A spectromicroscopy study of the corrosion of fusion-bonded epoxy–coated rebar

Reported herein is an analysis of accelerated corrosion of a commercially coated fusion-bonded epoxy rebar sample using an X-ray spectromicroscopy methodology that involves the combination of X-ray fluorescence mapping (XRF) and micro X-ray absorption near-edge spectroscopy (μ-XANES). XRF maps collected using an excitation energy of 7115 eV reveal a sharp contrast between corroded and noncorroded sample areas after correction for topography effects that can be confirmed by Fe K-edge μ-XANES. This X-ray spectromicroscopy methodology allows for the study of corrosion through commercially prepared polymer-coated rebar coatings without any modification to the polymer film prior to analysis and is suitable for long-term testing of the corrosion of these materials under real-world conditions.     

Utilization of biowaste as an eco-friendly biodegradable corrosion inhibitor for mild steel in 1 mol/L HCl solution

This report focuses on the application of a biodegradable biowaste [human hair-(HHR)], to produce a mild steel corrosion inhibitor. The performance of HHR extract in inhibiting metallic corrosion in 1 mol/L HCl was investigated. The analysis of the metal corrosion behavior using electrochemical and weight loss techniques revealed that HHR exhibits an efficient corrosion-mitigating effect via adsorption on the metal surface following a Langmuir isotherm. Tafel-plot results revealed the mixed-mode corrosion protection behavior of HHR. Surface analysis using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and Fourier transform infrared (FT-IR) spectroscopy provided evidence for the precipitation of a protective HHR film on the metal surface.     

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.     

Soft X-ray spectromicroscopy studies of pitting corrosion of reinforcing steel bar

Pitting corrosion of reinforcing steel bar (rebar) imbedded in concrete by chloride ions can cause concrete degradation. It is thus necessary to develop methods to mitigate concrete corrosion which could include using a protective polymer rebar coating. Corrosion studies of polyvinyl butyral-carbon black polymer-coated rebar using soft X-ray fluorescence (XRF) microprobe and micro-X-ray absorption near edge spectroscopy (μ-XANES) are reported in this study. After removal of the polyvinyl butyral-carbon black polymer coating, Fe Lα₁, Mn Lα₁, and O Kα₁ XRF maps were collected as well as Fe and Mn L₃-edge μ-XANES spectra from different regions across the whole rebar surface by collection of total electron yield (TEY) and partial XRF yield (PFY) spectra. The distribution of metallic Fe and Fe corrosion products was determined by analysis of the Fe XRF map. The μ-XANES spectra indicated a higher fraction of Fe (III) phases on the corroded rebar surface, while Fe (II/III) phases were the major corrosion products beneath the surface region. In addition, Mn (II) and Mn (III) were determined as the valence states of the manganese corrosion products.     

Electrochemical and Spectroscopic Study of EuIII and EuII Coordination in the 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid

Separation processes based on room temperature ionic liquids (RTIL) and electrochemical refining are promising strategies for the recovery of lanthanides from primary ores and electronic waste. However, they require the speciation of dissolved elements to be known with accuracy. In the present study, Eu coordination and Eu^III/Eu^II electrochemical behavior as a function of water content in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf₂]) was investigated using UV–visible spectrophotometry, time-resolved laser fluorescence spectroscopy, electrochemistry, and X-ray absorption spectroscopy. In situ measurements were performed in spectroelectrochemical cells. Under anhydrous conditions, Eu^III and Eu^II were complexed by NTf₂, forming Eu−O and Eu−(N,O) bonds with the anion sulfoxide function and N atoms, respectively. This complexation resulted in a greater stability of Eu^II, and in quasi-reversible oxidation–reduction with an E₀’ potential of 0.18 V versus the ferrocenium/ferrocene (Fc⁺/Fc) couple. Upon increasing water content, progressive incorporation of water in the Eu^III coordination sphere occurred. This led to reversible oxidation–reduction reactions, but also to a decrease in stability of the +II oxidation state (E₀’=−0.45 V vs. Fc⁺/Fc in RTIL containing 1300 mm water).     

