2024铝合金浸锌工艺研究

试验研究了浸锌工艺及溶液组成对2024铝合金基体浸锌层及电镀镍层外观和结合力的影响,优化了浸锌液的组成及工艺条件.发现良好的浸锌层是提高镀层与基体结合力的关键.     

Thermochemical surface treatment of titanium

Abstract

Titanium has very poor tribological properties. Various coatings can be used, for example, TiN, to improve them, but the loading is limited by the low strength of the substrate. Thermochemical treatments produce a layer that is sufficiently thick to support a load, but have to be carried out at high temperatures, 950 and 1050°C, for oxidation and nitriding processes respectively, degrading the core properties. An alternative treatment is desirable that could produce a substantive load bearing layer with good wear properties at 850°C or lower. The obvious candidate species were oxygen, nitrogen and carbon to form hardened diffusion layers, under a thin TiO₂, TiN or TiC surface layer. Nitrogen was not found to be sufficiently active at lower treatment temperature to have any beneficial effects and tended to block the diffusion of other species. Layers formed using various sources of nascent nitrogen, carbon and oxygen were studied. It was found that all the species forming hardened surface layers with the highest values of surface hardness and case depth (72 μm and 922 HV after 24 h at 850°C) were produced using carbon monoxide.     

Effect of magnesium content on the high temperature adhesion of Al-Mg alloys to steel surfaces

The transfer and adhesion of material to die surfaces during the rolling or stamping of aluminum alloy sheets reduce the surface quality of the finished product, particularly when these operations are conducted at elevated temperatures. This study investigates the effect of magnesium content on high-temperature adhesion between aluminum alloys containing different percentages of magnesium, and an AISI 52100 steel. 5000 series aluminum alloys with magnesium contents ranging to 4.7 wt.% were tested using a pin-on-disc configuration under a normal force of 0.5 N at 713 K, establishing an adhesive junction with the steel counterface. The tangential force required to break this junction (the junction strength) was measured. The junction strength of 99.99 purity aluminum was 0.69 ± 0.03 N. The junction strength decreased in alloys that featured a higher magnesium content, with the 4.7 wt.% Mg alloy displaying the lowest strength of 0.36 ±0.03 N. Magnesium diffusion to the surface during heating formed a magnesium-rich layer, with thicker layers appearing in alloys with high magnesium content. These layers decreased the junction strength and reduced adhesion between the Al-Mg alloy and the steel.     

Oxidation behavior of a Ni3Al PM alloy

The oxidation behavior of a Ni₃Al powder-metallurgical (PM) alloy doped with boron was investigated by means of discontinuous isothermal tests in the temperature range of 535° to 1020°C for exposures of up to 150 hr. The oxidation kinetics were characterized by a sharp decrease in the oxidation rate at about 730°C which is associated with a change in the oxidation mechanism. Below 730°C, the scale exhibited an outer NiO layer and an internal-oxidation zone consisting of a fine dispersion of alumina in a diluted Ni-Al solid solution. Between these two layers a very thin layer of nickel could be observed. Above 730°C, a three-layered scale was observed consisting of an outer NiO layer, an intermediate layer that depending on temperature consisted of a mixture of nickel and aluminum oxides or NiAl₂O₄, and an inner layer of Al₂O₃, which accounts for the higher oxidation resistance. Oxidation at the higher temperatures resulted in extensive void formation at the scale/metal interface which led to poorly adherent scales. It is worth noting that at the early oxidation stage the scale was characterized by planar interfaces. Roughening of the air/scale and, specially, the scale/metal interfaces after long exposures at the low-temperature range or after short times at higher temperatures could be related to the formation of the inner Al₂O₃ layer at the grain boundaries which favor oxygen penetration through the grain interior.     

铜/铝磁脉冲半固态辅助钎焊界面扩散过程

结合分子动力学模拟和试验研究,对铜/铝管磁脉冲半固态辅助钎焊界面原子扩散过程进行了研究.结果表明,在铝侧扩散界面原子主要在界面的无序原子层中相互扩散,且各元素的扩散行为不均匀,铝基体原子向钎料的扩散速度远小于钎料原子向铝基体扩散的速度;铜侧界面在模拟设置的冲击速度下,扩散层很薄且厚度变化并不明显.测量不同冲击速度下铝侧界面的扩散层厚度发现,随着冲击速度增加,模拟的扩散层厚度呈线性增加,与试验结果相符.根据模拟与试验结果建立了在相同或相近的冲击速度下,模拟界面扩散层厚度与试验界面扩散层厚度之间的关系,模拟结果能够较好地预测试验界面扩散层厚度,最大误差为2.8%.     

