In this study, the biocompatible protective coating was formed using plasma electrolytic oxidation(PEO) on bioresorbable Mg-0.8Ca alloy. The composition of the formed coating was studied using XRD, SEM-EDX analysis, a...In this study, the biocompatible protective coating was formed using plasma electrolytic oxidation(PEO) on bioresorbable Mg-0.8Ca alloy. The composition of the formed coating was studied using XRD, SEM-EDX analysis, and micro-Raman spectroscopy. The uniform distribution of hydroxyapatite over the thickness of protective PEO-layer was established. Using traditional(EIS, PDP, OCP) and local scanning electrochemical methods(SVET, SIET with H^(+)-selective microelectrode), the level of protective properties of PEO-layer in a biological environment(mammalian cell culture medium, MEM) was determined. It was established that modification of Mg-0.8Ca alloy surface by PEO contributes to a significant increase in the corrosion resistance of the surface layer, making it possible to control the process of material‘s biodegradation. The maximum local electrochemical activity was recorded after 72 h of testing, while for the uncoated sample,intense corrosion degradation was recorded in the first 12 min of exposure to the cell culture medium. Formation of the PEO-coating results in a twofold decrease in the corrosion current density(2.8·10^(-6)A cm^(-2)) and an increase in the impedance modulus measured at a low frequency(1.7·10^(4)Ω cm^(2)) in comparison with the uncoated material(9.5·10^(-6)A cm^(-2);8.1·10^(3)Ω cm^(2)). The mechanism of material bioresorption was established and a model for biodegradation process of Mg-0.8Ca alloy with hydroxyapatite-containing PEO-coating in MEM was proposed. Analysis of these results and comparing with others obtained by various scientific groups indicate the prospects for application of biocompatible PEO-coating on Mg-Ca alloy in implant surgery.展开更多
The high corrosion rate of magnesium and its alloys in chloride-containing solution significantly reduces the potential of this material for diverse applications.Therefore,the formation of a smart protective coating w...The high corrosion rate of magnesium and its alloys in chloride-containing solution significantly reduces the potential of this material for diverse applications.Therefore,the formation of a smart protective coating was achieved in this work to prevent degradation of the MA8 magnesium alloy.A porous ceramic-like matrix was obtained on the material by plasma electrolytic oxidation(PEO).Further surface functionalization was performed using layered double hydroxides(LDH) served as nanocontainers for the corrosion inhibitor.Several methods of LDH intercalation with benzotriazole(BTA) were proposed.The composition and morphology of the formed coating were studied using SEM-EDX analysis,XRD,XPS,and Raman microspectroscopy.The corrosion behavior of the coated samples was evaluated using electrochemical impedance spectroscopy and potentiodynamic polarization.The corrosion rate was estimated using volumetry and gravimetry methods.The formed composite coating provides the Mg alloy with the lowest corrosion activity(|Z|_(f)=0.1 Hz)=8.48·10^(5) Ω·cm^(2),I_(c)=1.4·10^(-8)A/cm^(2),P_(H)=0.21 mm/year) and improves the protective properties of the PEO-coated sample(|Z|_(f)=0.1 Hz)=8.37·10^(3) Ω·cm^(2),I_(c)=4.1·10^(-7)A/cm^(2),P_(H)=0.31 mm/year).The realization of the self-healing effect of the inhibitor-containing LDH/PEO-coated system was studied using localized electrochemical methods(SVET and SIET) with two artificial defects on the surface.A mechanism involving three stages for the active corrosion protection of the alloy was proposed.These findings contribute to the follow-up work of developing modified LDH/PEO-based structures that promote the Mg alloy with high corrosion resistance,superior electrochemical performance for applications in various fields of industry and medicine.展开更多
A comprehensive study of the properties of coatings formed on a magnesium alloy by plasma electrolytic oxidation(PEO) using the electrolytes with nanosized particles of anatase(titanium dioxide) has been carried out. ...A comprehensive study of the properties of coatings formed on a magnesium alloy by plasma electrolytic oxidation(PEO) using the electrolytes with nanosized particles of anatase(titanium dioxide) has been carried out. Formed coatings reduce corrosion current density 2.5-fold and increase hardness by 25% compared to a coating without particles. Confocal micro-Raman spectroscopy revealed the presence of anatase and rutile phases in the composition of PEO coating due to the incorporation of TiO2nanoparticles during plasma electrolytic treatment. The presence of titanium dioxide had a positive effect on the photocatalytic properties of coatings: the constant rate of the methyl orange and methyl blue decomposition is increased in 1.6 and 1.8-fold, respectively, compared to the coating formed in electrolyte without TiO_(2) particles.展开更多
