Formation of corrosion resistant plasma electrolytic oxidation coatings on aluminium alloy with addition of sodium tungstate species

Plasma electrolytic oxidation (PEO) coatings were formed in silicate based electrolytes without and with the addition of sodium tungstate on AA?6063 aluminium alloy. Microstructure, composition and corrosion resistance of PEO coatings were investigated by scanning electron microscopy, X-ray diffraction and electrochemical impedance spectroscopy and potentiodynamic polarisation test respectively. The effects of additive sodium tungstate were examined. The results showed that the additive containing PEO coatings were of dense structure with additional phase (WO₃) and of less cracks than the additive free PEO coating. In addition, additive containing coatings were of better corrosion resistance than the additive free PEO coating, which was confirmed by electrochemical impedance spectroscopy and potentiodynamic polarisation tests. Furthermore, long time immersion test revealed that the PEO coated alloy with the addition of 12?g?L^??1 sodium tungstate maintained high impedance over 82?h in 3.5?wt-%NaCl, while the PEO coating without additive was unable to protect the substrate after such long time immersion.     

添加剂四氟硼酸四乙基铵对石墨负极界面性能的影响

采用恒流充放电、循环伏安(CV)和交流阻抗(EIS)测试方法研究四氟硼酸四乙基铵(Et4NBF4)作为锂离子电池电解液添加剂对石墨负极材料界面性质的影响,通过傅里叶变换红外光谱(FTIR)对固体电解质界面膜(SEI)的成分变化进行分析。结果表明:添加剂Et4NBF4参与了SEI膜的形成,提高了人造石墨(AG)/Li半电池充电容量和后续的循环效率,但是降低了首次充放电效率;首次放电过程中1.0～0.5 V是SEI膜形成和生长的电位区间,而0.5 V以下SEI膜进行不断的修复;添加少量Et4NBF4降低了SEI膜阻抗,提高了电解液与石墨负极的相容性。     

Effect of benzyl alcohol and thiourea on electrodeposition of cadmium: electrochemical impedance spectroscopy study

Abstract

The adsorption effect of the benzyl alcohol (BA) and thiourea (TU) on the electrodeposition of cadmium from an acid sulphate bath has been studied by electrochemical impedance spectroscopy (EIS). Maximum adsorption of additive was obtained in BA containing medium. Results show that the adsorption increases when the concentration of the additives is increased. The surface adsorption of the additives has lead to a decrease in the double layer capacitance and to an increase in polarisation resistance. The adsorption process is a spontaneous one and follows the Langmuir adsorption isotherm model. From the impedance analysis, it is observed that Cd–TU complexes inhibit the hexagonal like morphology revealed by SEM.     

Electrochemical performance of tris(2-chloroethyl) phosphate as a flame-retarding additive for lithium-ion batteries

We studied tris(2-chloroethyl) phosphate (TCEP) as a potential flame-retarding additive and its effect on the electrochemical cell performance of lithium-ion battery electrolytes. The electrochemical cell performance of additive-containing electrolytes in combination with a cell comprised of a LiCoO₂ cathode and a mesocarbon microbeads anode was tested in coin cells. The cyclic voltammetry results show that the oxidation potential of TCEP-containing electrolyte is about 5.1 V (vs. Li/Li⁺). A cell with TCEP has a better electrochemical cell performance than a cell without TCEP in an initial charge and discharge test. In a cycling test, a cell containing a TCEP-containing electrolyte has a greater discharge capacity and better capacity retention than a TCEP-free electrolyte after cycling. The results confirm the promising potential of TCEP as a flame-retarding additive and as a means of improving the electrochemical cell performance of lithium-ion batteries.     