Fabrication,Characterization, and Application of ‘Sandwich‐Type’ Electrode Based on Single‐Walled Carbon Nanotubes and Room Temperature Ionic Liquid

The much‐enhanced electrochemical responses of potassium ferricyanide and methylene blue (MB) were firstly explored at the glassy carbon electrode modified with single‐walled carbon nanotubes (SWNT/GCE), indicating the distinct electrochemical activity of SWNTs towards electroactive molecules. A hydrophobic room temperature ionic liquid (RTIL), 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆), was used as electrode modification material, which presented wide electrochemical windows, proton permeation and selective extraction ability. In consideration with the advantages of SWNTs and RTIL in detecting target molecules (TMs), a novel strategy of ‘sandwich–type’ electrode was established with TMs confined by RTIL between the SWNT/GCE and the RTIL membrane. The strategy was used for electrochemical detection of ascorbic acid (AA) and dopamine (DA), and detection limits of 400 and 80 fmol could be obtained, respectively. The selective detection of DA in the presence of high amount of AA could also be realized. This protocol presented many attractive advantages towards voltammetric detection of TMs, such as low sample demand, low cost, high sensitivity, and good stability.     

弱碱性介质中氯离子对铜电极腐蚀行为的影响

应用循环伏安法、X射线光电子能谱法、电化学阻抗谱法以及现场椭圆偏光法研究了在弱碱性介质中添加Cl－对铜电极腐蚀行为的影响.结果表明, Cl－的加入能加剧铜电极的腐蚀,使腐蚀电流以及现场椭圆偏振参数Δ的变化范围都增大1个数量级, Cl－对Cu2O的掺杂将使铜电极的表面膜变得疏松,膜的耐蚀性变差.椭圆偏光实验不仅与电化学和能谱实验的结果一致,而且还能定性地、清楚地分辨出铜电极腐蚀过程中Cu2O的生成、Cl－对Cu2O的掺杂、CuO的生成等不同阶段;同时,利用恰当的模型还能定量地确定各个阶段铜电极表面膜的组成、厚度的变化,从而为研究铜电极的腐蚀与防护机理提供更多有用信息.     

Variation of electrochemical capacitor performance with Room Temperature Ionic Liquid electrolyte viscosity and ion size

The use of Room Temperature Ionic Liquid (RTIL) electrolytes promises to improve the energy density of Electrochemical Capacitors (ECs) by allowing for operation at higher voltages. RTIL electrolytes 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF(4)), 1-ethyl-3-methylimidazolium dicyanamide (EMImN(CN)(2)), 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide (DMPImTFSI), and 1-butyl-3-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMPyFAP) were studied. Tetraethylammonium tetrafluoroborate 1 molar solution in anhydrous propylene carbonate (Et(4)NBF(4)-PC 1M) was studied for comparison purposes. Carbon was produced from phenolic resin activated in CO(2). The porosity of the carbon samples were characterised by N(2) adsorption-desorption at 77 K and the relevant electrochemical behaviour was characterised by galvanostatic charge-discharge, electrochemical impedance spectroscopy and cyclic voltammetry. The highest operating voltage of 3.5 V was obtained for BMPyFAP, whilst the best capacitive performance was obtained for EMImBF(4). The maximum energy density increased to 70 Wh kg(-1) (carbon) for RTIL EMImBF(4) from 35 Wh kg(-1)(carbon) for the organic electrolyte Et(4)NBF(4)-PC 1M. It was found that the performance of the RTIL electrolytes could be related to the IL viscosity and ion size whilst the electrolyte equivalent series resistances produced a linear relationship with viscosity. It was found that the capacitance performance of the RTIL electrolytes followed the order EMImBF(4) > DMPImTFSI > BMPyFAP > EMImN(CN)(2). The electrolyte and equivalent series resistance were in the order EMImN(CN)(2) < EMImBF(4) < DMPImTFSI < BMPyFAP.     

