酸性镀镍中有机添加剂对镍电沉积的作用机理

为了进一步弄清常用镀镍添加剂邻磺酰苯酰亚胺、1,4-丁炔二醇及2者的混合物对酸性镀镍中镍电沉积的作用机理,通过循环伏安、交流阻抗和电势阶跃等电化学方法进行了试验研究.结果表明:加入有机添加剂后均能使镍电沉积电位负移,且该电极过程不可逆;同时镍沉积过程经历了2个电子转移步骤和中间产物吸附步骤;当2种添加剂联合使用时,镍电沉积的阴极过电位增大约650 mV,并能有效增大成核数密度,更有利于得到光亮镍层;加入有机添加剂后镍电沉积,I2/Im2-t/tm曲线均靠近瞬时成核理论曲线,说明在有机添加剂作用下镍的沉积遵循瞬时成核三维生长的电结晶机理.     

氨络合物体系中镍在玻璃碳上的电化学成核机理

采用循环伏安法和计时电流法研究了氨络合物体系中镍在玻璃碳上电结晶的初期行为。结果表明．镍在该基体上的沉积没有经历UPD过程，镍的电沉积经历了晶核形成过程，在所研究的外加电位范围内其电结晶按连续成核和三维生长方式进行，外加电位对晶体生长具有显著的影响。通过分析恒电位暂态曲线，求出镍离子的扩散系数D，以及不同外加电位下的饱和晶核数密度Nsat，探讨了外加电位对成核作用的影响。     

离子液体对PbO_2电沉积形核生长过程的影响研究

为揭示1-乙基-3-甲基-咪唑四氟硼酸盐([Emim]BF_4)添加对PbO_2阳极形核和生长过程的影响机制,利用电化学工作站测试PbO_2在玻碳电极上沉积的电化学行为特征,包括:循环伏安曲线、计时电位曲线及计时电流曲线,并与氧化沉积的PbO_2涂层表面形貌进行对比分析。结果表明,PbO_2电沉积过程遵循三维连续成核模式,离子液体辅助时虽未明显改变PbO_2电结晶机理,但对PbO_2电沉积过程中成核和结晶长大速率均有抑制作用,其中以抑制核长大为主,从而明显地减小了PbO_2结晶颗粒尺寸,得到致密的电极表面结构,使得电化学综合性能增强。     

硫酸盐体系中铟在玻璃碳电极上的电化学成核机理

关于硫酸盐体系中镀铜的沉积机理少见报道,采用循环伏安法和计时电流法研究了铟在硫酸盐体系中电沉积的循环伏安特性与电结晶机理.通过分析恒电位暂态曲线,求出铟离子的扩散系数D和不同电压下的晶核密度N_0.结果表明:铟的电沉积没有经历欠电位沉积过程,而是经历了晶核形成过程,其电沉积反应是一个不可逆过程;在外加电位范围内铜的电结晶按照瞬时成核方式和三维生长方式进行.     

SnO2修饰石墨毡电极的制备及其性能表征

采用H₂O₂对石墨毡（GF）进行预处理,然后在其表面电沉积Sn,最后在120℃烘箱氧化24 h制备出SnO₂修饰的石墨毡电极。通过扫描电镜（SEM）对SnO₂修饰前后的石墨毡表面形貌进行表征,采用循环伏安法研究了SnO₂修饰后石墨毡电极的电化学性能。结果表明：SnO₂能够均匀地包覆在石墨毡表面;SnO₂修饰石墨毡后V⁴⁺/V⁵⁺电对的氧化峰的峰电流由0.0538 A增加到0.0708 A,与未处理石墨毡相比增加了31.5%,反应峰出峰持续时间提高,说明SnO₂对V⁴⁺/V⁵⁺电对电极过程具有一定的催化作用。析氧电位由1.382 V增加到了1.517 V,使电极在VOSO₄溶液中的电化学窗口变宽。     

