Preparation, characterization, and electrochemical studies of sulfur-bearing nickel in an ammoniacal electrolyte: the influence of thiourea

Sulfur-bearing nickel was prepared by a direct electrodeposition in an ammoniacal Ni(II) electrolyte containing thiourea. This sulfur-bearing nickel showed an excellent dissolving activity when used as anodic materials in the traditional Watt bath. The influence of thiourea on the surface microstructure, crystallization texture, and electrocrystallization process of sulfur-bearing nickel were investigated by scanning electron microscopy, X-ray diffraction, and electrochemical techniques. The results show that the S element is uniformly distributed in the electrodeposited nickel. The prepared nickel samples present a blade shape microstructure, and the blade size decreases by the addition of thiourea. Sulfur-bearing nickel exhibits face-centered cubic structure and (111) preferred orientation, and the orientation distribution is strengthened with increased thiourea concentration. The nucleation parameters, such as N ₀, A, and J ₀, are obtained from the initial parts of the transients making use of Sharifker–Mostany theoretical model. Both the nucleation rate and the vertical growth rate are increased by the addition of thiourea, leading to finer grains and better dissolving activity.     

Electrodeposition of Zn–Ni alloys from sulfate bath

The electrodeposition of zinc–nickel (Zn–Ni) alloys from sulfate baths has been studied at different deposition times and H₂SO₄ and NiSO₄ concentrations; various characteristics have been observed during alloy deposition and dissolution. The deposit has been investigated by using scanning electron microscopy (SEM) and X-ray diffractometry. Cyclic voltammetry and galvanostatic measurements during electrodeposition have been conducted. Electrochemical and surface analysis indicate that deposition takes place with the formation of two different structures corresponding to γ-phase and δ-phase zinc–nickel alloys. During anodic part of the cyclic voltammetry of the alloys, a reduction process has been observed, which may be due to hydrogen evolution. With the increase of nickel concentration in the bath, the amount of γ-phase increases, as indicated by the relative increase in the height of the peaks in the X-ray patterns and anodic peaks in the cyclic voltammograms. Also, the corrosion resistance of the zinc–nickel alloy has been improved with an increased concentration of nickel. Under these experimental conditions the electrodeposition of the alloys is of anomalous type.     

纳米陶瓷颗粒的电催化效应及其在复合刷镀层中的化学状态

采用循环伏安法和电位阶跃法研究了nano-Al₂O₃ / Ni复合电刷镀体系的电化学响应，探讨了纳米颗粒对复合电沉积的影响；用X射线光电子谱研究了复合镀层中nano-Al₂O₃颗粒与基质金属之间的相互作用。结果表明纳米颗粒能使金属沉积过电位显著降低，电流效率、金属成核率及晶体生长速度增加，从而对金属镍的电结晶表现出明显的催化效应；在金属镍电结晶过程中，部分到达阴极附近的nano-Al₂O₃颗粒被电极表面捕获。金属生长面上的吸附态镍原子到达纳米颗粒与电极表面接触处，与该处纳米颗粒表面的不饱和氧原子形成Ni-O化学键，纳米颗粒与基质镍以化学键形式结合。纳米颗粒与电极表面的结合区域成为新的成核或生长中心，在随后的刷镀过程中纳米颗粒逐渐被电沉积的金属镍包埋，从而形成复合镀层。     

从2AlCl3/Et3NHCl离子液体中电沉积制备Ni 和Ni-Al 合金

在含Ni2+的2AlCl3/Et3NHCl离子液体中的铜电极上通过恒电位电沉积制备出金属Ni和Ni-Al合金.采用循环伏安和计时电流方法,揭示铜电极上沉积金属Ni的成核机理,研究了电沉积Ni-Al合金的机理,以及恒电位沉积Ni-Al合金工艺条件对沉积Ni-Al合金表面形貌和电流效率的影响.结果表明:在铜电极上电沉积金属Ni的成核机理为受扩散控制的三维瞬时成核过程.在电量≥3.0 C时,电沉积Ni-Al合金的组成基本不再变化.Ni-Al合金的电沉积机理为,Ni的电沉积受扩散控制,同时进行Al的欠电位沉积,在Ni-Al合金电沉积过程中某些Ni-Al合金相的沉积可能受动力学限制而使Ni-Al合金的组成偏离热力学预测结果.在电沉积Ni-Al合金的沉积电流小且平稳,电沉积速率慢条件下,Ni-Al合金表面形貌致密均一,反之就会出现瘤节.电沉积Ni-Al合金的电流效率＞90％.电沉积物的组成接近于Ni3Al合金.     

