Advances in Replacements for Cadmium Plating in Aerospace Applications

This paper examines some of the problems associated with the replacement of cadmium plating for the protection of aircraft components and fasteners manufactured from steel. It reviews the range of coatings which are available commercially and are currently being considered as alternatives to cadmium plating. Results of research being undertaken into the corrosion behaviour and galvanic compatibility of electrodeposited zinc alloy coatings and aluminium-magnesium alloy coatings are presented. Other aspects of coating performance are also considered including frictional properties, effects of coatings on fatigue strength, hydrogen embrittlement of steels and the repair of damaged coatings. It is concluded that although the corrosion performance of cadmium plating may be achieved with several coating systems, no one coating is likely to be acceptable as a replacement for cadmium for all aerospace applications.     

Zn-Ni合金镀层中添加第三种元素和纳米颗粒的研究新进展

介绍了在汽车、航空航天等行业中得到广泛应用的钢铁零件电镀Zn-Ni合金镀层,以及往碱性、氯化物等锌镍合金镀液中加入Fe、Co、Mn、Ce、P等第三种元素所获得的锌镍三元合金镀层,具有更优良的耐腐蚀性、催化性等性能的情况。介绍了往Zn-Ni合金镀液里加入氧化硅、氧化铈、氧化钛、氧化铝、碳化硅等纳米颗粒的进展情况,发现含有纳米颗粒的锌镍复合镀层具有耐腐蚀性、耐磨损性、热稳定性更好,硬度更高等优点。梳理了2016年以来在Zn-Ni合金电镀中添加第三种元素和纳米颗粒的多层镀层研究新进展。从Zn-Ni单一镀液中沉积Ni-P和Zn-Ni合金多层镀层时,在低电流密度下沉积出Ni-P层;在较高电流密度下,沉积出含3.2%P的Zn-Ni-P合金镀层,这种多层镀层可以大幅度提高钢铁零件的防腐蚀性能。介绍了在含12%Ni的Zn-Ni镀层上镀覆Ni-Co-SiC纳米复合镀层的情况,这种多层结构既可以提高镀层的结合力,又可提高其在3.5%NaCl溶液中的耐腐蚀性能。该复合镀层是一种硬度高、磨损量低的新型Zn-Ni合金复合镀层。     

金属氢渗透研究综述

综述了氢渗透的研究方法和研究历史,总结了当前对氢损伤机理的研究,以及在易发生氢脆环境下的氢渗透行为规律和影响氢行为的因素。在这些研究的基础上,国内外先后开发了许多氢渗透防护技术,如:阻碍氢原子渗入基体,在材料表面制备涂镀层;消除钢中有害元素的方式,改变中氢原子陷阱的数目;从组织入手,开发高纯度、高抗氢钢,包括一些系列铁素体合金钢等。综述了从传统的电沉积阻氢合金镀层,到新工艺制备阻氢陶瓷层的发展。阻氢涂层具有阻氢性能极佳,兼具保护作用的优点,但容易失效,破损后会加快基体的局部腐蚀;而通过冶金、热处理来净化钢材,改变组织成分开发的纯净钢,其实际抗氢脆性能并不理想,仍然会出现氢引起的力学性能下降,并且具有控制工艺复杂、能耗大的缺点。由此认为,氢一旦进入金属材料内部,造成材料的性能损伤不可避免,防止氢进入金属材料是该领域的关键科学问题。氢渗透过程是氢损伤发生的关键步骤,那么阻碍氢渗透过程的进行就成了氢损伤防护措施的重中之重。抑制氢渗透过程的发生需要从降低氢原子浓度梯度、降低材料内部氢陷阱密度和结合能两方面入手,开发有效的抑氢手段,抑制氢渗透过程,使材料内部的氢原子浓度小于临界氢原子浓度。     

