EDTA体系无氰碱性镀铜的电化学成核机理

采用循环伏安法和计时电流暂态曲线研究了EDTA(乙二胺四乙酸)体系无氰碱性镀铜的电化学成核机理。结果表明,铜在玻碳电极上的沉积遵循3D"成核/生长"机制;计时电流暂态曲线分析表明,在高负电位下铜离子的结晶成核方式遵循瞬时成核机制,低负电位下则趋向遵循连续成核机制,且过电位增加会促进铜离子结晶形核,随最大电流Im增大,电结晶成核数增多。     

不同氯化锰含量对铁电沉积过程的影响

过去,鲜见氯化锰对铁电沉积阴极过程影响的报道,对铁沉积机理研究相对较少。采用线性扫描伏安法、单电位阶跃计时电流法、交流阻抗谱等技术对基础镀铁液和加入氯化锰后的镀铁液中铁在玻碳电极上的电沉积进行了对比性研究。结果表明:加入氯化锰增大了阴极电化学极化,并有效降低了浓差极化,氯化锰含量超过34g/L后提高含量对阴极极化影响不明显;在-1.225~-1.300 V阶跃电位内,不管镀液中是否含有氯化锰,铁在玻碳电极上的电结晶都遵循三维瞬时成核理论,添加氯化锰后扩散系数D显著升高,添加50 g/L MnCl2镀液中的扩散系数相对于基础镀液涨幅达74%;氯化锰使溶液/电极界面电荷传递电阻Rct显著提高、溶液电阻Rsol呈小幅度降低,双电层电容Cdl显著增大,与阴极极化结果相吻合。     

盐酸体系中电沉积制备砷锑合金

在含As3+和Sb3+的盐酸水溶液中通过恒电流沉积制备砷锑合金。利用循环伏安、计时电流暂态技术研究阴极的电结晶过程,结合SEM和EDS观察分析沉积物的表面形貌及成分。结果表明:在该体系中,AsH3气体的析出得到有效抑制;Sb3+的加入有利于合金的电沉积;砷锑在玻碳电极上的电结晶遵循液相传质控制的三维生长机理,随着Sb3+浓度的增大以及柠檬酸络合剂的加入,其形核速率增大,沉积物晶粒细小;增加酸度可进一步细化晶粒,但酸度过高将产生粉末状沉积物。锑离子浓度的增大或柠檬酸络合剂的加入均导致沉积层中砷含量的减少。     

硫酸铈(Ⅳ)对镍沉积层晶粒细化和电结晶行为的影响EI北大核心CSCD

在工业电沉积镍的过程中,镍的晶粒尺寸将会直接影响其在工业生产中的使用情况。因此,细化沉积层晶粒就显得尤为重要。本文选用三电极体系,通过测试工业电解液中不同(0~1.5 g/L)硫酸铈(Ⅳ)浓度下阴极极化曲线、循环伏安曲线和计时电流曲线,探究硫酸铈(Ⅳ)对电沉积镍电结晶行为的影响规律;通过扫描电镜和X射线衍射对哈林槽实验获得的镍沉积层的晶粒尺寸和结构取向进行分析,探究硫酸铈(Ⅳ)对工业电解中镍沉积层晶粒细化及晶体生长取向的影响。结果表明:添加硫酸铈(Ⅳ)后,镍的起始沉积电位发生负移,阴极过电位增大,硫酸铈(Ⅳ)的加入对镍的电结晶起促进作用。未加入硫酸铈(Ⅳ)时,沉积层晶粒粗大不均匀;随着添加剂的加入,使镍沉积层晶粒明显细化;当硫酸铈(Ⅳ)的浓度为0.6 g/L时,峰值电流最大且形核弛豫时间最短,沉积层晶粒尺寸最小,细化效果最优,因此,0.6 g/L硫酸铈(Ⅳ)为硫酸铈(Ⅳ)的最优添加浓度。     

光亮镍在甜菜碱盐酸盐-乙二醇离子液体中的电沉积行为（英文）

采用循环伏安和计时电流法,在14.3%~85.7%(摩尔分数)的甜菜碱盐酸盐-乙二醇离子液体中研究镍在玻碳电极和碳钢电极上的电沉积行为。结果表明:相比Ni(Ⅱ)在玻碳电极上受扩散控制的三维瞬时形核过程,Ni(Ⅱ)在碳钢电极上受扩散控制的准可逆还原过程更容易。SEM和EDAX表明在碳钢片上电沉积得到的镀层为金属镍,且镀层致密、均匀,晶粒细小(平均粒径为(80±4)nm)。XRD表明,(111)晶面为镍在碳钢片上的最优生长晶面。镀层表面平整光亮,与碳钢基体有良好的附着力。     