Homogeneous coating of graphite felt by nickel electrodeposition to achieve light nickel felts with high surface area

We have developed a method of electrodeposition of nickel on a graphite felt of high specific surface area. We have solved the problems linked to the heterogeneous potential distribution in the 3D porous structure by using low concentrations of nickel salts and high applied current densities. This will result in being limited by the diffusion of ions to the electrode on the area of highest potential. The obtained nickel foams present interesting properties such as high surface areas and low densities.     

Fabrication of flexible conducting thin films of copper-MWCNT from multi-component aqueous suspension by electrodeposition

Flexible thin films of metal–carbon nanotube (CNT) with densely populated CNT morphology were fabricated by electrodeposition from an optimized copper bath. The substrate used for the present work is polyethylene film that was pre-deposited with electroless copper as a seed layer before CNT deposition. Optimum concentration of CNT was incorporated into copper bath and the electrodeposition was done at quiescent and agitation conditions. The bonding between the seed layer and the electrodeposited copper was good as revealed from adhesion test. Electrical as well as physical-mechanical property of the film was improved by CNT incorporation within the metal matrix. The topography and the texture of the metal–CNT deposit showed a well-refined structure as per scanning electron microscope (SEM), field emission scanning electron microscope (FE-SEM), and scanning probe microscope (SPM) analysis. The stability of the film was tested by cyclic voltammetric and stripping analysis under various applied conditions. Raman spectra and Fourier transfer infrared spectroscopic (FT-IR) analysis revealed the presence of CNT and the functionality of CNT within the copper matrix. Transmission electron microscope (TEM) analysis showed nucleation of copper on the surface of CNT walls.     

纳米二氧化硅对镍电沉积影响及在复合镀层中的化学键合状态

用线性扫描伏安法和电位阶跃法研究了n-SiO2/Ni复合电刷镀体系的电化学响应,探讨了纳米颗粒的影响;用X射线光电子谱研究了复合镀层中n-SiO2/Ni颗粒表面与基质金属间的相互作用．结果表明纳米颗粒使金属沉积过电位显著降低,电流效率、金属成核率及晶体生长速度增加,纳米颗粒对金属镍电结晶有明显的催化效应;n-SiO2/Ni表面氧的不饱和化学键与表面扩散过程中吸附态金属Ni原子键合形成Ni-O键,纳米颗粒与基质镍以化学键方式结合．     

玻碳材料脉冲电沉积纳米晶体镍的制备及其性能研究

由于纳米晶体镍具有电催化甲醇的活性,本文采用双脉冲法在玻碳表面上电沉积制备了纳米晶体镍,并分析了脉冲条件对其晶粒尺寸的影响。电沉积的溶液组成为300 g·L^-1 NiSO₄·6H₂O,45 g·L^-1 NiCl₂·6H₂O,40 g·L^-1 H₃BO₃,5 g·L^-1 C₇H₅NO₃S,0.05 g·L^-1 C₁₂H₂₅NaO₄S,最优的脉冲工艺参数是脉冲平均电流密度为100 mA·cm^-2、脉冲占空比为30%,脉冲频率为100 Hz, pH为1.5、温度为55 ^oC。利用XRD、TEM、循环伏安以及电化学阻抗分析了纳米晶体镍的晶粒尺寸、结构及性能。制备的电沉积层致密均匀,为典型的面心立方结构,晶体镍的平均粒径在18 nm左右,玻碳材料表面上通过电沉积得到的纳米晶体镍在碱性环境下对甲醇具有良好的电催化活性。     

金属线电极分形生长的模拟

电沉积金属过程中,阴极沉积的金属边缘会出现包括枝晶生长在内的许多复杂形态,这会严重影响电沉积产品的质量和加工过程中的电流效率. 对枝晶分形生长的过程以及形貌进行研究,可以实现对沉淀物的可控生长. 本研究使用Python和Matlab软件相互结合,基于扩散限制凝聚（DLA）模型,建立平行线电极电沉积的模型. 通过分析不同粒子数、沉积概率、电极间距、运动步长、定向漂移条件下的分形生长的变化规律,以及模拟参数与实际电沉积因素对分形生长影响的内在联系,发现只要合理控制模拟的粒子数、沉积概率、线电极间距、运动步长、定向漂移概率参数即可与实际电化学体系的浓度和沉积时间、还原概率、两极间距、温度和电压、电极的相对位置和形状一一对应,从而模拟得到跟实际电沉积接近的分形图,最终可实现对分形生长的可控操作,对分形生长在工业电沉积等方面应用有很大的意义.     

Generation and growth mechanism of metal (Fe, Co, Ni) nanotube arrays.

