应用多孔阳极氧化电流—时间曲线比较壁垒膜厚

在有壁垒膜存在的表面,多孔膜的生长在氧化初期受到延迟阻碍,这一现象在直流恒压多孔阳极氧化电流一时间曲线上反映出来。电流达到稳态氧化的时间愈长,壁垒膜愈厚。文中应用此法判断了0.5MH_3BO_3介质的pH值、温度对壁垒阳极氧化膜厚的影响,并应用记录同一介质环境壁垒恒流阳极氧化的槽压一时间曲线得到验证。     

铝质材料的摩擦学表面改性

铝质材料阳极氧化膜系均匀、规则的微观多孔质结构，利用物理、化学或电化学的方法在其中沉积或原位合成润滑性物质，在保持阳极氧化膜质硬、耐磨特性的基础上，使其具有一定的白润滑性，是近十多年来铝质材料表面改性研究的热点领域之一，本文对该研究的基本原理和国内外发展概况进行了概述，并重点介绍了我们在这一方面研究中的一些最新进展和结果，分别介绍了三种新型体系的自润滑改性阳极氧化铝材料．     

Species separation during coating growth on aluminium by spark anodizing

The mechanism of coating growth during sparking anodizing of aluminium is probed by use of an electrolyte containing both silicate and phosphate ions, with subsequent determination of the locations of silicon and phosphorus species through the coating thickness. Importantly, the main alumina-based layer of the coating contains incorporated silicon and phosphorus species of differing distributions. Phosphorus species are primarily found in a region next to the metal, representing roughly about 30% of the layer thickness. Silicon species are located mainly above this region to the layer surface. New coating material is added in discreet amounts associated with breakdown events, which provide short-circuit paths through the layer. The growth processes within the discharge region result in separation of the silicate- and phosphate-derived species, which may relate to their different mobilities, dependent upon factors such as charge, size and bonding with other species. Further, silicon-rich material is deposited at the surface of the alumina-based layer, which is often encountered in spark anodizing in silicate electrolyte.     

Development of three-electrode type micro-electrochemical reactor on anodized aluminum with photon rupture and electrochemistry

Photon rupture with a focused single pulse of pulsed YAG-laser irradiation was used to fabricate an aluminum electrochemical micro-reactor. Porous type anodic oxide film formed on aluminum specimens was irradiated in solutions with a pulsed Nd-YAG laser beam through a convex lens to fabricate micro-channels, micro-electrode, and through holes (for reference electrode, solution inlet, and outlet). During irradiation, specimens were moved by a computer controlled XYZ stage. After irradiation, the surface of the micro-channel and through hole were again treated to form anodic oxide film and the surface of the micro-electrode was treated electrochemically to provide an Au layer. The calculated volume of the micro-reactor including micro-channel and through holes is about 1.5 μl. The cyclic voltammogram of the micro-electrochemical cell was measured in K₃Fe(CN)₆/K₄Fe(CN)₆ with both static and flowing solution at different scanning rates. The anodic and cathodic peak currents were measured and the values depended on scanning rate and ion concentration when the solution was static. With the flowing solution, limiting currents were observed and the anodic limiting current was increased with the cubic root of the solution flow rate.     

Role of metal ion impurities in generation of oxygen gas within anodic alumina

The generation of oxygen gas within an amorphous anodic alumina film is reported. The film was formed by anodizing aluminum, which was first electropolished and then chemically polished in CrO₃-H₃PO₄ solution, in sodium tungstate electrolyte. The procedure results in incorporation of mobile Cr³⁺ species, from the chemical polishing film, and mobile W⁶⁺ species, from the electrolyte, into the amorphous structure. The tungsten species are present in the outer 27% of the film thickness, while Cr⁶⁺ species occupy a thin layer within the tungsten-containing region. Above the Cr³⁺ containing layer, a band develops that contains oxygen bubbles of a few nanometres size. The oxygen is generated by oxidation of O²⁻ ions of the alumina. A mechanism of oxygen generation within the alumina is proposed based on the electronic band structure of the oxide, modified by the Cr³⁺ and W⁶⁺ species, and on the ionic transport processes during oxide growth.     

