从氨性柠檬酸溶液中电沉积Ni-Mo的机理研究

含钼大于约27％（质量分数）Ni－Mo合金，具有较高的耐蚀性，特别是在盐酸和硫酸溶液中，其耐蚀性优于SUS304不锈钢［1］．因此，人们对该种合金的电沉积进行了广泛的研究［1－4］．对合金共沉积机理也作了一定的研究．一般认为，钼不能单独进行电沉积，但它可以同铁族元素共沉积［5］．对钼与铁族元素的共沉积机理，人们已提出了几种假设．一般认为［3］，钼可能是多步还原，即六价钼首先被电化学还原成低价钼化合物，而后由吸附在诱导金属（铁族元素）上的原子氢进一步还原成合金中的零价钼，为了进一步弄清Ni－Mo合金的共沉积机理，本…     

化学沉积Ni-P-Al2O3和Ni-P-SiC复合材料的微观组织与物理性能

采用化学沉积方法,可以制备以镍磷合金为基质的复合硬质相粒子的复合材料［１］．镍磷合金颇受青睐之处在于可以调整成分和时效处理温度来改变其组织结构,进而获得广泛变化的性能［２,３］．本文报道化学沉积获得的ＮｉＰ氧化铝和ＮｉＰ碳化硅复合材料的微观组织与...     

(p-CH3C6H4SO3)3Nd+DMF体系中电沉积钕-铁族合金膜

本世纪３０年代Ａｕｄｒｅｉｔｈ等人基于分离稀土元素的目的，在某些有机溶剂电解液中用汞阴极电沉积了个别的稀土汞齐［１］．１９５４年Ｍｏｅｌｅｒ等在乙二胺中电沉积了Ｙ、Ｌａ和Ｎｄ（稀土含量只有５０％左右）［２］．随着电子和信息技术的发展，稀土合金功能薄膜...     

模板合成法制备金纳米线的研究

近年来,利用化学和物理方法制备各种高度有序的纳米结构材料已经成为学术界的研究热点之一．其中,在特定的模板中沉积各种材料而构建纳米点阵的方法,具有制备简便,成本较低等优点,而且在尺度上可以突破刻蚀技术的局限性,具有广泛的应用前景［１］．常用的模板有阳极氧化多孔铝（ＡＡＯ）、多孔硅和聚合物等,其中ＡＡＯ模板具有耐高温,绝缘性好,孔洞分布均匀有序,而且大小可控等特点［２］,是使用较为广泛的一种．利用阳极氧化铝为模板,采用电化学方法［３～７］或压差注入法［８］制备有序的纳米粒子点阵,已经在润滑［９］、电…     

电沉积银铟硒薄膜的(光)电化学特性研究

银铟硒是继铜铟硒之后新发展起来的另一种能源、信息功能材料，它的禁带宽度Ｅｇ＝１．２０ｅＶ，更接近于光电转换效率最高的太阳能电池所应具有的能隙值［１］，因此具有广泛的应用前景．早在六十年代，前苏联就对银铟硒的物理性质及电子特性有过报道．目前有关光电化学电池（ＰＥＣ）所利用的银铟硒薄膜材料的制备大多是采用大晶粒熔融生长法［２，３］．８０年代，ＲａｖｉｅｎｄｒａＰ．Ｔ．Ｋ．Ｓｈａｒａｍａ［４］曾报道应用电沉积法制作ｐ＿ＡｇＩｎＳｅ２／ＣｄＳ液结太阳能电池，但真正利用电化学沉积制备银铟硒的报道不多，由电…     

DMF溶液中导电玻璃上沉积类金刚石薄膜

液相法制备类金刚石膜设备简单,操作容易,能大面积成膜,越来越受到研究者们的关注．Ｎａｍｂａ［１］以乙醇为介质,在１２００Ｖ电压７０℃以下沉积膜,得到了类金刚石膜;Ｓｕｚｕｋｉ等［２］以水乙二醇溶液为介质制膜,只得到了石墨相的碳膜;以乙醇的水溶液为介质利用电解热沉积膜,得到了玻璃碳和石墨碳,同时阴极钨发生碳化有ＷＣ和Ｗ２Ｃ生成［３］;Ｎｏｖｉｋｏｖ等［４］在乙炔的液氨溶液中沉积膜,Ｒａｍａｎ谱表明他们得到了类金刚石（ＤＬＣ）膜;Ｋｗｉａｔｅｋ等［５］重复了Ｎａｍｂａ的实验,证明沉积膜主要为非晶态…     

p—Si上激光诱导局部沉积铂

现代电子工业中，电子器件基体材料多为半导体或绝缘体，因此，不用外加电源的激光诱导微区沉积技术引起了人们的重视［‘－‘j．这种高度选择性、高速沉积性、工艺简单的技术在电接插件局部镀，多芯层模块制作中的基板联线，加成法制造微带电路及其修复，半导体集成电路中布线的修复等方面有着广泛的应用前景．激光诱导液相金属沉积可在多种基体上，多种电解质溶液中进行”－“’，本课题组自90年代初从事激光镀的研究以来，已利用Ar”激光在硅片上分别实现了Ni－P合金「“］和Cll［“j的镀覆．本文采用3种不同的镀铂溶液作为电解质，在…     

