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.     

黑色微弧氧化膜的制备及其表征

利用二次微弧氧化法,通过在磷酸盐体系的电解液中添加柠檬酸铁,在AZ40M镁合金基底表面成功制备了黑色的微弧氧化膜层。并利用扫描电子显微镜（SEM）、能谱仪（EDS）、X射线衍射（XRD）和X射线光电子能谱（XPS）分别对黑色膜层的形貌和成分组成进行了表征,探讨了黑色微弧氧化膜层的形成过程及机理。结果显示,黑色膜层的主要成分为氧化镁,同时伴随着一定量的铁氧化物,包括四氧化三铁、氧化亚铁和单质铁。因此镁基底表面黑色膜层的形成可归因于柠檬酸铁中的铁离子在成膜过程中参与反应形成了黑色的四氧化三铁、氧化亚铁和单质铁混合物,并均匀地沉积在氧化膜中。     

硼砂-对苯二甲酸电解液中AZ91D镁合金的阳极氧化处理

研究了硼砂-对苯二甲酸环保型电解液中AZ91D镁合金的阳极氧化.考察了对苯二甲酸对镁合金阳极氧化过程及其氧化膜性能的影响,并利用扫描电镜(SEM)、X射线衍射(XRD)、能量散射谱(EDS)、动电化极化和电化学交流阻抗谱(EIS)等进行了分析表征.结果表明,对苯二甲酸的浓度对阳极氧化成膜过程、氧化膜的表面形貌、厚度、相结构和耐腐蚀性能都有重要影响.在硼酸盐电解液中加入适量的对苯二甲酸后,氧化电流密度降低,过度放电现象受到了明显的抑制,所制得的阳极氧化膜的质量也有了显著改善.氧化膜表面变得光滑、致密,膜厚度略有降低.氧化膜与镁合金基底的结合更紧密,而且其耐腐蚀性能也得到了明显增强.该研究对于镁合金阳极氧化处理工艺的环保化及阳极氧化膜质量的提高都具有积极意义.     

镁合金阳极氧化膜的结构、成分及其耐蚀性

采用电压-时间曲线、膜厚-时间曲线、X射线衍射法、扫描电镜、能量色散谱仪、X射线光电子能谱法、全浸腐蚀实验和极化曲线等方法分别研究了AZ91D铸镁合金阳极氧化成膜动力学过程、阳极氧化膜的表面形貌、结构、元素组成、元素价态以及相成分和膜层的耐蚀性.结果表明,在阳极氧化的4个阶段中,由于各个阶段所生成膜的厚度、结构和成分等均不同,因此膜的耐蚀性相差很大;镁合金阳极氧化时耐蚀性最好的膜层是在阳极氧化过程中的第阶段和第阶段的交界处所生成的膜层;镁合金阳极氧化膜中含有Mg,O,Si,B和少量的Al,Na元素,膜层主要由MgO,MgSiO₃和Mg3B2O6组成.     

L-半胱氨酸功能化三维石墨烯的制备及其对亚甲基蓝的吸附行为研究

在常压下制备了L-半胱氨酸功能化三维石墨烯(L-3DRGO),研究了L-3DRGO对MB分子的吸附机理。氧化石墨烯(GO)在常压水浴中与L-半胱氨酸(L-cys)反应后,结构中的含氧官能团被大量去除,L-cys被氧化为胱氨酸,实现了GO的还原和接枝改性,并通过酰胺反应将还原后的GO片-片相连,构建成三维网络结构。L-3DRGO对MB的吸附符合Langmuir等温吸附模型,为单层吸附,通过Langmuir等温吸附模型计算得到的相关系数(RL)在0～1之间,增大MB初始浓度可以有效克服固液两相之间的传质阻力,有利于吸附的进行。拟二级动力学模型能更好地描述MB在L-3DRGO上的吸附,当MB的初始浓度为500mg/L时,L-3DRGO对MB的最大吸附量为446.43mg/g。吸附过程的焓变与熵变均为正值,说明L-3DRGO对MB的吸附是一个吸热和熵增的过程。在298～338K范围内,ΔG~0为负值并随温度的升高而减小,说明MB在L-3DRGO上的吸附可自发进行,适当升温利于吸附过程。整个吸附过程均伴随有液膜扩散和颗粒内扩散,吸附速度的主控步骤由液膜扩散转化为颗粒内扩散。     