镁合金表面冷喷涂层防护研究进展

镁合金作为最轻质的金属结构材料,由于其密度低和比强度高等优良的物理和力学性能,在航空、航天、汽车以及电子等领域引起广泛关注。然而,镁合金化学性质活泼、耐腐蚀和耐磨损性差等缺点严重制约其进一步应用。近些年发展起来的冷喷涂技术,在固态下制备涂层,涂层致密且与基体结合良好,因此可为镁合金表面防护提供一种新的有效方法。主要综述了镁合金表面冷喷涂耐腐蚀涂层(纯铝、铝合金和复合材料涂层)和耐磨损涂层(合金和复合材料涂层),论述了影响冷喷涂层耐腐蚀、耐磨损以及其他力学性能(硬度和涂层/基体结合强度)的主要因素,包括杂质元素含量、合金种类以及复合材料涂层中陶瓷颗粒含量、尺寸和形貌等。对比了几种常用表面处理技术制备的纯铝涂层的耐腐蚀性能,并阐述了冷喷涂技术在镁合金表面防护方面的优势。此外,还分析了热处理对冷喷涂纯铝和复合材料涂层耐蚀性的影响。最后提出了目前冷喷涂技术在镁合金防护方面的局限性以及发展难题,对未来研究趋势进行了展望。     

电沉积电位对锌镍合金镀层耐蚀性的影响

采用电化学沉积方法在DH36船板钢表面制备了锌镍合金镀层。采用扫描电镜(SEM),能谱仪(EDS)和X射线衍射仪(XRD)等研究了电化学沉积电位对锌镍合金镀层形貌、化学成分和晶体结构的影响。结果表明:随着沉积电位的升高,锌镍合金镀层由无法覆盖整个基底表面到均匀致密覆盖,再到较大微纳米颗粒层覆盖,证明沉积速率越来越大。由EDS和XRD分析可知,在较低电位下沉积,锌镍电沉积过程属于正常共沉积,而在较高电位沉积时,锌镍电沉积过程属于异常共沉积。电化学极化曲线测试表明,在电沉积电位为-1.2 V时所获得的锌镍合金镀层的耐腐蚀性最好。     

The effects of sacrificial coatings on hydrogen embrittlement and re-embrittlement of ultra high strength steels

This paper describes an investigation of electrodeposited Zn-14% Ni and aluminium-based SermeTel 1140/962 coatings as possible replacements for cadmium. Slow strain rate tests were performed to measure the extent of direct hydrogen embrittlement of a high strength steel substrate as a result of the coating process and of hydrogen re-embrittlement caused by coating corrosion. The level of re-embrittlement was shown to depend on both the electrochemical potential of the coating and its barrier properties. Zn-14% Ni coatings caused the most re-embrittlement as they had the most active potential and contained through-thickness defects which left the steel exposed to hydrogen uptake. The microstructure of the high strength steel was also shown to be an important factor affecting the extent of embrittlement. AerMet 100 steel was more resistant than 300M steel and this was attributed to the presence of reverted austenite surrounding the martensite laths in AerMet 100, which trapped absorbed hydrogen and prevented a critical hydrogen concentration being reached in the more susceptible martensite phase.     

Einfluß der Festigkeit unlegierter und niedriglegierter Stähle auf H-induzierte Korrosionserscheinungen bei zügiger plastischer Belastung

