Zum Verhalten rost‐ und säurebeständiger Stähle unter Komplexbeanspruchung. Teil 1 Passivität und Lochkorrosionsbeständigkeit

Some Aspects on Corrosion Fatique of Stainless Steels. Part 1 Passivity and Pitting Corrosion Susceptibility Iron‐Chromium‐Nickel alloys are of special interest for many applications because of their excellent resistance to corrosion. The nature and composition of passive films formed on stainless steels depend on the prevailing conditions, viz. steel‐composition, passivation potential, aging, pH, electrolyt composition and temperature. Passive films may be damaged by local breakdown. At least two mechanisms are possible for this localisation: mechanical breakdown by slip steps and electrochemical breakdown (for e.g. by the effects of chloride ions). Because of this, steels suffer a degradation of their fatique properties when exposed to an aqueous environment. Passivation of austenitic, ferritic‐austenitic and martensitic stainless steels has been studied in different solutions using electrochemical techniques. The results clarified that for two of the investigated alloys the prediction of fracture initiation based on pitting corrosion in chlorid containing solutions is possible. (To be continued.)     

Galvanisches Verzinken von Magnesiumlegierungen

Zinc‐Plating of Magnesium Alloys Magnesium alloys are highly susceptible to corrosion that limits their application when exposure to corrosive service conditions is needed. One of the ways to prevent corrosion is to coat the magnesium‐based substrate to avoid a contact with an aggressive environment. Results concerning corrosion behaviour of wrought AZ31 magnesium alloy with electrolytic zinc coatings deposited from different electrolyte solutions are described. Evaluation of corrosion processes in chlorides containing solutions was performed by electrochemical measurements. It was found that thick and dense electrolytic zinc coatings formed on AZ31 significantly improve the corrosion behaviour of magnesium alloy after one hour immersion of zinc coated magnesium alloys in corrosive media. Further increase of immersion time leads to relatively fast decrease of corrosion properties. Electrolytic zinc coatings obtained in consecutive alkaline / acidic process demonstrate an improvement of corrosion resistance of coated AZ31. The time to coating degradation strongly increases.     

塑性成形方法对镁合金耐蚀性的影响及展望

随着镁合金产业的快速发展,如何通过塑性成形方法提高镁合金的耐蚀性成为了重要课题。镁及其合金因具有低密度、高比强度和较好的回收性等优点而受到广泛关注,然而室温变形能力和耐腐蚀性能差等缺点是其广泛应用的瓶颈。在总结镁合金腐蚀特点及面临问题的基础上,综合分析了国内外塑性成形方法对镁合金腐蚀领域的相关研究,综述了不同加工成形方法在提高镁合金耐蚀性应用方面的进展,从腐蚀机理和工艺参数2个方面进行了讨论。介绍了不同塑性成形方法对镁合金耐蚀性的影响机制,其中包括挤压–ECAP、超声滚压处理、等通道转角挤压、热轧处理、触变成形、板材挤压、板材轧制、交叉轧制、异步轧制和异步交叉轧制、压铸、快速凝固、搅拌摩擦焊、增材制造、喷丸等。从成分分布、析出相等微观角度阐述了影响镁合金腐蚀行为的机制,指出了塑性成形方法在提高镁合金耐蚀行为方面存在的问题,为提高镁合金的耐蚀性提出建议。     

Korrosionsverhalten binärer Magnesium‐Zink‐Legierungen in salzhaltigen Medien

Aluminum is a prevalent alloying element to improve the corrosion resistance of magnesium alloys. Recent investigations found out that alloying small amounts of zinc can decrease the corrosion rate of binary magnesium‐zinc alloys. Based on these results low‐alloyed MgZn‐alloys have been analyzed in gravimetric and electrochemical measurements using varied chloride containing media. It was detected that small amounts of zinc have positive effects on the corrosion behavior; in low as well as high concentrated sodium chloride solutions. The overall tendencies of the results from the gravimetric and electrochemical investigations can be correlated. This was underlined using micro‐tomography analyses.     

In vitro corrosion behaviour of Mg alloys in a phosphate buffered solution for bone implant application

The corrosion behaviour of Mg–Mn and Mg–Mn–Zn magnesium alloy in a phosphate buffered simulated body fluid (SBF) has been investigated by electrochemical testing and weight loss experiment for bone implant application. Long passivation stage and noble breakdown potential in the polarization curves indicated that a passive layer could be rapidly formed on the surface of magnesium alloy in the phosphate buffered SBF, which in turn can protect magnesium from fast corrosion. Surfaces of the immersed magnesium alloy were characterized by SEM, EDS, SAXS and XPS. Results have shown that Mg–Mn and Mg–Mn–Zn alloy were covered completely by an amorphous Mg-containing phosphate reaction layer after 24 h immersion. The corrosion behaviour of magnesium alloys can be described by the dissolving of magnesium through the reaction between magnesium and solution and the precipitating of Mg-containing phosphate on the magnesium surface. Weight loss rate and weight gain rate results have indicated that magnesium alloys were corroded seriously at the first 48 h while Mg-containing phosphate precipitated fast on the surface of magnesium alloy. After 48–96 h immersion, the corrosion reaction and the precipitation reaction reach a stable stage, displaying that the phosphate layer on magnesium surface, especially Zn-containing phosphate layer could provide effective protection for magnesium alloy.     

