A radioanalytical study of the chromate conversion coating formed on aluminium

Phosphate/chromate and accelerated chromate coatings were produced on commercially available aluminium. The Cr, P and Fe components of the conversion coatings were determined by radioactive tracer technique. The tracer technique was combined with ion-exchange and film-sectioning methods to determine the chromium (III)/total chromium ratio in the accelerated chromate coating. It was found that during the acidic dissolution of the conversion coating the chromium (III)/total chromium ratio may suffer changes. The filmforming components in the metal/bath interface are supersaturated and deposited onto the aluminium. The identified components of the accelerated chromate coatings are Cr/OH/₃, Cr/OH/CrO₄ and Cr₄[Fe/CN/₆]₃ and the chromium (III)/total chromium ratio was found to be cca. 2/3.     

Effect of Cu in electroless Ni–Cu–P coating on passivation process

Electroless Ni–P and Ni–Cu–P coatings were passivated by chromate conversion treatment respectively. The anticorrosive performances of passivated coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The passivated Ni–Cu–P coating exhibited a high corrosion resistance with the i_corr of 0.236 μA/cm,² while the value of passivated Ni–P coating was only 1.030 μA/cm,² indicating the passive film could improve the corrosion resistance of Ni–Cu–P coating to a significant extent. High‐resolution X‐ray photoelectron spectroscopy was used to determine the chemical states of elements detected in the passive film. Compared with passivated Ni–P coating, the passive film on Ni–Cu–P coating exhibited a higher ratio of Cr₂O₃ to Cr(OH)₃ with the value of 72:28, which was the main factor for passivated Ni–Cu–P coating showing excellent corrosion resistance. The effect of Cu in electroless Ni–Cu–P coating on passivation process was discussed by the contrast experiment. Copyright © 2016 John Wiley & Sons, Ltd.     

The MOF+ Technique: A Significant Synergic Effect Enables High Performance Chromate Removal

A significant synergic effect between a metal–organic framework (MOF) and Fe₂SO₄, the so‐called MOF⁺ technique, is exploited for the first time to remove toxic chromate from aqueous solutions. The results show that relative to the pristine MOF samples (no detectable chromate removal), the MOF⁺ method enables super performance, giving a 796 Cr mg g⁻¹ adsorption capacity. The value is almost eight‐fold higher than the best value of established MOF adsorbents, and the highest value of all reported porous adsorbents for such use. The adsorption mechanism, unlike the anion‐exchange process that dominates chromate removal in all other MOF adsorbents, as unveiled by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), is due to the surface formation of Fe_0.75Cr_0.25(OH)₃ nanospheres on the MOF samples.     

Preparation and adhesive properties of colored Ti/Zr-based conversion coating on aluminum foil for lithium battery packaging

In this study, an aluminum (Al) foil used for lithium ion battery packaging film was treated with titanium (Ti)/zirconium (Zr) solution containing hexafluorotitanic acid and hexafluorozirconic acid using tannic acid as a colorant and metavanadate as an accelerator, respectively, and a golden conversion coating was successfully deposited on the surface of Al foil. The morphology and composition of the coating were characterized by scanning electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy, and the hydrophilicity was assessed by contact angle measurement. The effect of Ti/Zr treatment on the adhesion properties of Al foil was evaluated by T-peeling test and compared with that of traditional chromate-phosphate treatment. The results show that tannic acid contributes to the formation of the golden coating, and metavanadate accelerates the formation of the conversion coating. The results also indicate that the Ti/Zr-based conversion coating is mainly composed of Al₂O₃, Al (OH)₃, AlF₃, TiO₂/ZrO₂, NH₄VO₃, and V₂O₅. The Ti/Zr treatment cannot only improve the heat-sealing strength, but also the T-peeling strength by approximately 12 times compared with that of untreated Al foil. Thus, Ti/Zr treatment has the potential to replace the traditional chromate conversion treatment.     

镀锡薄钢板在功能饮料中的腐蚀行为

应用电化学阻抗谱(EIS)技术,结合扫描电镜(SEM)、能量散射X射线谱(EDS)、X射线光电子能谱(XPS)、扫描探针显微镜(SPM)等表面分析技术,研究了镀锡薄钢板在功能饮料中的腐蚀过程并探讨了腐蚀机制.结果表明:浸泡前期,EIS低频阻抗模值的增加与前31 h镀锡薄钢板表面形成的腐蚀产物膜有关;随着浸泡时间的增加,EIS低频阻抗模值有所下降,这与腐蚀产物膜的部分脱落以及暴露的基底金属碳钢的腐蚀有关.镀锡薄钢板在功能饮料中浸泡24天后其表面的腐蚀产物膜由外层的富锡层和内层的富铁层组成,XPS结果表明其成分主要是Sn(Ⅱ)/Sn(Ⅳ)与柠檬酸阴离子及Fe(Ⅲ)与柠檬酸阴离子组成的化合物,其腐蚀类型主要是功能饮料中的有机酸对镀锡薄钢板的腐蚀.     

