Effect of rare earth (Ce, La) compounds in the electroless bath on the plating rate, bath stability and microstructure of the nickel-phosphorus deposits

Effects of added rare earth elements (RE) in the acidic hypophosphite plating bath on the plating rate, bath stability and microstructure of the electroless nickel-phosphorus (EN) deposits were studied. The surface appearance and microstructure were examined under a reflection optical microscope and a scanning electron microscope equipped with an in-situ energy dispersive X-ray spectroscopy, which can evaluate the elemental analysis of deposits. It was demonstrated that the rare earth elements can decrease grain size and refine microstructure.The deposition rate of the Ni-P deposits was estimated by gravimetric, polarization and quartz crystal microbalance (QCM) methods. Results revealed that up to an optimum concentration of rare earth elements, the deposition rate increases. The stability test method was used to determine the stabilization effect of RE on the stability of the bath. It was found that the addition of RE significantly improved the Pd stability of the EN bath.     

添加稀土元素对Ni-P/PVDF化学复合镀层耐蚀性的影响

在化学镀Ni-P/PVDF合金镀液中添加稀土元素Y³⁺和La³⁺制备Ni-P/PVDF(RE)复合镀层,用电化学腐蚀测试系统测试复合镀层的耐蚀性,研究了稀土元素的添加量对镀层耐蚀性能的影响。结果表明,在基础镀液中加入适量稀土元素后,所获得的Ni-P/PVDF(RE)复合镀层的晶粒较Ni-P/PVDF镀层更为细小,表面更加均匀和致密;镀层的耐蚀性随着稀土元素加入量的增加呈现先增强后减弱的趋势;在稀土元素的添加量为0.1g/L时,复合镀层的耐蚀性最好。在PVDF微粒和稀土元素的共同影响下,进一步提高Ni-P/PVDF(RE)镀层的耐蚀性。     

镀液中的稀土元素对Ni－P合金镀层耐蚀性能的影响

镀液中的稀土元素对Ｎｉ－Ｐ合金镀层耐蚀性能的影响邵光杰，王玉林，沈德久，于金库（燕山大学材料工程系秦皇岛０６６００４）１前言电刷镀Ｎｉ－Ｐ合金镀层作为设备的局部防护处理手段已经得到了广泛应用。但单纯的Ｎｉ－Ｐ合金镀层还不能满足某些部门的要求，进一步提...     

新型三元复合络合剂体系对AZ91D镁合金表面酸性化学镀Ni-P的影响

利用含新型三元复合络合剂的酸性化学镀镍液体系,在AZ91D镁合金表面通过化学镀制备Ni-P防护镀层。结果表明,镀层沉积速率随着镀液中三元复合络合剂浓度的变化而改变。利用X射线衍射（XRD）、扫描电子显微镜（SEM）和差热分析（DSC）对镀层结构、形貌以及热稳定性进行表征和分析。通过交流阻抗（EIS）和动电位扫描极化曲线对Ni-P镀层在3.5%NaCl溶液中的耐蚀性能进行评价。镀液中三元复合络合剂的浓度对Ni-P镀层的结构与形貌有显著影响。Ni-P镀层的热稳定性随着三元复合络合剂浓度的增加而降低。当镀液中三元复合络合剂浓度为0.035 mol/L时,所制备的Ni-P镀层致密、均一,在3.5%NaCl溶液中表现出良好的耐蚀性能。     

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。     

混合稀土对Ni-P化学镀工艺的影响

研究了混合稀土氧化物对Ni-P化学镀工艺的影响。结果表明,镀液中加入适量的稀土氧化物能提高镀速、稳定镀液;稀土能与Ni、P粒子共沉积,起微合金化作用,形成含RE的化学镀层。     

Preparation of amorphous-nanocrystalline composite structured Ni-P electrodeposits

Amorphous-nanocrystalline composite structured Ni-P deposits (with phosphorus content of 5-9 wt.%) show better corrosion resistance than that of microcrystalline structured Ni-P deposits, and better abrasion resistance than that of amorphous Ni-P deposits. In order to get amorphous-nanocrystalline composite structured Ni-P deposits on AISI 431 stainless steel, electroplating parameters that affect phosphorus content in Ni-P deposits (temperature, current density, pH, H₃PO₃ concentration and agitation rate) are analysed by orthogonal experimental design (OED) in this paper. The analysis indicates that pH value and phosphorous acid concentration are key variables, their interactive effect on Ni-P composition should be taken into account. The effects of pH and H₃PO₃ concentration of the electroplating bath on phosphorus content in Ni-P deposits are further examined by the method of steepest ascent and central composition design (CCD). On the basis of results and discussion in experimental design sections, various Ni-P deposits with approx. 5-9 wt.% phosphorus can be galvanostatically electroplated by controlling the key variables and these deposits are confirmed to be amorphous-nanocrystalline composite structure in XRD, TEM tests.     

