The Study on Electrochemical Stability of Amorphous Ni-S Alloy Electrode

Development of cathode material which has low HER (hydrogen evolution reaction) overpotential and high durability is significant to electrolysis industry and antifouling with electrolyzing seawater. The amorphous Ni-S alloy electrode was prepared by means of electrodeposition. Its electrocatalytic activity and stability for HER in 5 mol/L NaOH solution at 353 K was investigated. The result showed that the amorphous Ni-S alloy in which sulphur content is 29.4%, has high electrocatalytic activity and excellent stability. In addition, the morphology and phase structure of the NiS_x alloy electrode before and after electrolysis were studied by SEM (scanning electron microscope) and XRD (X-ray diffraction).     

镍硫析氢活性阴极的电化学制备及其电催化机理

以硫代硫酸钠作为硫源, 在基本的瓦特浴镀液体系中通过恒电流电沉积方法获得了不同晶体结构的镍硫合金活性阴极. 通过能量散射谱(EDS)、X射线衍射(XRD)以及扫描电子显微镜(SEM)对镀层的化学成分、晶体结构以及表面形貌进行了分析, 并对活性阴极的电催化活性以及析氢过程机理进行了研究. XRD测试结果表明, 随着镀层中硫含量的变化, 镀层的晶体结构呈现出非晶态/Ni3S2混晶和金属间化合物(Ni3S2)两种晶体结构, 其中, 硫含量为33.9%(原子分数)的非晶态/Ni3S2混晶结构的活性阴极在碱性溶液中具有很好的析氢活性, 其优良的析氢活性主要来自于Ni3S2很强的吸附氢能力. 交流阻抗的测试结果表明, Ni3S2金属间化合物的析氢过程只存在一个电化学反应步骤, 而非晶态/Ni3S2混晶镍硫合金活性阴极的析氢过程存在三个电化学反应步骤.     

Properties of nanocrystalline electrodeposited CoFeP alloy with low phosphorus content

CoFe and low phosphorus containing (<4 at.%) CoFeP alloy films were electrodeposited from NaH₂PO₂ containing solutions at pH 4 on copper substrates under galvanostatic conditions. At the low phosphorus composition, nanocrystalline CoFeP alloy films are formed. The structure, composition and morphology of the thin films were studied using X-ray diffraction, energy dispersive spectroscopy and atomic force microscopy. The magnetic properties of the film were studied using superconducting quantum interference device magnetometer. The thin film performance features were explained on the basis of microstructural features developed during deposition. Whereas the electrodeposited CoFe alloy thin film exhibited mixed hcp and fcc phase structure in the absence of phosphorus, the low phosphorus containing thin film exhibited an increasing mixed bcc and hcp phase structure as its phosphorus content increases, showing modification in the grain size morphology and magnetic properties. In addition to applied current, the amount of P co-deposited in CoFeP alloy depends on the concentration of NaH₂PO₂ source in the bath. Qualitative analysis of the Tafel slope of CoFe and CoFeP deposition suggests that the presence of P in the CoFe deposit does not affect the mechanism of anomalous deposition of Co and Fe, thereby suggesting that CoFeP deposition is anomalous.     

催化增强化学蒸气沉积法在聚酰亚胺上沉积钯-铂合金薄层

以N₂，O₂作载气，通过催化增强化学蒸气沉积(CECVD)分别制得在聚酰亚胺上的金属铂、钯及其合金薄层。铂、钯配合物的共同沉积可生成Pt-Pd合金薄膜。在Pd-Pt合金的沉积过程中，Pd/Pt的原子数比率随共同沉积的条件改变而变化。O₂为载气、300 ℃条件下,用Pd(η³-allyl)(hfac)和Pt(COD)Me₂作前驱体共沉积制备Pd-Pt合金，得到含Pd 37.2%，Pt 62.8%且不     

STRUCTRE AND PROPERTIES OF COMPOSITE Ni/HARD CARBON FILMS PREPARED BY PLASMA DEPOSITION

IntroductionHardcarbonfilmsprcparcdb}'vari0usplasmaprocesscsareofc0nsidcrablcinterestbccauscofthcirunusualmcchanical-opticalandelcctricalpropertiesll~3l.Rccently,ithasReceive(IJl111c5,l9`)5;,.`,1iis()tI1ie)\tioII,1'ceil'edJtl1)'l4,l995*'I11isprojectiss[1pportcdh}tl1cNatiol1a1Nat[lntlScicl1ccI`()ul1dati()l1ofCl1il1aal1dtl1eI,aboraton'ofSolidI,ubricati()l1,l.al1/l10ulnstitutcofCl1cn1icalPh\'sics,111cChincscAcadcl11\'ofScicnccs.benfoundthattheinc0rporati0nofmetaIintocarbonfilmscangrcatl}'…     

