Rate Law for Photoelectrochemical Water Splitting Over CuO

Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.

Self-repairing Al_(2)O_(3)-TiO_(2)coatings fabricated through plasma electrolytic oxidation with various cathodic pulse parameters

The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.

封孔电弧喷涂铝涂层在盐雾环境中的防护性能

对于采用某种有机涂料封孔处理的电弧喷涂铝涂层,采用电化学阻抗谱(EIS)、扫描电镜(SEM)和能谱(EDS)分析并结合划格试验,研究了封孔铝涂层在盐雾条件下腐蚀防护性能。结果表明,封孔电弧喷涂铝涂层很快腐蚀,但经过2 400h盐雾加速试验(SST)后仍能对基体提供牺牲阳极保护;反应生成的铝离子可以通过封孔层孔隙渗透至面漆涂层表面并最终生成白絮状产物;根据EIS结果提出了相应的特征等效电路;SST后封孔涂层与喷涂层结合仍然良好。

牙科粘结剂对纯钛耐腐蚀性能的影响

目的探讨临床常用的牙科粘结剂对纯钛材料耐腐蚀性能的影响。方法用常用牙科粘结剂玻璃离子(GC)和聚羧酸锌水门汀(PC)粘结钛片,将试件浸泡于人工唾液中8周后,进行电化学阻抗谱和极化曲线检测。结果电化学阻抗谱显示GC组试件的阻抗弧明显小于其余两组,相同频率(中低频区)下的阻抗值最小,相位角最大值及所处频率范围也最小。等效电路图拟合结果显示:GC组电容值明显大于其余两组(P<0.05);阻抗值由小到大为:GC组<PC组<对照组(CC)(P<0.05)。极化曲线检测显示,各组极化电阻由小到大为:GC组<PC组<CC组(P<0.05);GC组的自腐蚀电流密度及自腐蚀电位的绝对值均明显大于其余两组(P<0.05)。结论玻璃离子粘结剂的使用会降低纯钛的耐腐蚀性能,聚羧酸锌粘结剂对纯钛耐腐蚀性能影响较小。

低合金耐蚀钢筋在两种pH混凝土模拟孔溶液中的耐氯离子点蚀性能

对比研究了普通低碳钢筋（LC）和2种耐蚀钢筋（1%Cr和6%Cr）在未碳化（p H=12.6）与碳化（p H=10.6）模拟混凝土孔溶液中加入氯离子后的腐蚀行为.采用线性极化电阻（LPR）和电化学阻抗谱（EIS）表征钢筋的电化学行为,并通过扫描电子显微镜（SEM）和X射线能谱仪（EDS）对腐蚀产物进行微观形貌观察和元素分析.结果表明：在点蚀阶段,与LC钢筋相比,1%Cr钢筋的临界氯离子值未提高,而6%Cr钢筋则提高5~10倍;在腐蚀扩展阶段,1%Cr的耐蚀性能与LC钢筋相比有小幅提升,可能的原因是1%Cr钢筋中的Cr促使生成致密锈层.

Galvanic corrosion behavior of copper/titanium galvanic couple in artificial seawater

The corrosion behaviors of copper and copper/titanium galvanic couple （GC） in seawater were studied by electrochemical impedance spectroscopy （EIS） and electrochemical noise （EN） techniques in conjunction with scanning electron microscopy （SEM） method. The results show that the corrosion process of copper in seawater can be divided into two stages, in which corrosion resistance and SE show the same evolution trend of initial increase and subsequent decrease, while SG changes oppositely. However, the ensemble corrosion process of copper/titanium GC in seawater includes three stages, in which corrosion resistance and SE show the evolution features of initial decrease with a subsequently increase, and the final decrease again;while SG changes oppositely. The potential difference between copper and titanium in their galvanic couple can accelerate the initiation of pitting corrosion of copper, and both the minimum and maximum corrosion potentials of copper/titanium GC are much more positive than those of pure copper.

