焦磷酸盐电镀铜初始过程研究

应用恒电流法研究了铁基体上焦磷酸盐电镀铜电位时间变化类型与镀层结合强度之间的关系.提出了临界起始电流密度(DKC)概念.当起始工作电流DKI大于DKC时,铁电极首先被极化至铁表面的活化电位,即基体表面被活化,随后极化至铜的析出电位,使铜层沉积在活化的铁基体表面上,形成具有良好结合强度的铜镀层.反之,如DKI小于DKC,则铜层只能在"钝化"的含氧层表面上析出,得到的镀层结合强度很差.由氩离子溅射深度刻蚀和X射线光电子能谱(XPS)检测出结合强度差的镀层和基体间界面含氧层的存在.调整工艺条件,优化了焦磷酸盐直接镀铜工艺,可降低工艺的DKC,得到与铁基体具有良好结合强度的电镀层.     

铝箔在盐酸中的交流电侵蚀的研究——Ⅳ.有机酸等弱酸添加剂的作用

选用了草酸等9种有机酸作为铝箔在盐酸溶液中交流电侵蚀的添加剂。与添加硫酸同样,再一次表明添加剂为形成高质量致密膜因而获得高表面积扩大率所必需。对应于一定频率存在着最佳添加剂浓度C_m,一级电离常数大的酸,相应的C_m低。用有机酸阴离子在铝表面与Cl^-竞争吸附并形成pH缓冲层,从而提高膜的保护性并降低膜的溶解度解释了这些现象。文中讨论了盐酸浓度、电流密度以及Cl^-浓度等对侵蚀过程的影响。     

表面包覆改性对纳米CeO2分散性的影响

了改善纳米CeO2在Zn-Al类共晶合金中的分散性,采用超声液相包覆法对纳米CeO2进行表面活性剂表面包覆改性,并用AES测定了包覆层的厚度,用TEM研究了CeO2的团聚状况,用TGA分析了有机物包覆层的炭化温度范围,最后用FE-SEM观察了CeO2在复合材料中的分散情况。结果表明,包覆在纳米CeO2表面的厚度约为20 nm的表面活性剂层提高了微粒的分散性,而且该包覆层在495℃时已经炭化。热力学计算的结果也表明,炭化层能与氧化膜反应,该反应提高了CeO2与基体间的润湿性,并使其均匀分布在基体合金中。     

铝合金阳极氧化膜上交流电沉积制备含铈复合膜

通过交流电解沉积的方法在铝合金阳极氧化膜上制备了稀土铈复合膜, 并考察了氧化膜的厚度对形成复合膜的影响. 电解成膜溶液为含1 g · L-1 CeCl3 · 7H2O和10 mL · L-1 H2O2的水溶液, 正弦交流电的平均电压为10 V, 交流沉积的时间为5 min. 结果表明, 阳极氧化膜的厚度是影响成膜的主要因素, 在实验中, 氧化膜的厚度大于6.8 μm时才能形成连续均匀的复合膜. 测试分析结果表明, 复合膜表面的铈元素分布均匀, 平均含量为1.70%(质量分数);Ce元素主要分布在氧化膜多孔层的表层, 分布深度约1.5 μm.     

电位活化现象与金属电沉积初始过程的研究

进行了恒电流电位-时间曲线和循环伏安曲线的测定，显示了铁电极进行氰化物镀铜时，镀层沉积前铁表面的电位活化过程. 对铁电极上焦磷酸盐镀铜的初始过程研究表明，由于铜的析出电位较正，铜是在未活化的电极表面上沉积的，因此镀层的结合强度很差.采用氩离子溅射和X射线光电子能谱相结合的方法，检测焦磷酸盐镀铜层和铁基体界面区含氧量的变化，证明了氧化层的存在. 通过添加辅助络合剂和控制起始电流密度的方法，可以增强无氰电镀时阴极的极化. 当铜的析出电位负于铁基体的活化电位时，可显示出铁表面的电位活化过程，定量测量镀层的结合强度也与氰化物电镀相近.     

