Determination of Iron in Zirconium by Electrolytic Dissolution and Atomic Absorption Spectroscopy

Abstract

A simple method for the determination of iron in the range of 0.01–1.00% in zirconium metal and its alloys is described. The method is based on the electrolytic dissolution of zirconium into an organic solvent and the subsequent measurement of iron by atomic absorption spectroscopy. The method is rapid, requiring 30 minutes for one measurement.     

Determimation of Cu and Fe in Hobium by Electrolytic Dissolution and Atomic Absorption Spectroscopy

Abstract

The method of electrolytic dissolution in organic solvents (saturated with NH₁Cl) followed by atomic absorption spectroscopy was applied to the determination of Fe and Cu impurities in niobium metal. It was found that a previously reported decrease in sensitivity could be attributed to precipitation of NH₄Cl on the walls of the feeding chamber of the spectrometer and could be avoided by diluting the solution before measurement.     

等离子体电解沉积的研究现状

等离子体电解沉积(PED)是一门新兴的材料表面处理技术.本文详细介绍了等离子体电解沉积的机 理及其在材料表面改性、生物材料、电子材料、高性能材料等方面的应用.其基本原理是: 当两极之间的电势差达到一定程度时, 电极与电解液界面处的电势突变产生的高电场强度, 可以击穿界面处的钝化膜、气体等电介质, 使得电极表面局部瞬间高温并发生复杂的物理、 化学反应, 从而在电极表面制备特定性能的陶瓷层或渗透层.在结构材料的应用方面, 可以 利用PED技术在铝合金、钛合金、镁合金等轻金属表面制备陶瓷层、可以对钢铁基体进行快 速碳氮共渗或涂覆金属镀层, 以提高这些材料的抗磨擦、耐腐蚀等性能.选择含有钙、磷元 素的电解液或是在电解液中添加羟基磷灰石粉末进行PED处理, 可以在钛合金表面制备具有 生物活性的陶瓷膜, 从而使植入体与自然骨形成分子水平的化学键合.选择适当的电解液, 可以制备BaTiO等离子体电解沉积;陶瓷层;表面改性;生物 材料;电子薄膜;DLC薄膜;氮化碳Plasma electrolytic deposition,Ceramic layer,Surface modification,Biomaterials,Electrolytic films,DLC films,Nitrogen-containing carbon films国家自然科学基金(50071066)2004年5月25日等离子体电解沉积(PED)是一门新兴的材料表面处理技术.本文详细介绍了等离子体电解沉积的机 理及其在材料表面改性、生物材料、电子材料、高性能材料等方面的应用.其基本原理是: 当两极之间的电势差达到一定程度时, 电极与电解液界面处的电势突变产生的高电场强度, 可以击穿界面处的钝化膜、气体等电介质, 使得电极表面局部瞬间高温并发生复杂的物理、 化学反应, 从而在电极表面制备特定性能的陶瓷层或渗透层.在结构材料的应用方面, 可以 利用PED技术在铝合金、钛合金、镁合金等轻金属表面制备陶瓷层、可以对钢铁基体进行快 速碳氮共渗或涂覆金属镀层, 以提高这些材料的抗磨擦、耐腐蚀等性能.选择含有钙、磷元 素的电解液或是在电解液中添加羟基磷灰石粉末进行PED处理, 可以在钛合金表面制备具有 生物活性的陶瓷膜, 从而使植入体与自然骨形成分子水平的化学键合.选择适当的电解液, 可以制备BaTiO等离子体电解沉积;陶瓷层;表面改性;生物 材料;电子薄膜;DLC薄膜;氮化碳Plasma electrolytic deposition,Ceramic layer,Surface modification,Biomaterials,Electrolytic films,DLC films,Nitrogen-containing carbon films国家自然科学基金(50071066)2004年5月25日等离子体电解沉积(PED)是一门新兴的材料表面处理技术.本文详细介绍了等离子体电解沉积的机 理及其在材料表面改性、生物材料、电子材料、高性能材料等方面的应用.其基本原理是: 当两极之间的电势差达到一定程度时, 电极与电解液界面处的电势突变产生的高电场强度, 可以击穿界面处的钝化膜、气体等电介质, 使得电极表面局部瞬间高温并发生复杂的物理、 化学反应, 从而在电极表面制备特定性能的陶瓷层或渗透层.在结构材料的应用方面, 可以 利用PED技术在铝合金、钛合金、镁合金等轻金属表面制备陶瓷层、可以对钢铁基体进行快 速碳氮共渗或涂覆金属镀层, 以提高这些材料的抗磨擦、耐腐蚀等性能.选择含有钙、磷元 素的电解液或是在电解液中添加羟基磷灰石粉末进行PED处理, 可以在钛合金表面制备具有 生物活性的陶瓷膜, 从而使植入体与自然骨形成分子水平的化学键合.选择适当的电解液, 可以制备BaTiO等离子体电解沉积;陶瓷层;表面改性;生物 材料;电子薄膜;DLC薄膜;氮化碳Plasma electrolytic deposition,Ceramic layer,Surface modification,Biomaterials,Electrolytic films,DLC films,Nitrogen-containing carbon films国家自然科学基金(50071066)2004年5月25日等离子体电解沉积(PED)是一门新兴的材料表面处理技术．本文详细介绍了等离子体电解沉积的机理及其在材料表面改性、生物材料、电子材料、高性能材料等方面的应用．其基本原理是：当两极之间的电势差达到一定程度时，电极与电解液界面处的电势突变产生的高电场强度，可以击穿界面处的钝化膜、气体等电介质，使得电极表面局部瞬间高温并发生复杂的物理、化学反应，从而在电极表面制备特定性能的陶瓷层或渗透层．在结构材料的应用方面，可以利用PED技术在铝合金、钛合金、镁合金等轻金属表面制备陶瓷层、可以对钢铁基体进行快速碳氮共渗或涂覆金属镀层，以提高这些材料的抗磨擦、耐腐蚀等性能．选择含有钙、磷元素的电解液或是在电解液中添加羟基磷灰石粉末进行PED处理，可以在钛合金表面制备具有生物活性的陶瓷膜，从而使植入体与自然骨形成分子水平的化学键合．选择适当的电解液，可以制备BaTiO3、SrTiO3、NaTaO3、SrZrO3等钙钛矿结构电子薄膜．利用有机溶液高电压电解，可以制备类金刚石(DLC)薄膜、氮化碳等高性能的材料．文中对PED涂层的残余应力、涂层与基体的结合力、界面断裂韧性、微观缺陷对宏观性能的影响等力学问题进行了讨论．等离子体电解沉积在轻金属特别是铝合金表面制备陶瓷层已经取得了成功，在钢铁材料的表面处理、DLC薄膜和氮化碳的制备等方面有一些初步进展，在生物活性陶瓷薄膜和电子薄膜方面也有应用前景．     

