Greatly enhanced corrosion/wear resistances of epoxy coating for Mg alloy through a synergistic effect between functionalized graphene and insulated blocking layer

The poor corrosion and wear resistances of Mg alloys seriously limit their potential applications in various industries.The conventional epoxy coating easily forms many intrinsic defects during the solidification process,which cannot provide sufficient protection.In the current study,we design a double-layer epoxy composite coating on Mg alloy with enhanced anti-corrosion/wear properties,via the spin-assisted assembly technique.The outer layer is functionalized graphene(FG)in waterborne epoxy resin(WEP)and the inner layer is Ce-based conversion(Ce)film.The FG sheets can be homogeneously dispersed within the epoxy matrix to fill the intrinsic defects and improve the barrier capability.The Ce film connects the outer layer with the substrate,showing the transition effect.The corrosion rate of Ce/WEP/FG composite coating is 2131 times lower than that of bare Mg alloy,and the wear rate is decreased by~90%.The improved corrosion resistance is attributed to the labyrinth effect(hindering the penetration of corrosive medium)and the obstruction of galvanic coupling behavior.The synergistic effect derived from the FG sheet and blocking layer exhibits great potential in realizing the improvement of multi-functional integration,which will open up a new avenue for the development of novel composite protection coatings of Mg alloys.

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.

Advancements in enhancing corrosion protection of Mg alloys:A comprehensive review on the synergistic effects of combining inhibitors with PEO coating

Magnesium(Mg)alloys are lightweight materials with excellent mechanical properties,making them attractive for various applications,including aerospace,automotive,and biomedical industries.However,the practical application of Mg alloys is limited due to their high susceptibility to corrosion.Plasma electrolytic oxidation(PEO),or micro-arc oxidation(MAO),is a coating method that boosts Mg alloys'corrosion resistance.However,despite the benefits of PEO coatings,they can still exhibit certain limitations,such as failing to maintain long-term protection as a result of their inherent porosity.To address these challenges,researchers have suggested the use of inhibitors in combination with PEO coatings on Mg alloys.Inhibitors are chemical compounds that can be incorporated into the coating or applied as a post-treatment to further boost the corrosion resistance of the PEO-coated Mg alloys.Corrosion inhibitors,whether organic or inorganic,can act by forming a protective barrier,hindering the corrosion process,or modifying the surface properties to reduce susceptibility to corrosion.Containers can be made of various materials,including polyelectrolyte shells,layered double hydroxides,polymer shells,and mesoporous inorganic materials.Encapsulating corrosion inhibitors in containers fully compatible with the coating matrix and substrate is a promising approach for their incorporation.Laboratory studies of the combination of inhibitors with PEO coatings on Mg alloys have shown promising results,demonstrating significant corrosion mitigation,extending the service life of Mg alloy components in aggressive environments,and providing self-healing properties.In general,this review presents available information on the incorporation of inhibitors with PEO coatings,which can lead to improved performance of Mg alloy components in demanding environments.

Improved Corrosion Behavior of Biodegradable Mg-4Zn-1Mn Alloy Modified by Sr/F co-doped CaP Micro-arc Oxidation Coatings

The Sr/F co-doped CaP(Sr/F-CaP)coatings were prepared by micro-arc oxidation(MAO)under different voltages to modify the microstructure and corrosion behavior of Mg-4Zn-1Mn alloy.The surface and interface characteristics investigated using scanning electron microscopy(SEM)and energy dispersive X-ray spectrometer(EDS)showed that the MAO coatings displayed uneven crater-like holes and tiny cracks under lower voltage,while they exhibited relatively homogeneous crater-like holes without cracks under higher voltage.The thickness of MAO coatings increased with increasing voltage.The corrosion behavior of Mg-4Zn-1Mn alloy was improved by the MAO coatings.The MAO coatings prepared under 450 V and 500 V voltages possessed the best corrosion resistance with regard to the electrochemical corrosion tests and immersion corrosion tests,respectively.The MAO coatings fabricated under 450-500 V could provide a better corrosion protection effect for the substrate.

