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.     

无铬转化膜预处理提高AZ91D镁合金化学镀Ni-P的腐蚀性能(英文)

在化学镀Ni-P层和AZ91D镁合金之间生成磷酸锰、单宁酸或钒转化膜预处理层,以取代传统的铬酸盐加氢氟酸预处理工艺。电化学测试结果表明:与传统的铬酸盐处理加化学镀相比,镁合金上的无铬转化膜加化学镀镍磷具有低的腐蚀电流密度和更正的腐蚀电位,能够减少基体上化学镀层的腐蚀。因此,镀层具有致密的细晶结构,适当的磷含量、低孔隙度和良好的耐蚀性并且和基体结合良好的涂层可以取代传统的铬酐钝化加化学镀的工艺。     

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...     

AZ91D 镁合金表面 Ni-P / Ni-Sn-P 双镀层的制备与性能研究

目的提高AZ91D镁合金的耐腐蚀性能,扩大其应用范围。方法先在AZ91D镁合金表面化学镀Ni-P镀层,再化学镀Ni-Sn-P镀层,形成Ni-P/Ni-Sn-P双镀层。研究Ni-P/Ni-Sn-P双镀层的表面形貌和耐腐蚀性能,并与Ni-P单镀层进行对比。结果 Ni-P/Ni-Sn-P双镀层表面分布更均匀平整,缺陷较少,孔隙率较低,具有无定形结构。二次Ni-Sn-P镀层的腐蚀电位约为-0.77 V,略低于一次化学镀Ni-P层(约-0.68 V),两镀层间的电位差使得其构成了微腐蚀电偶,Ni-P层作为阴极,Ni-Sn-P层作为阳极,阳极优先被腐蚀。结论 Ni-P/Ni-Sn-P双镀层的Ni-Sn-P外层能为Ni-P内层提供阴极保护,较好地横向分散腐蚀电流,从而增强AZ91D镁合金基底的耐腐蚀性能。     

以硫酸镍为主盐的AZ91D镁合金化学镀镍研究

研究了以硫酸镍为主盐的AZ91D镁合金化学镀镍.采用无铬前处理在AZ91D镁合金表面形成高锰酸盐和磷酸盐化学转化膜,用SEM、EDX、XRD和极化曲线等方法研究化学转化膜和化学镀镍层的形貌、组成及在3.5%的NaCl溶液中的耐腐蚀性能.结果表明,在高锰酸盐转化膜表面形成的化学镀镍层呈胞状,较致密,有微裂纹;在磷酸盐转化膜上形成的化学镀镍层也呈胞状,晶胞大小不均匀,没有微裂纹.镀层厚度均匀,致密,无孔隙.在3.5%的NaCl溶液中的极化曲线表明化学转化膜对镁合金基体的耐腐蚀性能提高不大,经高锰酸盐和磷酸盐前处理的化学镀镍层腐蚀电位分别为-0.48V_(SCE)和-1.12 V_(SCE).以硫酸镍为主盐的经磷酸盐前处理的化学镀镍层较好地提高了镁合金的耐腐蚀性能.     

添加剂对AZ91D镁合金化学镀镍磷耐蚀性的影响研究

采用常温碱性超声波清洗、酸洗和活化的前处理工艺在AZ91D镁合金表面化学镀镍,研究了辅助络合剂氨基乙酸和加速剂巯基乙酸对镀层耐蚀性的影响。结果表明:镀层表面由Ni-P固溶体组成,呈现尖锐的晶态峰,磷原子与镍原子形成置换固溶体,表面平整致密,无明显缺陷。氨基乙酸含量对镀层耐蚀性和腐蚀速率影响不大,随着巯基乙酸含量的增加,镀层腐蚀电位先升高后降低,腐蚀速率整体比镁合金基体慢,镀层总体呈现钝化趋势,在4 g/L时腐蚀电位最高。     

AZ91D镁合金的化学镀镍

使用硫酸镍作为化学镀镍磷镀液的主盐,直接在AZ91D镁合金基体上化学镀镍.使用扫描电镜和X射线衍射技术分析镀层的表面形貌和组织.化学镀镍磷镀层是致密的,无明显缺陷,其磷含量约为372 mass%.化学镀镍磷镀层的显微硬度值约为660 VHN,化学镀镍的沉积速度为23 μm/h.前处理过程中的酸洗步骤使镁合金基体产生粗糙的表面,从而使镀层和基体之间起到了互锁的作用,增加了镀层的结合力.     