离子选择性电极多次标准加入法测量氟离子电极电势

建立了选择性电极中离子传递的模型。活化后的离子选择性电极 ,在电极表面形成活化层 ,阳离子和等量的阴离子分布在电极活化层的两侧 ,离子由溶液与活化层的界面经活化层传递到固定组成膜与活化层界面。在一定的条件下 ,电极膜电势随时间的变化与溶液和活化层的界面离子浓度随时间的变化成正比。在控制电势随时间的变化率基本恒定的情况下 ,方法被用于手工测量氟离子选择性电极电势 ,电极斜率。溶液离子浓度直接由 Gran方程求解。     

阳极氧化/GCD新工艺法制备镍基超级电容器薄膜电极

采用磷酸阳极氧化法在金属镍表面形成阳极氧化复合膜,在1 mol·L^-1氢氧化钾溶液中进行大电流密度恒流充放电(GCD)处理, 使基体表面形成一层多孔纳米花瓣状膜. 采用扫描电镜(SEM), X射线光电子能谱(XPS), X射线衍射(XRD)仪, 对膜的形貌、组成和结构进行了表征, 使用电化学工作站、电池寿命测试仪对该膜的电容特性进行了测试. 结果表明, 所制氧化膜由三维多孔纳米花瓣状的NiO、α-Ni(OH)₂和β-Ni(OH)₂构成, 该膜具有优异的电容特性, 其在电流密度为6.7 A·g^-1时,比电容量达1509 F·g^-1, 而当电流密度为66.7 A·g^-1时,比电容量为1120 F·g^-1 (为6.7A·g^-1时的74%).在电流密度为66.7 A·g^-1时, 经过2000次循环测试后比电容量基本保持不变.     

自组装膜吸附钯的化学镀前活化研究

提出了一种无需氯化亚锡敏化、基于分子自组装膜（SAMs）吸附钯的活化方法,成功地引发了在氧化铝粉末表面的化学镀铜.用XPS、AES、FTIR研究了钯的吸附机理,认为是由于氯化钯与SAMs上向外突出的氨基形成了化学键,并提出了相应的活化机理.金属化产物经XRD、FTIR、剖面金相显微表征分析与压片电阻率测定,示为金属铜完全包覆氧化铝的复合材料.该活化工艺具有活性引发层厚度薄、寿命长和与基底结合力强等优点,也可应用于其它表面富羟基的基底材料.     

具有低表面自由能有机介电薄膜的制备及表征

通过自主开发的有机镀膜技术在Mg-Mn-Ce镁合金表面制备了具有低表面自由能和较高介电常数的有机纳米薄膜. 利用X射线光电子能谱(XPS)分析了表面有机镀膜过程的反应机理, 借助傅里叶变换红外(FT-IR)光谱进一步确认表面有机膜层的存在, 采用接触角测量仪测定了有机薄膜的蒸馏水接触角和表面自由能变化, 使用椭圆偏振光谱仪研究了薄膜的厚度, 并借助精密阻抗分析仪评价了薄膜的介电性能. 有机镀膜后镁合金表面形成了一层纳米级厚度的有机薄膜, 接触角从基体的70.8°上升至150.5°, 表面自由能从基体的37.96 mJ·m^-2降低到1.57 mJ·m^-2, 镁合金表面从亲水性转变为疏水性; 薄膜的厚度和质量随有机镀膜时间延长先增加后有所减小, 在镀膜20 min时薄膜性能最佳, 此时膜重达到23.5 μg·cm^-2, 膜厚最大为147.48 nm, 其相对介电常数也达到最大, 在1 kHz下可达24.922.     

卟啉在纯铁表面上的化学与电化学修饰

通过在卟啉的丙酮－水溶液中循环阳极电位扫描，在工业纯铁表面形成一层修饰层．此修饰层呈淡黄色，结晶细密．与基体结合牢固，耐腐蚀性能良好．质谱分析及反射红外分析说明有铁卟啉螯合物生成．若将工业纯铁直接浸入卟啉的丙酮－水溶液中，其表面同样也可形成一层修饰膜, 此膜较之电化学修饰层疏松而厚．卟啉在纯铁表面的电化学修饰层与化学修饰膜的形成机制有着本质的不同．     

含镓、锡的铝合金在碱性溶液中的活化机理

镓锡合金沉积于铝阳极表面 ,形成活化点 ,是铝阳极活化的根本原因 .简单的Al_Sn、Al_Ga二元合金在碱性介质中不能活化 .Al_Sn_Ga多元合金阳极溶解时 ,Ga、Sn溶解进入溶液 .锡离子首先还原沉积于铝阳极表面 ,镓离子又在沉积的锡上沉积 ,在铝合金阳极表面不断形成Ga_Sn合金活性点 .低溶点的合金由于其良好的流动性 ,以单个或多个原子的形式嵌入氧化膜 ,形成活性点 ,起到了局部分离氧化膜的作用 ,是铝合金阳极活化的关键     

Refinement of the Theory of Electrodissolution of Difficultly-Soluble Compounds from Metal Surfaces: Taking into Account Nonuniform Film Thickness Along the Electrode Surface

An equation that describes the electrodissolution of a film of a difficultly-soluble compound from the surface of metallic electrode during a linear potential scan is derived and solved numerically. The model accounts for a nonuniform deposit distribution over the electrode surface and for the diffusion of the deposit particles through the film. Voltammograms for the compound electroreduction display peaks whose shape is dependent on the deposit distribution over thickness. The obtained results are analyzed.     