Preparation and characterization of ZnO nanocrystallines in the presence of an ionic liquid using microwave irradiation and photocatalytic activity

Fast, simple and template-free method is proposed for preparation of ZnO nanocrystallines in the presence of 1-ethyl-3- methylimidazolium ethyl sulfate, [EMIM][EtSO₄], a room-temperature ionic liquid (RTIL) under microwave irradiation. The powder X-ray diffraction (XRD) studies display that products are excellently crystallized in the form of wurtzite hexagonal structure. Energy dispersive X-ray spectroscopy (EDX) investigations reveal that the products are extremely pure. The results obtained by scanning electron microscopy (SEM) demonstrate that mean size of ZnO nanocrystallines decreases with microwave irradiation time and the RTIL content of media. Diffuse reflectance spectra (DRS) of the ZnO nanocrystallines shows blue shift relative to the bulk ZnO, which can be attributed to quantum confinement effect of ZnO nanocrystallines. A possible formation mechanism of the ZnO nanocrystallines in aqueous solution of the RTIL is presented. Photocatalytic activity of the ZnO nanocrystallines towards photodegradation of methylene blue (MB) was carried out. The results demonstrate that photocatalytic activity of the ZnO nanocrystallines increases with microwave irradiation time and the RTIL content of media.     

Electrocatalysis of Chemical Warfare Agent Sulfur Mustard in Room Temperature Ionic Liquid

Room temperature ionic liquids (RTILs) have the potential for being ideal alternatives for organic solvents in chemical warfare agent (CWA) electrochemical reactions. In this paper, electrocatalysis of CWA sulfur mustard (SM) was achieved by exploring the potential advantage of RTIL methyltrioctylammonium bis (trifluoromethylsulfonyl) imide and further this methodology was used for the detection of CWA. The hydrophobicity of this RTIL offers the opportunity to use this methodology in field condition without environmental humidity effect. The diffusion coefficient calculated for SM in RTIL was 0.196×10⁻⁹ cm²/s. The electrochemical parameters deduced from cyclic voltammetry such as electron transfer coefficient (α), electron transfer number (n) and heterogenous rate constant were estimated 0.11, 2 and 4.41 s⁻¹, respectively. The electrocatalytic activity of the RTIL toward the electrochemical reduction and oxidation of CWA is evidenced, showing the potential of this novel approach for the oxidation of other toxic CWAs. The new RTIL based strategy provides an opportunity to develop field deployable detection of CWA and could provide a new paradigm shift in CWA detection approach, addressing the escalating threat of CWA.     

Simple and low temperature preparation and characterization of CdS nanoparticles as a highly efficient photocatalyst in presence of a low-cost ionic liquid

A simple and low temperature method is proposed for preparation of CdS nanoparticles in presence of 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM] [EtSO₄], a room-temperature ionic liquid (RTIL). The powder X-ray diffraction (XRD) studies display that the products are excellently crystallized in the form of cubic structure and size of the nanparticles prepared in presence of the RTIL is smaller than that prepared in water. Energy dispersive X-ray spectroscopy (EDX) investigations reveal that the products are very pure and nearly stoichiometric. The results obtained by scanning electron microscopy (SEM) demonstrate that the CdS nanoparticles prepared in presence of the RTIL have lower tendency for aggregation relative to the prepared sample in water. Diffuse reflectance spectra (DRS) of the product prepared in the neat RTIL, shows 1.52 eV blue shift relative to bulk CdS, which can be attributed to quantum confinement effect of the CdS nanoparticles. A possible formation mechanism for CdS nanoparticles in presence of the RTIL is presented. Photocatalytic activity of the CdS nanoparticles towards photodegradation of methylene blue (MB) using UV and visible lights was performed. The results demonstrate that observed firstorder rate constant for photodegradation of MB on CdS nanoparticles prepared in the neat RTIL are about 20 and 6 times greater than the prepared sample in water using visible and UV lights, respectively.     

