Carboxylates as green corrosion inhibitors of magnesium alloy for biomedical application

The efficiency of the green inhibitors(sodium salts of fumarate,glycolate and gluconate)in suppressing corrosion of the structural MA8 magnesium alloy(Mg–Mn–Ce)and the biomedical Mg–0.8Ca alloy was studied using the hydrogen evolution measurements,mass loss test,EIS,PDP,SVET/SIET.The analysis of the morphology,chemical composition,and growth kinetic of corrosion films formed in 0.9 wt%NaCl solution with and without corrosion inhibitors was carried out.The most compact surface film with the smallest thickness was formed in a saline solution with sodium fumarate.The Mg alloy samples exhibited the highest polarization resistance,the lowest localized electrochemical activity,and the lowest corrosion rate in saline with the addition of sodium fumarate and sodium glycolate.The efficiency of the applied inhibitors was up to 81%.The model of the corrosion mechanism based on the sorption of molecules of organic inhibitors is proposed.The results show the high compatibility of the used inhibitors with the calcium-phosphate PEO-matrix,indicating the possibility of forming a self-healing coating by means of these active substances.

Antibacterial HA-coatings on bioresorbable Mg alloy

In this study,a calcium-phosphate coating was formed on a Mg-Mn-Ce alloy by the plasma electrolytic oxidation(PEO).The antibiotic vancomycin,widely used in the treatment of infections caused by Staphylococcus aureus(S.aureus),was impregnated into the coating.Samples with vancomycin showed high bactericidal activity against S.aureus.The mechanical and electrochemical properties of the formed coatings were studied,as well as in vitro cytotoxicity tests and in vivo tests on mature male rats were performed.According to SEM,EDS,XRD and XPS data,coatings had a developed morphology and contained hydroxyapatite,which indicates high biocompatibility.The analysis of roughness of coatings without and with vancomycin did not reveal any differences,confirming the high roughness of the samples.During electrochemical tests,an increase in corrosion resistance by more than two times after the application of PEO coatings was revealed.According to the results of an in vivo study,after 28 days of the implantation of samples with calcium phosphate PEO coating and vancomycin,no signs of inflammation were observed,while an inflammatory reaction developed in the area of implantation of bare alloy,followed by encapsulation.Antibiotic release tests from the coatings show a sharp decrease in the concentration of the released antibiotic on day 7 and then a gradual decrease until day 28.Throughout the experiment,no significant deviations in the condition and behavior of the animals were observed;clinical tests did not reveal a systemic toxic reaction.

Effect of Ta_(2)O_(5)nanoparticles on bioactivity,composition,structure,in vitro and in vivo behavior of PEO coatings on Mg-alloy

The present study investigates the physical and chemical characteristics,behavior in vitro and in vivo,and biocompatibility of coatings containing Ta_(2)O_(5),which are obtained by plasma electrolytic oxidation(PEO)on MA8 magnesium alloy.The obtained coatings demonstrate in vivo biocompatibility and in vitro bioactivity.Compared to the base PEO coating,the layers containing Ta_(2)O_(5)facilitate the development of apatite in simulated body fluid,suggesting that the inclusion of nanoparticles improves bioactivity of the coatings.It was found that incorporation of Ta_(2)O_(5)nanoparticles increases roughness and porosity of the formed layers by increasing particle concentration in electrolytes for the PEO process contributing to sufficient soft tissue ingrowth in vivo.Based on in vivo studies,these coatings also provide favorable tissue response and minimal inflammatory reaction in comparison with the bare magnesium alloy due to protection of living tissues from deleterious corrosion events of magnesium implant such as local alkalization and intense hydrogen evolution.The results obtained in the present study concluded biocompatibility,tissue integration of the PEO coatings containing Ta_(2)O_(5)nanoparticles making them a promising protective layer for biodegradable magnesium implants.

The detailed corrosion performance of bioresorbable Mg-0.8Ca alloy in physiological solutions

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.

Smart composite antibacterial coatings with active corrosion protection of magnesium alloys

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.

Design of self-healing PEO-based protective layers containing in-situ grown LDH loaded with inhibitor on the MA8 magnesium alloy

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.

Hydroxyapatite-containing PEO-coating design for biodegradable Mg-0.8Ca alloy: Formation and corrosion behaviour

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.

Influence of ZrO_(2)/SiO_(2) nanomaterial incorporation on the properties of PEO layers on Mg-Mn-Ce alloy

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)).

