Electrodeposition and corrosion behaviour of some Zn–Fe group metal alloys by pulsed current

Abstract

The corrosion and electrochemical behaviour of pulse plated Zn–Fe group metal alloy deposits obtained from chloride bath have been studied as a function of pulse parameters such as duty cycle, frequency and average current density. The frequencies of electric current, T _on, T _off, pulse duty cycles have large effects on the chemical composition and surface morphology of the deposits. Results of the electrochemical tests indicate that the corrosion resistance of pulse plated Zn–Fe group metal alloy coatings is superior to that of the alloy deposited by the direct current technique. The on time and off time had no significant influence on the deposit characteristics. Characterisations of deposits were carried out by cyclic voltammetry and the surface morphology was studied by scanning electron microscopy. The composition of the alloy deposits were analysed by spectrophotometry. Refinements in grain size and deposit composition have been made for better corrosion performance with the advent of pulse plating. A minimum corrosion rate was observed at 50% duty cycle and pulse frequency range of 100 Hz in all cases and is proposed as optimal conditions for development of a bright, smooth and uniform deposit of Zn–Fe group metal alloy over steel.     

Zinc–nickel alloy coatings electrodeposited from a chloride bath using direct and pulse current

Zinc–nickel alloys were electrodeposited on steel from chloride bath by direct and pulse current. Some electric variables (average current density, pulse frequency, duty cycle) and some important bath conditions (ratio of Ni²⁺/Zn²⁺ in bath, temperature) on chemical compositions, current efficiency, microhardness and surface appearance of coatings were studied. At low current densities, transition from anomalous to normal co-deposition was observed for both direct and pulse current. Pulse current seems to increase brightness of the coating and to decrease the precipitation of zinc hydroxide at the cathode surface. In addition, applied pulse current increases the percentage of nickel in deposits. Pulse frequency and duty cycle had little effect on the chemical composition of deposits. The polarization curve of zinc–nickel deposition with pulse current is shifted to positive potentials in comparison with direct current curves. The temperature of the plating bath had a very strong effect on the composition of the deposits. This is primarily the result of intrinsically slow nickel kinetics. The hardness of Zn–Ni alloy coatings (approx. 220 VHN) was greater than the hardness of zinc coating (approx. 161 VHN). The hydroxide suppression mechanism for Zn–Ni co-deposition has been confirmed.     

脉冲镀金工艺研究进展

金镀层具有良好的耐腐蚀性、抗氧化性、导电性及延展性,广泛应用于精密微纳元器件制造。电化学镀金是实现微纳元器件镀金的主要工艺之一,主要分为直流镀金工艺和脉冲镀金工艺。相较于直流镀金工艺,脉冲镀金工艺可通过控制脉冲波形、频率、占空比及电流密度等脉冲参数,改变金属离子电沉积过程中的电化学极化和浓差极化,灵活调控镀层的物理化学性能。近年来,国内外在微纳元器件脉冲镀金工艺领域开展了系列研究工作,并取得了不错的进展。综述了电化学脉冲镀金的基本原理,描述了电镀金试验中金由离子形态转化为金属的过程。此外,还综述了占空比、频率、电流密度、脉冲导通时间、脉冲关断时间等脉冲参数对金镀层形成的影响,以及镀层性能评价方式;另外,介绍了无氰和有氰两大典型镀液获得金镀层的基本情况,分析了它们各自的优缺点,主要表现为有氰镀液稳定性好,所得金镀层较均匀,而无氰镀液的突出优势为无毒,但其稳定性有待进一步提高。最后,展望了脉冲镀金工艺的发展方向,可为发展新型脉冲镀金工艺及应用拓展提供有益的参考和启示。     

