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An Overview on Study of Phytic Acid Conversion Coatings on Metal Surface
LU Yong, FENG Huixia, ZHANG Xiaofang
Materials Reports
2019,33(9 ):1455 -1461. DOI:10.11896/cldb.18030037
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Chemical conversion coating technology is widely used in metal surface treatment, and exhibit favorable protective effect, which holds extensive applications in metal anti-corrosion, wear resistance, antifriction, coating bottom layer. Its application involves automobile manufactu-ring, household appliances and hardware processing and many other industries. As the most commonly used pretreatment technology, chemical conversion coating technology has attracted more and more attention because of its advantages such as simple treatment process, remarkable effect, uniform precipitation, low processing cost, as well as the easy control of the coating thickness etc.
Conventional approaches involving conversion of chromate and phosphate may produce lasting harm to the environment, and have been gra-dually replaced by the environmental-friendly approaches. Currently, the development and application of green metal surface pretreatment techno-logy has become a very important research direction in this field. After more than ten years of effort, researchers have developed diverse kinds of environment-friendly conversion coating. In this papers, we introduce the progress of a variety of chromium-free and environment-friendly conversion coatings, such as zirconium, titanium, vanadium, molybdate, stannic acid, niobium and rare earth conversion coatings, in view of their preparation process and corrosion resistance effects. Although the chromium-free conversion coatings technology has been applied practically, and it fail to achieve satisfactory anti-corrosion effect, therefore a composite approach is needed for further improving the anti-corrosion efficiency.
In this paper, we focus on the deposition mechanism, influencing factors and technical development of phytic acid conversion coating. Phytic acid is a non-toxic natural organic macro-molecules extracted from plants. It contains six phosphate groups that can chelate with metal ions. Each phosphate group bear two hydroxyl groups and four oxygen atoms, which are capable of forming stable complexes with most of the bivalent and above valence metal ions by chelating in a wide range of pH value. Phytic acid has been widely used as film-former for constructing chemical conversion coating in the field of metal anti-corrosion and protection. Numerous research results have demonstrated that metal ions on the metal surface were chelated with phytic acid molecules by electrochemical reaction in phytic acid treatment solution, and the phytic acid chemical conversion coating is formed. Phytic acid can be used in chemical coating processing for magnesium alloy, steel, iron and other metal. By analyzed the preparation process of phytic acid conversion coating, we also elaborate the three importment influence factors which affect the surface morphology and corrosion resistance of the conversion coating, including the concentration of phytic acid, pH of the solution and processing time. Meanwhile, we summarize the defects after the treatment of the metal substrate with single phytic acid, such as the micro-cracks on metal surface, thin film, short corrosion resistance duration, low anti-corrosion efficiency. It has been proved that the protection performance of phytic acid conversion coating can be enhanced by alkali pretreatment, thermal post-treatment, coordination with metal ions, as well as combination with other conversion films and other materials. Finally, we point out the development prospect of phytic acid in metal surface treatment.
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Materials Selection of Titanium Alloy OCTG Used for Oil and Gas Exploration and Their Applicability Under Service Condition: a Survey
LIU Qiang, HUI Songxiao, SONG Shengyin, YE Wenjun, YU Yang
Materials Reports
2019,33(5 ):841 -853. DOI:10.11896/cldb.201905017
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Titanium alloy has become a promising candidate material for oil country tubular goods(OCTG) and offshore components in rigorous service environment, owing to its high specific strength, low density, low elastic modulus, excellent toughness,fatigue and corrosion resistance. Numerous researchers at home and abroad have carried out extensive researches on titanium alloys used for oil and gas exploration, including the feasibility of titanium alloy for oil country tubular goods, the processing technical of titanium alloy pipes, the performance evaluation of titanium alloy in laboratory and the field application.
