三价铬复合镀铬的研究现状及发展

电化学复合电沉积是将惰性固体颗粒加入到电解液中,以得到金属基复合镀层。由于Cr(Ⅵ)的毒性及对环境的严重危害,三价铬电沉积具有明显的优越特性。综述了从环保的三价铬镀液中电沉积复合镀层的实验研究现状,并对三价铬复合电沉积工艺、镀液和镀层特性及应用进行了讨论,预计三价铬复合电镀有着广阔的应用和发展前景。     

亚铁离子对三价铬电沉积的影响

文章在三价铬电沉积研究基础上,以甘氨酸——氯化物型铬基镀液为基础,研究了亚铁离子是否在三价铬电沉积中起到催化作用;并在此基础上,对电流密度、镀液温度、施镀时间做出研究。结果表明,微量亚铁离子对三价铬电沉积能起到催化的作用;在电沉积条件方面,随着电流密度增大镀层的厚度增大,而外观则先变好再变差;温度升高,镀层厚度和外观质量都降低;时间越长镀层越厚,但外观会变差。     

响应曲面法优化氯化物体系三价铬电沉积工艺

[目的]三价铬电沉积过程中伴随的剧烈析氢反应导致局部pH升高,是镀速急剧下降、镀层难以增厚及镀层性能恶化的主要原因。[方法]采用甲酸钠、草酸钠和尿素为氯化物体系三价铬电镀的配位剂,以在150 mA/cm²电流密度下电沉积10 min的沉积速率为响应因子,采用响应曲面法优化了镀液配方,建立了氯化物体系三价铬电沉积速率的多项式模型方程。通过单因素实验研究了添加剂、pH、温度、电流密度和沉积时间对沉积速率、镀液深镀能力和镀层耐蚀性的影响。[结果]三价铬电沉积的最佳配方和工艺条件为：三氯化铬0.6 mol/L,甲酸钠0.8 mol/L,草酸钠0.2 mol/L,尿素0.3 mol/L,p H 1.8,温度30℃,电流密度150 mA/cm²,时间30 min。在该条件下所得Cr镀层为非晶态结构,厚度在12μm以上,耐蚀性良好。[结论]选用合适的配位剂抑制电沉积过程中铬的羟桥化反应,是维持较高镀速和改善镀层性能的有效手段。     

三价铬电沉积机理研究及镀层表征

在硫酸盐三价铬电沉积体系中,通过赫尔槽实验对不同络合剂含量进行了筛选,得到络合剂最佳含量配比为甲酸铵80 g/L、草酸铵20 g/L以及尿素30 g/L,最佳电流密度范围为5.11 A/dm²～20.68 A/dm²;通过循环伏安曲线和阴极极化曲线分析三价铬电沉积机理,发现三价铬的沉积过程分两步进行：第一步为Cr³⁺+e→Cr²⁺,过程不可逆;第二步为Cr²⁺+2e→Cr,可逆;草酸铵会增大阴极极化,甲酸铵和尿素会降低阴极极化;电沉积20 min得到的铬镀层,XPS分析表面镀层由单质Cr、Cr₂O₃及Cr(OH)₃构成;微观结构观测发现,随着电沉积时间增加,镀层由表面平整形貌逐渐转变为瘤状结构形貌;镀层呈现明显的(110)择优取向;电化学研究表明,相比20 min铬镀层,5 min铬镀层的耐蚀性较好,腐蚀电位由-0.6377 V提高至-0.5633 V,腐蚀电流由6.1030×10^-6 A/...     