Fe-Ni-S软磁薄膜的电沉积

酸性镀液中以硼酸为缓冲剂、柠檬酸三钠为配合剂,在紫铜箔上电沉积得到非晶Fe-Ni-S合金薄膜。 采用扫描电子显微镜和能谱分析技术(EDS)研究了镀液组成和沉积条件对镀层表面形貌和组成的影响。 结果表明,在镀液中加入2 g/L C7H5O3NS（糖精）和0.4 g/L 1,4-丁炔二醇可获得表面平整无裂缝和较小内应力的合金镀层;电流密度和镀液pH值对镀层组成影响较小,但施镀温度对镀层组成影响较大。 获得了理想的镀液组成和沉积条件,所得Fe73Ni9.5S17.5薄膜的X射线衍射表明其为非晶结构,在室温下具有较高的饱和磁化强度(Ms约为876.25 kA/m)和较低的矫顽力(Hc约为4.96 kA/m),具有良好的软磁性能。 循环伏安曲线和阴极极化曲线均表明,镀液中CS(NH2)2会促进Fe-Ni-S共沉积。     

ρ-Si上电沉积制备镍-磷非晶薄膜催化剂

非品态合金作为一类新型催化材料，越来越引起人们的广泛关注．Ni－P非晶态合金催化剂的催化加氢性能研究尤为活跃［‘，’］，研究结果表明其活性明显高于Ni－P晶态合金和比表面积相当的Ni粉L＼从而具有实用价值．传统的非品态合金催化剂的制备方法，如真空蒸镀、真空溅射、液相急冷及离子注入等，存在设备复杂、耗能大，难以批量生产等缺点；化学法可制备粒度均匀的催化剂＊；但给提纯带来了一定困难，而电沉积制备非晶薄膜催化剂由于具有纯度高、能耗低、制作方便等优势而倍受青睐问利用半导体做载体沉积Ni－P非晶态合金，在光电催化…     

Ni—S油脂氢化催化剂的EXAFS研究

用EXAFS法测定了Ni-S油脂氢化催化剂的结构。Ni催化剂被硫中毒生成了Ni_3S_2,致使由3个Ni原子组成的空穴(3CN)数目减少,这样虽引起该催化剂的活性降低,但却提高了油脂氢化对生成反式油酸酯的选择性。     

Influence of monolayer amounts of HNO3 on the evaporation rate of H2O over ice in the range 179 to 208 K: a quartz crystal microbalance study

The evaporation flux J(ev) of H2O from thin H2O ice films containing between 0.5 and 7 monolayers of HNO3 has been measured in the range 179 to 208 K under both molecular and stirred flow conditions in isothermal experiments. FTIR absorption of the HNO3/H2O condensate revealed the formation of metastable alpha-NAT (HNO(3).3H2O) converting to stable beta-NAT at 205 K. After deposition of HNO3 for 16-80 s on a 1 mum thick pure ice film at a deposition rate in the range (6-60) x 10(12) molecules s(-1) the initial evaporative flux J(ev)(H2O) was always that of pure ice. J(ev)(H2O) gradually decreased with the evaporation of H2O and the concomitant increase of the average mole fraction of HNO3, chi(HNO3), indicating the presence of an amorphous mixture of H2O/HNO3 that is called complexed or (c)-ice whose vapor pressure is that of pure ice. The final value of J(ev) was smaller by factors varying from 2.7 to 65 relative to pure ice. Depending on the doping conditions and temperature of the ice film the pure ice thickness d(D) of the ice film for which J(ev) < 0.85J(ev)(pure ice) varied between 130 and 700 nm compared to the 1000 nm thick original ice film at 208 and 191 K, respectively, in what seems to be an inverse temperature dependence. There exist three different types of H2O molecules under the present experimental conditions, namely (a) free H2O corresponding to pure ice, (b) complexed H2O or c-ice, and (c) H2O molecules originating from the breakup of NAT or amorphous H2O/HNO3 mixtures. The significant decrease of J(ev)(H2O) with increasing chi(HNO3) leads to an increase of the evaporative lifetime of atmospheric ice particles in the presence of HNO3 and may help explain the occurrence of persistent and/or large contaminated ice particles at certain atmospheric conditions.     