Unfortunately, there exist quite harsh environment for oil and gas exploration in China. The underground oil well pipes not only confronted with challenges of high temperature and high pressure, but also suffered from impacts by hydrogen sulfide, carbon dioxide, high concentration saline/completion fluid, elemental sulfur and strong acid. Consequently, the requirement of oil country tubular goods in China exceeds the general stan-dard of other countries. Besides, titanium alloy is a general term for a family of metal whose titanium content is over 50%, and there are 76 kinds of titanium alloy with various components listed in national standard of China. Most of these standardized titanium alloys are applied in aerospace, petrochemical refining, biomedicine, shipping and marine engineering, whereas, there is huge difference in application environments of the above mentioned fields and oil & gas exploration, whether these titanium alloys can be employed for oil and gas exploration remains unexplained. Moreover, the lack of research results and application experiences of titanium alloy OCTG in service of harsh environment with H
2
S, CO
2
, concentrated brine workover/completion fluids, elemental sulfur and strong acids in China will pose risk in selecting and using of titanium alloy OCTG for oil & gas exploration. For the sake of preventing the loss of life and property caused by large safety accident in the application of titanium alloy, it is urgent to select and evaluate titanium alloy materials which will be used in oil & gas exploration in China according to domestic and foreign research experience, and define the service condition applicability and limit of each titanium alloy material to ensure the safety and reliability.
On the basis of the related overseas research achievements of titanium alloy OCTG published in recent 30 years and the latest research results of titanium alloy OCTG in China, this article summarize the latest developments of titanium alloy materials selection for OCTG and oil & gas exploration service condition applicability of seven typical titanium alloys. Finally, the existing problems of the current application about titanium alloy OCTG are pointed out and the future development direction of titanium alloy OCTG is also proposed, providing a reference for the selection of titanium alloy materials for oil & gas exploration.
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Effect of Work Hardening on Mechanical Properties of Stress Corrosion Crack Tip of 304 Stainless Steel
ZHANG Jianlong, XUE He, CUI Yinghao, CHEN Hao
Materials Reports
2019,33(24 ):4147 -4151. DOI:10.11896/cldb.19010071
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Stress corrosion cracking (SCC) is one of the main failure mode of austenitic steel in pressure piping, and cold working deformation has a certain influence on the material mechanical properties and the crack propagation. Firstly, the constitutive parameters of 304 stainless steel under different cold working hardening conditions were obtained by fatigue stretching machine, and then finite element simulation method was adopted to establish the SCC crack tip analysis model and sub-model in this paper. The SCC crack tip stress strain, J-integration and crack growth rate of 304 austenitic stainless steel were studied under different work hardening. Results show that with the increasing of the material work har-dening degree, the Mises stress and J integral at the SCC tip increase gradually, but the crack tip strain (PEEQ) gradually decreases. To some extent, the work hardening promotes and accelerates the stress corrosion cracking of 304 stainless steel.
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Effect of Alloying on Anti-corrosion Performance of Stainless Steel: a Review
BI Fengqin, ZHOU Bang, WANG Yong
Materials Reports
2019,33(7 ):1206 -1214. DOI:10.11896/cldb.17070037
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Stainless steel holds widespread application in daily life and industry, especially in petrochemical industry, owing to its high mechanical strength, generally good oxidation resistance at complex environment and excellent comprehensive properties. Unfortunately, stainless steel cannot ether escape from corrosion, one of the three tough problems causing the loss of materials, which seriously blocks the further application of stainless steel. Presently, there are primarily two approaches to prevent metal from corrosion, namely coating and changing the element and content of the materials (alloying). Certain progress has been achieved in study of coating protection, but there are still serious deficiencies. The secondary pollution caused by coating in the process of production and application deprives itself of the room for survival. Besides, the corrosion of materials in petrochemical industry is not only the direct erosion of chemical medium, but also the result of the combined action of high temperature, high pressure and continuous operation in practical production. Accordingly, the protective approach that mainly change the elements and contents of materials has become the research focus in this area, because it can not only overcome some malpractice of coating protection, but also effectively improve service life of petrochemical pipeline equipment.
