Preferential anodic oxidation of second‐phase constituents during anodising of AA2024‐T3 and AA7075‐T6 alloys

Model analogues of the metallurgical phases found in 2xxx and 7xxx series aluminium alloys were produced by magnetron sputtering and employed to investigate the local and general anodising behaviour of the alloys. Electrochemical tests, allied with scanning and transmission electron microscopy, enabled insight into the local anodising behaviour of the constituents and related effects on the overall porous oxide morphology. Under potentiodynamic conditions, the observed anodic current peaks of the commercial alloys were related with the anodic oxidation of specific second‐phase particles. At 0 V, magnesium‐containing particles, including S‐phase, were preferentially removed from the alloy surface; at 5–6 V_SCE, the copper‐ and/or iron‐containing particles, such as θ phase and Al₇Cu₂Fe particles were anodically oxidised. The initial voltage transient revealed for the commercial alloys during galvanostatic anodising was related to the previous findings and reproduced by the use of coupled alloy analogues. Transmission electron microscopy revealed that the voltage transient associated with oxidation of second‐phase material influence the morphology of the anodic film formed on the aluminium matrix. Copyright © 2010 John Wiley & Sons, Ltd.     

Performance of Al alloys following excimer LSM—anodising approaches

The potential application of laser surface melting (LSM) as a pre‐treatment prior to conventional anodising in sulfuric acid electrolyte has been evaluated. For this purpose, AA2050‐T8 (Al? Cu? Li) and AA2024‐T351 (Al? Cu? Mg) aerospace alloys were compared. For LSM, a KrF excimer laser (248 nm) was used, with variation of the number of pulses received per unit area. After LSM, the specimens were anodised at a constant voltage of 12 V in 0.46 M H₂SO₄ for different times from 4 to 20 min, followed by sealing in boiling water for 30 min. Material characterisation, in terms of surface morphology, microstructural and laser‐induced phase transformations, was performed using scanning and transmission electron microscopies (TEMs). The corrosion behaviour was evaluated using the ASTM G34‐01 EXCO test at 25 °C for 6 h. The results showed that excimer LSM, used as a pre‐treatment prior to anodising, greatly improved the anodising performance, through the dissolution of intermetallic phases in the near‐surface alloy. Further, different exfoliation susceptibility was observed by comparing both alloys, being strongly dependent on the presence and distribution of the main constituent phases, e.g. T₁ (Al₂CuLi) and S (Al₂CuMg) phases, for AA2050‐T8 and AA2024‐T351, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Novel use of glow discharge optical emission spectroscopy (GDOES) to study corrosion of AA2024‐T3 in the presence and absence of inhibitors – part 3: investigating the effects of various proportions of inhibitor in the coating matrix or in nanocontainers

Elemental depth profiling by glow discharge optical emission spectroscopy has been used to characterize the corrosion products on AA2024‐T3. In previous work, the aluminium, oxygen and copper depth profiles were shown to provide information regarding surface roughening, the thickness of corroded layers and extent of copper de‐alloying/relocation. Nitrogen, sulfur, phosphorus and chromium depth profiles were examined in the hope of detecting inhibitor species within the corroded/altered layers after 5 h of exposure to a corrosive solution. In the present work, the study is extended to longer exposure time. The work presents a further study of the leaching of benzotriazole from the coating matrix or from nanocontainers during various times of exposure to a corrosive environment. Copyright © 2016 John Wiley & Sons, Ltd.     