复合配位剂对硫酸盐三价铬电沉积的影响

采用动电位扫描法和计时电流法研究了丁二酸、1,6-己二醇、尿素和乙二胺作辅助配位剂时,以甘氨酸为主配位剂的硫酸盐镀液中三价铬的电沉积机理。测试了不同配位体系镀液中所得铬镀层的外观和耐蚀性。辅助配位剂的加入可增强三价铬电沉积的阴极极化作用,但不会改变其三维瞬时成核机理。以尿素或乙二胺作辅助配位剂时,铬镀层均匀、光亮,耐蚀性好,因此尿素和乙二胺较适用于装饰性镀铬工艺。     

三价铬电沉积工艺研究进展

传统的铬电沉积工艺普遍使用六价铬，其过程中会产生有毒酸雾等污染性物质，造成环境污染。相比六价铬，三价铬电沉积工艺具有能耗低、毒性小、污染小等优势，有长远的应用前景。由于不同镀液体系中离子沉积方式存在差异，三价铬的电沉积机理一直缺乏充分阐明，尤其是铬离子还原的中间历程及控制步骤。故研究镀液体系及不同镀液中三价铬的电沉积机理是解决沉积过程中一系列问题的关键。金属铬电沉积工艺包括铬的电镀和电解，文章基于三价铬电沉积工艺，从电镀及电解两个方面进行综述分析，重点围绕铬电沉积机理、铬镀液组成及组分应用、隔膜电解铬进行论述。最后对三价铬电沉积工艺未来研究方向提出了进一步改进膜电解装置和研究沉积过程中铬的非线性非平衡行为等展望。     

脉冲电沉积镍及其合金的研究现状与展望

回顾了近几年来脉冲电沉积在镀镍及Ni-P、Ni-Fe、Ni-Zn、Ni-Co及Ni-Cu等镍合金镀层的应用研究现状,对直流电沉积和脉冲电沉积所得镀层的硬度、耐磨性、耐蚀性、孔隙率及镀层的晶粒尺寸等进行了比较,并对脉冲电沉积今后的发展前景作了展望.     

电沉积镍铬合金的研究

本文研究了在含三价铬离子的水溶液中电沉积镍铬合金的工艺条件对镀层镍含量的影响。还研究了醋酸盐对电沉积的催化作用。结果表明，在一定范围内提高电流密度和镀液的ＰＨ值增加镀层中的含铬量；当电流密度为２５Ａ／ｄｍ＾２，ｐＨ值为２．５时，沉积出的镍合金含铬量为１１．１％。０．０３７－０．０７３ｍｏｌ／Ｌ醋酸根离子的加入可以提高镀层中铬含量（２－３）ｗｔ％。     

脉冲技术电沉积铅镉合金的研究

通过对氨基磺酸盐体系中铅、镉产铅－镉镀液的阴极化曲线的研究，结果表明镀液中加入添加剂间苯二酚，显著增加电极化及改善镀层性能；用脉冲电沉积代替常规直流电沉积铅－镉，结果表明，脉冲电沉积所得镀层质量上流法有明显改善；原子吸收分光光度法测定表明，直流电沉积和脉冲电沉积可以得到不同含量的铅镉合金镀层。     

氨基磺酸盐体系电沉积铅镉合金的研究

研究了在氨基磺酸盐体系中铅，镉和铅－镉镀液的阴极极化曲线，结果表明，镀液中加入添加剂间苯二酚著增加阴极极化及改善镀层性能；用脉冲电沉积代替常规的直流电沉积进行铅－镉合金的电沉积，表观状态比较表明，脉冲电沉积所得镀层质量较直流法有明显改善。     

N80钢电镀Ni-Cr合金工艺的研究

研究了以N 80钢为基体,在含三价铬离子的电解液中,电沉积Ni-Cr合金的工艺条件对镀层中铬的质量分数的影响,以及镀层中铬的质量分数对耐蚀性的影响.结果表明:在一定范围内提高电流密度、镀液的pH值和温度可以增加镀层中铬的质量分数,镀层的耐蚀性也得到相应的提高;Ni-Cr合金表面均匀致密,无微裂纹;合金镀层经过铜盐加速乙酸盐雾试验后的腐蚀产物主要是尖晶石型复合氧化物NiO·Cr2O3和FeO·Cr2O3.     

