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.

Improving corrosion resistance of additively manufactured WE43 magnesium alloy by high temperature oxidation for biodegradable applications

Laser powder bed fusion(L-PBF)has been employed to additively manufacture WE43 magnesium(Mg)alloy biodegradable implants,but WE43 L-PBF samples exhibit excessively rapid corrosion.In this work,dense WE43 L-PBF samples were built with the relativity density reaching 99.9%.High temperature oxidation was performed on the L-PBF samples in circulating air via various heating temperatures and holding durations.The oxidation and diffusion at the elevated temperature generated a gradient structure composed of an oxide layer at the surface,a transition layer in the middle and the matrix.The oxide layer consisted of rare earth(RE)oxides,and became dense and thick with increasing the holding duration.The matrix was composed ofα-Mg,RE oxides and Mg_(24)RE_(5) precipitates.The precipitates almost disappeared in the transition layer.Enhanced passivation effect was observed in the samples treated by a suitable high temperature oxidation.The original L-PBF samples lost 40%weight after 3-day immersion in Hank’s solution,and broke into fragments after 7-day immersion.The casted and solution treated samples lost roughly half of the weight after 28-day immersion.The high temperature oxidation samples,which were heated at 525℃ for 8 h,kept the structural integrity,and lost only 6.88%weight after 28-day immersion.The substantially improved corrosion resistance was contributed to the gradient structure at the surface.On one hand,the outmost dense layer of RE oxides isolated the corrosive medium;on the other hand,the transition layer considerably inhibited the corrosion owing to the lack of precipitates.Overall,high temperature oxidation provides an efficient,economic and safe approach to inhibit the corrosion of WE43 L-PBF samples,and has promising prospects for future clinical applications.

Effect of low concentration electrolytes on the formation and corrosion resistance of PEO coatings on AM50 magnesium alloy

In this paper,the formation process,morphology,and electrochemical performance of PEO coatings on AM50 magnesium alloy prepared in low concentration phosphate,aluminate,and phosphate-aluminate electrolytes were systematically studied.The results show that the coatings prepared from the phosphate electrolytes have a higher thickness and better corrosion resistance properties compared to the other electrolytes.The coatings prepared from low concentration phosphate-aluminate mixed electrolytes have slightly thinner thickness,a similar coating structure and an order of magnitude lower value of electrochemical impedance compared with phosphate electrolyte coatings.The Coatings prepared from low concentration aluminate electrolytes have the lowest thickness and the worst corrosion resistance properties which gets close to corrosion behavior of the bare AM50 under the same test conditions.Considering application,coatings prepared from single low concentration phosphate electrolytes and low concentration phosphate-aluminate electrolytes have greater potential than single low concentration aluminate coatings.However,reducing the electrolyte concentrations of coating forming ions too much has negative influence on the coating growth rate.

Developing super-hydrophobic and corrosion-resistant coating on magnesium-lithium alloy via one-step hydrothermal processing

Formation of super-hydrophobic and corrosion-resistant coatings can provide significant corrosion protection to magnesium alloys.However,it remains a grand challenge to produce such coatings for magnesium-lithium alloys due to their high chemical reactivity.Herein,a one-step hydrothermal processing was developed using a stearic-acid-based precursor medium,which enables the hydrothermal conversion and the formation of low surface energy materials concurrently to produce the super-hydrophobic and corrosion-resistant coating.The multiscale microstructures with nanoscale stacks and microscale spheres on the surface,as well as the through-thickness stearates,lead to the super-hydrophobicity and excellent corrosion resistance of the obtained coating.

Valence electron structures and properties of Ni-based corrosion resistant alloy

The corrosion resistance and mechanical properties were tested and compared for the newly synthesized as-cast,as-solution Ni-Cr-Mo-Cu corrosion resistant alloys and 1Cr18Ni9Ti austenitic stainless steel. Their valence electron structural units were constructed,and the relative parameters were calculated by means of the Empirical Electron theory of Solids and Molecules(EET). The results show that,during alloy elements Cr,Mo and Cu entering Ni-matrix,the bonding strength nA and bonding energy EA of the strongest bond of the alloy are greatly increased,causing the stronger solid solution strengthening effects(about 30% increase in σb). Also,as reinforcement of the main bond network and the improvement of stability of the alloy system due to the solution of these alloying elements in γ-Ni,the ionization of metal atoms in corrosion solution and the flow of electrons from anode to cathode would all be impeded during electro-chemical corrosion processes,which leads to the excellent corrosion resistant ability of the present Ni-Cr-Mo-Cu alloy(about 2-3 orders of magnitude as high as 1Cr18Ni9Ti austenitic stainless steel) in several highly aggressive solutions.

