镁合金化学镀Ni-Cu-P/Ni-P复合镀层及腐蚀防护机理研究

目的为提高镁合金化学镀Ni-P合金镀层的腐蚀防护性能。方法在AZ31B镁合金表面,先化学镀Ni-Cu-P,再化学镀Ni-P,制备Ni-Cu-P/Ni-P复合镀层。研究复合镀层的表面形貌、成分、厚度和腐蚀电流密度随镀液硫酸铜浓度的变化规律,表征1.0 g/L硫酸铜质量浓度下,复合镀层的截面形貌、成分和晶态结构。结合动电位极化曲线和盐雾试验,分析复合镀层的耐蚀性能和腐蚀防护机理。结果复合镀层中的铜含量随硫酸铜浓度的增加而升高,铜对复合镀层的结构和性能影响很大。通过抑制镀层表面胞状物的生长和增加形核点数量,铜的共沉积能够大幅提高复合镀层的致密性。随硫酸铜浓度的增加,样品表面的催化活性下降,镀液稳定性升高,由此导致复合镀层的厚度随硫酸铜浓度的增加而明显下降。硫酸铜质量浓度为1.0 g/L时,复合镀层均匀致密,并具有可钝化性,按照ISO 9227,其耐盐雾腐蚀时间超过180 h。结论化学镀Ni-Cu-P/Ni-P复合镀层能够赋予镁合金表面优异的耐蚀性能,复合镀层所具有的可钝化性和均匀致密的镀层结构,是镀层腐蚀防护性能提升的主要原因。     

Wear and corrosion properties of laser cladded Cu47Ti34Zr11Ni8/SiC amorphous composite coatings on AZ91D magnesium alloy

To improve the wear and corrosion properties of AZ91D magnesium alloys, Cu-based amorphous composite coatings were fabricated on AZ91D magnesium alloy by laser cladding using mixed powders of Cu47Ti34Zr11Ni8 and SiC. The wear and corrosion behaviours of the coatings were investigated. The wear resistance of the coatings was evaluated under dry sliding wear condition at room temperature. The corrosion resistance of the coatings was tested in 3.5% （mass fraction） NaCl solution. The coatings exhibit excellent wear resistance due to the recombined action of amorphous phase and different intermetallic compounds. The main wear mechanisms of the coatings and the AZ91D sample are different. The former is abrasive wear and the latter is adhesive wear. The coatings compared with AZ91D magnesium alloy also exhibit good corrosion resistance because of the presence of the amorphous phase in the coatings.     

Ni-P-TiN(纳米)化学复合镀层研究

为了提高AZ31镁合金的耐磨性能并扩大其在相关领域的应用,采用化学复合镀技术在AZ31镁合金基体上制备了Ni-P—TiN（纳米）复合镀层,同时制备Ni—P镀层进行比较。研究了复合镀层形貌、成分、硬度和耐磨性能与镀液中纳米TiN颗粒含量的关系。结果表明,复合镀层和Ni—P镀层表面都是由胞状物排列而成;纳米TiN颗粒沉积于Ni—P—TiN（纳米）复合镀层中。当镀液中纳米TiN颗粒浓度为3g／L时,复合镀层硬度达最大值,为826HV,而Ni—P镀层只有508HV;同时复合镀层表现出优异的耐磨性能,在同等条件下其磨损失重只有Ni—P化学镀层的25％。     

