活性原子数增加，促使MACu40Ni合金的腐蚀速度高于CACu-40Ni合金。     

稀土对Ni-Cr-Cu合金铸铁组织及耐碱腐蚀性能的影响

设计了不同含量的稀土镍-铬-铜合金铸铁,采用光学显微镜观察组织,用失重法测定合金铸铁在动态、高温、高浓度碱液中的腐蚀速率。结果表明,添加稀土可以改善合金铸铁中石墨的形态及分布,使之由长条形逐渐球化;并且随着稀土含量的增加,石墨数量增加,合金铸铁的耐蚀性增强。但稀土过量会使得合金铸铁的耐蚀性减弱。     

Effect of zinc addition to copper in improving its corrosion resistance in sulfide polluted synthetic seawater

In an endeavor to develop a cost effective substitute of Cu-10Ni alloy for seawater application (especially for sulfide polluted seawater) few Cu-Ni-Zn-Mn alloys were developed in our laboratory. The Cu-Ni-Zn-Mn alloy was found to have better corrosion resistance than Cu-10Ni both in clean and sulfide polluted synthetic seawater. Resistance to sulfide in Synthetic Seawater was attributed to the formation of ZnS. To ensure that the resistance to sulfide attack is due to Zn alone, a series of studies were carried out with binary alloys of Cu and Zn with increasing weight percentage of Zn (12% and 36%). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) was used for the purpose. Polarization studies gave the corrosion data and EIS was effective in depicting the nature of corrosion product (film). It was found that among the test alloys, Cu-36Zn is most corrosion resistant in sulfide polluted seawater due to formation of ZnS in the film. As it is a binary alloy, the corrosion resistance against sulfide is attributed to Zn alone.     

Effect of Zn addition on corrosion resistance of Cu-10Ni alloy in clean and sulphide contaminated seawater

Cu-10Ni alloy has an outstanding resistance to corrosion in seawater due to formation of protective Cu₂O film. However, in presence of S^2? ions, it suffers accelerated corrosion. The present paper investigates the corrosion behaviour of Cu-10Ni, Cu-10Ni-6Zn and Cu-10Ni-12Zn alloys using weight loss, electrochemical impedance spectroscopy and potentiodynamic polarisation technique. The experiments were performed in clean seawater and sulphide contaminated seawater. The Cu-10Ni-6Zn and Cu-10Ni-12Zn alloys were found to exhibit lower corrosion rate than Cu-10Ni alloy in clean and sulphide contaminated seawater. Lower corrosion rate of Zn containing alloys in clean seawater is attributed to the incorporation of Zn²⁺ ions in Cu₂O lattice. Lower corrosion rate of Zn containing alloys sulphide contaminated seawater is attributed to formation of ZnS in the film.     

Corrosion resistance of new copper alloy containing 29Zn, 10Ni and up to 5Mn vis-a-vis Cu-10Ni in sulphide polluted synthetic seawater

Cu-10 Ni alloy suffers from accelerated corrosion in sulphide-polluted seawater. New copper alloys containing 29% Zn, 10Ni and 3 or 5% Mn have been found to be more corrosion resistant than Cu-10Ni alloys in sulphide polluted synthetic seawater. The studies were carried out in synthetic seawater (ASTM D 114–75) and sulphide was added through Na₂S (1 gpl ≈ 41ppm S²⁻). Testing was carried out using cathodic and anodic potentiodynamic polarization methods. Corrosion product film formed on the Cu-29Zn-10Ni-5Mn alloy in sulphide polluted synthetic seawater was characterized using SEM and XRD. The film was found to contain Cu₂O, Cu₂S, NiS and ZnS. Better corrosion resistance of new alloys as compared to that of Cu-10Ni alloy is attributed to formation of ZnS, a bad conductor, in the film and incorporation of Mn³⁺ cations in Cu₂O and Cu₂S lattice.     

