NdFeB磁体表面化学镀Ni-P合金防腐研究

采用正交试验法对NdFeB磁体表面化学镀镍磷合金的工艺进行了优化，测量了镀层和基体在3．5％（ω）NaCl溶液、10％（φ）盐酸和20％（ω）NaOH溶液中的腐蚀速度，以及在3．5％NaCl溶液中的极化曲线和电化学阻抗谱，对比分析了在酸性和碱性条件下所得Ni-P镀层的结构和表面形貌。结果表明，采用EIS谱图及等效电路模型可对镀层和磁体在介质中的电化学参数进行拟合分析，化学镀Ni-P合金能够显著改善NdFeB磁体的耐腐蚀性能，且酸性条件下所获得的镀层为非晶态结构，表面胞状组织呈密集连续分布，耐腐蚀性能更佳。     

A novel electroless plating of Ni-P-TiO2 nano-composite coatings

A new processing concept has been developed to produce nano-structured metal-matrix composite coatings. This method combines sol-gel and electroless plating techniques to prepare highly dispersive oxide nano-particle reinforced composite coatings. Transparent TiO₂ sol was added into the standard electroless plated Ni-P solution at a controlled rate to produce Ni-P-TiO₂ nano-composite coatings on Mg alloys. The coating was found to have a crystalline structure. The nano-sized TiO₂ particles (∼ 15 nm) were well dispersed into the Ni-P coating matrix during the co-deposition process. This technique can effectively avoid the agglomeration of nano-particles in the coating matrix. As a result, the microhardness of the composite coatings were significantly increased to ∼ 1025 HV₂₀₀ compared to ∼ 710 HV₂₀₀ of the conventional composite coatings produced with solid particle mixing methods. Correspondingly, the wear resistance of the new composite coatings was also greatly improved.     

化学镀Ni-P和Ni-Cu-P合金耐蚀性研究

研究了硫酸铜加入量对化学镀Ni-Cu-P合金的镀层成分、组织及热稳定性影响,用中性盐雾实验和在20%H2SO4+20 g/LAl2O3溶液中的冲刷腐蚀实验研究了Ni-P与Ni-Cu-P合金的耐蚀性和耐冲刷腐蚀性能.结果表明,Ni-Cu-P合金镀层具有比Ni-P合金镀层更好的热稳定性、耐蚀性和耐冲刷腐蚀性能.     

Effect of the microstructure on the properties of Ni-P deposits on heat transfer surface

In the present work Ni-P deposits with various microstructures were prepared on the low carbon steel substrate by adjusting the electroless plating processing parameters. The results of anti-fouling experiments show that Ni-P deposits can greatly inhibit the adhesion of crystallization fouling in comparison with uncoated copper, stainless steel and carbon steel surfaces. The further experiments indicated that the amount of nanocrystalline phase in the Ni-P deposit affects the surface free energy, as well as changing the anti-fouling and corrosion-resistant properties of the deposit. When the phase structure of the Ni-P deposit is almost amorphous phase, the Ni-P deposit exhibits the best anti-fouling and corrosion-resistant properties. The amorphous Ni-P deposit exhibits high corrosion resistance which is attributed to its extreme structure homogeneity without preferential corrosion paths like grain boundaries or other structural defects, and the higher corrosion resistance could ensure this deposit is not easy to form “transitional interface” connecting fouling and matrix.     

