Synthesis and properties of electrodeposited Ni/ceria nanocomposite coatings

Composite plating is a method of co-depositing fine particles of metallic or non-metallic compounds or polymers in the plated layer to improve material properties such as lubrication, wear resistance and corrosion resistance. In the present study, Ni was chosen as the matrix material and ceria nanoparticles were chosen as the distributed phase. Nanocrystalline ceria powder was synthesized by the solution combustion process and characterized by powder X-ray diffractometry (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The nanosize ceria particles were co-deposited with nickel from a nickel sulfamate bath using conventional electrodeposition method. The electrodeposition was carried out at current densities of 0.23, 0.77, 1.55, 3.1 and 5.4 A/dm². The microhardness of the Ni matrix was enhanced by the incorporation of ceria particles. Potentiodynamic polarization, electrochemical impedance spectroscopy and SEM were used to characterize the corrosion behaviour of Ni and Ni/CeO₂ coatings. These studies showed improved corrosion resistance for Ni/CeO₂ when compared to Ni. The microhardness, corrosion resistance and wear resistance of Ni and Ni/CeO₂ were compared.     

Ni-TiO2 nanocomposite coating with high resistance to corrosion and wear

Ni-TiO₂ nanocomposite coatings with various contents of TiO₂ nanoparticles were prepared by electrodeposition in a Ni plating bath containing TiO₂ nanoparticles to be codeposited. The influences of the TiO₂ nanoparticle concentration in the plating bath, the current density and the stirring rate on the composition of nanocomposite coatings were investigated. The composition of coatings was studied by using energy dispersive X-ray system (EDX). The wear behavior of the pure Ni and Ni-TiO₂ nanocomposite coatings were evaluated by a pin-on-disc tribometer. The corrosion performance of coatings in 0.5 M NaCl, 1 M NaOH and 1 M HNO₃ as corrosive solutions was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy methods (EIS). The microhardness and wear resistance of the nanocomposite coatings increase with increasing of TiO₂ nanoparticle content in the coating. With increasing of TiO₂ nanoparticle content in the coating, the polarization resistance increases, the corrosion current decreases and the corrosion potential shifts to more positive values.     

Microstructure and properties of nanocrystalline nickel coatings prepared by pulse jet electrodeposition

The fabrication of nanocrystalline nickel coatings was conducted by pulse jet electrodeposition on the substrate of 45# carbon steel. The effects of average current density on the surface morphology, microstructure, average grain size and microhardness of nickel coatings were investigated by scanning electron microscopy (SEM), X-ray diffractometry (XRD) and microhardness measurement. In addition, the corrosion resistances of coating and substrate were compared. It is revealed that the nickel coatings prepared by pulse jet electrodeposition exhibit a fine-grained structure with a smooth surface and a high density, although some pores and defects are still present in coatings. With the increase of average current density, the average grain size of nickel coatings is reduced at first and then increased. The coating with the optimum compactness, the smallest average grain size (13.7 nm) and the highest microhardness are obtained at current density of 39.8 A/dm2. The corrosion resistance is obviously increased for the coatings prepared by pulse jet electrodeposition; however, the corrosion rate is increased after a certain period due to the penetration of the corrosive media.     

Corrosion study of Ni/Zn compositionally modulated multilayer coatings using electrochemical impedance spectroscopy

Ni/Zn compositionally modulated multilayer (CMM) coatings were deposited using dual bath technique. Coatings corrosion performance was evaluated using electrochemical impedance spectroscopy (EIS) during extended immersion times up to 48 h. The results of electrochemical impedance spectroscopy showed that Ni/Zn CMM coatings had better corrosion resistance compared to that of the zinc single layer coating. The modified corrosion product which is formed on the Ni/Zn CMM coatings during extended exposure times and also a good barrier effect of the nickel layer against aggressive species in these coatings can be two important reasons for high corrosion performance and so protection performance of the Ni/Zn CMM coatings.     