Ni元素对Al-Cu-Mn合金组织及力学性能的影响

为研究添加Ni元素对Al-5.0Cu-0.6Mn合金组织及力学性能的影响,通过硬度试验、拉伸力学试验及摩擦磨损试验对合金力学性能进行研究;采用扫描电子显微镜、激光共聚焦显微镜及透射电子显微镜对合金微观组织进行检测分析。结果表明:向Al-5.0Cu-0.6Mn合金中添加Ni元素后,由于Al₃CuNi相析出的强化作用,并且与基体结合良好的增强相颗粒能均匀分布于合金中,使得合金硬度和强度大幅提高,摩擦磨损深度显著降低,综合力学性能得到有效的提升。当Ni元素的添加量为0.3%（质量分数）时,由于T相（Al₂₀Cu₂Mn₃）和Al₃CuNi相分布比较均匀,合金综合性能较为理想,其HV硬度、抗拉强度、摩擦磨损系数分别为126.4 MPa、395.2 MPa、0.12。      

Influence of rare earth elements on corrosion resistance of BFe10-1-1 alloys in flowing marine water

The corrosion behavior of BFe10-1-1 alloy with different rare earth (RE) contents in simulated flowing marine water was investi-gated by X-ray diffractometer and scanning electron microscope (SEM). It was demonstrated that the corrosion rate of BFe10-1-1 alloy with the same chemical compositions in faster flow velocity of marine water was higher than that in a lower flow velocity of marine water. Fixing the flow velocity, BFe10-1-1 alloy had the best flushing corrosion resistance when the RE content was 0.04wt.%. The consequence of such good corrosion resistance was attributed to the formation of compact protective film on alloy surface containing RE phase such as CeNi5- The RE-contained film combines with other corrosion products firmly, which was difficult to fall off from the alloy surface in the flowing marine water. Additionally, SEM analysis confirmed that pitting mechanism, which would be transformed to spalling mechanism gradually with further increasing RE content, was the prevalent mechanism when the alloy contained 0.04wt.%RE.     

孕育剂对硼铸铁耐腐蚀性的影响

本文利用含硼生铁作加硼剂,采用７５硅铁,１＃稀土合金,稀土硅钡等孕育剂研究了孕育后硼铸铁（含硼量为０．０６％）的组织和耐腐蚀性能。对硼铸铁进行孕育,其组织发生了明显的变化。随孕育剂加入量的增加,石墨形态发生了明显的变化,珠光体增加,碳化物减少。孕育硼铸铁在酸性介质中,耐蚀性明显好于未孕育硼铸铁,１＃稀土合金孕育剂孕育的硼铸铁的耐蚀性最好。     

稀土Ce对1Cr18Mn8Ni5N不锈钢耐均匀腐蚀性能影响

利用电化学的极化曲线及交流阻抗技术研究了不同稀土含量的1Cr18Mn8Ni5N不锈钢在硫酸介质中的腐蚀行为。应用扫描电镜对试样的腐蚀形貌及夹杂物形态进行了观察,利用EDS对夹杂物成分进行了分析。结果表明:钢中加入稀土Ce可改变夹杂物形态,并使其交流阻抗的极化电阻增大,极化曲线的腐蚀电位正移,降低了腐蚀电流密度,抵制了均匀腐蚀,改善了1Cr18Mn8Ni5N不锈钢的耐蚀性。当钢中稀土Ce质量分数为0.022%时,1Cr18Mn8Ni5N不锈钢可获得最好的耐均匀腐蚀性能。     

稀土对铁基自熔合金喷焊层组织与耐蚀性能的影响

通过熔炼—雾化工艺制备了稀土铁基自熔合金粉末,并考察了稀土对铁基自熔合金喷焊层的显微组织及其在弱酸、中性盐溶液中耐蚀性能的影响。采用金相显微镜、SEM、EDAX对合金喷焊层的物相结构、显微组织进行了观察和分析。在实验结果的基础上,对稀土的有关作用机制进行了分析和讨论。     

Effect of Rare Earths on Microstructure and Properties of TiC-based Cermet／Cu Alloy Composite Wear Resistant Materials

The effect of rare earth (RE) oxide on the microstructure and properties of TiC-based cermet/Cu alloy composite hardfacing materials was investigated by using scanning electron microscope (SEM), transmission electron microscope(TEM), impact test and wear test. The mechanism of RE oxide for improving the phase structure and the impact toughness was also discussed. The experimental results indicate that the microstructure of the matrix can be refined, and the micro- porous defects can be eliminated by adding RE oxide into the composite materials. The polycrystalline and amorphous phase structure is formed at the interface of cermet and matrix metal. The formed structure enhances the conjoint strength of interface. The frictional wear resistance can be improved obviously, although the microhardncss of the matrix metal can not be effectively increased by adding RE oxide.     

