Electrodeposition and characterization of Zn–Sn alloy coatings from a deep eutectic solvent based on choline chloride for corrosion protection

With the aim of obtaining high corrosion resistant Zn–Sn alloy coatings from an ionic liquid, the effects of electrodeposition potential and electrolyte composition on the electrodeposition behavior, film composition, morphology and corrosion performance were investigated. Cyclic voltammograms indicate that Zn and Sn were co‐deposited at distinct reduction potentials as pure Zn and Sn elements. In addition, the phase composition analysis also showed that the obtained Zn–Sn alloy deposits (8 wt.%–45 wt.% Zn) consist of a two‐phase mechanical mixture of small aggregates of Zn and Sn metals. The Zn content of the alloy significantly increases as the electrodeposition potential and electrolyte Zn (II)/Sn (II) ratio increase. The corrosion performance study of the obtained Zn–Sn coatings showed that they have a passivation behavior and their corrosion resistance increases as the alloy‐Sn content increases. To improve their morphological properties, ethylene diamine tetraacetic acid additive was introduced into the electrolyte and greatly improved the morphology and corrosion resistance of the deposits. For the first time, it was shown that high corrosion resistance Zn–Sn coatings can be obtained from ionic liquids. Copyright © 2014 John Wiley & Sons, Ltd.     

Polypyrrole coatings on rheocast aluminum-silicon alloy: A correlation between properties and electrodeposition conditions

The effect of the electrolyte composition and the deposition potential range on the physical properties and possible corrosion protection effect of polypyrrole coatings on rheocast aluminum–2.5 % silicon alloy is investigated. Solutions with different concentrations of sodium nitrate and an electron transfer mediator reagent were used for the electrodeposition. Polypyrrole coating is able to hinder the entrance of electrolyte. Upon the penetration of chloride ions, the coating can induce passivation of the alloy's surface by its reduction. The thickness of the coating and its ion-barrier properties, controlled by the electrodeposition conditions, are shown as the important factors influencing the protection efficiency. However, localized drastic galvanic coupling at the polypyrrole/aluminum interface forms blisters, causes failure, and limits the possible protection.     

从2AlCl3/Et3NHCl离子液体中电沉积制备Ni 和Ni-Al 合金

在含Ni2+的2AlCl3/Et3NHCl离子液体中的铜电极上通过恒电位电沉积制备出金属Ni和Ni-Al合金.采用循环伏安和计时电流方法,揭示铜电极上沉积金属Ni的成核机理,研究了电沉积Ni-Al合金的机理,以及恒电位沉积Ni-Al合金工艺条件对沉积Ni-Al合金表面形貌和电流效率的影响.结果表明:在铜电极上电沉积金属Ni的成核机理为受扩散控制的三维瞬时成核过程.在电量≥3.0 C时,电沉积Ni-Al合金的组成基本不再变化.Ni-Al合金的电沉积机理为,Ni的电沉积受扩散控制,同时进行Al的欠电位沉积,在Ni-Al合金电沉积过程中某些Ni-Al合金相的沉积可能受动力学限制而使Ni-Al合金的组成偏离热力学预测结果.在电沉积Ni-Al合金的沉积电流小且平稳,电沉积速率慢条件下,Ni-Al合金表面形貌致密均一,反之就会出现瘤节.电沉积Ni-Al合金的电流效率＞90％.电沉积物的组成接近于Ni3Al合金.     

Corrosion evolution of UNS C90300 bronze in simulated acid rain of Hong Kong

Corrosion evolutions of UNS C90300 bronzes with and without artificial patina were investigated in the simulated acid rain of Hong Kong. The corrosion products mainly composed of cuprite were formed on the surface exhibiting slight protection for the bronze substrate. The ratios of Sn and Zn in the corrosion products are lower than in the alloy. The artificial patina effectively enhances the corrosion resistance of bronze substrate, even after 30 days of immersion. For both bare and patinated bronzes the Sn- and Zn-based species are absent in the outer layers of corrosion products, and Cu₂O species in the outer layer can partially transform into Cu (II) ionic state due to the abundant supply of dissolved oxygen.     