碳酸亚乙烯酯添加剂对LiFeP04／石墨电池高温循环性能的影响

研究成膜添加剂对材料结构稳定性及LiFePO4/石墨电池高温循环性能的影响。分别测试添加和未添加碳酸亚乙烯酯（VC）的18650电池的高温循环性能,并通过充放电测试、交流阻抗、扫描电镜、X射线能量色散光谱以及拉曼光谱等方法研究 VC 对电池正、负材料结构的影响。结果表明：VC 添加剂在提高石墨结构稳定性的同时显著抑制LiFePO4材料中的溶铁行为;此外,VC添加剂阻止电解液在负极表面还原分解及负极表面SEI膜的增厚,也阻止电解液在LiFePO4电极表面的分解;含有VC添加剂的电解液可以有效改善LiFePO4/石墨电池在高温下的循环稳定性。     

Effects of additives on zinc electrodeposition from alkaline zincate solution

The effects of additives on the surface and cross-sectional morphologies of zinc deposits on iron substrate from alkaline zincate solution were characterized by scanning electron microscope (SEM). The cathodic reaction mechanisms under various concentrations of additives were investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. It is found that with increasing the additive A content in the bath solution, the nucleation overpotential (NOP) value is obviously increased and the inhibition effect is strengthened. This may be mainly due to the adsorption of additive A on the cathodic electrode surface, which can cover the active sites and block the discharge reduction. The results of EIS analysis indicate that the rate-determining step of zinc electrodeposition process is changed from mixed control step into electrochemical reduction step in the presence of additive A. However, any quantity of additive B has little effect on the NOP value and the inhibition effect is not obvious. Furthermore, addition of additive A and additive B at the same time displays the strongest inhibition effect and shows a strong synergism because of their co-adsorption on the cathodic electrode surface.     

Electrochemical study of modified cerium-silane bi-layer on Al alloy 2024-T3

In this paper, the performance of bis-1, 2-(triethoxysilyl) ethane (BTSE) as a pre-treatment to protect the AA 2024-T3 against corrosion has been investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, and the scanning vibrating electrode technique (SVET). The microstructural and morphological characterizations were carried out via scanning electron microscopy and atomic force microscopy and the chemical composition evaluated using contact angle measurements and X-ray photoelectron spectroscopy (XPS). The electrochemical results showed that the additives improved the anticorrosion properties of the coating. The chemical characterization indicated that additives contribute to an increased degree of surface coverage, as well as to a more complete reticulation. The SVET results evidenced the self-healing abilities of Ce ions.     

Effects of Trioctyl Phosphate and Cresyl Diphenyl Phosphate as flame-retarding additives for Li-Ion battery electrolytes

Safety concerns related to lithium-ion batteries have been the key obstacle to their application in hybrid electric vehicles. Trioctyl Phosphate (TOP) and Cresyl Diphenyl Phosphate (CDP) were studied as potential flame-retarding additives for lithium-ion batteries. The electrochemical performance and thermal stability of the additive-containing electrolytes, in combination with a cell comprising a LiCoO₂ cathode and Mesocarbon Microbeads (MCMB) anode, were tested in coin cells. Cyclic Voltammetry (CV), Differential Scanning Calorimetry (DSC), Electrochemical Impedance Spectroscopy (EIS), and Scanning Electron Microscopy (SEM) were used for the experimental analysis. The study results revealed that CDP addition at 5 wt.% improved the cell stability due to the lower rate of the charge-transfer resistance increase over 30–50 cycles. CDP was demonstrated to be a better flame-retarding additive than TOP.     

Influence of molybdate species on the tartaric acid/sulphuric acid anodic films grown on AA2024 T3 aerospace alloy

AA2024 T3 alloy specimens have been anodised in tartaric acid/sulphuric media and tartaric acid/sulphuric media containing sodium molybdate; molybdate species were added to the anodising bath to enhance further the protection provided by the porous anodic film developed over the macroscopic alloy surface. Morphological characterisation of the anodic films formed in both electrolytes was undertaken using scanning electron and transmission electron microscopies; the chemical compositions of the films were determined by Rutherford backscattering spectroscopy that was complemented by elemental depth profiling using rf-glow discharge optical emission spectrometry. The electrochemical behaviour was evaluated using potentiodynamic polarisations and electrochemical impedance spectroscopy; the corrosion performance was examined after salt spray testing. The porous anodic film morphology was little influenced by the addition of molybdate salt, although thinner films were generated in its presence. Chemical composition of the anodic film was roughly similar; however, addition of sodium molybdate in the anodizing bath resulted in residues of molybdate species in the porous skeleton and improved corrosion resistance measured by electrochemical techniques that was confirmed by salt spray testing.     