Existence of optical phonons in the room temperature ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate

The technologically important properties of room temperature ionic liquids (RTILs) are fundamentally linked to the ion-ion interactions present among the constituent ions. These ion-ion interactions in one RTIL (1-ethyl-3-methylimidazolium trifluoromethanesulfonate, [C(2)mim]CF(3)SO(3)) are characterized with transmission FTIR spectroscopy and polarized attenuated total reflection (ATR) FTIR spectroscopy. A quasilattice model is determined to be the best framework for understanding the ionic interactions. A novel spectroscopic approach is proposed to characterize the degree of order that is present in the quasilattice by comparing the dipole moment derivative calculated from two independent spectroscopic measurements: (1) the TO-LO splitting of a vibrational mode using dipolar coupling theory and (2) the optical constants of the material derived from polarized ATR experiments. In principle, dipole moment derivatives calculated from dipolar coupling theory should be similar to those calculated from the optical constants if the quasilattice of the RTIL is highly structured. However, a significant disparity for the two calculations is noted for [C(2)mim]CF(3)SO(3), indicating that the quasilattice of [C(2)mim]CF(3)SO(3) is somewhat disorganized. The potential ability to spectroscopically characterize the structure of the quasilattice, which governs the long-range ion-ion interactions in a RTIL, is a major step forward in understanding the interrelationship between the molecular-level interactions among the constituent ions of an ionic liquid and the important physical properties of the RTIL.     

Novel strategy in enhancing stability and corrosion resistance for hydrophobic functional films on copper surfaces

A rod-like 1-dodecanethiol film assisted with the preferential adhesion of polydopamine was prepared on the non-etching copper surfaces by a simple dip-coating method. The formation and surface structure of the film were characterized by water contact angle measurement, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Once the 1-dodecanethiol film formed on the polydopamine-coated copper surface, the hydrophilic surface changed to hydrophobic. The corrosion behavior of the functional films was evaluated by the electrochemical impedance spectroscopy (EIS). The excellent corrosion resistance property could be ascribed to the compact film structure and good seawater stability for modified copper surface, especially in limiting the infiltration of Cl⁻.     

Ti, F复合掺杂改进LiNi1/3Co1/3Mn1/3O2正极材料的电化学性能

采用复合离子掺杂技术对LiNi1/3Co1/3Mn1/3O2进行改性, 并对材料的结构及电化学性能进行了考察.     

盐湖地区暴露25个月的碳钢表面锈层分析

通过扫描电镜(SEM)、电子探针(EPMA)、X射线衍射(XRD)、红外光谱(IRS)和电化学测试技术分析了碳钢在盐湖大气环境下暴露25个月后上下表面的锈层特征. 结果表明, 碳钢上下表面腐蚀量相似, 锈层中均富有Cl、Mg和Si等外来元素. 两个表面的腐蚀产物都主要由β-FeOOH、Fe8(O,OH)16Cl1.3和少量的γ-FeOOH组成, 最外部分的锈层中还检测到Fe3O4和δ-FeOOH. 电化学测试结果表明, 锈层对基体腐蚀具有抑制作用, 锈层保护性随暴露时间增加而增加.     

Electrochemical and computational studies of an expired vilazodone Drug as environmentally safe corrosion inhibitor for aluminum in chloride medium

Through using chemical and electrochemical methods, the theoretical and experimental investigation of the expired vilazodone drug's ability to prevent corrosion on aluminium (Al) in a corrosive medium of HCl (1 M) has been examined. Weighing tests (WL), electrochemical (impedance spectroscopy (EIS), potentiodynamic polarization (PDP)), atomic force microscopy (AFM), scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) tests at 25 °C have all been used to investigate Vilazodone's capability to prevent corrosion of Al in 1 M HCl in the concentration in the range of 25–150 ppm. The corrosion inhibition effect of the investigate Vilazodone's against Al in acid environment was investigated weight loss and electrochemical methods. The highest % inhibition efficiency (%IE) was 95% resulted from weight loss technique at the highest concentration for inhibitor. According to the PDP data, this examined vilazodone function as a mixed-type inhibitor, impacting both the anodic and cathodic reactions. The inhibitors covered the active points of the metal surface, according to electrochemical impedance spectroscopy (EIS), to prevent corrosion. It was discovered that the inhibitor adsorption on the Al surface obeyed the Langmuir adsorption isothermal model. AFM, SEM, and FTIR surface examinations proved the inhibitor had a significant protective effect against Al dissolution in 1 M HCl. The outcomes from chemical and electrochemical methods are relatively consistent. Vilazodone acted as an effective corrosion inhibitor, according to all of the experimental data.     