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。     

模拟海洋环境中Ni-Co合金镀层对AZ91D镁合金的腐蚀防护研究

目的提高AZ91D镁合金的腐蚀防护性能。方法采用化学镀前处理在AZ91D镁合金表面制备一种保护性的Ni-Co合金镀层。分别采用环境扫描电镜(ESEM)、X射线衍射(XRD)和能量散射谱(EDS)分析合金镀层的表面形貌、微结构特点和化学成分。采用动电位极化(PC)和电化学阻抗谱(EIS),分析测试在模拟海洋环境(中性3.5%Na Cl溶液)中Ni-Co合金镀层对AZ91D镁合金的腐蚀防护性能。结果镁合金表面化学镀Ni-P镀层均匀覆盖,晶粒生长较致密,表面呈菜花状形貌,Ni-P镀层中P质量分数约为5.6%。Ni-Co合金镀层表面均匀且呈金字塔状形貌,形成了面心固溶体(FCC),镀层中Co质量分数约为31%。Ni-P镀层和Ni-Co合金镀层的厚度分别约为11μm和19μm。在模拟海洋(中性3.5%Na Cl溶液)环境中,镁合金裸基体、化学镀前处理Ni-P镀层、Ni-Co合金镀层的腐蚀电位分别为-1485、-372、-284 m V,其腐蚀电流密度分别是3.4×10-5、1.8×10-6、2.9×10~(-7) A/cm2,所拟合的电荷转移电阻分别为4.72×103、1.70×104、2.06×106?/cm2。结论化学镀前处理Ni-P镀层可为镁合金提供较好的腐蚀防护,Ni-Co合金镀层能够为镁合金提供更显著的腐蚀防护。     

Deposition of electroless Ni-P/Ni-W-P duplex coatings on AZ91D magnesium alloy

The electroless Ni-P/Ni-W-P duplex coatings were deposited directly on AZ91D magnesium alloy by an acid-sulfate nickel bath.Nickel sulphate and sodium tungstate were used as metal ion sources and sodium hypophosphite was used as reducing agent.The coating was characterized for its structure,morphologies,microhardness and corrosion properties.The presence of dense and coarse nodules in the duplex coatings was observed by SEM and EDS.Tungsten content in Ni-P/Ni-W-P alloy is about 0.65%(mass fraction) and t...     

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。     

AZ91D镁合金的均一化前处理与化学镀Ni-P

采用新型环保的均一化前处理工艺在AZ91D镁合金表面制备了化学镀Ni-P镀层。研究了前处理过程中AZ91D基体微观形貌、镀层沉积过程、成分和相结构。研究结果表明：基体表面的β相在前处理过程中被选择性去除,表面组织得到均一化,从而获得均匀致密的浸Zn层。Ni-P颗粒均匀形核生长,并最终形成致密的镀层。镀层具有优良的耐腐蚀性能。     

镁合金化学镀中预处理氟化镁膜的特征与作用

对镁合金的表面前处理工艺进行研究,探讨氟化镁在化学镀层中的存在形式及作用。结果表明：酸浸使镁合金表面形成一层氧化物膜;活化过程生成的氟化镁不具备反应活性,对镁合金基体有保护作用,使之免于受镀液的过度腐蚀;对化学镀层断口进行SEM元素分布分析显示氟化镁层集中存在于镁合金基体与Ni-P镀层之间;但过度活化会导致化学镀层孔隙率升高,以3.5%NaCl溶液为介质的动电位极化测试表明,过度活化会导致化学镀层耐蚀性下降。     

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。     

AZ91D镁合金表面激光熔覆Al-TiC涂层组织和性能的研究

目的研究Al-TiC涂层组织和性能的特性,以提高镁合金涂层的硬度和耐蚀性能。方法采用Nd:YAG固体激光器,在AZ91D镁合金表面通过激光熔覆制备Al-TiC涂层,采用光学显微镜、X射线衍射仪、显微硬度计、电化学工作站,对熔覆层的组织形貌、物相结构、显微硬度和耐蚀性能进行测定和分析。结果 Al-TiC涂层的主要组成相有AlTi_3(C,N)_(0.6),Al_3Mg_2,Mg_2Al_3,Al和TiC等。激光熔覆层的厚度约为0.35 mm,表面成型良好,结合层晶粒细小,熔覆层与镁合金基体之间结合良好,呈大波浪形。熔覆层试样的平均显微硬度为224HV,约为基体显微硬度(62HV)的4倍,由此表明熔覆层对镁合金硬度有明显的增强作用。镁合金基体的自腐蚀电位为-1.475 V,自腐蚀电流密度为7.556×10~(–5) A/cm~2,熔覆层试样的自腐蚀电位为-1.138V,自腐蚀电流密度为4.828×10~(–5) A/cm~2,与镁合金基体相比,熔覆层的腐蚀电位值增加,腐蚀电流密度值变小,熔覆层的耐蚀性能得到提高。结论采用激光熔覆技术,能够在AZ91D镁合金基体表面制备Al-TiC涂层,由于硬质相AlTi_3(C,N)_(0.6),Al_3Mg_2,Mg_2Al_3,TiC等的存在,熔覆层的显微硬度和耐蚀性能显著提高。     