电沉积非晶态镍磷合金的研究

本文用电化学方法, X射线衍射及电子能谱方法研究了阴极恒电位沉积非晶态镍磷合金镀层,实验结果表明,影响镍磷合金非晶结构的主要因素是镀层中的磷含量,当磷含量大于9%时,镀层具有良好的非晶结构,镀层中镍和磷主要以元素态形式存在,磷的析出具有诱导共析特点。     

真空沉积TCNQ薄膜的手性分形结构

分形是非线性科学中的一个重要分支,自１９７３年Ｍａｎｄｅｌｂｒｏｔ提出分形这一概念以来［１］,关于分形的实验和理论研究日益受到人们的重视［２,３］．自发现７,７,８,８ 四氰基对苯醌二甲烷（ＴＣＮＱ）与某些电子给体的复合物薄膜具有独特的电学特性［４,５］,至今人们对ＴＣＮＱ类薄膜器件进行了广泛的研究［６ -１０］．Ｇａｏ等［１１,１２］ 最早报导了真空离子团束 (ＩＣＢ)沉积的Ｃ６０ ＴＣＮＱ复合薄膜有独特的“海马”分形结构．由于ＩＣＢ沉积技术中的粒子有一定的荷电几率,而外加电场又会影响薄膜生长初期的分…     

电沉积制备的PtNi纳米粒子用于氧还原反应:成核和生长机理

质子交换膜燃料电池(PEMFCs)电堆中阴极Pt基催化剂的高用量造成其成本居高不下,成为阻碍燃料电池汽车商业化推进的重要原因,因此开发低Pt、高活性的Pt基催化剂势在必行.Pt合金催化剂能够有效地降低Pt用量,并通过对合金颗粒的元素比例、晶面、粒径等实行精确调控,显著提升氧还原(ORR)催化活性.然而,目前常用的制备方法由于原料与制备成本高昂、过程复杂大都难以适应规模化生产需求.电化学方法通过控制施加的电流或电位控制晶体生长.在水体系中该方法已得到验证,但由于Pt化合物的热力学标准电极电位与过渡金属元素之间相差较大,且对于过渡金属来说,电负性大多小于铂,因此还原电位通常负于析氢电位,使得二者难以实现共沉积.有机体系中电位窗口比水体系大得多,Pt与电位较负的过渡金属可实现共沉积,采用小分子有机溶剂也可避免溶剂清洗问题,具有应用潜力.本文提出了一种简单的一步电沉积方法,选择易溶于水的N,N-二甲基甲酰胺(DMF)作为溶剂,将碳载体滴涂到玻碳电极上作为工作电极,通过电化学方法直接将Pt-Ni合金沉积到碳载体上,并利用物化表征与密度泛函理论(DFT)理论计算来探究共沉积机理.透射电镜表征结果表明,在不同的沉积电位下均可得到分散均匀、粒径适当的催化剂;且随着电位值降低,催化剂颗粒分散得更均匀,颗粒粒径不断减小.元素分布和晶面结果表明,铂镍元素均匀分布于颗粒中.所有样品均表现出优异的ORR性能,最高的面积比活性达到商业催化剂的6.85倍.将材料表征、电化学表征与DFT计算结合,建立起了铂镍合金生长过程的模型,并发现了有机体系中独特的成核-生长机理.将体系中的DMF换成超纯水,用同样的方法进行沉积,得到的催化剂颗粒团聚严重,说明DMF的使用能够避免颗粒团聚.在单独铂的体系中沉积发现,负载量极小,表明体系中镍前驱体的添加对于催化剂的沉积过程起到重要作用.电化学表征结果表明,在所选用的DMF有机体系中,镍的还原电位与铂的十分接近,但还原动力学更慢,趋向于先形成吸附原子后快速还原.由此可以推测,在二者合金的形成过程中,镍在碳载体表面的缓慢还原而形成的吸附原子能够成为铂还原的活性位点,从而降低了铂还原成核所需的能量,使得载体上的成核位点大大增加,这与DFT模拟结果一致.DFT建立了碳上镍的位点和铂的位点,分别在上面进行铂的还原,发现镍位点上比铂位点上更容易实现铂沉积.本文提出了铂镍共沉积的机理:在过电位(即还原能量)下,铂的还原动力学较镍稍快,于是铂先还原形成晶核,但难以达到生长的临界半径,于是单独铂体系中的沉积负载量很少.载体上还原的镍为铂还原提供了大量的活性位点,促进了铂还原,并与镍共沉积.Pt-Ni表面则进一步促进了铂的沉积和颗粒的生长.综上,本文提出了一种用于制备铂合金催化剂的有机电沉积体系,实现了单分散的碳载铂镍合金催化剂的一步制备.随后,本文将材料表征、电化学表征与DFT计算相结合,建立起了有机体系中铂镍合金成核-生长过程的机理模型.     