脉冲偏压占空比对TiN/TiAlN多层薄膜微观结构和硬度的影响

目的研究脉冲偏压占空比对TiN/TiAlN多层薄膜微观结构和硬度的影响规律。方法利用脉冲偏压电弧离子镀的方法,改变脉冲偏压占空比,在M2高速钢表面制备5种TiN/TiAlN多层薄膜,对比研究了薄膜的微观结构、元素成分、相结构和硬度的变化规律。结果 TiN/TiAlN多层薄膜表面出现了电弧离子镀制备薄膜的典型生长形貌,随着脉冲偏压占空比的增加,薄膜表面的大颗粒数目明显减少。此外,脉冲偏压占空比的增加还引起多层薄膜中Al/Ti原子比的降低。结论 TiN/TiAlN多层薄膜主要以(111)晶面择优取向生长,此外还含有(311),(222)和(200)晶相结构。5种多层薄膜的纳米硬度均在33GPa以上,当脉冲偏压占空比为20%时,可实现超硬薄膜的制备。     

脉冲电沉积法制备高P镍基合金镀层

研究了脉冲参数(脉冲高度、宽度、以及反向脉冲等参数)对Ni-P合金镀层P含量、微观形貌等特性影响的规律。结果表明,平均电流密度与反向脉冲电流密度对镀层的P含量有较大地影响;占空比、频率对镀层的微观形貌影响较大。与直流电沉积法制备的Ni-P镀层相比,在不改变镀液组成的条件下,脉冲电沉积法可以显著提高Ni-P合金镀层的P含量。     

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.     

The effect of additives on the pulsed electrodeposition of copper

Abstract

The pulsed electrodepostion of copper has been systematically investigated from a copper sulphate bath. Pulse duty cycles of 5–80%, at frequencies from 10 to 100 Hz with current densities ranging from 2·5 to 7·5 A dm^?2 were employed. The influences of pulsed current duty cycle, peak current density and frequency on the thickness and hardness of the copper deposit, current efficiency and throwing power of the plating process were studied. The effect of additives, polyethylene glycol and di-sodium EDTA on the properties of deposit were investigated.     

Ni/n-SiO2 Composite Coating Prepared by Brush Plating with Pulse Current

Nickel and silicon dioxide nanoparticle composite coatings were prepared by brush plating with direct and pulse current.The surface morphology,microstructure,hardness and wear resistance of the coatings were investigated by scanning electron microscope(SEM),transmission electron microscope(TEM),mirohardness tester and ball-on-disk tribotester.The results show that the technical parameters,pulse current,duty circle and frequency,are of great influence on the growth of crystalline and properties of the coating.Compared with the coating plated with direct current,the coatings plated with pulse currents have smaller nanocrystalline,contain more SiO2 nanoparticle and have higher hardness and wear resistance.     

Effect of direct current and pulse plating parameters on tin whisker growth from tin electrodeposits on copper and brass substrates

Abstract

Electroplated tin finishes are widely utilised in the electronics industry due to their advantageous properties such as excellent solderability, electrical conductivity and corrosion resistance. However, the spontaneous growth of tin whiskers during service can be highly deleterious, resulting in localised electrical shorting or other harmful effects. The formation of tin whiskers, widely accepted as resulting from the formation of compressive stresses within the electrodeposit, has been responsible for a wide range of equipment failures in consumer products, safety critical industrial and aerospace based applications. The numbers of failures associated with tin whiskers is likely to increase in the future following legislation banning the use of lead in electronics, the latter when alloyed with tin, being an acknowledged tin whisker mitigator. Using a bright tin electroplating bath, the effect of process parameters on the characteristic structure of the deposit has been evaluated for deposition onto both brass and copper substrates. The effect on whisker growth rate of process variables, such as current density and deposit thickness, has been evaluated. In addition, the effect of pulse plating on subsequent whisker growth rates has also been investigated, particularly by varying duty cycle and pulse frequency. Whisker growth has been investigated under both ambient conditions and also using elevated temperature and humidity to accelerate the growth of whiskers. Studies have shown that whisker formation is strongly influenced by pulse plating parameters. Furthermore, increasing both current density and thickness of the deposit reduce whisker growth rates. It is also observed that whisker formation is greatly accelerated on brass substrates compared with copper. The basis for this observation is explained.     