Galfan镀层镧盐转化膜的制备和耐蚀性能研究

将热浸镀Galfan钢板浸入含有20 g·L-1La(NO3)3·6H2O,10 m L·L-1H2O2,0.1 g·L-1Na F的处理液中,在70℃下处理10 s~30 min,从而在其表面获得镧盐转化膜。采用扫描电子显微镜(SEM)观察膜层的微观形貌,能谱仪(EDS)分析膜层的化学成分。采用中性盐雾试验和电化学极化曲线来研究膜层的耐蚀性能。结果表明,镧盐转化膜在晶界或相界等活性区域优先成膜并迅速生长,膜层形成不均匀。随着处理时间的延长,镧盐转化膜逐渐增厚,膜层的裂纹变多、扩大并脱落;膜层主要由Zn,Al,O和La元素组成。与未处理的热浸镀Galfan镀层相比,镧盐转化膜的腐蚀电流密度显著降低,极化电阻显著提高,基体耐腐蚀性能明显提高。     

富勒烯修饰电极微分脉冲伏安法测定盐酸克伦特罗

将1.08mg富勒烯(C60)分散在10mL二氯甲烷中,取40μL悬浮液滴涂在玻碳电极表面,吹干后在1mol·L-1氢氧化钾溶液中进行活化,制得C60修饰电极。用循环伏安法研究了修饰电极的电化学行为。结果表明:经氢氧化钾处理后的修饰电极,在5mmol·L-1铁氰化钾溶液中,可见一对准可逆的氧化还原峰,且峰电流显著高于在裸玻碳电极和未处理电极上的峰电流。据此提出了用微分脉冲伏安法测定盐酸克伦特罗的方法。盐酸克伦特罗的浓度在0.1～20μmol·L-1范围内与其氧化峰电流呈线性关系,检出限(3S/N)为3.26×10-2μmol·L-1。方法用于尿样分析,回收率在99.5%～110%之间。     

镁合金化学转化膜的制备及其性能研究

在磷酸钠-磷酸二氢铵-高锰酸钾体系中对镁合金进行化学转化处理.研究了磷酸钠、磷酸二氢铵、高锰酸钾、温度、时间和添加剂对转化膜性能的影响.通过对转化膜结构、成分及性能的测试评价,得到了性能较好的化学转化溶液配方:Na3PO4为5g·L-1,NH4H2PO4为15 g· L-1,KMnO4为1g· L-1,添加剂(NH4)6 Mo7O24为0.5g·L-1.由SEM可观察到转化膜的表面成“干枯河床”状.XRD和EDS检测表明,膜层的主要成分是Mg,Al12 Mg17和无定形相,膜层表面主要有Mn,Mg,K,O和Al等元素组成.腐蚀实验和电化学测试表明,添加剂能够降低转化膜的腐蚀率,转化膜较基体的腐蚀电位正移了0.73 V,提高了镁合金的耐蚀性.     

硝酸镧处理对微弧氧化二氧化钛膜光催化性能的影响

以磷酸钠为电解液,采用交流微弧氧化技术在钛网上直接制备TiO2膜,利用硝酸镧浸渍方法对该膜进行表面处理,以酸性大红染料模拟废水来评价TiO2膜光催化水中有机污染物的能力。利用X射线衍射仪、SEM和EDX对微弧氧化膜晶型、表面形貌和成分进行分析。结果表明:微弧氧化TiO2膜主要由锐钛矿TiO2组成,由于膜表面钠离子的沉积,微弧氧化TiO2膜的光催化性能较差;硝酸镧浸渍处理可以减少微弧氧化TiO2膜表面钠离子含量,改善膜的光催化性能,120min酸性大红染料废水的光催化脱色率由15%提高到34.8%以上。     

