高择优锌-镍合金电沉积的现场ECSTM研究

采用"二步包封"法制备了性能良好的电化学STM针尖.以此为基础采用ECSTM现场研究了工艺条件下HOPG上高择优锌-镍合金的电沉积过程.研究结果表明这种高择优沉积层以侧向生长方式生长,而表面上电化学活性差的晶面构成了晶体生长过程的保留面,从而进一步形成了与基底表面方向一致的高择优沉积层,X射线研究表明这一择优面为(100)晶面.     

Electrodeposition of nanocrystalline Ni–Cu alloy from environmentally friendly lactate bath

A new environmentally friendly electroplating bath for Ni–Cu alloy deposition was developed. Lactic acid was used as a complexing agent. The influence of bath composition, current density, pH and temperature on cathodic polarization, cathodic current efficiency and alloy composition was studied. Different proportions of the two metals were obtained by using different deposition parameters, but at all [Ni²⁺] / [Cu²⁺] ratios studied, preferential deposition of Cu occurred and regular co‐deposition took place. The Ni content of the deposit increased with Ni²⁺ content and current density and decreased with temperature. The surface morphology of the deposited Ni–Cu alloy was investigated using scanning electron microscopy. The crystal structure was examined using the X‐ray diffraction technique. The results showed that the deposits consisted of a single solid solution phase with a face‐centered cubic structure. The crystallite size lies in the range of 12 to 25 nm for as‐plated alloys. Copyright © 2014 John Wiley & Sons, Ltd.     

碱性电镀光亮锌镍合金研究

在总结镀液的电化学特性和锌镍合金镀层的晶体结构与性能等实验结果的基础上,提出碱性电镀光亮锌镍合金的工艺规范和直接把锌酸盐镀锌液转化为碱性电镀光亮锌镍合金镀液的方法。生产实践证明,该工艺稳定,镀层光亮、耐腐性好、硬度较高、无氢脆,镍含量可在９～２０ｗｔ％范围内随意控制。     

The electrodeposition and properties of Zn-Ni + Ni composite coatings

The Zn-Ni+Ni coatings were deposited under galvanostatic conditions at the current density range from 20 to 60 mA cm^?2. The influence of deposition current density on surface morphology, chemical and phase composition and corrosion resistance of obtained coatings, was investigated. Structural investigations were conducted by X-ray diffraction method. Surface morphology and surface chemical composition of the obtained coatings were determined by a scanning electron microscope. Studies of electrochemical corrosion resistance were carried out in the 5% NaCl solution, using potentiodynamic and Scanning Kelvin Probe (SKP) methods. A possibility of incorporation of nickel powder from a suspension bath to the Zn-Ni matrix, during galvanostatic deposition was demonstrated. The results of chemical composition analysis show that the Zn-Ni + Ni coatings contain approximately 15?C18% at Ni. It was found that surface morphology, surface chemical and phase composition of Zn-Ni + Ni coatings depend in small degree on deposition current density. However, the current density influences distribution of nickel powder on the surface of these coatings. The optimal values of current density on account of corrosion resistance, are found to be j = 40?C50 mA cm^?2.     

穆斯堡尔谱研究电镀镍铁合金层

用穆斯堡尔谱研究了电镀镍铁合金层的形成过程,镀液中Al~(3 ),Mn~(2 ),Cr~(3 ),Zn~(2 )及Cu~(2 )等离子的存在对镀层组成、织构等的影响以及不同铬处理后镍铁镀层的织构和耐蚀性;分析了铬、锰等元素在其中所起的作用;并初步探讨了形成层状结构的原因.     

电镀锌—镍合金的影响因素和反应机理

用原子发射光谱和扫描电镜等仪器研究了电镀锌－镍合金过程中诸多因素对镀层组成、性能的影响，探讨了施镀机理并了异常共沉积结论。     

Growth and field crystallization of anodic films on Ta–Nb alloys

The growth behavior of amorphous anodic films on Ta–Nb solid solution alloys has been investigated over a wide composition range at a constant current density of 50 A m⁻² in 0.1 mol dm⁻³ ammonium pentaborate electrolyte. The anodic films consist of two layers, comprising a thin outer Nb₂O₅ layer and an inner layer consisting of units of Ta₂O₅ and Nb₂O₅. The outer Nb₂O₅ layer is formed as a consequence of the faster outward migration of Nb⁵⁺ ions, compared with Ta⁵⁺ ions, during film growth under the high electric field. Their relative migration rates are independent of the alloy composition. The formation ratio, density, and capacitance of the films show a linear relation to the alloy composition. The susceptibility of the anodic films to field crystallization during anodizing at constant voltage increases with increasing niobium content of the alloy.     