The hydrophobicity of Ni–Fe alloy electrodeposits obtained at different current densities

A simple one-step method was used to fabricate a hydrophobic surface by electrodepositing Ni–Fe coating on low carbon steel at various current densities ranging from 2 to 6 A?dm^?2. The as prepared coatings were hydrophilic showing a water contact angle (CA) of zero. After 17 days exposure of the coatings in ambient air, the wettability of the Ni–Fe coatings changed to hydrophobic. Increasing the current density of electrodeposition from 2 to 6 A?dm^?2 led to a reduction in the CA. The hydrophobic behavior of the Ni–Fe coatings after storage in air is related to two factors including the formation of airborne hydrocarbon compounds and the micro/nano pinecone-like structure of the Ni–Fe coating. Polarization tests and electrochemical impedance spectroscopy measurements indicated that the hydrophobic surfaces had higher corrosion resistance in comparison to the as-deposited coatings.     

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.     

DCOIT复合Zn-Ni合金抗菌镀层的制备及其耐SRB腐蚀性能研究

目的 提高Zn-Ni合金镀层的耐微生物腐蚀性能。方法 在硫酸盐电镀液中添加梯度浓度的4,5-二氯-N-辛基-4-异噻唑啉-3-酮（DCOIT）,利用恒电流沉积方法,在碳钢表面阴极电沉积获得DCOIT复合Zn-Ni合金镀层。通过电沉积电位监测与电流效率计算评价DCOIT对电沉积过程的影响,利用扫描电子显微镜、电子能谱、X射线晶体衍射等研究DCOIT对Zn-Ni复合镀层形貌、结构与Ni含量的影响,使用傅里叶红外吸收光谱和荧光显微观察法验证DCOIT的成功复合及复合镀层的抗菌性能,最后将DCOIT复合Zn-Ni合金镀层暴露于硫酸盐还原菌（SRB）中,监测菌液的pH与菌体浓度,同时计算镀层的腐蚀速率,并观察镀层的腐蚀形貌,评价复合镀层的耐SRB腐蚀性能。结果 DCOIT在电沉积过程中会吸附在沉积表面,造成沉积电位负移,并略微降低了电流效率。DCOIT的添加显著改变了复合镀层的形貌、结构与Ni含量,其Ni含量与DCOIT的添加量呈线性增长关系,导致其晶体结构转变。DCOIT以有效形式存在于复合Zn-Ni合金镀层中,并显示出抗菌性能,DCOIT添加量为2 mmol/L时,镀层中的复合量最高,抗菌性能最好。最后,DCOIT复合Zn-Ni合金镀层能有效抑制环境中SRB的生长与代谢,自身腐蚀速率减慢,耐蚀性能明显增强。结论 DCOIT能够以有效形式复合于Zn-Ni合金镀层内部,并有效提高了镀层的抗菌性能,使其获得增强的耐SRB腐蚀性能。     

Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

The correlation among deposition parameters,structure and corrosion behaviour of ZnNi/nano-SiC composite coating deposited by pulsed and pulsed reverse current

The present work shows how the parameters of pulsed current (PC) deposition affect structural and morphological characteristics of electrodeposited ZnNi/nano-SiC composite coating and its corrosion properties. In this regard, ZnNi coatings containing SiC nanoparticles were electrodeposited from chloride bath by PC and pulsed reverse current (PRC) methods, and the effect of duty cycle, frequency and reverse current density were studied. With low and high duty cycles the SiC content of the coating was more than the coating deposited by medium duty cycle. Changing the duty cycle affected the coating composition, structure and morphology. Elevation of the pulse frequency increased SiC content of the coating. Application of PRC produced a coating with a complex and dendritic structure. In most of the electrodeposition conditions, in addition to direct effects of PC on coatings characteristics, it was seen that the more SiC was deposited in the coating the less Ni was deposited, and this also affected the corrosion behaviour. The best corrosion resistance behaviour was shown by coatings with more compact structure and less porosity.     

Electrodeposition behavior and characteristics of Ni-carbon nanotube composite coatings

Ni-CNT (carbon nanotube) composite coatings were processed by electrodeposition and their hardness and corrosion characteristics were investigated with variations of CNT concentration in an electrolyte solution and electrodeposition current density. With increasing the CNT concentration in the electrodeposition bath and the current density, more CNTs are incorporated into Ni matrix. Hardness values of the Ni-CNT coatings are irrelevant to the CNT concentration in the solution, the current density, and current mode, implying poor adhesion of CNTs to Ni matrix. With increasing the CNT content in the coating, the corrosion resistance of the Ni-CNT composite coating becomes inferior due to the porous microstructure.     