Corrosion properties of double layer nickel coatings obtained by pulse plating techniques

Abstract

In this study, the influence of pulse plating on the microstructure, morphology and corrosion properties of semibright nickel layers was investigated and it was observed that applied pulse sequences led to deposits with higher corrosion resistance than those obtained by direct current. Moreover, the study of the effect of pulse plated semibright nickel deposits on double layer nickel coatings showed that the applied pulse sequences provoked an increase in potential difference between individual nickel layers, favouring the lateral spread of pitting corrosion and reducing its penetration to substrate. In addition, the influence of the applied pulse sequences on the consumption of the organic additives in the semibright nickel electrolyte was evaluated, observing that this influence was similar to that given by direct current.     

Microstructure and wear behaviour of pulse electrodeposited alumina nanoparticle reinforced Co–W nanocomposite coatings

Abstract

The microstructure and wear behaviour of alumina nanoparticle reinforced Co–W alloy coatings have been investigated for potential replacement of hard chrome coatings. The composite coatings were pulse electrodeposited on steel substrates using a citrate bath. The effects of current density, in the range of 1–9 A dm^?2, on the particle reinforcement, phase/microstructure, microhardness, and wear properties of the coating have been studied. The coatings codeposited with current density of 5 A dm^?2 at 333 Hz pulse frequency and 33% duty cycle exhibited microhardness comparable to hard chromium coatings.     

Influence of pulse parameters on electrocodeposition of Cr–Al2O3 nanocomposite coatings from trivalent chromium bath

Abstract

Cr and Cr–Al₂O₃ coatings were electrodeposited from Cr(III) bath with both pulsating and direct current onto copper substrates. Pulsating current resulted in homogeneous films of higher Al₂O₃ content and lower particle agglomeration than the direct current. Differences were more tangible at shorter duty cycles and pulse frequencies. Pulsating current improved both microhardness and corrosion resistance. The presence of alumina nanoparticles resulted in greater current efficiency, higher film microhardness and better corrosion resistance. Maximum current efficiency, highest microhardness and densest electrodeposited coatings were achieved at current density of 20 A dm^?2, duty cycle of 40% and pulse frequency of 10 Hz.     

The influence of pulse parameters on Zn-Ni alloy coatings plated on AZ91 magnesium alloy

The influence of pulse parameters on zinc-nickel coatings plated on AZ91 magnesium alloy is investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The particles of zinc-nickel alloy plated on AZ91 magnesium alloy become smaller and the surface roughness decreases with the increase of current density and frequency. However, long plating times and a high ratio of t_on/t_off have decremental effects on the particles and surface roughness. The contents of crystal phases of zinc-nickel alloy coatings are higher under pulse current deposition than under direct current. The frequency, current density, plating time and ratio of t_on/t_off have different impacts on the thickness and Ni content of zinc-nickel coatings.     

Pulse plating of tantalum from 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide ionic liquids

Abstract

This paper briefly reviews the preparation of layers of reactive metals and compounds from ionic liquids (ILs) using pulsed electrodeposition. Special focus is given to tantalum electrodeposition from the IL 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide [BMP][TFSA] onto Ti substrates at room temperature by potentiostatic square pulses. It has been shown that by varying the pulse plating parameters (such as the potential of the on pulse, as well as the frequency and the duty cycle) the morphology of the deposits can be optimised. Thus, experimental conditions have been identified with which uniform and crack free deposits can be obtained.     

Electrochemical Properties of Pulse Plating Amorphous Ni-Mo-W Alloy Coating in Alkaline Medium

采用脉冲电镀技术获得了高活性Ni-Mo-W析氢合金阴极。以析氢反应过电位为考察指标,确定了脉冲镀Ni-Mo-W合金的最佳电镀条件,如Na2WO4·2H2O浓度、平均电流密度和占空比等。同时,系统研究了Mo和W含量对Ni-Mo-W合金镀层成分和组成的影响规律。结果表明,在二元合金中添加W能有效提高电极的析氢反应活性(η200＝80 mV);非晶态Ni-Mo-W合金的组织结构主要取决于Mo含量;与非晶态Ni-Mo合金镀层相比,Ni-Mo-W合金析氢阴极的电化学稳定性得到一定程度的提高。     