Alloying is one of the important approaches to improve the corrosion resistance of stainless steel. And it is the main stream of stainless steel alloying to fully explore the potential of microelements by controlling the types and contents of the introduced microelements. By controlled addition of microelements, the performance of the matrix will be enhanced due to the alteration of the precipitation process, distribution and structure of the original alloy elements; more importantly, grain refinement and strengthening will be achieved through the specific precipitated phase of the microelements in the alloying process. Consequently, it is the key to obtain specific precipitates and achieve performance improvement by reasonably controlling the type and amount of introduced elements. Up to now, the researches on improving corrosion resistance of stainless steel by doping alloying elements are mainly focused on doping single alloying elements or rare earth elements. Some related studies have demonstrated that the addition of trace Co, Nb, Ru, is also capable of optimizing the corrosion resistance of stainless steel. In addition, the combined additions of alloying elements not only preserve the specific advantages of a single element, but also boost the effect through the interaction between elements. meanwhile, numerous research results have demonstrated that the addition amount of alloying elements play a dominant role in improving the performance of the alloy, regardless of the single or compound doping.
From the point of view of improving the corrosion resistance of stainless steel, we summarize research progress of the effects of alloying elements, rare earth elements, other microelements, as well as the existence of various alloying elements on the anti-corrosion performance of stainless steel. meanwhile, we point out the existing problems, the improvement measures and development trends in the research of corrosion beha-vior of stainless steel.
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Synthesis and Acidification Corrosion Inhibition Performance of a Novel Quinoline Quaternary Ammonium Salt — Phenacyl Quinoline Chloride (PCQ)
WANG Yefei, QIAN Cheng, YANG Zhen, DING Mingchen, WANG Renzhuo
Materials Reports
2019,33(4 ):699 -704. DOI:10.11896/cldb.201904026
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In this contribution, we present the preparation of a novel (firstly originated) corrosion inhibitor, i.e. phenacyl quinoline chloride (PCQ), and the comparative analyses upon the corrosion inhibition performances between PCQ and benzyl quinoline chloride (BQC, a commonly used corrosion inhibitor for acidizing). The PCQ was synthesized through the quaternarization reaction of quinoline, benzyl chloride and 2-chloroacetophenone under the condition of 75 ℃ and 20 h reflux, by using acetone as solvent and ethanol as recrystallizing agent. The chemical structures of PCQ and BQC were characterized by elemental analysis, NMR and IR. The corrosion inhibition performances of the two quaternary ammonium salts (use in isolation, use in combination with propargyl alcohol(PA), and use in combination with potassium iodide) were evaluated by static weight loss method in 15% hydrochloric acid at 90 ℃. Our experiments show that the inhibition efficiency of BQC and PCQ are 82.17% and 94.25%, respectively, under the adding amount of 1.00%. The inhibition efficiency of the combination of 0.50% PCQ+0.50% propargyl alcohol is 99.88%. The adsorption behaviors of BQC and PCQ on the surface of N80 steel coincide well with Langmuir adsorption isotherm. Moreover, the adsorption equilibrium constants
k
ads of BQC and PCQ are 483.10 L/mol and 1 092.75 L/mol, respectively, and the Gibbs free energy change values are -30.77 kJ/mol and -33.24 kJ/mol with respect to BQC and PCQ, indicating the chemical-adsorption-dominated, also spon-taneous and exothermic adsorption processes of these two quaternary ammonium salts onto the N80 steel surface.