低温硫钼复合渗镀工艺及其渗镀层的综合性能考察

本文首先阐述了低温硫钼复合渗镀方法的基本原理与工艺流程,接着又对硫钼复合渗镀层的物相组成和物理性能进行了测试与分析,并且着重就其减摩性能及抗粘着磨损性能与低温电解渗硫层的作了对比试验研究和讨论,最后还通过诸多例证综合说明了硫钼复合渗镀层的实用效果明显地比电解渗硫层的好。文章指出,由于这种渗镀层的物相组成主要是FeS和MoS_2等而具有良好的自润滑性能,故其特别在干摩擦条件下的摩擦学性能更佳。不仅如此,硫钼复合渗镀工艺还具有处理温度低、时间短、操作简便、无公害和成本低廉等优点,而且被处理零件无变形,尺寸变化可以控制在6μm左右,因而适用于精密零件和刀具的处理,应用前景相当广阔。     

Characterization of oxide coatings formed on tantalum by plasma electrolytic oxidation in 12-tungstosilicic acid

Oxide coatings were formed on tantalum by plasma electrolytic oxidation (PEO) process in 12-tungstosilicic acid. The PEO process can be divided into three stages with respect to change of the voltage-time response. The contribution of electron current density in total current density during anodization results in the transformation of the slope of voltage-time curve. The surface morphology, chemical and phase composition of oxide coatings were investigated by AFM, SEM-EDX, XRD and Raman spectroscopy. Oxide coating morphology is strongly dependent of PEO time. The elemental components of PEO coatings are Ta, O, Si and W. The oxide coatings are partly crystallized and mainly composed of WO₃, Ta₂O₅ and SiO₂. Raman spectroscopy showed that the outer layer of oxide coatings formed during the PEO process is silicate tungsten bronze.     

Thermal behavior and catalytic activity in naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium

The present paper is devoted to studies of the composition and surface structure, including those after annealing at high temperatures, and catalytic activity in the reaction of naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium obtained by means of the plasma electrolytic oxidation (PEO) method. The composition and structure of the obtained systems were investigated using the methods of X-ray phase and energy dispersive analysis and scanning electron microscopy (SEM). It was demonstrated that Ce- and Zr- containing structures had relatively high thermal stability: their element and phase compositions and surface structure underwent virtually no changes after annealing in the temperature range 600-800 °C. Annealing of Ce- and Zr-containing coatings in the temperature range 850-900 °C resulted in substantial changes of their surface composition and structure: a relatively homogeneous and porous surface becomes coated by large pole-like crystals. The catalytic studies showed rather high activity of Ce- and Zr-containing coatings in the reaction of naphthalene destruction at temperatures up to 850 °C. Mn-containing structures of the type MnO_x + SiO₂ + TiO₂/Ti have a well-developed surface coated by “nano-whiskers”. The phase composition and surface structure of manganese-containing layers changes dramatically in the course of thermal treatment. After annealing above 600 °C nano-whiskers vanish with formation of molten structures on the surface. The Mn-containing oxide systems demonstrated lower conversion degrees than the Ce- and Zr-containing coatings, which can be attributed to substantial surface modification and formation of molten manganese silicates at high temperatures.     

