Long-term anticorrosion behaviour of polyaniline on mild steel

Anticorrosion performances of polyaniline emeraldine base/epoxy resin (EB/ER) coating on mild steel in 3.5% NaCl solutions of various pH values were investigated by electrochemical impedance spectroscopy (EIS) for 150 days. In neutral solution (pH 6.1), EB/ER coating offered very efficient corrosion protection with respect to pure ER coating, especially when EB content was 5-10%. The impedance at 0.1 Hz of the coating increased in the first 1-40 immersion days and then remained constant above 10(9) Omega cm(2) until 150 days, which in combination with the observation of a Fe2O3/Fe3O4 passive film formed on steel confirmed that the protection of EB was mainly anodic. In acidic or basic solution (pH 1 or 13), EB/ER coating also performed much better than pure ER coating. However, these media weakened the corrosion resistance due to breakdown of the passive film or deterioration of the ER binder.

Measuring the electronic decay constant of alkanedithiols by electrochemical impedance spectroscopy

Several methods have been used for the measurement of the electronic decay constant (beta) of organic molecules. However, each of them has some disadvantages. For the first time, electrochemical impedance spectroscopy (EIS) was used to obtain the 18 value by measuring the tunneling resistance through alkanedithiols. The tunneling resistance through alkanedithiols increases exponentially with the molecular length in terms of the mechanism of coherent nonresonant tunneling. beta was 0.51 +/- 0.01 per carbon.

Poly(vinylidene fluoride-hexafluoropropylene)/organo-montmorillonite clays nanocomposite lithium polymer electrolytes

Polymer-clay nanocomposite (PCN) materials were prepared by intercalation of an alkyl-ammonium ion spacing/coupling agent and a polymer between the planar layers of a swellable-layered material, such as montmorillonite (MMT). The nanocomposite lithium polymer electrolytes comprising such PCN materials and/or a dielectric solution (propylene carbonate) were prepared and discussed. The chemical composition of the nanocomposite materials was determined with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, which revealed that the alkyl-ammonium ion successfully intercalated the layer of MMT clay, and thus copolymer poly(vinylidene fluoride-hexafluoropropylene) entered the galleries of montmorillonite clay. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of the lithium polymer electrolyte. Equivalent circuits were proposed to fit the EIS data successfully, and the significant contribution from MMT was thus identified. The resulting polymer electrolytes show high ionic conductivity up to 10(-3) S cm(-1) after felling with propylene carbonate.

IrO2/SnO2 electrodes: prepared by sol-gel process and their electrocatalytic for pyrocatechol

IrO2/SnO2 (10%:90%, molar ratio) electrodes (ITEs) were prepared by the sol-gel method as an alternative to the electrode-position and thermal decomposition process. The electrodes were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), cyclic voltammetry (CV) and electrochemical impedance spectra (EIS). From the results of XRD, oxide films prepared at low temperature were in amorphous state, while hydrous IrO2 crystal and cassiterite phase SnO2 were formed at 300 degreesC or even to 500 degreesC. The highly porous structure was confirmed by AFM. The electrochemical experiments demonstrated that the sol-gel method made the ITEs having a fast electron transfer process with good stability and the optimal preparation temperature was 400 degreesC for the highest electroactivity. Furthermore, the electrocatalysis of pyrocatechol on the electrodes was investigated. A quasi-reversible process occurred and a linear range over three orders magnitude (1 x 10(-2) - 10 mM) was obtained by differential pulse voltammetry (DPV). Meanwhile the detection limit of pyrocatechol was 5 x 10(-3) mM. This study indicated that the sol-gel method was an appropriate route to prepare the IrO2/SnO2 electrodes for the electrocatalytic of pyrocatechol.