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Research Progress on Arc Sprayed Metal Coatings for Seawater Corrosion Protection
XU Jinyong, WU Qingdan, WEI Xinlong, XIAO Jinkun, ZHANG Chao
Materials Reports
2020,34(13 ):13155 -13159. DOI:10.11896/cldb.19060047
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Arc sprayed metal coating is an important method for the protection of steel structure. Due to development of last several decades, it has become a mature surface engineering technology and industry. Meanwhile, with the development and research of new spraying processes, equipment and materials, the application fields of it are increasingly widespread. At the same time, the shortcomings of arc spraying technology are becoming more and more prominent, especially the problems of harmful substances discharged during the spraying process, which seriously restricts its development. The coating prepared by arc spraying exhibits low porosity, compact microstructure, high bonding strength and good economy. Compared with other traditional anti-corrosion technologies, arc-sprayed metal coatings have the following advantages: (ⅰ) high efficiency of arc spray deposition, easy operation, and easy on-site construction; (ⅱ) the service life of the coatings is long.
However, the coatings fabricated by arc spraying technology are used in different service environments, which puts higher requirements on the corrosion resistance of the coating. Therefore, in addition to studying the parameters of arc spraying process in recent decades, researchers have focused on the development of multi-functional, high-performance spraying materials, and have achieved fruitful results. Basing on the advantages of arc spraying technology, the performance of coating will be enhanced significantly. At present, materials employed to deposited coatings are developing in the direction of composite and new-type.
Materials, such as Zn, Al and their alloys, Ni-based alloys, Fe-based alloys and Cu-based alloys, have been widely used in the protection of steel structures. Among them, Zn, Al and their alloys are the earliest and most used spraying materials; Ni-based alloys can improve the corrosion resistance of materials by adding Cr, Mo and other alloying elements, which are resistant to pitting and crevice corrosion; the addition of a small amount of Mo and other elements to the Fe-based alloy can effectively inhibit the occurrence of grain boundary corrosion; the incorporating of 1% Sn to the Cu-based alloy can inhibit the dezincification process of the alloy and improve the mechanical properties. Recently, the research focuses on the use of a variety of alloy materials and the use of new alloy materials, and the arc spray technology is used as a means to prepare corrosion-resistant coatings, which can achieve double improvement in the function and performance of coatings.
Based on the analysis of the corrosion law of steel structures in various areas of the coastal marine environment, this paper compares the current methods for corrosion protection of steel structures and their advantages and disadvantages. The research status and anti-corrosion mechanism of arc spray coatings are expounded. From the aspects of microstructure, coating properties and anti-corrosion mechanism of arc sprayed mental coatings, the problems of anticorrosion of arc sprayed metal coatings are analyzed and their prospects are prospected, and ultimately as a reference to provide long-term protection for steel structures in industrial fields.
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Fabrication of Ni
3
S
2
Micro-nanostructure Superhydrophobic Surface with Anti-corrosion Property
YIN Xiaoli, YU Sirong, HU Jinhui
Materials Reports
2019,33(20 ):3372 -3376. DOI:10.11896/cldb.18080178
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With the rapid development of surface science and bionics, superhydrophobic materials have become a hot issue in current research, and their excellent properties have a very broad application prospect. In this paper, a Ni
3
S
2
micro-nano composite structure was grew directly on the nickel foam by hydrothermal reaction, then the superhydrophobic surface with excellent properties was obtained after modification by tetradecanoic acid. The effects of reaction temperature and time on the water contact angles were investigated. It was found that the properties of the superhydrophobic surface were optimal while the reaction temperature was 180 ℃ and the reaction time was 6 h so that the static contact angle was up to 160.28°. Scanning electron microscopy was used to observe the microstructure of the superhydrophobic surface, and the interleaved cone arrays were found on the substrates. The chemical compositions of the superhydrophobic surface were analyzed by X-ray diffractometer and energy dispersive spectrometer. It was worth noting that a new Ni
3
S
2
phase was formed compared to the nickel foam. The properties of the superhydrophobic surface were tested, finding that the surface had good acid and alkali resistance and corrosion resistance.