Post-treatment of thermal spray coatings on magnesium

Magnesium alloys have a beneficial combination of high strength to weight ratio, good machinability and high recycling potential. Despite this, the application of magnesium still is behind that of other constructive materials mainly due to low wear and corrosion resistance. For more demanding applications, a large amount of surface treatment methods are developed to overcome this problem. Thermal spraying is an efficient and flexible method of coating deposition and is widely used for protection of different materials against corrosion and wear. Nevertheless, the bonding of thermal spray coatings on magnesium alloys is not sufficient, so the following post-treatment processes are needed. One of such possibilities is high energy beam treatment of thermally sprayed coatings. During the heat treatment of magnesium substrates with coating the remelting of coating and a thin surface layer of substrate occurs. Depending on the combination of applied coating system and treatment method, different processes can be realised in modified layers: the alloying of magnesium substrate with other elements to improve corrosion properties, redistribution of hard particles from composite coating and new phases formation during the processing to improve the wear resistance of magnesium alloys. In the present work some examples concerning the laser and electron beam treatment of aluminium based composite coatings as well as infra red irradiation of zinc based coatings are described. Coatings are deposited on magnesium substrates (AM20, AZ31, AZ91) by arc spraying with Zn, ZnAl4 and ZnAl15 solid wires and cored wires in aluminium core with powder filling containing different hard particles, such as boron, silicon and tungsten carbide or titanium oxide. Remelting of thermal spray coatings is carried out by means of continuous irradiation of СО₂-laser in nitrogen or argon atmosphere, electron beam in vacuum and focused tungsten halogen lamp line heater in atmosphere. Microstructure of sprayed coatings as well as that of modified surface layers is investigated by metallographic methods. Corrosion properties are estimated by electrochemical measurements. Abrasion wear resistance of the modified layers is determined by scratch test, corundum grinding disk test and Rubber wheel test. It is shown that all methods applied for processing of thermal spray coatings lead to formation of modified surface layers in magnesium substrate with improved wear and corrosion properties. Different mechanisms of microstructure formation such as redistribution of chemical composition of composite coating components, partial remelting of hard phase particles, and new phases formation are discussed. Electrochemical behaviour of modified surface layers is mostly improved due to alloying, homogenization of element distribution and strong decrease of as-sprayed coating porosity. Abrasion wear resistance of processed magnesium substrates strongly depends on the microstructure and usually is 5 to 20 times higher compared with base material.     

镁合金表面化学镀 Ni-P 和 Ni-P-SiC 的对比

目的提高镁合金的耐磨性、耐蚀性,扩大其应用领域。方法采用"磷酸+钼酸铵酸洗→HF活化"的方法进行前处理,直接在AZ91D镁合金表面化学镀Ni-P合金镀层和Ni-P-SiC复合镀层。对两种镀层的表面和截面形貌、成分、结构、硬度、耐蚀性及耐磨性进行了系统比较。结果在Ni-P合金镀层中引入SiC粉末后,镀层的胞状颗粒细化,硬度提高至643HV,但其腐蚀电流密度有所增大。结论与Ni-P合金镀层相比,Ni-P-SiC复合镀层的耐蚀性有所下降,但耐磨性能大大提高。     

Mg3Sb2含量对Al-Mg3Sb2复相涂层耐磨性的影响

目的研究Mg_3Sb_2含量对Al-Mg_3Sb_2复相涂层的组织、硬度和摩擦学性能的影响,对比分析AZ31B镁合金基体、纯Al涂层和添加不同含量的Mg_3Sb_2之后涂层性能的差异。方法通过火焰喷涂技术在AZ31B镁合金表面制备了Al-Mg_3Sb_2复相涂层。利用扫描电镜(SEM)观察了涂层的截面形貌,利用X射线衍射仪(XRD)分析了涂层的物相组成。通过显微硬度计测试了AZ31B和涂层的硬度,通过摩擦磨损试验仪测试了AZ31B和涂层的摩擦学性能,并通过超景深三维显微镜测试了试样的磨痕宽度、深度及磨损体积。结果经火焰喷涂后可得到组织致密的复相涂层,涂层中的物相主要为Mg_3Sb_2和Al。涂层的平均硬度随Mg_3Sb_2含量的增加而增加,最高可达334.2HV0.025,是AZ31B的4.14倍。摩擦磨损试验中,涂层的摩擦系数随着Mg_3Sb_2含量的增加而减小,但都大于AZ31B的摩擦系数;涂层的磨损率随着Mg_3Sb_2含量的增加而减小,60%Mg_3Sb_2和80%Mg_3Sb_2涂层的磨损率小于AZ31B的磨损率,其他涂层的磨损率大于AZ31B的磨损率,80%Mg_3Sb_2涂层的耐磨性最好,比AZ31B下降了63.26%。随着Mg_3Sb_2含量的增加,Al-Mg_3Sb_2复相涂层的磨痕表面犁沟逐渐变浅并消失。结论 Mg_3Sb_2的加入可以提高涂层的硬度,随着其含量的增加,涂层的耐磨性逐渐提高。     

Structure and wear resistance of TiN and TiAlN coatings on AZ91 alloy deposited by multi-arc ion plating

In order to investigate the microstructure of TiN and TiAlN coatings and their effect on the wear resistance of Mg alloy, TiN and TiAlN coatings were deposited on AZ91 magnesium alloy by multi-arc ion plating technology. TiN and Ti70Al30N coatings were prepared on the substrate, respectively, which exhibited dark golden color and compact microstructure. The microstructures of TiN and Ti70Al30N coatings were investigated by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The micro-hardness and wear resistance of TiN and Ti70Al30N coatings were investigated in comparison with the uncoated AZ91 alloy. The XRD peaks assigned to TiN and TiAlN phases are found. The hardness of TiN coatings is two times as high as that of AZ91 alloy, and Ti70Al30N coating exhibits the highest hardness. The wear resistance of the hard coatings increases obviously as result of their high hardness.     