电沉积与铁基体电位活化的增强拉曼光谱研究

为探讨电沉积初始过程对电镀层结合强度的影响,采用循环伏安法和表面增强拉曼(SERS)光谱研究了光亮铁电极在5%KCl溶液中表面氧化物随电位负移的还原过程,并应用循环伏安法和恒电流电位-时间法研究了氰化物镀铜体系铁基体的电位活化现象和电沉积初始过程.结果表明,在电位-0.9 V时,特征波数为424 cm-1和499 cm-1的Fe3O4谱峰消失,电位-1.2 V时,特征波数671 cm-1的FeO、谱峰明显降低,说明Fe3O4和FeO在不同电位下依次实现还原过程.循环伏安曲线在-0.9 V及-1.2 V附近也依次出现了铁氧化物的还原电流平阶.在氰化物镀液中,铜的析出电位(约-1.4 V)负于铁表面氧化物的还原电位,电极过程首先实现铁表面氧化物的还原,随后铜沉积在活化的铁基体上.     

超声辅助电沉积Ni-Co/Y2O3复合镀层的电化学研究

为了研究Y_2O_3纳米粒子在与Ni~(2+)和Co~(2+)共沉积过程中的电化学行为,揭示Ni-Co/Y_2O_3复合镀层的电结晶机理,针对Ni-Co/Y_2O_3的超声辅助电沉积进行了循环伏安(CV)、计时电流(CA)、交流阻抗(EIS)等电化学测试,并通过对实验曲线的拟合计算出共沉积过程的动力学参数。结果表明,Y_2O_3纳米粒子与基质金属的共沉积使形核/生长电位正移,阴极极化度减小。Ni-Co合金和Ni-Co/Y_2O_3复合镀层的形核/生长符合Scharifker-Hill瞬时成核模型:低负电位下,复合镀层的成核速率更高,Y_2O_3纳米粒子对Ni-Co合金的形核起促进作用;高负电位下,Y_2O_3纳米粒子抑制了Ni-Co合金的形核过程。拟合计算结果与实验曲线的理论分析一致。EIS测试表明,Y_2O_3纳米粒子对电极/电解液界面处的双电层无明显影响,但会减小复合共沉积过程的电荷转移电阻。     

有机染料对酸性镀铜电沉积的影响

为了有效地研究添加剂对铜电沉积的影响,选择合成了有机染料酸性镀铜添加剂AQ,用旋转圆盘电极动电位扫描、交流阻抗和微分电容等方法研究其对铜离子电沉积过程的影响,得到了铜的电沉积机理.发现这种染料主要影响亚铜离子的放电还原过程,具体表现为染料与亚铜离子形成配位化合物[AQCu(I)]吸附在电极表面,阻碍吸附铜原子在晶面扩散结晶的过程.原子力显微镜对镀层微观形貌观察表明,AQ是性能良好的酸性镀铜添加剂.     

镍锰合金的电沉积行为

为了了解镍锰合金沉积的电极过程,采用线性扫描伏安法、单电位阶跃计时电流法和交流阻抗谱技术对镍锰合金的电沉积与镍的电沉积进行了对比性研究.结果表明:氯化锰的加入增大了阴极极化;镍和镍锰合金的电结晶都与三维连续成核理论相吻合,但加入氯化锰后电结晶成核速率常数增大,晶体向外生长速度和镍离子的扩散系数下降;电荷传递电阻增大,双电层电容下降.这些变化可能都与Mn(OH)2在阴极表面的吸附有关.     

在不连续Pd粒子覆盖的非导体表面电沉积铜的研究

考察了在覆盖有分散Pd粒子的非导体表面电沉积铜的初始阶段,发现非导体在电沉积前的面电阻达到100MΩ/cm时可实现较快速度的电沉积.铜层生长前沿分为厚镀层区和薄镀层区两部分,厚镀层区外观为红色,形成致密的结晶;薄镀层区颜色发黑,小的铜晶粒在高能表面首先生成.离挂具点近的地方结晶致密,反之则结晶稀疏.SEM照片显示出最初沉积的铜层是以Pd为沉积点的不规则块状,其大小为2～5μm2,随后在众多连续状上有晶体缺陷的高能表面沉积出具有立方形状的铜晶体.电沉积铜过程的推动力是生长前沿高达106A/dm2的电流密度,先沉积的铜层起到挂具的作用直到非金属表面被完全覆盖.     