Influence of Ga and Bi on electrochemical performance of Al-Zn-Sn sacrificial anodes

The influence of Ga and Bi on the microstructure and electrochemical performance of Al-7Zn-0.1Sn （mass fraction,%） sacrificial anodes was investigated by means of optical microscopy （OM）,scanning electron microscopy/energy dispersive X-ray analysis （SEM/EDAX） and electrochemical measurements.It was found that the coarse dendrites structure transformed into the equiaxed grains as well as a small amount of dendrite grains after adding Ga and Bi into Al-Zn-Sn alloys.A high current efficiency of 97% and even corrosion morphology were obtained for Al-7Zn-0.1Sn-0.015Ga-0.1Bi alloy.The results indicate that the proper amount of Ga and Bi is effective on improving the microstructure and electrochemical performance of Al-Zn-Sn alloy.

Corrosion behavior of tinplate in NaCl solution

The corrosion process of tinplate in 0.5 mol/L NaCl solution was investigated using the electrochemical impedance spectroscopy（EIS）,and the morphology and structure of the corrosion products were characterized by scanning electron microscope（SEM）,scanning probe microscopy（SPM）,X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS）.The results showed that the resistance of tin coating,Rc,was essentially constant but the charge transfer resistance,Rct,decreased by 2 orders of magnitude,which indicated that the tin coating was not seriously corroded while the carbon steel substrate was corroded continuously.The corrosion of tinplate in 0.5 mol/L NaCl solution was mainly the dissolution of carbon steel substrate because of the defects in the tin layer and the corrosion product was mainly γ-FeOOH.

Characterization of pitting corrosion of 7A60 aluminum alloy by EN and EIS techniques

The pitting corrosion behaviors of 7A60 aluminum alloy in the retrogression and re-aging （RRA） temper were investigated by electrochemical impedance spectroscopy （EIS） and electrochemical noise （EN） techniques, and the microstructure and the second phase content of the alloy were observed and determined by scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS）. The results show that there exist two different corrosion stages for 7A60 alloy in 3.5%NaCl solution, and the corrosion process can be detected by the appearance of EIS spectrum with two capacitive time constants and the wavelet fractal dimension D extracted from EN. SEM and EDS results also demonstrate that severe pitting corrosion in 7A60 alloy is mainly caused by electrochemical active MgZn2 particles, secondly by Al2MgCu and Mg2Si. Al7Cu2Fe particles make little contribution to the pitting corrosion of 7A60 alloy.

Corrosion and electrochemical behaviors of 7A09 Al-Zn-Mg-Cu alloy in chloride aqueous solution

The corrosion and electrochemical behaviors of 7A09 Al？Zn？Mg？Cu alloy were investigated in 3.5% NaCl （mass fraction） solution using complementary techniques such as scanning electron microscopy （SEM）, metallographic microscopy and electrochemical measurements. The results show that both pitting corrosion from or around the intermetallic particles and intergranular corrosion are observed after the immersion test due to the inhomogeneous nature of the microstructure of the 7A09 alloy. The preferential dissolution of the anodic Cu-depleted zone along grain boundaries is believed to be the possible cause of intergranular corrosion. The passivation and depassivation of this alloy show significant dependence of immersion time, owing to the formation and dissolution of various passive films on the sample surfaces. Furthermore, the corrosion process and corrosion mechanism were also analyzed.

Effect of aging time on precipitation behavior, mechanical and corrosion properties of a novel Al-Zn-Mg-Sc-Zr alloy

The precipitation behavior, mechanical properties and corrosion resistance of a novel Al-Zn-Mg-Sc-Zr alloy aged at different time were studied by optical microscopy（OM）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, tensile tests, potentiodynamic polarization and electrochemical impedance spectroscopy. The results revealed that with increasing aging time at 120 ℃, the hardness and tensile strength of the alloy increased rapidly at first and then slightly decreased. The resistance of exfoliation corrosion（EXCO） and intergranular corrosion（IGC） increased gradually with increasing aging time. The same trend of corrosion properties was demonstrated by electrochemical polarization curves and EIS test. The characteristics of grain boundary precipitates and precipitate free zone（PFZ） had a significant influence on the mechanical and corrosion behaviors of the studied alloy. On the basis of TEM observations, the size of grain boundary precipitates and the width of PFZ became larger, and the distributed spacing of grain boundary precipitates was enhanced with increasing aging time.