Fatigue of Magnesium Alloys

Magnesium alloys show a high specific strength and are therefore increasingly used for light‐weight constructions in transportation industry.^[1,2] To predict the behaviour of the material under the influence of cyclic loading it is vital to understand the fatigue behaviour of magnesium alloys. Only when understood properly, it is possible to fully apply the potential weight reduction by using magnesium alloys. A very important aspect in fatigue of magnesium alloys is the influence of a corrosive media and elevated temperatures, of which both are relevant in automotive applications. These two factors tend to have deleterious effects on magnesium alloys and therefore also have to be considered in investigations on the fatigue behaviour of magnesium alloys.     

可生物降解镁合金血管支架管坯的材料制备及成形研究进展

对可生物降解镁合金血管支架的研究现状进行了综述。镁合金作为新型可降解物材料成为了研究热点,其中血管支架是其最有前景的应用方向之一。镁合金微细管材成形困难及镁合金血管支架腐蚀速率过快,是制约其大规模临床应用的2个主要因素。作者介绍了近期国内外的相关研究,包括改善镁合金力学性能,以及为提高成形极限采取的新成形方法,为提高镁合金耐腐蚀性而采取的各种处理方法等。     

Electrochemical noise analysis on the pit corrosion susceptibility of biodegradable AZ31 magnesium alloy in four types of simulated body solutions

Magnesium alloys have been investigated as biodegradable implant materials since the last century. Non-uniform degradation caused by local corrosion limits their application, and no appropriate technology has been used in the research. In this study, electrochemical noise has been used to study the pit corrosion on magnesium alloy AZ31 in four types of simulated body solutions, and the data have been analyzed using wavelet analysis and stochastic theory. Combining these with the conventional polarization curves, mass loss tests and scanning electron microscopy, the electrochemical noise results implied that AZ31 alloy in normal saline has the fastest corrosion rate, a high pit initiation rate, and maximum pit growth probability. In Hanks’ balanced salt solution and phosphate-buffered saline, AZ31 alloy has a high pit initiation rate and larger pit growth probability, while in simulated body fluid, AZ31 alloy has the slowest corrosion rate, lowest pit initiation rate and smallest pit growth probability.     

不同工艺制备的纳米晶Ag-25Ni合金在NaCl溶液中的腐蚀性能

分别通过粉末冶金法(PM)、机械合金化(MA)和液相还原(LPR)法借助于热压制备了一种常规尺寸和两种纳米晶Ag-25Ni块体合金。与相应常规尺寸合金对比,研究了两种不同工艺制备的块体纳米晶Ag-25Ni合金在0.3mol/L NaCl溶液中的腐蚀电化学性能。结果表明,三种不同工艺制备的Ag-25Ni合金的腐蚀电流密度按LPR Ag-25Ni、PM Ag-25Ni和MA Ag-25Ni的顺序降低,它们的交流阻抗谱均由单容抗弧组成,且电荷传递电阻按MA Ag-25Ni、PM Ag-25Ni和LPR Ag-25Ni的顺序降低。与常规尺寸PM Ag-25Ni合金对比,纳米晶LPR Ag-25Ni合金的腐蚀速度增大;相反,纳米晶MA Ag-25Ni合金的腐蚀速度则降低。三种合金形成的钝化膜均为n型半导体,载流子密度大小按LPR Ag-25Ni、PM Ag-25Ni、MA Ag-25Ni的顺序降低,MA Ag-25Ni合金的钝化性能最好,这归因于三种合金显微组织的不同,MA Ag-25Ni合金中晶粒尺寸的降低和组元间固溶度的增加,导致其具有良好的化学稳定性。     