Fabrication and electrochemical properties of the Sn–Ni–P alloy rods array electrode for lithium-ion batteries

A new ternary Sn–Ni–P alloy rods array electrode for lithium-ion batteries is synthesized by electrodeposition with a Cu nanorods array structured foil as current collector. The Cu nanorods array foil is fabricated by heat treatment and electrochemical reduction of Cu(OH)₂ nanorods film, which is grown directly on Cu substrate through an oxidation method. The Sn–Ni–P alloy rods array electrode is mainly composed of pure Sn, Ni₃Sn₄ and Ni–P phases. The electrochemical experimental results illustrate that the Sn–Ni–P alloy rods array electrode has high reversible capacity and excellent coulombic efficiency, with an initial discharge capacity and charge capacity of 785.0 mAh g^?1 and 567.8 mAh g^?1, respectively. After the 100th discharge–charge cycling, capacity retention is 94.2% with a value of 534.8 mAh g^?1. The electrode also performs with an excellent rate capacity.     

Antibacterial and physicochemical properties of co‐sputtered CuSn thin films

Copper‐tin thin films (CT TFs) were deposited on p‐type Si(100) by radio frequency (RF) magnetron co‐sputtering method. The atomic ratio of Cu and Sn showed complementary tendency with various RF powers on metal targets. Antibacterial test was conducted with Gram‐negative Escherichia coli. The ratio of Cu and Sn ions and the contact time with E. coli affected the antibacterial efficiency. Increasing the ratio of Cu ions and contact time showed higher antibacterial activity. Cu₂₀Sn₆ called as bronze structure, metallic Cu, and copper oxide phases were identified from X‐ray diffraction data after sterilization. The lattice strain that was changed due to the substitution of Cu and Sn was also calculated. The surface morphology of CT TFs was entirely grown to round shape when the dominant element was Sn. But, as the content of Cu increased, the surface morphology was changed from ball shape to sharp column shape. When fixed contact time, the intensities of Cu 2p increased but the intensities of Sn 3d decreased as increasing the atomic ratio of Cu. The oxidation of Cu was more sharply progressed as the RF power on Cu target increased. When fixed CT TFs, the intensities of Cu 2p were consistent but the intensities of Sn 3d_3/2 decreased as increasing contact time between CT TF and E. coli.     

以多孔铜为集流体制备Cu6Sn5合金负极及其性能

以氢气泡为动力学模板电沉积获得多孔铜, 并通过热处理增强其结构稳定性. 进一步将多孔铜作为基底通过电沉积制备Cu-Sn合金负极. XRD结果给出其组成为Cu6Sn5合金, 扫描电子显微镜(SEM)观察到Cu6Sn5合金电极为三维(3D)多孔结构. 充放电结果指出, Cu6Sn5合金电极具有较好的充放电性能, 其首次放电(嵌锂)和充电(脱锂)容量分别为735和571 mAh·g-1, 并且具有较好的容量保持率. 运用电化学阻抗谱研究了Cu6Sn5合金电极在商业电解液中的界面特性.     

Effect of TMAB concentration on structural,mechanical and corrosion properties of electrodeposited Ni–B alloys

The influence of trimethylamine borane (TMAB) concentration as a boron (B) source on the structural and corrosive properties of Ni–B alloy coatings produced by electrodeposition was investigated. The crystal structure of the Ni–B coatings is influenced by the B content in the coating, having a slight (220) preferred orientation. The B content in the coating increased from 16 to 34 at.% with the corresponding increase in the concentration of TMAB from 1 to 20 g/L, while interestingly retaining a crystal structure. The hardness of the coatings increased with increasing B content owing to the formation of smaller crystallites. An increase in B content in the alloy coatings, led to a shift in the E_corr values to more anodic potentials, indicating increase corrosion protection for the Ni–B coatings. This study achieved to reach 34 at.% B content in Ni–B alloy coatings produced by electrodeposition while preventing amorphization of the coating layer.     

Co-deposition of Copper and Tin from Acidic Sulfate Solutions Containing Polyether Laprol 2402C: The Effect of Halides

Voltammetry and x-ray photoelectron spectroscopy data show micromolar amounts of halides to noticeably affect co-deposition of copper and tin from acidic sulfate solutions containing polyether Laprol 2402C as the surface-active substance. The reduction of Cu(II) slows down and that of Sn(II) accelerates in the series Cl^– < Br^– < I^–. Compounds on the surface of bronze coatings are oxides of Cu(I) and Sn(II) and halides of Cu(I).     

