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Journal of Materials Science & Technology 2023年第21期152卷 169-180页

作者： Chengbao Liu Li Cheng lan-yue cui Peimin Hou Bei Qian Rong-Chang Zeng College of Materials Science and Engineering Shandong University of Science and TechnologyQingdao 266590China University of Chinese Academy of Sciences Beijing 100049China State Key Laboratory of Marine Coatings Marine Chemical Research InstituteQingdao 266071China College of Chemistry and Pharmaceutical Sciences Qingdao Agricultural UniversityQingdao 266109China

Polymeric coatings are susceptible to microdefects that are difficult to detect thus leading to premature failure of metallic components or even catastrophic accidents.Although obtaining considerable progress in damage healing and detecting,it is still challenging for anticorrosion coating to realize warning the damage generation and tracing the healing process simultaneously.This article validates a robust strategy based on damage-induced fluorescence enhancement effect to visualize dynamic damage-healing processes in anticorrosion coatings on magnesium alloy AZ31.Through embedding fluorescent poly-dopamine nanoparticles into thermo-responsive epoxy resin,immediate fluorescence was intensified at coating damages.Localized electrochemical impedance and salt spray results proved that the prepared coating possessed pronounced healing and corrosion protection capability with near-infrared irradiation.Notably,the healing behavior can be traced and visualized based on the decrease in fluorescence intensity.This work opens a new avenue to monitor the failure and self-healing mechanism of anticorrosion coatings,providing guideline for engineering of next generation smart protection materials.

关键词： Damage warning Healing tracing Corrosion protection Photothermal conversion Coating

Comparison of microstructure,mechanical property,and degradation rate of Mg-1Li-1Ca and Mg-4Li-1Ca alloys

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Bioactive Materials 2023年第8期26卷 279-291页

作者： Li-Xin Long Fen-Fen Chen lan-yue cui Ze-Song Wei Hai-Tao Wang Rong-Chang Zeng Yu-Feng Zheng College of Materials Science and Engineering Shandong University of Science and TechnologyQingdao266590China Institute of Corrosion Science and Technology Guangzhou510530China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou450002China School of Materials Science and Engineering Peking UniversityBeijing100871China International Research Organization for Advanced Science and Technology(IROAST) Kumamoto University2-39-2 Kumamoto860-8555Japan

Mg-1 wt.%Li-1 wt.%Ca(LX11)and Mg-4 wt.%Li-1 wt.%Ca(LX41)alloys share the same hexagonal closed-packed crystalline structure.However,the differences in microstructure,mechanical properties,and degradation rates between the two alloys are not well understood.Hereby,the above three aspects of LX11 and LX41 alloys were studied via optical microscopy,tensile tests,and electrochemical polarization and electrochemical impedance spectroscopy,together with hydrogen evolution.The concentration of the released Mg^(2+),Ca^(2+),and Li+ions was analyzed using a flame atomic absorption spectrophotometer.Results demonstrated that the LX11 alloy was composed of finerα-Mg grains,fewer twins,and smaller volume fractions of the intermetallic phases Mg_(2)Ca than the LX41 alloy.The increasing Li concentration generated a weak decrease in the yield strength of the Mg-Li-Ca alloys,a remarkable increase in elongation to failure,and a stable ultimate tensile strength.The LX11 alloy had better corrosion resistance than the LX41 alloy.The release rate of the cations(Mg^(2+),Ca^(2+),and Li+)varied significantly with time.The release rate of metallic ions in Hank’s solution cannot reflect the true corrosion rate of Mg-Li-Ca alloys due to the formation of the precipitated corrosion products and their difference in solubility.The dealloying corrosion mechanism of the Mg_(2)Ca phase in Mg-Li-Ca alloys was proposed.

关键词： Magnesium alloys Dealloying Intermetallic compound Biomaterial Ionic release

Corrosion resistance and mechanisms of smart micro-arc oxidation/epoxy resin coatings on AZ31 Mg alloy: Strategic positioning of nanocontainers

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Journal of Magnesium and Alloys 2023年第12期11卷 4562-4574页

作者： Ai-meng Zhang Chengbao Liu Pu-sheng Sui Cong Sun lan-yue cui M.Bobby Kannan Rong-Chang Zeng College of Materials Science and Engineering Shandong University of Science and TechnologyQingdao 266590China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450002China School of Engineering University of NewcastleCallaghanNew South Wales 2308Australia

Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.