Effects of solid polymer electrolyte coating on the composition and morphology of the solid electrolyte interphase on Sn anodes

In order to discuss the effect of polymer coating layer on the Sn anode, the composition and morphology of the solid electrolyte interphase (SEI) film on the surface of Sn and Sn@PEO anode materials have been investigated. Compared with the bare cycled Sn electrode, the SEI on the surface of cycled Sn@PEO electrode is thinner, smoother, and more stable. Therefore, the Sn@PEO nanoparticles can basically keep the original appearance during cycling. Based on the results obtained from X-ray photoelectron spectroscopy (XPS), the SEI formed on the Sn@PEO electrode is characterized by inorganic components (Li₂CO₃)-rich outer layer and organic components-rich inner which could make the SEI more stable and inhibit the electrolyte immerging into the active materials. In particular, the elastic ion-conductive polyethylene oxide (PEO) coating could increase the toughness of SEI and allow the SEI to endure the stress variation in repetitive lithium insertion and extraction process. As a result, the Sn@PEO electrodes show significantly better capacity retention than bare Sn electrodes. The findings can serve as the theoretical foundation for the design of lithium-ion battery electrode with high energy density and long cycle life.     

Dispersed platinum and tin polyaniline film electrodes for the anodes of the direct methanol fuel cell

To develop better and cheaper electrocatalysts for the oxidation of methanol in direct methanol fuel cells, several combinations of a conductive polymer polyaniline (PANI) and dispersed metal particles such as Pt and Sn were examined. The anodic current for the methanol oxidation (i _MeOH) showing the electrocatalytic activity of Pt particles was remarkably enhanced when the particles were dispersed on PANI films that should provide higher surface areas for the dispersed particles. The activity strongly depended on the morphology and the electric conductivity of the PANI films electropolymerized in five different acid solutions: H₂SO₄, HNO₃, HClO₄, HBF₄, and HCl. The highest activity was achieved using the dispersed Pt particle on PANI film electropolymerized from H₂SO₄ polymerizing solution. In order to reduce the dispersed amount of the expensive Pt particles, other metal particles were pre-dispersed on the PANI film prepared from the H₂SO₄ polymerizing solution, and then Pt particles were dispersed on the film. Among the pre-dispersed metal particles attempted here (Sn, Cu, Cr, Ni, In, Co, Sb, Bi, Pb, and Mn), the highest activity was obtained with Sn particles. When the ratio of dispersed Pt to Sn particles ranges from 32:68 to 100:0, i _MeOH is higher than that measured with the dispersed Pt particle on PANI films without the Sn particles. This means that the dispersed amount of the Pt particles could be reduced by utilizing dispersed Sn particles.     

XPS和AES研究锡表面的防变色膜

通过比较多种防锡变色剂的防变色效果,发现乙二胺四甲叉膦酸(EDTMP)是一种优良的防锡变色剂。用XPS、AES及Raman光谱探讨了EDTMP的防变色机理,结果表明EDTMP在锡表面形成了一种耐蚀性保护膜。在深度剖析曲线的元素组成近似恒定区测得膜的相对原子浓度(A.C.％)为:O 48.0％;Sn 10.7％;N 7.7％;C 23.1％;P 10.5％。     

A novel spinel coating on cobalt‐based Superalloy GH605 via an in‐situ oxidation approach

Cr‐Mn‐O spinel coating was prepared on the surface of cobalt‐based superalloy GH605 via an in‐situ oxidation method in H₂O‐H₂ environment. The composition, morphology, and chemical value state of the oxide spinel coatings were investigated by SEM, EDS, XRD, Raman spectra, and XPS. It indicated that the morphology of coating varied with oxidation temperature, and granular surface appeared when oxidation temperature increased to 1100°C. The formed Cr‐Mn‐O spinel coating was composed of Cr₂O₃ and MnCr₂O₄, and the thickness increased significantly with oxidation temperature. In the coating, Cr element existed in the state of Cr³⁺ ions and Cr⁶⁺ ions, while Mn element only existed in the form of Mn²⁺ ions.     