Corrosion stability of electrodeposited cyclic multilayer Zn–Ni alloy coatings

Abstract

This paper reports on a study of electrodeposition and characterisation of cyclic multilayer coatings of Zn–Ni alloy from a sulphate bath. Cyclic multilayer alloy coatings were deposited on mild steel through the single bath technique by appropriate manipulation of cathode current densities. The thickness and composition of the individual layers of the CMA deposits were altered precisely and conveniently by cyclic modulation of the cathode current during electrodeposition. Multilayer deposits with sharp change in composition were developed using square current pulses, using thiamine hydrochloride and citric acid as additives. Laminar deposits with different configurations were produced and their corrosion behaviours were studied by AC and DC methods in 5%NaCl solution. It was observed that the corrosion resistance of the CMA coating increased progressively with the number of layers (up to certain optimal numbers) and then decreased. The decrease in corrosion resistance at high degree of layering was attributed to interlayer diffusion due to less relaxation time for redistribution of metal ions at cathode during deposition. The coating configurations have been optimised for peak performance of the coatings against corrosion. It was found that CMA coating developed at cyclic cathode current densities of 3·0/5·0 A dm^?2 with 300 layers showed the lowest corrosion rate (0·112×10^?2 mm/year) which is ～54 times better than that of monolithic Zn–Ni alloy, deposited from the same bath. The protection efficacy of CMA coatings is attributed to the difference in phase structure of the alloys in successive layers, deposited at different current densities, evidenced by X-ray diffraction analysis. The formation of multilayers and corrosion mechanism were examined by scanning electron microscopy.     

Improving corrosion resistance of aluminium metal matrix composites using cerium sealed electroless Ni–P coatings

Abstract

A conversion coating treatment using cerium salts was developed for the surface sealing of electroless nickel–phosphorus (Ni–P) coatings on carbon fibre reinforced aluminium (Cf/Al) composites. The corrosion resistances of uncoated and coated materials (i.e. the Ni–P coating, the Ce conversion coating and Ce sealed Ni–P coatings) were evaluated in 3·5 wt-%NaCl solution using potentiodynamic polarisation and electrochemical impedance spectroscopy. Ce sealed Ni–P coating showed the highest corrosion resistance and clearly improved the overall corrosion resistance of Cf/Al composites. Thus, the Ce sealed Ni–P coating had no obvious microcracks that were generally evident in the more conventional Ce conversion coatings. This is presumed to occur because the electroless nickel surface is relatively homogeneous, compared with the Cf/Al composite surface on which different local coating thicknesses would encourage increased microcrack formation. X-ray photoelectron spectroscopy analysis showed that the Ce conversion coating mainly contained both Ce³⁺ and Ce⁴⁺ species; however, Ce⁴⁺ species were the dominant oxidation state on Ce sealed Ni–P coatings.     