AZ91D镁合金化学复合镀Ni-P-ZrO2的工艺与性能

对镁合金传统化学镀工艺进行了改进,避免了使用氢氟酸和六价铬等有毒物质。采用化学镀与化学复合镀相结合方法,在AZ91D镁合金上获得了Ni-P-ZrO2纳米化学复合镀层,并研究了新工艺化学镀前处理和镍沉积机理及复合镀层的结构和性能。结果表明:新工艺方法获得的Ni-P镀层更均匀、致密,耐蚀性优于传统工艺化学镀层;Ni-P-ZrO2复合镀层与AZ91D合金基体在3.5%NaCl溶液中的动电位极化曲线对比表明,该复合镀层对镁合金可以起到明显的保护作用;从磨损实验结果可见,Ni-P镀层的磨损质量损失率几乎为Ni-P-ZrO2镀层的3倍,说明ZrO2纳米粉的加入能改善镀层的耐磨性。     

Ni-P金刚石化学复合镀层制备及摩擦磨损性能分析

目的研究不同粒径微米金刚石对Ni-P金刚石化学复合镀层摩擦磨损性能的影响。方法选择出一组优良的Ni-P化学镀工艺参数,在镀液中分别加入不同粒径的金刚石微粒,制备含不同粒径微米级金刚石颗粒的化学复合镀层。用SEM和XRD,观察并分析了不同粒径金刚石对热处理前后Ni-P金刚石化学复合镀层微观形貌和组织结构的影响;通过硬度和摩擦磨损实验,研究了不同粒径金刚石颗粒对复合镀层硬度及摩擦磨损性能的影响。结果制备的复合镀层厚度为30μm左右,金刚石质量分数达到21%~25%,且金刚石均匀分散在Ni-P镀层中。热处理前镀层为非晶结构,经过400℃×2 h的热处理后,镀层晶化为硬度更高的Ni3P。金刚石能提高镀层硬度,其中粒径为9μm的复合镀层硬度最高,达到1261HV。Ni-P金刚石复合镀层的摩擦系数为0.4~0.52,随着金刚石粒径的增大,摩擦系数不断减小。金刚石使镀层的磨损机制发生了变化,随着金刚石粒径的增大,硬质合金球的磨损加剧。结论随着金刚石粒径的增大,镀层硬度增加,摩擦系数减小,耐磨性增大。     

A new method for electroless Ni-P plating on AZ31 magnesium alloy

Coating Ni-P films on AZ31 magnesium alloys via electroless plating and organic coatings (organsilicon heat-resisting varnish), was studied. An organic coating was proposed as the interlayer between Ni-P coating and AZ31magnesium alloy substrate, to replace the traditional chromium oxide plus HF pretreatment. The Ni-P deposited on the interlayer was also characterized by its structure, morphology and corrosion-resistance. The interlayer on the substrate not only reduces the corrosion of magnesium during Ni-P plating process, but also reduces the potential difference between the matrix and the second phase. The result of the cross-cut test indicates the adhesion between the substrate and the interlayer is good enough. A Ni-P film with fine and dense structure was obtained on the AZ31 magnesium alloy. The electrochemical measurements show that the sample with Ni-P film exhibits lower corrosion current density and more positive corrosion potential than the substrate. Furthermore, the Ni-P coating on the AZ31 magnesium alloy exhibits high corrosion resistance in the rapid corrosion test illustrated in this paper. The method proposed in this work is environmentally friendly: no fluoride or hexacalent chromium compounds are used. In addition, it provides a new concept for plating the metals, which are considered difficult to plate due to high reactivity.     