The electrochemical behaviour of Ti‐13Nb‐13Zr alloy in various solutions

The electrochemical behaviour of a near‐β Ti‐13Nb‐13Zr alloy for the application as implants was investigated in various solutions. The electrolytes used were 0.9 wt% NaCl solution, Hanks' solution and a culture medium known as minimum essential medium (MEM) composed of salts, vitamins and amino acids, all at 37 °C. The electrochemical behaviour was investigated by the following electrochemical techniques: open circuit potential measurements as a function of time, electrochemical impedance spectroscopy (EIS) and determination of polarisation curves. The obtained results showed that the Ti alloy was passive in all electrolytes. The EIS results were analysed using an equivalent electrical circuit representing a duplex structure oxide layer, composed of an inner barrier layer, mainly responsible for the alloy corrosion resistance, and an outer and porous layer that has been associated to osteointegration ability. The properties of both layers were dependent on the electrolyte used. The results suggested that the thickest porous layer is formed in the MEM solution whereas the impedance of the barrier layer formed in this solution was the lowest among the electrolytes used. The polarisation curves showed a current increase at potentials around 1300 mV versus saturated calomel electrode (SCE), and this increase was also dependent on the electrolyte used. The highest increase in current density was also associated to the MEM solution suggesting that this is the most aggressive electrolyte to the Ti alloy among the three tested solutions.     

锂硫电池用气相生长碳纤维增强硫-多壁碳纳米管复合正极的影响(英文)

制备了锂硫电池用硫-多壁碳纳米管纳米复合材料,并分别采用气相生长碳纤维(VGCFs)和导电炭黑作为复合正极的导电添加剂,通过形貌表征(SEM)、恒流充放电测试和交流阻抗分析(EIS)研究VGCFs对硫-多壁碳纳米管复合正极的影响。结果表明:采用VGCFs作添加剂的硫-多壁碳纳米管复合电极具有三维网状结构,其首次放电比容量为1254 mA·h/g,40次循环后容量保持在716 mA·h/g。与采用导电炭黑为添加剂的电极相比,采用VGCFs为添加剂的电极具有更高的活性物质利用率和更好的循环稳定性。相互搭接的纤维状VGCFs可形成稳定的导电网络,抑制正极材料及残存放电产物的团聚堆积,维持电极的多孔性,从而改善电池的电化学性能。     

Electrochemical and SEM characterization of NiTi alloy coated with chitosan by PLD technique

The production of a wide variety of biocompatible thin films by laser ablation deposed on the biomaterial substrates does not induce inflammatory response and repulsion by the immunization human body. Anodic potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used for the study of the electrochemical behavior of coated NiTi with chitosan through pulsed laser deposition (PLD) technique. Experiments were carried out using two different electrolytes: physiological 0.9 wt% NaCl solution (PS) and PS + hydrochloric acid (APS) at 37 ± 1 °C. In addition, scanning electron microscopy was employed to observe the surface morphology after maintaining in both electrolytes. The corrosion resistance was evaluated by means of the corrosion and passive corrosion currents. The electrochemical properties of the coated NiTi sample at the open circuit potential at different immersion time in PS and APS were studied by EIS. Equivalent circuits were used to model EIS data, in order to characterize samples' surface.     

