Constructing a functional hybrid coating appears to be a promising strategy for addressing the poor corrosion resistance and insufficient endothelialization of Mg-based stents.Nevertheless,the steps for preparing comp...Constructing a functional hybrid coating appears to be a promising strategy for addressing the poor corrosion resistance and insufficient endothelialization of Mg-based stents.Nevertheless,the steps for preparing composite coatings are usually complicated and time-consuming.Herein,a novel composite coating,composed of bioactive magnesium thioctic acid(MTA)layer formed by deposition and corrosion-resistant magnesium hydroxide(Mg(OH)_(2))layer grown in situ,is simply fabricated on ZE21B alloys via one-step electrodeposition.Scanning electron microscopy(SEM)shows that the electrodeposited coating has a compact and uniform structure.And the high adhesion of the MTA/Mg(OH)_(2)hybrid coating is also confirmed by the micro-scratch test.Electrochemical test,scanning kelvin probe(SKP),and hydrogen evolution measurement indicate that the hybrid coating effectively reduces the degradation rate of Mg substrates.Haemocompatibility experiment and cell culture trial detect that the composite coating is of fine biocompatibility.Finally,the preparation mechanism of MTA/Mg(OH)_(2)hybrid coatings is discussed and proposed.This coating shows a great potential application for cardiovascular stents.展开更多
Recently, functional molecules such as Polydopamine(PDA), Hyaluronic Acid(HA) and heparin have been widely studied in the field of surface modification of magnesium(Mg) alloy stents for better degradation behavior and...Recently, functional molecules such as Polydopamine(PDA), Hyaluronic Acid(HA) and heparin have been widely studied in the field of surface modification of magnesium(Mg) alloy stents for better degradation behavior and biocompatibility, but their further application is limited by undesirable anticoagulant function, uncontrollable degradation and easy bleeding, respectively.Regarding to this consideration, a magnesium Fluoride/Polydopamine/Sulphonated hyaluronic acid(Mg F2/PDA/S-HA) composite coating was successfully prepared by applying S-HA with sulfur content of 9.71 wt% on the surface of ZE21B alloy in this study. The results showed that the composite coating with a unique mesh structure not only inherited the anticoagulant effect of sulfonic acid group and the excellent cyto-compatibility of S-HA with high sulfur content, but also significantly improved the corrosion performance of ZE21B alloy.These results indicate a great application potential of the composite coating in the field of cardiovascular biomaterials.展开更多
The clinic applications of bioabsorbable magnesium(Mg)and its alloys have been significantly restricted owing to their poor corrosion resistance.Besides elemental alloying,surface modification and functionality is a m...The clinic applications of bioabsorbable magnesium(Mg)and its alloys have been significantly restricted owing to their poor corrosion resistance.Besides elemental alloying,surface modification and functionality is a major approach to increasing corrosion resistance for magnesium alloys.This article reviews the cutting-edge advances and progress of biodegradable surface coatings upon Mg alloys over the last decades,aims to build up a knowledge framework of surface modification on biodegradable Mg alloys.A considerable number of conversion,deposition,mechanical and functional coatings and their preparation methods are discussed.The emphasis has been placed on the composition of chemical conversion and deposited coatings to overcome the disadvantages of adhesion,corrosion resistance and biocompatibility of a single coating for biomedical materials.The issues have been addressed on the integration of the structural and functional factors of the composite coatings.展开更多
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 gen...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.展开更多
Protein adsorption preferentially occurs and significantly affects the physicochemical reactions once the biodegradable magnesium alloys as bone replacements have been implanted. To date, interactions mechanisms betwe...Protein adsorption preferentially occurs and significantly affects the physicochemical reactions once the biodegradable magnesium alloys as bone replacements have been implanted. To date, interactions mechanisms between Mg implants and proteins remain unclear at a molecular level. Thereby, a combination of molecular dynamic(MD) simulations and experimental exploration is used to investigate the adsorption behavior and conformational change of bovine serum albumin(BSA), a representative protein of blood plasma, upon the surface of microarc oxidation(MAO) coated Mg alloy AZ31. The influences of absorbed proteins on the cytocompatibility of MAO coating are evaluated by virtue of cytotoxicity assay. Results indicate that the negatively charged O atoms(BSA) exhibit strong interaction with Mg^(2+) ions