Surface of Ru/Fe2O3 catalysts used in water-gas shift reaction studied by auger electron spectrometry

Summary Carbon deposits on the surface ofRu/Fe₂O₃ catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to reduce the amount of carbon deposit. .      

碳纤维表面羰基铁的原位生长及吸波性能

以Fe(CO)5为前驱体,通过金属有机化学气相沉积(MOCVD),在碳纤维(CF)表面构筑厚度为纳米级的羰基铁(CI)壳层,通过改变沉积温度,调控核壳粉体的形貌结构和吸波性能。用X射线衍射仪、扫描电子显微镜和矢量网络分析仪对粉末的结构及电磁性能进行表征并对其吸波性能进行研究。结果表明:随着沉积温度升高(210~240℃),沉积到CF表面的羰基铁颗粒互相“吞并-融合”,此时CF-CI形成了完整的薄膜包覆型核壳结构;沉积温度太高时(270℃)会造成CF表面羰基铁壳层形貌的恶化。通过调节沉积温度,在纳米尺度上可以有效调控CI壳层的形貌,从而调节CF-CI核壳粒子的电磁性能。以核壳形貌及吸波性能为考察指标,最终确定最佳的沉积温度为240℃。以沉积温度为240℃时所获样品的电磁参数,模拟计算出涂层厚度为0.9 mm时,小于-10 dB的吸波带宽最大为4.6 GHz(13.4~18 GHz);涂层厚度为2.0 mm时,反射率达到最小值为-21.5 dB;厚度为0.9~3.9 mm时,在2~18 GHz均能实现吸波强度低于-10 dB。     

Influence of Nanoporosity and Roughness on the Thickness-Dependent Coercivity of Iron Nanonetworks

Summary.  We have studied the coercivity of magnetic nanonetworks as a function of thickness, nominal pore diameter, and surface/interface roughness in the thickness range of approximately 2 to 45 nm where a Néel-type domain wall has been theoretically predicted. Such magnetic nanonetworks have been prepared by sputtering iron on the walls of commercially available porous nano-channel alumina (NCA) membranes. The thickness dependence of coercivity has also been studied on films deposited on surface-oxidized Si and glass subtrates. These substrates are essentially non-porous and much smoother than NCAs. Our investigation shows that the coercivity of films deposited on Si and glass depends on the spatial fluctuation of thickness which arises from the roughness of the apparently smooth substrates. On the other hand, NCAs are found to be inherently quite rough, and films on NCAs show a complex thickness dependence which arises from the interplay between surface/interface roughness, domain pinning due to porosity, surface anisotropy, surface torques, and oxidation of the iron films. It was found that the growing films on NCA substrates led to partial filling up of the pore entrance, thereby reducing its effective diameter. The film growth also affects the roughness of the film, which in turn affects its coercivity. We propose a model for the thickness dependence of coercivity based on the pore fill-up geometry considering the effective pore diameter and the critical thickness at which the pore will be completely filled up. Experimental results on coercivity with thickness variation of iron network deposited on NCA generally agree with the suggested model. Received October 16, 2001. Accepted (revised) January 11, 2002     

Mechanism of film growth of tellurium by electrochemical deposition in the presence and absence of cadmium ions

The growth morphology and the kinetics of a thin film of Te on Au during electrochemical deposition at -62 mV (vs Ag/AgCl/3 M NaCl) have been studied. The deposition conditions are similar to those used previously by us to grow nanowires inside Au nanotubes by electrochemical deposition in the presence of Cd ions (Cd(2+)). By using electrochemical deposition on a planar Au electrode, we explored the growth of the Te film for two conditions: in the presence of Cd(2+) (0.1 mM TeO(2) + 1 mM CdSO(4) + 50 mM H(2)SO(4) solution) and in the absence of Cd(2+) (0.1 mM TeO(2) + 50 mM H(2)SO(4) solution). We used several surface investigation techniques to study the growth such as: in situ electrochemical atomic force microscopy (EC-AFM), in situ electrochemical surface plasmon resonance (EC-SPR), electrochemical methods, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). In the presence of Cd(2+), in situ electrochemical atomic microscopy showed that Cd(2+) acted as a mediator at the early deposition stage and caused smoothing of the Te deposit obtained. In the absence of Cd(2+), Te had an island growth. The electrochemical surface plasmon resonance showed that the deposit was characterized by a slower deposition rate in the presence of Cd(2+) than in the absence of Cd(2+). Additionally, the thickness of the film was evaluated using EC-AFM measurements, electrochemical stripping analysis, and EC-SPR. The results obtained from all three measurements agree well with the Te film obtained in the presence of Cd(2+), where a continuous and uniform film was formed. In the presence of Cd(2+), a Te film with a thickness of 1.04 nm and atomically flat surface was deposited on an ultraflat Au surface. The XPS spectrum showed no significant amount of Cd in the deposit, indicating that the Cd ion acted as a mediator and not as a co-deposition element.     