Cr颗粒对Ni-Graphene复合沉积层组织结构及性能的优化

目的电沉积技术制备Ni-Cr-Graphene复合沉积层,调查不同Cr颗粒浓度对复合沉积层组织结构及性能的优化影响。方法利用电沉积技术在镍铝青铜(NAB)表面制备出Ni-Cr-Graphene复合沉积层。采用X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)与拉曼光谱仪(Raman),对复合沉积层的形貌、成分与组织结构(晶粒大小、结晶形状及结晶织构)进行表征,并采用显微硬度计与电化学工作站分别对沉积层的硬度及耐腐蚀性能进行调查。结果Graphene颗粒使得纯Ni沉积层中的Ni晶粒尺寸由175.3 nm减小到Ni-0Cr-4Graphene沉积层中的Ni晶粒尺寸60.5nm。随着Cr颗粒质量浓度进一步从0g/L增加到100 g/L,Ni-Cr-Graphene复合沉积层中的Cr质量分数从0%增加到23.8%,且Ni晶粒尺寸进一步减小到Ni-100Cr-4Graphene沉积层的29.1nm,Ni[200]结晶织构被消除。Graphene与Cr颗粒显著提高了Ni-CrGraphene复合沉积层的表面硬度,所有复合沉积层的显微硬度均高于纯Ni沉积层(260.1HV0.2),且在100 g/L Cr颗粒浓度下,沉积层平均显微硬度为489.8HV0.2。同时Graphene与Cr颗粒改善了Ni-Cr-Graphene复合沉积层在3.5%NaCl溶液中的耐腐蚀性能,在100 g/L Cr颗粒浓度下,复合沉积层的自腐蚀电位(Ecorr)为-0.21 V,自腐蚀电流密度(Jcorr)为0.25μA/cm^2,其相对纯Ni沉积层Jcorr(7.01μA/cm^2)降低了1个数量级。结论溶液中Cr颗粒浓度的增加引起了Ni-Cr-Graphene复合沉积层中Cr含量的增加,使得更多Cr颗粒与Graphene颗粒共同作为Ni金属结晶形核点,促进了Ni的晶粒细化与织构转变,最终提高了复合沉积层的硬度与耐腐蚀性能。     

脉冲电沉积WC-Co-Ni镀层的制备及性能研究

目的提高WC-Co-Ni纳米晶复合镀层的综合性能。方法利用脉冲电沉积法制备WC-Co-Ni纳米晶复合镀层,分析镀层的结构、表面形貌及元素成分,测试镀层的显微硬度。对WC-Co-Ni纳米晶复合镀层和304不锈钢进行5%(质量分数)H2SO4溶液浸泡实验,计算腐蚀速率,对比其耐蚀性。结果当脉冲参数为阴极电流密度5 A/dm2、脉冲占空比50%、脉冲频率2000 Hz时,施镀2 h制备的WC-Co-Ni复合镀层为纳米晶结构。镀层表面平整、光亮,无裂纹,由立方晶型的Ni、六方结构的WC和立方晶型的Co组成,WC-Co颗粒均匀弥散在纳米晶Ni镀层内,且m(Ni)∶m(W)∶m(C)∶m(Co)=6∶2∶1∶1。WCCo纳米颗粒起到了促进形核的作用,晶粒尺寸大多分布在20 nm左右。WC-Co纳米颗粒对镀层起到了弥散强化作用,使复合镀层的显微硬度达到600HV。在浸泡腐蚀实验中,随着温度从20℃升高至80℃,复合镀层的腐蚀速率增加缓慢,20℃下的腐蚀速率仅为0.4192 mm/a,80℃下的腐蚀速率也低于20mm/a。结论脉冲电沉积法制备的WC-Co-Ni纳米晶复合镀层硬度高于传统的不锈钢材料,耐蚀性也优于304不锈钢,综合性能较好。     

Water-Lubricated Ni-Based Composite(Ni-Al_2O_3,Ni-SiC and Ni-ZrO_2)Thin Film Coatings for Industrial Applications

In this work,pure nickel and Ni-based nanocomposite coatings(N1-Al_2O_3,Ni-SiC and Ni-ZrO_2) were produced on steel substrate by using pulse electrodeposition technique.The industrial performance tests were conducted to evaluate the wear resistance,corrosion resistance,adhesion strength and wettability behaviour of newly developed coatings.Rolling contact ball-on-disc tribometer was used to assess anti-wear behaviour of these coatings under waterlubricated contacts.The results showed that the wear- and corrosion resistance properties of nickel alumina and Ni-SiC composite coatings significantly improved than that of pure Ni and Ni-ZrO_2 coatings.The adhesion and wettability results of Ni-Al_2O_3 composite showed better performance when compared to the rest of the coatings.The effects of incorporating nanoparticles on the surface microstructure,interface adhesion and distribution of the particles were also investigated.The coatings were characterized by using scanning electron microscopy,X-ray diffraction analysis and 3D white light interferometry.The wear failure behaviour of these coatings was further examined by post-test surface observation under optical microscope.     