of Mg(OH)_(2), revealing that BSA molecules are ionically adsorbed on the AZ31 surface. Interestingly, MD simulation reveals that MAO coating demonstrates superior ability to capture BSA molecules during the process of adsorption owing to strong electric attraction between the negatively charged O atoms in BSA molecules with Mg atoms of MgO in MAO coating. Moreover, the α-helix part of absorbed BSA molecules on AZ31 substrate and MAO coating markedly decreases with an increase in β-sheet, β-turn and unordered contents, which is attributed to the reduction in the number of hydrogen bonds in BSA molecules. Furthermore, the adsorbed BSA molecules improve the cytocompatibility of MAO coating since the positively charged-NH_(3)^(+) group and β-sheet content of absorbed BSA molecules mediate the cell adhesion by interacting with the negatively charged cell membrane.展开更多
One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to th...One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)2 film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium(EDTA-2 Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)2 hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)2 coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating.The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)2 film. The current density of Mg(OH)2-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)2-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.展开更多
A SnO_2-doped calcium phosphate(Ca-P-Sn) coating was constructed on Mg-1 Li-1 Ca alloy by a hydrothermal process. The fabricated functional coatings were investigated using scanning electron microscopy(SEM), X-ray dif...A SnO_2-doped calcium phosphate(Ca-P-Sn) coating was constructed on Mg-1 Li-1 Ca alloy by a hydrothermal process. The fabricated functional coatings were investigated using scanning electron microscopy(SEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FT-IR). A triple-layered structure, which is composed of Ca_3(PO_4)_2,(Ca, Mg)_3(PO_4)_2, SnO_2, and MgHPO_4·3 H_2O, is evident and leads to the formation of Ca_(10)(PO_4)_6(OH)_2 in Hank's solution. Electrochemical measurements, hydrogen evolution tests and plating counts reveal that the corrosion resistance and antibacterial activity were improved through the coating treatment. The embedded SnO_2 nanoparticles enhanced crystallisation of the coating.The formation and degradation mechanisms of the coating were discussed.展开更多
A hexagonal nanosheet Mg(OH)2 coating was prepared through a one-step hydrothermal method using LiOH solution as mineralizer and then modified by ethylenediaminetetraacetic acid(EDTA) to minimize the rapid corrosion o...A hexagonal nanosheet Mg(OH)2 coating was prepared through a one-step hydrothermal method using LiOH solution as mineralizer and then modified by ethylenediaminetetraacetic acid(EDTA) to minimize the rapid corrosion of AZ31 Mg alloy.The performance of the coating was evaluated using electrochemical technique,hydrogen evolution measurements, nanoscratch test,Fourier-transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) patterns and field-emission scanning electron microscopy(FESEM).The results suggested that the corrosion rate of bare AZ31 Mg alloys was significantly reduced by one and two orders of magnitude through the protection from Mg(OH)2 coating and modification with EDTA(i.e., EDTA-Mg(OH)2 coating), respectively.FESEM micrographs indicated that the modification in EDTA elicits to the formation of an EDTA-Mg(OH)2 composite with a thickness as twice as that of as-prepared Mg(OH)2 coating.Nanoscratch tests revealed strong adhesion between the composite or Mg(OH)2 coating and the substrate.The study of formation and corrosion mechanisms of the coatings manifested that Mg(OH)2 was first formed near the intermetallic compound AlMn particles and gradually covered the entire surface, wherein the AlMn particles played an important role in the coating growth process.And it also proved that EDTA accelerated the formation of Mg(OH)2.展开更多
Mg(OH)2/Mg-Al-layered double hydroxide (LDH) coatings were modified with methyltrimethoxysilane (MTMS) on magnesium alloys. Effect of hydrolysis degree of silane solution on coating formation was investigated. Chemica...Mg(OH)2/Mg-Al-layered double hydroxide (LDH) coatings were modified with methyltrimethoxysilane (MTMS) on magnesium alloys. Effect of hydrolysis degree of silane solution on coating formation was investigated. Chemical compositions and surface morphologies of the coatings were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electronic microscopy (FESEM). Results indicated that the composite coatings consisted of polymethyltrimethoxysilane (PMTMS), LDH and Mg(OH)2. Electrochemical and hydrogen evolution measurements revealed that the composite coatings possessed good corrosion resistance, especially the ones prepared in a high hydrolysis degree of silane. The optimum corrosion resistance of the composite coati ng was LDH/PMTMS-3 coating, which had the lowest value of corrosion current density (5.537×10^-9 A·cm^-2) and a dense surface.Plausible mechanism for coating formation and corrosion process of MTMS-modified Mg(OH)2/Mg-Al-LDH coatings were discussed.展开更多