Nanotubes composed of layered or nonlayered materials have been synthesized through various methods, among which template-based electrodeposition technology provides a versatile technique for synthesizing one-dimensional nanostructured materials. However, the growth mechanism of nanotubes using the template method is seldom clarified. Herein, we present the systematic preparation of metal nanotube arrays and put forward the growth mechanism, termed current-directed tubular growth (CDTG), for template-based electrodeposition. There are competitive growth rates for metal atoms entering the crystal lattice, that is, v( parallel) (growth rate parallel to current direction) and v( perpendicular) (growth rate perpendicular to current direction). Metal nanotubes can be obtained at v( parallel)>v( perpendicular), while nanowires can be obtained at v( parallel) approximately v( perpendicular). The as-synthesized metal (Fe, Co, Ni) nanotubes are constructed from nonlayered materials, which are of body-centered cubic iron structure, hexagonal close packed cobalt structure, and face-centered cubic nickel structure, respectively. The CDTG mechanism is expected to have applications in designing and synthesizing other metal nanotubes and even compound nanotubes via template-based electrodeposition technology.     

Electrochemical detection of amino acids at carbon nanotube and nickel-carbon nanotube modified electrodes

The oxidation and enhanced detection of traditionally 'non-electroactive' amino acids at a single-wall carbon nanotube (SWNT) surface and at a nickel hydroxide film electrochemically deposited and generated upon the SWNT layer is reported. Different CNT are compared, with Nafion-dispersed SWNT offering the most favorable layer for constant-potential amperometric detection. Factors affecting the oxidation process, including the pH or applied potential, are assessed. The response of the SWNT-Nafion coated electrode compares favorably with that of copper and nickel disk electrodes under flow injection analysis (FIA) conditions. The electrodeposition of nickel onto the SWNT-Nafion layer (Ni-CNT) led to a dramatic enhancement of the analytical response (vs. that observed at the SWNT or nickel electrodes alone). The oxidative process at the Ni(OH)(2) layer has been studied and the increase in sensitivity rationalized. In the presence of amino acid the Ni-CNT layer undergoes an electrocatalytic process in which the amino acid reduces the newly formed NiO(OH) species. Furthermore, the attractive response of both the CNT and Ni-CNT layers has allowed these electrodes to be used for constant-potential FIA of various amino acids and indicates great promise for monitoring chromatographic effluents. Once again an improved signal was observed at the Ni-CNT electrode compared to nickel deposited upon a bare glassy carbon electrode (Ni-GC).     

Structure and magnetic properties of Co nanowires electrodeposited into the pores of anodic alumina membranes

Cobalt nanowires were obtained in the process of electrodeposition into pores of an alumina membrane. Structural research (XRD, TEM) of Co revealed the face-centered cubic structure. However, the existence of the hexagonal structure cannot be excluded due to strong texture. The influences of an external magnetic field and Al₂O₃ membrane geometry on magnetic properties of obtained wires were examined. It was found that cobalt nanowires exhibit pronounced shape anisotropy in a direction parallel to the wire axis. The highest influence on the magnetic properties is ascribed to the nanowires geometry i.e., height, diameter, and distances between single wires. Application of an external magnetic field in a perpendicular direction to the sample surface during cobalt electrodeposition increases magnetic anisotropy with a privileged direction along the wire axis. Application of the magnetic field in a parallel direction to the sample surface changes the direction of magnetization.     

Effects of Organic Compounds on the Electrocrystallization of Nickel

It is shown how electrodeposited nickel crystallizes from a Watts bath containing different organic compounds. Rigaku-Denki Geigerfiex DS X-ray diffractometer is used to determine the preferred orientation. Factors determining the development of the coating texture are discussed and the adsorption at a metallic solid surface is considered. The possibilities of the appearance of the oriented adsorption in the process are also discussed. The oriented adsorption of the studied organic compounds on crystallographic planes of nickel is presented in the discussion. There is a direct relationship between the degree of random orientation and brightness. Random orientation is attributed to domination of growth inhibition of the normally faster growing lattice plane. Growth inhibition of lattice planes depends on the oriented adsorption of molecules of the organic compounds.     

Understanding the copper underpotential deposition process at strained gold surface

Copper underpotential deposition (UPD) on a gold surface is investigated by cyclic voltammetry coupled with in situ cyclic strain to understand the strain-modulated electrodeposition. Our work emphasizes quantification of an electrocapillary coupling coefficient ς, which relates the response of Cu electrodeposition potential, E, to applied strain, ε. The different responses to the strain are observed at two Cu UPD stages. The data indicate that tensile strain could enhance the formation of a Cu monolayer on the Au surface. The typical electrodeposition process could be modulated by an external mechanical strain.     

