Study on kinetics of cathodic reduction of dissolved oxygen in 3.5% sodium chloride solution

Electrochemical reduction of dissolved oxygen in seawater on metals is of great importance for corrosion studies. The present paper studied cathodic reduction of dissolved oxygen on Q235 carbon steel in 3. 5% sodium chloride(NaCl)solutions by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), rotating disk electrode(RDE)and rotating ring-disk electrode(RRDE). The cyclic voltammetric results demonstrated the cathodic process on Q235 carbon steel in O2-saturated 3. 5% NaCl solution contains three reactions:dissolved oxygen reduction, iron oxides reduction and hydrogen evolution. The peak potential of oxygen reduction reaction(ORR)is-0. 85 V vs Ag/AgCl, 3 molL-1 KCl. The E1S results indicated that the ORR occurring on Q235 carbon steel is a 4-electron process and that no finite diffusion is caused by the intermediate of H2O2 produced by ORR. The RDE and RRDE voltammograms confirmed the EIS results and it was found that the number of transferred electrons for ORR was nearly 4, I. E. , dissolved oxygen reduced to water.     

Surface modification of ZrO2 nanoparticles with styrene coupling agent and its effect on the corrosion behaviour of epoxy coating

The surface of ZrO2 nanoparticles was modified by styrene coupling grafting method to improve the dispersion and interaction of the nanoparticles with the epoxy coating in which the modified ZrO2 nanoparticles were used as an additive. The grafting performance and microstructure of the nano- ZrO2/epoxy coating were analyzed by Fourier transformation infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The corrosion behavior of the nano-ZrO2/epoxy coating on mild steel was evaluated in neutral 3.5 wt% NaC1 solution using electrochemical impedance spectroscopy （EIS）. Both the coating capacitance and coating resistance fitted by the equivalent circuit from EIS were used to evaluate the protective performance of the coating towards the mild steel. The results show a superior stability and efficient corrosion protection by the modified ZrO2 nanoparticles. The epoxy coating containing 2 wt% modified ZrO2 nanoparticles exhibited the best corrosion performance among all the coating specimens. This research may provide an insight into the protection of mild steel using modified epoxy coatings.     

Corrosion performance of zinc coated steel in seawater environment

Considering the continuous exploitation of marine resources,it is very important to study the anticorrosion performance and durability of zinc coated streel(ZCS) because its increasing use as reinforcements in seawater.Tafel polarization curves and linear polarization curves combined with electrochemical impedance spectroscopy(EIS) were employed to evaluate the corrosion performance of ZCS at Qingdao test station during long-term immersion in seawater.The results indicated that the corrosion rate of the ZCS increased obviously with immersion time in seawater.The corrosion products that formed on the zinc coated steel were loose and porous,and were mainly composed of Zn_5(OH)_8Cl_2,Zns(OH)_6(CO_3)_2,and ZnO.Pitting corrosion occurred on the steel surface in neutral seawater,and the rate of ZCS corrosion decreased with increasing pH.     

The influence of the corrosion product layer generated on the high strength low-alloy steels welded by underwater wet welding with stainless steel electrodes in seawater

The high strength low-alloy steels are welded by underwater wet welding with stainless steel electrodes. The micro-structural and electrochemical corrosion study of base metal (BM), weld zone (WZ) and heat affected zone (HAZ) are carried out to understand the influence of the corrosion product layer generated on the high strength low-alloy steels welded by underwater wet welding with stainless steel electrodes, methods used including, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and scanning electron microscope (SEM). The results indicate that the WZ acts as a cathode and there is no corrosion product on it throughout the immersion period in seawater. The HAZ and BM acts as anodes. The corrosion rates of the HAZ and BM change with the immersion time increasing. In the initial immersion period, the HAZ has the highest corrosion rate because it has a coarse tempered martensite structure and the BM exhibites a microstructure with very fine grains of ferrite and pearlite. After a period of immersion, the BM has the highest corrosion rate. The reason is that the corrosion product layer on the HAZ is dense and has a better protective property while that on the BM is loose and can not inhibit the diffusion of oxygen.     