AZ91D镁合金表面钙系磷酸盐膜层的制备及其耐蚀性

为了降低AZ91D镁合金活泼的化学性质,使其成为耐蚀性更好的医用金属材料,在不同pH值及反应温度等条件下对AZ91D镁合金进行钝化,观察了不同条件下制备的膜层的表面形貌、元素构成,并测试了其电化学性质,研究了磷化的pH值和温度对磷化膜性能的影响。结果表明:磷化液的温度及pH值对磷化膜性能有重要影响,当pH值为2.8,温度为40℃时,制备的磷化膜为针状鳞片、尺寸均一,膜层覆盖最为致密细腻,表面膜层中主要生成了CaHPO_4·2H_2O化合物,即DCPD,还有少量Ca_3(PO_4)_2,膜层在AZ91D表面形成了稳定的钝化层,有效降低了其化学活泼性,大幅提高了其耐蚀性。     

Recent Progress in Corrosion and Protection of Magnesium Alloys

Magnesium alloys are advanced light structural and functional materials being increasingly used in the automotive, aerospace, electronic, and energy industries. However, their corrosion performance at the current stage of development is still not good enough for increasingly diverse practical applications. The Cooperative Research Centre for Cast Metals Manufacturing (CAST) in Australia is one of the most active research organizations in the world established to cope with the problems associated with the development and application of advanced light metals. Corrosion and prevention of magnesium and its alloys is an important part of CAST's research program. This paper presents a brief summary of recent research achievements by CAST and relevant research work in this area in the world. This overview covers “anodic hydrogen evolution”, estimation of corrosion rate, corrosion of aluminum‐ and non‐aluminum‐containing magnesium alloys, influences of composition and microstructure on corrosion, corrosion of a die‐cast magnesium alloy, galvanic corrosion, coolant corrosion, and an aluminum‐alloyed coating. The aim of this overview is to deepen the current understanding of corrosion and protection of magnesium and its alloys and to provide a base for future research work in this field.     

Magnesium based degradable biomaterials: A review

Magnesium has been suggested as a revolutionary biodegradable metal for biomedical applications. The corrosion of magnesium, however, is too rapid to match the rates of tissue healing and, additionally, exhibits the localized corrosion mechanism. Thus it is necessary to control the corrosion behaviors of magnesium for their practical use. This paper comprehensively reviews the research progress on the development of representative magnesium based alloys, including Mg-Ca, Mg-Sr, Mg-Zn and Mg-REE alloy systems as well as the bulk metallic glass. The influence of alloying element on their microstructures, mechanical properties and corrosion behaviors is summarized. The mechanical and corrosion properties of wrought magnesium alloys are also discussed in comparison with those of cast alloys. Furthermore, this review also covers research carried out in the field of the degradable coatings on magnesium alloys for biomedical applications. Calcium phosphate and biodegradable polymer coatings are discussed based on different preparation techniques used. We also compare the effect of different coatings on the corrosion behaviors of magnesium alloys substrate.     

Biodegradable behaviour and fatigue life of ZEK100 magnesium alloy in simulated physiological environment

The fatigue life of ZEK100 magnesium alloy in the phosphate buffered solution for various immersion intervals was investigated by experiments and theoretical predictions. The biodegradable behaviours of ZEK100 magnesium alloy were also studied. Microstructure observation showed that the corrosion behaviours were characterized by pitting corrosion. The corrosion rate decreased a lot in the initial 7 d and then almost stayed unchanged. After 28 d immersion, the elastic modulus almost kept stable, while the yield strength and the ultimate strength decreased a lot, which indicated that corrosion had important effects on the tensile mechanical properties. It showed that the fatigue life of the samples under the same stress conditions decreased with increasing immersion time under the asymmetric stress‐controlled cyclic loading. Considering the effect of corrosion on the material failure, a modified fatigue life model was proposed for magnesium alloy under corrosion.     

氯盐环境中新型合金耐蚀钢筋Cr10Mo1的钝化行为

应用线性极化、电化学阻抗谱与电容电位法等方法对比研究了合金耐蚀钢筋Cr10Mo1和普通碳素钢筋在预含不同浓度(0mol·L~(-1)、0.1mol·L~(-1)、0.3mol·L~(-1)、0.6mol·L~(-1))氯盐的较低碱度(pH=12.5)模拟混凝土孔溶液中的钝化行为,利用XPS方法分析钢筋钝化膜组成结构,分析了氯盐作用下两种钢筋钝化行为变化存在差异的原因,揭示了合金耐蚀钢筋强易钝化机制。结果表明:在各氯盐浓度下,合金耐蚀钢筋均能良好致钝且钝化效果并无较大差距,而普通碳素钢筋随氯盐浓度增大钝化效果显著减弱,当氯盐超过一定浓度则几乎不钝化,甚至发生明显点蚀。Cr氧化物作为合金耐蚀钢筋钝化膜不同于普通碳素钢筋的关键成分,高浓度氯盐作用下仍可保持稳定并维持钝化膜层完整密实,从而使耐蚀钢筋呈现强易致钝特性。     