碱性锌酸盐镀锌中锌的电化学成核机理

过去对碱性锌酸盐镀锌电化学成核机理的研究较少。为此,采用循环伏安法和计时电流法研究了碱性锌酸盐体系中锌在玻碳电板上的电化学成核机理。结果表明：锌在玻碳电极上的电沉积没有经历欠电位沉积过程,而是经历了晶核形成过程,按三维瞬时成核生长方式进行;锌配离子的平均扩散系数D为4．27×10^-6cm^2／s,晶体生长速率和晶核数...     

Electrolytic recovery of chromium salts from tannery wastewater

Tannery wastewater collected from a local leather industry in Peshawar, Pakistan was subjected to DC electrolysis in a simple cell having two static sheet electrodes and stirring assembly after proper dilution and adjustment to desired conditions. One percent HNO(3) and 1% NaHCO(3) were used as electrolytes and pH adjusters. The latter salt also worked as sodium source for anodic deposition of Na(2)Cr(2)O(7). Various combinations of electrodes were tested and conditions optimized for best electrode couple with increased recovery and removal of chromium in the form of Cr(OH)(3) and/or Na(2)Cr(2)O(7) at cathode and anode, respectively. The recovery of 99% chromium was achieved after 2h electrolysis at a cell potential of 1.0 V, pH 5.0 and stirring rate of 500 rpm using Pb sheet as anode and Cu sheet as cathode. The most interesting and novel finding of this work was the recovery of the mentioned salt(s) alone at Cu cathode or Pb anode or collectively at both electrodes by proper control of pH. Such treatment not only minimizes the environmental water pollution, but results in the formation of useful products employed for recycling purpose in tannery or other related industry to make the process economical.     

2A96铝合金表面含三价铬转化膜制备 及其电化学性能研究

通过调整Cr_2(SO_4)_3浓度和K_2ZrF_6浓度,在2A96铝合金表面制备了含三价铬转化膜;采用极化曲线和交流阻抗谱研究了所制备含三价铬转化膜的电化学性能,利用金相显微镜和扫描电镜(SEM)对铝合金成膜前后的表面形貌进行观察和分析。结果表明,在单因素试验中,质量浓度分别为5 g/L Cr_2(SO_4)_3和2.0 g/L K_2ZrF_6溶液中制备含三价铬转化膜的自腐蚀电位最大,交流阻抗谱的相位角最大,阻抗弧长也最大,耐腐蚀性能最好;显微形貌分析得出成膜后的2A96铝合金表面覆盖了一层转化膜。     

配位剂对电沉积Fe-Ni-Cr合金电化学行为的影响

利用线性电势扫描法和循环伏安法分别讨论了配位剂对Fe2 、Ni2 、Cr3 单独电沉积和Fe-Ni-Cr合金共沉积电化学行为的影响,并采用SEM和XRD技术对合金镀层表面形貌和结构进行了表征.实验结果表明,有配位剂存在时,Fe2 单独沉积电势向正方向移动,Ni2 单独沉积电势向负方向移动,且两者析出电势均在-0.85V附近;在简单铬离子水溶液中,不能沉积出金属铬,有配位剂存在时,Cr3 溶液可以得到金属铬;在合金镀液中,没有配位剂存在时,不能得到Fe-Ni-Cr合金镀层,有配位剂存在时,可以得到晶粒平均尺寸为87nm的光亮致密的Fe-Ni-Cr合金镀层,说明配位剂能与Cr3 在电极表面形成电活性配合物,使Cr3 容易在电极上放电,另一方面说明Ni、Fe的析出对Cr的沉积有诱导的作用,使铬在合金镀液中沉积电势正移,实现Fe-Ni-Cr合金共沉积.     