辉光放电光谱法分析镀锌钢板

介绍了利用辉光放电光谱法分析不同种类的热镀锌板和电镀锌板的镀层定量分析；在锌铁合金化热镀锌板上界面定量计算方法的设计；锌铁合金化热镀锌板表面问题的发现。试验结果表明，辉光放电光谱法是配合镀锌板产品质量控制、研究开发的一种有效的分析手段。     

用化学镀法制备 Pd/Ag 膜时膜厚和组成的控制

 研究了不同 Pd2+含量的镀液在多孔陶瓷载体上的化学沉积规律, 发现当 Pd 沉积层厚度达到约 5 μm 后, 即使镀液中反应物的消耗比例很小, 膜厚增长也明显变缓, 沉积反应主要受膜层表面的催化活性位控制; 当镀液中 Pd2+含量只能沉积形成小于 4 μm 的 Pd 膜时, 在 323 K 化学镀 180 min 后, 镀液中 Pd2+的转化率高于 90%. 与之相似, 当 Ag 镀液中的 Ag+含量等于 0.5~2 μm 的 Ag 膜层所需量时, 在 333 K 化学镀 120 min 后, Ag+的转化率可达 95%. Ag+的高转化率与 Ag 颗粒的择向生长特性有关. 根据 Pd 和 Ag 的化学镀沉积规律, 通过调节镀液中金属离子的含量能够预先设计和精确控制超薄 Pd/Ag 膜的膜厚和组成.     

Preparation of Amorphous Film on Ni-S Alloy by Electroplating Method

IntroductionRecently,amorphousalloyshaveattTactedconsiderableattentionasnewfunctionalmaterial.Theycanbeattainedbyelectroplating,suchasplatingNi-P,Ni-B,Fe-W,Ni-Mo,Fe-P,etc..ThestructureofcodepositednickelandsulfurwasfirststudiedbyBrilllwithXRD.He,however,didnotdiscussthemethodofcodepositingnickelandsulfur.Afterwards,thereweresomereportsonNi-Sdeposit.Ingeneral,aNi-SdepositcanbeobtainedbyelectroplatingfromaWattsbathcontainingsuchsulfursourcesasthiocyanateKCNS',thioureaNH,CSNH,',andso…     

Electrodeposition of Zn–Mn alloys at high current densities from chloride electrolyte

The Zn–Mn alloy electrodeposition on a steel electrode in chloride electrolyte was investigated with the aim of obtaining deposits with as high as possible Mn percent. It was found that the deposition current density and concentration of Mn²⁺ ion in the chloride electrolyte significantly affect the Mn content in the alloy coating as well as the coating surface morphology. There was a transition from dendritic and spongy to smooth, bright, and amorphous structure of Zn–Mn deposits, when some critical deposition current density was reached, probably due to the metal oxyhydroxide inclusion in the coatings. Several plating additives were tested in order to decrease the hydroxide content and to improve surface appearance of the deposits. The 4-hydroxy-benzaldehyde was found to decrease oxygen and increase Mn percent in the coatings, and to significantly improve their surface morphology.     

Anomalous codeposition of cobalt and ruthenium from chloride–sulfate baths

Codeposition of Ru and Co was studied at room temperature and at 50 °C with various Ru³⁺ and Co²⁺ concentrations in the electrolyte. The codeposition of Co and Ru proved to be anomalous since no pure Ru could be obtained in the presence of Co²⁺ in the electrolyte, but a significant Co incorporation into the deposit was detected at potentials where the deposition of pure Co was not possible. The composition of the deposits varied monotonously with the change of the concentration ratio of Co²⁺ and Ru³⁺. The deposition of Ru was much hindered, and the current efficiency was a few percent only when the molar fraction of Co in the deposit was low. Continuous deposits could be obtained only when the molar fraction of Co in the deposit was at least 40 at.%. The deposit morphology was related to the molar fraction of Co in the deposit. The X-ray diffractograms are in conformity with a hexagonal close-packed alloy and indicate the formation of nanocrystalline deposits. Two-pulse plating did not lead to a multilayer but to a Co-rich alloy. Magnetoresistance of the samples decreased with increasing Ru content.     