脉冲偏压占空比对电弧离子镀TiAlN涂层的影响

通过优化电弧离子镀工艺参数改善TiAlN涂层结构及性能对TiAlN涂层应用具有重要的实用价值。本文利用脉冲偏压电弧离子镀制备了TiAlN涂层,研究了偏压占空比对TiAlN涂层结构及性能的影响,结果发现：随着占空比增加,涂层表面缺陷密度和表面粗糙度先降低后增大,占空比为70%时,制备的涂层表面缺陷密度和表面粗糙度最低。随着占空比增加,涂层的硬度和耐磨性得到明显改善,但占空比超过50%后继续增加占空比反而降低了涂层的硬度和耐磨性。TiAlN涂层与Si3N4球对磨时的主要磨损机制为黏着磨损和氧化磨损。     

Preparation of highly preferred orientation TiB2 coatings

This paper focuses on the preparation of titanium diboride （TiB2） coatings on the graphite substrate by continuous current plating （CCP） and pulse current plating （PIC） electrochemical techniques in fluoride electrolytes （LiF-NaF-KF） containing K2T1F6 and KBF4 as the electrochemically-active components at 700℃. Thick leveled and uniform coatings were obtained and were composed of relatively pure TiB2. The effect of the experimental parameters on the microstructure of the coatings was studied. The results showed the electrodeposition with PIC produced coatings with better quality, when compared with those obtained by CCP, under the conditions of the current density i = 0.6 A/cm^2, frequency = 100 Hz, and todtofr = 4/1. XRD analysis indicated that the preferred orientation of coatings is （110） plane, which is in accordance with the prediction of the two-dimensional crystal nuclei theory. The effect of a ratio of ton/toff and frequency on the crystal size, textule coefficient and microstress was also investigated.     

双脉冲电源参数对电铸金刚石-镍复合膜品质的影响

采用电铸法制备了金刚石-镍复合膜,研究了平均电流密度、正向脉冲频率、正向脉冲占空比、反向脉冲占空比等双脉冲电源参数对镀层厚度的均匀性、沉积速率、硬度、表面形貌的影响.结果表明:随着平均电流密度的增加,沉积速率增大并趋于稳定,复合膜硬度先增大后减小,厚度的均匀性变差;随着正向脉冲频率的增加,沉积速率和硬度都增大,厚度的均...     

The effects of electro-deposition current parameters on performance of tungsten coating

Tungsten coatings prepared on heat sink materials (Al₂O₃–Cu) as PFC not only can release amount of impinging thermal power but also can resist erosion under plasma particles bombardment in the ITER reactor. Therefore electro-deposition technique using for obtaining tungsten coating on Al₂O₃–Cu substrate was a novel technique especially for fusion applications. In this paper, pure tungsten coatings were successfully deposited under various pulsed current densities at 1173 K in Na₂WO₄–WO₃ melts. Furthermore pulse current density, duty cycle and period were investigated respectively so as to obtain well defined structures for tungsten coatings. The composition, crystal structure and microstructure of tungsten coatings were characterized by XPS, SEM and XRD techniques. The results indicated that pulsed current density, duty cycle and period have significant influence on tungsten nucleation and electro-crystallization phenomena.     

Study on Properties of Pulse Electrodeposited RE-Ni-W-P-SiC Composite Coatings

The effects of pulse frequency f and duty cycle r on the deposition rate, composition, morphology, and hardness of pulse electrodeposited RE （rare earth）-Ni-W-P-SiC composite coatings have been studied. The results indicate that pulse current can improve the deposition rate of RE-Ni-W-P-SiC composite coatings; W, P, and SiC contents in the coating decrease with the increase of pulse frequency and reach the lowest value at f = 33Hz, whereas the RE content in the composite coatings increases with the increase of pulse frequency. SiC content decreases with the increase of duty cycle, W content reaches the lowest value, and P content reaches the highest value at r = 0.4; pulse current and RE can lead to smaller size of the crystalline grains; however, the effects of different pulse frequency and duty cycle on the morphologies of RE-Ni-W-P-SiC composite coatings are not obvious. The hardness of RE-Ni-W-P-SiC composite coatings is the highest when the duty cycle is at 0.6 and 0.8 and pulse frequency is at 50Hz. At the same pulse frequency, the hardness of RE-Ni-W-P-SiC composite coatings at r= 0.8 is higher than that at r= 0.6.