A study on the electroless Ni-P deposition on WE43 magnesium alloy

In this paper an attempt has been made to understand the mechanism of the deposition process of an electroless Ni-P (EN) coating on WE43 magnesium alloy. Also a number of properties concerning the deposited coatings have been reviewed. The results show that the starting microstructure of the alloy consists of a primary α phase together with some eutectic β phase at triple points and along with some grain boundaries. Microstructural studies reveal an uneven distribution of alloying elements in the phases and they are predominantly segregated to the eutectic β phase. This phenomenon can result in galvanic coupling between eutectic β and primary α phases. Detailed studies prove that the replacement reaction takes place at the early stages of coating, and is followed by the autocatalytic reaction at the next stages of deposition.The X-ray diffraction patterns of primitive coatings show a broad peak around 2θ of 45°, which is an indication of an amorphous or an extremely fine crystalline structure. Annealing at 400 °C for an hour led the nature of deposits to be changed to crystalline phases of Ni, Ni₃P, and NiP₃. Microhardness values of coatings are considerably higher than those of the bare substrate. These further increase when they are annealed at 400 °C for 1 h. Electrochemical polarization curves and calculated corrosion values reveal higher corrosion potential (E_corr) for the coating than for the bare substrate. This decreases again when the coating is annealed at 400 °C for 1 h.     

A new process for preparing conducting wood veneers by electroless nickel plating

A new, simple electroless Ni-P plating process for preparing a conductive wood veneer has been developed. In this process, the activation was combined with electroless deposition in the plating solution. This provides a simple, environmentally friendly method, by which a Ni-P layer was successfully deposited on the surface of Manchurian ash veneer. It was observed by scanning electron microscopy that the deposited layer was uniform, compact and continuous. Results from energy-dispersive spectroscopy showed that a low-phosphorus layer was obtained, which contained about 4 wt.% phosphorus and 96 wt.% nickel. X-ray diffraction analysis indicated that the coating was crystalline. It is considered that the crystalline structure is related to the low-phosphorus content of the layer. Veneers plated with the crystalline Ni-P coating had good electrical conductivity, with a surface resistivity less than 200 mΩ/cm² and a firm adhesion of the Ni-P coating to the wood.     

Corrosion behavior of electroless Ni-P alloy coatings containing tungsten or nano-scattered alumina composite in 3.5% NaCl solution

The corrosion protection performance of electroless deposited nickel-phosphorus (Ni-P) alloy coatings containing tungsten (Ni-P-W) or nano-scattered alumina (Ni-P-Al₂O₃) composite coatings on low carbon steel was studied. The effect of heat treatment on the coating performance was also studied. The optimum conditions under which such coatings can provide good corrosion protection to the substrate were determined after two weeks of immersion in 3.5% NaCl solution. Electrochemical impedance spectroscopy (EIS) and polarization measurements have been used to evaluate the coating performance before and after heat treatment. The Ni-P-W coatings showed the highest surface resistance compared with Ni-P-Al₂O₃ and Ni-P. The surface resistance of Ni-P-W coatings was 12.0 × 10⁴ Ω cm² which is about the double of the resistance showed by Ni-P-Al₂O₃ (7.00 × 10⁴ Ω cm²) and twenty times greater than the surface resistance of Ni-P (0.78 × 10⁴ Ω cm²). XRD analysis of non-heat-treated samples revealed formation of a protective tungsten phosphide phase. Heat treatment has an adverse effect on the corrosion protection performance of tungsten and alumina composite coatings. The surface resistance decreased sharply after heat treatment.     

Nanoscratching deformation and fracture toughness of electroless Ni-P coatings

In the present investigation electroless Ni-P coatings were prepared. Structural characterizations indicated that the as-deposited coating had an amorphous structure with a P content of 23 at.%. The deformation behavior of an electrolessly amorphous Ni-P coating was investigated by using the Vickers indentation and the Tribo-indenter instrumented nano-indentation technique. The hardness of the Ni-P coating is remarkably improved after proper heat-treatment and the hardness is as high as 12.7 GPa for the coating annealed at 400 °C for 1 h. However, the cracks were observed during the indentation of the Ni-P coatings annealed at 400 °C and 500 °C for 1 h. The corresponding fracture toughness was evaluated as 2.58 MPa m^0.5 and 1.33 MPa m^0.5, respectively. Nanoscratching tests indicated that the wear resistance of the Ni-P coatings was improved significantly with an increasing ratio of hardness (H) to elastic modulus (E). It was observed that the friction coefficient increased from 0.083 ± 0.006 for the Ni-P coating annealed at 300 °C up to 1.337 ± 0.009 for the IF steel substrate, while the H/E simultaneously decreased from 0.084 (10.7/128) to 0.009 (1.85/200). The study revealed that the electrolessly amorphous Ni-P coating had offered better corrosion resistance than the Ni-P coatings after heat-treatment. An annealing temperature of 300 °C is preferentially suggested for the trade-off between the wear resistance property and anti-corrosion property of the Ni-P coating.     