Stability of chromium dioxide particles in aqueous media

An investigation was carried out to characterize the dissolution behavior of stabilized and unstabilized CrO₂ particles in water, used in magnetic recording. Special attention was paid to the measurement of Cr(VI) concentration in the contact solution and to the elucidation of the effects of the stabilizing treatment by x-ray photoelectron spectroscopy (XPS). The experimental results indicate that both stabilized and unstabilized CrO₂ particles predominantly release hexavalent chromium when in contact with water. The solubility of freshly stabilized CrO₂ is considerably smaller than that of unstabilized CrO₂, but the difference in solubility diminishes with aged particles. The XPS study indicated that stabilization of CrO₂ particles with a bisulfite solution results in the formation of Cr₂O₃ or a Cr₂O₃-like product on the particle. However, it appears that Cr(III) oxide coating does not uniformly form on all particles.     

表面修饰的TiO_2太阳能电池界面特性研究

用水热法制备了具有典型锐钛矿晶型的TiO2纳米材料,采用Cr(NO3)3对TiO2薄膜电极进行修饰改性。用X射线衍射(XRD)、扫描电子显微镜(SEM)和光电子能谱(XPS)测试电极的物相及表面结构,结果显示TiO2薄膜表面包覆一层粒径较大的氧化铬颗粒,整个电极仍保持均匀的多孔结构。电流-电压(I-V)曲线测试结果显示,改性后最佳电极的短路电流和光电转换效率分别比改性前提高了31.1%和40.4%。用电化学阻抗谱(EIS)测试电池的界面特性,从测试结果可以看出,相同偏压下,改性后电池的TiO2/染料/电解质界面电阻更大,说明氧化铬包覆层在一定程度上抑制了界面的电子复合,改善了电池的光电输出特性。     

铭酸溶液中金属铬电沉积的机理

从铬酸溶液中电沉积金属铬的机理曾经有过不少探索.许多研究者认为,阴极表面形成难溶的膜层金属铬的电沉积起着关键性的作用.本文应用交流阻抗谱研究金属铬电沉积过程中阴极表面膜的形成,利用X光电子能谱(XPS)和俄歇电子能谱(AES)分析了表面膜的组成,并且对SO_4~(2-)的作用进行了初步的探讨。     

In Vitro Reduction of Hexavalent Chromium by Cytoplasmic Fractions of <Emphasis Type="Italic">Pannonibacter phragmitetus</Emphasis> LSSE-09 under Aerobic and Anaerobic Conditions

Hexavalent chromate reductase was characterized and was found to be localized in the cytoplasmic fraction of a chromium-resistant bacterium Pannonibacter phragmitetus LSSE-09. The Cr(VI) reductase activity of cell-free extract (S₁₂) was significantly improved by external electron donors, such as NADH, glucose, acetate, formate, citrate, pyruvate, and lactate. The reductase activity was optimal at pH 7.0 with NADH as the electron donor. The aerobic and anaerobic Cr(VI)-reduction enhanced by 0.1 mM NADH were respectively 3.5 and 3.4 times as high as that without adding NADH. The Cr(VI) reductase activity was inhibited by Mn²⁺, Cd²⁺, Fe³⁺, and Hg²⁺, whereas Cu²⁺ enhanced the chromate reductase activity by 29% aerobically and 33% anaerobically. The aerobic and anaerobic specific Michaelis–Menten constant K _m of S₁₂ fraction was estimated to be 64.95 and 47.65 μmol L⁻¹, respectively. The soluble S₁₅₀ fractions showed similar activity to S₁₂ and could reduce 39.7% and 53.4% of Cr(VI) after 1 h of incubation aerobically and anaerobically while the periplasmic contents showed no obvious reduction activity, suggesting an effective enzymatic mechanism of Cr(VI) reduction in the cytoplasmic fractions of the bacterium. Results suggest that the enzymatic reduction of Cr(VI) could be useful for Cr(VI) detoxification in wastewater.     

Conversion‐coating treatment applied to in situ TiB2p reinforced Al?Si‐alloy composite for corrosion protection

In this work, continuous conversion coatings on the surface of in situ TiB₂ particulate reinforced A356 composite were formed successfully by cerium surface treatment for the first time. Scanning electron microscope (SEM) analysis showed that the conversion coatings were inhomogeneous and could be divided into two types of regions, namely, fine crack region and noncrack region. Many cerium‐rich nano‐nodules were uniformly distributed in the whole coatings. Energy dispersive spectroscopy (EDS) analysis testified that the crack coatings mainly covered the interdendritic sites occupied by TiB₂ particulates and Si phases. X‐ray photoelectron spectroscopy (XPS) analysis indicated that the conversion coatings were composed of CeO₂, Ce₂O₃, Ce(OH)₄, Ce(OH)₃, and a little amount of Al₂O₃. The electrochemical polarization tests showed that the cerium‐conversion treatment markedly improved the corrosion resistance of in situ TiB_2p/A356 composite in chloride environment, and the protection degree of the coatings was superior to that of conventional chromate‐conversion coating. According to these results, the formation mechanism of cerium‐conversion coatings was discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Formation of Cr(VI) compounds during the thermal decomposition of amorphous chromium hydroxide