Effect of nano-CaO particle on the microstructure,mechanical properties and corrosion behavior of lean Mg-1Zn alloy

The effects of nano-CaO contents on the microstructure,mechanical properties and corrosion resistance of lean Mg-1Zn alloy were investigated.The results showed that the addition of nano-CaO significantly refined the grain size and improved mechanical properties of the Mg-1Zn alloy.At the same time,CaO reacted with molten Mg in situ to form nano-MgO,whose corrosion product in SBF solution was the same with the degradation product of Mg matrix,resulting in the enhanced compactness of the Mg(OH)_(2) layer and reduced corrosion rate of matrix.The Mg-1Zn alloy had lower corrosion resistance due to excessively large grain size and shedding of corrosion products.The composite with 0.5 wt.%CaO had the best corrosion resistance with a weight loss of 9.875 mg·y^(-1)·mm^(-2)due to the small number of Ca_(2)Mg_(6)Zn_(3) phase and suitable grain size.While for composites with high content of CaO(0.7 wt.%and 1.0 wt.%),they had lower corrosion resistance due to the coexistence of large number of Ca_(2)Mg_(6)Zn_(3) and Mg_(2)Ca at grain boundaries,especially for 1.0 wt.%CaO composite,resulting from the strong micro-galvanic corrosion.

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.

Corrosion resistance and anti-soiling performance of micro-arc oxidation/graphene oxide/stearic acid superhydrophobic composite coating on magnesium alloys

Magnesium(Mg)alloys,the lightest metal construction material used in industry,play a vital role in future development.However,the poor corrosion resistance of Mg alloys in corrosion environments largely limits their potential wide applications.Therefore,a micro-arc oxidation/graphene oxide/stearic acid(MAO/GO/SA)superhydrophobic composite coating with superior corrosion resistance was fabricated on a Mg alloy AZ91D through micro-arc oxidation(MAO)technology,electrodeposition technique,and self-assembly technology.The composition and microstructure of the coating were characterized by scanning electron microscopy,X-ray diffraction,energy dispersive spectroscopy,and Raman spectroscopy.The effective protection of the MAO/GO/SA composite coating applied to a substrate was evaluated using potentiodynamic polarization,electrochemical impedance spectroscopy tests,and salt spray tests.The results showed that the MAO/GO/SA composite coating with a petal spherical structure had the best superhydrophobicity,and it attained a contact angle of 159.53°±2°.The MAO/GO/SA composite coating exhibited high resistance to corrosion,according to electrochemical and salt spray tests.

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.

Corrosion resistance and electrical conductivity of V/Ce conversion coating on magnesium alloy AZ31B

A V/Ce conversion coating was deposited in the surface of AZ31B magnesium alloy in a solution containing vanadate and cerium nitrate.The coating composition and morphology were examined.The conversion coating appears to consist of a thin and cracked coating with a scattering of spherical particles.The corrosion behavior of the substrate and conversion coating was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS).Compared with AZ31B magnesium alloy,the corrosion current density of the conversion coating is decreased by two orders of magnitude.The total impedance of the V/Ce conversion coating rise to 1.6×10^(3)Ω·cm^(2)in contrast with2.2×10^(2)Ω·cm^(2)of the bare AZ31B.In addition,the electrical conductivity of the coating was assessed by conductivity meter and Mott-Schottky measurement.The results reveal a high dependence of the conductivity of the coating on the semiconductor properties of the phase compositions.

Self-repairing functionality and corrosion resistance of in-situ Mg-Al LDH film on Al-alloyed AZ31 surface

A novel Mg-Al LDH film was in-situ prepared hydrothermally in an alkaline aqueous solution on an Al-alloyed AZ31 substrate.The structural,chemical and functional characteristics of the film were explored by means of scanning electron microscope(SEM),X-ray diffraction(XRD),energy dispersive spectrometer(EDS),polarization curve,AC impedance and salt immersion tests,respectively.The anti-corrosion results indicated that the Mg-Al LDH film on the Al-alloyed AZ31 surface could effectively protect the AZ31 from corrosion attack even after 90 days of immersion in 3.5 wt.%NaCl solution.The protection performance is surprisingly better than most of the reported coatings on Mg alloys.More interestingly,when the Mg-Al LDH film was scratched,the exposed Al-alloyed surface might gradually release metal ions and re-generate dense LDH nano-sheets in the corrosive environment to inhibit the further corrosion there,exhibiting a self-repairing behavior.The combination of the benign long-term protection and desirable self-repairing performance in this new process of surface-alloying and LDH-formation may significantly extend the practical application of magnesium alloys.