Features of intermetallic compounds in aluminized steels formed using aluminum foil

Foil aluminizing of steel, wherein Al diffuses to the base steel material by diffusion treatment after hot pressing of the aluminum foil at a lower temperature than the melting point, was performed in this study. Alloy layers formed by diffusion at temperatures ranging from 700 to 1000 °C were investigated, and their features were compared with those of hot-dip aluminized steel. In hot-dip aluminizing, an intermediate Fe₂Al₅ layer was formed between the aluminum layer and the base steel during aluminum coating before the diffusion treatment. In contrast, the coating layer of the foil-aluminized steel specimen after diffusion bonding of the aluminum foil consisted only of the Al layer. An Fe₂Al₅ layer, an FeAl layer and an Al diffused layer were formed in both the aluminized specimens subsequent to the diffusion treatment. The numbers of voids formed in the Fe₂Al₅ layer and at the FeAl/Al diffused layer interface of the foil-aluminized specimens are smaller than those for hot-dip aluminizing. Moreover, the FeAl and Al diffused layers are formed with a greater thickness in the foil-aluminized steel under identical diffusion conditions. The Al concentration in hot-dip aluminized steel decreased in stages from the surface to the base steel, whereas, in the foil-aluminized steel, it decreased gradually. The Fe₂Al₅/base steel interface in the foil-aluminized steel was thus indistinct, and cross-sectional hardness also decreased gradually.     

铝硅合金压铸件浸锌对化学镀Ni-P层的影响

从锌合金层的微观形貌、组成、厚度、耐蚀性等以及化学镀Ni-P层的微观形貌、成分、相结构、孔隙率、耐蚀性、结合力等方面研究了浸锌层对化学镀Ni-P ?层的影响.结果表明,浸锌层对铝硅合金压铸件基体与化学镀层的结合起重要作用,浸锌层厚度薄且致密、均匀;后续的化学镀Ni ?合金层也细致均匀,结合力好,耐蚀性强.     

Effect of Zincation/Sonication on Electroplated Gold Deposited on Aluminum Substrate

The adhesion strength of gold plated layers on Al substrates has been investigated. Conventional zincation and modified zincation under ultrasonication of aluminum samples are done. Zincation is done by two ways: single zincation and double zincation. Both are repeated under ultrasonic agitation. Ultrasonic agitation during zincating produced dense population of small Zn particles and increased the coverage of Zn intermediate layer. Subsequent nickel strike by electrochemical nickel plating is carried out to form an intermediate nickel layer over the aluminum substrate. As the final step, gold electrochemical plating is done which produced spindle-like gold particles upon the nickel substrate. Gold-plated samples are characterized using E-log I polarization, SEM, and adhesion pull-off test. Gold-plated sample pre-treated with double zincation and ultrasonication shows the best result in terms of corrosion potential, surface morphology and pull-off test.     

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.     

铝基化学镀镍浸镍前处理的研究进展

铝基表面欲获得结合力好的镀层,关键在于前处理工艺的选择。尽管浸锌法是目前研究较多、效果较好的前处理方法,但仍存在一些不足,而浸镍法可以避免这些不足,有望取代浸锌法。较详细地阐述了浸镍法的原理及研究现状,并将文献中涉及的浸镍法分为活化浸镍、碱性预镀镍和二次浸镍。活化浸镍液中一般不含还原剂,主要通过置换反应生成一层具有催化作用的镍,进而促使化学镀过程中镍紧密均匀地沉积;碱性预镀镍则是通过含有还原剂的镍盐溶液,在铝基表面预化学镀上一薄层镍,其原理与化学镀镍相同。同时,对比分析了两种浸镍法及其组合处理法之间的区别与联系。最后,指出了浸镍法未来的发展方向:其一,简化工艺,用一次浸镍法代替二次浸镍法;其二,无毒、低污染,研发出无氟浸镍液;其三,获得高性能,即优化浸镍液配方,使得镀层与基体结合强度更好。     

Alloying of Stacked Tin and Nickel Surface Films on Iron Substrate and Its Limitation

Stacked single layers of tin and nickel usually made by electrodeposition were prepared by a sputtering process in this study and the alloying behaviour through heating in an electric furnace was investigated by SEM-EDX and X-ray analysis. No remarkable chemical compounds between tin and nickel were produced. The substrate atoms diffused into both surface layers, and a compound or a solid solution was formed. The iron diffusion was driven by the strong affinity between tin and iron. The results suggest the following two basic rules: I. When tin is the underlayer in direct contact with the iron substrate, the alloying of stacked tin and nickel layers hardly occurs. 2. When the nickel underlayer was very thin (e g submicron thickness), the substrate iron atoms can penetrate into the top tin layer through the intermediate one, but there is little evidence for the alloying of tin and nickel.     