ZIF-8-based micro-arc oxidation composite coatings enhanced the corrosion resistance and superhydrophobicity of a Mg alloy

Mg alloys are considered the most promising engineering materials because of their unique properties.However,the uncontrolled corrosion rate of these alloys limits their applications.Therefore,in this study,a micro-arc oxidation layer was used as a transition layer to“directly”grow a zinc-based metal-organic framework(MOF)composite coating on the surface of a Mg alloy(AZ91D).Herein,the two zeolitic imidazolate framework(ZIF-8)coatings with different morphologies were separately prepared by homologous metal oxide induction and a one-step in-situ growth method.The superhydrophobic composite coating showed strong hydrophobicity and self-cleaning properties,which could prevent the penetration of water and corrosive ions(Cl^(−))into the surface of AZ91D.Electrochemical tests demonstrated that the super-hydrophobic composite coatings greatly enhanced the corrosion resistance of AZ91D,and the corrosion current density decreased from 10^(−5)to 10^(−9)A/cm^(2).These results indicate that the ZIF-8 coatings are beneficial for improving the hydrophobicity and enhancing the corrosion resistance of Mg alloys.Therefore,MOF composite coatings provide a new strategy that can be used to prepare multifunctional anticorrosion coatings on metal substrates.

Advances in Mg-Al-layered double hydroxide steam coatings on Mg alloys:A review

Layered double hydroxide(LDH)coatings on magnesium(Mg)alloys shine brightly in the field of corrosion protection because of their special ion-exchange function.State-of-the-art steam coating as a type of LDH film preparation technique has emerged in recent years because only pure water is required as the steam source and its environmentally friendly LDH coating fits the current need for green development.Moreover,this coating can effectively inhibit the corrosion of the Mg alloy substrate due to the chemical bonding between the coating and the Mg alloy substrate.This review systematically explains cutting-edge advancements in the growth mechanism and corrosion behavior of LDH steam coatings,and analyzes the advantages and limitations of the steam-coating method.The influencing factors including pressure,CO_(2)/CO_(3)^(2-),aluminum content of the substrate alloy,solution type,and acid-pickling pretreatment,as well as the post-treatment of steam-coating defects,are comprehensively elucidated,providing new insights into the development of the in situ steam-coating technique.Finally,existing issues and future prospects are discussed to further accelerate the widespread application of Mg alloys.

Corrosion behavior of composite coatings containing hydroxyapatite particles on Mg alloys by plasma electrolytic oxidation: A review

Mg and its alloys have been introduced as promising biodegradable materials for biomedical implant applications due to their excellent biocompatibility, mechanical behavior, and biodegradability. However, their susceptibility to rapid corrosion within the body poses a significant challenge and restricts their applications. To overcome this issue, various surface modification techniques have been developed to enhance the corrosion resistance and bioactivity of Mg-based implants. PEO is a potent technique for producing an oxide film on a surface that significantly minimizes the tendency to corrode. However, the inevitable defects due to discharges and poor biological activity during the coating process remain a concern. Therefore, adding suitable particles during the coating process is a suitable solution. Hydroxyapatite(HAp)has attracted much attention in the development of biomedical applications in the scientific community. HAp shows excellent biocompatibility due to its similarity in chemical composition to the mineral portion of bone. Therefore, its combination with Mg-based implants through PEO has shown significant improvements in their corrosion resistance and bioactivity. This review paper provides a comprehensive overview of the recent advances in the preparation, characterization, corrosion behavior and bioactivity applications of HAp particles on Mg-based implants by PEO.