Mechanisms of electrode processes on the iron metals

Mechanisms of the electrode processes occurring on the iron metals which are complicated by the generation of a chemisorbed film on the surface are discussed. The film can be either partially reduced or desorbed at elevated temperatures. It can also be removed during the generation of fresh surface. In its absence, the overall reversible electrode reaction includes consecutive elementary steps of the charge transfer from active centers of adsorption and the step where unstable intermediate univalent metal ions undergo disproportionation. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

Epitaxy and thermal behaviour of metastable metal films

We demonstrate the complexity of metal-on-metal epitaxy. Low-energy ion scattering and medium-energy electron diffraction were used to study the growth, structure and thermal stability of iron deposited on a Cu(001) surface. The system exhibits as a function of film thickness a rich variety of morphological and structural phases. At smallest coverages (< 2 ML) iron does not grow layer-by-layer at room temperature. Iron is even partially incorporated into the copper substrate. Near 2 ML the substrate is covered for the most part (90%) with Fe and at even higher coverages layer-by-layer growth occurs, leading to well-ordered fcc iron films. Above 10 ML a structural phase transition into the bcc equilibrium modification is observed. All of the deposited films exhibit additional thermal metastability. Heating the samples causes enrichment of the surface with copper, resulting in a Cu/Fe/Cu sandwich morphology with a Cu overlayer of initially monoatomic height on top of the iron layers, which remain essentially intact. The onset temperature of Cu diffusion depends on the film thickness, but is always far below the values for regular bulk diffusion.     

纳米多孔阳极氧化铁膜的形成及其形貌演变

阳极氧化法制备具有纳米多孔结构的阳极氧化铁膜因其潜在的应用价值而倍受关注。然而,在阳极氧化过程中多孔结构的形成机制至今尚不清楚。本文结合电流密度-电位响应（I-V曲线）及法拉第定律的推导,分析了形成纳米多孔阳极氧化铁膜的过程中阳极电流的组成。结果表明,离子电流（导致离子迁移形成氧化物）和电子电流（导致析出氧气）共同组成阳极电流,并且纳米多孔阳极氧化铁膜的形成与两种电流的占比相关。分段式氧化物之间的空腔以及在阳极氧化初期纳米孔道上覆盖的致密膜,表明氧气泡可能是从氧化膜内部析出。此时,阳离子和阴离子绕过作为模具的氧气泡实现传质,最终导致纳米多孔结构的形成。此外,在阳极氧化铁膜形貌演变过程中,氧气泡不断向外溢出会使表面氧化物被冲破,导致表面孔径不断增大。     

A study of corrosion on a rotating iron disk electrode

Corrosion of iron in slightly acidified sodium sulphate solutions (mainly pH 4.5) in the open air was studied with a rotating disk electrode method at room temperature.Microscopic observations of corroded iron disk surfaces in the pH 4.5 solution revealed that iron initially corrodes locally with the formation of round pits of 10–30 μm in diameter and of(0.6–1.3) × 10³ in number per apparent square centimetre followed by the U-shaped brown protective wall formation of precipitates (rust) outside the pits. Each protective wall is formed along the lines of flow of the solution adjacent to the iron surface and each pit is located near the upstream end of the wall. Steady state of corrosion sets in when the parts of surface area surrounded by the wall are completely covered with a microscopically non-porous rust film.The amount of iron in the rust film and the total amount of corrosion of iron including that in the film increase parabolically with the increase in the time of immersion. The amount of iron in the film increases in proportion to the total amount of corrosion independently of the speed of rotation of the disk electrode even in the steady state.The fraction of area of iron surface not covered with the film decreases with time and reaches a certain fixed value in the steady state: the value is smaller at higher rotational speed. The corrosion rate is proportional to the uncovered area, as the corrosion is near the steady state. The pH of the bulk solution increases as corrosion progresses.The corrosion rate of iron can be well interpreted by assuming that the rate is controlled by the diffusion of oxygen from the bulk solution to the surface of iron and that the rust film on iron impedes the diffusion of oxygen.