稀土铈对镍-钴-磷合金电极的析氢催化性能的影响

采用自行研制的复合配合剂,用化学沉积法在酸性体系中制备了Ni-Co-P和Ni-Co-P稀土合金电极.研究了稀土元素铈对Ni-Co-P合金电极的析氢电催化活性和电化学稳定性的影响.通过电化学方法测定合金电极在7 mol/L KOH溶液中的阴极极化曲线、Tafel曲线和电化学稳定性曲线,结果表明,与Ni-Co-P合金电极相比,Ni-Co-P(RE)合金电极的析氢电位正移约90 mV,Ni-Co-P(RE)合金电极具有较优的析氢电催化活性和电化学稳定性.此外,还通过X射线衍射、扫描电镜和合金镀层成分分析,结果表明,稀土元素铈的加入使非晶态Ni-Co-P合金镀层晶粒细化,但稀土元素铈不与合金共沉积,只是起到改变镀层组织结构的作用.     

Mg2Ni alloy for metal hydride electrodes

A study was made of the effects of ball-milling Mg2Ni alloy with nickel powder, and chemically coating it with nickel on the alloy properties. Three types of alloys, nickel mixed, nickel ball-milled and nickel coated Mg2Ni alloy, were used as the active material of metal hydride electrodes. The ball-milling of the alloy with nickel powder results in an amorphous or nanocrystaline phase. Chemical coating of the alloy with nickel was carried out at 25°C. The alloy particles were pulverised by the colliding process during the ball-milling and possibly by a hydrogen decrepitation mechanism during the coating process. Electrochemical measurements show that the electrode fabricated from the nickel mixed Mg2Ni alloy was very difficult to charge and discharge at room temperature, while the characteristics of the electrode prepared by nickel ball-milling or nickel coating were greatly improved because of the changed phase structure and surface behaviour.     

Interaction between the TiC(TiCN)-Ni-Mo hardmetals and chromium vapours

The interaction between TiC or TiCN-based hardmetals with a Ni-Mo binder, or cermets, and chromium vapour in a vacuum was investigated over a wide temperature range acceptable for depositing wear-resistant coatings without the formation of a liquid phase in the cermets. Computer modelling in the Ti-C-Cr system showed that a direct interaction of TiC with chromium, leading to the formation of chromium carbides, is not possible because of the high thermodynamic stability of titanium carbide. It was established experimentally that as a result of the interaction between the cermets and chromium vapours, a coating characterized by a two-layer structure was deposited on the cermet surface. The coating consists of an inner layer adjacent to the substrate, which is composed of the chromium and carbon solid solution in nickel, and an outer layer composed of a mixture of (Cr, Ni)₇C₃ and (Cr, Ni)₂₃C₆. The activation energy of the deposition process is 387 kJ mol^–1 which is close to the value of the chromium heat of evaporation. The coating deposition process is supposed to be limited by the rate of the external supply of chromium from the vapour phase. The results of the investigation of the structure, composition and morphology of the coating are presented. A mechanism responsible for the interaction of the cermets with chromium vapour leading to the formation of the two-layer coating, is proposed.     

用镍基薄带钎料真空熔结Cr3C2-NiCr涂层的组织和性能

提出了一种采用薄带钎料进行真空熔结的新方法，用BNi-2薄带钎料粘贴在Cr3C2-NiCr预置层表面进行了真空熔结处理，对涂层的组织和微动磨损性能进行了研究。结果表明，真空熔结涂层组织致密，涂层与基体、涂层内部硬质相与粘结相之间可形成良好的冶金结合。涂层主要由Cr3C2，Cr7C3，Cr23C6，Ni的硼化物、Cr的硼化物等硬质相和镍基固溶体韧性相组成。基于致密的组织、良好的结合和硬质相强化，真空熔结Cr3C2-NiCr涂层的抗微动磨损性能明显优于等离子喷涂Cr3C2-NiCr涂层和1Crl8Ni9Ti不锈钢。