Cyclic oxidation processes during anodizing of Al-Cu alloys

The influence of copper on the morphologies of porous anodic alumina has been investigated under current and voltage control using a sputtering-deposited Al-2.7 at.% Cu alloy and a commercial AA 2024-T3 aluminium alloy anodized in either sulphuric acid electrolyte or the same electrolyte but with addition of tartaric acid. The findings indicate that film development involves repeated formation of embryo cells of anodic alumina at the metal/film interface. During the initial stages of anodizing at constant voltage, cell formation is accompanied by current peaks in the current-time response. The porosity of the resultant films has a lateral aspect due to the layering of embryo cells. The thickness of individual layers is proportional to the formation voltage, with a ratio of the order 1 nm V⁻¹. The cell formation is accompanied by enrichment of copper in the alloy, incorporation of copper species into the anodic film, in low amounts relative to the alloy, and evolution of oxygen. These processes disrupt the formation of the classical pore morphology, characteristic of high purity aluminium, due to continuous formation of fresh embryo cells and re-direction of pores. The main effect of the tartaric acid addition to the sulphuric acid was to reduce the rate of anodizing of the alloys at constant voltage by about 10-20%.     

Grain orientation effects on copper enrichment and oxygen generation during anodizing of an Al-1at.%Cu alloy

Anodizing of solid-solution Al-1at.%Cu alloy in ammonium pentaborate electrolyte is shown to develop two distinct types of amorphous film. On alloy grains of {1 0 0} orientation, the alumina film is of uniform thickness and relatively featureless. For other grains, the film is of non-uniform thickness and contains oxygen bubbles. In both cases, copper species are distributed throughout the film. Copper is enriched in the alloy to ∼5.8×10¹⁵ Cu atoms cm⁻² for bubble-free grains, with similar or slightly lower levels for other grains. Evidently, copper enrichment alone does not lead to generation of oxygen. Other factors suggested to be involved, each dependent upon grain orientation, are the structure of the enriched alloy layer, the cyclic nature of the oxidation of copper, and the generation of modulated film compositions.     

Initial stages of plasma electrolytic oxidation of titanium

The initial stages of oxide growth on titanium are examined in a recently developed commercial alkaline pyrophosphate/aluminate electrolyte of interest for plasma electrolytic oxidation of light metal alloys. Constant current anodizing was employed, with resultant films examined by scanning and transmission electron microscopies and Rutherford backscattering spectroscopy. The initial film is relatively uniform and composed of TiO₂, with low concentrations of aluminium and phosphorus species incorporated from the electrolyte. With increase in voltage the film breaks down locally, and regions of original and modified film develop simultaneously, with the latter occupying more of the surface as the voltage rises. Porous regions due to dielectric breakdown also become increasingly evident. At 240 V, sparking commences, and the surface reveals extensive, relatively uniform porosity, with the coating now containing much enhanced concentrations of aluminium and phosphorus species compared with the coating at lower voltages. The films develop at low efficiency due to generation of oxygen. The oxygen is produced within the original film material and at sites of dielectric breakdown. The former type of film develops a two-layered morphology, with an outer layer of amorphous TiO₂ and an inner layer with numerous fine and course cavities. The cavities are due to the generation of oxygen that may be associated with the formation of anatase in the inner layer.     

Photoluminescence emission of nanoporous anodic aluminum oxide films prepared in phosphoric acid

The photoluminescence emission of nanoporous anodic aluminum oxide films formed in phosphoric acid is studied in order to explore their defect-based subband electronic structure. Different excitation wavelengths are used to identify most of the details of the subband states. The films are produced under different anodizing conditions to optimize their emission in the visible range. Scanning electron microscopy investigations confirm pore formation in the produced layers. Gaussian analysis of the emission data indicates that subband states change with anodizing parameters, and various point defects can be formed both in the bulk and on the surface of these nanoporous layers during anodizing.     

Functionalization of Ti6Al4V scaffolds produced by direct metal laser for biomedical applications

Direct metal laser sintering (DMLS) is a powerful tool to produce titanium based biomaterials because the ease to convert 3D medical imaging data into solid objects with excellent mechanical and corrosion properties. DMLS samples can be functionalized by anodizing, allowing the growth of titanium oxide layers of enhanced properties. In the present paper, a complete characterization of the microstructure, mechanical properties and particularly, the corrosion behavior has been carried out to assess their possible use as biomaterial. The results of the anodized scaffolds are very promising, showing a Young Modulus near to the cortical bone and a low corrosion rate, ensuring their suitability for medical applications.