Corrosion Mechanism of 5083 Aluminum Alloy in Seawater Containing Phosphate

As a material with good corrosion resistance,5083 aluminum alloy has a great application prospect in marine environment.In this work,the corrosion characteristics of 5083 aluminum alloy in seawater containing phosphate were investigated with Potentiodynamic Polarization,Electrochemical Impedance Spectroscopy (EIS),Scanning Electron Microscope (SEM),Energy Dispersive Spectroscopy Analysis (EDSA),X-ray Photoelectron Spectroscopy (XPS) and Laser Confocal Microscope.The results indicated that the effects of phosphate in seawater were two-fold.Firstly,phosphate slightly accelerated the corrosion of 5083 in seawater in the early stage of corrosion.HPO_4~(2-)competed with OH~-in the adsorption process on the alloy surface,which weakened the contact between OH~-and Al~(3+)near the interface of the alloy,and inhibited the formation as well as the self-repair of the passive film,thus accelerating the activation dissolution process.Compared with the natural seawater,the charge transfer resistance of 5083 in the seawater containing phosphate decreased faster during the early stage of corrosion,and the corrosion current density i_corr was higher in seawater containing phosphate.On the other hand,the addition of phosphate would not affect the cluster distribution of the second phase of 5083 in seawater,but it changed the composition of the corrosion product layer and had an obvious inhibitory effect on the local corrosion of 5083 in seawater.After 16-day exposure,shallower and more sparsely distributed pits could be observed on the derusted surface of 5083 in the seawater containing phosphate,and the pitting coefficient in the seawater containing phosphate was significantly lower than that in natural seawater.The reduction of pitting tendency could be realized mainly through two ways.First,the HPO_4~(2-)adsorbed on the surface of the passive film in the early stage of corrosion and repeled the corrosive anions such as Cl~-.Second,phosphate participated in the construction of the Ca HPO_4 precipitation film,which acted as a barrier and protection.     

Corrosion Behavior of Anodic Oxidized TiO_2 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.     

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.     

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.     

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 hot dip coating in artificial seawater

INTR0DUCnONAlloycoatingscandetivelyproteCtsteelagainstcormsioninseri0uscormsionenvir-orunent,suchasthedrinesplashandtidalzones-TwoInainhodiptincaldrinumalloycOaingswidelyusedcommroiallyareGalfancoaing(contalningZn-5wt%kl-us)devel-oPedbytheIntemaionaltalZincReenhheZaionandhocoating(c0n-talningZn-55Wt%Al-1.6Wt%Si)develoPedbytheBethlehemSteelCorpOration-Anewrinc-basedalloycOaingdevel0PedbyNortheaStemUniversityisdiscussedinthesPaperbyelecthehendcalmethod.FromSun(l996),welmOWthecorms…     

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.     

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.     

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.     

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.     

Effect of Carbonation and Drying-Wetting Cycles on Chloride Diffusion Behavior of Coral Aggregate Seawater Concrete

Based on seawater immersion,drying-wetting cycles,carbonation and drying-wetting cycles for coral aggregate sea-water concrete(CASC)with different strength grades,the effect of carbonation and drying-wetting cycles on chloride diffusion be-havior of CASC is studied.The results show that the free surface chloride concentration(Cs),free chloride diffusion coefficient(Df)and time-dependent index(m)of CASC in the drying-wetting cycles is obviously higher than that in seawater immersion.The Df and m of CASC of carbonation and drying-wetting cycles is higher than that in the drying-wetting cycles.Carbonation increases the Df and m of CASC,which is against CASC to resist chloride corrosion.The corrosion possibility of CASC structures in different ex-posed areas is as follows:splash zone(carbonation and drying-wetting cycles)>tidal zone(drying-wetting cycles)>underwater zone(seawater immersion).Besides,the chloride diffusion rate of C65-CASC is 17.8%-63.4%higher than that of C65-ordinary aggre-gate concrete(OAC)in seawater immersion(underwater zone).Therefore,anti-corrosion measures should be adopted to improve the service life of CASC structure in the oceanic environment.     

磺酸基改性梳状有机硅聚醚破乳剂的制备及性能分析

在铂催化剂条件下,利用含氢聚硅氧烷(PHMS)、烯丙基磺酸盐(COPS-1)和烯丙基聚醚(Y-1)的硅氢化反应生成磺酸盐有机硅聚醚破乳剂(COPESO),采用红外光谱、GPC、粒度、界面张力和破乳性能测试等,对破乳剂进行结构表征,分析破乳性能的影响因素.结果表明:当反应温度为90℃、pH=3、COPS-1质量分数为5%时,对破乳剂引入磺酸基活性基可以得到性能优良多支链高相对分子质量的COPESO,其表面活性高,出水快,水色透明且界面齐,对乳液破乳效果高达94.8%.     