纯铜表面热喷涂扩散制备铝化物层工艺与组织结构

在纯铜表面电弧喷涂纯铝涂层,然后于800℃～900℃加热扩散2h～5h,获得厚度不同的铜铝化合物渗层;并对该工艺与其组织结构进行了研究.结果表明,除加热温度与加热时间外,喷涂铝涂层的厚度也直接影响形成铝扩散层的深度和组织结构,喷涂的铝涂层越厚得到的铝扩散层越厚;铝扩散涂层具有两层结构,外层继承了原喷涂层的一些特征,存在一些氧化铝和孔洞,并且溶入了很大比例的铜原子,扩散层的内层是铝原子扩散入铜基体生长的结果;内、外扩散层的主体均由金属间化合物Cu9Al4和含铝的α-Cu固溶体相构成,但在各区中两相的比例不同.     

Dissolution mechanism of solid nickel in liquid zinc saturated with Fe

The dissolution behavior of solid nickel in static liquid zinc saturated with Fe at 723 K was studied. The results show that when immersing solid Ni in liquid Zn saturated with Fe, the intermetallic compound layers consisted of γ and δ phases are formed on nickel substrate, which is the same as that in liquid pure zinc. However, some F2 particles are formed in the liquid near the solid/liquid interface. These Г2 particles can easily heterogeneously nucleate on （particles and grow fast. The dissolution process is governed by diffusion of nickel atom across a concentration boundary layer in liquid Zn saturated with Fe, and is different from a mixed control mechanism of nickel in liquid pure zinc. The participation of Г2 particles makes the dissolution of solid Ni in the liquid accelerated.     

The Effect of Surface-Layer Modification of Nickel Alloys on the Heat Resistance of Aluminide Coatings Applied on Gas-Turbine Blades

A method for the preparation of a complex diffusion coating by preliminary saturation of the surface layer of heat-resistant nickel alloys with nickel and by subsequent chrome aluminizing in vacuum using powder mixtures at processing temperatures of 1000 and 1200°C is analyzed. The characteristics of the chemical composition and structure of coatings and comparative data on the heat resistance at temperatures of 1000, 1050, and 1100°C under the conditions of isothermal oxidation are given. It is shown that the complex coating exhibits increased heat resistance owing to an increase in the uniformity of the surface alloy layers obtained by the diffusion nickel plating.     

Novel processing in inert atmosphere and in air to manufacture high‐activity slurry aluminide coatings modified by Pt and Pt/Ir

Slurry‐derived coatings are an interesting alternative method to pack aluminization of nickel‐base superalloys, which provide similar properties and protection at high temperatures. For highest performance, these aluminide coatings are modified by the addition of Pt or, as recent research suggests, with Pt/Ir. While the combination of Pt and Pt/Ir with an out‐of‐pack process is state of the art, slurry coatings are of special interest as a repair method for turbine blades. In this study, the microstructural evolution of slurry‐derived coatings manufactured on CM 247 in inert atmosphere as well as in air was investigated. Layers of Ni, Pt, and Pt/Ir mixtures were electrodeposited. After annealing, a diffusion heat‐treatment with a slurry containing aluminum or aluminum–silicon powder was applied on the samples. The addition of silicon is well known to be beneficial for hot corrosion environments. The reaction and interdiffusion behavior of aluminum/aluminum–silicon determines the microstructural evolution of the coatings. Depending on the initial electroplated layer on the surface, different microstructures can be obtained, such as the Pt/Ir‐modified beta phase (Ni,Pt)Al or two‐phase layers of PtAl₂ and NiAl. Additionally, the reactivity between the elements at the surface and those from the slurry was shown to determine homogeneity and surface roughness of the diffusion coating, also depending on the atmosphere used during slurry aluminization. Finally, it was demonstrated that iridium has a high influence on the diffusion behavior and especially the distribution of platinum in the coatings. Such new coatings have the potential to overcome some disadvantages of conventionally manufactured high‐activity aluminide coatings, as the combination of Pt/Ir‐electroplating with the slurry process results in less detrimental substrate elements like molybdenum or tungsten close to the surface.     