Rh-V alloy formation in Rh-VOx thin films after high-temperature reduction studied by electron microscopy

Rh nanoparticles (mean size 10 and 15 nm), prepared by epitaxial growth on NaCl surfaces, were covered with layers of crystalline vanadium oxide (mean thickness 1.5 and 25 nm) by reactive deposition in 10(-2) mbar O2. The 1.5 nm film was further stabilized with a coating layer of 25 nm amorphous alumina. The so-obtained Rh/vanadia films, containing vanadium in the V3+ and V2+ state, were treated in 1 bar O2 at 673 K for 1 h and thereafter reduced in 1 bar H2 at increased temperatures, particularly between 723 and 873 K. The structural and morphological changes were followed by (high-resolution) transmission electron microscopy and selected area diffraction. Oxidation at 673 K transforms the purely vanadia-supported samples into Rh/V2O5, while in the alumina-supported films containing only small amounts of VOx, the formation of topotactic V2O3 is observed. The formation of Rh-V alloys during the subsequent reduction is strongly determined by the intimate contact and the structural and orientational relationship between Rh particles and the surrounding VOx phase. Reduction above 473 K transforms the support into substoichiometric vanadium oxides of composition VO and V2O. Analysis of high-resolution images and diffraction patterns reveals the presence of different alloy phases after reduction with increasing T (from 573 up to 823 K). In the alumina-supported film (low V/Rh ratio) the epitaxial alignment between the Rh particles and the surrounding V2O3 phase apparently favours the primary formation of defined alloys of type V3Rh and VRh3, followed by VRh at higher temperature. On the contrary, mainly V3Rh5 is formed in the purely VOx-supported Rh/films, due to different epitaxial relations in the initial state. Possible pathways of alloy formation are discussed.     

退火前后镍钨硼合金电沉积层的结构与性能

采用电化学技术、XPS、DSC、XRD等方法研究Ni W B合金电沉积及热处理前后合金镀层的结构和显微硬度.结果表明,在Ni W B合金电沉积过程中伴随着化学沉积镍等过程以及Na2B4O7在镀层中的夹杂;Ni W和Ni W B合金电沉积层分别表现为纳米晶结构和非晶态结构;热处理过程中合金电沉积层发生晶粒粗化过程以及Ni W B合金镀层发生新相形成过程,产生Ni4W和镍硼化物如Ni2B、Ni3B等沉淀物;400 ℃热处理2 h后Ni W合金镀层有最大的显微硬度达919.8 kg•mm－2,而在500 ℃下Ni W B合金有最大的硬度达1132.2 kg•mm－2.     

Optimization of CuW alloy electrodeposition towards high-tungsten content

With the help of the factorial design of experiments, optimization of the deposition of the CuW alloy was successfully done. The important deposition parameters were identified as pH, current density, and—the most important one—copper ion concentration. All of them were examined in their wide ranges. Under optimal conditions, in a citrate bath, with copper ion concentration of 1.0 mM, at current density of −100 mA cm⁻² and at pH ca. 8.3, the alloy layer had the highest tungsten content (circa 30 wt.%), satisfactory adhesion and a smooth and crackless morphology. The structure of the electrodeposited alloy can be described as an amorphous solid solution of Cu in W with built-in Cu nanocrystals.

     

电沉积非晶态铁—铬合金镀层的研究

本实验通过控制镀液组成和操作条件获得了非晶态铁－铬合金镀层，实验分析了ＰＨ值，电流密度以及镀层中铬含量对所形成镀层的非晶态结构的影响，阳极极化曲线测量结果表明，与晶态层相比，非晶态度层具有较高的耐蚀性。     

脉冲激光沉积非晶态Ni-V2O5 复合薄膜及其电化学性能研究

首次报道了用355 nm脉冲激光沉积非晶态Ni-V2O5复合薄膜电极的电化学性能.采用不同摩尔比的NixV2O5 靶(x=0.1,0.3,0.5),在不同的基片温度(Ts)和O2气压力下制备了Ni-V2O5复合薄膜.XRD 和SEM测定表明, 在不锈钢基片上, Ts=300℃和氧气压力为14 Pa沉积0.5 h得到的是非晶态的Ni-V2O5薄膜.将此非晶态的Ni0.3V2O5薄膜电极用于锂电池的正极,与纯V2O5薄膜相比,不仅具有良好的放电速率性能和高的比容量,而且其充放电循环稳定性优异.该薄膜电极在放电速率为20 C时测得的比容量达200 mAh/g,并经1000次以上的充放电循环无明显的衰减.     

半导体硅上电沉积Ni-Pd-P薄膜及其结构

采用控电位的沉积方式在半导体硅上制备出ＮｉＰｄＰ薄膜,结果表明镀液中Ｈ３ＰＯ３含量的增加对Ｐ、Ｎｉ的析出有促进作用,对Ｐｄ的析出有抑制作用．随ｐＨ值的升高,镍含量不断升高,Ｐｄ、Ｐ含量不断下降．Ｐ含量对薄膜内应力有很大影响,含Ｐ质量分数为１４９％的ＮｉＰｄＰ镀层表面上有许多裂缝,当Ｐ含量增加到２６１％时,镀层表面的裂缝已基本消失,继续增加Ｐ含量到３５０％时,裂缝完全消失．ＮｉＰｄＰ镀层的结构与其组成密切相关,Ｐ含量小于２００％的ＮｉＰｄＰ镀层形成的是面心立方结构的固溶体．Ｐ含量大于４００％的薄膜为非晶态结构．     