Effectiveness of 2‐mercaptobenzothiazole, 8‐hydroxyquinoline and benzotriazole as corrosion inhibitors on AA 2024‐T3 assessed by electrochemical methods

In this study, the effectiveness of 2‐mercaptobenzothiazole (2‐MBT), 8‐hydroxyquinoline and benzotriazole as corrosion inhibitors for AA 2024‐T3 aluminium alloy was evaluated. The corrosion behaviour in the presence of each compound was investigated by image‐assisted electrochemical noise analysis, electrochemical impedance spectroscopy, potentiodynamic polarization and the split cell technique. It was found that 2‐MBT has superior inhibition properties compared with the other inhibitors. In particular, the specimens immersed in 3.5% NaCl in the presence of 2‐MBT displayed high values of noise resistance that were maintained for over 400 h of testing, and high values of low‐frequency impedance, measured after immersion for 24 h. The split cell technique and potentiodynamic polarization tests indicated that only 2‐MBT decreases significantly both the anodic and the cathodic reaction rates. Scanning electron microscopy observations and energy dispersive X‐ray measurements complement the findings from electrochemical measurements indicating that only 2‐MBT protects the second phase particles, preventing dealloying, trenching and initiation of corrosion. © 2015 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd.     

Simple preparation routes for corrosion protection hybrid sol‐gel coatings on AA 2024

In recent years, many hybrid inorganic‐organic systems have been proposed in order to replace the traditional conversion coatings on metals like aluminum, and some results have been promising. However, many proposed solutions are based on complicated processes which are not easy to be adapted to industrial scale. The aim of this study was to establish a simple process leading to the production of highly efficient corrosion protective hybrid sol‐gel coating systems for the aluminum alloys as replacement for the highly hazardous conventional chromate conversion coatings. Hybrid coatings have been realized by means of the sol‐gel process. CeO₂ and ZnO have been introduced as dispersions of nanoparticles in the system and used as corrosion inhibitors. The aim of this work was to obtain pore‐free coatings with increased barrier properties using nanoparticles that possess the double function of pore fillers and corrosion inhibitors. The proposed processes led to coating materials with good adherence to the aluminum substrate and an extremely long life in the accelerated neutral salt spray test according to DIN ISO 9227. Electrochemical impedance spectroscopy approves these results by high impedance values in the low‐frequency region of the Bode plot. Copyright © 2011 John Wiley & Sons, Ltd.     

Boronic Acid Functionalized Core–Satellite Composite Nanoparticles for Advanced Enrichment of Glycopeptides and Glycoproteins

A core–satellite‐structured composite material has been successfully synthesized for capturing glycosylated peptides or proteins. This novel hybrid material is composed of a silica‐coated ferrite “core” and numerous “satellites” of gold nanoparticles with lots of “anchors”. The anchor, 3‐aminophenylboronic acid, designed for capturing target molecules, is highly specific toward glycosylated species. The long organic chains bridging the gold surface and the anchors could reduce the steric hindrance among the bound molecules and suppress nonspecific bindings. Due to the excellent structure of the current material, the trap‐and‐release enrichment of glycosylated samples is quite simple, specific, and effective. Indeed, the composite nanoparticles could be used for enriching glycosylated peptides and proteins with very low concentrations, and the enriched samples can be easily separated from bulk solution by a magnet. By using this strategy, the recovery of glycopeptides and glycoproteins after enrichment were found to be 85.9 and 71.6 % separately, whereas the adsorption capacity of the composite nanoparticles was proven to be more than 79 mg of glycoproteins per gram of the material. Moreover, the new composite nanoparticles were applied to enrich glycosylated proteins from human colorectal cancer tissues for identification of N‐glycosylation sites. In all, 194 unique glycosylation sites mapped to 155 different glycoproteins have been identified, of which 165 sites (85.1 %) were newly identified.     

Effect of AA2024‐T3 surface pretreatment on the physicochemical properties and the anticorrosion performance of poly(γ‐glycidoxypropyltrimethoxysilane) sol‐gel coating