电极用纳米Ag_2O的电化学阻抗行为

用电化学阻抗技术(EIS)对具有不同粒径分布组成的氧化银电极进行了研究。通过建立合理的模拟等效电路,解析了各测试电极间电化学性能的差异。在充放电循环过程中,具有合适配比的混配电极A非法拉第电荷消耗减少,电极的传质传荷性能明显优于传统电极C和纯纳米粒子组成电极F,展示出可逆电极的电化学行为。通过对动电位阻抗谱的解析,发现电极反应经历了4个明显的动力学过程,对不同组成电极的动力学可控程度有了大致了解。

Structure and identity of 4,4 '-thiobisbenzenethiol self-assembled monolayers

Self-assembled monolayers (SAMs) of 4,4'-thiobisbenzenethiol (TBBT) can be formed on Au surface spontaneously. The structural characteristics and adsorption behavior of TBBT SAMs on Au have been investigated by surface enhanced Raman scattering (SERS), electrochemical cyclic voltammetry (CV), ac impedance spectroscopy (EIS), and atomic force microscopy (AFM). It is demonstrated that TBBT adsorbed on Au by losing a H atom, forming one Au-S bond, and the other mercapto group is free at the surface of the monolayer owing to the presence of the nu(S-H) at 2513 cm(-1) and the delta(C-S-H) at 910 cm(-1) in SERS. The enhancement of the vibration of C-S (1064 cm(-1)), the aromatic C-H vibration (3044 cm(-1)), and the absence of the vibration of S-S illustrate TBBT adsorbed on Au forming a monolayer with one benzene ring tilted with respect to the Au surface. The interpretation of the observed frequencies is aided by ab initio molecular orbital (MO) calculations at the HF/6-31G* level of theory. Electrochemical CV and EIS indicate TBBT monolayers can passivate the Au effectively for its low ratio of pinhole defects (theta = 99.6%). AFM studies give details about the surface morphology. The applications of TBBT SAMs have been extensively investigated by exposure of Cu2+ ion to TBBT SAMs on Au and covalent adsorption of metal nanoparticles.

Application of electrochemical impedance spectroscopy for monitoring allergen-antibody reactions using gold nanoparticle-based biomolecular immobilization method

Gold nanoparticles were used to enhance the immobilization amount and retain the immunoactivity of recombinant dust mite allergen Der f2 immobilized on a glassy carbon electrode (GCE). The interaction between allergen and antibody was studied by electrochemical impedance spectroscopy (EIS). Self-assembled Au colloid layer (Phi = 16 nm) deposited on (3-mercaptopropyl)trimethoxysilane (MPTS)-modified GCE offered a basis to control the immobilization of allergen Der f2. The impedance measurements were based on the charge transfer kinetics of the [Fe(CN)(6)](3-/4-) redox pair, compared with bare GCE, the immobilization of allergen Der f2 and the allergen-antibody interaction that occurred on the electrode surface altered the interfacial electron transfer resistance and thereby slowed down the charge transfer kinetics by reducing the active area of the electrode or by preventing the redox species in electrolyte solution from approaching the electrode. The interactions of allergen with various concentrations of monoclonal antibody were also monitored through the change of impedance response. The results showed that the electron transfer resistance increased with increasing concentrations of monoclonal antibody.

Copper hexacyanoferrate multilayer films on glassy carbon electrode modified with 4-aminobenzoic acid in aqueous solution

4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation during the electrooxidation process in 0.1 M KCl aqueous Solution. X-ray photoelectron spectroscopy (XPS) measurement proves the presence of 4-carboxylphenylamine on the GCE. Electron transfer processes of Fe(CN)(6)(3-) in solutions of various pHs at the modified electrode are studied by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Changing the solution pH would result in the variation of the terminal group's charge state, based on which the surface pK(a) values were estimated. The copper hexacyanoferrate (CuHCF) multilayer films were formed on 4-ABA/GCE prepared in aqueous solution, and which exhibit good electrochemical behavior with high stability.