Development of compositionally modulated multilayer Zn-Ni deposits as replacement for cadmium

Compositionally modulated multilayer (CMM) Zn-Ni deposits were electrodeposited from single acidic bath (pH = 4.7) by using a potentiostatic sequence. The Zn and Ni composition in the alloy was tailored as a function of distance from the steel substrate. X-ray diffraction studies of the deposit showed the presence of γ-phase with a composition of Ni₅Zn₂₁. The corrosion properties of modulated multilayer coatings were studied in 5% NaCl solution using electrochemical corrosion techniques. The polarization resistance of the deposits varied as a function of Ni content between 1700 and 3440 Ω. CMM Zn-Ni with 20 wt% Ni exposed in ASTM B117 salt spray test did not show any red rust formation after 400 h.     

Improved microhardness and wear resistance of the as-deposited electroless Ni-P coating

The coatings with different phosphorus contents were obtained by varying the ratio of lactic acid to acetic acid in the electroless plating bath. With the increase of phosphorus content, the structure of the electroless Ni-P coating transformed from nanocrystalline to a mixture of nanocrystalline and amorphous phases, then to amorphous phase. A record high hardness value of 910 HV_0.1 of as-deposited Ni-P coating was obtained at 7.97 at.% phosphorus content, and high wear resistance was accordingly achieved. The refined nanocrystalline grains with an average size of ~ 4 nm were found to be responsible for the record high hardness and improved wear resistance of the as-deposited Ni-P coating.     

络合剂对Ni-P化学镀层在含硫介质中耐蚀性的影响

针对进口原油S含量高腐蚀严重的实际,用电化学和失重法研究方法,结合显微分析和X射线衍射分析手段,研究以柠檬酸和乳酸为络合剂的化学镀Ni-P镀层在Na2S介质中的耐蚀性。结果表明,利用两种络合剂形成的Ni-P镀层均为非晶态,其中以乳酸为络合剂的镀层含P量为10.04%,以柠檬酸为络合剂的镀层含P量为11.93%,在1.0%-2.5%的Na2S介质中,随着Na2S浓度的增加,阳极极化曲线的极化率增大,自腐蚀电位和自腐蚀电流降低。以乳酸为络合剂的镀层耐蚀性更好;两种络合剂形成的镀层在Na2S为1.5mass%时,腐蚀速度出现极大值。     

CoCl2在Ni-P基化学沉积中的作用

在Ni-P基化学沉积液中加入氯化钴,得到Ni-Co-P合金镀层,与Ni-P镀层相比较其性能得以改善。研究了氯化钴对化学沉积所起的作用及其影响机制,结果表明:加入适量的CoCl2可有效提高镀层的硬度和耐热溶液腐蚀性能,并能抑制镀层的晶化,提高其晶化温度。     