Evaluation of long-term corrosion durability and self-healing ability of scratched coating systems on carbon steel in a marine environment

Defects in protective-coating systems on steel surfaces are inevitable in practical engineering applications.A composite coating system,including a primer,middle coat and topcoat,were used to protect carbon steel from corrosion in a marine environment.Two environmental additives,glass fi bers and thiourea,were applied in the middle coat to modify the coating system.The long-term corrosion durability and self-healing ability of the scratched coating system were evaluated by multiple methods.Results of the electrochemical technologies indicated that the coating system that contained 0.5 wt.%fi bers and 0.5 wt.%thiourea presented good corrosion protection and self-healing for carbon steel when immersed in 3.5%Na Cl for 120 d.Evolution of localized corrosion factors with time,as obtained from the current distribution showed that fi bers combined with thiourea could inhibit the occurrence of local corrosion in scratched coating systems and retarded the corrosion development signifi cantly.Surface characterization suggested that adequate thiourea could be absorbed uniformly on fi bers for a long time to play an important role in protecting the carbon steel.Finally,schematic models were established to demonstrate the action of fi bers and thiourea on the exposed surface of the carbon steel and the scratched coating system in the entire deterioration process.     

IMPEDANCE CHARACTERISTICS OF CALCAREOUS DEPOSIT

The electrochemical impedance spectra for bare steel and sample covered with calcareous deposit in artificalseawater were determined; the dependence of the impedance on the potential was investigated, thesignificance of the impedance parameter R_f reflecting the effective protectiveness of the deposit is emphasized.Optimization of the cathodic polarization condition is discussed.     

Research on protection of steel piles of Baoshan general steel factory wharf by using DZ and DZ-2 tapes

Steel piles at the tidal zone can be seriously corroded. Common protective methods such as painting or coating with rubber or other protective materials, etc. cannot provide full protection when used as supplementary protection because these traditional methods require strict pretreatment and sealing of the metallic surface from the corrosive mediums, and time for the protective coatings to solidify. This is very difficult under the severe action of waves and surges on the sea. With our oil-soluble DZ-2 tape, protection efficiency for hanging steel plates at the tidal and splash zones reaches to 82–99%. The protection efficiency of water soluble DZ tape at the tidal zone reaches to 92.9%. The DZ and DZ-2 tapes can rapidly reduce the original corrosion velocity to ten percent and one percent respectively as fully proved by the 500 hour rapid corrosion testing with indoor salt fog and by the relevant electrochemical parameters of instantaneous corrosion velocity, etc. DZ tape absorbs much OH⁻ to cause a pH rise. A synergistic protective effect is gained when DZ tape is used together with cathodic protection of steel piles at the tidal zone. The working principle of DZ tape is different from that of DZ-2 tape even though they are composed of the same chemical materials. The latter provides protection because of the close affinity between metal and its carboxyl group shields the active centre at the metal surface to reduce the activation energy of metal. The carbon chain forms a covering oil film of netted structure. Dai Tao, Dai Wei and Xia Caiyuan et al. participated in the research and made useful contribution. Contribution No. 1656 from the Institute of Oceanology, Academia Sinica.     

Study of the Corrosion Resistance of Electroless Ni-P Deposits in a Sodium Chloride Medium

The corrosion resistance of electroless Ni-P deposits with phosphorous contents from 12% to 14% in sodium chloride solutions was studied. The deposits were immersed in 3.5% NaCl solutions for 29 d to obtain the electrochemical parameters and were examined in a standard salt spray test for 15 d respectively. The corrosion resistance of the deposits was studied by poten- tio-dynamic scan, electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and cold-field emission scanning electron microscopy (FE-SEM) equipped with an energy dispersive X-ray detector (EDX). The patterns of XRD and the results of FE-SEM showed that the prepared deposits were amorphous. But after a 15 d standard salt spray test, a few pinholes appeared on the surface of the deposit and the weight content of phosphorus on the surface of the deposit was higher (which was beneficial to the formation of the passivation films) than that before the standard salt spray test when the nickel content was lower because the dissolved weight of nickel was greater than that of phosphorus. The results from potentio-dynamic scan and EIS showed that passivation films formed on the Ni-P deposit after immersion in the NaCl solutions, which decreased the corrosion rate of Ni-P samples. The results of this work show their potential applications in marine corrosion.     

ELECTROCHEMICAL CORROSION BEHAVIOR OF STEEL IN THE JUNCTURE AREA OF SEA CLAY AND SAND

Corrosion behavior of steel in the juncture area of sea clay and sand was studied. The results show that galvanic corrosion occurred between steel samples buried in sea clay and sand, and that the polarity of the galvanic cell reversed after some testing later. The cause of reversing of polarity is discussed.     