Electrochemical corrosion behavior of arc sprayed Al-Zn-Si-RE coatings on mild steel in 3.5% NaCl solution

Al-Zn-Si-RE coating with high Al content was deposited on mild steel by arc spraying. The electrochemical behavior of Al-Zn-Si-RE coating in 3.5%NaCl solution was systematically studied by potentiodynamic polarization, corrosion potential (φcor ) and electrochemical impedance spectroscopy techniques (EIS). The impedance data were fitted to appropriate equivalent circuits to explain the different electrochemical processes occurring at the electrode-electrolyte interface. The results indicate that Al-Zn-Si-RE coating reveals the similar polarization behavior as Zn-15Al coating. The coating has no passive region in the anodic polarization, but far lower corrosion current and much higher corrosion potential. Al-Zn-Si-RE coating provides effective sacrificial protection for steel substrate and the sacrificial anodic protection plays dominant role during the immersion process. In addition, theφcor evolution and EIS plots indicate that the corrosion process can be divided into five stages: pitting-dissolution-redeposition, activation corrosion, cathodic protection, physical barriers and the coating failure.

Electrochemical behaviors of tantalum in anhydrous ethanol containing hydrogen sulfate ions

The electrochemical behaviors of Ta in tetrabutylammonium hydrogen sulfate（TBAHS） ethanol solutions were studied using potentiodynamic polarization,cyclic voltammetry,potentiostatic current time transient and impedance techniques.The results revealed that no active-passive transition is presented in the cyclic voltammogram,and the anodic current density increases with the increase of solution temperature,TBAHS concentration,potential scan rate and water content.The apparent activation energy is about 43.389 kJ/mol and the dissolution process is diffusion-controlled.Potentiostatic measurements showed that the current density gradually decays to a steady value when the potential is low;however,when the potential is higher than a certain value,the current density initially declines to a minimum value and then increases gradually.The resistance of passive film decreases with increasing potential,and inductive loops are presented when the potential is higher than 2.0 V.

Cycle life prediction and match detection in retired electric vehicle batteries

The lifespan models of commercial 18650-type lithium ion batteries （nominal capacity of 1150 mA-h） were presented. The lifespan was extrapolated based on this model. The results indicate that the relationship of capacity retention and cycle number can be expressed by Gaussian function. The selecting function and optimal precision were verified through actual match detection and a range of alternating current impedance testing. The cycle life model with high precision （〉99%） is beneficial to shortening the orediction time and cutting the prediction cost.

Synthesis of aluminum tri-polyphosphate anticorrosion pigment from bauxite tailings

Aluminum tri-polyphosphate was synthesized from bauxite tailings and phosphoric acid with a P/A1 molar ratio of 3. This is highly advantageous from a waste recycling perspective as bauxite railings are generally regarded as unusable waste. The acidity, whiteness and mean particle size of prepared aluminum tri-polyphosphate are all improved after modification. The possibility of using modified aluminum tri-polyphosphate as an anticorrosive pigment was also investigated by electrochemical impedance spectroscopy. The resistance of the coatings with modified aluminum tri-polyphosphate is 7×10^7Ω for 40 d of immersion, which is superior or at least comparable to that of coatings containing APW-2, which exhibits a resistance of 5.7×10^7Ω.

In situ investigation of atmospheric corrosion behavior of PCB-ENIG under adsorbed thin electrolyte layer

The effects of relative humidity (RH) on a printed circuit board finished with electroless nickel immersion gold (PCB-ENIG) under an adsorbed thin electrolyte layer (ATEL) were investigated in situ via the measurement of cathodic polarization curves, electrochemical impedance spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to clearly elaborate the corrosion behavior of PCB-ENIG in the atmospheric environment. Results indicated that the cathodic process of PCB-ENIG under ATEL was dominated by the reduction of dissolved oxygen, corrosion products, and H2O. The cathodic current density of PCB-ENIG increased progressively with increasing RH. Moreover, its cathodic current density in the solution was greater than that under ATEL. This result demonstrated that the diffusion process was not the controlling step during the limiting reduction of cathodic oxygen. When the polarization potentials were located in a more negative region, the cathodic polarization current density gradually decreased under 75% and 85% RH. Notably, the anodic process became the controlling step in the extremely thin liquid film during the remainder of the experiment.