Ti_(0.17)Zr_(0.08)V_(0.34)Nb_(0.01)Cr_(0.1)Ni_(0.3)氢化物电极合金微观结构及电化学性能研究

采用XRD、FESEM-EDS、ICP及EIS等方法研究了Ti0.17Zr0.08V0.34Nb0.01Cr0.1Ni0.3氢化物电极合金微观结构和电化学性能。X射线衍射分析表明:该合金由体心立方结构(bcc)的V基固溶体主相和少量六方结构的C14型Laves相组成;FESEM及EDS分析表明:V基固溶体主相形成树枝晶,C14型Laves相呈网格状围绕着树枝晶的晶界,元素在两相中的分布呈现镜像关系。电化学性能测试结果表明:该合金的氢化物电极在303￣343K较宽的温度区间内,表现出较高的电化学容量,在303K和343K时,电化学容量分别为337.0mAh·g-1和327.9mAh·g-1。在303K循环100周后,容量为282.7mAh·g-1。ICP分析结果表明,氢化物电极在充放电循环过程中,V及Zr元素向KOH电解质中的溶出较为严重。EIS研究表明,金属氢化物电极表面电化学反应的电荷转移电阻(RT)随循环次数的增加而增加,相应的交换电流密度则随循环次数的增加而降低。氢化物电极循环过程中RT的增大以及V和Zr元素的溶解,可能是导致电极容量衰减的主要原因。

Layer-by-layer assembly of multilayer films composed of avidin and biotin-labeled antibody for immunosensing

Protein multilayers composed of avidin and biotin-labeled antibody (bio-Ab) were prepared on gold surface by layer-by-layer assembly technology using the high specific binding constant (K-a: approximate to 10(15) M-1) between avidin and biotin. The assembly process of the multilayer films was monitored by using real-time BIA technique based on surface plasmon resonance (SPR). The multilayer films were also characterized by electrochemical impedance spectroscopy (EIS) and reflection absorption Fourier transform infrared spectroscopy (FTIR). The results indicate that the growth of the multilayer is uniform. From response of SPR for each layer, the stoichiometry S for the interaction between avidin and bio-Ab is calculated to be 0.37 in the multilayer whereas 0.82 in the first layer. The protein mass concentration for each layer was also obtained. The schematic figure for the multilayer assembly was proposed according to the layer mass, concentration and S value. The utility of the mutilayer films for immunosensing has been investigated via their subsequent interaction with hIgG. The binding ability of the multilayer increased for one to three layers of antibody, and then reach saturation after the fourth layer. These layer-by-layer constructed antibody multilayers enhance the binding ability than covalently immobilized monolayer antibody. This technology can be also used for construction of other thin films for immunosensing and biosensor.

Chitosan mediated assembly of gold nanoparticles multilayer

We initiate a systematic exploration of a natural polymer, chitosan, as a structural material for designing functional layers on electrode surfaces in this work. Au colloid films are organized on chitosan layer by adsorption. We have successfully constructed a multilayer An nanoparticle assembly through electrostatic interactions on chitosan functionalized quartz substrates by the alternate treatment of the substrate with solution of citrate-stabilized gold nanoparticles (negatively charged) and chitosan solution (positively charged). The resulting substrates were characterized by UV-Vis spectrometry, atomic force microscopy (AFM), and electrochemical impedance spectroscopy (EIS) measurements. These assemblies of colloid An multilayer are highly stable, and can be kept for a long time in distilled water, only being removed by scratching or extreme electrochemical conditions.

Assembly of alternating polycation and DNA multilayer films by electrostatic layer-by-layer adsorption

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. The real-time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. Electrochemical impedance spectroscopy (EIS) and UV-vis absorbance measurements were also used to study the film assembly, and linear film growth was observed. All the results indicate that the uniform multilayer can be obtained on the poly(ethylenimine)- (PEI-) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by the real-time BIAcore technique; the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1).

Fabrication of layer-by-layer deposited multilayer films containing DNA and its interaction with methyl green

Multilayer films were fabricated by layer-by-layer electrostatic deposition techniques between poly(diallyIdimethylammonium chloride) (PDDA) and calf thymus DNA (CT DNA) on glassy carbon and quartz substrates. Electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FTIR) spectroscopy and UV-vis spectroscopy demonstrated the uniform assembly of PDDA/DNA multilayer films, and X-ray photoelectron spectroscopy confirmed the elemental composition of the films. Moreover, the interaction of DNA in PDDA/DNA films with methyl green was investigated by UV-vis spectroscopy and circular dichroism (CD). (C) 2001 Elsevier Science B.V. All rights reserved.

