The Study of the Varying Characteristics of Cathodic Regions for Defective Coating in 3.5% Sodium Chloride Solution by EIS and WBE

The current distributions over carbon steel under iron red alkyd primer exposed to 3.5% sodium chloride solution were mapped using the wire beam electrode(WBE). The electrochemical impedance spectroscopy(EIS) of the WBE was carried out to analyze the performance of coating delamination and corrosion behavior of carbon steel beneath defective coating. The EIS data revealed that protective capability of coating decreased with immersion time and the degree of cathodic delamination showed a rapid rise. The current density distribution of WBE indicated that cathodic sites was located at the defect at the beginning of immersion and gradually spread into the intact coating. The cathodic regions were distinguished from the anodic area and distributed over the WBE. The changes of cathodic sites could reflect the deterioration process of defective coating. The cathodic area ratio was a more useful parameter than the cathodic delamination degree to evaluate the coating cathodic delamination. The polarity reversals of electrodes at the defect and beneath coating were observed. A simple discussion of relationship between the blister and the polarity reversal was made from a standpoint of electrochemical distribution. WBE method was able to map and record the changes of local cathodic sites beneath defective coating in real time, which could provide more detailed information about the local degradation of coating.     

Marine antifouling behavior of the surfaces modified by dopamine and antibacterial peptide

Marine biofouling causes serious harms to surfaces of marine devices in transportation, aquaculture, and offshore construction. Traditional antifouling methods pollute the environment. A novel and green antifouling strategy was developed to prevent effectively the adhesion of bacteria and microalgae. An antifouling surface was fabricated via coating Turgencin B_Mox2 (TB) onto dopamine-modified 304 stainless steel (304 SS). The surface physical and chemical properties before and after modification were characterized by Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectrometer (XPS), contact angle measurement (CA), 3D optical profilometer, ellipsometer, and atomic force microscope (AFM). Antimicrobial peptide was coated onto the surface of 304 SS successfully, and the surface morphology and wettability of the modified sample were modified. Moreover, cytocompatibility of the peptide was evaluated by co-culture of peptide and cells, indicating promising cell biocompatibility at the modified sample surface. At last, antifouling performance and electrochemical corrosion were tested. Results show that the adhesion rates of Vibrio natriegens and Phaeodactylum tricornutum on the antifouling surface were reduced by 99.85% and 67.93%, respectively from those of untreated samples. Therefore, the modified samples retained superior corrosion resistance. The study provide a simply and green way against biofouling on ship hulls and marine equipment.

     

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.     

Cathodic protection of A1 hull ship

Heavy paint coating loss and localized corrosion of the Al alloy hull occur red after less than a year's service of a ship at sea. Examination and analysis showed that the Mg-basic sacrificial anodes originally used for cathodic protection were not suitable as the resulting −1.3V-plus (vs Ag/AgCl) protection potential for the hull was too negative for the purpose. A new protection system was designed in which the protection current densities were 15mA/m² for the hull and 350mA/m² for the propeller. The hull protection potential under actual condition at sea was between −920mV and −1100mV (Ag/AgCl) and the protection efficiency was over 90%. The protection areas were calculated by using the formulas A=1.8×LBP×D+BC×LB×B for the hull and A_s=2Aa_s for the propeller. Contribution No. 1640 from the Institute of Oceanology, Academia Sinica.     

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.     

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 on rust layers on steel in different marine corrosion zone

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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.     