离子色谱法测定水果和蔬菜中2,4-二氯苯氧乙酸的含量

采用离子色谱法测定水果和蔬菜中2,4-二氯苯氧乙酸的含量。水果或蔬菜样品10.0g经0.2mol·L-1硫酸溶液10.0 mL提取后,用二氯甲烷10.0 mL萃取,二氯甲烷层再用35mmol·L-1氢氧化钾溶液5.00mL反萃取,取水相,经AG-19保护柱及AS-19阴离子分离柱分离,以35mmol·L-1氢氧化钾溶液淋洗色谱柱,所得淋出液采用抑制电导检测器检测。2,4-二氯苯氧乙酸的质量浓度在5.0mg·L-1以内与其峰面积呈线性关系,检出限(3S/N)为0.05 mg·L-1。加标回收率在93.6%~105%之间,测定值的相对标准偏差(n=6)在2.1%~5.5%之间。     

Optical Viscometry of Spinning Sol Coatings

Optical interferometric monitoring of spin coating (optospinography) has allowed close observation of the temporal evolution of a thin silicate sol film (typically at 2000 rpm, 100 Hz data acquisition). The kinematic viscosity data obtained, using a simple analytical model, are validated with those from a mineral oil standard, with agreement well within the experimental uncertainties. For spin coating in open air, the influence of variations in refractive index, rheological properties and air flow are discussed. Inflections in the temporal evolution of the optical thickness of silicate sol films are analyzed, which indicate the usefulness of optospinography, particularly when applied in the proximity of the rotation axis and evaporation is minimized, to monitor time variations in the kinematic viscosity of these sols during spin coating.     

Anti-Reflective Coatings for CRTs by Sol-Gel Process

Anti-reflective and electromagnetic shielding double-layered coatings were developed for cathode ray tubes (CRTs) by wet chemical process. An outer SiO₂ layer is formed over a porous inner tin-doped indium oxide (ITO) particle layer. ITO particles used in the inner layer lower the sheet resistance below 10³ohm/sq. and an electromagnetic shielding property is attained. To improve the abrasion wear resistance of the film, the structure of the film and hydrolysis-polymerization condition of tetraethoxy-silane (TEOS) are estimated. An outer SiO₂ layer component penetrates into the inner layer and adheres to the glass surface. As the extent of hydrolysis of TEOS proceeds and the molecular weight of hydrolyzed TEOS becomes small, the abrasion wear resistance of the film enhances. The relation between the curing condition of the film and surface resistance of the film is investigated. The surface resistance of the film lowers by curing the film in reductive atmosphere. The transmittance of the film in the near-infrared region shows that the lowering of surface resistance of the film is caused by the increase of carrier concentration of ITO particles. The double layered coatings are successfully applied to the panel glass for CRTs on an industrial-scale.     

Laminated Composition Coatings

The present paper discusses the results of research into production of thermally stable composition coatings that have nanostructured inorganic non-metallic coating (NIN coating) of different compositions on zirconium alloy substrate as their part, as well as metals introduced into coating pores. Researchers identified optimal conditions of microplasma treatment, as well as composition of electrolyte solutions for each stage of composition material production. Was used to construct and analyze current-voltage characteristics obtained in the course of electrical impact upon samples. Phase and element composition of NIN coatings, surface morphology of NIN coatings and coatings with metal injected into were studied.     

Investigation of Glass-Like Sol-Gel Coatings for Corrosion Protection of Stainless Steel Against Liquid and Gaseous Attack

Glass-like sol-gel coatings have been investigated as corrosion protective coatings on stainless steel. Magnesium- and borosilicate coatings with thickness of about 100–700 nm and methyl-modified SiO2 coatings with a thickness of about 2 m were deposited on stainless steel plates by dip-coating. The coatings were densified between 400°C and 500°C in different atmospheres (N2, air) for 1 h. The corrosion protection against gaseous attack was investigated by accelerated corrosion tests, at 800°C in air for 1 h. A corrosion protection factor was calculated from the relation Fe/Fe2O3, determined by XRD on the surface of coated and uncoated samples. Methyl-modified SiO2 coatings showed a protection factor, which was 2 orders of magnitude higher than for the other coatings. Electrochemical investigations were performed on samples submerged in a NaCl solution for 200 h. The corrosion propagation, polarization resistance and impedance vector were measured. For accelerated corrosion tests, polarization intensity curves were determined for high potentials of up to 1 V. Again excellent results were obtained for the methyl-modified SiO2 coatings, which remained passive for 200 h. Results of the salt spray corrosion test, however, showed no corrosion protection by the sol-gel coatings. After 2000 h in the salt spray chamber the steel was corroded and the coatings peeled off. It is concluded that for the further development of these coatings an improved interfacial passivation will be required.     