Anodic and cathodic process of hypophosphite on a Ni-Ag electrode

The reduction and the oxidation of hypophosphite on a Ni-Ag electrode have been studied to provide the information about the phosphorus incorporation mechanisms during the electro-less deposition and the electrodeposition of Ni-P alloys.In the electrooxidation process,an absorbency band around 240nm,which was ascribed to the formation of an intermediate PHO2-,was observed by in situ UV-Vis subtractive reflectance spectroscopy.Accordingly,the electrooxidation of hypophosphite might undergo an H abstraction of hypophosphite from the P-H bond to form the phosphorus-centred radical ' PHO2- ,which was subsequently electrooxidized to the final product,phosphite.In the reduction process Ni-phos-phine compound Ni-(PH3)n was observed by in situ surface Raman spectroscopy.The results from the Raman experiments show that,in the NiSO4-free solution,hypophosphite was reduced only to Ni-phosphine compound,while in the case where NiSO4 coexisted in the solutions,the Ni-phosphine compound,as an intermediate,was oxidise     

In situ surface Raman study of the induced codeposition mechanism of Ni–Mo alloys

The induced codeposition of molybdenum with nickel on a Ni–Cu alloy electrode has been investigated by means of in situ surface Raman spectroscopy to obtain information about the codeposition mechanism during electrodeposition of Ni–Mo alloys. The experimental results show that, in the NiSO₄-free solution, molybdate can only be reduced to a mixture of polyvalent molybdenum oxides and/or hydroxide, while, in the case where NiSO₄ coexisted in the solution, molybdate is first reduced to Mo(IV) oxide, which, as an intermediate, subsequently is reduced to molybdenum in alloy under the catalysis of inducing nickel.     

Effect of 3-Amino-5-mercapto-1,2,4-triazole on Electroless Nickel Deposition

The effects of organic additive, 3-amino-5-mercapto-1,2,4-triazole （AMTA） on bath stability, deposition rate, reaction activation energy, and Ni-P coating composition in acidic electroless nickel plating were investigated. Polarization curve method and infrared reflection spectroscopy were used to analyze the mechanism of the effect of AMTA on electroless nickel deposition. It was observed that AMTA improved bath stability, decreased the deposition rate, and increased the reaction activation energy. It was also revealed that AMTA decreased the phosphorus content and increased the sulfur content in Ni-P coating. In addition, AMTA inhibited the anodic oxidation of hypophosphite and accelerated the cathodic reduction of Ni^2＋. Infrared reflection spectroscopy result indicates that AMTA was adsorbed on the surface of Ni-P and interacted with Ni^2＋ to form an AMTA-Ni^2＋ compound. On the basis of the results of this study, the mechanism of the effect of AMTA on electroless nickel deposition was deduced.     

Ni-Mo合金电沉积层织构及形成机理

在组成为：０．２２ｍｏｌ／Ｌ硫酸镍、０．０６ｍｏｌ／Ｌ钼酸钠和０．３ｍｏｌ／Ｌ柠檬酸钠的溶液,于纯铜片上采用恒电流沉积,所得Ｎｉ－Ｍｏ合金沉积层经Ｘ射线衍射测定,结果表明在温度为２５℃～５０℃,电流密度为１０ｍＡ·ｃｍ－２～３０ｍＡ·ｃｍ－２范围,Ｎｉ－Ｍｏ合金沉积层表现为（１１１）择优取向．循环伏安和电位阶跃实验表明镍钼合金电结晶过程按照连续成核和三维生长方式进行．Ｎｉ－Ｍｏ合金电沉积过程的电化学交流阻抗谱表明Ｎｉ－Ｍｏ共沉积过程经历了吸附中间产物步骤,由于吸附态物种氢氧化镍和钼的氧化物将阻化晶粒（１１１）晶面的生长,从而使镍钼沉积层表现为（１１１）择优取向．     

Electrodeposition mechanism of Ni-Mo-P alloy in the solution of ammoniac citrate

The induced codeposition mechanism of Mo, P and Ni from the solution of ammoniac citrate was studied by means of steady-state polarization, AC impedance and X-ray Photoelectron Spectroscopy (XPS). The result of electrochemical measurements proved that [NiCit(NH3)2]- is the electro-active species of nickel, though nickel ions exist mainly as [NiCit(NH3)3]- in ammoniac citrate. XPS experiments proved the existence of tetravalent molybdenum corresponding to MoO2 on the surface of some deposits. The intermediate product, MoO2, was probably reduced to Mo in the alloy deposit by atomic hydrogen adsorbed on the induced metal nickel. The reduction of H2PO2- occurs through two distinctive steps with PH3 as an intermediate, which subsequently reacts with atomic hydrogen to form P in the alloy deposit. The electrodeposition mechanism was proposed in this paper.     

