Influence of alkylpyridinium ionic liquids on copper electrodeposition from acidic sulfate electrolyte

The effect of two alkylpyridinium ionic liquids （py-iLs） including N-butylpyridinium hydrogen sulfate （BpyHSO4） and N-hexylpyridinium hydrogen sulfate （HpyHSO4） on the kinetics of copper electrodeposition from acidic sulfate solution was investigated by cyclic voltammetry and potentiodynamic polarization measurements. Results from cyclic voltammetry indicate that these py-iLs have a pronounced inhibiting effect on CuE＋ electroreduction and there exists a typical nucleation and growth process. Kinetic parameters such as Tafel slope, transfer coefficient and exchange current density obtained from Tafel plots, lead to the conclusion that py-iLs inhibit the charge transfer by slightly changing the copper electrodeposition mechanism through their adsorption on the cathodic surface. In addition, scanning electron microscope （SEM） and X-ray diffraction analyses reveal that the presence of these additives leads to more leveled and fine-grained cathodic deposits without changing the crystal structure of the electrodeposited copper but strongly affects the crystallographic orientation by significantly inhibiting the growth of （111）, （200） and （311） planes.

Microstructure and crystallographic characteristics of nanocrystalline copper prepared from acetate solutions by electrodeposition technique

Methane sulphonic acid is an alternative electrolyte for conventional sulphuric acid for copper deposition.Theelectrodeposition of copper from eco-friendly acetate-based electrolytes consisting of copper acetate,sodium acetate and methanesulphonic acid was dealt.Thamine hydrochloride(THC),saccharin and4-amino-3-hydroxynaphthalene1-suphonic acid were used asadditives in depositing electrolytes.The cathode current efficiency was calculated using the Faraday’s law.Metal distrbution ratio ofthe solutions was determined using Haring?Blum cell.These additives impact the surface morphology of deposited copper films bydowngrading,the grain size was analyzed by scanning electron microscopy(SEM)and X-ray diffiraction technique.XRD patternacquired for electrodeposited copper film shows polycrystalline and face centered cubic structure(FCC).The crystal size of thecopper film was calculated using the Debye?Scherrer’s equation.The crystal size revealed that deposits produced from additivecontaining electrolytes exhibited the lowest grain size.Texture coefficient analysis studies revealed that all copper film deposits arepolycrystalline and the crystals are preferentially oriented and parallel to the surface.A uniform and pin-hole free surfacemorphology and grain refining were brought about by the additives.

Electrodeposition of aluminium and aluminium-copper alloys from a room temperature ionic liquid electrolyte containing aluminium chloride and triethylamine hydrochloride

The electrodeposition of A1 and A1-Cu binary alloys on to gold substrates from a room temperature ionic liquid electrolyte containing A1C13-EtaNHC1 was studied. The electrochemical behavior of the electrolyte and the mechanism of deposition were investigated through cyclic voltammetry （CV）, and the properties of deposits obtained were assessed by scanning electron microscopy with energy dispersive X-ray spectroscopy （SEM-EDS） and X-ray diffraction （XRD）. A1 of 70μm in thickness and an A1-Cu alloy of 30μm in thickness with 8at% copper were deposited from the electrolyte. SEM images of the deposits indicate that the A1 deposit was smooth and uniform, whereas the Al-Cu deposit was nodular. The average crystalline size, as determined by XRD patterns, was found to be （30±5） and （29±5） nm, respectively, for A1 and A1-Cu alloys. Potentiodynamic polarization （Tafel plots） and electrochemical impedance spectroscopic （EIS） measurements showed that Al-Cu alloys are more corrosion resistant than Al.

Electrodeposition of Copper by IMPC Method

In order to develop an energy saving electrodeposition process of copper, the electrodeposition of copper in copper sulfate solution by the ion exchange membrane primary cell (IMPC) method has been studied. The experiments were carried out in an ion exchange membrane primary cell with dimensions of 200 mm in length, 52 mm in width and 90 mm in height. The influences of temperature(294 323 K), interval between the anode and cathode (1.5 3.5 cm), mass concentrations of Cu 2+ (6 40 g/L), H 2SO 4(0 120 g/L) and Fe 3+ (3 9 g/L) in catholyte and solution flow rate (0 8 cm/s) on current density and current efficiency were investigated experimentally. The current density increases with the increase of temperature and concentrations of Cu 2+ and H 2SO 4 in catholyte. Cathode current efficiency decreases with the increase of concentration of Fe 3+ in catholyte and anode current efficiency decreases with the increase of temperature. The high quality cathodic copper can be obtained and the current density of membrane can be higher than 150 A/m 2 and the current density of cathode can be higher than 300 A/m 2. The experiment results show that IMPC method is effective for electrodeposition of copper.