The electrochemical behaviour of biodegradable magnesium alloy Mg-0.8Ca was evaluated in a mammalian cell culture medium(MEM)and Na Cl solutions(0.9 wt.%, 0.3 wt.%) using traditional(EIS, PDP, OCP) and local scanning ...The electrochemical behaviour of biodegradable magnesium alloy Mg-0.8Ca was evaluated in a mammalian cell culture medium(MEM)and Na Cl solutions(0.9 wt.%, 0.3 wt.%) using traditional(EIS, PDP, OCP) and local scanning electrochemical(SVET, SIET with p H-selective microelectrode) methods at the micro-and meso-level. Corrosion rates of samples in two different media were determined using weight loss tests. The influence of testing media components, alloy composition and microstructure on the material’s degradation process was determined.The SVET/SIET test parameters were optimized for in vitro investigation of the bioresorbable material surface. The mechanism of the alloy’s bioresorption was suggested. The effect of microsized phases on the corrosion behaviour of the alloy was proved using complementary in situ monitoring and SKPFM measurements. The rapid degradation rate of the alloy is related to the presence of local microgalvanic cells formed by cathodic α-magnesium matrix and anodic Mg_(2)Ca phase. The highest corrosion activity was revealed in the first 12 min of sample exposure to MEM, followed by stabilization of corrosion process due to the material’s passivation. Using SEM-EDX analysis, micro-Raman spectroscopy and XPS analysis the composition of the corrosion products was determined. Degradation in MEM proceeds with a formation of magnesium-and-carbonate substituted hydroxyapatite-containing film on the sample’s surface. The low possibility of application of Mg-0.8Ca alloy without coating protection in implant surgery was highlighted.展开更多
A new method of the formation of composite coatings with the function of active corrosion protection of magnesium alloys was developed using the plasma electrolytic oxidation(PEO) method. Susceptibility of PEO-layers ...A new method of the formation of composite coatings with the function of active corrosion protection of magnesium alloys was developed using the plasma electrolytic oxidation(PEO) method. Susceptibility of PEO-layers to pitting formation was evaluated using localized electrochemical methods(SVET/SIET). The morphological features and electrochemical properties of composite coatings were studied using SEM/EDX, XRD, micro-Raman spectroscopy and EIS/PDP measurements, respectively. The effect of surface layers impregnation with corrosion inhibitor on their protective properties in a corrosive environment was established. Additional protection was achieved using controllable coating pore sealing with polymer. It was found that the polymer treatment of the PEO-layer does not reduce the inhibitor’s efficiency. The formed protective composite inhibitor-and-polymer-containing layers decrease the corrosion current density of a magnesium alloy in a 3 wt.% Na Cl solution to three orders of magnitude. This predetermines the prospect of new smart coatings formation that significantly expand the field of application of electrochemically active materials. The mechanism of smart composite coating corrosion degradation was established. The antibacterial activity of the inhibitor-containing coatings against S. aureus methicillin-resistant strain was proved using the in vitro model. These protective layers are promising for reducing the incidence of implant-associated infections.展开更多
The properties of coatings formed on the MA8 magnesium alloy by the plasma electrolytic oxidation in electrolytes containing mechanical mixture of zirconia and silica nanoparticles in concentrations of 2,4 and 6 g/l h...The properties of coatings formed on the MA8 magnesium alloy by the plasma electrolytic oxidation in electrolytes containing mechanical mixture of zirconia and silica nanoparticles in concentrations of 2,4 and 6 g/l have been investigated.It has been established by SEM,EDS,and XPS that ZrO_(2)/SiO_(2)nanoparticles successfully were incorporated into the coatings.Micro-Raman spectroscopy showed the presence of ZrO_(2)in tetragonal and monoclinic forms in the PEO-coating composition as well as Mg_(2)SiO_(4) in tetrahedral configuration uniformly distributed in the outer part of coatings.Obtained coatings significantly reduce corrosion current density in comparison with bare Mg alloy and base PEOlayer(from 2.4×10^(–7)A/cm^(2) for base PEO layer to 0.7×10^(–7)A/cm^(2) for coatings with nanoparticles).It has been found that the presence of solid nanoparticles in the composition of coating has a positive effect on their hardness(this parameter was increased from 2.1±0.3 GPa to 3.1±0.4 GPa)and wearproof(the wear was reduced from(4.3±0.4)×10^(–5)mm^(3)/(N×m)to(3.5±0.2)×10^(–5)mm^(3)/(N×m)).展开更多