沉积时间对AZ91D合金表面Ni-P-SiC复合镀层性能的影响

目的提高镁合金的耐蚀性和耐磨性。方法以AZ91D镁合金为基体,采用SiC颗粒质量浓度为3 g/L的Ni-P化学镀溶液,在其表面沉积不同时间,制备Ni-P-SiC复合镀层。通过扫描电子显微镜(SEM)、显微硬度测试、粗糙度仪、电化学腐蚀和磨损等试验来分析和评价Ni-P-SiC复合镀层的厚度、表面粗糙度、显微硬度、耐腐蚀性能和耐磨性能。结果 Ni-P-SiC复合镀层的厚度和表面粗糙度随沉积时间增加而增加,沉积时间为150 min时,镀层厚度可达53μm,表面粗糙度为2.5μm。沉积时间为120 min时,镀层的显微硬度最高,为641HV,此时复合镀层的耐蚀性和耐磨性最好,自腐蚀电位高达-0.73 V,腐蚀电流密度为0.78μA/cm~2,磨损体积最小,为1.04×10~(-3)mm~3。与AZ91D镁合金基体相比,沉积复合镀层后的样品更耐蚀,说明复合镀层有效改善了镁合金基体的耐蚀性。结论沉积时间对Ni-P-SiC复合镀层的性能有一定影响,在沉积时间为120 min时获得的复合镀层具有较好的耐蚀性和耐磨性。     

Corrosion and wear properties of electroless Ni-P plating layer on AZ91D magnesium alloy

A direct electroless Ni-P plating treatment was applied to AZ91D magnesium alloy for improving its corrosion resistance and wear resistance. Corrosion resistance of the Ni-P coatings was evaluated by potentiodynamic polarization and immersing experiments in 3.5% NaCl solution. The wear resistance of the coatings was investigated by the wear track and the mass change after ball-on-disk experiment. The results show that corrosion resistance and wear resistance of the AZ91D alloy are greatly improved after direct electroless Ni-P plating. No discoloration is noticed until 4 d of immersion in 3.5% NaC1 solution. Potentiodynamic polarization experiments show that the free corrosion potential of magnesium alloy is shifted from -1 500 mV to -250 mV and passivation occurs at 1 350 mV after direct electroless plating. The friction coefficients and wear rates of Ni-P coating and Ni-P coating after tempering are 0.10-0.351, 9.038×10^-3 mm^3/m and 0.13-0.177, 3.056×10^-4 mm^3/m, respectively, at a load of 1.5 N with dry sliding. Although minor hurt on corrosion resistance was caused, significant improvement of wear resistance was obtained after tempering treatment of the coating.     

TiN颗粒对镁合金微弧氧化过程及膜层性能的影响

目的分析Ti N颗粒在镁合金微弧氧化过程中的作用,并研究其在膜层中对镁合金硬度、耐磨和耐蚀等性能的影响。方法通过在微弧氧化电解液中添加2.7μm Ti N颗粒,并使其充分分散于电解液中,使电解液中Ti N颗粒的质量浓度分别为0、2、4、6 g/L,并控制其他实验参数(如电流密度、频率、占空比和氧化时间)一样的情况下进行实验,通过电子显微镜、涂层厚度测厚仪、显微维氏硬度计、X射线衍射和电化学工作站,分别从膜层的表面形貌、厚度、硬度、相组成及耐蚀性等方面,研究了Ti N颗粒对镁合金微弧氧化膜层性能的影响。结果在微弧氧化电解液中添加Ti N颗粒后,相同电化学参数下制得的微弧氧化膜层变得致密,厚度、硬度有所增加,氧化膜层主要由Mg、MgO、Mg2Zr5O12、Ti N组成。极化曲线显示,加入Ti N颗粒,制备的微弧氧化膜层比未加入Ti N颗粒制得的膜层的腐蚀电流下降了2个数量级。阻抗图谱表明,电阻值增加了1个数量级。结论 Ti N颗粒能够随镁合金的微弧氧化过程进入制得的氧化膜层中,并且能够增加膜层厚度和硬度,使膜层的耐磨、耐蚀性得到提高。     

A novel dual nickel coating on AZ91D magnesium alloy

Magnesium alloys covered with metal coating display excellent corrosion resistance,wear resistance,conductivity and electromagnetic shielding properties.The electroless plating Ni-P as bottom layer following the electroplating nickel as surface layer on AZ91D magnesium alloy was investigated.The coating surface morphology was observed with SEM and the structure was analyzed with XRD.Electrochemical tests and salt spray tests were carried out to study the corrosion resistance.The experimental results indi...     