Stress corrosion of Cu- Zn and Cu- Zn- Ni alloys: The role of dealloying

Evidence is presented to demonstrate the occurrence of strain induced dealloying during stress corrosion of Cu-Zn alloys with 15-30 pct Zn and a Cu-28 pct Zn-12 pct Ni alloy. The binary Cu-Zn alloys cracked intergranularly in the ammoniacal solutions used, whereas cracking was transgranular in the ternary alloy. Dealloying was thus found to be a common feature of both modes of cracking. The results further indicate that this dealloying occurs only during crack propagation and not during the incubation period before crack initiation. Additional support for these observations was provided by slow strain rate stress corrosion tests on the Cu-30 pct Zn alloy. These results are consistent with a dealloying model for stress corrosion cracking. The possible mechanisms for the enhanced room temperature transport of solute atoms, required in this model, are discussed.     

含锶钪2099型铝锂合金的晶间腐蚀和剥落腐蚀性能

采用维氏硬度计(HV)、金相显微镜(OM)和扫描电镜(SEM)显微分析技术,研究了一种锶钪复合微合金化2099型铝锂合金(其化学成分为:Al-2.57Cu-1.86Li-1.31Zn-0.420Mg-0.321Mn-0.0735Zr-0.0943Sr-0.0433Sc)的晶间腐蚀性能和剥落腐蚀性能。结果表明,该合金经均匀化退火处理(475℃×24 h)、热锻压变形加工处理(三次变形量均约为100%)、固溶处理(540℃×2 h)、冷水淬火(水温大约5℃)、T8时效处理(121℃×14 h+151℃×48 h)后,合金显微硬度值达到174.6 HV,比2024-T6合金(固溶处理500℃×2 h+时效处理191℃×12 h)高23.1%。合金具有良好的抗晶间腐蚀性能和抗剥落腐蚀性能,其抗腐蚀性能明显优于2024-T6合金。该合金Sr,Zr,Sc的复合微合金化作用(细化粗大第二相、抑制再结晶和晶粒长大),第二相分散、分布不连续,以及Zn的含量高,是合金抗腐蚀性能高的主要原因。研究结果还说明了微量复合添加对铝锂合金具有奇效微合金化作用的过渡族金属元素Sr,Sc,是得到抗腐蚀性能良好的铝锂合金的一种有效途径。     

Combined effect of chloride and pH on corrosion resistance of Cu-10Ni alloy

Cu-10Ni alloy is a standard heat exchanger material for saltwater (including seawater) applications owing to its excellent thermal conductivity and corrosion resistance. The excellent corrosion resistance is due to formation of Cu₂O film, which accords protection. However, when varying amount of H⁺, OH^? and Cl^? ions are present, CuCl₂ ^? may also form. The CuCl₂ ^? is not protective as Cu₂O and hence corrosion resistance may be affected. Present paper investigates combined effect of chloride ion and pH on corrosion resistance of Cu-10Ni alloy. Cathodic and anodic polarization test results are presented for saltwater containing various amounts of NaCl at pH 6 and 8. It is found that, i_corr increases with increasing chloride concentration. The results are discussed using dissolution mechanisms, semi-conducting behaviour of Cu₂O film and deterioration of the film in presence of chloride ions.     

Improving corrosion resistance of RE-containing magnesium alloy ZE41A through ECAP

Significant grain refinement was achieved in rare earth (RE) containing aeronautic magnesium alloy ZE41A through equal-chan-nel angular pressing (ECAP) using rotary die at 603 K. Influence of ECAP pass number on its microstructure change and corrosion behavior was investigated by optical microscope (OM)/scanning electron microscope (SEM) observation and potentiostatic polarization tests in aque-otis solution of NaCl, respectively. The results showed that ultrafine equiaxial grains (about 2.5 μm) were obtained over 16 passes due to plastic-induced grain refinement accommodated by dynamic recrystallization. The lower corrosion current density and nobler corrosion po-tential correlated with large number of pressing passes were attributed to the low tendency toward localized corrosion with broken secondary phase after homogenization on ultrafine-grained Mg matrix. The multi-pass ECAP method made the ZE41A aeronautic magnesium alloy more attractive since severe plastic deformation may significandy improve its corrosion resistance besides superior mechanical properties.     