Chromium hydroxide (CH) was prepared by the reduction of purified sodium chromate using starch. CH was then used to prepare chromium oxide (Cr₂O₃). Results of thermogravimetric, X-ray diffraction, Fourier transform infrared spectroscopy, and chemical analyses suggested that a small amount of the initial Cr(VI) content speeds up the oxidation and reduction reactions, thereby promoting the purity and crystallization of Cr₂O₃. Cr(VI) in CH induced the evolution of CH and the formation of Cr(VI) containing compounds including CrO₃, NaCr(CrO₄)₂, Cr₃O₈, and Cr₅O₁₂ at low sintering temperature. Furthermore, homogeneous Cr₂O₃ nanoparticles with 99 % purity and particle size of 50 nm were obtained.     

Molecular structures of [(Ph3Sn)2O3Se] and [(Ph3Sn)2O4Cr](CH3OH)

Molecular structures of [(Ph₃Sn)₂O₃Se] (1) and [(Ph₃Sn)₂O₄Cr](CH₃OH) (2) have been determined using spectroscopic techniques and X-ray analysis. Each structure consists of polymers containing two types of tin centres: one of them is bridged by two oxygen atoms of the trifunctional oxyanion into a helical chain while the other is pendant to this chain. In the case of the chromato derivative the pendant tin is also bonded to the oxygen atom of the solvent (methanol); hydrogen bonds between the methanol and the non-coordinated oxygen of the chromate generate a three-dimensional structure containing tin atoms in a trigonal bipyramidal environment. In contrast, the two tin centres in the non-solvated selenito derivative have distinct geometries (tetrahedral and trigonal bipyramidal). Variable temperature Mössbauer spectroscopy data are consistent with the polymeric structure of the selenito derivative while NMR spectroscopy shows the presence of monomeric species in solution.     

Influence of metallurgy on the protective mechanism of chromium-based conversion coatings on aluminum–copper alloys

Several important aspects relating to the mechanism of formation of protective Cr-based oxide films on aluminum alloy 2024-T3 generated from CrO₃ + NaF-containing solutions were observed with electrochemical, AES and XPS measurements. Although the film deposition rate and surface composition were very much influenced by the presence of both Fe- and Cu-containing intermetallic phases, a uniform composition and thickness was eventually reached with increased coating time. This behavior is believed to be responsible for obtaining corrosion-resistant films on such heterogeneous surfaces. Surface Cr was consistently found to be in both the 3+ and 6+ oxidation states in an approximately 40:60 ration, respectively, if x-ray beam reduction of Cr(VI) was accounted for. The enriched Cu layer found on the surface of polished 2024-T3 was found to remain intact during Cr O film formation. The presence of Cr(VI) provides a ‘self-healing’ aspect to the film's protective mechanism by remaining available for reduction to Cr(III) during oxidative attack. Addition of potassium ferro- or ferricyanide to the bath resulted in a film which obtained Fe, C and N enriched at the surface on both the matrix and intermetallic regions. These constituents were found, however, to be enriched and distributed throughout the entire depth of the film on the high Cu-bearing intermetallic regions, suggesting that the formation of a Cu–ferrocyanide complex is responsible for the benefit derived from these compounds.     

Two-Layer Nano-Oxide Composite Films on Fe-18Cr Alloys

A two-layer film composed of a reactive element (RE) oxide (ZrO₂, Y₂O₃, CeO₂, or La₂O₃) and aluminum oxide (Al₂O₃) was prepared on the surface of Fe-18Cr alloys by an electrochemical process combined with sintering. High-resolution field emission scanning electron microscopy (FE-SEM) was used to characterize the two-layer film, which showed nanostructure. SEM, EDS and mass gain measurement were used to study the oxidation resistance of the film on Fe-18Cr alloy. It is proved that this kind of film is effective in protecting the substrate from oxidation. The results also indicated that the two-layer film possesses superior oxidation resistance than a single Al₂O₃ film. The mechanisms accounting for such effects have been discussed.     

Organotin(IV) isothiocyanatochromates

Summary Several new compounds of the type [R₃Sn]₃[Cr(NCS)₆] and [R₃Sn][Cr(NCS)₄L₂], where R = Ph or n-Bu and L = NH₃, PhNH₂ or CO(NH₂)₂, have been synthesized and characterized by analytical data, i.r. and electronic spectral studies. Conductance measurements indicate that the compounds are ionic.