Improvements on the wear resistance of high thermal conductivity Cu alloys using an electroless Ni-P coating prior to PVD deposition

An attempt to improve the load support for hard PVD coatings on soft Cu alloys has been made by using a medium phosphorous content electroless Ni-P coating prior to PVD deposition, envisaging the application of these coating/substrate systems in plastic injection moulding. Several PVD coatings, including TiN, CrN, CrAlN, multilayered CrAlN, WC-C, multilayered CrAlN/WC-C were deposited onto an Ampcoloy 940 Cu alloy in two conditions: ‘standard’ and electroless Ni-P plated. The effect of the electroless Ni-P coating on the coating/substrate performance was evaluated by pin-on-disc wear and impact tests. Ultra-microhardness and surface roughness measurements were also used to characterise the resulting coating/substrate systems. The electroless Ni-P coating reduced the wear rates of the PVD-coated Cu alloys and increased the impact wear resistance. Among the PVD coatings trialled, CrN, CrAlN and multilayered CrAlN coatings on electroless Ni-P provided the lowest wear rates.     

锡酸盐转化前处理对镁合金化学镀镍镀层的影响

目的利用锡酸盐转化膜中间层避免化学镀镍镀层与金属基体的直接接触,降低其产生原电池腐蚀的趋势,提高镁合金化学镀镍层的耐蚀性及稳定性。方法采用锡酸盐化学转化膜技术在AZ31镁合金表面制备锡酸盐转化膜层,然后通过直接化学镀镍技术在该膜层上沉积Ni-P镀层。利用SEM、EDS、浸泡析氢、电化学测试等手段,研究了复合镀层的显微结构、相组成、耐蚀性。结果锡酸盐转化膜由细小均匀的球形颗粒堆积而成,颗粒之间存在空隙,为直接化学镀镍时镍磷的初始沉积提供了可能。化学转化膜表面沉积的化学镀镍层均匀致密,形成典型的胞状结构。基体-化学转化膜-化学镀Ni-P合金层三者之间的结合良好,保证了复合镀层优良的耐蚀性能。结论化学镀Ni-P层能够在不经过钯活化处理的条件下直接在锡酸盐转化膜上沉积,锡酸盐转化膜中间层避免了Ni-P阴极性镀层与阳极性镁基体的直接接触,降低了Ni-P镀层局部缺陷对整体防护效果的影响,提高了镀层的耐蚀性及耐久性。     

Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy

In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were added to fabricate Ni–P–TiN composite coating by electrodeposition. The surface, cross-section morphology and composition were examined using SEM, EDS and XRD, and the corrosion resistance was checked by electrochemical technology. The results indicate that TiN nanoparticles were doped successfully in the Ni–P matrix after a series of complex pretreatments including activation, zinc immersion and pre-electroplating, which enhances the stability of magnesium alloy in electrolyte and the adhesion between magnesium alloy and composite coating. The microhardness of the Ni–P coating increases dramatically by adding TiN nanoparticles and subsequent heat treatment. The corrosion experimental results indicate that the corrosion resistance of Ni–P–TiN composite coating is much higher than that of uncoated AZ91D magnesium alloy and similar with Ni–P coating in short immersion time. However, TiN nanoparticles play a significant role in long-term corrosion resistance of composite coatings.     

添加纳米TiO2的Ni-P化学复合镀层显微结构与性能

采用化学复合镀法制备了Ni-P-纳米TiO2复合镀层,研究了纳米TiO2添加对Ni-P复合镀层的显微结构、硬度、耐磨性、孔隙率及耐蚀性的影响,并讨论了其影响机理。结果表明:纳米TiO2粒子较为均匀地分布在Ni基镀层,未发生明显团聚;纳米TiO2粒子的弥散强化作用,使复合镀层具有较高的表面硬度和良好的耐摩擦性能,晶化热处理后的复合镀层表面硬度达到了10 925 MPa,耐摩擦性能也显著提高。添加纳米TiO2粒子后,镀层的孔隙率增加,耐碱和耐盐腐蚀的能力稍有降低,耐HCl溶液腐蚀的能力较差。     

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。     

Effect of Hot Extrusion on Microstructures and Properties of TiB2/AZ31 Magnesium Based Composites

采用原位合成-半固态搅拌铸造法制备了TiB2/AZ31镁基复合材料,研究了热挤压对TiB2/AZ31镁基复合材料组织和力学性能的影响。结果表明：热挤压不仅能显著细化合金组织,而且能有效改善TiB2颗粒分布的均匀性。与铸态AZ31镁合金相比,铸态TiB2/AZ31镁基复合材料的硬度、抗拉强度都有一定程度的提高。经过热挤压后,TiB2/AZ31镁基复合材料的硬度和抗拉强度分别比基体合金提高了126.2%和98.8%,达到950 MPa和322 MPa。磨损表面形貌显示,TiB2颗粒的引入以及对TiB2/AZ31镁基复合材料进行热挤压,都可有效地提高材料的耐磨性。