重稀土元素对氢氧化镍电极高温性能的影响

研究了在覆钴球镍中低量添加重稀土元素对镍电极性能的影响。结果表明,60℃时添加1%(原子分数)重稀土的镍电极的1C充放电效率比无添加剂的镍电极有所提高;重稀土氧化物的添加对镍电极的常温高倍率放电性能有一定的负面影响;在常温时,重稀土氧化物的加入增大镍电极氧化-还原反应的电位差,从而增大电极反应的不可逆性,其中添加氧化铥与氧化镥的电极最为明显;在60℃时,添加重稀土氧化物的镍电极的氧化峰与析氧峰区别明显,且镍电极的氧化峰电位与析氧电位普遍负移,还原峰电位普遍正移,显著提高镍电极在高温下的析氧过电位以及可逆性。     

Ir／IrOx金属氧化物电极的H^＋响应行为研究

通过热氧化法制备了铱氧化物电极，研究了电极的各种H^ 响应行为：电极响应开路电位与溶液pH值的线性关系、响应范围、响应速度、滞后效应。分别利用循环伏安法SEM、XPS对铱氧化物电极的内外表面组成、表面形貌与元素价态进行了分析。根据建立的内、外表面电荷积分模型分析了电极H^ 响应速度、滞后效应和氧化膜厚度、形态的关系，提出了水合氧化膜存在下的H^ 响应机理。     

短时间热处理后镍磷合金镀层的性能

研究了镍磷合金镀层短时间热处理后的性能变化。结果表明,短时间热处理对镍磷合金镀层的非晶态性质有一定影响。镀层表面部分有Ｎｉ３Ｐ相晶体析出,硬度增加,在７００℃达到最大值。由于短时间热处理,镀层表面氧化,将使其腐蚀电位发生变化;形成的氧化物膜亦能有效地降低腐蚀电流和阳极溶解电流,增加其耐蚀性。     

金属催化化学沉积反应的电化学本质研究

以次磷酸盐酸性化学沉积镍体系为对象,研究了基体对化学沉积反应具有催化活性的电化学本质。首先利用稳定电位的测量明确化学沉积镍反应中次磷酸盐氧化的决定性作用,并发现次磷酸盐的氧化反应也具有特征反应电位。基于先前研究得到的次磷酸盐阳极氧化机制,提出对化学沉积镍反应具有催化活性的金属需符合的条件是,在化学镀液中金属的电位高于次磷酸盐的氧化还原电位的同时,必须低于该金属在此特定镀液中的零电荷电位值。并选取5种具有代表性的金属进行了实验验证     

化学镀镍磷合金废液处理研究

采用氢氧化钙对化学镀镍废液进行沉淀处理，镍的去除率可达99％以上，亚磷酸根和硫酸根的去除率可达82％和18％。在弱酸性条件下用氯化钙再生镀液，亚磷酸根及硫酸根的去除率可达83％和55－70％，而镍的损失不超过14％。     

化学镀镍磷合金废液处理研究

采用氢氧化钙对化学镀镍废液进行沉淀处理．镍的去除率可达99％以上．亚磷酸根和硫酸报的去除率可达82％和18％。在弱酸性条件下用氧化钙再生镀液．亚磷酸根及硫酸报的去除率可达83％和55-70％．而镍的损失不超过14％。     

镍黄铁矿电化学生物氧化过程的分解机理(英文)

应用表面粘附和没有粘附Acidithiobacillus ferrooxidans的镍黄铁矿粉末微电极进行电化学测试,以说明镍黄铁矿氧化分解的机理。循环伏安CV结果显示,在-0.2V的低电位区域,在镍、铁离子析出时镍黄铁矿转变为中间相Fe4.5-yNi4.5-xS8-z;当电位在-0.2V到0.2V区间时,有不稳定的紫硫镍矿Fe3Ni3S4和FeNi2S4形成并在表面伴有元素硫的产生;当电位增加到0.2V以上时,不稳定相将全部分解;在高电位0.7V时,析出的亚铁离子被氧化为高铁离子。嗜酸氧化亚铁硫杆菌Acidithiobacillus ferrooxidans的存在使峰电位增高,反应起始电位负移,并对表面形成的元素硫有氧化去除作用。这一过程可通过-0.75到-0.5V电位区间发生的的还原反应证实。生物浸出和电化学实验结果均表明当pH2时溶液酸度的增加对氧化过程有轻度的阻碍作用。     