Free release static coating of glass capillary columns; Static coating at elevated pressure — Theoretical considerations and practice

Summary Static coating of glass capillary columns has hitherto solely been carried out by evaporation of the stationary phase solvents under vacuum conditions. However, since a solvent vapour pressure higher than the external pressure is the only requirement for the vapour to flow out of the column, evacuation should not be necessary. Several important factors in the static coating procedure, such as mass (solvent vapour) — and heat transfer, heat of vaporisation of the solvent and viscosity of the stationary phase solution at elevated temperature and outlet pressure are discussed, principally to rationalise an improved static coating procedure. The alternative, so-called free-release static coating procedure, was evaluated practically by coating several columns with OV-101 and SE-30. Coating speed was found to be rapid and relatively constant whereas coating efficiency was between 80 and 100%.     

Development of Heteropolysiloxane Coatings on Electrogalvanized Steel

The development of heteropolysiloxane coatings on electrogalvanized steel by sol-gel processing has been studied from the sol state to the solid state using techniques such as 29Si NMR, SIMS, XPS, and the three point flexure test. It was possible, from the results obtained, to propose a simplified model for the coatings which brings into play two layers of differing molecular structure: an extremelly thin internal layer and an outer layer, respectively called the anchoring and volume layers.     

Acceleration of free release static coating of capillary columns by the presence of polar solvents in the coating solution – a theoretical study

The cause of an observed acceleration in the free release static coating process of a capillary when more polar solvents are added to alkanes as stationary phase solvents has been studied. By using a computer program, 9 of the relevant physical parameers were calculated in relation to the composition of the solvent hixtures. Curves of these parameters vs composition of the mixures were drawn. From the results it can be deduced that the change of these parameters with the increase of polar solvents in the solution, is probably insufficient to explain the drastic increase of the free release static coating speed. A physical model is proposed to calculate the depth of the meniscus around which sufficient heat can be transferred into the evaporating surface per unit time, to evaporate the solvent at a rate that the coating speed indicates. It is demonstrated that when pentane-acetone mixtures are used to coat a capillary, the depth of the meniscus indeed is greater than when pure pentane is used. The proposed model may lead to a better understanding of phenomena involved in the static coating process.     

Sol-Gel Coatings on 316L Steel for Clinical Applications

SiO2 and SiO2-CaO-P2O5 coatings have been prepared by dipping electropolished stainless steel 316L samples and microscope glass slides in three different sol-gel solutions. Multilayered dense SiO2 coatings, and thick silica films obtained from equimolar contents of TEOS and MTES were used. The latter were able to strongly reduce both the corrosion attack on the steel and the iron diffusion to the sample surface. SiO2-CaO-P2O5 coatings were also obtained and applied onto the silica films, in order to provide a bioactive external surface for contact with living tissue. In-vitro evaluation of these coatings and films is discussed.     

镀液中金属杂质离子对电镀镍层性能的影响

向镍电镀原液中引入2 g/L的Co~(2+),Cr3+,Mn~(2+),Fe~(2+),Cd~(2+),Zn~(2+)等离子,通过电镀得到不同的镀层.X射线衍射(XRD)、X射线光电子能谱(XPS)及扫描电子显微镜(SEM)的结果表明,不同金属离子对镍沉积影响不同,金属杂质离子的存在会使镀层中晶粒尺寸变小,影响镍镀层的均匀性和致密度.通过阴极极化曲线、计时电位和交流阻抗等方法探讨了含有不同金属杂质的镀液在电镀过程中电化学行为的规律性.通过镀液的浓度梯度、耐腐蚀、耐热循环及耐高温等实验获得了不同条件下金属杂质在镀液中所允许的浓度范围.     

Preparation and properties of sol-gel coating films

The present state of our knowledge on sol-gel coating films has been reviewed. A qualitative discussion is made on the limit of the film thickness which can be achieved in the sol-gel method and the factors affecting the film thickness. Considering that properties of the film are intimately related to the microstructure, types of microstructures accomplished by the sol-gel coating are introduced with examples.