关键词： Nanocontainers Self-healing coating Micro-arc oxidation Corrosion protection Magnesium alloys

Corrosion resistance of Mg-Al-LDH steam coating on AZ80 Mg alloy:Effects of citric acid pretreatment and intermetallic compounds

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Journal of Magnesium and Alloys 2023年第8期11卷 2967-2979页

作者： Jin-Meng Wang Xiang Sun Liang Song M.Bobby Kannan Fen Zhang lan-yue cui Yu-Hong Zou Shuo-Qi Li Rong-Chang Zeng Corrosion Laboratory for Light Metals College of Materials Science and EngineeringShandong University of Science and TechnologyQingdao 266590China School of Engineering University of NewcastleCallaghanNew South Wales 2308Australia College of Science and Engineering James Cook UniversityTownsvilleQueensland 4811Australia College of Chemical and Environmental Engineering Shandong University of Science and TechnologyQingdao 266590China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450002China

In this study,the effects of intermetallic compounds(Mg_(17)Al_(12)and Al_(8)Mn_(5))on the Mg-Al layered double hydroxide(LDH)formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)_(2)steam coatings on AZ80 Mg alloy were investigated.Citric acid(CA)was used to activate the alloy surface during the pretreatment process.The alloy was first pretreated with CA and then subjected to a hydrothermal process using ultrapure water to produce Mg-Al-LDH/Mg(OH)_(2)steam coating.The effect of different time of acid pretreatment on the activation of the intermetallic compounds was investigated.The microstructure and elemental composition of the obtained coatings were analyzed using FE-SEM,EDS,XRD and FT-IR.The corrosion resistance of the coated samples was evaluated using different techniques,i.e.,potentiodynamic polarization(PDP),electrochemical impedance spectrum(EIS)and hydrogen evolution test.The results indicated that the CA pretreatment significantly influenced the activity of the alloy surface by exposing the intermetallic compounds.The surface area fraction of Mg_(17)Al_(12)and Al_(8)Mn_(5)phases on the surface of the alloy was significantly higher after the CA pretreatment,and thus promoted the growth of the subsequent Mg-Al-LDH coatings.The CA pretreatment for 30 s resulted in a denser and thicker LDH coating.Increase in the CA pretreatment time significantly led to the improvement in corrosion resistance of the coated AZ80 alloy.The corrosion current density of the coated alloy was lower by three orders of magnitude as compared to the uncoated alloy.

关键词： Magnesium alloy Citric acid pretreatment Steam coating Layered double hydroxide Intermetallic compounds Corrosion resistance

In vitro degradation,photo-dynamic and thermal antibacterial activities of Cu-bearing chlorophyllin-induced Ca-P coating on magnesium alloy AZ31

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Bioactive Materials 2022年第12期7卷 284-299页

作者： Zhen-Yu Zhang Yan-Lin An Xiao-Shi Wang lan-yue cui Shuo-Qi Li Cheng-Bao Liu Yu-Hong Zou Fen Zhang Rong-Chang Zeng College of Materials Science and Engineering Shandong University of Science and TechnologyQingdao266590China College of Chemical and Biological Engineering Shandong University of Science and TechnologyQingdao266590China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou450002China

Surgical failures,caused by postoperative infections of bone implants,are commonly met,which cannot be treated precisely with intravenous antibiotics.Photothermal therapy(PTT)and photodynamic therapy(PDT)have attracted widespread attention due to their non-invasive antibacterial effects on tissues and no bacterial resistance,which may be an excellent approach to solve infections related to bone implants for biodegradable magnesium alloys.Herein,a sodium copper chlorophyllin(SCC)with a porphyrin ring induced Ca-P coating was prepared on AZ31 magnesium alloy via layer-by-layer(LbL)assembly.The morphology and composition of the samples were characterized through field emission scanning electron microscope(FE-SEM)with affiliated energy dispersive spectrometer(EDS),X-ray diffractometer(XRD),and Fourier infrared spectrometer(FTIR)and X-ray photoelectron spectrometer(XPS)as well.Potentiodynamic polarization,electrochemical impedance spectroscopy(EIS)and hydrogen evolution experiments were employed to evaluate the corrosion behavior of the samples.Atomic absorption spectrophotometer was used to measure Cu elemental content of different immersion periods.Cytocompatibility and antibacterial performance of the coatings were probed using in vitro cytotoxicity tests(MTT assay),live/dead cell staining and plate counting method.The results showed that the obtained(Ca-P/SCC)10 coating exhibited good corrosion resistance,antimicrobial activity(especially under 808 nm irradiation)and biocompatibility.The antibacterial rates for E.coli and S.aureus were 99.9%and 99.8%,respectively;and the photothermal conversion efficiency was as high as 42.1%.Triple antibacterial mechanisms including photodynamic,photothermal reactions and copper-ions release were proposed.This coating exhibited a promising application for biodegradable magnesium alloys.