Magnesium(Mg)alloys as a bioabsorbable light metal have shown great clinical potential as bone replacement implants.In this review,the categories,progress in cutting-edge preparation technologies and antibacterial mec...Magnesium(Mg)alloys as a bioabsorbable light metal have shown great clinical potential as bone replacement implants.In this review,the categories,progress in cutting-edge preparation technologies and antibacterial mechanisms of Mg alloys and considerable numbers of corrosion-resistant and functional coatings are summarized.The relationship among the microstructure(grain size,intermetallic compounds),biocorrosion resistance and biocompatibility for antibacterial Mg alloys is discussed.The challenge and outlooks of biomedical Mg alloys and coatings are proposed from an antibacterial perspective.展开更多
Organic coatings are the most widely employed approach for the promotion of corrosion resistance of magnesium(Mg)alloys.Unfortunately,traditional organic coatings are weakly bonded to Mg substrates due to physical ads...Organic coatings are the most widely employed approach for the promotion of corrosion resistance of magnesium(Mg)alloys.Unfortunately,traditional organic coatings are weakly bonded to Mg substrates due to physical adsorption.Herein,a polyethylacrylate(PEA)coating was fabricated on Mg-Zn-YNd alloy via electro-grafting.The surface structure and chemical composition were characterized by means of scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),atomic force microscope(AFM)and Fourier transform infrared(FTIR)as well as time of flight-secondary ion mass spectrometer(To F-SIMS).The results showed that the surface roughness of PEA coating was dominated by scan rate;while the coverage and integrity of PEA coating were mainly affected by the monomer concentration and sweep circles.To F-SIMS results indicated that PEA coating was wholly covered on Mg alloy,and the presence of C2H3Mg-fragment confirmed the covalent bond between PEA coating and Mg alloy.In addition,DFT calculation results of the adsorption of EA molecules with Mg substrate agree well with the experimental phenomena and observation,suggesting that the electrons in 3s orbit of Mg atoms and 2pz orbit of C1 atom participated in the formation of covalent bond between PEA coating and Mg substrate.Potentiodynamic polarization curves and immersion test demonstrated that the PEA coatings could effectively enhance the corrosion resistance of Mg alloy.The platelet adhesion results designated that platelets were barely visible on PEA coating,which implied that PEA coating could effectively prevent the thrombosis and coagulation of platelets.PEA coating might be a promising candidate coating of Mg alloy for cardiovascular stent.展开更多
Exfoliation on as-extruded Mg-1 Li-1 Ca magnesium alloy was investigated after an immersion in 3.5 wt%NaCl aqueous solution for 90, 120 and 150 days through optical microscope, digital camera, scanning electron micros...Exfoliation on as-extruded Mg-1 Li-1 Ca magnesium alloy was investigated after an immersion in 3.5 wt%NaCl aqueous solution for 90, 120 and 150 days through optical microscope, digital camera, scanning electron microscope, electrochemical workstation, scanning Kalvin probe, X-ray diffraction and Fourier transform infrared spectroscope. The results demonstrated that exfoliation corrosion occurred on extruded Mg-1 Li-1 Ca alloy due to elongated microstructure parallel to surface, and delamination of lamellar structure resulted from galvanic effect and wedge effect. Skin layer with fine grains exhibited better corrosion resistance, whereas the interior with coarse grains and the intermetallic compound,Mg_2 Ca particles existing in a fibrous structure, dispersed along grain boundaries and extrusion direction in a line. Furthermore, galvanic effect between Mg_2 Ca particles and their neighboring a-Mg matrix facilitated dissolution of Mg_2 Ca particles and a-Mg matrix; wedge effect was caused by formation of corrosion products. Exfoliation corrosion of extruded Mg-Li-Ca alloys might be a synergic effect of pitting corrosion,filiform corrosion, intergranular corrosion and stress corrosion. Finally, exfoliation corrosion mechanism was proposed.展开更多