On the Role of Boric Acid in the Copper-Tin Alloy Bath

The role of boric acid in the copper tin alloy bath has been investigated by means of the cathodic polarization curves,cyclic voltammograms,rate of alloy electrodeposition and morphological analysis of deposits.The results indicate that the presence of boric acid in weak acidic solution for electrodeposition of Cu Sn alloy raises the overvoltage of hydrogen discharge and lowers the overvoltage of Cu,Sn and Cu Sn alloy deposition on the Pt,and accelerates the rate of depostion.Boric acid was adsorbed on the surface of cathode and inhibited reduction of hydrogen,then the adsorbed boric acid promoted electrodeposition of metals as a catalyzator.However,as the concentration of boric acid is more than 0.50 mol/L,the above effect was weakened due to the complexation reaction between the excessive boric acid and metallic ions.

In Situ Acquisition of Equivalent Circuit Parameters of Crystal Resonance during Copper Deposition and Dissolution in Acidic Solution by Electrochemical Quartz Crystal Impedance System

Electrochemical quartz crystal impedance system (EQCIS) which allows in situ dynamic quartz crystal impedance measurement in an electrochemical experiment was developed by combining an HP 4395A Network/Spectrum/Impedance analyzer with an EG&G M283 potentiostat. Equivalent circuit parameters of crystal resonance change significantly during electrodeposition and dissolution of copper in 0.1 mol/L H2SO4 aqueous solution in a cyclic potential sweep experiment, which is explained with an overall picture of mass loading, solution density and viscosity, etc..

Electrochemical behavior of different shelled microcapsule composite copper coatings

Copper/liquid microcapsule composite coatings with polyvinyl alcohol （PVA）, gelatin or methyl cellulose （MC） as shell materials were prepared by electrodeposition. The influence of shell materials on the corrosion resistance of the composite coatings in 0.1 M H2SO4 was investigated by means of electrochemical techniques, scanning electron microscopy （SEM）, and energy dispersion spectrometry （EDS）. The results show that the participation of microcapsules can enhance the corrosion resistance of the composite coatings compared with the traditional copper layer. Based on the analysis of electrochemical test results, the release ways of microcapsules were deduced. Gelatin and MC as the shell materials of microcapsules are easy to release quickly in the composite coating. On the contrary, the releasing speed of PVA microcapsules is relatively slow due to their characteristics.

STRUCTURE AND PROPERTIES OF Cu-Co MULTILAYER FILMS PRODUCED BY ELECTRODEPOSITION

Multilayer Cu-Co film has been produced from a single bath by the method of pulse electrodeposition. Its structure and some magnetic properties were analysed by TEM,AES, XRD and VSM. The results indicated that the film was layed structure, consisted of alternating pure copper and copper-cobalt alloy layers. The results have shown the possibility of producing multilayer films with perpendicular magnetic anisotropy byelectrodeposition.

Electroforming of a Complex Mould Using an Acid-Mediated Copper Sulphate Bath

This work reports a procedure for the fabrication of a complex mould using the technique of electroforming. This was with a view to finding a cheaper and less labour-intensive mould production route practicable locally. A Plaster of Paris electroforming mandrel in the shape of a water bottle was produced and made electrically conducting with a layer of copper conducting paint. Considerations for electroform removal were made by applying a thin, chloroform-dissolvable epoxy layer beneath the conducting copper paint. Uniformity of deposition on the mandrel was accomplished with the construction of a special deposition bath with multiple copper anodes around its perimeter. The electroforming was done in the galvanostatic electro deposition mode for about 240 hrs in a 1 M Cu2SO4 bath with the deposition of elemental copper on the mandrel. Incidences of rising bath pH were mediated with concentrated H2SO4. A free-standing electroform representing the mould cavity was formed in the deposition. The product so formed was a reproduction of the net-shape of the mandrel exhibiting smooth surface finish. The electroforming was cast with an aluminum backing layer to complete its transformation into a split mould. The finished mould was comparable in appearance to the imported moulds in terms of appearance and reproduction of intricate surface patterns. The simplicity and low cost of this method significantly reduced the requirements for expensive instrumentation and highly skilled labour for mould production.