前处理工艺对AZ91D镁合金直接化学镀的影响

通过不同的酸洗配方工艺,对比讨论了前处理工艺对AZ91D镁合金直接化学镀镍(DEN)的沉积速率及镀层与基底结合性能的影响。结果表明,AZ91D镁合金表面活化后,虽然粗糙界面由于更多的结合点和更大的机械互锁作用,能提高镀层与基体间的结合力,但是镀层结合的致密程度对结合力的影响作用更为显著。以磷酸和氟化钾为酸洗配方的前处理工艺,更适合AZ91D镁合金直接化学镀。     

Electroless Ni-Sn-P coating on AZ91D magnesium alloy and its corrosion resistance

An electroless Ni-Sn-P coating was deposited on AZ91D magnesium alloy in an alkaline-citrate-based bath where nickel sulphate and sodium stannate were used as metal ion sources and sodium hypophosphite was used as a reducing agent. The phase structure of the coating was amorphous. SEM and attached EDS observation revealed the presence of dense and uniform nodules in the ternary coating and the content of tin was 2.48wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution proved that the ternary Ni-Sn-P coating exhibited better corrosion resistance than the Ni-P coating in protecting the magnesium alloy substrate.     

Electrodeposition of zinc on AZ91D magnesium alloy pre‐treated by stannate conversion coatings

A stannate chemical conversion process followed by an activation procedure was employed as the pre‐treatment process for AZ91D magnesium alloy substrate. Zn was electroplated onto the pre‐treated AZ91D magnesium alloy surface from pyrophosphate bath to improve the corrosion resistance and the solderability. The surface morphologies of conversion coating and zinc coating were examined with scanning electron microscope (SEM). The phase composition of conversion coating was investigated by X‐ray diffraction (XRD). The electrochemical corrosion behavior of the coatings in the corrosive solution was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The experimental results showed that the activated stannate chemical conversion coating provided a suitable interface between zinc coating and the AZ91D magnesium alloy substrate. The corrosion resistance of the AZ91D substrate was improved by the zinc coating.     

前处理工艺对镁合金化学镀Ni-P质量的影响

采用扫描电镜和性能检测的方法,分析了表调、活化和浸锌等前处理工艺对镁合金化学镀Ni-P质量的影响.结果表明,表调可使晶界凸出于α-Mg基体,降低镁合金的表面粗糙度,提高化学镀层的结合强度.活化及浸锌后,促进了化学镀的进行.按表调、活化、一次浸锌、退镀、二次浸锌的工艺进行前处理后实施化学镀,得到的Ni-P镀层致密、平整,与基体结合力强,有效提高了镁合金表面耐蚀性及显微硬度.     

Influence of substrate composition on the formation of phytic acid conversion coatings

In this paper, the formation and corrosion resistance of the phytic acid conversion coatings on Mg, Al, and AZ91D magnesium alloy were contrastively investigated using scanning electronic microscopy (SEM), Auger electron spectroscopy (AES), Fourier transform infrared spectroscopy (FTIR), electronic probe microscopic analyzer (EPMA), electronic balance, and electrochemical methods. The influence of phytic acid conversion coating as a middle layer on the properties of the paint on magnesium alloys was also investigated. The results show that the formation process of the conversion coatings is evidently influenced by the compositions of the substrate. The coating on pure aluminum is thinner and compacter than that on pure magnesium and the coating formed on α phase in AZ91D magnesium alloy is thinner but denser than that on β phase. The phytic acid conversion coatings formed on Mg, Al, and AZ91D magnesium alloy can all increase their corrosion resistance. The active functional groups of hydroxyl and phosphate radical are rich in the conversion coatings, which can improve the bonding between the organic paint and magnesium alloy and then improve their corrosion resistance.