Magnesium(Mg)and its alloys,as potential biodegradable materials,have drawn wide attention in the cardiovascular stent field because of their appropriate mechanical properties and biocompatibility.Nevertheless,the occ...Magnesium(Mg)and its alloys,as potential biodegradable materials,have drawn wide attention in the cardiovascular stent field because of their appropriate mechanical properties and biocompatibility.Nevertheless,the occurrence of thrombosis,inflammation,and restenosis of implanted Mg alloy stents caused by their poor corrosion resistance and insufficient endothelialization restrains their anticipated clinical applications.Numerous surface treatment tactics have mainly striven to modify the Mg alloy for inhibiting its degradation rate and enduing it with biological functionality.This review focuses on highlighting and summarizing the latest research progress in functionalized coatings on Mg alloys for cardiovascular stents over the last decade,regarding preparation strategies for metal oxide,metal hydroxide,inorganic nonmetallic,polymer,and their composite coatings;and the performance of these strategies in regulating degradation behavior and biofunction.Potential research direction is also concisely discussed to help guide biological functionalized strategies and inspire further innovations.It is hoped that this review can give assistance to the surface modification of cardiovascular Mg-based stents and promote future advancements in this emerging research field.展开更多
In this article, the microstructure, hardness, and corrosion resistance of the Al0.3CrFe1.5MnNi0.5Tixand Al0.3CrFe1.5MnNi0.5Six(x = 0, 0.2, 0.5, 1.0) high-entropy alloys were investigated via X-ray diffraction(XRD)sca...In this article, the microstructure, hardness, and corrosion resistance of the Al0.3CrFe1.5MnNi0.5Tixand Al0.3CrFe1.5MnNi0.5Six(x = 0, 0.2, 0.5, 1.0) high-entropy alloys were investigated via X-ray diffraction(XRD)scanning electron microscopy(SEM), digital display Vickers hardness tester, and electrochemical technique These alloys are mainly composed of BCC solid-solution structure. When adding high content of Ti or Si elemen(x C 0.5), some intermetallic compounds are found in the microstructure, which makes the alloys have a high hardness, high brittleness, and easy cracking. While the alloys with low content of Ti or Si(x = 0.2) have a hardness of HV 420–HV 430, and its hardness increases about 14 %compared with that of Al0.3CrFe1.5MnNi0.5. Electrochemical results in 3.5 % NaCl solution show that the alloying elements Ti and Si have a negative influence on the corrosion resistance of the Al0.3CrFe1.5MnNi0.5alloys.展开更多
Friction stir spot welding was successfully applied to the 1.2-mm-thick DH590 dual-phase steel plates by using a polycrystalline cubic boron nitride rotating tool.During welding,the rotation speed ranged from 600 to 1...Friction stir spot welding was successfully applied to the 1.2-mm-thick DH590 dual-phase steel plates by using a polycrystalline cubic boron nitride rotating tool.During welding,the rotation speed ranged from 600 to 1000 r/min and the penetration depth ranged from 0.1 to 0.3 mm.In the spot joints,the size of the stir zone increased with the increase in rotation speed as well as the penetration depth of the tool.Comparing with the banded ferrite and martensite structure of the base metal,a mixed microstructure of ferrite and tempered martensite,refined bainite structure and coarse martensite structure were found in the heat-affected zone,thermomechanically affected zone and stir zone of the joints,respectively.Two kinds of interfacial shapes were formed between the upper and lower steel plates,and the formation of the bonded interface was dominated mainly by the penetration depth of the rotating tool rather than the rotation speed.It was revealed that the joints with straight interfaces showed higher shear tensile loads comparing with those with hook-like interfaces.Shear tensile tests showed that the maximum shear tensile load reached about 15.56 kN when the rotation speed and penetration depth were set as 800 r/min and 0.3 mm,respectively.The specimen was fractured through plug failure mode with a total elongation of about 5.6 mm.展开更多
基金the National Key Research and Development Program of China(2018YFC1106703)the National Natural Science Foundation of China(No.U1804251)。
文摘Constructing a functional hybrid coating appears to be a promising strategy for addressing the poor corrosion resistance and insufficient endothelialization of Mg-based stents.Nevertheless,the steps for preparing composite coatings are usually complicated and time-consuming.Herein,a novel composite coating,composed of bioactive magnesium thioctic acid(MTA)layer formed by deposition and corrosion-resistant magnesium hydroxide(Mg(OH)_(2))layer grown in situ,is simply fabricated on ZE21B alloys via one-step electrodeposition.Scanning electron microscopy(SEM)shows that the electrodeposited coating has a compact and uniform structure.And the high adhesion of the MTA/Mg(OH)_(2)hybrid coating is also confirmed by the micro-scratch test.Electrochemical test,scanning kelvin probe(SKP),and hydrogen evolution measurement indicate that the hybrid coating effectively reduces the degradation rate of Mg substrates.Haemocompatibility experiment and cell culture trial detect that the composite coating is of fine biocompatibility.Finally,the preparation mechanism of MTA/Mg(OH)_(2)hybrid coatings is discussed and proposed.This coating shows a great potential application for cardiovascular stents.