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Plasma Polymerized Poly (Ethylene Oxide)-like Coating for Enhancing Corrosion Resistance of Magnesium Alloy Cardiovascular Stents
YU Donghai, XIONG Kaiqin, HUANG Nan
Materials Reports
2020,34(6 ):6166 -6171. DOI:10.11896/cldb.19040174
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In this paper, in order to enhance the corrosion-resistance of MgZnMn alloy, plasma polymerization coatings were synthesized by using diethylene glycol dimethyl ether (diglyme) as organic monomer. Two kinds of an ultra-thin, pinhole-free with poly (ethylene oxide)-like (PEO-like) characteristics prepared with two different discharge power. X-ray photoelectron spectroscopy (XPS) and attenuated total internal reflection Fourier transform infrared spectroscopy (ATR-FTIR) results showed that, higher cross-linked structure formed when using high power (HPEO) than low power (LPEO). Electrochemical and in vitro immersion tests showed that two coatings had good anti-corrosion effect, especially the HPEO coating. The HPEO coating adhered well on the MgZnMn stent after the balloon expansion test, and significantly slowed down the degradation rate of the stent in the subsequent in vitro immersion test.
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Preparation and Properties of Eucommia Ulmoides Gum/Epoxy Resin Anticorrosive Coating
FENG Xiao, KANG Hailan, YANG Feng, FANG Qinghong
Materials Reports
2019,33(22 ):3847 -3852. DOI:10.11896/cldb.18090258
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Eucommia ulmoides gum (EUG) was epoxidized by emulsion method, the obtained epoxidized eucommia ulmoides gum (EEUG) and epoxy resin (E44) were blended as a film-forming substance, and an anti-corrosive coating was prepared by using ethyl acetate as a solvent; the coating was carried out by changing the epoxidizing degree of eucommia ulmoides gum and the matrix ratio (EEUG/E44), and testing by infrared spectroscopy, nuclear magnetic resonance, electrochemical impedance, adhesion test and salt spray corrosion test. Through infrared spectroscopy and nuclear magnetic resonance analysis, it could be obtained that EEUG was successfully prepared and its epoxidation was calculated. In electrochemical impedance analysis, adhesion analysis, coating morphology analysis and salt spray resistance analysis, it was known that the epoxy eucommia rubber coating with low epoxidation had better adhesion effect and better corrosion resistance. It could be concluded that proper addition of EEUG could enhance the interaction between coating and metal matrix, and effectively retarded the corrosion of coating. The optimum ratio of film-forming material was 0.5/1 (EEUG/E44).
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Effect of Trace Co on Microstructures and Corrosion Properties of 7056
Aluminum Alloy
ZHOU Liang, CHEN Songyi, PENG Zhenling, ZHANG Xinglin, FAN Shumin, CHANG Jiangyu, YUAN Dingling, CHEN Kanghua
Materials Reports
2019,33(2 ):314 -320. DOI:10.11896/cldb.201902021
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The effect of trace Co element on the microstructures and corrosion properties of 7056 aluminum alloy was studied by metallographic observation, intergranular corrosion test, electrochemical corrosion test, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results indicated that the 7056 aluminum alloy with trace Co presented a 22.57% increase of stress corrosion life, an improved fracture strength of stress corrosion from 511 MPa to 559 MPa and a dropped stress corrosion factor from 0.118 to 0.064, compared with the alloy without Co. The 7056 aluminum alloy with Co formed more uniform and fine Al
3
Zr dispersion phase, which effectively pinned the dislocation and subboundary, made the base keep deformation response structure and small angle grain boundary, thus restrained the recrystallization.and kept fine subcrystalline structure. The precipitation phase in the subgrain boundary is close to that in the intracrystalline, which reduced the electrochemical motivation of intergranular corrosion and improved the resistance to intergranular corrosion. Besides, the area fraction of the precipitated phase at the grain boundary increased, corresponding to the increase of the ratio of anode to cathode in electrochemical reaction process, which resulted in a decrease of the anode current and a decrease of the dissolution rate of the precipitated phase at the grain boundary. The disconti-nuous grain boundary precipitates can block anodic dissolution channels along grain boundaries, slow down the intergranular corrosion and improve the stress corrosion resistance of the alloy.