Assessment of Mg(OH)_(2)/TiO_(2) coating in the Mg-Ca-Zn alloy for improved corrosion resistance and antibacterial performance

The high activity of metallic magnesium and alloys limits its potential in biomedical applications;in recent years,extensive efforts have been devoted to modulating this reactivity.In this work,we present Mg(OH)_(2) and TiO_(2)barrier coatings to reduce the degradation of magnesium alloy(Mg-Ca-Zn)surfaces.These coatings were deposited by the anodization method and the spin-coating technique,respectively.The anodized layer was coated with TiO_(2)generated from the hydrolysis of 3%weight of TTIP(Ti[OCH(CH_(3))_(2)]_(4),Titanium(IV)isopropoxide)in 2-Propanol deposited by the spin-coating method.Studying the degradation in Ringer’s solution by electrochemical impedance spectroscopy and OCP revealed a 98%reduction in pittings in uncoated samples after 14 days of immersion.The p H measurements revealed that the TiO_(2)coating reduced the alkalization of the physiological environment,keeping the pH at 6.0 values.In vitro studies of two types of bacteria(E.coli and S.aureus)exhibited zones of inhibition in the agar and activity bactericidal(kill time test).The mechanisms behind the improved degradation resistance and enhanced antibacterial activity are presented and discussed here.Surface modification with Mg(OH)_(2)/TiO_(2)coatings is a promising strategy to control the biodegradation of magnesium implants for bone regeneration.

基于冷喷涂工艺的Mg-Zn-Al-Sn-Mn合金防腐Al涂层制备

采用冷喷涂技术在Mg-Zn-Al-Sn-Mn合金表面制备Al涂层,以提高其耐腐蚀性能。研究工作气体温度和压力对Al涂层显微组织和腐蚀行为的影响。结果表明,随着气体温度和压力的升高,Al涂层的致密度和厚度均明显增加。高的气体温度能降低颗粒沉积的临界速度,并提高沉积效率。高的气体压力不仅提升机械结合质量,而且对沉积的涂层具有较强的夯实作用。由于孔隙的减少,Al涂层的耐蚀性随着气体温度和压力的升高而提高。Al(OH)_(3)和Al_(2)O_(3)等腐蚀产物可以堵塞涂层中的孔隙,并作为阻碍腐蚀的物理屏障,从而有效保护Mg合金免受腐蚀。

Ce对Zn-Al-Mg合金镀层组织和耐腐蚀性能的影响

为了考察Ce含量对热浸镀Zn-Al-Mg合金镀层的组织和耐腐蚀性能的影响,采用SEM、EDS、XRD等方法对镀层的形貌、组织成分及物相进行了观察分析,结合盐雾试验对腐蚀产物形貌、组成及含量以及去除腐蚀产物后的镀层形貌进行了分析,并进一步通过电化学测试考察了不同镀层在3.5%NaCl溶液中的电化学行为。结果表明,Zn-5Al-1.5Mg-xCe (x=0, 0.05, 0.10, 0.25,质量分数,%)合金镀层的组织由富Zn相、富Al相和Zn/Al/MgZn_(2)(或Mg_(2)Zn_(11))三元共晶组织组成,少量Ce的加入增加了镀层中三元共晶组织的比例。Ce可以减薄镀层,细化富Al相,提高镀层的均匀性。当Ce添加量为0.10%时,细化效果最好。另外,Zn-5Al-1.5Mg-0.10Ce合金镀层的耐腐蚀性能最好,是Zn-5Al-1.5Mg合金镀层的2.6倍左右。Ce提高了镀层的均匀性,减少了局部腐蚀,提高了Zn_5(OH)_8Cl_(2)·H_(2)O腐蚀产物保护层的均匀性和致密性,从而提高了镀层的耐腐蚀性能。

ZnO@ZIF-8 core-shell structure nanorods superhydrophobic coating on magnesium alloy with corrosion resistance and self-cleaning