基金Local electrochemical tests,biocompatible coating formation and modeling the mechanism of the material degradation were supported by the Grant of Russian Science Foundation,Russia (project no.21-73-10148,https://rscf.ru/en/project/ 21-73-10148/)The study of material‘s structure,composition,and kinetics of the corrosion processes using traditional electrochemical methods was supported by the Grant of Russian Science Foundation,Russia (project no.20-13-00130,https://rscf.ru/en/project/20-13-00130/)XRD data were acquired under the government assignments from the Ministry of Science and Higher Education of the Russian Federation,Russia (project no.FWFN(0205)-2022-0003)。
文摘In this study, the biocompatible protective coating was formed using plasma electrolytic oxidation(PEO) on bioresorbable Mg-0.8Ca alloy. The composition of the formed coating was studied using XRD, SEM-EDX analysis, and micro-Raman spectroscopy. The uniform distribution of hydroxyapatite over the thickness of protective PEO-layer was established. Using traditional(EIS, PDP, OCP) and local scanning electrochemical methods(SVET, SIET with H^(+)-selective microelectrode), the level of protective properties of PEO-layer in a biological environment(mammalian cell culture medium, MEM) was determined. It was established that modification of Mg-0.8Ca alloy surface by PEO contributes to a significant increase in the corrosion resistance of the surface layer, making it possible to control the process of material‘s biodegradation. The maximum local electrochemical activity was recorded after 72 h of testing, while for the uncoated sample,intense corrosion degradation was recorded in the first 12 min of exposure to the cell culture medium. Formation of the PEO-coating results in a twofold decrease in the corrosion current density(2.8·10^(-6)A cm^(-2)) and an increase in the impedance modulus measured at a low frequency(1.7·10^(4)Ω cm^(2)) in comparison with the uncoated material(9.5·10^(-6)A cm^(-2);8.1·10^(3)Ω cm^(2)). The mechanism of material bioresorption was established and a model for biodegradation process of Mg-0.8Ca alloy with hydroxyapatite-containing PEO-coating in MEM was proposed. Analysis of these results and comparing with others obtained by various scientific groups indicate the prospects for application of biocompatible PEO-coating on Mg-Ca alloy in implant surgery.
基金supported by the Grant of Russian Science Foundation,Russia (project no.21-73-10148,https://rscf.ru/en/project/ 21-73-10148/)supported by the Grant of Russian Science Foundation,Russia (project no.20-13-00130,https://rscf.ru/en/ project/20-13-00130/)。
文摘The high corrosion rate of magnesium and its alloys in chloride-containing solution significantly reduces the potential of this material for diverse applications.Therefore,the formation of a smart protective coating was achieved in this work to prevent degradation of the MA8 magnesium alloy.A porous ceramic-like matrix was obtained on the material by plasma electrolytic oxidation(PEO).Further surface functionalization was performed using layered double hydroxides(LDH) served as nanocontainers for the corrosion inhibitor.Several methods of LDH intercalation with benzotriazole(BTA) were proposed.The composition and morphology of the formed coating were studied using SEM-EDX analysis,XRD,XPS,and Raman microspectroscopy.The corrosion behavior of the coated samples was evaluated using electrochemical impedance spectroscopy and potentiodynamic polarization.The corrosion rate was estimated using volumetry and gravimetry methods.The formed composite coating provides the Mg alloy with the lowest corrosion activity(|Z|_(f)=0.1 Hz)=8.48·10^(5) Ω·cm^(2),I_(c)=1.4·10^(-8)A/cm^(2),P_(H)=0.21 mm/year) and improves the protective properties of the PEO-coated sample(|Z|_(f)=0.1 Hz)=8.37·10^(3) Ω·cm^(2),I_(c)=4.1·10^(-7)A/cm^(2),P_(H)=0.31 mm/year).The realization of the self-healing effect of the inhibitor-containing LDH/PEO-coated system was studied using localized electrochemical methods(SVET and SIET) with two artificial defects on the surface.A mechanism involving three stages for the active corrosion protection of the alloy was proposed.These findings contribute to the follow-up work of developing modified LDH/PEO-based structures that promote the Mg alloy with high corrosion resistance,superior electrochemical performance for applications in various fields of industry and medicine.
基金carried out within the framework of the grant of the Russian Science Foundation.project No. 22-23-00937。
文摘A comprehensive study of the properties of coatings formed on a magnesium alloy by plasma electrolytic oxidation(PEO) using the electrolytes with nanosized particles of anatase(titanium dioxide) has been carried out. Formed coatings reduce corrosion current density 2.5-fold and increase hardness by 25% compared to a coating without particles. Confocal micro-Raman spectroscopy revealed the presence of anatase and rutile phases in the composition of PEO coating due to the incorporation of TiO2nanoparticles during plasma electrolytic treatment. The presence of titanium dioxide had a positive effect on the photocatalytic properties of coatings: the constant rate of the methyl orange and methyl blue decomposition is increased in 1.6 and 1.8-fold, respectively, compared to the coating formed in electrolyte without TiO_(2) particles.