Enhancement of Corrosion Resistance of Zinc Coatings Using Green Additives

In the present work, morphology, microstructure, and electrochemical behavior of Zn coatings containing non-toxic additives have been investigated. Zn coatings were electrodeposited over mild steel substrates using Zn sulphate baths containing four different organic additives: sodium gluconate, dextrose, dextrin, and saccharin. All these additives are “green” and can be derived from food contents. Morphological and structural characterization using electron microscopy, x-ray diffraction, and texture co-efficient analysis revealed an appreciable alteration in the morphology and texture of the deposit depending on the type of additive used in the Zn plating bath. All the Zn coatings, however, were nano-crystalline irrespective of the type of additive used. Polarization and electrochemical impedance spectroscopic analysis, used to investigate the effect of the change in microstructure and morphology on corrosion resistance behavior, illustrated an improved corrosion resistance for Zn deposits obtained from plating bath containing additives as compared to the pure Zn coatings.     

Self-healing properties of protective coatings containing isophorone diisocyanate microcapsules on carbon steel surfaces

Microcapsules containing isophorone diisocyanate (IPDI) were used as self-healing additives in the alkyd varnish coatings (AVCs), and their self-healing performance was evaluated in the case of artificial defects on Q235 steel surfaces, using scanning micro-reference electrode technique and Fourier-transform infrared spectroscopy. Comparison of the micromechanical properties between the water-insoluble self-healing products (polyurethanes) and AVCs indicates that the former significantly enhanced the capability of the scratched crevice to successfully endure outer stress. The electrochemical impedance spectroscopy experiments analysed the different stages in the self-healing process. This study successfully demonstrated the self-healing activity of IPDI-AVCs in protecting steel surfaces.     

Anticorrosive zinc decanoate additive in acrylate varnish

This work is focused on the inhibitory effect of zinc decanoate on steel substrates for improvement of acrylate varnish anticorrosion performance. Experiments were carried out on a bare steel surface in sodium sulphate solution as well as on samples painted with acrylate varnish. The efficiency of inhibition was estimated by electrochemical impedance spectroscopy and an exposure test in a condensation chamber. A cross-section of the modified varnish was observed by scanning electron microscopy. Decanoate mobility on the surface was estimated by energy-dispersive X-ray analysis and infrared spectroscopy. Zinc decanoate provides very good inhibiting efficiency, about 65%. The mobility of decanoate on the surface is limited and it can protect rather small defects. Zinc decanoate can be used as an environmentally friendly anticorrosive additive in varnishes for preservation practice.     

Corrosion and electrochemical behaviors of pure aluminum in novel KOH‐ionic liquid‐water solutions

The corrosion and electrochemical behaviors of pure aluminum in KOH‐ionic liquid‐water solutions with variable volume ratios of water and the ionic liquid 1‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMIMBF₄) were for the first time investigated by means of hydrogen collection, polarization curve, galvanostatic discharge, and electrochemical impedance spectroscopy (EIS). The results of hydrogen collection experiments showed that aluminum has a low corrosion rate in KOH‐BMIMBF₄‐H₂O solutions, and the corrosion rate decreases with increase in BMIMBF₄ content in the electrolytes. The results of electrochemical experiments revealed that aluminum is electrochemically active over a very wide potential window in the KOH‐BMIMBF₄‐H₂O solutions, and its electrochemically kinetic mechanism is similar to that in the corresponding aqueous solution; the increase in KOH and water contents in the electrolytes may improve the anodic dissolution performance of aluminum. It was found that aluminum presents excellent galvanostatic discharge performance in the 2.0 M KOH BMIMBF₄‐H₂O mixed solution with 60% water.     

Atmospheric Plasma Surface Modification on Stainless Steel Bipolar Plate in PEMFC

In this research,stainless steel bipolar plates for proton exchange membrane fuel cell(PEMFC)have been treated by an atmospheric plasma surface modification technology.The chemical composition and thickness of the oxide film formed by plasma are conducted to verify by Auger electron spectroscopy(AES).Pitting resistance,potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS)are measured to evaluate the corrosion mechanism and electrochemical properties.The results show that the treated plates have a much thicker oxide film which leads to higher pitting potential,improved corrosion rate,less and smaller pitting holes than those without treatment.The stable chemical and electrochemical properties of the treated stainless steel bipolar plate indicate the stabilization of cell performance and longer service life.     