A longstanding quest in material science has been the development of superhydrophobic coating based on a single material, without the requirement of fluorination or silane treatment. In this work, the micro-arc oxidation(MAO) coating as transition layer can effectively enhance the bonding force of the superhydrophobic coating. The semiconductor@metal organic frameworks(MOFs) core-shell structure was synthesized by a simple self-templating method, and obtained ZnO@2-methylimidazole zinc salt(ZIF-8) nanorods array on magnesium(Mg)alloy. ZnO nanorods not only act as the template but also provide Zn^(2+) for ZIF-8. In addition, we proved that the ligand concentration,synthesis time and temperature are the keys to the preparation of ZnO@ZIF-8 nanorods. As we expect, the ZnO@ZIF-8 nanorods array can trap air in the gaps to form an air layer, and the coating exhibits superhydrophobic properties(154.81°). Excitingly, ZnO@ZIF-8 nanorods array shown a superhydrophobic property, without the requirement of fluorination or silane treatment. The results shown that the coating has good chemical stability and self-cleaning performance. Meanwhile, the corrosion resistance has been significantly improved, R_(ct) was increased from 1.044×10^(3) to 1.414×10^(6) Ω/cm^(2) and I_(corr) was reduced from 4.275×10^(-5) to 5.611×10^(-9)A/cm^2. Therefore, the semiconductor@MOFs core-shell structure has broad application prospects in anti-corrosion.

Recent progress in self-repairing coatings for corrosion protection on magnesium alloys and perspective of porous solids as novel carrier and barrier

Featuring low density and high specific strength, magnesium(Mg) alloys have attracted wide interests in the fields of portable devices and automotive industry. However, the active chemical and electrochemical properties make them susceptible to corrosion in humid, seawater, soil,and chemical medium. Various strategies have revealed certain merits of protecting Mg alloys. Therein, engineering self-repairing coatings is considered as an effective strategy, because they can enable the timely repair for damaged areas, which brings about long-term protection for Mg alloys. In this review, self-repairing coatings on Mg alloys are summarized from two aspects, namely shape restoring coatings and function restoring coatings. Shape restoring coatings benefit for swelling, shrinking, or reassociating reversible chemical bonds to return to the original state and morphology when coatings broken;function self-repairing coatings depend on the release of inhibitors to generate new passive layers on the damaged areas. With the advancement of coating research and to fulfill the demanding requirements of applications, it is an inevitable trend to develop coatings that can integrate multiple functions(such as stimulus response, self-repairing, corrosion warning,and so on). As a novel carrier and barrier, porous solids, especially covalent organic frameworks(COFs), have been respected as the future development of self-repairing coatings on Mg alloys, due to their unique, diverse structures and adjustable functions.

Pitting corrosion behavior and corrosion protection performance of cold sprayed double layered noble barrier coating on magnesium-based alloy in chloride containing solutions

Nitrogen processed, cold sprayed commercially pure(CP)-Al coatings on Mg-based alloys mostly lack acceptable hardness, wear resistance and most importantly are highly susceptible to localized corrosion in chloride containing solutions. In this research, commercially pure α-Ti top coating having good pitting potential(~1293 mV_(SCE)), high microhardness(HV_(0.025): 263.03) and low wear rate was applied on a CP-Al coated Mg-based alloy using high pressure cold spray technology. Potentiodynamic polarization(PDP) curves indicated that the probability of transition from metastable pits to the stable pits for cold spayed(CS) Al coating is considerably higher compared to that with the CS Ti top coating(for Ti/Al/Mg system). In addition, CS Ti top coating was in the passivation region in most pH ranges even after 48 h immersion in 3.5 wt% NaCl solution. The stored energy in the CS Ti top coating(as a passive metal) was presumed to be responsible for the easy passivation. Immersion tests indicated no obvious pits formation on the intact CS Ti top coating surface and revealed effective corrosion protection performance of the CS double layered noble barrier coatings on Mg alloys in 3.5 wt% NaCl solution even after 264 h.