Corrosion and Wear Response of Oxide-Reinforced Nickel Composite Coatings

Various grades of fuels are used in automobiles, as a result the engine components are continuously subjected to simultaneous action of corrosion and wear. Ni-SiC composite coating is the most widely investigated and commercialized wear-resistant coating in the automotive industry. However, this coating cannot be used at temperatures above 450 °C due to the tendency of SiC to react with Ni and form brittle silicides. An alternate approach is to use oxide-reinforced coatings. In the present study, zirconia, ZrO₂ and, yttria-stabilized zirconia, YSZ-reinforced Ni composite coatings have been developed by electrodeposition method. It was observed from the microhardness studies that there is no significant difference in the values for Ni-SiC and Ni-ZrO₂ coatings. The corrosion behavior was evaluated using polarization and electrochemical impedance studies. The studies showed that oxide particle-reinforced Ni coatings possessed better corrosion resistance due to their lower corrosion current density, I _corr. Tribo-corrosion studies were carried out to understand the synergistic effect of wear and corrosion on the performance of Ni-based composite coatings in 0.5 M Na₂SO₄. Among various composite coatings, Ni-YSZ exhibited less material loss thereby showing better tribo-corrosion behavior.     

纳米结构黑镍薄膜的电沉积制备及其电化学行为

采用电沉积方法制备具有整体纳米结构的黑镍镀层,并通过肉眼观察结合扫描电镜、X射线衍射等测试技术研究电沉积过程中的主要参数(电解液pH、搅拌速度、制备温度及电流密度)对镀层颜色及整体微观结构的影响。进一步采用动电位极化及电化学阻抗等电化学测量技术研究黑镍镀层在中性3.5%NaCl溶液中的腐蚀行为及腐蚀机理。结果表明：黑镍镀层的颜色变化趋势决定于电沉积制备参数的选择;通过优化本工艺制备的黑镍镀层平均粒径约为50 nm。对比了近似条件下制备的光亮镍镀层,发现黑镍镀层在耐蚀性方面具有较大优势。     

含稀土镀液电沉积镍镀层耐蚀性的研究

借用扫描电镜、电化学分析和腐蚀失重实验方法研究了镀液中添加RE经直流和单向脉冲电沉积方法制备的镍镀层的耐蚀性。结果表明：单向脉冲法制备的镍镀层抗腐蚀能力优于直流法制备的镍镀层抗腐蚀能力，其原因主要归于单向脉冲镀层结晶比较细小致密，直流镀层结晶较粗大且致密性差。     

碳纳米管镍基复合镀层材料耐腐蚀性的初步研究

制备了碳纳米管镍复合镀层材料，并利用静态浸泡法对同等条件下制备的镍镀层样品的碳纳米管复合镀层样品的耐腐蚀性进行了研究，用扫描电镜观察了样品腐蚀前后的表面形貌变化，同时对碳纳米管复合镀层材料的腐蚀机理进行了探讨，结果表明，复合碳纳米管镍基镀层的耐腐蚀性明显优于同条件下制备的镍镀层。     

Relationship between dispersibility of ZrO2 nanoparticles in Ni-ZrO2 electroplated nanocomposite coatings and mechanical properties of nanocomposite coatings

Ni-ZrO2 nanocomposite coatings with monodispersed ZrO2 nanoparticles were prepared from the composite plating bath containing dispersant under DC electrodeposition condition. It is found that the morphology, orientation and hardness of the composite coating with monodispersed ZrO2 nanoparticles have lots of difference from the composite coating with agglomerated ZrO2 nanoparticles and pure nickel coating. Especially, the result of hardness shows that only a very low volume fraction (less than 1%) of monodispered ZrO2 nanoparticles in Ni-ZrO2 composite coatings will result in higher hardness of the coating. The hardness of Ni-ZrO2 nanocomposite coatings with monodispersed and agglomerated ZrO2 nanoparticles are HV 529 and HV 393, respectively. The hardness value of the former composite coatings is over 1.3 times higher than that of the later. All these composite coatings are 2 - 3 times higher than that of pure nickel plating (HV 207) prepared under the same conditions.