Zn-Ni合金镀层中添加第三种元素和纳米颗粒的研究新进展

介绍了在汽车、航空航天等行业中得到广泛应用的钢铁零件电镀Zn-Ni合金镀层,以及往碱性、氯化物等锌镍合金镀液中加入Fe、Co、Mn、Ce、P等第三种元素所获得的锌镍三元合金镀层,具有更优良的耐腐蚀性、催化性等性能的情况。介绍了往Zn-Ni合金镀液里加入氧化硅、氧化铈、氧化钛、氧化铝、碳化硅等纳米颗粒的进展情况,发现含有纳米颗粒的锌镍复合镀层具有耐腐蚀性、耐磨损性、热稳定性更好,硬度更高等优点。梳理了2016年以来在Zn-Ni合金电镀中添加第三种元素和纳米颗粒的多层镀层研究新进展。从Zn-Ni单一镀液中沉积Ni-P和Zn-Ni合金多层镀层时,在低电流密度下沉积出Ni-P层;在较高电流密度下,沉积出含3.2%P的Zn-Ni-P合金镀层,这种多层镀层可以大幅度提高钢铁零件的防腐蚀性能。介绍了在含12%Ni的Zn-Ni镀层上镀覆Ni-Co-SiC纳米复合镀层的情况,这种多层结构既可以提高镀层的结合力,又可提高其在3.5%NaCl溶液中的耐腐蚀性能。该复合镀层是一种硬度高、磨损量低的新型Zn-Ni合金复合镀层。     

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。     

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。     

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。     

碳纳米管-镍磷化学复合镀层的组织与性能研究

目的研究碳纳米管对Ni-P化学镀层组织与性能的影响。方法将碳纳米管(CNTs)加入到镀液中,采用化学镀的方法在45#钢表面制得碳纳米管-镍磷化学复合镀层。利用扫描电镜、X射线衍射仪综合分析复合镀层的表面形貌和结构,并采用多功能材料表面性能测试仪对复合镀层的摩擦磨损性能进行了研究。利用动电位极化技术对Ni-P-CNTs复合镀层在3.5%NaCl溶液中的电化学腐蚀行为进行了研究。结果Ni-P-CNTs化学复合镀层是非晶态结构,CNTs均匀地嵌埋在基质镀层中。在耐磨性试验中,Ni-P-CNTs复合镀层的磨损率比Ni-P镀层降低了7.6×10~(-11) m~3/(N·m),而平均摩擦因数减小了0.074。在电化学腐蚀试验中,Ni-P-CNTs复合镀层的腐蚀电位比Ni-P镀层正移了222 mV,而腐蚀电流密度降低了5.234×10~(-6) A/cm~2。结论碳纳米管填补了镍磷非晶胞间的间隙,改善了复合镀层的组织结构,使Ni-P-CNTs化学复合镀层具有更好的耐摩擦磨损性能和耐腐蚀性能。     

Ni-P-PTFE-SiO2化学复合镀工艺研究

运用化学复合镀技术,在Ni-P合金镀液中添加PTFE及SiO2粒子进行试验,获得了Ni-P-PTFE-SiO2复合镀层.对复合镀的工艺及复合粒子PTFE和SiO2的添加量进行了研究分析;通过金相显微组织、显微硬度,结合强度和镀层孔隙率等测试对Ni-P-PTFE-SiO2化学复合镀层性能进行了表征.结果表明:当PTFE粒...     