This study investigated the dependence of the anticorrosion performance of a poly(γ‐glycidoxypropyltrimethoxysilane) (poly(γ‐GPTMS)) sol‐gel coating on AA2024‐T3 aluminum alloy surface state. Two different AA2024‐T3 surface pretreatment procedures were tested: a degreasing with acetone and a chemical multistep etching process (industrial chemical etching pretreatment). Poly(γ‐GPTMS) coatings were deposited onto both pretreated surfaces using the dip‐coating technique. Surfaces were characterized principally by scanning electron microscopy, X‐ray photoelectron spectroscopy, Fourier transform infrared attenuated total reflectance, contact angles, and roughness measurements. Moreover, for the coated AA2024‐T3 surfaces, a pull‐off test was used to evaluate the poly(γ‐GPTMS) adhesion to the pretreated surface. Bare surface properties depended on the applied pretreatment. The chemically etched surface was the roughest and the most concentrated in hydroxyl groups. In addition, comparatively to the degreased surface, it has a more hydrophobic character. Poly(γ‐GPTMS) coating revealed an uneven nature and a poor adhesion once it was deposited onto the degreased surface. Coatings anticorrosion performances were evaluated using electrochemical impedance spectroscopy measurements (EIS). Electrochemical impedance spectroscopy data proved that the sol‐gel coating applied onto the chemically etched surface had better anticorrosion performance.     

Sheet AA2024‐T3: a new investigation of microstructure and composition

Sheet AA2024‐T3 is probably one of the most studied aluminium alloys in the corrosion field, because, with copper as an alloying addition, it is one of the most corrosion‐prone aluminium alloys. This paper reports new findings on the composition and distribution of intermetallic (IM) particles in AA2024‐T3 through the examination of over 80 000 compositional domains in nearly 18 000 IM particles. This work was achieved by using an electron microprobe to map out 2 × 2 mm² at a step size of 400 nm. This study revealed that the composition of individual particles can vary considerably from ‘accepted’ compositions. Domains within particles were extensive across the surface. Because such a large area was mapped, it was possible to subdivide this area and to look at the variation of particle statistics from region to region, providing some information on the statistical variation for small electrodes. Copyright © 2010 John Wiley & Sons, Ltd.     

An investigation of rare earth chloride mixtures: combinatorial optimisation for AA2024‐t3 corrosion inhibition

Rare earth (lanthanides) cations have demonstrated exceptional activity as cathodic corrosion inhibitors for aluminium alloys (AAs). While Ce is generally regarded as the most active, there have been reports of synergistic interactions between mixtures of rare earths, which show increased inhibitive activity. In this study a combinatorial experimental approach was used to evaluate the corrosion inhibition of four rare earth chlorides (Ce, La, Pr, Nd) singly and as mixtures. The estimation of corrosion currents using both potentiodynamic scans and electrochemical impedance spectroscopy (EIS) provided the quantification of corrosion inhibition. The results were then modelled to determine the best predicted inhibition activity. A partial least squares (PLS) regression indicated that the optimal response directly correlated with the amount of Ce present. From the regression analysis, Ce alone demonstrated the best inhibition activity, with the optimum mixture predicted to contain 100% Ce. The addition of La, Pr or Nd, was not observed to improve the inhibition activity. This study represents one of the first applications of combinatorial design to a fundamental question of corrosion inhibition. Copyright © 2010 John Wiley & Sons, Ltd.     

Novel use of glow discharge optical emission spectroscopy (GDOES) to study corrosion of AA2024‐T3 in the presence and absence of inhibitors

Recent interest in environmentally friendly alternatives to chromate‐based corrosion inhibitors has led to the development of a range of novel coating formulations. The work described herein is aimed at developing a novel methodology to contribute to investigation of the self‐healing and active corrosion protection of the new coatings. An experimental procedure has been developed to model a defect in the coating by fixing coated specimens in close proximity to the uncoated AA2024‐T3, each separated by a narrow gap containing sodium chloride solution. After exposure to the corrosive environment, elemental depth profiles of the uncoated specimens were acquired by glow discharge optical emission spectroscopy (GDOES). The depth profiles of selected elements (notably aluminium, oxygen and copper) were shown to have characteristics which can be correlated with bulk surface roughening/intensity of corrosion, the thickness of the corroded layer and de‐alloying/re‐distribution of copper. An unanticipated inhibitory effect was noted in the case of a coating doped with γ‐Al₂O₃ (γ‐alumina or AluOx). Copyright © 2015 John Wiley & Sons, Ltd.     