表面处理对Mg-Al-Zn耐蚀性的影响

利用涡流测厚仪、场发射扫描电镜、盐雾腐蚀试验箱、电化学测试系统研究了以微弧氧化为预处理,以硫酸镍为主盐的镁合金"无氟酸性"化学镀工艺及其镀层性能。获得Mg-Al-Zn合金耐蚀性较强的微弧氧化层,并确定了微弧氧化工艺,即:起始电压为265 V,占空比为12,频率为500 Hz,电流0.75 A,正脉冲数48,时间20 min。在微弧氧化层上进行了化学镀镍,获得了Mg-Al-Zn合金微弧氧化-化学镀镍复合镀层。结果表明:镀镍层为低磷镍镀层,其中含镍89.42%,含磷2.51%;复合镀层明显提高了Mg-Al-Zn镁合金的腐蚀电位,提高了Mg-Al-Zn合金的耐蚀性。     

中国科学院成功研制出氧化钛“光开关”材料

采用循环伏安电沉积技术在钛基上获得水合氧化钌(RuOx·nH2O),其比容量为105F/g。通过电化学测试(循环伏安、恒电流充放电)、X射线衍射(XRD)、扫描电镜(SEM)以及X射线光电子能谱(XPS)等方法研究了沉积物的电化学性质、物相及组成。结果表明:电沉积法获得的水合氧化钌呈非晶态结构,它由多氧化态钌混合羟基氧化物组成。在1.0mol·L-1H2SO4溶液中,该氧化物呈准电容特征,有较高电化学可逆性,可用作电化学电容器电极材料。     

铁酸锌薄膜电化学水热合成及性能表征

利用电化学和水热法相结合的方法在碳钢表面合成了纳米铁酸锌薄膜,采用氧化电压为2 V,在不同pH值的氨水溶液中将碳钢表面氧化生成水合氧化铁,然后将其放入高压釜,在含Zn2+溶液中转化成铁酸锌.通过X射线粉末衍射(XRD),扫描电镜(SEM),对薄膜的物相和表面形貌进行表征,通过可见-紫外光吸收谱(UV-vis)确定其光响应范围;用IM6e电化学工作站测定其光生电位和光电流曲线.     

The growth and structure of thin oxide films on ceria-sol-coated nickel

The influence of 14-nm thick ceria ceramic coatings deposited by the sol-gel technique on the early-stage oxidation of polycrystalline nickel at 973 K was studied by analytical electron microscopy, Auger electron spectroscopy, Rutherford backscattering spectrometry and X-ray diffraction. The size of the ceria particles in the coating was modified prior to oxidation by vacuum annealing. It was found that ceria particle size is a crucial factor affecting the oxidation kinetics, oxide microstructure, and distribution of cerium within the oxide film. Coarse ceria particles applied to the nickel surface were ineffective in the inhibition of oxidation and were spread throughout the whole oxide. Coatings with small ceria particles markedly improved the oxidation resistance. After oxidation such particles were present in the surface region of nickel oxide, acting as the sources of cerium ions segregated at the nickeloxide grain boundaries. The stereological analysis of oxide microstructure as well as microchemical examination supported the predominant role of grain-boundary segregation of cerium ions decreasing the oxidation rate. The results are discussed in terms of reactive-element effect on the development of microstructure of nickel oxide film during initial stages of oxidation.     

A comparison of the effects of small additions of various second elements on the oxidation of nickel at 1200°C