Characterization of alkaline-earth oxide additions to the MnO2 cathode in an aqueous secondary battery

The effect of alkaline-earth oxide additions on aqueous rechargeable battery is investigated using microscopic and spectroscopic techniques. The alkaline-earth oxide additions such as magnesium oxide (MgO) and barium oxide (BaO) were physically mixed to the manganese dioxide (MnO₂) cathode of a cell comprising zinc as an anode and aqueous lithium hydroxide as the electrolyte. The results showed that such additions greatly improved the discharge capacity of the battery (from 145 to 195 for MgO and 265 mAh/g for BaO). Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. With an aim to understand the role of these additives and its improvement in cell performance, we have used microscopy, spectroscopy, ion beam analysis and diffraction based techniques to study the process. Transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy analysis (EDS) results showed evidence of crystalline MnO₂ particles for MgO as additive, whereas, MnO₂ particles with diffused structure leading to mixture of phases is observed for BaO additives which is in agreement with X-ray diffraction (XRD) data. This work relates to improvement in the electrochemical behaviour of the Zn-MnO₂ battery while the MgO additive helps to reduce the formation of manganese and zinc such as hetaerolite that hinders the lithium intercalation.     

席夫碱基季铵盐型双子表面活性剂对碱性锌电极电化学性能的影响

目的选择席夫碱基季铵盐型双子表面活性剂作为电解液添加剂,改善碱性锌电极的电化学性能,提高其耐蚀性能。方法通过电化学分析法,如失重法、塔菲尔极化曲线法、交流阻抗法等分析研究三种席夫碱基季铵盐型双子表面活性剂(D1、D2、D3)对锌电极电化学性能的影响,利用X射线光电子能谱(XPS)和扫描电子显微镜(SEM)研究在6 mol/L KOH电解液(饱和ZnO)浸泡48 h后,锌片表面的成分和形貌。结果室温下,缓蚀率随席夫碱基季铵盐型表面活性剂浓度升高而增加,当浓度进一步增大,缓蚀率变化不大。三种席夫碱基表面活性剂中,D3缓蚀能力最强,缓蚀率最高达95.67%,抑制腐蚀的效果顺序为:D3D2D1,属于抑制阳极型缓蚀剂。结论 D1、D2、D3作为碱性锌电极的电解液添加剂,可以有效减缓锌电极的腐蚀、变形、钝化及枝晶形成的能力,改善了碱性锌电极的电化学性能,D1、D2、D3适合作为碱性锌电池的缓蚀添加剂。     

Microstructure and crystallographic characteristics of nanocrystalline copper prepared from acetate solutions by electrodeposition technique

Methane sulphonic acid is an alternative electrolyte for conventional sulphuric acid for copper deposition. The electrodeposition of copper from eco-friendly acetate-based electrolytes consisting of copper acetate, sodium acetate and methane sulphonic acid was dealt. Thamine hydrochloride (THC), saccharin and 4-amino-3-hydroxynaphthalene 1-suphonic acid were used as additives in depositing electrolytes. The cathode current efficiency was calculated using the Faraday's law. Metal distrbution ratio of the solutions was determined using Haring–Blum cell. These additives impact the surface morphology of deposited copper films by downgrading, the grain size was analyzed by scanning electron microscopy (SEM) and X-ray diffiraction technique. XRD pattern acquired for electrodeposited copper film shows polycrystalline and face centered cubic structure (FCC). The crystal size of the copper film was calculated using the Debye–Scherrer's equation. The crystal size revealed that deposits produced from additive containing electrolytes exhibited the lowest grain size. Texture coefficient analysis studies revealed that all copper film deposits are polycrystalline and the crystals are preferentially oriented and parallel to the surface. A uniform and pin-hole free surface morphology and grain refining were brought about by the additives.