关键词： Magnesium alloy Coating Degradable biomaterial Biocompatibility Antibacterial activity

Advances in bioorganic molecules inspired degradation and surface modifications on Mg and its alloys

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Journal of Magnesium and Alloys 2022年第3期10卷 723-745页

作者： Lei Cai Di Mei Zhao-Qi Zhang Yuan-ding Huang lan-yue cui Shao-Kang Guan Dong-Chu Chen M.Bobby Kannan Yu-feng Zheng Rong-Chang Zeng Corrosion Laboratory for Light Metals College of Materials Science and EngineeringShandong University of Science and TechnologyQingdao 266590China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450002China MagIC-Magnesium Innovation Centre and Institute of Metallic Biomaterials Helmholtz-Zentrum HereonMax-Planck Straûe 1Geesthacht 21502Germany School of Materials Science and Energy Engineering Foshan UniversityFoshan 528000China School of Engineering University of NewcastleCallaghanNSW 2308Australia College of Science and Engineering James Cook UniversityTownsvilleQL 4811Australia School of Materials Science and Engineering Peking UniversityBeijing 100871China Hubei Key Laboratory of Advanced Technology for Automotive Components Wuhan University of TechnologyWuhan 430070China

Mg alloys possess biodegradability,suitable mechanical properties,and biocompatibility,which make them possible to be used as biodegradable implants.However,the uncontrollable degradation of Mg alloys limits their general applications.In addition to the factors from the metallic materials themselves,like alloy compositions,heat treatment process and microstructure,some external factors,relating to the test/service environment,also affect the degradation rate of Mg alloys,such as inorganic salts,bioorganic small molecules,bioorganic macromolecules.The influence of bioorganic molecules on Mg corrosion and its protection has attracted more and more attentions.In this work,the cutting-edge advances in the influence of bioorganic molecules(i.e.,protein,glucose,amino acids,vitamins and polypeptide)and their coupling effect on Mg degradation and the formation of protection coatings were reviewed.The research orientations of biomedical Mg alloys in exploring degradation mechanisms in vitro were proposed,and the impact of bioorganic molecules on the protective approaches were also explored.

关键词： Magnesium alloy Biomaterial Bioorganic molecules Degradation Coating Glucose.

In vitro degradation and multi-antibacterial mechanisms ofβ-cyclodextrin@curcumin embodied Mg(OH)_(2)/MAO coating on AZ31 magnesium alloy

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Journal of Materials Science & Technology 2023年第1期132卷 179-192页

作者： Kui Xue Pei-Hong Tan Ze-Hui Zhao lan-yue cui M Bobby Kannan Shuo-Qi Li Cheng-Bao Liu Yu-Hong Zou Fen Zhang Zhuo-Yuan Chen Rong-Chang Zeng Corrosion Laboratory for Light Metals College of Materials Science and EngineeringShandong University of Science and TechnologyQingdao 266590China School of Engineering The University of NewcastleCallaghanNSW 2308Australia College of Chemical and Environmental Engineering Shandong University of Science and TechnologyQingdao 266590China School of Materials Science and Energy Engineering Foshan UniversityFoshan 528000China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450002China

It is a challenging task to prepare a coating on Mg alloys for desirable corrosion resistance,good antibac-terial ability and biocompatibility.In this research work,an in-situ Mg(OH)_(2)coating incorporated with sodium alginate(SA)andβ-cyclodextrin(β-CD)@curcumin(Cur)was formed on the surface of micro arc oxidation(MAO)coated AZ31 alloy via a low temperature hydrothermal method.Characterization tech-niques such as X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectrometer(FT-IR)and scanning electron microscope(SEM)were employed to characterize the chemi-cal composition and surface morphology of the coatings.The corrosion protection ability of the coatings was monitored via electrochemical polarization,hydrogen evolution and immersion tests.Photothermal antibacterial ability and cytocompatibility of the coatings were evaluated by plate counting method under the irradiation of 808 nm-near infrared light,in vitro cytotoxicity tests(MTT)and live/dead cell staining.The results indicate that a chelation of the organic molecules led to the formation of a MAO/(β-CD@Cur)-SA-Mg(OH)_(2)coating with excellent corrosion protection,multi-antibacterial ability and almost no toxic-ity to the cells.Especially,the coating provided photothermal performance through the light absorption of Cur,which was encapsulated byβ-CD to improve its bioavailability.SA enhanced the binding force between the drug and the substrate.This novel coating designated the potential application on bioab-sorbable magnesium alloys.