Electrochemical and corrosion behaviors of pure Mg in neutral 1.0% NaCl solution

The corrosion behaviors and corresponding electrochemical impedance spectroscopy（EIS） and polarization curves of pure Mg in neutral 1.0% NaCl solution were investigated.The fractal dimension of EIS at different time was studied.The corrosion process and EIS evolution are divided into three stages.In the initial stage,EIS is composed of two overlapped capacitive arcs,the polarization resistance and charge transfer resistance increase rapidly with immersion time,and the corrosion rate decreases.Then,two well-defined capacitive arcs appear,and the charge transfer resistance and corrosion rate remain stable.After a long immersion time,inductive component appears in a low frequency range,the charge transfer resistance decreases and the corrosion rate increases with the immersion time.The fractal dimension obtained from the time records of EIS seems to be a promising tool for the analysis of corrosion morphology because of its direct relationship with the metal surface.

EIS studies the effect of Zinc to Al-Zn alloy used for cathodic protection in 3% NaCl solution

Electrochemical impendence spectroscopy （EIS） is applied to investigate the dissolution behavior of Al-Zn alloys in 3% NaCl solution at different polarization potentials. A new reaction model is proposed, and the activation mechanism of zinc in Al-Zn alloys is achieved. There are three intermediates in the dissolution process： Znad^＋, Znad^2＋ and Alad^＋, ,of which only Zni can activate Al-Zn alloys. Most Znnd^＋ is produced by β-phase,and the alloys with 2. 3% - 3. 8% （wt） Zn dissolve rapidly. The Al-Zn alloys of heart-shaped EIS are active in 3% NaCl solution, thus EIS characteristic can be used to distinguish the activa-tion of Al-Zn alloys.

Oxidation behavior of high-entropy alloys Al_xCoCrFeNi(x=0.15, 0.4) in supercritical water and comparison with HR3C steel

The oxidation behaviors of high-entropy alloys AlxCoCrFeNi(x=0.15, 0.4) in supercritical water at 550 and 600 °C were studied, and compared with HR3 C steel. All oxide films formed on alloys are composed of spinel type(Fe, Cr)3O4 oxides. Compared with the oxide film on HR3 C steel, thinner oxide films with smaller size of oxide particles were realized on Al0.15 CoCrFeNi and Al0.4CoCrFeNi, indicating a superior oxidation resistance of Al0.15 CoCrFeNi and Al0.4CoCrFeNi to HR3 C steel. Electrochemical test results reveal that surface oxide films greatly affect the electrochemical corrosion behavior of the oxidized alloys in 3.5% Na Cl solution. The relatively high corrosion resistance of oxidized Al0.15 CoCrFeNi and HR3 C is attributed to the formation of thick and multi-layer oxides.

Electrodeposition and corrosion behavior of nanostructured Ni-TiN composite films

The Ni-TiN nanocomposite film was successfully electrodeposited on brass copper substrates.The microstructures of the Ni-TiN nanocomposite film were investigated using scanning electron microscopy（SEM） and transmission electron microscopy（TEM）.Its average grain size was analyzed through X-ray diffraction（XRD）,and its anti-corrosion property was studied through potentiodynamic scanning curves and electrochemical impedance spectroscopy（EIS）.The results show that the morphology of Ni-TiN composite film is sensitively dependent on the electroplating current density,TiN nanoparticle concentration,solution stirring speed,bath temperature and pH value of solution.The average grain size of the optimized nanocomposite film is about 50 nm.Meanwhile,the Ni-TiN nanocomposite films are much more resistant to corrosion than pure Ni coatings.