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

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

Incorporation of Mg-phenolic networks as a protective coating for magnesium alloy to enhance corrosion resistance and osteogenesis in vivo

Magnesium(Mg) and its alloys have been intensively studied to develop the next generation of bone implants recently, but their clinical application is restricted by rapid degradation and unsatisfied osteogenic effect in vivo. A bioactive chemical conversion Mg-phenolic networks complex coating(e EGCG) was stepwise incorporated by epigallocatechin-3-gallate(EGCG) and exogenous Mg^(2+)on Mg-2Zn magnesium alloy. Simplex EGCG induced chemical conversion coating(c EGCG) was set as compare group. The in vitro corrosion behavior of Mg-2Zn alloy, c EGCG and e EGCG was evaluated in SBF using electrochemical(PDP, EIS) and immersion test. The cytocompatibility was investigated with rat bone marrow mesenchymal stem cells(r BMSCs). Furthermore, the in vivo tests using a rabbit model involved micro computed tomography(Micro-CT) analysis, histological observation, and interface analysis. The results showed that the e EGCG is Mgphenolic multilayer coating incorporated Mg-phenolic networks, which is rougher, more compact and much thicker than c EGCG. The e EGCG highly improved the corrosion resistance of Mg-2Zn alloy, combined with its lower average hemolytic ratios, continuous high scavenging effect ability and relatively moderate contact angle features, resulting in a stable and suitable biological environment, obviously promoted r BMSCs adhesion and proliferation. More importantly, Micro-CT, histological and interface elements distribution evaluations all revealed that the e EGCG effectively inhibited degradation and enhanced bone tissue formation of Mg alloy implants. This study puts forward a promising bioactive chemical conversion coating with Mg-phenolic networks for the application of biodegradable orthopedic implants.

Fabrication of corrosion-resistant superhydrophobic coating on magnesium alloy by one-step electrodeposition method

A one-step electrodeposition method was used to construct a superhydrophobic coating on the surface of magnesium alloy.Using magne-sium nitrate and ethanol solution of stearic acid as electrolyte,four groups of electrolytes with different ratios of stearic acid and magnesium nitrate were designed to explore the influence of electrolyte to the process.The contact angles of the four coating samples were 136.4±5.8°,152.7±2.8°,156.2±4.9°and 155.1±4.4°The addition of magnesium nitrate in the solution increased the hydrogen evolution reaction in the electrodeposition process,which was not conducive to electrodeposition process.During the deposition process,the sample prepared in a molar ratio of stearic acid to magnesium nitrate of 10:1 had the best corrosion resistance,and its corrosion circuit density was 3.74×10^(−8)A/cm^(2),far lower than the corrosion current density of the magnesium alloy substrate.

Microstructure and Corrosion Resistance of CrN and CrN/TiN Coated Heat-Resistant Steels in Molten Aluminum Alloy

The components of the equipment for processing the Al melts into the molded parts can be markedly corroded by the molten Al. In this study, a 4 μm CrN coating or CrN/TiN multilayer coating for providing the physical and chemical barriers between the molten reactive Al and the steel substrate were deposited by Cathodic Arc Evaporation onto 10 mm-thick heat-resistant steel plates. The dipping tests were conducted in a 700℃ A356 melt for 1 to 21 h at intervals of 3 h. The damage of the coated steel was eva...

Superhydrophobic Light Alloy Materials with Corrosion-Resistant Surfaces

Metals and their alloys are irreplaceable engineered materials showing great importance in our society.Light alloy materials(i.e.,Mg,Al,Ti,and their alloys)have tremendous application potential in the aerospace,automotive industries,and biomedical fields for they are lighter and have excellent mechanical properties.The corrosion of light alloys is ubiquitous and greatly restricts their utilization.Inspired by the natural anti-water systems,many new designs and conceptions have recently emerged to create artificial superhydrophobic surfaces with great potential for corrosion resistant of light alloy.This review firstly introduces the concept of superhydrophobicity and strategies of producing superhydrophobic surfaces to inhibit the corrosion of light alloys.In addition,we elaborate the durability of superhydrophobic light alloy materials for commercial and industrial applications,and present their anticorrosion mechanism in the corrosive media.