(110)晶面全择优取向Cu镀层的制备及其条件优化

研究了添加剂聚乙二醇(PEG)、氯离子(Cl－)和电流密度对Cu的电沉积过程的影响, 着重探讨了制备(110)晶面全择优取向Cu镀层的电沉积条件及其形成机理. 循环伏安(CV)结果表明, PEG阻化Cu的电沉积, Cl－加快Cu的电沉积速率. XRD实验结果表明, PEG和Cl－在一定浓度范围有利于(110)晶面择优取向; 这两种不同特性的添加剂的协同作用可以制得(110)晶面全择优取向的较薄的Cu镀层; 所制备的全择优Cu镀层较稳定. 全择优取向Cu镀层形成的机理在于PEG和Cl－吸附过程联合起作用, 在不同晶粒的不同晶面进行选择吸附, 改变了晶面的生长速率及晶粒的快生长方向.     

Fabrication of biaxial textured NiO on Ni in a one-step process

A novel method for the preparation of biaxial textured nickel oxide on commercially available nickel via a modified surface oxidation epitaxy (SOE) process has been developed. Following studies of different heat-treatment procedures for both texturing of nickel and for the fabrication of nickel oxide the following method was found to yield the best results. Nickel was first textured under an argon — hydrogen atmosphere at 1000°C for 120 min, then the temperature was lowered to 800°C and the atmosphere was changed to argon with 3 ppm oxygen. Smooth and crack free c-axis textured and a–b aligned NiO buffer layers with an out-of-plane texture of 7.8° and an in-plane texture of 9.4° were successfully produced. Higher oxygen partial pressure and temperatures resulted in increased surface roughness and excessive grain growth.      

Modification of nickel-plating electrolyte for deposition of coatings onto aluminum and its alloys

Composition of an electrolyte for nickel-plating of anodized surface of aluminum and its alloys was developed. It is suggested to use ammonium sulfate having rather high buffer properties in acid electrolytes as a buffer additive. It is suggested to introduce fluorine-containing substances into the electrolyte in order to obtain nickel coatings with finely crystalline structure and to raise the cathodic current efficiency. To improve the operation of the nickel anode and stabilize the cathodic process, it is recommended to introduce into the electrolyte substances of the pyridine series belonging to the class of imides. The optimal working modes of the electrolyte of this kind were determined. The electroplated nickel coatings exhibit a high adhesion to the aluminum base without an additional thermal treatment, which makes shorter the technological process of deposition of multilayer coatings.     

Influence of pulse plating conditions on the structure and properties of pure and composite nickel nanocrystalline coatings

An additive-free Watts type bath containing micron- and nano-SiC particles (1 μm and 20 nm respectively), as well as ultrafine-WC particles (200 nm), was used for the production of pure Ni and nickel matrix composite electrocoatings under both direct and pulse current conditions. Moreover, nickel nanocrystalline deposits were obtained from a Watts type bath containing small amounts of 2-butyne-1,4-diol, in order to investigate the combined advantages of additives and pulse technique on the properties of the deposits. The influence of the variable electrolysis parameters, the particle size and the organic additive concentration on the surface morphology, the structure and properties of the deposits were discussed. It has been proved that the application of pulse electrodeposition affects drastically the structural characteristics and properties of the deposits and under well-defined conditions could lead to the preparation of nanostructured materials with improved mechanical properties. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 6, pp. 802–811. The text was submitted by the authors in English.     

Microstructural investigation of nickel deposits obtained by pulsed current

Electrodeposited nickel coatings are applied in functional applications to modify or improve corrosion resistance, hardness, wear, magnetic, and other properties. In this work, Nickel deposits were produced by simple pulse electrodeposition using a free-additive Watts bath. It has been shown that pulse current deposition is able to produce coatings with excellent properties in morphology, particle distribution, structure, grain size, hardness and wear resistance. Pulsed techniques present a larger number of variables, so we propose to optimize the parameters which define the pulsed current to obtain deposits with improved properties. The optimization of the conditions of deposition was established and the influence of pulse parameters, namely, pulse on-time, off-time and average current density, on the grain size, surface morphology and crystal orientation was determined. The morphology of the coatings was characterized by observations in scanning electronic microscopy (SEM). X-ray diffraction in symmetric mode was also used to evaluate the structure and principal crystallographic orientations of the deposits. The study showed that pulse current results in better properties of deposits and significantly refined the crystal grain.     

TiO2-Based Porous Materials Obtained from Gels, in Different Experimental Conditions

The gels which are precursors of TiO₂ porous materials are prepared by the controlled hydrolysis-condensation of titanium isopropoxide by polymeric method. In the present work, a study of the influence of different experimental conditions (water/alkoxide ratio, solvent/alkoxide ratio and temperature) on the structure and texture of the polymeric gels obtained with the same type of alkoxide has been investigated. The structural and textural modifications for the unsupported materials have been detected using DTA/TGA, XRD, specific surface area and pore size computerized measurements. The optical properties of the supported materials deposited on silicon wafers have been investigated using ellipsometric method. Supported and unsupported porous materials with different structure and texture have been obtained depending on different experimental and thermal treatment conditions.