基金funded by the Key Projects of the Joint Fund of the National Natural Science Foundation of China(U1804251)National Key Research and Development Program of China (2017YFB0702500, 2018YFC1106703, and 2016YFC1102403)Top Doctor Program of Zhengzhou University (grant number 32210475)。
文摘Recently, functional molecules such as Polydopamine(PDA), Hyaluronic Acid(HA) and heparin have been widely studied in the field of surface modification of magnesium(Mg) alloy stents for better degradation behavior and biocompatibility, but their further application is limited by undesirable anticoagulant function, uncontrollable degradation and easy bleeding, respectively.Regarding to this consideration, a magnesium Fluoride/Polydopamine/Sulphonated hyaluronic acid(Mg F2/PDA/S-HA) composite coating was successfully prepared by applying S-HA with sulfur content of 9.71 wt% on the surface of ZE21B alloy in this study. The results showed that the composite coating with a unique mesh structure not only inherited the anticoagulant effect of sulfonic acid group and the excellent cyto-compatibility of S-HA with high sulfur content, but also significantly improved the corrosion performance of ZE21B alloy.These results indicate a great application potential of the composite coating in the field of cardiovascular biomaterials.
基金This research was financially supported by National Natural Science Foundation of China(51571134)SDUST Research Fund(2014TDJH104).
文摘The clinic applications of bioabsorbable magnesium(Mg)and its alloys have been significantly restricted owing to their poor corrosion resistance.Besides elemental alloying,surface modification and functionality is a major approach to increasing corrosion resistance for magnesium alloys.This article reviews the cutting-edge advances and progress of biodegradable surface coatings upon Mg alloys over the last decades,aims to build up a knowledge framework of surface modification on biodegradable Mg alloys.A considerable number of conversion,deposition,mechanical and functional coatings and their preparation methods are discussed.The emphasis has been placed on the composition of chemical conversion and deposited coatings to overcome the disadvantages of adhesion,corrosion resistance and biocompatibility of a single coating for biomedical materials.The issues have been addressed on the integration of the structural and functional factors of the composite coatings.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 51571134 )the SDUST Re- search Fund ( 2014TDJH104 )the Science and Technol- ogy Innovation Fund of SDUST for graduate students ( SD- KDYC180371 ).
基金National Natural Science Foundation of China(Grant No.52071191)Open Foundation of Hubei Key Laboratory of Advanced Technology for Automotive Components(No.XDQCKF2021006)。
文摘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.