电沉积条件对钴-锰合金结构和磁性能的影响

以柠檬酸为络合剂和硼酸为缓冲剂的酸性硫酸盐镀液中电沉积Co-Mn合金,循环伏安实验显示Co-Mn的起始共沉积电位约-1.282 V(vs.Hg-Hg2SO4 , sat.K2SO4)。借助扫描电镜(SEM)、能谱分析(EDS) 、X射线衍射(XRD)和振动样品磁强计(VSM) 研究了沉积条件对镀层结构和磁性能的影响。结果表明,Co-Mn镀层的组成受沉积条件影响较大;在镀液pH 4.0时,随着阴极电流密度从10 mA•cm-2增加到40 mA•cm-2,镀层中锰含量从0.3 at%增大到6.6 at%;镀层结构由hcp的固溶体转为fcc的固溶体;随着镀层中锰含量增加,膜的饱和磁化强度开始增大,然后降低,最大饱和磁化强度为1926.0 kA•m-1,膜的矫顽力在31.6 ~ 33.9 kA•m-1范围。     

Contribution of cell-surface components to Cu2+ adsorption by Pseudomonas putida 5-x

The contribution of various cell-surface components to Cu²⁺ adsorption by a Gram-negative bacterium, Pseudomonas putida 5-x, that was isolated from local electroplating effluent with a high capability to accumulate heavy metal ions was studied. The cell superficial layer had a negative effect on Cu²⁺ adsorption of the bacterial cells. Cu²⁺ adsorption capacity of the separated cell envelopes was fivefold more than that of the intact cells, owing to the liberation of more and more binding sites during the separation process. Some main components in the cell envelope, such as the peptidoglycan (PEG) layer, outer membrane, and inner membrane, provide the capability for Cu²⁺ adsorption. The content of the components in the cell envelope is in the order inner membrane > outer membrane > PEG layer, and their Cu²⁺ adsorption capacity was in the order PEG layer > outer membrane > inner membrane. The total contribution of the separated PEG layer material to Cu²⁺ adsorption by the cell envelope was no more than 15%, and the outer membrane and inner membrane contributed about 30–35% and 25–30%, respectively. The relatively high phospholipid content in the outer membrane may be the major reason for the higher adsorption capacity of the outer membrane to Cu²⁺ and, hence, such a high Cu²⁺ adsorption capacity of P. putida 5-x cell envelope.     

Synergism of Saccharum officinarum and Ananas comosus extract additives on the quality of electroplated zinc on mild steel

Synergism of Saccharum officinarum (sugarcane) and Ananas comosus (pineapple) extract additives on the quality of electroplated zinc on mild steel in acid chloride solution was investigated experimentally at ambient temperature (~28 °C). The experiments were performed at different plating times (15 and 18 min), additive concentrations (2, 2.5, 3 ml/50 ml of acid chloride solution), pH 5, temperature (27–30 °C), current (0.08 A), and voltage (13 V DC) conditions. Zinc electroplating on mild steel was performed using a DC-supply. The surface of the plated steel was examined with scanning electron microscopy, and energy dispersive spectroscopy for surface elemental composition analysis. Different surface characteristics were obtained depending upon the concentration of the additive and the plating time. The corrosion resistance of the plated surface was determined by a gravimetric method. Microstructural morphology of the plated surface indicated a good quality electroplating that was better than either the sugarcane or pineapple extracts alone. The electroplating process was sensitive to changes in additive concentration and plating time. Any variation in the plating parameter produced an entirely new and different surface crystal morphology.     

Electrodeposition of Fe70Pd30 nanowires from a complexed ammonium–sulfosalicylic electrolyte with high stability

A highly stable plating bath for the electrodeposition of Fe–Pd nanowires into nanoporous alumina templates has been developed. Complexing of both metal ions and exchanging Fe²⁺ by Fe³⁺ avoid chemical reduction of Pd ions and, therefore, undesirable deposition. By using a pulse potential mode and appropriate adjustment of deposition potentials homogeneously filled templates without surface deposits and nanowires close to the desired composition of Fe₇₀Pd₃₀ have been achieved. These alloy nanowires represent a key step towards nanoactuators based on magnetic shape memory alloys.     