Influence of mechanical strength on hydrogen-induced corrosion effects on unalloyed and low-alloysteels subjected to slow strain rate tests Three steels were subjected to various heat treatments or cold working to produce 7 variants of strength. Specimens from these materials were tested in 9 aqueous solutions containing various acidic components by the constant strain rate technique under cathodic polarisation or free corrosion conditions. Hydrogen induced cracks were only observed after passing the maximum load. Hydrogen induced cracking and the decrease in the reduction of area (hydrogen embrittlement) show a good correlation with the mechanical properties of the materials. For less ductile materials the number of cracks decreased with increased embrittlement. The magnitude of hydrogen embrittlement depends on the concentration of undissociated acid in the test solution and is independent of pH value. O₂ can reduce the embrittlement. The effect of test solution composition decreases as the cathodic polarisation potential becomes more negative, because hydrogen will then be generated from H₂O. There is no correlation between the type of corrosion effects and the strength of the material, except in the case of highly sensitive high strength variants with R_m in excess of 1000 N/mm². Quenched and tempered low alloy steels, even at high strength levels, have significantly higher resistance to hydrogen embrittlement than significantly higher resistance to hydrogen embrittlement than unalloyed steels. The same is also ture for workhardened variants. For unalloyed steels, metallurgical cleanness seems to have a favourable influence. No hydrogen induced corrosion effects were observed in specimens tested at 907°C under free corrosion conditions.     

Vermeidung der Wasserstoffversprödung vergüteter Stähle bei galvanotechnischen Prozessen durch thermische Legierungsbildung

Avoidance of hydrogen embrittlement of high strength steels during electroplating processes by thermal alloying Low alloyed high strength steels are often electroplated by metal layers protecting against corrosion. For ultra high strength, quenched and tempered steels with yield strengths > 1000 Nmm^?2 embrittlement by hydrogen being envolved during the electrochemical pretreatment as well as metal deposition has to be avoided. More over the corrosion protecting layers should form a diffusion barrier for hydrogen which can be formed during corrosion processes under special circumstances. In this paper two problem solutions including thermal alloying processes will be discussed. Plating the steel substrate with a nickel layer subsequently annealed at a temperature above 800°C in an inert gas atmosphere an austenitic iron-nickel-alloy at the boundary is formed, being a high efficient diffusion barrier for hydrogen. Further zinc plating is improving the corrosion resistance avoiding at the same time pitting corrosion problems. Plating the steel substrate with a copper and a following nickel layer on top and annealing it at the temperature of 800°C a highly corrosion resistant copper-nickel-alloy is formed showing excellent barrier behaviour for hydrogen diffusion. In both cases hydrogen being formed during the plating process itself and penetrating into the base metal does not lead to embrittlement as it is effusing during the annealing procedure.     

一种用于显示中高强度钢晶粒的方法

中高强度钢随着碳含量的逐渐增加,组织愈发细小,通过直接腐蚀等传统方法得到的晶界往往比较模糊。为了能够清晰地显示中高强度钢的晶粒度,利用其具有氢脆敏感性以及氢脆易于产生沿晶断裂形貌的特点,提出了一种晶粒度检测方法。通过对 55SiCr弹簧钢和 440冷墩钢分别使用直接腐蚀、电子背散射法（EBSD）与氢致开裂断口法显示晶界,对比可以发现在中高强度钢的晶粒度检测中,氢致开裂断口法显示的晶界更为清晰,评定的结果更加准确。     

Hot-Dip Galvanizing Alloys

Activity in the development of hotdip galvanizing alloys has been quite successful in achieving two major goals. First, the use of a zinc-nickel bath provides a workable solution to the problem of batch galvanizing reactive steels, to achieve both an attractive surface appearance and a thin, durable and protective coating. Second, for continuously galvanized steel products, specific zinc-aluminum alloys have provided a means to greatly increase corrosion resistance, increase the maximum use temperature of zinc coatings, achieve the fabrication of severely formed products without damage to the zinc alloy coating, and allow such products to be formed from prepainted as well as unpointed coated steel.     