基金supported by the National Natural Science Foundation of China (52071191)。
文摘Protein adsorption preferentially occurs and significantly affects the physicochemical reactions once the biodegradable magnesium alloys as bone replacements have been implanted. To date, interactions mechanisms between Mg implants and proteins remain unclear at a molecular level. Thereby, a combination of molecular dynamic(MD) simulations and experimental exploration is used to investigate the adsorption behavior and conformational change of bovine serum albumin(BSA), a representative protein of blood plasma, upon the surface of microarc oxidation(MAO) coated Mg alloy AZ31. The influences of absorbed proteins on the cytocompatibility of MAO coating are evaluated by virtue of cytotoxicity assay. Results indicate that the negatively charged O atoms(BSA) exhibit strong interaction with Mg^(2+) ions of Mg(OH)_(2), revealing that BSA molecules are ionically adsorbed on the AZ31 surface. Interestingly, MD simulation reveals that MAO coating demonstrates superior ability to capture BSA molecules during the process of adsorption owing to strong electric attraction between the negatively charged O atoms in BSA molecules with Mg atoms of MgO in MAO coating. Moreover, the α-helix part of absorbed BSA molecules on AZ31 substrate and MAO coating markedly decreases with an increase in β-sheet, β-turn and unordered contents, which is attributed to the reduction in the number of hydrogen bonds in BSA molecules. Furthermore, the adsorbed BSA molecules improve the cytocompatibility of MAO coating since the positively charged-NH_(3)^(+) group and β-sheet content of absorbed BSA molecules mediate the cell adhesion by interacting with the negatively charged cell membrane.
基金supported by the National Natural Science Foundation of China(Nos.51571134 and 51601108)the SDUST Research Fund(No.2014TDJH104)
文摘One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)2 film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium(EDTA-2 Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)2 hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)2 coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating.The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)2 film. The current density of Mg(OH)2-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)2-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.
基金supported by the National Natural Science Foundation of China (51571134)the Research Fund of Shandong University of Science and Technology (2014TDJH104)
文摘A SnO_2-doped calcium phosphate(Ca-P-Sn) coating was constructed on Mg-1 Li-1 Ca alloy by a hydrothermal process. The fabricated functional coatings were investigated using scanning electron microscopy(SEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FT-IR). A triple-layered structure, which is composed of Ca_3(PO_4)_2,(Ca, Mg)_3(PO_4)_2, SnO_2, and MgHPO_4·3 H_2O, is evident and leads to the formation of Ca_(10)(PO_4)_6(OH)_2 in Hank's solution. Electrochemical measurements, hydrogen evolution tests and plating counts reveal that the corrosion resistance and antibacterial activity were improved through the coating treatment. The embedded SnO_2 nanoparticles enhanced crystallisation of the coating.The formation and degradation mechanisms of the coating were discussed.
基金financially supported by the National Natural Science Foundation of China (No.51571134)the Shandong University of Science and Technology Research Fund (No.2014TDJH104)
文摘A hexagonal nanosheet Mg(OH)2 coating was prepared through a one-step hydrothermal method using LiOH solution as mineralizer and then modified by ethylenediaminetetraacetic acid(EDTA) to minimize the rapid corrosion of AZ31 Mg alloy.The performance of the coating was evaluated using electrochemical technique,hydrogen evolution measurements, nanoscratch test,Fourier-transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) patterns and field-emission scanning electron microscopy(FESEM).The results suggested that the corrosion rate of bare AZ31 Mg alloys was significantly reduced by one and two orders of magnitude through the protection from Mg(OH)2 coating and modification with EDTA(i.e., EDTA-Mg(OH)2 coating), respectively.FESEM micrographs indicated that the modification in EDTA elicits to the formation of an EDTA-Mg(OH)2 composite with a thickness as twice as that of as-prepared Mg(OH)2 coating.Nanoscratch tests revealed strong adhesion between the composite or Mg(OH)2 coating and the substrate.The study of formation and corrosion mechanisms of the coatings manifested that Mg(OH)2 was first formed near the intermetallic compound AlMn particles and gradually covered the entire surface, wherein the AlMn particles played an important role in the coating growth process.And it also proved that EDTA accelerated the formation of Mg(OH)2.
基金financially supported by the National Natural Science Foundation of China (Nos.51601108 and 51571134)the Natural Science Foundation of Shandong Province (No. 2016ZRB01A62)+1 种基金the Shandong University of Science and Technology Research Fund (No. 2014TDJH104)the Opening Fund of Ministry-Province Jointly Constructed Cultivation Base for State Key Laboratory of Processing for Non-ferrous Metal and Featured Materials
文摘Mg(OH)2/Mg-Al-layered double hydroxide (LDH) coatings were modified with methyltrimethoxysilane (MTMS) on magnesium alloys. Effect of hydrolysis degree of silane solution on coating formation was investigated. Chemical compositions and surface morphologies of the coatings were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electronic microscopy (FESEM). Results indicated that the composite coatings consisted of polymethyltrimethoxysilane (PMTMS), LDH and Mg(OH)2. Electrochemical and hydrogen evolution measurements revealed that the composite coatings possessed good corrosion resistance, especially the ones prepared in a high hydrolysis degree of silane. The optimum corrosion resistance of the composite coati ng was LDH/PMTMS-3 coating, which had the lowest value of corrosion current density (5.537×10^-9 A·cm^-2) and a dense surface.Plausible mechanism for coating formation and corrosion process of MTMS-modified Mg(OH)2/Mg-Al-LDH coatings were discussed.