Preparation of Pt–Co alloy catalysts by electrodeposition for oxygen reduction in PEMFC

Direct current (DC) and pulse current (PC) electrodeposition of Pt–Co alloy onto pretreated electrodes has been conducted to fabricate catalyst electrodes for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). The effect of plating mode and pulse plating parameters on the Pt–Co alloy catalyst structure, composition and electroactivity for the ORR in PEMFC has been investigated. The electrodeposited Pt–Co alloy catalyst indicates higher electrocatalytic activity towards the ORR than the electrodeposited Pt catalyst. The activity of the electrodeposited Pt–Co catalysts is further improved by applying the current in a pulse waveform pattern. The electrodeposition mode and the pulse plating parameters do not have the significant effect on the Pt:Co composition of deposited catalysts, but show the substantial effect on the deposit structures produced. The Pt–Co catalysts prepared by PC electrodeposition have finer structures and contain smaller Pt–Co catalyst particles compared to that produced by DC electrodeposition. By varying the Pt concentration in deposition solution, the Pt:Co composition of the electrodeposited catalyst that exhibits the highest activity is found. The Pt–Co alloy catalyst with the Pt:Co composition of 82:18 obtained at the charge density of 2 C cm⁻², the pulse current density of 200 mA cm⁻², 5% duty cycle and 1 Hz was found to yield the best electrocatalytic activity towards the ORR in PEMFC.     

(Ni-W-P)-SiC复合镀层的脉冲电沉积及其耐蚀性

研究了(Ni—W—P)—SiC复合镀层的脉冲电沉积工艺及耐蚀性。结果表明：(Ni—W—P)—SiC复合镀层的脉冲电沉积速率比直流电沉积大,脉冲镀层的耐蚀性优于直流镀层和1Cr18Ni9Ti不锈钢;脉冲频率和占空比对镀层的沉积速率、镀层成分以及镀层的耐蚀性都有较大的影响。     

Soft magnetic properties of Ni–Cr and Co–Cr alloy thin films electrodeposited from aqueous solutions containing trivalent chromium ions and glycine

Ferromagnetic Ni–Cr and Co–Cr alloy thin films were electrodeposited from aqueous solution containing trivalent chromium (Cr³⁺) ions and glycine. According to the Tafel slopes obtained from the cathode polarization curves for Ni–Cr and Co–Cr alloy deposition, it was estimated that Cr³⁺ ions inhibited Ni²⁺ and Co²⁺ ions from electrodepositing. Ni and Co preferentially electrodeposited rather than Cr and the electrodeposition process of Ni–Cr and Co–Cr was categorized to “normal co-deposition type.” At the cathode potential of −1.8 V versus Ag/AgCl/KCl sat., Ni—9.5 %Cr and Co—8.4 %Cr alloy deposits were obtained. X-ray diffraction patterns of the electrodeposits revealed that pure Ni and pure Co consist of large crystal grains, while Ni—9.5 %Cr and Co—8.4 %Cr alloys were composed of a solid solution phase with fine crystal grains. Magnetization of Ni—9.5 %Cr and Co—8.4 %Cr alloy thin films with fine crystalline phase reached to saturation at ca. 2.5 kOe in perpendicular direction to the film plane, while pure Ni and pure Co thin film with large crystal grains were hardly magnetized in the perpendicular direction. Soft magnetic properties were improved with increasing Cr content in the deposits.     

非晶态铁铬合金镀层的研究

实验研究了从三价铬镀液中电沉积非晶态Fe-Cr合金镀层，加入适量的NaF能明显减少并细化镀层的微裂纹。XPS分析说明电沉积初始阶段的蓝膜可能为Cr、Fe以及Cr(OH)3、Cr2O3的混合物，而镀层中的Cr、Fe以单质形式存在。XRD表明镀层相结构与镀层的Cr含量有关，镀层非晶态结构的形成可能是Fe晶格畸变和晶粒细化的综合作用。在(NH4)2CO3和H2SO4溶液中的实验表明非晶态Fe-Cr合金镀层的耐蚀性优于晶态Fe-Cr镀层。     

Simultaneous recovery of Cr(III) and Cr(VI) from the aqueous phase with ion-exchange membranes

The simultaneous recovery of trivalent and tetravalent chromium ions through charged ion-exchange membranes by using three detachable cells was tested at different current densities. The effect of mono- and divalent valence ions corresponding to trivalent and hexavalent chromium ions in the feed phase was investigated. The recovery factor values of chromium (III) and (VI) ion without current density were obtained and found that it was higher in the absence of binary monovalent and divalent ions, but increased with increasing current density and decreased in the presence of the binary mono- and divalent ions. The transport of both oxidation states of chromium ions through membranes was also correlated with the flux data.     