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。     

锡青铜化学镀 Ni-P 合金工艺及镀层性能

目的在锡青铜基体上化学镀Ni-P合金镀层,提高锡青铜的耐磨性和耐腐蚀性。方法以酸性含锌活化液活化锡青铜试样,在相同的条件下实施化学镀,并对镀态试样进行不同温度(250,400,500℃)下的热处理。对比基体、镀态试样和热处理试样的性能,研究热处理温度对锡青铜化学镀Ni-P合金层微观结构、显微硬度、耐磨性和耐腐蚀性的影响。结果锡青铜表面形成了Ni-P合金镀层,并且镀层无孔隙缺陷,与基体结合良好,沉积速率较快,为10.00μm/h。经热处理后,镀层的微观结构由非晶态向晶态转变,在500℃热处理的镀层显微硬度最大,耐磨性最好。镀态镀层和经250℃热处理的镀层在10%HNO3溶液和10%H2SO4溶液(10%均为体积分数)中的耐腐蚀性明显好于锡青铜基体,镀态镀层在两种介质溶液中的腐蚀速率分别为0.225,0.146 mg/(cm2·d)。结论采用酸性含锌活化液活化锡青铜基体,可以在锡青铜表面制备出化学镀Ni-P合金镀层,且镀覆效果较好。这表明紫铜化学镀Ni-P合金工艺同样适用于锡青铜。     

Corrosion of AZ91D magnesium alloy with a chemical conversion coating and electroless nickel layer

A chemical conversion treatment and an electroless nickel plating were applied to AZ91D alloy to improve its corrosion resistance. By conversion treatment in alkaline stannate solution, the corrosion resistance of the alloy was improved to some extent as verified by immersion test and potentiodynamic polarization test in 3.5 wt.% NaCl solution at pH 7.0. X-ray diffraction patterns of the stannate treated AZ91D alloy showed the presence of MgSnO₃ · H₂O, and SEM images indicated a porous structure, which provided advantage for the adsorption during sensitisation treatment prior to electroless nickel plating. A nickel coating with high phosphorus content was successfully deposited on the chemical conversion coating pre-applied to AZ91D alloy. The presence of the conversion coating between the nickel coating and the substrate reduced the potential difference between them and enhanced the corrosion resistance of the alloy. An obvious passivation occurred for the nickel coating during anodic polarization in 3.5 wt.% NaCl solution.     

A study of chromium-free pickling process before electroless Ni-P plating on magnesium alloys

A chromium-free pickling process of magnesium alloys in H₃PO₄ + Na₂MoO₄ solution for electroless Ni-P plating was described. The dosage of Na₂MoO₄ was established by detecting adhesion and corrosion resistance of chemical nickel coatings. Electrochemical behaviors of pickling solution of H₃PO₄ + Na₂MoO₄ and NH₄HF₂ activation solution were investigated with the open circuit potential curves and the polarization curves. The results show that the Na₂MoO₄ has strong inhibition ability. Na₂MoO₄ in H₃PO₄ solution can reduce active sites of microcathodic and microanodic zones in the corrosion cells of the substrate surface of magnesium alloys and plays an inhibition role. The activation film with some oxides and fluorides can prevent the substrate magnesium from the fierce displacement and corrosion reaction of electroless plating bath. The chemical Ni-P coating with good adhesion and corrosion resistance was obtained by the pretreatment of 200 cm³ dm⁻³ 85% H₃PO₄ + 5 g dm⁻³ Na₂MoO₄ pickling bath and activation in 200 g dm⁻³ NH₄HF₂ solution. This procedure of surface pretreatment before electroless nickel plating can replace the existing acid pickling containing chromium and HF activation.     

Deposition and corrosion resistance of electroless Ni-PCTFE-P nanocomposite coatings

The present work deals with the process of electroless deposition and electrochemical corrosion behavior of nickel-polychlorotrifluoroethylene-phosphorous (Ni-PCTFE-P) nanocomposite coatings. The process of autocatalytic-catalytic reduction of Ni in nickel sulfate and sodium hypophosphate solution with PCTFE suspended particles has been employed for the formation of the electroless Ni-PCTFE-P composite coatings. Surface morphology and composition of the composite coatings are characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) measurements and X-ray diffraction (XRD) analysis. Corrosion behavior of coatings is evaluated using open-circuit potential (E_OCP) measurements, electrochemical impedance spectroscopy (EIS) and polarization techniques in 3.5 wt.% NaCl solution. The study reveals significant shift in corrosion potential towards the noble direction, decrease in corrosion current density, increase in charge transfer resistance and decrease in double‐layer capacitance values with the incorporation of PCTFE particles in the Ni-P matrix. The significant improvement in corrosion resistance observed for Ni-PCTFE-P nanocomposite coatings (25.3 kΩ cm²) compared to Ni-P (16 kΩ cm²) could have resulted from the microstructural differences of pure Ni-P with Ni-PCTFE-P nanocomposite coatings.     