The electrochemical behaviour of bronze in synthetic seawater

This paper reports a voltammetric study of bronze in synthetic seawater (SSW). The effects of buffering and deoxygenating were particularly visible in the transpassive region. The breakdown of the anodic passive film on bronze leads to a well-defined activation peak in the transpassive region typical of a nucleation and growth of pits. The breakdown potential of the passivity was shown to vary with the experimental conditions, namely, with buffering and deoxygenating. Buffering has shown to lead to more stable passive films and deoxygenating to higher oxidation currents. Scanning electron microscopy with energy dispersive spectrometer (SEM/EDS) studies of bronze samples with 1-month exposure in non-deoxygenated buffered and non-buffered SSW under open circuit potential have shown significant differences in their morphology: a uniformly cracked surface and a surface showing large and spherical precipitates of about 50 μm uniformly distributed along the surface, respectively, for bronze coupons in buffered (pH 9) and in non-buffered SSW. The EDS technique has identified Cu, O, Cl and Na on the corrosion products of bronze in non-buffered SSW, whilst in buffered media, Sn was also identified. In non-buffered media, open circuit potentials have shown to be all the time less negative than in the buffered media. After 1-month exposure the E _OCP of bronze samples in both media seem to converge to −0.131 and −0.155 V vs Ag|AgCl, respectively. This potential can be assigned to the formation of cuprite, Cu₂O and nantokite, CuCl. The analysis of the SEM images after the removal of the corrosion products has shown descuprification with higher intensity on the surface from coupons in non-buffered SSW.     

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.     

Modeling of the solution composition and a study of the electrodeposition of the Cu-Zn alloy

Choice of ligands in development of new solution compositions for electrodeposition of alloys was simulated and the possibility of electrodeposition of the Cu-Zn alloy from a solution of gluconate complexes of ions of these metals was experimentally verified. The effect of various factors on the admissible current density of electrodeposition of high-quality Cu-Zn alloy coatings, brass composition, current efficiency by the alloy, and strength of brass adhesion to rubber was studied.     

青铜表面GPTS/MTMS复合防蚀涂层的成分分析

利用缓蚀剂BTA及NBS等助剂改性的GPTS/MTMS复合材料,在青铜表面制成透明防蚀涂层,用XPS分析了涂层组成。结果表明,涂层主要由C、Si、O、N以及Cu元素组成,改性前后C、Si、O、N元素的价态不变,Cu元素以Cu2 形式存在,其含量在改性后有明显增加。     

Synthesis, infrared stealth and corrosion resistance of organically modified silicate-polyaniline/carbon black hybrid coatings

Hybrid coatings based on organically modified silicate-polyaniline/carbon black (Ormosil-PANI/CB) were synthesized through a sol-gel technique with different carbon black (10-30 wt%) and PANI/CB (10-30 wt%) contents. These hybrid films were deposited via spin coating onto an aluminum alloy in order to improve the corrosion protection and to act as infrared stealth coatings. The effects induced by the PANI/CB composites on the chain dynamic, thermal properties, infrared stealth, and anticorrosion performances of the coated samples were investigated. The rotating-frame spin-lattice relaxation times and scale of the spin-diffusion path length indicated that the configuration of the hybrid films was highly cross-linked and dense. Thermal properties of these Ormosil-PANI/CB hybrids have been improved over the pure Ormosil analyzed by thermal gravimetric analysis (TGA). The thermal extinction of the hybrid coatings increased with the increase in the carbon black and PANI/CB content. Potentio-dynamic and salt-spray analysis revealed that the hybrid films provided an exceptional barrier and corrosion protection in comparison with untreated aluminum alloy substrates.     

Electrochemical corrosion behaviors and corrosion protection properties of Ni–Co alloy coating prepared on sintered NdFeB permanent magnet

In this study, a protective Ni–Co alloy coating was prepared on sintered NdFeB magnet applying electrodeposition technique. A pure nickel coating was also studied for a comparison. The microstructure, surface morphologies, and chemical composition of coatings were investigated using X-ray diffraction, scanning electron microscope, and energy dispersive spectroscopy, respectively. The corrosion protection properties of coatings for NdFeB magnet in neutral 3.5 wt.% NaCl solutions were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The microstructure and surface morphologies analysis showed that the addition of cobalt element into matrix metal Ni altered the preferential orientation of pure nickel coating from (2 0 0) crystal face for pure nickel coating to (1 1 1) crystal face for Ni–Co alloy coating, and made the surface morphologies more compact and uniform due to the grain-refining. The results of potentiodynamic polarization test showed that compared with pure nickel coating, Ni–Co alloy coating exhibited much nobler corrosion potential (E _corr) and lower corrosion current density (j _corr), indicating better anticorrosive properties. The long-term immersion test by dint of EIS indicated that the Ni–Co alloy coating still presented high impedance value of 1.9 × 10⁵ Ω cm² with the immersion time of 576 h indicating the excellent anticorrosive properties, and corrosion protection properties of nickel coating for NdFeB magnet practically disappeared with the immersion time of 144 h, which also indicated that the Ni–Co alloy coating provided better corrosion protection properties for the NdFeB magnet compared with nickel coating.     