New superhydrophobic composite coatings on Mg-Mn-Ce magnesium alloy

A novel combined method for the formation of composite coatings on the Mg-Mn-Ce alloy is developed.Ceramic like matrix was formed on the Mg alloy surface by the plasma electrolytic oxidation.Then the samples were subsequently processed by dip-coating in an alcohol suspension of superdispersed polytetrafluoroethylene and spraying with the tetrafluoroethylene telomers solution.SEM,OSP,and SPM was used to study structure of formed surfaces.It was established by measurements of CA and CAH,as well as surface free energy calculations that formed coatings demonstrate superhydrophobic properties due to the presence of an irregular hierarchical surface structure and low surface free energy of fluoropolymers.The coating preserves its hydrophobic properties after exposure to high and low temperatures,for a long time as well as being in corrosive environments.EDS and XRD data analysis confirmed the presence of organofluorine compounds in the composite layers,including in the form of crystalline polytetrafluoroethylene.Using potentiodynamic polarization test and EIS,it was found that the resulting coatings significantly increase the corrosion resistance of Mg material.These data are also confirmed by salt spray tests for 40 days.Incorporation of fluoropolymers additionally decrease coatings coefficient of friction.

New approach to formation of coatings on Mg-Mn-Ce alloy using a combination of plasma treatment and spraying of fluoropolymers

This paper presents a method of the formation of composite polymer-containing coatings on a Mg–Mn–Ce magnesium alloy by forming a ceramic-like layer using plasma electrolytic oxidation(PEO)and subsequent spraying superdispersed polytetrafluoroethylene suspension.The coating composition and their morphological features were studied by SEM,EDS,GDOES,and XRD.The presented data confirm the embedding of fluoropolymer in the PEO coating.The evaluation of the corrosion properties of the formed composite polymer-containing coatings indicates a decrease in the corrosion current density by more than 3 orders of magnitude in comparison with the base PEO coating.The incorporation of a fluoropolymer in a PEO layer by more than 32%increases the load value at which abrasion of the coating to the substrate occurs and reduces the wear of the coating by more than 27 fold in comparison with the PEO layer.It has been established that composite coatings possess hydrophobic properties:the value of the contact angle attains 152°.

Effect of TiO_(2) nanoparticles on the photocatalytic properties of PEO coatings on Mg alloy

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.

Electrochemical synthesis of boron-containing coatings on Mg alloy for thermal neutron shielding

The work provides the results of the one-step formation of boron-containing coatings on an Mg–Mn–Ce alloy by plasma electrolytic oxidation. The results of studies of the composition, structure and morphology of heteroxide coatings are presented. It was established that the boron is contained in the coating mainly in the form of B or B_(2)O_(3). The introduction of B changes the color of coatings, and also helps to increase their porosity. The method of determining the full cross section of the interaction of thermal neutron absorption efficiency by samples material using the installation of neutron-activation analysis based on ^(252)Cf was developed. It was shown that the introduction of boron into the formed coatings allows to increase the macroscopic cross-section of the interaction of samples with thermal neutrons by 3.8 times. This effect opens the potential for the use of synthesized material in the field of nuclear technologies and aerospace industry.

Plasma electrolytic oxidation of the magnesium alloy MA8 in electrolytes containing TiN nanoparticles

The formation of protective multifunctional coatings on magnesium alloy MA8 using plasma electrolyt- ic oxidation （PEO） in an electrolytic system containing nanosized particles of titanium nitride was investigated. Electrochemical and mechanical properties of the obtained layers were examined. It was established that microhardness of the coating with the nanoparticle concentration of 3 gl-1 increased twofold （4.2 ± 0.5 GPa）, while wear resistance decreased （4.97 × 10-6 mm3 N-1 m-1）, as compared to re- spective values for the PEO-coating formed in the electrolyte without nanoparticles （2.1 ± 0.3 GPa, 1.12 × 10.5 mm3 N-1 m-1）.

A first look at the formation of PEO-PDA coatings on 3D titanium

Additive manufacturing has revolutionized implantology by enabling the fabrication of customized,highly porous implants.Surface modifications using electrochemical methods can significantly enhance the bioactivity and biocompatibility of biomaterials,including 3D-printed implants.This study investigates novel coatings on 3D titanium(Ti)samples.Mesh Ti samples were designed and subjected to plasma electrolytic oxidation(PEO)to form a calcium phosphate coating.Subsequently,a layer of polydopamine(PDA)was applied.The electrochemical properties and morphology of the coatings were analyzed.Scanning electron microscopy(SEM)and energy-dispersive X-ray spectroscopy(EDS)revealed well-developed coatings containing calcium phosphates(including hydroxyapatite),titanium dioxide,and polymerized dopamine,suggesting promising bioactive potential.Composite layers incorporating PDA exhibited superior protective properties compared to base PEO coatings.