The oxidation behaviour of Ni-4.2% Mo, Ni-4.0% W, Ni-2.5% Al, Ni-4.2% V and Ni-5.0% Cr (all wt. %) at 1200 °C in flowing oxygen at 1 atm. pressure has been studied using various techniques. In particular, the solubility of the second element in NiO, its distribution across the NiO scale and the effects of these on the oxidation rates and scale morphologies have been examined. The oxidation rates of all the alloys are greater than that of nickel, although for Ni-4.2% Mo, where incorporation of internal oxide into the scale does not occur and molybdenum does not dope the oxide, the small increase in weight gain during oxidation Compared with that for nickel is due to internal oxide formation only. As the internal oxide particles pileup at the alloy/oxide interface, they exert a blocking effect to outward diffusion of Ni²⁺ ions, especially in the later stages of oxidation. Ni-4.0% W behaves similarly, although a few internal oxide particles are incorporated into the scale and a small amount of doping of the oxide ensures that it thickens at a slightly faster rate than the scale on nickel and for Ni-4.2% Mo. The oxidation rates of the other alloys are significantly faster than that of nickel and increase in the order Ni-2.5% Al, Ni-4.2% V, Ni-5.0% Cr. These increased rates are largely caused by increases in the total cation vacancy concentrations in the scales, although internal oxide formation can make a significant contribution to the oxidation kinetics. The influence on the oxidation behaviour of a number of factors, namely doping of the scale, internal oxidation, dissociation of NiO and transport of gaseous oxygen within the scale, blocking effects in the oxide and at the alloy/oxide interface, and grain growth of the oxide, are considered in detail.     

Electrochemical oxidation of binary copper-nickel alloys in cryolite melts

Anodic oxidation of copper, nickel and two copper-nickel alloys was studied in cryolite melts at 1000 °C. In an oxide-free melt, anodic dissolution of each material was observed, and the dissolution potential increases with the content of copper. SEM characterization of a Cu55-Ni45 alloy showed that nickel is selectively dissolved according to a de-alloying process. In an alumina-containing melt, a partial passivation occurs at the copper-containing electrodes, at potentials below the oxygen evolution potential. A passive film forms on the copper electrode, while on the nickel electrode no dense oxide layer develops. Copper-nickel alloys were found to form a mixed oxide layer. At higher potentials, the formation of oxygen bubbles on the electrodes results in a degradation of the passive films and a strong corrosion.     

Effect of grain size on high-temperature oxidation behavior of Cu-80Ni alloy

1　INTRODUCTIONTheoxidationofunalloyedcopperandnickelhasalreadybeenstudiedindetail.Whilethehigh tem peratureoxidationofCu Nialloys ,alsostudiedanumberoftimestodate[13] ,isanexampleofarela tivelysimpleclassofscalingofbinaryalloysbyasin gleoxidant,becausethemetalsformacontinuousse riesofsolidsolutions ,whiletheiroxides ,CuO ,Cu2 OandNiO ,exhibitsmallmutualsolubilitiesandshowsignificantdifferencesinthethermodynamicstabilityandparabolicgrowthrates .Thus ,copper richalloysformexternalscales…     

不同混合气氛下9Ni钢的高温氧化行为研究

对9Ni钢在不同氧分压及不同湿度条件下的高温氧化行为进行了研究。结果表明,9Ni钢的氧化行为会随着氧分压降低而受到阻碍,在低氧分压条件下没有Ni富集层产生,氧化进程受供氧量严重制约。而在不同湿度条件下,随着相对湿度的增大,氧化增重、氧化速率常数均增大;总氧化层厚度、Ni富集层厚度均增大,且增厚趋势趋于一致。潮湿环境下铁氧化层形成的大量裂纹、孔洞等缺陷,有利于气相物质的扩散,起到加速氧化的作用。     

Short-circuit diffusion in the growth of nickel oxide scales on nickel crystal faces

A study has been made of the growth of nickel oxide layers on the (100), (110), and (111) crystal faces of nickel exposed to oxygen for periods up to 100 hr at temperatures in the range 500–800°C, These layers grow at a rate dependent upon the crystallographic orientation of the nickel face even at thicknesses within the scaling range. The (100) face oxidized more rapidly than the (110) and (111) nickel faces while the latter faces oxidized at different relative rates dependent upon temperature. A diffusional model is employed to interpret the oxidation kinetics wherein nickel transport proceeds in nickel oxide both by short-circuit diffusion at grain boundaries and by lattice diffusion.This work forms part of a research program sponsored by the National Research Council of Canada.     

The oxidation of chromium- and nickel-implanted nickel at high temperatures

The isothermal oxidation behaviour in oxygen of nickel, implanted with nickel and chromium ions, has been studied in the range 950–1150°C using kinetic and electronoptical techniques. Implantation with nickel ions has a significant and lasting effect on the oxidation kinetics and on the morphology and grain configuration of the NiO scale. The oxide grains are generally smaller, more facetted and more mismatched for the implanted surfaces and there is more extensive stress generation during oxide growth. After an initially slower rate, the oxide on the implanted surfaces develops at a faster rate than that on the unimplanted surfaces, particularly at the higher temperatures. Implantation with chromium ions inhibits the initial development of the NiO scale. However, subsequently, the oxidation rate is more rapid for the implanted surfaces and increases progressively with increasing chromium ion dose. The results can be accounted for in terms of doping of the NiO and the much decreased grain size of the oxide. It is concluded that short-circuit grain boundary diffusion processes, as well as bulk lattice diffusion of Ni²⁺ ions, are important in the oxidation of nickel at high temperatures.     