Antibacterial activities and corrosion behavior of novel PEO/nanostructured ZrO_2 coating on Mg alloy

Plasma electrolytic oxidation（PEO） was developed as a bond coat for air plasma sprayed（APS） nanostructure ZrO2 as top coat to enhance the corrosion resistance and antibacterial activity of Mg alloy. Corrosion behavior and antibacterial activities of coated and uncoated samples were assessed by electrochemical tests and agar diffusion method toward Escherichia coli（E. coli） bacterial pathogens, respectively. The lowest corrosion current density and the highest charge transfer resistance, phase angle and impedance modulus were observed for PEO/nano-ZrO2 coated sample compared with those of PEO coated and bare Mg alloys. Nano-ZrO2 top coat which has completely sealed PEO bond coat is able to considerably delay aggressive ions transportation towards Mg alloy surface and significantly enhances corrosion resistance of Mg alloy in simulated body fluid（SBF） solution. Moreover, higher antibacterial activity was also observed in PEO/nano-ZrO2 coating against bacterial strains than that of the PEO coated and bare Mg alloys. This observation was attributed to the presence of ZrO2 nanoparticles which decelerate E. coli growth as a result of E. coli membranes.

Applications of carbonic acid solution for developing conversion coatings on Mg alloy

Works on exploring an environmentally clean method for producing an Mg,Al-hydrotalcite(Mg6Al2(OH) 16CO3·4H2O) layer and/or calcium carbonate(CaCO3) layer on Mg alloy in a carbonic acid solution system(aqueous HCO3-/CO3 2-or Ca 2+ /HCO3-) at 50℃ were reviewed.Conversion treatment for the Mg,Al-hydrotalcite conversion coating was as follows.Mg alloy was treated first in acidic HCO3-/CO3 2-aqueous for precursor layer formation on Mg alloy surface and then in alkaline HCO3-/CO3 2-aqueous to form a crystallized Mg,Al-hydrotalcite coating.Duration of an Mg,Al-hydrotalcite coating on Mg alloy surface was reduced from 12 h to 4 h by the conversion treatment.On the other hand,for reducing the formation time of CaCO3 coating on Mg alloy,the aqueous Ca 2+ /HCO3-with a saturated Ca 2+ content was employed for developing a CaCO3 coating on Mg alloy.A dense CaCO3 coating could yield on Mg alloy surface in 2 h.Corrosion rate(corrosion current density,Jcorr) of the Mg,Al-hydrotalcite-coated sample and CaCO3-coated AZ91D sample was 7-10μA/cm 2,roughly two orders less than the Jcorr of the as-diecast sample(about 200μA/cm 2) . No corrosion spot on the Mg,Al-hydrotalcite-coated sample and CaCO3-coated sample was observed after 72 h and 192 h salt spray test,respectively.

Comparison of the corrosion behavior of AM60 Mg alloy with and without self-healing coating in atmospheric environment

Coatings on the surface of Mg alloys are inevitably damaged during their practical applications,and corrosion can easily initiate from the damaged areas to accelerate the failure of Mg parts.A dual self-healing coating has already been developed to solve this problem in our previous work.Considering the practical application of this coating,it is necessary to investigate its service behavior in atmospheric environment.Thus,the corrosion behavior of AM60 Mg substrate with and without the self-healing coating was compared in Shenyang industrial atmospheric environment.The results show that the enrichment of sediments and rainwater on the scratch areas can accelerate the corrosion of the exposed Mg substrate.The inhibitors can be released from the damaged coating to inhibit corrosion.The dual self-healing coating shows better inhibition ability to narrow scratches due to the higher inhibitor concentration and less resumption.Also,the coating with wide scratches displays enough inhibition ability as well.The dual self-healing coating is a good alternative for Mg alloy parts in the practical applications.