关键词： Magnesium alloys Photothermal ability Antibacterial coating Corrosion Biomaterials

Corrosion Resistance of Superhydrophobic Mg-Al Layered Double Hydroxide Coatings on Aluminum Alloys

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Acta Metallurgica Sinica(English Letters) 2015年第11期28卷 1373-1381页

作者： Fen Zhang Chang-Lei Zhang Liang Song Rong-Chang Zeng lan-yue cui Hong-Zhi cui College of Materials Science and Engineering Shandong University of Science and Technology State Key Laboratory of Mining Disaster Prevention and Control Co-founded by Shandong Province and the Ministry of Science and Technology Shandong University of Science and Technology Qingdao Institute of Bioenergy and Bioprocess Technology Chinese Academy of Sciences

A superhydrophobic surface was successfully constructed to modify the layered double hydroxide （LDH） coatings on aluminum alloy using stearic acid. The characteristics of the coatings were investigated using SEM, XRD, FT- IR and XPS. The corrosion resistance of the prepared coatings was studied using potentiodynamic polarization and electrochemical impedance spectrum. The results revealed that the superhydrophobic surface considerably improved the corrosion-resistant performance of the LDH coatings on the aluminum alloy substrate. The formation mechanism of the superhydrophobic surface was proposed.

关键词： Aluminum alloy Layered double hydroxide Superhydrophobic Stearic acid Corrosion

Corrosion resistance of a novel SnO2-doped dicalcium phosphate coating on AZ31 magnesium alloy

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Bioactive Materials 2018年第3期3卷 245-249页

作者： lan-yue cui Guang-Bin Wei Rong-Chang Zeng Shuo-Qi Li Yu-Hong Zou En-Hou Han College of Materials Science and Engineering Shandong University of Science and TechnologyQingdao266590China College of Chemical and Environmental Engineering Shandong University of Science and TechnologyQingdao266590China National Engineering Centre for Corrosion Control Institute of Metals ResearchChinese Academy of SciencesShenyang110016China

A SnO2-doped dicalcium phosphate coating was prepared on AZ31 alloy by means of hydrothermal deposition.The results showed that the coating possessed a globular morphology with a long lamellar crystalline structure and a thickness of approximately 40 mm.The surface of the coating became smooth with an increase additive amount of the SnO2 nanoparticles.The corrosion current density and hydrogen evolution rate of the coating prepared in presence of SnO2 were reduced compared to the coating without SnO2 and the bare AZ31 substrate,indicating an improvement in the corrosion resistance of the SnO2-doped coating.

关键词： Phosphate coating Biomaterials Magnesium alloys Corrosion Stannic oxide

In vitro corrosion resistance of a Ta2O5 nanofilm on MAO coated magnesium alloy AZ31 by atomic layer deposition

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Bioactive Materials 2020年第1期5卷 34-43页

作者： Chang-Yang Li Chi Yu Rong-Chang Zeng Bo-Cheng Zhang lan-yue cui Jun Wan Yang Xia Corrosion Laboratory for Light Metals College of Materials Science and EngineeringShandong University of Science and TechnologyQingdao266590China Jiaxing Microelectronics Engineering Center Chinese Academy of SciencesJiaxing314022China Institute of Microelectronics Chinese Academy of SciencesBeijing100029China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou450002China

Micro-arc oxidation(MAO)coating with outstanding adhesion strength to Mg alloys has attracted more and more attention.However,owing to the porous structure,aggressive ions easily invaded the MAO/substrate interface through the through pores,limiting long-term corrosion resistance.Therefore,a dense and biocompatible tantalum oxide(Ta2O5)nanofilm was deposited on MAO coated Mg alloy AZ31 through atomic layer deposition(ALD)technique to seal the micropores and regulate the degradation rate.Surface micrography,chemical compositions and crystallographic structure were characterized using FE-SEM,EDS,XPS and XRD.The corrosion resistance of all samples was evaluated through electrochemical and hydrogen evolution tests.Results revealed that the Ta2O5 film mainly existed in the form of amorphousness.Moreover,uniform deposition of Ta2O5 film and effective sealing of micropores and microcracks in MAO coating were achieved.The current density(icorr)of the composite coating decreased three orders of magnitude than that of the substrate and MAO coating,improving corrosion resistance.Besides,the formation and corrosion resistance mechanisms of the composite coating were proposed.

关键词： Magnesium alloys Micro-arc oxidation Atomic layer deposition Coatings