Pulse current electrodeposition and corrosion properties of Ni–W alloy coatings

Ni–W alloy coatings were prepared on a mild steel substrate by means of pulse current (PC) and compared to the coatings electrodeposited by direct current (DC). In particular the study dealt with the influence of the frequency using pulse current on the surface morphology while maintaining a constant duty cycle. A constant charge for DC and PC electrodeposition of Ni–W alloy coatings was used. The morphology of the coatings was explored by scanning electron microscopy and the composition of the coatings was analysed by X-ray powder diffraction and energy dispersive X-ray analysis. Corrosion resistance of Ni–W alloy coatings was investigated by potentiodynamic polarization in a chloride medium. The corrosion products were analysed by Raman spectroscopy. It was found that the temperature of the electrolysis affects current efficiency of the DC and PC electrodeposition. The frequency of pulse electrodeposition alters the morphology of the Ni–W alloy coatings. There was evidence of the positive influence of increased tungstate concentration in the electrolyte on corrosion resistance of the Ni–W alloy coatings.     

Electrodeposition and characterization of amorphous Cr-P alloys

The influence of plating variables and bath composition on electrodeposition of chromium-phosphorous alloy composition was investigated. The plating bath, prepared at a pH of approximately 1.25, consisted of a trivalent chromium source, sodium hypophosphite, ammonium sulphate, boric and formic acids, and sodium lauryl sulphate. Energy dispersive spectroscopy and Auger electron spectroscopy were utilized to evaluate alloy composition. These alloys were determined to be amorphous by X-ray diffraction. The influence of temperature, and bath ageing, and deposition time on deposit composition and structure and the deposition rate were also investigated.     

硫酸盐体系三价铬镀液中六价铬离子的积累及去除

绘制了分光光度法测定六价铬的标准曲线,研究了硫酸盐体系三价铬镀液中六价铬的积累规律,并测试了不同的去除方法.结果表明,添加有机醛类稳定剂或溴化铵可以降低六价铬的生成速率,使用小电流电解和添加过氧化氢能降低三价铬镀液中六价铬的质量浓度.     

Tribological and electrochemical behavior of thick Cr-C alloy coatings electrodeposited in trivalent chromium bath as an alternative to conventional Cr coatings

Alternative process to hexavalent chromium plating, substitute materials and new designs are urgently needed owing to the requirement of “clean” manufacture. This comparative study was conducted to systematically investigate the tribological and electrochemical behavior of the Cr-C alloy coatings electrodeposited from a trivalent chromium bath and the hard Cr coatings electrodeposited from conventional hexavalent chromium bath, using reciprocating ball-on-disc tribometer and electrochemical analyzer. The electroplated Cr-C alloy coatings with thickness of 50 μm and acceptable quality that can be used for wear resistance as well as corrosion resistance purposes were produced successfully. The results show that the as-deposited Cr-C alloy coatings exhibited crack-free surface and amorphous/microcrystalline structure. The following heat treatment resulted in the cracked surface and the increase in hardness for the electroplated Cr-C alloy coatings. In contrast, the conventional Cr coatings exhibited cracked surface and their hardness decreased with the increase in annealing temperature. The electroplated Cr-C alloy coatings after heat treatment at 200 °C for 1 h exhibited better wear resistance than the conventional Cr coatings. In regard to the electrochemical behavior, the as-deposited Cr-C alloy coatings exhibited better corrosion resistance than the conventional Cr coatings. Therefore, the electroplated Cr-C alloy coatings are environmentally acceptable candidates to replace the conventional Cr coatings.