Al－Mn合金镀层的组成结构及其耐蚀性

研究了在低温熔盐中（低于２００℃）电沉积Ａｌ－Ｍｎ合金镀层成分的控制,镀层化学组成与结构之间的关系以及镀层的耐蚀性能．提出影响镀层锰含量的主要因素是熔盐中锰离子的浓度．镀层含锰量在２５～４０（ｗｔ）％之间可形成非晶态结构．实验表明,Ａｌ－Ｍｎ合金镀层在０．５ｍｏｌ／ＬＨ＿２ＳＯ＿４熔液及ＮａＣｌ溶液中具有优良的耐蚀性,非晶态结构的Ａｌ－Ｍｎ合金镀层的耐蚀性更为优异．     

Electrodeposition and characterization Zn-Co alloy

The present work details optimization of a stable acid chloride bath for electroplating of bright Zn-Co alloy on mild steel using gelatin and glycine as additives. It was found that the addition of gelatin along with glycine changed the deposition pattern markedly. A suitable bath has been formulated using conventional Hull cell experiments. The bath under plating conditions were found to exhibit anomalous codeposition with preferential deposition of less noble (zinc) over more noble (cobalt) as characterized by Zn-Fe group metal alloys. Investigation revealed that the current density (c.d.), temperature, and pH of the bath have strong effect on the composition of the deposit. Influence of bath constituents and operating parameters on appearance and composition of deposits were studied as measure of their performance against corrosion. A variety of deposits were obtained and their corrosion resistances were measured by Tafel method with/without chrome passivation. Experimental results demonstrated the fact that the corrosion resistances of Zn-Co alloys increased with percent of Co in the deposit except at very high c.d. This is due to the fact at very high c.d. the deposit becomes very porous and thick as evidenced by SEM image. The formation of Zn-Co alloy is confirmed by EDAX analysis. A stable chloride bath for Zn-Co alloy deposition has been proposed and discussed. The formation of passive film on chromatization is indicated by almost same E _corr value of all Zn-Co electroplates irrespective of the current densities at which they have been deposited. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 811–816. The text is published in the original.     

Characterization of electrodeposited Co + Ni alloys by application of the ALSV technique Professor Aleksandar Despic to commemorate his 70th birthday

Anomalous codeposition of Co and Ni onto a gold RDE was investigated in a solution containing simple sulfate salts with the addition of sodium citrate. It was shown that the dependence of the percentage of Co in the deposit on the percentage of Co in the bath follows the shape found in the literature, with the percentage of Co in the deposit being slightly higher than in electrolytes containing pure simple salts. Alloy layers of different composition, electrodeposited at constant charge Q_dep = 1 C cm⁻² (thickness 0.34 μm) were submitted to anodic dissolution at a sweep rate of 1 mV s⁻¹ (ALSV technique) in a solution of 1 M NaCl, pH 2. All samples were found to dissolve through a single anodic peak, indicating that both constituents of the alloy dissolve simultaneously. Alloys with higher Ni content (above 40at.%) were found to dissolve at potentials more positive than the potential of pure Ni dissolution as a consequence of the Gibbs energy change of formation of electrodeposited solid solution type Co + Ni alloys. The composition of electrodeposited alloys was determined by the atomic absorption technique. An attempt was made to obtain a correlation between the peak potentials of anodic dissolution of alloy samples and the composition of alloys, to determine the composition of the alloy from the peak potential of its dissolution. It is found that such a correlation can be used only for strictly defined conditions of alloy deposition and dissolution, caused by the contribution of the Gibbs energy change of formation of electrodeposited alloys. Also, the presence of a CoNi₃ ordered structure in the system is not detected as a separate ALSV peak, but its existence could be the cause of the shape of the Gibbs energy change with composition of the alloy for alloys electrodeposited at low current density.     

Morphology and composition of Ni–Co alloy powders electrodeposited from ammoniacal electrolyte

In this paper, the morphology and phase structure of Ni–Co powders electrodeposited from ammoniacal electrolyte are investigated as a function of alloy powder composition. Composition of the electrolyte, i.e. the ratio of Ni²⁺/Co²⁺ concentration is found to influence both, the phase structure and the morphology of Ni–Co alloy powders. It is shown that the current density practically does not influence the morphology of Ni–Co alloy powders as well as alloy powder composition. At the highest ratio of the Ni²⁺/Co²⁺ ions typical spongy particles were obtained. With the decrease of the Ni²⁺/Co²⁺ ions ratio agglomerates of the size of about 100 μm, composed of a large number of fern-like dendrites on their surface were obtained. At the lowest Ni²⁺/Co²⁺ concentration ratio, among more dendritic particles, agglomerates typical for pure Co powder deposition were detected. It is also shown that depending on the Ni²⁺/Co²⁺ ratio different types of Ni and Co codeposition could be detected: anomalous and irregular. At the Ni²⁺/Co²⁺ ions ratio higher than 1 only β-Ni phase was detected, while at concentration ratios Ni²⁺/Co²⁺<1 h.c.p. α-Co phase together with β-Ni phase was detected in the alloy powder deposit.