Microstructure and Performances of Nanocrystalline Zinc-nickel Alloy Coatings

THE STUDY on zinc-nickel alloy coatings isdeveloped rapidly because of their higher corrosionresistance and better mechanical characteristics[1-8].The zinc-nickel coatings provide improved corrosionprotection for steels in relatively aggressiveenvironments.It has been found that the maximumprotective ability can be reached with the nickel contentbetween12%and15%[9].Recently,several newzinc-nickel alloy technologies have been developed[10-15]and further researches for better coating andchara…     

电弧喷涂Zn-Al伪合金涂层耐腐蚀性能研究进展

通过在钢基体表面制备涂层可以很好地延长钢铁材料的服役时间,减少因腐蚀造成的重大事故和人员伤亡。相较于传统的纯Zn涂层、纯Al涂层以及Zn-Al合金涂层,Zn-Al伪合金涂层能够为基体材料提供长久有效的腐蚀防护,在钢铁材料的腐蚀防护中具有巨大的应用潜力。简述了Zn-Al伪合金涂层电弧喷涂制备工艺的特点;介绍了Zn、Al、Zn-Al合金及Zn-Al伪合金涂层在模拟海洋环境下的腐蚀防护原理;在此基础上从组分、喷涂工艺参数(喷涂距离、喷涂电流和喷涂电压)、元素掺杂(Mg、Si及Re)及后处理工艺(封孔、激光重熔)等角度,论述了其对Zn-Al伪合金涂层耐蚀性的影响;讨论了Zn-Al伪合金涂层防腐体系在桥梁、海洋钢结构件、地下运输管道中的应用现状;最后总结了目前研究工作中存在的挑战,提出了电弧喷涂Zn-Al伪合金涂层尚需深入研究的重点问题,为提高钢铁材料使用寿命提供了参考。     

Electrodeposition of Zn–Ni coatings as Cd replacement for corrosion protection of high strength steel

Electrodeposition of Zn–Ni coatings performed in acidic baths are not suitable for high strength steels due to their high susceptibility to hydrogen embrittlement.In this work, Zn–Ni coatings were deposited on a high strength steel (4340) upon stirring conditions from an alkaline bath. A complete characterisation of the coatings (corrosion, morphology and composition) has been accomplished, correlating the electrodeposition conditions with these features. The best protective properties of the grown coatings were achieved for the alloys with a single phase structure of γ-Ni₅Zn₂₁ and a denser morphology. Additionally, the hydrogen content incorporated is lower than even cadmium-coated 4340 steel which has undergone a postbaking dehydrogenation treatment.     

Dilution and Ferrite Number Prediction in Pulsed Current Cladding of Super-Duplex Stainless Steel Using RSM

Super-duplex stainless steels have an excellent combination of mechanical properties and corrosion resistance at relatively low temperatures and can be used as a coating to improve the corrosion and wear resistance of low carbon and low alloy steels. Such coatings can be produced using weld cladding. In this study, pulsed current gas tungsten arc cladding process was utilized to deposit super-duplex stainless steel on high strength low alloy steel substrates. In such claddings, it is essential to understand how the dilution affects the composition and ferrite number of super-duplex stainless steel layer in order to be able to estimate its corrosion resistance and mechanical properties. In the current study, the effect of pulsed current gas tungsten arc cladding process parameters on the dilution and ferrite number of super-duplex stainless steel clad layer was investigated by applying response surface methodology. The validity of the proposed models was investigated by using quadratic regression models and analysis of variance. The results showed an inverse relationship between dilution and ferrite number. They also showed that increasing the heat input decreases the ferrite number. The proposed mathematical models are useful for predicting and controlling the ferrite number within an acceptable range for super-duplex stainless steel cladding.     

装饰性Zn-Ni/Ni-P镀层的研究

为进一步提高镀层的耐蚀性、降低脆性,在含有缩合物添加剂的镀液中制备了结晶为14～33nm的Zn-Ni合金镀层.采用SEM、XRD对镀层的微观形貌及相组成进行了研究.将此Zn-Ni合金镀层作为底层,制备了双层Zn-Ni/Ni-P镀层,结果表明:双层镀层的耐蚀性比装饰铬组合镀层提高1倍以上,而且镀层的氢脆大大降低,尤其适合于高强度零件的电镀.     