Electrochemical determination of Sn(IV)/Sn(II) ratio in tin sol formed in copper–tin sulphate solution containing laprol 2402C

The electrochemical method was applied to determine Sn(IV)/Sn(II) molar ratio in negatively charged colloid which forms in bronze plating sulphate solution containing laprol 2402C as a surface-active substance. An analysis of characteristic voltammetric minimum the onset of which is highly sensitive to Sn²⁺ concentration was used for this purpose. The Sn(IV)/Sn(II) ratio was found to be constant for completely formed colloid and independent on Cu(II) concentration in the solution. Particles involving Sn(IV) are supposed to be the main component responsible for stability of the sol.     

Interface analysis of pure Sn,pure Ag and Sn?Ag binary alloys in H2SO4

The electrochemical and passivation properties of three selected binary xSn? Ag (x = 26, 50 and 70 wt%) alloys were studied by means of open‐circuit potential variation, potentiodynamic curves and a.c. impedance spectroscopy techniques.The specimens were polarized between ?1.0 and 0.5 V versus saturated calomel electrode (SCE) in naturally oxygenated sulfuric acidsolutions of different concentrations The experimental results indicate that i_corr increases with increasing either the acid concentration or the Sn content in the solid phase. Electrochemical impedance spectroscopyresults measured at the free corrosion potential confirm that alloy I (26Sn? Ag) characterizes by thicker passive film with higher protective ability compared to the other two samples richer in tin component. The exponential variation of the relative thickness of the surface film on any of the tested samples assumes an almost constant thickness for a thin barrier layer and a much larger outer porous layer that dominates the total film thickness on the alloy. Copyright © 2010 John Wiley & Sons, Ltd.     

Theoretical investigation of the viscosity of some liquid metals and alloys

The viscosities of some liquid metals and liquid binary alloys have been determined using the theoretical model developed by Morioka et al. (Z. Metallkd. 93, 4 (2002)). The model was applied successfully to the liquid mono-component metals Hg and Na and to the liquid binary alloys Hg–Na, Ag–Cu, Bi–Sn and Ag–Sb. The model successfully described the temperature dependence of viscosity for Hg and Na for a wide range of temperatures. The values of the adjustable parameters k and z were obtained for Hg and Na. For the liquid binary alloys, calculations were done at a particular temperature for each alloy and our results show that for Hg–Na and Ag–Cu there are both qualitative and quantitative agreements between calculated and experimental viscosity data. However, Bi–Sn and Ag–Sb manifested significant levels of quantitative discrepancies between calculated and experimental viscosity data.     

碳布负载高致密Sn/SnBi合金的电催化CO2还原性能

通过分步电沉积法制备碳布(CC)负载高致密Sn/SnBi合金催化剂：首先在CC上电沉积致密Sn颗粒,而后利用酸性电解液部分溶解Sn为Sn²⁺离子,实现在Sn颗粒表面共沉积SnBi合金枝晶,随后经过原位化学氧化及电化学还原步骤将SnBi合金枝晶转变为SnBi合金纳米颗粒(SnBi NPs)。得益于Sn提供形核位点,SnBi枝晶在碳织物表面垂直致密生长,并通过后续氧化还原转化实现了直径约20 nm的SnBi合金颗粒在CC上致密均匀生长。CC/Sn/SnBi NPs三维电极在-1.08 V (vs RHE)下显示出较高的电催化还原CO₂活性,电流密度高达36 mA·cm^-2且甲酸盐产物选择性为94.9%。同时,在连续12 h恒电压测试中性能未发生衰减,表明电极具有良好的稳定性。     

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of “non-traditional” isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ ⁶⁵Cu results with similar uncertainty budgets in all cases (±0.02–0.04 per mil in delta units, k?=?2, n?=?4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ ⁶⁵Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n?=?42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06–0.16 per mil (2 s), for all the ratios monitored.