FS-1化学镀Ni-P镀层的性能研究

采用XRD与SEM分析技术、电化学阳极极化曲线测试和 摩擦磨损试验等，系统地研究了FS-1化学镀Ni-P镀层的结构和性能.结果表明：该镀层具有 优良的耐蚀和耐磨性能，热处理虽可以显著地提高镀层的耐磨性能，但使其耐蚀性能有所降 低.     

Effect on Corrosion Resistance of Ce-Rich-Sealed Ni-P Coatings on Cf/Al Composite Surface

In this study, Ni-P coatings and sealing of the coatings by Ce-rich solution on Cf/Al composite surface for enhanced corrosion resistance are investigated. The corrosion resistance of uncoating sample in 3.5 wt.% NaCl solution was investigated and a comparison with Ni-P and Ce-sealed Ni-P coatings is given. Effect of Ce-sealing on Ni-P coating is discussed. The results of electrochemical measurements of corrosion performance of Cf/Al composites show that sealing of Ni-P coatings with Ce-rich solution can improve the corrosion resistance. The Ce-rich-sealed Ni-P coating has higher corrosion resistance than the coating without Ce, and the electroless plated Ni-P coating on composite surface has higher corrosion resistance than the bare sample, as evidenced by EIS and potentiodynamic polarization measurements. The microstructure of the Cf/Al composites and the two kinds of coatings (i.e., Ni-P coating and Ce-sealed Ni-P coating) were examined by scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. The Ce-sealed Ni-P coatings on Cf/Al composite surface have a total thickness of ~11 μm of which 10 μm is the thickness of the Ni-P coating and ~1 μm is the thickness of the Ce-rich sealing. It shows that the selected area electron diffraction ring pattern of Ce-rich sealing on Ni-P plated composite is consistent with Ce₆O₁₁ or CeO₂. X-ray photoelectron spectroscopy results show that Ce⁴⁺ was the dominant oxidation state for Ce-rich sealing on Ni-P plated composite. The Ce-sealing treatment on Ni-P coating has improved the corrosion resistance over and above the corrosion resistance offered by the Ni-P mono-coating to the bare substrate.     

Characterization of Electroless Ni-P Deposits on Surface of AZ91D Magnesium Alloy

Characterization of electroless nickel deposits on magnesium alloys was investigated by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive spectrometer(EDS)and electrochemical potentiodynamic polarization analysis.The result of XRD showed that the electroless nickel deposits on magnesium alloys were composed mostly of amorphous Ni-P and partially of microcrystalline nickel.The phosphorus content in the Ni-P deposits was 10.8%by the calculation of EDS.SEM micrographs showed that morphology of electroless nickel deposits on magnesium alloys was a typical cellular structure,and the growth of cellular structure was influenced by surface condition of substrate.Zinc layer between substrate and electroless nickel deposits was not found by the results of SEM and EDS,which indicated that the zinc layer on the surface of magnesium alloy was very thin,and the zinc would dissolved while being immersed in electroless nickel plating solution.The thin zinc layer was almost dissolved completely before Ni-P plating.The result of electrochemical potentiodynamic polarization analysis showed that the corrosion potential Ecorr of electroless nickel deposits in 3.5%NaCl solution was about-0.53 V,which was 1 V higher than that of magnesium alloys substrate.And corrosion current density of Ni-P deposits in 3.5%NaCl solution was much smaller than that of magnesium alloys substrate at the same potential value,which indicated that corrosion resistance of electroless Ni-P deposits was excellent.Discoloration time of concentrated nitric acid test for electroless nickel deposits on magnesium alloys was 445 s,which also indicated excellent corrosion resistance.