Innovation of Ultrafine Structured Alloy Coatings Having Superior Mechanical Properties and High Temperature Corrosion Resistance

High temperature protection requires full coating density, high adhesion, minor oxide inclusions, and preferably fine grains, which is not achievable in most thermal spray processes. High velocity oxygen fuel (HVOF) thermal spray process has been applied extensively for making such coatings with the highest density and adhesion strength, but the existence of not melted or partially melted particles are usually observed in the HVOF coatings because of relatively low flame temperature and short particle resident time in the process. This work has investigated the development of an innovative HVOF process using a liquid state suspension/slurry containing small alloy powders. The advantages of using small particles in a HVOF process include uniform coating, less defective microstructure, higher cohesion and adhesion, full density, lower internal stress, and higher deposition efficiency. Process investigations have proven the benefits of making alloy coatings with full density and high bond strength attributing to increased melting of the small particles and the very high kinetic energy of particles striking on the substrate. High temperature oxidation and hot corrosion tests at 800 °C have demonstrated that the alloy coatings made by novel LS-HVOF process have superior properties to conventional counterpart coatings in terms of oxidation rates and corrosion penetration depths.     

Non-Chromate Conversion Coating Treatments For Electrodeposited Zinc-Nickel Alloys

Molybdate-based conversion coating solutions have been examined as to their suitability as possible replacements for chromate formulations on electrodeposited zinc-nickel alloy coatings. Investigations have concentrated on producing passive surfaces from simple molybdate solutions using immersion or cathodic coating processes. Passivated surfaces have been examined using scanning electron microscopy to elucidate the coating morphology. The corrosion resistance of the treated surfaces has been assessed using simple, rapid electrochemical techniques as well as more long term salt fog immersion. Initial findings indicate molybdate-based treatment solutions improve times to white and red rust of the zinc-nickel surfaces, but as yet are surpassed by a more conventional chromate-based treatment.     

Evaluation of hydrogen entry into high strength steel under atmospheric corrosion

Hydrogen entry into high strength steels by atmospheric corrosion has been investigated to evaluate their susceptibility to hydrogen embrittlement. High strength steels were corroded by dry/wet cyclic corrosion after NaCl deposition. The maximum diffusible hydrogen concentration around the surface was successfully obtained by means of thermal desorption analysis after keeping the specimens at high humidity to reproduce enhanced hydrogen entry influenced by the rust layer and to homogenize the hydrogen distribution. Despite decrease in corrosion rate, hydrogen content in specimens did not decrease. Decrease of pH in inner rust layer is responsible for the enhanced hydrogen entry into steel.     

Study of a New Chromium-Free Conversion Coating Formed on ZnAl Alloy

BECAUSE OF A HIGHER CHEMICAL ACTIVITYzinc and zinc alloys(in bulk or in coating form)corrode rapidly in moist atmospheres recovering withwhite corrosion products—white rust and in acidicclimatic conditions becoming grey[l].So passivition orchemical conversion treatments is often needed fortheir corrosion protection.This is generally done bymeans of chromate treatment which offers a goodcorrosion inhibition.However,chromates are highlytoxic and carcinogenic[2]and their use can lead…     

超音速火焰喷涂316L不锈钢涂层性能研究

采用超音速火焰喷涂技术(HVOF)在高强钢表面制备了316L不锈钢涂层,利用扫描电镜、显微硬度仪、电化学测试系统等设备对涂层金相组织、硬度、结合性能和抗腐蚀性能等进行了测试,并分析了WC-CoCr中间层对316L不锈钢粉末涂层结合强度及涂层界面的影响。结果表明:超音速火焰喷涂316L不锈钢粉末颗粒在喷涂中变形充分,形成较致密的涂层,并具有超过400 HV0.1的显微硬度;涂层具有较高自腐蚀电位,耐蚀性优于高强钢;涂层结合强度随着涂层厚度的减小、基体硬度的增加而提高;WC-CoCr底层可改善涂层界面结合,从而改善316L不锈钢涂层的结合性能。