湿法炼铜萃取-电积铁的影响及控制研究

湿法炼铜过程中,由于矿石性质不同,浸出的富铜液性质也不同,铁作为最常见的杂质以Fe2+和Fe3+与铜一起溶出,在萃取过程中铁被萃取并和物理夹带进入电积液而累积起来,造成电积液中铁含量达不到电积生产要求,电积工序电流效率降低,电耗增加,本文针对某矿山生物湿法炼铜过程(萃取-电积铁)的控制进行研究,为生产实践控铁提供较优的处理方法。

1,3-二甲基-2-咪唑啉酮-AlCl_(3)-Cu_(2)O离子液体电沉积金属铜

为找到一种电沉积金属铜的新方法,选用1,3-二甲基-2-咪唑啉酮(DMI)、AlCl_(3)和Cu_(2)O(摩尔比为90∶10∶4)的溶剂化离子混合液体进行铜的恒电位电沉积,并分析了电解质的离子结构、电导率、黏度和密度等。拉曼光谱和核磁共振分析表明DMI-AlCl_(3)-Cu_(2)O体系中存在[AlCl2(DMI)_(4)]^(+)、AlCl_(3)(DMI)2和[AlCl_(4)]^(-)等离子团,DMI-AlCl_(3)-Cu_(2)O体系的电导率、黏度和密度随温度在323~373 K区间内呈线性变化。循环伏安研究表明,铜的起始还原电位为-0.4 V(vs Al),还原峰电位为-1.35 V;在-1.1 V至-1.4 V条件下恒电位电沉积得到金属铜,在-1.1 V和-1.4 V电位下电沉积得到的产物表面较平整,在-1.2 V和-1.3 V电位下电沉积得到的产物为纳米针状结构的铜颗粒,直径约为20~40μm。

铜纳米修饰电极的制备及电化学葡萄糖和亚硝酸盐的测定

纳米结构材料由于具有独特的物理和化学性质,将其结合至电极表面可显著提高电化学反应的性能,而基于纳米结构修饰电极制备的高性能便携式传感器在环境保护、食品安全等领域具有广阔的应用前景。该实验以无需抛光打磨、可一次性使用的氧化铟锡(ITO)导电玻璃为基底工作电极,通过一步电沉积法制备了铜纳米修饰的ITO(Cu/ITO)电极。所制备的Cu/ITO电极可用于电化学葡萄糖和亚硝酸盐的高灵敏度、高选择性测定。该实验将最新的科研成果转换为“仪器分析实验”课程中的研究设计性实验,选择贴近生活的课题,并通过全方位的实验操作和训练,能够使学生了解纳米材料的制备方法、现代分析仪器的检测原理及应用领域。通过两种不同原理传感器的构建、性能测试和实际应用,能够使学生了解科学研究的基本流程,培养勤于思考、善于动手的科学精神,激发对科学研究的兴趣,全面提升科学素养和创新能力。

2-巯基噻唑啉对电解铜箔组织结构和力学性能的影响

[目的]研究电解液中2-巯基噻唑啉(2-MTZ)浓度对电解铜箔组织结构、表面粗糙度、力学性能及电沉积行为的影响。[方法]采用钛板为基材,在由80 g/L Cu2+、100 g/L硫酸和0~20 mg/L 2-MTZ组成的电解液中直流电沉积制备铜箔。利用X射线衍射仪(XRD)、扫描电镜(SEM)、表面粗糙度仪、拉伸试验机和电化学工作站分析了所得铜箔的组织结构和性能。[结果]2-MTZ的加入能够细化铜箔晶粒,当2-MTZ的质量浓度为5mg/L时,铜箔展现出最均匀致密的表面,粗糙度最低,抗拉强度最高(约为525MPa)。循环伏安测试结果显示,2-MTZ能够增强铜电沉积过程的阴极极化。随着2-MTZ质量浓度增大,铜电沉积的形核密度先增大后减小,扩散系数逐渐降低。[结论]电解液中添加适量2-MTZ有利于获得微观结构和力学性能良好的电解铜箔。