Corrosion behavior of anodic oxidized TiO<Subscript>2</Subscript> film in seawater

TiO₂ films were formed on metallic titanium substrates by the anodic oxidation method in H₂SO₄ solution under the 80V D.C.. Phase component and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Water contact angles on titanium oxide film surface were measured under both dark and sunlight illumination conditions. Corrosion tests were carried out in seawater under different illumination conditions by electrochemistry impedance spectrum (EIS) and polarization curves. The result showed that the TiO₂ film prepared by the anodic oxidation method was anatase with a uniform structure and without obvious pores or cracks on its surface. The average water contact angle of the film was 116.4° in dark, in contrast to an angle of 42.7° under the UV illumination for 2 hours, which demonstrates good hydrophobic property. The anti-corrosion behavior of the TiO₂ film was declining with the extended immersion time. Under dark conditions, however, the hydrophobic TiO₂ film retarded the water infiltrating into the substrate. The impedance changed slowly and the corrosion current density was 2 orders of magnitude lower than that with the film illuminated by sunlight. All of those mentioned above indicate that the TiO₂ film possesses much better performance under dark condition, and it can be applied as an engineering material under dark seawater environment.     

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.     

Effect of Fe2+ ions on polarization behavior of X60 steel in CO2 saturated salty water

The effects of ferrous ions on cathodic and anodic polarization behavior of the X60 steel in CO₂ saturated salty water were studied by potentio-dynamic polarization method. The results show that the reducing current peak of cathodic polarization is affected significantly if FeCl₂ is added to the salty solution of controlled pH, but not the anodic polarization. It is considered that the ferrous ions accelerate the formation of a protective ferrous carbonate film. Films formed by addition of ferrous ions and those formed by ferrous ions produced from steel corrosion have the same forming mechanism. The former can fully meet the formative condition of the film and can play the role of inhibitor.     

Predicting size effect on diffusion-limited current density of oxygen reduction by copper wire

The size effect of copper wire radius (0.04–0.82 mm) on the diffusion-limited current density of an oxygen reduction reaction in stagnant simulated seawater (naturally aerated 0.5 mol/L NaCl) is investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) and compared with the results obtained in 0.5 mol/L H2SO4. In the oxygen diffusion-limited range, size effect is found to occur independent of electrolytes, which is attributed to non-linear diffusion. Additionally, to satisfy application in a marine setting, an empirical equation correlating oxygen diffusion-limited current density to copper wire radius is proposed by fitting experimental data.     

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.     

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.     

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.     

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     

Influence of active marine organic matter on electrochemical corrosion

Chemical means were used to extract polyphenols from healthy brown algae collected in littoral seawater. Experiments on corrosion of A₃ steel, the time-potential curve, and polarization curve in polyphenols seawater showed stronger cathodic polarization compared with that in common seawater. This indicates that brown algae polyphenols might feasibly be used as corrosion inhibitor in seawater. Contribution No. 3763 from the Institute of Oceanology, Chinese Academy of Sciences. Project 59471054 supported by NSFC and National “Nineth Five Year” Project 96-916-04-01.     

EFFECT OF SULPHATE-REDUCING BACTERIA ON ELECTRO-CHEMICAL CORROSION BEHAVIOR OF 16Mn STEEL IN SEA MUD

ＩＮＴＲＯＤＵＣＴＩＯＮＩｔｗａｓｇｅｎｅｒａｌｌｙｃｏｎｓｉｄｅｒｅｄｐｒｅｖｉｏｕｓｌｙｔｈａｔｔｈｅｃｏｒｒｏｓｉｏｎｏｆｓｔｅｅｌｉｎｓｅａｍｕｄｗａｓｎｏｔｓｅｒｉｏｕｓ.Ｈｏｗｅｖｅｒ,ｉｔｗａｓｌａｔｅｒｆｏｕｎｄｔｈａｔｔｈｅｃｏｒｒｏｓｉｏｎｒａｔｅｏｆｓｔｅｅｌｉｎｓｏｍｅｓｅａｍｕｄｗａｓｈｉｇｈｅｒｔｈａｎｔｈａｔｉｎｓｅａｗａｔｅｒ(Ｋｉｎｇ,1980;Ｓｅｈｍｉｄｅ,1982;Ｇｕｏｅｔａｌ.,1997;Ｈｏｕ,1998).Ｔｈｅｒｅａｒｅｓｏｍｅｒｅｐｏｒｔｓｔｈａｔｔｈｅｃｏｒｒｏｓｉｏｎｒ…     

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.     

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.