AZ31镁合金表面磁控溅射Zr(Al,Ti)-SiN_x复合薄膜及其耐蚀性能

镁合金表面沉积薄膜可以提高其耐蚀性,但现有的几种沉积方法得到的膜疏松、与基体结合力差,影响了其耐腐蚀性能.为此,采用磁控溅射法在AZ31镁合金表面制备了Al,Zr,Ti膜及其与SiN_x的复合薄膜.用扫描电镜、X射线衍射、XPS研究了金属膜及其与SiNi_x复合薄膜的晶体结构、表面形貌和化学成分.结果表明:所制备的SiN_x薄膜为非晶态的富N膜;Zr膜的耐腐蚀性最好,Al膜的保护性最差;Zr-SiN_x复合薄膜比AZ31镁合金的腐蚀电流密度降低了3个数量级,Ti-SiN_x复合薄膜在阳极极化区出现了钝化.SiN_x复合薄膜的耐腐蚀性优于AZ31镁合金和单一金属膜.     

Verhalten geschweißter Magnesiumlegierungen unter mechanisch‐korrosiver Komplexbeanspruchung

Corrosion and corrosion fatigue of welded magnesium alloys In addition to the prevalent use of magnesium cast alloys a high potential for lightweight constructions is offered by magnesium‐wrought alloys, in particular in the automobile industry. The use of rolled and/or extruded magnesium alloys (profiles and sheet metals) requires suitable and economic join technologies like different welding procedures in order to join semi finished parts. Thus, the realization of lightweight constructions asks for high standards of materials‐ and joining‐technologies. In this context, the mechanical properties as well as the corrosion behaviour of the joints are of large interest. During welding of magnesium alloys, influences concerning the surface, the internal stresses and the microstructure occur. These influences particularly depend on the energy input and thus, on the welding procedure as well as the processing parameters, which all affect the corrosion behaviour of the joints. Sheets of magnesium alloys (AZ31, AZ61, AZ91) were joined with different welding procedures (plasma‐, laser beam‐ and electron‐beam welding in the vacuum and at atmosphere). The corrosion behaviour (with and without cyclic mechanical loading) of the welded joints was investigated by different methods such as corrosion tests, polarisation curves, scanning electron microscopy and metallography. Furthermore, substantial influencing variables on the corrosion behaviour of welded joints of magnesium alloys are pointed out and measures are presented, which contribute to the improvement of the corrosion behaviour.     

镁合金激光选区熔化研究进展

镁合金作为最轻的金属结构材料,在汽车制造、生物医疗等领域具有极大的应用潜力。激光选区熔化成形镁合金具有高效的制备性能、良好的成分均匀性、优异的力学性能和耐腐蚀性能,因此激光选区熔化成为一种重要的镁合金制备和改性方法。对近几年激光选区熔化镁合金的研究进展进行了综述,从激光工艺参数(激光类型、体能量密度、激光功率、扫描速度、扫描模式、层厚、扫描间距、气氛控制与进粉速度)和粉体状态(粉末形状、粒径分布、粉末对激光束能量吸收率、粉末化学成分)2个方面讨论了该工艺的关键技术;按照纯镁、非稀土镁合金体系、稀土镁合金体系的分类,对激光选区熔化成形镁及镁合金的致密度与微观结构、力学性能与耐腐蚀性能进行了总结;分析了工艺参数与合金成分两方面对该工艺成形镁合金缺陷的影响。为减少激光选区熔化成形镁合金缺陷、均匀化晶粒、溶解硬脆二次相或析出强化相进而改善合金的结构与性能,许多研究对激光选区熔化成形镁合金进行了热等静压、固溶热处理和时效热处理,总结了上述处理方式对AZ体系、WE体系与Mg-Gd体系镁合金的改善效果。最后展望了激光选区熔化成形镁及镁合金在各领域的应用前景与未来可以进行研究的方向。     

Entwicklung und Eigenschaften von Magnesium‐Lithium‐Legierungen

Development and Properties of Magnesium‐Lithium‐Alloys The application of Lithium in Magnesium alloys extends the properties of these regarding smaller density and clearly increased ductility. Hereby can be met to demands even on the part of the automobile industry for damage‐tolerant, better ductile magnesium components. Investigations of hexagonal Magnesium Lithium alloys show promising results, which contain not only more balanced mechanical properties but also an improved corrosion behavior.     

Magnesium — an old material with new applications

Magnesium alloys have been made more competitive for engineering applications through developments in alloys and casting techniques. The properties of magnesium alloys and the advantages of die casting are described. High strength-to-weight ratios allow thin-section designs which retain good fatigue and creep resistance and are suitable for EMI shielding applications. Machining, joining, surface treatment and corrosion resistance of alloys are considered.