铜离子对工业电解液中镍电结晶行为的影响EI北大核心CSCD

研究铜离子浓度对工业电解液中镍电结晶过程的影响。采用传统三电极体系,通过阴极极化法、循环伏安法、计时电流法分析铜离子对镍电结晶初期行为的影响。利用电位阶跃和霍尔槽实验制备沉积层并通过SEM观察其微观组织形貌,通过XRD分析其择优生长取向。结果表明:不同质量浓度铜离子的加入使得镍电结晶过电位降低,镍的起始沉积电位发生正移,但并不改变镍形核/长大的生长方式。铜离子的加入使镍形核弛豫时间t_(m)逐渐缩短,峰电流I_(m)逐渐增大;当铜离子质量浓度为0.5和1.0 g/L、阶跃电位为−0.85 V时,镍电结晶处于三维连续形核和三维瞬时形核之间;当阶跃电位处于−0.90~−1.00 V时,接近于三维瞬时形核。随着铜离子浓度增大到1.5 g/L、2.0 g/L时,镍电结晶由三维连续形核转变为三维瞬时形核;镍−铜电解液在电沉积过程中更适用于三维瞬时形核/生长机制。随着铜离子的引入,镍和铜发生共沉积,沉积层晶粒尺寸变大;沉积层的形貌由最初的小圆球颗粒逐渐变为金字塔状,生长方式以螺旋位错生长方式为主,晶粒逐渐由(111)面转变为(111)、(220)面生长。     

纳米结构黑镍薄膜的电沉积机理

采用直流电沉积技术在改性的Watt镀镍溶液中获得了纳米晶黑镍薄膜, 采用SEM和XRD对薄膜的表面形貌和相组成进行了表征, 采用循环伏安法和电化学阻抗谱对黑镍薄膜的初始电沉积行为进行了研究. 结果表明, 黑镍薄膜表面平整光亮, 具有纳米晶结构; 黑镍薄膜的电沉积过程遵循3D成核/生长机制; 随着阴极沉积电势(负偏压)的增大, 黄铜电极表面Ni的电沉积反应\linebreak 由UPD沉积、异质成核/生长转化为最终的同质成核/生长, 相应的电荷转移电阻R_t的值先增大然后减小; 在较高的阴极沉积电势作用下, 由于吸附H原子(H₂分子)的结晶阻止作用和(镍)羟基化合物的吸附作用, 电沉积EIS图出现低频和超低频感抗弧.     

NH4HF2对铁电沉积过程的影响

目的研究稳定剂NH4HF2对铁电结晶过程的影响。方法采用线性电位扫描伏安法、单电位阶跃计时电流法、电化学交流阻抗谱等技术,研究含不同浓度NH4HF2的镀铁溶液中,铁在玻碳电极上的电沉积行为。结果随着NH4HF2浓度的增加,铁沉积的阴极极化变小。在-1.225~-1.300 V阶跃电位范围内,铁在玻碳电极上的电结晶都遵循三维瞬时成核理论,稳定剂浓度的变化不会改变其成核机理。随着NH4HF2浓度的增加,晶核垂直生长速率和双电层电容明显增大,溶液/电极界面电荷传递电阻显著降低,而溶液电阻呈小幅度降低。结论稳定剂NH4HF2的加入可促进Fe2+的电沉积,并提高晶核的垂直生长速率。     

Sn-Cu合金的电沉积行为及添加剂的影响

利用循环伏安和计时安培研究Sn-Cu合金体系在玻碳电极上的电沉积行为,通过阴极极化曲线、SEM观察及EDS分析讨论柠檬酸和硫脲对Sn-Cu共沉积的影响。结果表明,Sn-Cu共沉积过程为扩散控制的不可逆过程;在沉积电位-600～-750mV的范围内Sn-Cu共沉积初期结晶行为满足三维Scharifker-Hills瞬时成核模型,随着过电位的增大,形核活性点增多,形核弛豫时间缩短;当沉积过电位大于-700mV时,Sn2+的扩散系数约为6.435×10-6cm2/s;柠檬酸和硫脲的加入细化了镀层晶粒,使镀层表面更加平整和致密。此外,硫脲的加入降低了镀层中铜的含量,使合金镀层中铜的含量维持在0.5%～2.0%(质量分数)。     