Enrichment of copper and nickel with solid phase extraction using multiwalled carbon nanotubes modified with Schiff bases

The behaviour of some Schiff bases in the presence of metal ions is very selective in complex formation. In this study, new, selective and easily prepared adsorbent materials have been developed. Multiwalled carbon nanotubes (MWCNTs) are quite suitable as supporting material for preparation of new solid phase adsorbents modified with Schiff bases due to their selective nature. Different Schiff bases were designed and synthesised as adsorbent agents for Ni(II) and Cu(II) ions, according to the literature, and MWCNTs were modified with these Schiff bases. The modification of CNTs was performed by adsorption from the alcoholic solution of Schiff base. The measurements of Ni(II) and Cu(II) ions were carried out using ICP-MS. Different parameters such as pH, model and eluent solution flow rates, eluent type, amount of ligand, sample volume and effect of foreign ions, which have an effect upon recovery of analytes, were investigated. The obtained results indicated that enrichment can be done with six modified adsorbent materials for Cu(II) at pH 9 and two modified adsorbent materials for Ni(II) at pH 8. It was concluded that four adsorbent materials were selective only for the enrichment of Cu(II). Merely one modified adsorbent material was noneligible for the enrichment of Cu(II) and Ni(II). The solid phase adsorbents prepared by modification with two of the Schiff bases used in this study showed an enrichment factor of 80 for both metal ions, whereas the solid phase adsorbents prepared by modification with four of the Schiff bases showed an enrichment factor of 40 for Cu(II) ions. The confirmation of the developed method was tested with certified reference materials with satisfactory results.     

基于纳米粒子的糖蛋白/糖肽分离富集方法

蛋白质糖基化是一种重要的蛋白质翻译后修饰方式,糖基化对蛋白质的结构和功能有着非常重要的影响。在血清或者组织提取液中,一些低浓度的糖蛋白/糖肽是具有高度临床灵敏性和特异性的生物标记物,这些生物分子可能对疾病发生机理探讨、疾病标记物发现及蛋白类新药开发提供重要信息。由于糖蛋白/糖肽的丰度低,从复杂的生物样品中高选择性富集糖蛋白/糖肽一直是糖蛋白组学的难点和重点。纳米结构的材料因其大比表面积、丰富的活性亲和位点和特殊结构,已经广泛应用于糖蛋白/糖肽的分离富集中。本文对基于金、SiO₂、TiO₂、Fe₃O₄、金刚石和聚合物纳米粒子为载体的糖蛋白/糖肽分离富集方法的研究进展作了简要概述,并且阐明了糖蛋白/糖肽分离富集方法所面临的挑战,最后,对其未来发展方向做了展望。     

Enrichment specificity of micro and nano‐sized titanium and zirconium dioxides particles in phosphopeptide mapping

Owning to their anion‐exchange properties, titanium and zirconium dioxides are widely used in phosphopeptide enrichment and purification protocols. The physical and chemical characteristics of the particles can significantly influence the loading capacity, the capture efficiency and phosphopeptide specificity and thus the outcome of the analyses. Although there are a number of protocols and commercial kits available for phosphopeptide purification, little data are found in the literature on the choice of the enrichment media. Here, we studied the influence of particle size on the affinity capture of phosphopeptides by TiO₂ and ZrO₂. Bovine milk casein derived phosphopeptides were enriched by micro and nanoparticles using a single‐tube in‐solution protocol at different peptide‐to‐beads ratio ranging from 1 : 1 to 1 : 200. Unsupervised hierarchical cluster analysis based on the whole set of Matrix Assisted Laser Desorption/Ionization time‐of‐flight mass spectra of the phosphopeptide enriched samples revealed 62 clustered peptide peaks and shows that nanoparticles have considerably higher enrichment capacity than bulk microparticles. Moreover, ZrO₂ particles have higher enrichment capacity than TiO₂. The selectivity and specificity of the enrichment was studied by monitoring the ion abundances of monophosphorylated, multiphosphorylated and non‐phosphorylated casein‐derived peptide peaks at different peptide‐to‐beads ratios. Comparison of the resulting plots enabled the determination of the optimal peptide‐to‐beads ratios for the different beads studied and showed that nano‐TiO₂ have higher selectivity for phosphopeptides than nano‐ZrO₂ particles. Copyright © 2013 John Wiley & Sons, Ltd.     