柠檬酸盐-氨体系化学镀Ni-B合金的研究

本文研究了柠檬酸盐-氨体系化学镀Ni-B合金的镀液成份和沉积条件对沉积速度和镀层含硼量的影响,确定了镀液的最佳组成和条件为:NiSO₄·7H₂O 40g/l,H₃BO₃ 30g/l,NH₄C130g/l,柠檬酸三铵20g/l,二甲氨基硼烷4g/l,pH9.5～10.0,45℃.测定了镀层的性能。该镀层的接触电阻约为0.126Ω,与银的相近。XPS和AES的研究结果表明,Ni-B镀层由Ni₂B合金和Ni组成,但其表面有部分Ni(Ⅱ)和B(Ⅲ)存在。     

电沉积条件对非晶态Fe-Mo合金结构及表面性质的影响

利用XRD、SEM和XPS等手段研究了电解液中x(Mo)(Mo在Mo+Fe中的摩尔分数)、电流密度及温度变化对电沉积非晶态Fe-Mo合金的结构和表面性质的影响.溶液中主要含有FeSO₄、Na₂MoO₄、H₃Cit和NaCl,pH值3～5.当x(Mo)大于50%,电流密度高于25mA/cm²,温度低于40℃时有利于形成非晶态结构.合金沉积层的表面呈颗粒状且有微裂纹,表面的化学性质很活泼,容易形成含低价Mo的有色氧化物表面膜.非晶Fe-Mo合金沉积层在3%NaCl溶液中的耐蚀性优于纯铁.     

载体γ-Al2O3和钐对非晶态NiB合金热稳定性的影响

用化学还原法制备了NiB、NiB/Al2O3和NiBSm/Al2O3三种催化剂，它们都呈非晶结构.用等离子耦合发射光谱仪(ICP)对催化剂组分进行了分析，采用差示扫描量热法（DSC）对三种催化剂进行了热稳定性分析.结果表明，载体的引入使非晶态NiB合金的体相组成中B的含量降低.将非晶态NiB合金负载到γ-Al2O3上,可以明显改善非晶态合金的热稳定性，少量Sm可以进一步提高晶化温度.晶化激活能数据亦表明了载体和Sm对非晶结构具有良好的稳定作用.载体和Sm可能通过不同的作用提高了非晶态合金的热稳定性.     

Electrolessly Plated Ni-Zn（Fe）-P Alloy and Its Corrosion Resistance Properties

The autocatalytic deposition of Ni-Zn(Fe)-P alloys has been carried out on substrate of carbon steel from a bath containing nickel sulfate, zinc sulfate, sodium hypophosphite, sodium citrate and boric acid. The effects of pH and the molar ratio of NiSO4/ZnSO4 on the deposition rate and the composition of deposits have been studied. It was found that the presence of zinc sulfate in the bath has an inhibitory effect on the alloy deposition. The structure and the surface morphology of Ni-Zn(Fe)-P coatings were characterized with XRD and SEM, respectively. The alloys plated under the experimental conditions consisted of an amorphous phase coexisting with a crystalline cubic Ni phase (poly-crystalline). The surface morphology of the coating is dependent on the deposition parameters. The corrosion resistance of the Ni-Zn(Fe)-P deposits was examined via mass loss tests and anodic polarization measurements, respectively. The results show that the surface morphologies of the deposits and the corrosion resistance of the deposits have been improved. The results of mass loss tests almost accord with those of anodic polarization measurements. The corrosion mechanisms of Ni-Zn(Fe)-P alloys in NaCl and NaOH solutions were investigated by means of EDX. The deposit immersed in an NaCI or an NaOH solution contains more content of oxygen and less contents of the metals(except Fe) than that placed in air, which shows that the NaCl or NaOH solution can accelerate the oxidation of the deposit.     

Ni-Mo-B非晶态合金纳米颗粒的抗氧化性能研究

在水溶液体系中用化学还原法制备Ni-B和Ni-Mo-B非晶态合金纳米颗粒.SEM测试表明,样品的颗粒形貌呈球形或类球形,平均粒径约10nm.XPS分析结果表明,Ni-Mo-B非晶态合金中钼元素主要以氧化态形成于合金的表面,并导致合金表面合金化硼原子浓度显著增加,氧化态硼（B3＋）的原子浓度显著减少,氧的原子浓度明显减少,合金化镍的原子浓度显著增加,氧化态镍（Ni3＋）的原子浓度显著减少.因此,Ni-Mo-B合金的抗氧化性能显著高于Ni-B合金.XPS谱图分析还表明,在Ni-B和Ni-Mo-B非晶态合金中,存在Ni和B的合金化物Ni2B,其中B失去部分电子,而Ni则富余电子.Ni2B的氧化产生副产物Ni2O3和B2O3.