Mitigation of hydrogen permeation into steel by bacteria:a new research proposal

A new research proposal was introduced aiming at solving the fundamental theory for reducing the risk of hydrogen embrittlement(HE) in high-strength steels by utilizing hydrogen-consuming microorganisms.The superior performance of high-strength steel can meet the material strength requirements for remote deep-sea marine engineering development.Due to the heavy corrosive marine environment,steel structures must be protected by cathodic protection.However,high-strength steel is sensitive to stress corrosion cracking and HE,and cathodic protection can promote hydrogen permeation into steel.Hydrogen-consuming microorganisms are widespread in the natural environment and they utilize the energy of hydrogen oxidation to survive.If we could make use of the hydrogen-consuming function of microorganisms to consume the hydrogen generated during the cathodic protection process,then the potential for cathodic protection can be reasonably lowered,ideally protecting the steel and simultaneously reducing the possibility of HE.     

Study on rust layers on steel in different marine corrosion zone

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Effect of Ca(OH)2, NaCl,and Na2SO4 on the corrosion and electrochemical behavior of rebar

The corrosion of rebar in reinforced concrete in marine environments causes significant damage to structures built in ocean environments. Studies on the process and mechanism of corrosion of rebar in the presence of multiple ions may help to control damage and predict the service life of reinforced concrete structures in such environments. The effect of interactions between sulfate and chloride ions and calcium hydroxide on the electrochemical behavior of rebar are also important for evaluation of structure durability. In this work, electrochemical impedance spectroscopy(EIS) plots of rebar in Ca(OH)_2 solution and cement grout, including NaCl and Na_2SO_4 as aggressive salts, were measured for different immersion times. The results show that corrosion of rebar was controlled by the rate of charge transfer as the rebar was exposed to chloride solution. In the presence of high concentrations of sulfate ions in the electrolyte, generation and dissolution of the passive film proceeded simultaneously and corrosion was mainly controlled by the diffusion rate. When Na_2SO_4 and NaCl were added to Ca(OH)_2 solution, the instantaneous corrosion rate decreased by a factor of 10 to 20 as a result of the higher p H of the corroding solution.     

Impedance characteristics of carbon steel under cathodic protection

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Protection of steel piles in harbours by using DZ tape and cathodic polarization

An anticorrosion method using wet DZ¹ tape and electrochemical cathodic protection is suggested. The advantages of this method over internationally patented sealing techniques lie in its electrochemically open system, high adsorption of OH⁻ with resultant rise of pH, exchangeable electrolytes, simple pretreatment of the steel pipe, simplicity of application, lower cost, better protection even under ebb tide, and low transmission of oxygen and corrosion products. Contribution No. 1455 from the Institute of Oceanology, Academia Sinica     

ELECTROCHEMICAL BEHAVIOR OF Al-BASIC SACRIFICIAL ANODE AT ESTUARY

The Al-basic sacrificial anode is widely used to protect steel construction from corrosion in seawater,but is not suitable for protecting steel in freshwater. In the estuary area, seawater and freshwater mix anddifferent seawater salinity can be formed in different mixing sites between freshwater and seawater. Basedon the requirements of the Shengli Petroleum Administrative Bureau of China, the effect of seawatersalinity on electrochemical properties of Al-basic anode was studied under laboratory conditions by themethod given in National Standard GB 4948-85 (China Starndard Bureau, 1985). No obvious effectwas found when seawater salinity was 30 to 10, but obvious effect on anodic open circuit potential, closedcircuit potential and current efficiency was found when seawater salinity was 5. These values are lowerthan those given in the Naional Standard.     

Influence of dissolved oxygen on the protectiveness and morphological characteristics of calcareous deposits with galvanostatic polarization

The influence of dissolved oxygen on calcareous deposits formed under galvanostatic polarization mode was studied.When the dissolved oxygen concentration was less than 7 mg L~(-1),the cathodic protection potential showed a plateau at the initial polarization,and then quickly shifted negatively.While the dissolved oxygen was more than 9 mg L~(-1),the potential shifted negatively in a linear form.After 168 h of polarization,the final protection potential shifted negatively with the decreasing dissolved oxygen concentration.The deposition progress was monitored by electrochemical impedance spectroscopy,and only one single loop was found in Nyquist diagram,indicating deposits of ineffective protectiveness precipitation under the experimental conditions.The protection factor of deposits increased with the decreasing dissolved oxygen concentration which was detected by linear polarization resistance technique.The cathodic electrochemical reaction could change very shortly from oxygen reduction to hydrogen evolution after cathodic protection under very low dissolved oxygen concentration,such as 1 mg L~(-1),resulting in the hydrogen bubbling from the metallic surface and the decrease of deposits protection factor.Observation by scanning electron microscopy and X-ray diffraction analysis demonstrated that the deposits were mainly of calcite under the experimental conditions,and that dissolved oxygen had no effect on the crystalline types of calcium carbonate.     