Influence of Li^(+)/Al^(3+) on the corrosion behavior of Li-Al layered double hydroxides(LDHs) film on LA51 magnesium alloys

A hierarchical superhydrophobic Al-Li layered double hydroxide(LDH)films with different Li^(+)/Al^(3+)molar ratios of 1:1,1:2,2:1,p H value of 11.5 and reaction temperature of 125°C,have been fabricated on the surface of Mg-5Li-1Al(LA51)alloys by hydrothermal method following the characteristics of controllable cation structure and exchangeable anion between layers.The properties of the films were investigated by X-ray diffractometer(XRD),scanning electron microscope(SEM)and energy dispersive spectrometer(EDS).XRD and SEM results indicate that the Al-Li LDH films are successfully prepared on LA51 alloys.The contact angle(CA)was measured to be about100.7°,indicating that the surface wettability of the film converted from hydrophilic to hydrophobic by surface modification.The corrosion resistance of Al-Li LDH films was evaluated by Tafel polarization curve and electrochemical impedance spectroscopy(EIS).Surprisingly,Tafel polarization curve and EIS test reveal that the Al-Li LDH films prepared at the molar ratio of Li^(+)/Al^(3+)1:2,p H 11.5 and temperature125°C have better corrosion resistance in 0.1 M Na Cl neutral solution.In addition,the formation mechanism and corrosion mechanism of the films on the surface of LA51 alloy are also proposed.It provides innovative synthetic materials and novel design ideas for the preparation of high-efficiency anti-corrosion coatings on LA51 alloys,whose application can be extended in industrial fields.

Novel PA encapsulated PCL hybrid coating for corrosion inhibition of biodegradable Mg alloys:A triple triggered self-healing response for synergistic multiple protection

Surface coatings have been extensively used to control the degradation rate of Mg alloys for bioimplant applications.However,these coatings only act as passive barriers.In corrosive media,structural damage impairs their barrier properties,resulting in rapid degradation of Mg alloys.The present study incorporates phytic acid(PA)as a healing agent in polycaprolactone(PCL)microcapsules with a unique honeycomb core matrix to obtain a self-healing PA-PCLcaps coating.The contact between simulated body fluid(SBF)and PA-PCLcaps coated ZM21 exhibited Cassie-Baxter interfacial states,resulting in significant hydrophobicity with a contact angle(CA)of 116.3.The corrosion potential(Ecorr)and current density(Icorr)were found to be-0.28 V and 1.1×10^(-9)A/cm^(2),respectively,for PA-PCLcaps coating,resulting in biosafe corrosion rate of 2.5×10^(-4)mm/year.After mechanical scratching,rapid HA mineralization at scratched regions recovered the hydrogen evolution rate(HER,0.36 mL/cm^(2)/day)and pH change(pH 7.10)of scratched PA-PCLcaps coated ZM21 samples to corresponding unscratched samples within one day of immersion.The coating’s self-healing ability could be attributed to PA released from punctured microcapsules,which facilitates HA chelation.The pH-triggered(pH 10)and Mg(II)-triggered(5 mM)conditions enhanced PA release from PA-PCLcaps coating by 2.5 and 3.1 times,respectively.As a result,dense HA mineralization occurred,which protects the coating from structural defects and ensures its durability in stimulating conditions.The findings of present study provide new insight for design of multiple stimuli-feedback based self-healing coatings on biodegradable Mg alloys.

Mechanical strength and corrosion resistance of Al-additive friction stir welded AZ31B joints

Compared to other structural alloys,magnesium alloys have a relatively poor corrosion resistance and low mechanical strength,which can be further deteriorated when these alloys are subjected to joining processes using the existing joining methods.Herein,we propose for the first time an additive friction stir-welding(AFSW)using fine Al powder as an additive to improve the mechanical strength as well as corrosion resistance of AZ31B weld joints.AFSW is a solid-state welding method of forming a high-Al AZ31B joint via an in-situ reaction between pure Al powders filled in a machined groove and the AZ31B matrix.To optimize the process parameters,AFSW was performed under different rotational and transverse speeds,and number of passes,using tools with a square or screw pin.In particular,to fabricate a weld zone,where the Al was homogenously dispersed,the effects of the groove shape were investigated using three types of grooves:surface one-line groove,surface-symmetric grooves,and inserted symmetric grooves.The homogenous and defect-less AFS-welded AZ31B joint was successfully fabricated with the following optimal parameters:1400 rpm,25 mm/min,four passes,inserted symmetric grooves,and the tool with a square pin.The AFSW fully dissolved the additive Al intoα-Mg and in-situ precipitated Mg_(17)Al_(12)particles,which was confirmed via scanning electron microscopy,transmission electron microscope,and X-ray diffraction analyses.The microhardness,joint efficiency,and elongation at the fracture point of the AFS-welded AZ31B joint were 80 HV,101%,and 8.9%,respectively.These values are higher than those obtained for the FS-welded AZ31 joint in previous studies.The corrosion resistance of the AFS-welded AZ31B joint,evaluated via hydrogen evolution measurements and potentiodynamic polarization tests,was enhanced to 55%relative to the FS-welded AZ31B joint.