A review of effective strides in amelioration of the biocompatibility of PEO coatings on Mg alloys

Recently,developing bioactive and biocompatible materials based on Mg and Mg-alloys for implant applications has drawn attention among researchers owing to their suitable body degradability.Implementing Mg and its alloys reduces the risk of long-term incompatibility with tissues because of their close mechanical properties and no need for re-operation to remove the implant.Nevertheless,the degradation rate of the implant needs to be controlled because production of hydrogen gas and accumulation of its bubbles increases local pH around the implants.To confine the integrity of implants and the body,the corrosion concern in the body fluid requires to be addressed.Surface modification as one of the effective strategies can improve corrosion resistance.Besides,it creates a suitable surface for bone grafting and cell growth.The development of proper surface-coated implants needs appropriate techniques and approaches.Plasma electrolytic oxidation(PEO)coating can provide long-term protection by providing a ceramic layer and improving the implant’s biocompatibility.Herein,a general review of in-vivo and in-vitro evaluation of PEO coatings on Mg and Mg-alloys has been carried out.Recent advances in surface modification on Mg and Mg-alloys have been discussed,however,the need for reliable laboratory models to predict in-vivo degradation is still valid.

Impressive strides in amelioration of corrosion and wear behaviors of Mg alloys using applied polymer coatings on PEO porous coatings:A review

Magnesium(Mg)and its alloys have received much attention in a lot of areas due to their special chemical and physical properties.Nevertheless,high corrosion rates are a limiting factor.The plasma electrolytic oxidation(PEO)technique is a simple approach to place an oxide film on the surface of light metals like Mg alloys.This method has been considered for controlling the rate of corrosion and improving some other properties.On the other hand,PEO coatings cannot make enough protection of Magnesium alloys for a long time due to porosity and fine cracks.Therefore,PEO-based composite coatings are used to make adequate corrosion protection on the Mg alloys surface.The popularity of these coatings is due to their good corrosion resistance,simplicity,high coating capability,and cost-effectiveness in complex segments.Formation of an organic layer on the surface of PEO coating is one of the effective methods to close the defects and thus prevent the corrosive species penetration into the substrate.Coating the PEO coating with a polymer layer can be a good solution to control the amount of damage and improve the corrosion and abrasion resistance.In addition,PEO coating can eliminate the problems of insufficient adhesion of polymer coatings and is considered as a suitable base for composite coatings.This review paper presents the corrosion and abrasion behavior of the PEO/Polymer dual coating system on Mg alloys.Given the fundamental role of coatings thickness and morphology in wear and corrosion behavior,these aspects have been highly discussed in this study.

Micro-arc oxidation coatings on Mg-Li alloys

Micro-arc oxidation (MAO) method was used for the surface modification of an Mg-5wt.%Li alloy. Ceramic coatings were in-situ fabricated on the Mg-Li alloy. The morphology feature,phase composition,and corrosion-resistance of the formed ceramic coatings were studied by SEM,XRD,and electrochemical methods,respectively. The results showed that the coatings produced in a sodium silicate solution system were composed of MgO and Mg2SiO4. The ceramic coating became thicker and the content of Mg2SiO4 phase increase...

Development of anti-corrosive coating on AZ31 Mg alloy subjected to plasma electrolytic oxidation at sub-zero temperature

Plasma electrolytic oxidation(PEO)is a promising surface treatment to generate adherent and thick anti-corrosive coating on light-weight metals(Al,Mg,Ti,etc.)using an eco-friendly alkaline electrolyte.High energy plasma,however,inevitably generates porous structures that limit their practical performance.The present study proposes a straight-forward simple method by utilizing sub-zero electrolyte(268 K)to alter the plasma characteristics during formation of the protective coating on AZ31 Mg alloy via PEO with a comparison to the electrolyte at room temperature(298 K).In refrigerated electrolyte,the formation of micro-defects is suppressed relatively at the expense of low coating growth,which is measured to be twice lower than that at 298 K due to the temperature-dependent soft plasma discharges contributing to the development of the present coating.As a consequence,corrosion resistance of the sample processed at 268 K is superior to that of 298K,implying that the effect of coating thickness is less dominant than that of compactness.This phenomenon is interpreted in relation to the ionic movement and oxide solidification controlled by soft plasma discharges arising from the temperature gradient between electrolyte and surface of the substrate during PEO.