Model test of the stability degradation of a prestressed anchored rock slope system in a corrosive environment

The long-term stability of a prestressed anchored slope might be influenced by the durability of the anchorage structure. To understand long-term stability of anchored rock slopes, the research presented herein evaluated the performance evolution of a prestressed anchored bedding slope system in a corrosive environment by model test. The corrosion process in a prestressed anchor bar was monitored in terms of its open-circuit potential(OCP), corrosion current density(CCD), and electrochemical impedance spectroscopy(EIS). The stability of the prestressed anchored slope was evaluated by monitoring changes in anchorage force and displacements. The experimental results show that prestress and oxygen could reduce the corrosion resistance of the anchor bar, and anchor bars in a chloride-rich environment are very susceptible to corrosion. Prestressed tendons in a corrosive environment suffer a loss of anchorage force, the prestress decreases rapidly after locking, and the rate thereof decreases until stabilising; in the later stage, corrosion leads to the reduction of the cross-sectional area of the steel bar which may cause the reduction in anchorage force again. Anchorage force controls the deformation and stability of the anchored slope, the prestress loss caused by later corrosion may lead to an increased rate of displacement and stability degradation of the prestressed anchored rock slope.     

Smart anticorrosion coating based on stimuli-responsive micro/nanocontainer: a review

Smart coating for corrosion protection of metal materials(steel,magnesium,aluminum and their alloys) has drawn great attention because of their capacity to prevent crack propagation in the protective coating by releasing functional molecules(healing agents or corrosion inhibitors) on demand from delivery vehicle,that is,micro/nanocontainer made up of a shell and core material or a coating layer,in a controllable manner.Herein,we summarize the recent achievements during the last 10 years in the field of the micro/nanocontainer with different types of stimuli-responsive properties,i.e.,pH,electrochemical potential,redox,aggressive corrosive ions,heat,light,magnetic field,and mechanical impact,for smart anticorrosion coating.The state-of-the-art design and fabrication of micro/nanocontainer are emphasized with detailed examples.     

Effect of geojute technique on density,diversity and carbon stock of plant species in landslide site of North West Himalaya

Mountainous regions of the globe experience landslides due to heavy rainfall and unplanned construction on slopes. Geojute is adopted globally as a landslide rehabilitation measure, but its impact on natural vegetation development is poorly understood. The present study was conducted to examine the impact of geojute application on vegetation restoration, ecology and carbon stock in a recently occurred landslide, during 2012. The results revealed that the geojute application improved the richness, diversity, density and basal area of plant species at the landslide site. Likewise, biomass production, carbon stock and carbon sequestration of plant species was observed significantly higher in geojute treatments compared to control (without geojute treatment). Moreover, significant improvement in soil moisture was recorded beneath the geojute treatments. Further, results showed that the geojute is highly effective in controlling soil erosion at the landslide site. The findings of this study revealed ecological and environmental benefits of geojute application in term of improvement in vegetation recovery processes, species diversity and carbon sequestration at the landslide site. The scientific outcome of this study can be helpful for planning the rehabilitation measures in landslide affected regions of the globe.     

三元复合驱采油污水阻垢缓蚀剂电化学分析

研制适用于三元复合驱采油污水工况条件下的MPM固体缓蚀阻垢剂,分析三元复合驱采油污水中MPM的电化学特性.结果表明:随着温度增加,20#钢在采油污水的腐蚀速率呈增加趋势,极化曲线显示钝化区表面材料在表面高温下处于钝化状态,产生的钝化膜能够降低腐蚀速度.在阻垢缓蚀剂质量浓度相同的情况下,不同温度的电化学阻抗谱在高频区出现容抗弧,显示优良的缓蚀性能.不同质量浓度MPM极化曲线表明,缓蚀率随MPM质量浓度的增加而增大,MPM极值质量浓度为80mg/L.污水体系中的Ca2+、Cl-对缓蚀率产生影响.MPM适用于高质量浓度Ca2+的三元复合驱采油污水处理.