The oxidation characteristics of electrodeposited nickel composites containing silicon carbide particles at high temperature

The oxidation behaviour of electrodeposited nickel and Ni-SiC composites containing up to 13% by volume of the carbide particles in flowing oxygen at 1100°C has been studied using various kinetic and electron-optical techniques. The electrodeposited nickel oxidized more slowly than cold-rolled nickel while the introduction of up to 13 vol.% coarse SiC particles (9 μm dia.) or up to 8 vol.% fine SiC particles (3 μm dia.) to the electrodeposited nickel did not significantly change its oxidation rate. The introduction of 12 vol.% fine SiC particles did cause a significant decrease in the oxidation rate due largely to internal oxide-derived particles acting as barriers to Ni²⁺ ions diffusing through the NiO scale. The roles played in the oxidation process by doping, blocking effects in the oxide and internal oxide formation are considered and related to the oxidation rates of the composites.     

On the use of the micromarker technique for studying the growth mechanism of thin oxide films

The high temperature behavior of microscopic markers, deposited on to pure and ceria-coated nickel, was tested. The markers, having a form of 20-nm-thick palladium bumps with a fractional surface coverage of 0.05 and 30-nm thick gold bumps with a surface coverage of 0.25, apparently interfered with the oxide growth, increasing the oxidation rate on their surface at 973 K over one order of magnitude. As detected by a combination of Auger electron spectroscopy and Rutherford backscattering spectrometry, for ceria modified nickel, the markers’ depth-position coincided with the ceria particles dispersed in the vicinity of the oxide–gas interface. For pure nickel oxide films, the markers were easily incorporated into the growing oxide during very early stages of oxidation and were difficult to detect at the oxide–metal interface. It is proposed that the catalytic behavior of the markers was caused by their fragmentation into a large number of islands, leading to the refinement of the oxide grains, which in turn accelerated the substrate oxidation rate. Some precautions necessary in conducting the marker experiments are defined.     

铜钴镍离子对镁合金微弧氧化膜的影响

目的提高镁合金微弧氧化膜的耐蚀性。方法在Na_2SiO_3-NaOH-Na_2B_4O_7组成的电解液体系中,分别加入铜离子、钴离子和镍离子对AZ91D镁合金进行微弧氧化,研究离子种类和组成对膜层性能的影响。采用点滴实验测试膜层的耐蚀性,采用电化学工作站测试膜层的电化学性能,采用扫描电子显微镜(SEM)和能谱分析(EDS)对微弧氧化膜层的表面形貌和元素组成进行分析。结果电解溶液中加入钴离子、铜离子、镍离子后,镁合金微弧氧化膜的耐腐蚀性能均有提高。其中铜离子的影响最大,加入1.5 g/L的铜离子后,镁合金微弧氧化膜的点滴时间提高了77.3 s,膜层耐腐蚀性能显著提高。电化学测试结果得出,不加金属离子的氧化膜的腐蚀电流密度为1.092×10~(-5) A/cm~2,腐蚀电位为-1.487 V;加入钴、铜、镍离子浓度分别为2、1.5、3 mol/L时,腐蚀电流密度分别为3.912×10~(-6)、6.027×10~(-6)、2.167×10~(-6) A/cm~2,腐蚀电位分别为-1.412、-0.832、-1.047 V;加入金属离子制得的微弧氧化膜的腐蚀电流密度均降低了1个数量级,腐蚀电位不同程度地正移,其中加入铜离子后腐蚀电位提高了0.655 V。加入金属离子后,陶瓷膜表面空隙和孔洞数量不同程度地变浅和减少,增加了膜层的致密性和均匀性。结论电解液中添加一定量的铜、钴、镍离子均能够提高AZ91D镁合金微弧氧化膜层的耐蚀性,其中铜离子的效果最明显。