化学镀镍-高磷合金晶化行为的现场XRD研究

从柠檬酸-酒石酸-乳酸-EDTA混合体系中得到含P 12％(质量比)的化学镀高磷Ni-P合金，其差热曲线显示，在350和420 ℃出现两个放热过程.现场XRD分析结果显示，镀层在300 ℃以下保持非晶态结构，在320 ℃之后开始晶化，首先析出介稳的Ni5P2和Ni12P5相，在360 ℃后开始有稳定的Ni3P和Ni相的衍射峰出现， 400 ℃以上只有Ni3P和Ni相. 325 ℃恒温时，镀层在4 min内保持非晶态的衍射特征，随即析出Ni5P2和Ni12P5相, 并在2 h内基本保持不变. 350 ℃恒温时，析出的Ni5P2和Ni12P5介稳相只存在40 min.实验结果表明, DTA曲线上350 ℃的放热峰不仅有非晶相转变为介稳相的过程，也包含部分介稳相转化为稳定相的过程.     

Electrodeposition of Zn–Ni alloys from sulfate bath

The electrodeposition of zinc–nickel (Zn–Ni) alloys from sulfate baths has been studied at different deposition times and H₂SO₄ and NiSO₄ concentrations; various characteristics have been observed during alloy deposition and dissolution. The deposit has been investigated by using scanning electron microscopy (SEM) and X-ray diffractometry. Cyclic voltammetry and galvanostatic measurements during electrodeposition have been conducted. Electrochemical and surface analysis indicate that deposition takes place with the formation of two different structures corresponding to γ-phase and δ-phase zinc–nickel alloys. During anodic part of the cyclic voltammetry of the alloys, a reduction process has been observed, which may be due to hydrogen evolution. With the increase of nickel concentration in the bath, the amount of γ-phase increases, as indicated by the relative increase in the height of the peaks in the X-ray patterns and anodic peaks in the cyclic voltammograms. Also, the corrosion resistance of the zinc–nickel alloy has been improved with an increased concentration of nickel. Under these experimental conditions the electrodeposition of the alloys is of anomalous type.     

Electrodeposition, Structure and Corrosion Resistance of Nanocrystalline Ni-W Alloy

Ni—W alloy was electrodeposited from the electrolyte solution containing sodium tungstate, nickel sulfate and ammonium citrate. The electrodeposition, heat treatment, structure, surface morphology and corrosion resistance in w=0.03 NaCl solution, of Ni-W alloys were studied by means of DSC, XRD, SEM and electrochemical techniques. The results showed that the obtained Ni-W alloy electrodeposit with W weight content (Ww=0.471) was presented in more typical nanocrystaUine, After heat treatment at 400 ℃ for 1 h, the phase structure of the deposits was not obviously changed whereas the agglomerate for the reunion of tiny grains on deposit surface caused the granule in a more smooth morphology, the microhardness was slightly increased and the corrosion resistance was enhanced.     

从2AlCl3/Et3NHCl离子液体中电沉积制备Ni 和Ni-Al 合金

在含Ni2+的2AlCl3/Et3NHCl离子液体中的铜电极上通过恒电位电沉积制备出金属Ni和Ni-Al合金.采用循环伏安和计时电流方法,揭示铜电极上沉积金属Ni的成核机理,研究了电沉积Ni-Al合金的机理,以及恒电位沉积Ni-Al合金工艺条件对沉积Ni-Al合金表面形貌和电流效率的影响.结果表明:在铜电极上电沉积金属Ni的成核机理为受扩散控制的三维瞬时成核过程.在电量≥3.0 C时,电沉积Ni-Al合金的组成基本不再变化.Ni-Al合金的电沉积机理为,Ni的电沉积受扩散控制,同时进行Al的欠电位沉积,在Ni-Al合金电沉积过程中某些Ni-Al合金相的沉积可能受动力学限制而使Ni-Al合金的组成偏离热力学预测结果.在电沉积Ni-Al合金的沉积电流小且平稳,电沉积速率慢条件下,Ni-Al合金表面形貌致密均一,反之就会出现瘤节.电沉积Ni-Al合金的电流效率＞90％.电沉积物的组成接近于Ni3Al合金.