STUDY ON THE CORROSION PEAK OF CARBON STEEL IN MARINE SPLASH ZONE

lNTRODUCTI0NSincetheoonceptofrnarinesplashzone(MSZ)wasfirstproposedbyHumble,rnanyresearchesprovedthatthecorrosionofsteelinthesplashzoneisthemostseriousinthemarineenvironninetandthatthisMSZcorrosionhasapeak(Zhu,l995).Howevertheenvironmentalfactorscatisingthecorrosionpeakwasnotkn0wnthen(Niat0,l975,Atsushi,l994)andtherangeoftheMSZwasnotyetdeariydefinedopzkaki,l985).ThispaperexplainsthemaincauseofthecormsionpeakanddefinestheexaCtrangeoftheMSZinsomeofChina'sharbours.MATERIALSANDMET…     

Research progress of TiO2 photocathodic protection to metals in marine environment

Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and titanium dioxide(TiO_2) is the most widely used photoanode.This review summarizes the progress in TiO_2 photo gene rated protection in recent years.Different types of semiconductors,including sulfides,metals,metal oxide s,polymers,and other materials,are used to design and modify TiO_2.The strategy to dramatically improve the efficiency of photoactivity is proposed,and the mechanism is investigated in detail.Characterization methods are also introduced,including morphology testing,light absorption,photoelectrochemistry,and protected metal observation.This review aims to provide a comprehensive overview of Ti02 development and guide photocathodic protection.     

Synthesis of three-dimensional agaric-like biomorphic TiO2 by a facile method with Coscinodiscus sp. frustule

The paper aims to expand the application of natural marine algae.Marine diatoms,which have intricate frustule structures,can serve as bio-template for preparing three-dimensional materials.A simple and effective approach to synthesize the corrugated agaric-like biomorphic TiO 2 templated with frustule of Coscinodiscus sp.is reported.In the sol-gel preparation process,the titania-coating on the frustule is prepared through the deposition and condensation with the aid of acetylacetone(acac) as a controlling agent to make the precursor Ti(BuO) 4 hydrolyze slowly.The as-prepared titania-coated frustule and biomorphic TiO 2 is characterized by scanning electron microscopy(SEM) attached with energy dispersive X-ray spectrometer(EMAX) and X-ray diffraction(XRD).The microstructure of the corresponding titania nanoparticles appears to be sphere with the diameters distributed around 10 20 nm.The templating process is repeated for three cycles.Subsequently,the three-dimensional freestanding corrugated agaric-like biomorphic TiO 2 structure is obtained by a selective removal in the NaOH solution.As far as we known,the 3D freestanding corrugated agaric-like biomorphic TiO 2 with greatly increased surface area is obtained for the first time.     

一种新型光纤光栅锈蚀传感器及其对混凝土结构钢筋锈蚀监测实验研究

设计一种新型光纤光栅锈蚀传感器,主要由锈蚀体、不锈钢体和2段串联的光纤布拉格光栅（FBG）组成。缠绕于锈蚀体表面的FBG监测钢筋的锈胀应变,缠绕于不锈钢体表面的FBG用作温度补偿器,消除温度变化对锈胀应变监测的影响。此外,设计电化学加速腐蚀实验,探究该传感器在不同强度等级混凝土中的工作性能。结果表明,该传感器监测质量腐蚀率的灵敏度为0.02%,监测范围大于1%,可实时监测混凝土中钢筋的锈蚀过程及特征,为预警钢筋锈蚀引起的钢筋混凝土结构耐久性损失提供阈值,在结构健康监测领域具有较大的应用价值。     

Simulation test apparatus for marine corrosion

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Optimization of four types of antimicrobial agents to increase the inhibitory ability of marine Arthrobacter oxydans KQ11 dextranase mouthwash

We adopted the response surface methodology using single factor and orthogonal experiments to optimize four types of antimicrobial agents that could inhibit biofilm formation by Streptococcus mutans, which is commonly found in the human oral cavity and causes tooth decay. The objective was to improve the function of marine Arthrobacter oxydans KQ11 dextranase mouthwash(designed and developed by our laboratory). The experiment was conducted in a three-level, four-variable central composite design to determine the best combination of Zn SO_4, lysozyme, citric acid and chitosan. The optimized antibacterial agents were 2.16 g/L Zn SO_4, 14 g/L lysozyme, 4.5 g/L citric acid and 5 g/L chitosan. The biofilm formation inhibition reached 84.49%. In addition, microscopic observation of the biofilm was performed using scanning electron microscopy and confocal laser scanning microscopy. The optimized formula was tested in marine dextranase Arthrobacter oxydans KQ11 mouthwash and enhanced the inhibition of S. mutans. This work may be promoted for the design and development of future marine dextranase oral care products.     

Crystals of suspended marine barite in the eastern equatorial Pacific: processes of dissolution and effects on crystal morphology

Suspended paniculate substances were sampled in the eastern equatorial Pacific in water column from surface to near bottom in five stations in 2005,from which 868 barite crystals were recovered.The barite crystals were examined under scanning electron microscopy.About 61%of the total barites crystals contained detectable Sr by energy dispersive X-ray spectrometry.Barite crystals could be classified into four groups based on their morphology:1) bladed;2) ovoid or rounded;3) arrow-like;and 4) irregularly shaped.The arrow-like barite crystals in natural environment has never been reported before.In addition,about a half of the studied crystals showed features of dissolution as cavities or holes inside of the crystals or around their edges.We found that differential dissolution of barite crystals is consequence of heterogeneous Sr distribution in barite crystals.Our results would help in understanding the biogeochemical processes of marine barite formation and preservation in seawater and marine sediments.