Metal content determination in polymerization catalysts by direct methods

Metal contents in polymerization catalysts were comparatively determined by Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF) spectroscopy. Catalysts were prepared by grafting metallocene onto bare silica or onto silica chemically modified with methylaluminoxane (MAO). Catalysts were compressed as self-supporting pellets (RBS and XRF), or mounted on adhesive copper tape (XPS). The proximity of the mass of the atomic nuclei did not allow resolution by RBS of the signals corresponding to Zr and Nb, nor Si and Al in catalyst systems such as (nBuCp)₂ZrCl₂/Cp₂NbCl₂/MAO/SiO₂. On the other hand, Zr, Nb, Si and Al lines were completely resolved in an XRF spectrum. For supported metallocenes on bare silica, XPS measurement was ca. 40% higher than that obtained by RBS. Silica-supported zirconocene showed good agreement in Zr content determination by XRF and RBS.     

1-Furoylthiourea-Sonogel-Carbon electrodes: Structural and electrochemical characterization

A new type of sensor based on Sonogel-Carbon materials modified with 1-(2-furoyl)-3-(1-naphthyl)thiourea is presented to be used as an amperometric sensor for metals. Different percentages of modifier were tested in order to optimise the structural and mechanical properties, as well as the electrochemical behaviour.Scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), Fourier transform-infrared spectroscopy (FTIR), single crystal X-ray diffraction (XRD) and powder XRD were used for the structural characterization of these electrodes. The 1-(2-furoyl)-3-(1-naphthyl)thiourea did not modify significantly the structural and mechanical properties of the Sonogel-Carbon electrodes, being similar to other modifications carried out previously in these materials. For the study of the electrochemical response, anodic stripping differential pulse voltammetry (ASDPV) was employed, optimising other parameters of measurement such as pH of the buffer, potential and accumulation time and pulse amplitude. The electrochemical response of the modified electrodes improved significantly with respect to the non-modified electrode, giving good signals and acceptable detection limit.     

Chemical capacitance of nanoporous-nanocrystalline TiO2 in a room temperature ionic liquid

The electrochemical behaviour of nanoporous TiO(2) in a room temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide (EMITFSI), was investigated by cyclic voltammetry (CV) and impedance spectroscopy. Exponentially rising currents in voltammetry were attributed to the charging/discharging of electrons in the TiO(2) film and a charge transfer mechanism. The main features of the voltammetry and impedance followed the same trends in the ionic liquid as in other organic solvents and also in aqueous electrolytes. In the presence of lithium ions, the onset potential of the charge accumulation increased due to the change of the initial position of the TiO(2) conduction band. The results show that substitution of organic solvents contained in solar cells, supercapacitors or other electrochemical devices is in general feasible, though requires some adjustment in the electrolyte composition for optimal performance.     

Synthesis and Acidizing Corrosion Inhibition Performance of N-Doped Carbon Quantum Dots

In this paper, citric acid was used as carbon source, diethylenetriamine and urotropine were used as precursors, and N-doped carbon dots (cdh-CDs) with luminescent properties were synthesized by microwave method. The structure of the sample was analyzed by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffractometry (XRD), ultraviolet spectrophotometer (UV), fluorescence spectroscopy, etc., and it was proved that cdh-CDs with an amorphous structure about 4–10 nm in diameter was synthesized. The corrosion inhibition performance of cdh-CDs in 1 M hydrochloric acid was evaluated by static weight loss and electrochemical method. The results showed that cdh-CDs have a good corrosion inhibition performance at 60°C, the inhibition efficiency can reach 81.2% when the dosage is 600 ppm. Electrochemical results showed that cdh-CDs are mixed inhibitors which mainly inhibit cathodes.