基金supported by the National Natural Science Foundation of China(No.51571134)the Shandong University of Science and Technology Research Fund(No.2014TDJH104)
文摘Magnesium(Mg)alloys as a bioabsorbable light metal have shown great clinical potential as bone replacement implants.In this review,the categories,progress in cutting-edge preparation technologies and antibacterial mechanisms of Mg alloys and considerable numbers of corrosion-resistant and functional coatings are summarized.The relationship among the microstructure(grain size,intermetallic compounds),biocorrosion resistance and biocompatibility for antibacterial Mg alloys is discussed.The challenge and outlooks of biomedical Mg alloys and coatings are proposed from an antibacterial perspective.
基金Acknowledgements The authors are grateful for the support by National Key Technology R＆D Program of China （Grant No. 2012BAI18B01） and the National Natural Science Foundation of China （Grant No. 51171174）.
基金the Key Projects of the Joint Fund of the National Natural Science Foundation of China(No.U1804251)the National Natural Foundation of China(No.51671175)+1 种基金the National Key Research and Development Program of China(No.2017YFB0702500)the Key Research Projects for Universities of Henan Province(No.15A430050)。
文摘Organic coatings are the most widely employed approach for the promotion of corrosion resistance of magnesium(Mg)alloys.Unfortunately,traditional organic coatings are weakly bonded to Mg substrates due to physical adsorption.Herein,a polyethylacrylate(PEA)coating was fabricated on Mg-Zn-YNd alloy via electro-grafting.The surface structure and chemical composition were characterized by means of scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),atomic force microscope(AFM)and Fourier transform infrared(FTIR)as well as time of flight-secondary ion mass spectrometer(To F-SIMS).The results showed that the surface roughness of PEA coating was dominated by scan rate;while the coverage and integrity of PEA coating were mainly affected by the monomer concentration and sweep circles.To F-SIMS results indicated that PEA coating was wholly covered on Mg alloy,and the presence of C2H3Mg-fragment confirmed the covalent bond between PEA coating and Mg alloy.In addition,DFT calculation results of the adsorption of EA molecules with Mg substrate agree well with the experimental phenomena and observation,suggesting that the electrons in 3s orbit of Mg atoms and 2pz orbit of C1 atom participated in the formation of covalent bond between PEA coating and Mg substrate.Potentiodynamic polarization curves and immersion test demonstrated that the PEA coatings could effectively enhance the corrosion resistance of Mg alloy.The platelet adhesion results designated that platelets were barely visible on PEA coating,which implied that PEA coating could effectively prevent the thrombosis and coagulation of platelets.PEA coating might be a promising candidate coating of Mg alloy for cardiovascular stent.
基金supported by the National Natural Science Foundation of China (No. 51571134)the SDUST Research Fund (No. 2014TDJH104)
文摘Exfoliation on as-extruded Mg-1 Li-1 Ca magnesium alloy was investigated after an immersion in 3.5 wt%NaCl aqueous solution for 90, 120 and 150 days through optical microscope, digital camera, scanning electron microscope, electrochemical workstation, scanning Kalvin probe, X-ray diffraction and Fourier transform infrared spectroscope. The results demonstrated that exfoliation corrosion occurred on extruded Mg-1 Li-1 Ca alloy due to elongated microstructure parallel to surface, and delamination of lamellar structure resulted from galvanic effect and wedge effect. Skin layer with fine grains exhibited better corrosion resistance, whereas the interior with coarse grains and the intermetallic compound,Mg_2 Ca particles existing in a fibrous structure, dispersed along grain boundaries and extrusion direction in a line. Furthermore, galvanic effect between Mg_2 Ca particles and their neighboring a-Mg matrix facilitated dissolution of Mg_2 Ca particles and a-Mg matrix; wedge effect was caused by formation of corrosion products. Exfoliation corrosion of extruded Mg-Li-Ca alloys might be a synergic effect of pitting corrosion,filiform corrosion, intergranular corrosion and stress corrosion. Finally, exfoliation corrosion mechanism was proposed.