CATHODIC PROCESS AND WEAR RESISTANCE OF ELECTRO-DEPOSITED RE-Ni-W-P-SiC COMPOSITE COATING

Cathodic deposition current density of the composite coatings increases when SiC par-ticles and rare earth (RE) were added in the bath, which is profitable for Ni- W-P alloy to deposit in the cathod, forming Ni-W-P-SiC and RE-Ni-W-P-SiC composite coatings. On the contrary, the addition of PTFE in the bath decreases cathodic deposition current density of the coatings. The current density increases a little when the amount of RE isγ-9g/l; however, the current density increases greatly when the amount of RE is increased to 11-13g/l. But if the amount of RE is raised further, the current density decreases. Hardness and wear resistance of RE-Ni-W-P-SiC composite coating have been studied, and the results show that the hardness and wear resistance of RE-Ni-W-P-SiC composite coating increase with increasing heat treatment tempera-ture, which reach peak values at 400℃; while the hardness and wear resistance of the coating decrease with the rise of heat treated temperature continuously.     

稀土和镁对热浸镀铝液和镀层组织的影响

研究了热浸镀铝液中添加微量稀土和镁对铝液质量和镀铝层厚度的影响及镀铝层的表面和第二相的形貌。结果表明，微量稀土改善了铝液的质量和镀层的组织，而微量镁有损铝液质量和镀层组织。     

Electrochemical behavior of nanocrystalline Ni–P alloys containing tin and tungsten

Autocatalytic ternary Ni-Sn-P, Ni-W-P and quaternary Ni-W-Sn-P films were prepared using an alkaline bath. Plain Ni-P films were also prepared for comparison. Corrosion resistance of the films was evaluated in 3.5% sodium chloride solution in non-deaerated condition by potentiodynamic polarization and electrochemical impedance spectroscopy methods. Deposits were also immersed in 3.5% sodium chloride solution for 7 days. All the coatings attained stable equilibrium potential within 30 minutes in NaCl medium. Lower corrosion current density values were obtained for ternary Ni-Sn-P coatings compared to the plain Ni-P coatings. Ternary Ni-W-P and quaternary Ni-W-Sn-P alloys did not show improved corrosion resistance compared to the ternary Ni-Sn-P coatings. Similar behavior of these coatings was further confirmed by the electrochemical impedance studies. After the potentiodynamic polarization test deposits were examined by scanning electron microscope. It was found that more corrosion occurred for the quaternary deposit compared to other deposits. Energy dispersive analysis of X-ray results indicated that more amount of Fe present on NiWP and NiWSnP coated samples. Similar behavior was confirmed from the optical images of the surfaces obtained for the deposits after the immersion test. The article is published in the original.     

稀土对化学镀镍磷合金镀层性能的影响

研究了在酸性镀液中制得的镍磷合金镀层的组织结构，探讨了稀土离子(La^3 、Y^3 )和稀土氧化物(CeO2、Y2O3)对化学镀镍磷的影响及作用机理，通过正交试验取得了稀土复合镀镍磷合金的最佳配方。同时，研究了在镀液中加入稀土元素后镀层的热处理工艺及强化机制。结果表明，酸性镀液中所得镀层为非晶态结构的胞状组织，稀土与镍共沉积在镀层中可提高镀层硬度、耐磨性，加入复合稀土元素的镀层耐磨性优于单一稀土镀层。稀土元素增强了热处理强化的效果，并使镀层与基体间产生新相FeNi3，镀层与基体的结合力明显增加。     

Corrosion-electrochemical behavior of Ni-P coatings in deaerated acidic sulfate solutions

The corrosion-electrochemical behavior of Ni-P coatings in acidic sulfate solutions (a pH of 0.5–2.0) has been studied. It has been found that the hydrogen evolution reaction occurs through the discharge-electrochemical desorption route. Ni-P coatings are more efficient cathode materials in acidic sulfate media than nickel is. Preliminary cathodic polarization and an inert atmosphere have little effect on the behavior of the polarization curves of Ni-P coatings containing 13.4% phosphorus and significantly accelerate the anodic dissolution of coatings containing 8.0 and 11.1% phosphorus.     

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.     

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 通过扫描电镜、电化学分析和腐蚀失重等方法，研究了镀液中添加RE对双脉冲电沉积法获得镍镀层的耐蚀性影响。结果表明：镀液中添加适量的RE，可使镀层组织细小且表面平整致密，耐蚀性提高，当镀液中含RE量为0.25 g/L时，镀层耐蚀性较好。