A study of the corrosion of aluminum alloy 2024-T3 under thin electrolyte layers

The corrosion of aluminum alloy 2024-T3 (AA2024-T3) under thin electrolyte layers was studied in 3.0 wt% sodium chloride solutions by cathodic polarization and electrochemical impedance spectroscopy (EIS) method. The cathodic polarization measurements show that, when the electrolyte layer is thicker than 200 μm, the oxygen reduction current is close to that of the bulk solution. But in the range of 200-100 μm, the oxygen reduction current is inversely proportional to the layer thickness, which shows that the oxygen diffusion through the electrolyte layer is the rate-determining step for the oxygen reduction process. In the range of 100 μm to about 58 μm, the oxygen reduction current is slightly decreased probably due to the formation of aluminum hydroxide or the change of the diffusion pattern from 2-dimensional diffusion to one-dimensional diffusion. The further decrease in electrolyte layer thickness increase the oxygen reduction current to some extent again, because the diffusion of oxygen plays more important role in thin electrolyte layers.The EIS measurements show that the corrosion is controlled by the cathodic oxygen reduction at the initial stage, showing the largest corrosion rate at the electrolyte layer thickness of 105 μm. But at the later stage of corrosion, the anodic process begin to affect the corrosion rates and the corrosion rates show a maximum at 170 μm, which may be the thickness where the corrosion changes from cathodic control to anodic control. The corrosion rate under the very thin electrolyte layer (62 μm in this study) is even smaller than that in bulk solution, this is due to that the anodic process is strongly inhibited.     

Relation between microstructure and adhesion of hot dip galvanized zinc coatings on dual phase steel

The microstructure of hot dip galvanized zinc coatings on dual phase steel was investigated by electron microscopy and the coating adhesion characterized by tensile testing. The zinc coating consists of a zinc layer and columnar ζ-FeZn₁₃ particles on top of a thin inhibition layer adjacent to the steel substrate. The inhibition layer is a thin compact and continuous layer that consists of η-Fe₂Al_5–xZn_x fine and coarse particles. The coarse faceted particles are on top and fine faceted particles are at the bottom. The steel surface is covered with small fraction manganese oxides, which may impair adhesion of the zinc coating. The adhesion at various interfaces that exist in zinc-coated steel was quantitatively estimated using a so-called “macroscopic atom” model. In addition, the adhesion at the interfaces in zinc-coated steel was qualitatively assessed by examining the fracture and delamination behavior upon tensile testing. In accordance with this model, fracture along zinc grain boundaries preceded fracture along the zinc layer/inhibition layer and ζ-FeZn₁₃ particle/inhibition layer interfaces.     

Einfluß von Calcium sowie Cer auf das Oxidationsverhalten hochwarmfester Nickelbasislegierungen

Influence of calcium and cerium on the oxidation behaviour of high temperature strength nickel base alloys Thermogravimetric investigation into the behaviour of Ni alloys having various Al, Co, Cr, Mo, Nb, Ta, Ti, V, W, and Zr contents; the investigations were carried out at temperatures between 800 and 1200°C; the influence of minor additions of Ca and Ce has been studied simultaneously. It turns out, that the improvement of scale adhesion which can be obtained by these additions is limited to a certain temperature range; above specific upper temperature limits the alloying additions lose their efficiency. From among the alloys investigated Inconel 713C turns out to be the alloy having the highest scaling resistance under these conditions. The scale layers formed are very thin and have excellent adhesion properties.     

预镀铜对铝基电沉积镍层的影响

为了改善铝基电沉积镍层的性能,在电沉积镍之前采用了预镀铜的工艺。通过SEM,EDS,划痕法和氦质谱检漏法等方法研究预镀铜层与化学浸锌层的相组成和组织形貌,以及各沉积镍层的气密性和结合力等性能。研究结果表明,预镀铜工艺的添加使电沉积镍层性能得到显著改善;镍层内表面光亮,气密性大大提高。     

Brazing zirconium alloys with an amorphous rapidly quenched strip brazing alloy

Application of aluminum alloy, which is a typical lightweight material, has been expected to achieve energy saving and prevention of pollution in many kinds of transportation vehicles. While the structure made of whole aluminum alloy, however, is lightweight, it still has problems, such as low mechanical strength and high cost. Hence, a hybrid or joining structure made of aluminum alloy and steel seems to be reasonable because of its light weight and higher strength.

To make a hybrid structure for transportation vehicles, we examined welding by friction stirring between aluminum alloy and low-carbon steel, which could be welded without melted weld materials. As a result, welding between aluminum alloy and low-carbon steel that had a thin intermetallic compound at the weld interface was obtained.

In recent automobile manufacturing, zinc-coated steel has been used for structural parts in general. On welding between zinc-coated steel and other materials such as aluminum alloy, existence of a Zn layer between aluminum and steel has to be taken into account to get a high-quality joint between the materials.

In this study, spot joining between aluminum alloy and several kinds of zinc-coated steels by friction stirring was carried out, and the effect of the coated layer both on the weld strength and weld interface microstructure was investigated. As a result, the joint between aluminum alloy and zinc-coated steel was stronger than that between aluminum alloy and non-coated steel, when the coated layer was removed at the weld interface by plastic flow of aluminum alloy.