基金This work was supported by the National Natural Science Foundation of China （Grant Nos. 51571134 and 51601108）, the SDUST Research Fund （2014TDJH104） and the Science and Technology Innovation Fund of SDUST for graduate students （SDKDYC180371）.
基金The authors are grateful for the financial support of the National Natural Science Foundation of China(No.U1804251)the National Key Research and Development Program of China(No.2017YFB0702504 and 2018YFC1106703).
文摘Magnesium(Mg)and its alloys,as potential biodegradable materials,have drawn wide attention in the cardiovascular stent field because of their appropriate mechanical properties and biocompatibility.Nevertheless,the occurrence of thrombosis,inflammation,and restenosis of implanted Mg alloy stents caused by their poor corrosion resistance and insufficient endothelialization restrains their anticipated clinical applications.Numerous surface treatment tactics have mainly striven to modify the Mg alloy for inhibiting its degradation rate and enduing it with biological functionality.This review focuses on highlighting and summarizing the latest research progress in functionalized coatings on Mg alloys for cardiovascular stents over the last decade,regarding preparation strategies for metal oxide,metal hydroxide,inorganic nonmetallic,polymer,and their composite coatings;and the performance of these strategies in regulating degradation behavior and biofunction.Potential research direction is also concisely discussed to help guide biological functionalized strategies and inspire further innovations.It is hoped that this review can give assistance to the surface modification of cardiovascular Mg-based stents and promote future advancements in this emerging research field.
基金financially supported by the Post-doctoral Scientific Research Foundation of Zhengzhou UniversityPost-doctoral Scientific Research Foundation of China(No.2013M541986)
文摘In this article, the microstructure, hardness, and corrosion resistance of the Al0.3CrFe1.5MnNi0.5Tixand Al0.3CrFe1.5MnNi0.5Six(x = 0, 0.2, 0.5, 1.0) high-entropy alloys were investigated via X-ray diffraction(XRD)scanning electron microscopy(SEM), digital display Vickers hardness tester, and electrochemical technique These alloys are mainly composed of BCC solid-solution structure. When adding high content of Ti or Si elemen(x C 0.5), some intermetallic compounds are found in the microstructure, which makes the alloys have a high hardness, high brittleness, and easy cracking. While the alloys with low content of Ti or Si(x = 0.2) have a hardness of HV 420–HV 430, and its hardness increases about 14 %compared with that of Al0.3CrFe1.5MnNi0.5. Electrochemical results in 3.5 % NaCl solution show that the alloying elements Ti and Si have a negative influence on the corrosion resistance of the Al0.3CrFe1.5MnNi0.5alloys.
文摘Friction stir spot welding was successfully applied to the 1.2-mm-thick DH590 dual-phase steel plates by using a polycrystalline cubic boron nitride rotating tool.During welding,the rotation speed ranged from 600 to 1000 r/min and the penetration depth ranged from 0.1 to 0.3 mm.In the spot joints,the size of the stir zone increased with the increase in rotation speed as well as the penetration depth of the tool.Comparing with the banded ferrite and martensite structure of the base metal,a mixed microstructure of ferrite and tempered martensite,refined bainite structure and coarse martensite structure were found in the heat-affected zone,thermomechanically affected zone and stir zone of the joints,respectively.Two kinds of interfacial shapes were formed between the upper and lower steel plates,and the formation of the bonded interface was dominated mainly by the penetration depth of the rotating tool rather than the rotation speed.It was revealed that the joints with straight interfaces showed higher shear tensile loads comparing with those with hook-like interfaces.Shear tensile tests showed that the maximum shear tensile load reached about 15.56 kN when the rotation speed and penetration depth were set as 800 r/min and 0.3 mm,respectively.The specimen was fractured through plug failure mode with a total elongation of about 5.6 mm.