纳米-Al2O3颗粒对镍电结晶初期阶段的影响

利用循环伏安(CV)、计时安培(CA)和电化学阻抗(EIS)研究了纳米Al2O3颗粒在不同电位(vs.SCE)下对Ni自硫酸盐镀液在铜基体上电沉积的影响。结果表明,Ni-Al2O3体系共沉积的起始电位为:–740mV左右;在不同的电位下,纳米-Al2O3颗粒对镍沉积过程的影响有所差别;在电位–740～–830mV范围,与纯Ni沉积相比较,Ni-Al2O3体系沉积的峰电流所对应的孕育期tm明显缩短,反映Al2O3颗粒在阴极表面有利于镍沉积成核,且促进了电结晶成核。Al2O3颗粒吸附在阴极表面可能会阻碍部分离子电荷放电和物质传输过程,尤其在电位–250～–650mV范围,致使Ni-Al2O3体系沉积阻抗增加。在较高的过电位下,Al2O3颗粒的促进作用有所减弱,许多颗粒堆积在电极表面上还可能减小Ni-Al2O3沉积的还原反应电流。在电位–890mV,Ni-Al2O3体系电沉积初期阶段的成核过程基本遵循三维的Scharifker-Hill瞬时成核模式。     

表面活性剂对电沉积镍/纳米二氧化钛复合层的影响

纳米TiO2在镀镍液中团聚严重,为选择能有效抑制纳米微粒团聚并使其充分分散的添加剂,在镍/纳米TiO2复合镀镍液中添加所选用的几种表面活性剂作为添加剂,研究其对微粒的复合量和表面形貌的影响.结果表明,阴离子表面活性剂或阴离子与非离子表面活性剂的联合使用会更好地改善微粒在镀液中的分散性,并能提高微粒在镀层中的含量.     

Electrodeposition of Copper-Nickel Alloys from a Citrate Bath Containing Boric Acid

Copper-nickel alloys have been electrodeposited on steel substrates from a bath containing copper sulphate, nickel sulphate, sodium sulphate, sodium citrate and boric acid. Galvanostatic cathodic polarization, cathodic current efficiency and composition of the alloys were studied as influenced by bath composition, current density and temperature.

The bath is characterized by high cathodic current efficiency. Current density is found to strongly influence the composition of the deposits. At low current densities (lower than a certain transition current density), a copper-rich alloy is deposited with copper (the more noble metal) being the preferentially deposited metal. At larger current densities, nickel becomes the nobler metal and is deposited preferentially. The magnitude of the transition current density depends upon the bath composition and temperature. The structure and surface morphology of the as-deposited alloys were examined by XRD and SEM. The results reveal the presence of a single solid solution phase with face centred cubic structure. The morphology of the deposits is mainly controlled by the alloy composition.     

Nickel electrodeposition from novel citrate bath

A new type of electroplating bath suitable for nickel electrodeposition was developed. Trisodium citrate was used as a complexing agent and a buffer in the bath. The buffering capacity between trisodium citrate and boric acid were compared. The effects were investigated under different conditions of bath composition, current density, pH and temperature on the potentiodynamic cathodic polarization curves, cathodic current efficiency and throwing index, as well as the electrical conductivity of these baths. The optimum conditions for producing sound and satisfactory nickel deposits were： NiSOn6H2O350 g/L, NiCl2·6H2O 45 g/L and Na3C6H5 O7 30 g/L at pH=4 and 55 ℃. The surface morphology of the as-plated Ni deposit was examined by SEM. The results reveal that the nickel deposition obtained from the optimum conditions are composed of compact, non-porous fine grains covering the entire surface. X-ray analysis shows that nickel deposits obtained from the citrate bath have a fine crystal structure compared with deposits from the Watts bath.     

Mechanism of crack decoration of oxides by electrodeposition

The cathodic behaviour of a duplex oxide on 9%Cr steel has been potentiostatically investigated in acidic plating baths based on copper sulphate or nickel sulphamate. Metallography and electron probe microanalysis of decorated specimens has shown that decoration from the copper plating bath involves cathodic dissolution of the outer layer oxide (magnetite). Thus the more stable inner layer of oxide is exposed at cracks and provides an effective site for copper deposition. It is proposed that decoration by nickel occurs by a similar mechanism, but is less readily achieved because magnetite is less readily dissolved in the sulphamate bath.     