DSC of etched aluminum foils for use in electrolytic capacitors

A DSC method for evaluating the surface area of etched Al foils for use in high performance electrolytic capacitors is presented. A linear relationship between the etching degree (effective surface area) and the thermal resistance of the sample is obtained by means of DSC, based on the transient phenomenon. This method using the transient state in DSC measurement is not only novel, but also rapid and simple in evaluating the surface area of an etched aluminum foil. The method is effective even when the Al foil has a naturally oxidized surface.The authors wish to thank to Mr. Adachi and Mr. Koike of ELNA Co., Ltd. for supplying us with etched aluminum foils. This work is partially supported by the Research Fund of North Shore College of SONY Institute. R. O. whishes to express her gratitude to the support.     

Formation of Al2O3–BaTiO3 nanocomposite oxide films on etched aluminum foil by sol–gel coating and anodizing

Barium titanate BaTiO₃ (BT) sol was dip-coated on the etched aluminum foils by a sol–gel process. After annealed at 600 °C in air, the foils were anodized in ammonium adipate solution. The voltage–time variations during anodizing were monitored. The structure, composition, and electric properties of the anodic foils were investigated. The obtained foils were fabricated into aluminum electrolytic capacitors and the load and shelf life test were measured. It was found that the slope of the voltage–time curve of aluminum foil covered with BT films became steeper. A triple layer of Al/Al₂O₃/BT was formed after anodizing Al/BT foil. The specific capacitance and the product of specific capacitance and withstanding voltage of anodic foil with a BT coating were about 46.36% and 38.90% larger than that without a BT coating. After the load life and shelf life of 2500 h at 85 °C, two kinds of capacitors have similar behaviores and meet with Nichicon standard of Japan. From the results, BaTiO₃ is promising to be used as the dielectric of aluminum electrolytic capacitor to increase the specific capacitance.     

Ti/TiO2 indicator electrodes formed by plasma electrolytic oxidation for potentiometric analysis

Ti/TiO₂ indicator electrodes were prepared by plasma electrolytic oxidation (PEO) method in the tetraborate electrolyte and were used for potentiometric indication of chemical reactions of different types and for analysis of surface and industrial wastewaters on the example of potentiometric determination of alkalinity and chloride. The electrodes formed at current densities of 0.05, 0.1, 0.15 and 0.2 A/cm² are different in composition, surface morphology and electroanalytical properties. The electrodes formed at a current density of 0.05 A/cm² exhibit the highest pH-sensitivity and generate the highest analytical signal at the equivalence point in the acid–base and precipitation titrations. The maximum analytical signal at the equivalence point, exceeding in magnitude the analytical signal, obtained by classical Pt electrode in oxidation–reduction and complexometric titrations generates PEO layers formed at a current density of 0.05 A/cm² and a platinum-modified nanoparticles. The results of the potentiometric titration of the surface and technogenic waters using as indicator Ti/TiO₂ electrodes are comparable with the conventionally used glass electrode (to determine alkalinity) and Ag electrode (to the determine chloride) and the results of visual titration. The advantage of the obtained metal oxide systems is the ability to determine two hydrochemical parameters due to their multifunctionality and opportunity to work with a single electrode. In addition, these sensors offer some analytical characteristics such as sensitivity, good reproducibility, high mechanical stability and a simple preparation procedure.     

Bioactivity Performance of Pure Mg after Plasma Electrolytic Oxidation in Silicate-Based Solutions

The biodegradable metals, including magnesium (Mg), are a convenient alternative to permanent metals but fast uncontrolled corrosion limited wide clinical application. Formation of a barrier coating on Mg alloys could be a successful strategy for the production of a stable external layer that prevents fast corrosion. Our research was aimed to develop an Mg stable oxide coating using plasma electrolytic oxidation (PEO) in silicate-based solutions. 99.9% pure Mg alloy was anodized in electrolytes contained mixtures of sodium silicate and sodium fluoride, calcium hydroxide and sodium hydroxide. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), contact angle (CA), Photoluminescence analysis and immersion tests were performed to assess structural and long-term corrosion properties of the new coating. Biocompatibility and antibacterial potential of the new coating were evaluated using U2OS cell culture and the gram-positive Staphylococcus aureus (S. aureus, strain B 918). PEO provided the formation of a porous oxide layer with relatively high roughness. It was shown that Ca(OH)₂ was a crucial compound for oxidation and surface modification of Mg implants, treated with the PEO method. The addition of Ca²⁺ ions resulted in more intense oxidation of the Mg surface and growth of the oxide layer with a higher active surface area. Cell culture experiments demonstrated appropriate cell adhesion to all investigated coatings with a significantly better proliferation rate for the samples treated in Ca(OH)₂-containing electrolyte. In contrast, NaOH-based electrolyte provided more relevant antibacterial effects but did not support cell proliferation. In conclusion, it should be noted that PEO of Mg alloy in silicate baths containing Ca(OH)₂ provided the formation of stable biocompatible oxide coatings that could be used in the development of commercial degradable implants.