NaCl+HCl溶液中Ce对双相不锈钢腐蚀行为的影响

为了研究酸性NaCl溶液中双相不锈钢的耐腐蚀性能,以含微量稀土Ce的UNS S31803双相不锈钢为研究对象,采用电化学阳极极化和交流阻抗相结合的方法测试其在NaCl + HCl混合溶液中的耐腐蚀性能。利用扫描电镜(SEM)观测腐蚀后的形貌特征,采用电子探针(EPMA)检测合金元素与杂质元素的分布特征,分析Ce元素的加入对双相不锈钢电化学腐蚀行为的影响机制。结果表明,钢中存在两相的选择性腐蚀并伴有局部点蚀,其中铁素体相是腐蚀较严重的相;阳极极化测试与交流阻抗测试结果相吻合,Ce拓宽了试验钢的钝化区间;Ce通过净化钢液、降低S和P元素在相界的偏聚及使Cr、Ni和Mo等合金元素在两相中的分布更均匀等作用,提高了钢的耐腐蚀性能。     

稀土对Cu-Ni-Al合金耐冲刷腐蚀性能的影响

在冲蚀试验机上模拟了耐蚀Cu-Ni-Al合金在人工海水冲刷作用下的腐蚀情况,分析了不同冲刷时间、不同海水流速下Cu-Ni-Al合金的腐蚀行为,重点研究了稀土元素对Cu-Ni-Al合金耐海水冲刷腐蚀性能的影响.结果表明,冲刷腐蚀96 h以前,腐蚀速率随着时间延长逐渐降低,96 h以后趋于稳定;海水流速对合金的腐蚀速率影响较大,5.0 m/s流速下合金腐蚀速率比1.5 m/s流速下高;相同冲刷时间和海水流速下,添加稀土后的合金腐蚀速率明显低于不添加稀土元素;1.5 m/s流速下冲刷168 h,稀土含量(质量分数)0.014 6%和0.035 2%的合金比不加稀土的合金腐蚀速率分别降低了2%和5%,在5.0 m/s流速下冲刷168 h后腐蚀速率分别降低了4%和43%;稀土添加后合金在腐蚀过程中表面钝化加快,合金的腐蚀速率降低较快,合金钝化膜质量更好.     

22Cr High-Mn-N Low-Ni Economical Duplex Stainless Steels

 A new family of economical duplex stainless steels in which N or Mn was substituted for Ni with composition of 22Cr-80Mn-xNi-10Mo-07Cu-07W-03N (x=05-20) have been developed by examining the microstructure, mechanical and corrosion properties of these alloys. The results show that these alloys have a balanced ferrite-austenite relation. In addition, the alloys are free of precipitation of sigma phase and Cr-nitride when solution-treated at 750 to 1300 ℃ for 30 min. The yield strength, tensile strength and fracture elongation values of experimental alloys solution-treated at 1050 ℃ for 30 min are about 500, 750 MPa and 400%, respectively. Low-temperature impact properties can be improved distinctly with the increase of nickel content. Among the designed DSS alloys, the alloy with Ni of 20% is found to be an optimum alloy with proper phase proportion, better low-temperature impact properties and higher pitting corrosion resistance compared with those of other alloys. The mechanical and corrosion properties and lower production cost of the designed DSSs are better than those of AISI 304.     

稀土铁基自熔基合金抗硫化氢腐蚀性能的实验研究

近年来关于稀土在热喷涂（焊）材料中的应用研究正日益受到人们的重视。铁基自熔合金末作为一种广泛使用的热喷涂（焊）材料具有价格低廉，喷涂（焊）层的耐磨性较好等优点，但其耐蚀性较差。为此，本研究引入稀土对其改性。通过熔炼－雾化工艺制备了稀土铁基自熔合金粉末，并考察了稀土对铁基自熔合金喷焊层在硫化氢介质中气蚀和在含硫化氢的中性氯化钠溶液中浸蚀的影响。结果表明，铁基自熔合金（含稀土和不含稀土）喷焊层试样表现出较强的抗硫化氢能力。铁基合金喷焊层试样在含硫化氢的4Wt%NaCl溶液中的腐蚀速率随稀土的添加量增加量增加而逐渐降低，且稀土添加量有最佳值0.2Wt%。