Nickel electrodeposition from novel lactate bath

Abstract

A new electroplating bath for nickel deposition has been developed. Lactic acid was used as a complexing agent in the bath replacing boric acid. The effect of bath composition, current density, pH and temperature on the cathodic polarisation, cathodic current efficiency, morphology and structure of the deposit was carried out. Optimum conditions for producing sound and satisfactory nickel deposits were: 0·30M NiSO₄.7H₂O, 0·50–1·0M lactic acid and 0·3M Na₂SO₄ at pH=10, c.d.=0·98 to 9·80 mA cm^?2 and 25°C. The surface morphology of the deposited nickel was investigated using SEM. The crystal structure was examined by X-ray diffraction analysis. The results showed that the nickel deposits have a face centred cubic structure.     

Electroplating of nickel from acetate based bath – Hull Cell studies

Abstract

Electroplating of nickel onto steel substrates from an electroplating bath containing nickel acetate, nickel chloride, boric acid and acetic acid has been investigated under different levels of operating conditions such as bath composition, current density and temperature. A detailed study has been made on the influence of these variables by measuring cathodic current efficiency and throwing power for various baths. Deposition parameters have been optimised using Hull Cell experiments. From potentiodynamic polarisation studies on Ni deposits it was revealed that E _corr moved towards the more negative direction. It is inferred from this fact that there is cathodic control of the corrosion reaction. The R _t value increases with increasing deposit thickness and the corresponding C _dl value is decreased.     

电沉积工艺对锌镍合金镀层镍含量的影响

实验分析了锌镍合金电沉积过程中温度、导电盐、添加剂量和pH值等工艺参数对镀层镍含量的影响。着重考察了pH值与添加剂之间的相互作用及其匹配关系对镀层镍含量的影响。发现pH值在有无添加剂时对镀层镍含量的影响规律不同,并试用极化曲线分析其原因。     

Beneficial effects of Co2＋ on co-electrodeposited Ni-SiC nanocomposite coating

Ni-SiC nanocomposites were fabricated by co-electrodeposition of nickel with silicon carbide nanoparticles on the pure nickel substrates from a nickel sulfate bath with and without the addition of Co2+. The presence of Co2+ in the electrolyte modifies the Ni matrix to Ni-Co solid solution matrix. It helps to refine the grain size of the nanocomposite coating and improves the content of SiC dispersed in the matrix, and consequently results in higher microhardness. The cathodic polarization curves and electrochemical impedance spectroscopy (EIS) at cathodic potential were investigated in the electrolyte with and without Co2+. A modified cathodic polarization curve with a positive shift in reduction potential and a smaller capacitive loop of EIS are observed. These are attributed to the strong adsorption of Co2+ on the SiC nanoparticles. Consequently, it increases the forces of electrostatic attraction between the SiC nanoparticles and the cathode, which promotes the codeposition of SiC nanoparticles in the matrix.     

The Electroplating Of Nickel From Aqueous Gluconate Baths

Preliminary experiments were carried out in order to electrodeposit good quality and satisfactory nickel plate on to copper substrates from gluconate baths. The effects were investigated of bath composition, pH, temperature and current density on cathodic polarization, cathodic current efficiency, on the quality of the deposits and on the throwing power of baths. Highly adherent and very bright plates with metallic lustre were obtained from an optimum bath containing: NiSO₄. 7H₂O 0.144 mol l^?1 and sodium gluconate 0.23 mol l¹ at pH = 4.3, temperature 40°C and current density 1 A dm^?2. The surface morphology of the as-plated nickel was examined by scanning electron microscopy (SEM) while the structure was examined by using X-ray diffraction analysis. The throwing power of the bath is greatly improved by increasing the gluconate concentration.     

Influence of SiO2 particles on zinc–nickel electrodeposition

Abstract

Zinc–nickel/SiO₂ electrodeposits have been produced from an acid sulphate bath. The complimentary (mutual) codeposition behaviour of SiO₂ and nickel was observed. The presence of SiO₂ in the zinc–nickel bath appears to change the alloy deposition behaviour. Rate of nickel deposition was considerably increased with SiO₂ particles in the bath. Similarly, nickel ions were found to enhance the rate of SiO₂ incorporation. The effect of particle size studied revealed that the rate of incorporation of larger (2 μm) particles was higher than that of the smaller (20 nm) particles. Changes in hydrodynamic conditions of the composite bath seem to influence the mass transport of nickel ions hence there is a notable increase in the rate of nickel deposition and SiO₂ incorporation. Morphological studies show that the presence of SiO₂ in the bath seems to have a marked effect on the morphology and microstructure of the zinc–nickel coatings. Cathodic polarisation studies carried out during electrodeposition show a decrease in cathodic current densities with increasing SiO₂ concentration in the bath.