阴极钛材表面处理工艺对其表面状态及铜离子电沉积初期行为的影响

目的研究表面处理工艺对钛材表面状态的影响,进一步探究阴极钛材表面状态对铜离子电沉积初期形核行为的影响。方法利用砂纸研磨、机械/电解抛光、化学腐蚀等不同的表面处理工艺,制备出不同表面状态的钛材,对钛材的表面粗糙度和形貌分别进行测试和扫描电镜观察。以不同表面状态的钛材作为阴极,进行铜离子的电沉积实验,对初始沉积层组织进行扫描电镜观察,并统计铜晶核的尺寸、覆盖率。结果砂纸研磨的钛材表面粗糙度最大,随着砂纸目数的增加,粗糙度降低,划痕变得细密,沉积的铜晶核尺寸较小、分布均匀、面覆盖率较高;抛光可显著降低钛材表面粗糙度,电解抛光的粗糙度最低,但铜晶核难以牢固附着;化学腐蚀会在钛材表面残留金属颗粒或暴露晶界组织,沉积的铜晶核分布不均匀且易发生团簇。结论铜离子的初始沉积形核行为与阴极钛材的表面粗糙度和缺陷状态密切相关,采用3000#~4000#砂纸精细研磨的方式,可使钛材表面粗糙度Rz保持在1~1.2μm,且表面覆盖有高密度均匀细小的划痕缺陷,最有利于铜离子的高密度均匀形核。

一步电沉积法制备铜表面稀土镧/石墨烯超疏水复合涂层及其耐腐蚀性能

海洋腐蚀的倾向性是制约铜基材料使用性能和安全性的一个重要因素。因此,提高铜表面耐腐蚀能力成为研究重点。采用一步快速电沉积工艺在铜基表面制备肉豆蔻酸镧/氧化石墨烯(LaM/GO)超疏水复合涂层,采用扫描电镜(SEM)、X射线光电子能谱仪(XPS)、水接触角测量和电化学测试等手段对复合涂层的结构及性能进行了表征。结果表明:电沉积阴极表面产生了低表面能材料和花瓣状微纳粗糙结构,涂层表面静态水接触角为154°±3°,滚动角为5°±3°;电位动态极化曲线测量表明,超疏水复合涂层表面的腐蚀电位增加、腐蚀电流密度降低了2个数量级,缓蚀效率达99.34%,耐腐蚀性能得到显著提升;此外,所获得超疏水复合涂层表面显示出优异的防污性能和机械稳定性。

铜-锌合金电沉积及脱合金化法制备多孔铜箔

[目的]纳米多孔铜由于其开放的多孔结构、较高的比表面积、较低的密度等独特的理化性能,在储能、催化剂、传感器等领域有巨大的应用潜力。为了解决金属锂作为锂离子电池负极材料时存在的锂枝晶及安全问题,采用脱合金化法制备多孔铜箔成为近年来的研究热点。[方法]先以钛板为基体电沉积铜箔基底,接着电沉积Cu-Zn合金,再脱合金化处理得到多孔铜箔。重点研究了工艺参数对Cu-Zn合金镀层形貌、结构和性能的影响。[结果]Cu-Zn合金电沉积的较优工艺条件为:电流密度1.0 A/dm^(2),温度40℃,时间20 min。该条件下所得Cu-Zn合金镀层表面平整、结构均匀、形成单一合金相,经脱合金化处理后Zn元素的去除率为70.6%。[结论]采用电沉积+脱合金化的方法有望制得孔径均匀的多孔铜箔,但会产生裂纹,有待进一步研究和改善。

碳钢在氯化胆碱-乙二醇室温离子液体中电沉积铜镍镀层的机理与性能表征

以氯化胆碱-乙二醇离子液体作为电解液溶剂,在Q235碳钢表面采用电沉积法制备了铜镍(Cu-Ni)合金镀层。通过分析各体系电解液的循环伏安曲线,判断电沉积过程金属离子的共沉积机理,结果显示Cu、Ni在此体系下容易实现共沉积。文中考察了电流密度的变化对镀层的微观形貌以及镀层的耐腐蚀性的影响,结果表明,随着电流密度增大,镀层中镍含量逐渐增大,镀层晶粒形貌也随之发生了显著变化;当电流密度从-1.5 mA/cm^(2)增加到-4.0 mA/cm^(2)时,镀层的耐腐蚀性先增大后减小,电流密度为-3.0 mA/cm^(2)时,所得镀层的耐腐蚀性较优。