硫化铜空心纳米球的融硫修饰及其对水中Hg^2+的高选择性吸附富集

通过简单便捷的方法合成出了单质硫改性的CuS空心球纳米材料(CuS@S HSs),并研究了该材料对水中典型重金属污染物Hg^2+的吸附富集性能及机理。研究结果表明,当硫的投料质量比值(wS/wCuS))为30%时,CuS@S HSs对Hg^2+的吸附量高达1207mg·g^-1,较未负载单质硫时提高了229%。CuS@S HSs可以在15 min内将水中超过99%的Hg^2+富集分离。最重要的是,在多种重金属离子(Pb^2+、Ni^2+、Cd^2+、Cr^3+)共存的情况下,CuS@S HSs对Hg^2+表现出优异的单一选择吸附性。     

Studies on the repassivation behavior of aluminum and aluminum alloy exposed to chromate solutions

This study explores the repassivation ability of a scratch in a chromate conversion coating (CCC) on aluminum alloy, AA2024‐T3, and hence evaluates the theory of migration of hexavalent chromium ions from the protected surface of the aluminum alloy to the exposed surface. To confirm that protection was indeed restored by hexavalent chromium ions, the repassivation of a scratch on pure aluminum exposed to a dichromate solution was studied. This forms the simplest subsystem model of the CCC on the alloy in which the CCC is replaced by pure hexavalent chromium and alloy with pure aluminum. Open‐circuit potential measurements, synchrotron infrared microspectroscopy (SIRMS) and secondary ion mass spectroscopy (SIMS) have been used judiciously to evaluate the repassivation behavior. Results indicate that the dichromate ions have high mobility. The slow migration of Cr(VI) ions from the protected surface to the scratch is observed to result in repassivation, as seen from the steady increase in the potential in 0.05 M NaCl solution. The results obtained from SIMS and SIRMS confirm the migration of the oxyanions from the protected region to the metal surface exposed by the scratch. The SIRMS results indicate the formation of an Al(III)–Cr(VI) complex, proposed and shown to be formed in the pits. Copyright © 2003 John Wiley & Sons, Ltd.     

A Highly Active and Magnetically Recoverable Tris(triazolyl)–CuI Catalyst for Alkyne–Azide Cycloaddition Reactions

Nanoparticle‐supported tris(triazolyl)–CuBr, with a diameter of approximately 25 nm measured by TEM spectroscopy, has been easily prepared, and its catalytic activity was evaluated in the copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction. In initial experiments, 0.5 mol % loading successfully promoted the CuAAC reaction between benzyl azide and phenylacetylene, in water at room temperature (25 °C). During this process, the iron oxide nanoparticle‐supported tris(triazolyl)–CuBr displayed good monodispersity, excellent recoverability, and outstanding reusability. Indeed, it was simply collected and separated from the reaction medium by using an external magnet, then used for another five catalytic cycles without significant loss of catalytic activity. Inductively coupled plasma (ICP) analysis for the first cycle revealed that the amount of copper leached from the catalyst into the reaction medium is negligible (1.5 ppm). The substrate scope has been examined, and it was found that the procedure can be successfully extended to various organic azides and alkynes and can also be applied to the one‐pot synthesis of triazoles, through a cascade reaction involving benzyl bromides, alkynes, and sodium azide. In addition, the catalyst was shown to be an efficient CuAAC catalyst for the synthesis of allyl‐ and TEG‐ended (TEG=triethylene glycol) 27‐branch dendrimers.     