基金the Grant of Russian Science Foundation,Russia(project no.20–13–00130,https://rscf.ru/en/project/20–13–00130/)the Grant of Russian Science Foundation,Russia(project no.21–73–10148,https://rscf.ru/en/project/21–73–10148/)the government assignments from the Ministry of Science and Higher Education of the Russian Federation,Russia(project no.0205–2021–0003)。
文摘The electrochemical behaviour of biodegradable magnesium alloy Mg-0.8Ca was evaluated in a mammalian cell culture medium(MEM)and Na Cl solutions(0.9 wt.%, 0.3 wt.%) using traditional(EIS, PDP, OCP) and local scanning electrochemical(SVET, SIET with p H-selective microelectrode) methods at the micro-and meso-level. Corrosion rates of samples in two different media were determined using weight loss tests. The influence of testing media components, alloy composition and microstructure on the material’s degradation process was determined.The SVET/SIET test parameters were optimized for in vitro investigation of the bioresorbable material surface. The mechanism of the alloy’s bioresorption was suggested. The effect of microsized phases on the corrosion behaviour of the alloy was proved using complementary in situ monitoring and SKPFM measurements. The rapid degradation rate of the alloy is related to the presence of local microgalvanic cells formed by cathodic α-magnesium matrix and anodic Mg_(2)Ca phase. The highest corrosion activity was revealed in the first 12 min of sample exposure to MEM, followed by stabilization of corrosion process due to the material’s passivation. Using SEM-EDX analysis, micro-Raman spectroscopy and XPS analysis the composition of the corrosion products was determined. Degradation in MEM proceeds with a formation of magnesium-and-carbonate substituted hydroxyapatite-containing film on the sample’s surface. The low possibility of application of Mg-0.8Ca alloy without coating protection in implant surgery was highlighted.
基金supported by the Grant of Russian Science Foundation, Russia (project no. 21–73– 10148, https://rscf.ru/en/project/21–73–10148/)The study of material‘s structure, composition, and corrosion processes kinetics was supported by the Grant of Russian Science Foundation, Russia (project no. 20–13–00130, https://rscf.ru/en/project/20–13–00130/)Raman spectra were acquired under the government assignments from the Ministry of Science and Higher Education of the Russian Federation, Russia (project no. FWFN(0205)-2022–0003)。
文摘A new method of the formation of composite coatings with the function of active corrosion protection of magnesium alloys was developed using the plasma electrolytic oxidation(PEO) method. Susceptibility of PEO-layers to pitting formation was evaluated using localized electrochemical methods(SVET/SIET). The morphological features and electrochemical properties of composite coatings were studied using SEM/EDX, XRD, micro-Raman spectroscopy and EIS/PDP measurements, respectively. The effect of surface layers impregnation with corrosion inhibitor on their protective properties in a corrosive environment was established. Additional protection was achieved using controllable coating pore sealing with polymer. It was found that the polymer treatment of the PEO-layer does not reduce the inhibitor’s efficiency. The formed protective composite inhibitor-and-polymer-containing layers decrease the corrosion current density of a magnesium alloy in a 3 wt.% Na Cl solution to three orders of magnitude. This predetermines the prospect of new smart coatings formation that significantly expand the field of application of electrochemically active materials. The mechanism of smart composite coating corrosion degradation was established. The antibacterial activity of the inhibitor-containing coatings against S. aureus methicillin-resistant strain was proved using the in vitro model. These protective layers are promising for reducing the incidence of implant-associated infections.
基金supported within the frames of the Grant of the Russian Science Foundation, project No. 20-73-00280carried out within the framework of the Grant of the Russian Science Foundation, project No. 20-13-00130collected under the government assignments from Ministry of Science and Higher Education of the Russian Federation (project no. 0265-2019-0001)。
文摘The properties of coatings formed on the MA8 magnesium alloy by the plasma electrolytic oxidation in electrolytes containing mechanical mixture of zirconia and silica nanoparticles in concentrations of 2,4 and 6 g/l have been investigated.It has been established by SEM,EDS,and XPS that ZrO_(2)/SiO_(2)nanoparticles successfully were incorporated into the coatings.Micro-Raman spectroscopy showed the presence of ZrO_(2)in tetragonal and monoclinic forms in the PEO-coating composition as well as Mg_(2)SiO_(4) in tetrahedral configuration uniformly distributed in the outer part of coatings.Obtained coatings significantly reduce corrosion current density in comparison with bare Mg alloy and base PEOlayer(from 2.4×10^(–7)A/cm^(2) for base PEO layer to 0.7×10^(–7)A/cm^(2) for coatings with nanoparticles).It has been found that the presence of solid nanoparticles in the composition of coating has a positive effect on their hardness(this parameter was increased from 2.1±0.3 GPa to 3.1±0.4 GPa)and wearproof(the wear was reduced from(4.3±0.4)×10^(–5)mm^(3)/(N×m)to(3.5±0.2)×10^(–5)mm^(3)/(N×m)).