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Equivalent Conversion Coefficient of Aluminum/Titanium Alloy Between Acidic NaCl Solution with Different Concentration and Water Based on Galvanic Corrosion Simulation
BIAN Guixue, CHEN Yueliang, ZHANG Yong, WANG Andong, WANG Zhefu
Materials Reports
2019,33(16 ):2746 -2752. DOI:10.11896/cldb.18060158
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Polarization curves and current of galvanic corrosion of 2A12 aluminum alloy and TA15 titanium alloy in solution with different NaCl concentrations and pH value were measured by electrochemical test. Conversion coefficient of galvanic corrosion between TA15/2A12 in different concentrations and pH of NaCl solution and aqueous was investigated. A galvanic corrosion simulation model was established by polarization curves of boundary condition in different concentrations NaCl solution with different pH. The galvanic corrosion current of two materials for corrosion simulation model was compared with the electrochemical test. The results showed that the self-corrosion potential of aluminum alloy was mainly affec-ted by the NaCl concentration, but it was less affected by the pH values which had a significant effect on the self-corrosion current. The simulation results agree with the electrochemical test results. Besides, the conversion factors between galvanic corrosion of 2A12-T4 aluminum alloy and TA15 titanium alloy in different NaCl concentrations and pH values solutions and self-corrosion in water medium were obtained by simulation.
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Inhibition Action and Adsorption Behavior of Sodium Lignosulphonate on Q235 Steel in Simulated Concrete Solution
XIE Wanchen, LI Jiansan
Materials Reports
2019,33(8 ):1401 -1405. DOI:10.11896/cldb.17090054
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Inhibition action and adsorption behavior of sodium lignosulphonate on Q235 steel in simulated concrete solution were investigated by means of potentiodynamic polarization and surface analysis techniques. The results indicated that sodium lignosulphonate have good pitting corrosion inhibition for Q235 steel in simulated concrete solution. The inhibition efficiency strengthened with increase of sodium lignosulphonate concentration. The adsorption reaction was a spontaneous exothermic process and followed Langmuir isotherm. It belonged to mix-type adsorption mainly dominated by chemisorption. The coadsorption of sulfonic acid group and Ca
2+
belonged to physisorption. Carboxyl and benzene ring structure had coordinated with Fe-3d orbitals, which belonged to chemisorption. Adsorption film of sodium lignosulphonate formed on Q235 steel can reduce adsorption of Cl
-
so pitting corrosion caused by Cl
-
can be effectively suppressed.
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Effect of Shot Peening on Wear and Corrosion Behavior of Micro-arc Oxidation Coating of TC4 Alloy
REN Chao, LUO Junming, CHEN Yuhai, HUANG Jun, XU Jilin
Materials Reports
2020,34(18 ):18081 -18085. DOI:10.11896/cldb.19090097
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The surface nanostructured film was prepared by shot peening (SP) on the surface of TC4 alloy.The ceramic layer was prepared in the electrolyte composed of NaH
2
PO
4
and Na
2
SiO
3
by micro-arc oxidation (MAO) constant voltage control mode, and the SP/MAO composite surface modified layer was obtained. The effects of shot peening on the microstructure, wear resistance and corrosion resistance of SP/MAO composite coatings were investigated. The results show that after shot peening, with the prolongation of shot peening time, the surface grain size of TC4 alloy decreases, while the microscopic strain and surface roughness increase gradually.The SP/MAO composite coating pretreated by shot peening for 30 min had the lowest friction coefficient and the wear rate was 71.3% lower than that of the micro-arc oxidation coating. With the prolongation of shot peening time,the corrosion potential of SP/MAO composite coating increased first and then decreased, and the corrosion current density decreased first and then increased. The SP/MAO coating had the best corrosion resistance when shot peening for 30 min.
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