液膜富集高纯稀土氧化物中痕量铜钴镍钙镁

本文建立了用Ｐ２０４－Ｎ２０５－煤油－ＨＣＬ－Ｈ２ＳＯ４液膜体系分离富集了高纯稀土氧化物中铜、钴、镍、钙、镁等杂元素的方法，并与火焰原子吸收相结合，测定氧化镱、氧化轧等样品中的杂质元素，结果令人满意。     

Investigation of molybdate–benzotriazole surface treatment against copper tarnishing

The synergistic effect of benzotriazole (BTAH) and molybdate on the inhibition of copper tarnish was studied in this paper. The antitarnish treatment of copper was conducted with BTAH solution containing molybdate. The surface morphology observation and composition analysis were investigated by SEM with energy dispersive X‐ray (EDX) spectroscopy. The addition of molybdate improved the protection of BTAH significantly. The BTAH + molybdate treated copper specimen has higher N concentration in its surface. The structure of the protective film was studied by XPS and AES measurements. It was characterized to be a complex of Cu(I)BTA. The antitarnish effect is certified by the formation of the protective Cu(I)BTA film. Molybdate does not participate in the formation of the protective film. The presence of molybdate promotes the passivation of copper. This facilitates the stabilization of the cuprous oxide film, and strengthens the adsorption of BTAH. Copyright © 2008 John Wiley & Sons, Ltd.     

SiO2介导的5 nm金颗粒的高效富集及其催化活性研究

粒径小于10 nm的金纳米颗粒（Au NPs）具有高的表面积与体积比,因此具有极强的催化活性,在催化领域应用广泛.传统湿法合成的金纳米颗粒浓度过低,需要进一步富集才能满足实验要求.然而,小粒径Au NPs在浓缩过程中容易聚集,失去催化活性.在保持催化活性的同时,浓缩小粒径的AuNPs是一个挑战.本工作用500 nm硅烷化修饰的SiO₂颗粒,通过静电相互作用吸附5 nm Au NPs,在室温下自组装形成Au NPs@SiO₂复合物.Au NPs的负载效率可达99.5%,每个SiO₂上负载的Au NPs高达800～1000个,大大提高了Au NPs有效浓度,并且富集到SiO₂表面的Au NPs不会团聚.催化活性研究结果显示,制备得到的Au NPs@SiO₂的催化活性是同浓度Au NPs的3倍.该复合物颗粒重复使用5次后,催化转换效率仍能保持在80%左右.该复合物颗粒能稳定保存一个月,结构和催化活性不变.并且,通过调节Au NPs在SiO₂表面的组装密度,可精确调控Au NPs@SiO₂催化活性.本工作提供了一种制备高浓度小粒径Au NPs的简单方法,并大大提高了Au NPs催化活性,该方法在富集其它小粒径纳米颗粒中具有广泛应用.     

Immobilization of copper nanoparticles on WO3 with enhanced catalytic activity for the synthesis of 1,2,3-triazoles

In this study, a heterogeneous catalyst based on copper nanoparticles immobilized on metal oxide, WO₃, was fabricated using an impregnation method as an easy and straightforward nanoparticle synthesis strategy. The successful synthesis of the nanocatalyst was confirmed using various spectroscopic techniques such as X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, and transmission electron microscopy. The catalytic performance of the well-characterized material was evaluated through the azide–alkyne cycloaddition reaction (click reaction) in the aqueous medium. To optimize reaction conditions, different reaction parameters such as nanocatalyst amount, reaction time, temperature, and solvents were studied. Experimental results showed that as-prepared nanocatalyst (Cu/WO₃) could act as an effective and reusable heterogeneous catalyst in water for the synthesis of 1,2,3-triazoles in good-to-excellent yields. In addition, Cu/WO₃ has some advantages such as simple preparation procedure, easy separation, and recyclability for three runs with no remarkable loss of catalytic activity, which is essential from a catalytic application point of view.