添加钛镁元素对热浸镀锌层性能的影响

热浸镀锌及其合金在世界各国已得到广泛的应用。为提高镀锌层性能，往镀浴中添加各种微量元素已经有了许多研究。但是对于在高纯锌中添加微量元素，排除由于锌浴不纯而导致的性能差异，报道很少。 本文选择高纯锌，在排除其它元素干扰的情况下，制备了添加钛、镁元素的热浸镀锌合金镀层，考察了分别添加钛、镁元素及同时添加钛镁元素后镀层在海水环境中的腐蚀行为及其耐蚀性能。 由于钛熔点（1668℃）远高于锌熔点（419.5℃），镁在高温下极易氧化，因而制备中间合金。在分别用分光光度法和原子吸收法测定准确含量后，按计算量进行添加。热浸镀层最外层和镀液合金成分基本一致，镀液合金性能可以反映镀层性能，制备锌钛、锌镁合金电极，进行电化学性能测试，发现添加钛、镁元素能够提高合金在海水中的耐腐蚀性能。 采用烘干溶剂法进行热浸镀，选择合适的工艺条件，助镀剂为ZnCl2、NH4Cl的混合溶液，温度460℃，镀液为添加不同含量钛镁的锌液。对所得镀层进行表观质量检测，镀层质量合格，其中添加钛元素后镀层亮度增加。镀层厚度是考察镀层性能的重要指标，通过测量发现镀层比较均匀，添加钛元素后镀层厚度减薄，添加镁元素后镀层厚度稍有增加，同时添加钛镁元素，镀层厚度稍高于单独添加钛元素，但比纯锌镀层要薄许多。添加微量钛镁后，镀层阻抗谱图和极化曲线图形状都没有大的改变，EIS等效电路拟合结果表明添加钛镁元素后镀层极化电阻增加，镀层在海水中耐蚀性能有所提高。 为进一步检测镀层的耐蚀性能，进行了中性盐雾试验，添加钛镁元素后镀层腐蚀失重减少，腐蚀失重率降低，耐盐雾腐蚀性能提高；室内模拟全浸实验所的结果与盐雾试验具有一致性，镀层刚开始时腐蚀较快随后比较稳定。

低碳钢在海底沉积物中的腐蚀行为

海底沉积物环境下钢铁的腐蚀和防护问题由于人们对海洋的广泛的开发和利用而逐渐引起人们的注意。本文对钢在海底沉积物中的腐蚀行为进行了模拟海底沉积物环境下的失重实验和电化学测量，以探讨海底沉积物环境下的钢的腐蚀行为和作用机制。失重法埋片实验表明，在没有微生物影响的海底沉积物中，钢的腐蚀速度与海洋腐蚀环境的其它区带相比是较低的。A3钢在砂型海底沉积物中的腐蚀速度约是其在粘土型海底沉积物中腐蚀速度的2倍。另外，主要用电化学方法研究了A3钢在海底沉积物中的腐蚀行为，包括线性极化阻力测量，弱极化区的动电位扫描测量和电化学交流阻抗谱（EIS）测量，计算了A3钢在海底沉积物中腐蚀的有关电化学参数，探讨了A3钢在两种类型海底沉积物中的腐蚀行为差异。认为A3钢在砂型和粘土型海底沉积物中腐蚀速度大小的差别主要是由于作为阴极去极化剂的氧在不同类型海底沉积物中的扩散速度不同。通过弱极化数据拟合和IES测量的结果表明，A3钢在海底沉积物中的腐蚀机制主要是受阴极去极化剂的氧扩散控制作用。并提出了初期腐蚀过程的等效电路和腐蚀模式图。本文较系统的研究了A3钢在海底沉积物中的电化学腐蚀行为，并首次将弱极化曲线拟合技术应用于海底沉积物腐蚀研究，得到了一些有意义的结果。结合A3钢在不同类型海底沉积物中的阻抗谱特征，提出了相应的等效电路和腐蚀模型。