射流电沉积流场变化对铜沉积层的影响

目的探究射流电沉积过程中电镀液流场参数对铜沉积层的微观形貌、粗糙度、定域性和沉积速率的影响。方法以铂丝为阳极、镍板为阴极,电镀液从内置阳极铂丝的喷嘴流出接触镍板阴极,在外加电场作用下铜离子还原形成铜沉积层。通过控制喷嘴形状、长宽比例(1∶1、2∶1、4∶1、6∶1)等来改变射流状态及流场参数。利用激光三维形貌仪、扫描电镜、COMSOL模拟等手段分析流场参数变化对铜沉积层粗糙度、定域性、缺陷的影响规律。结果当喷嘴面积固定时,矩形喷嘴长宽比的变化显著影响铜沉积层的粗糙度、瘤状沉积物、定域性以及内部缺陷。当长宽比为1∶1时,沉积层面粗糙度Sa=5.40μm,定域性差,沉积范围为喷嘴宽度的192%,且瘤状沉积物较多。随着长宽比的减小,表面粗糙度逐渐降低,结构趋于均匀,瘤状沉积物也相应减少,且定域性精度增加。当长宽比为6∶1时,铜沉积层面粗糙度Sa=2.76μm,定域性误差为-1%,瘤状沉积物显著减少。利用截面扫描电镜观察发现,当长宽比为6∶1时,沉积层内部的微裂纹、气孔最少。COMSOL流场模拟了不同长宽比下流场的速度分布,结果与实验一致。结论流场速度分布的均匀性显著影响铜沉积层的表面质量和内部结构。流场流速分布均匀性增加,则沉积层表面粗糙度降低,气泡、瘤状物等减少,且内部致密性增加,微裂纹、微孔洞等沉积缺陷明显减少。

电沉积铱镍薄膜电催化剂及其析氢性能

采用电沉积技术在泡沫铜上制备了铱镍(Ir-Ni)合金薄膜,并利用泡沫铜(CF)的三维多孔结构和Ir-Ni合金的优良催化及抗腐蚀性来提升薄膜的电催化析氢反应(HER)性能。本文在恒电流条件下通过电沉积技术在泡沫铜上制备了Ir-Ni薄膜,并与泡沫铜上电沉积制备的纯Ir和纯Ni薄膜进行了比较。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线光电子能谱仪(XPS)分析了薄膜的表面形貌和化学成分,采用线性扫描伏安法(LSV)测试了其电催化性能。结果表明:Ir-Ni薄膜成功附着在具有多孔结构和空心形貌的泡沫铜上,其表面比纯Ni薄膜粗糙。薄膜主要由金属态Ir组成,含量为(80.0±1.2)at.%。Ir-Ni/CF表现出出色的HER性能,仅需要60 mV的过电位就能获得10 mA·cm^(–2)电流密度,塔菲尔斜率(Tafel)低至40 mV·dec^(–1),交换电流密度j0为0.657 mA·cm^(–2),达到了商用Pt/C催化剂的87.6%。并且在碱性溶液中,长时间的析氢实验显示Ir-Ni/CF具有良好的电催化稳定性。相比于Ir/CF和Ni/CF,Ir-Ni/CF的电催化活性显著提升,这主要归因于两方面的因素:一方面是薄膜相对粗糙的表面增加了活性中心的表面积,另一方面是Ir与Ni在析氢反应中的协同效应。

基于COMSOL弯液面限域电沉积铜的仿真分析

[目的]为了更好地理解弯液面限域电沉积铜的动态过程,以硫酸铜溶液电沉积铜为研究对象,建立二维轴对称电沉积模型。[方法]使用COMSOL有限元软件对弯液面限域电沉积铜进行模拟,考虑多物理场协同作用,并研究了环境相对湿度、电压和沉积时间对动态电沉积铜的影响。[结果]环境相对湿度影响蒸发通量和离子通量,电压会改变阴极过电位,进而影响电沉积铜的品质和效率。随着电沉积时间的延长,弯液面的边缘铜沉积快于中心部位的铜沉积,出现边缘择优生长现象。[结论]通过调整弯液面限域电沉积铜的工艺参数可以优化电沉积铜的品质和效率。